A TEXT-BOOK OF

MACRO AND SEMIMICRO

QUALITATIVE
INORGANIC
ANALYSIS
BY

ARTHUR I. VOGEL, D.Sc.(LoND'), D.LC., F.R.I.C.

Head of Chemistry Department, Woolwich Polytechnic:
Sometime Beit Scientific Research Fellow of th'l
Imperial College .
ANGRAU Central Library
Hyderabad
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FOURTH EDITION

,\I'AU eEl.: fRAL LlH.< AR Y

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.. Date: k,.. 7- 83

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-book of
1937
1941
1942 (twice)
Reissue with Appendix 1943
New Impression 1944
Third Edition under the title 'A Text·book of
Qualitative Chemical Analysis including
Semimicro Qualitative Analysis', 1945
New Impressions 1946, 1947 (twice), 1948,
1951, 1952
Fourth Edition under Ihe lille 'A Text-book of
, M=~q, "l.wl. 'M:wimitt~q, "i,,.,ui.w.:'% r.WlT.1>"l....;.._
Analysis' . 1954
New Impression (with minor corrections) 1955
New Impressions , 1957. 1959. 1960

Translt1ted in/o Spanish and published by Editorial Kapelusz.

Buenos Aires, in April 1953

Rs. 16.50

MADB AND PBINTBD IN GREAT BR.ITAIN

wtJoLUII CLOWES .MD 80N8 :1.IKIT&D, LONDO" AND BJ:CCLE8
 PREFACE TO THE FOURTH EDITION

rHE text has been exhaustively revised, considerably enlarged

and completely reset in the present edition. The opportunity
nas been taken of rearranging certain sections and chapters
which, it is hoped, will enhance the value of the book: thus
hhe technique of semimicro analysis is now incorporated in
Chapter II (Experimental Technique of Qualitative Inorganic
Analysis). The author's aim has continued to be to provide a
hext-book of macro and semiIAicro qualitative inorganic
analysis at moderate cost wl.lich:.oo,n be employed by the
~tudent continuously throughout his study of the subject.
rhere is some duplication in the chapters devoted to the needs
)f the elementary student, but it is felt that this method of
~reatment will assist to lay a firm and sound foundation from
&he very outset and also retain the individuality' of Chapters
V and VI. The numerous new tests and procedures have been
&horoughly tested in the laboratory.
The following changes and new features in the present
edition may be mentioned:
1. The Br5nsted-Lowry treatment of acids and bases (1,5).
2. An extended treatment of activity coefficients and their
applications (I, 11 and I, 15).
3. An extended treatment of the determination of pH (I, 38
and I, 39).
4. Treatment of hydrolysis from the standpoint of the proton
theory of acids and bases (1,42).
5. The description of semimic:ro apparatus and semimicro
analytical operations (II, 3) has been revised in the light of
experience in the laboratory during the last eight years.
(Since both hand and electric semimicro centrifuges are now
comparatively inexpensive, the description of the pressure-
filter tube method of filtration has been omitted.)
6. All the group separation tables on the semimicro scale as
well as many on the macro scale have been revised; some
tables are new. The separation of Group IIA (copper group)
&nd IIB (arsenic group) by the potassium hydroxide method
h&fJ been included: this procedure has much to commend it
• T
vi Preface
and merits wider application than it has had in tlil} past.
The precipitation of Group IV (calcium group) after \ \'apora-
tion of the filtrate from Group IIIB (zino group) to ,lryness
and elimination of all ammonium salts has been ad, .ted as
standard practice. {The latter is based upon the . ork of
A. Scheinkman (1931) and of van Nieuwenburg and ( Dulfer
(1938); it seems to be insufficiently realised that h: !~h con-
centrations of ammonium salts hinder the complete I)rccipita-
tion of Group IV (calcium group) by ammonium c,· ;'bonate
solution.}
7. The zirconyl nitrate method for the separation .,f phos-
phate. {This is based upon the researches of D. J. Ccl . (1952)
in the laboratory of Dr. A. J. Lindsey at the Sir J. 'll Cass
College; it is superior to most other "phosphate sepp' Ltions"
and has therefore been given at the appropriate poin: in the
text.}
8. The reactions of palladous compounds (IX, 7).
9. A short chapter on inorganic paper chromat )'~raphy.
{This account is based largely upon the researche,' at the
Chemical Research Laboratory, Department of Scier, fio and
Industrial Research, Teddington; the writer desires to cknow-
ledge his indebtedness to Dr. F. H. Burstall and Mr. R. \.. Wells
for their kind help in supplying photographs of paper c1 romato-
grams and also certain experimental details.}
The book will be found suitable for students prep::ring for
the General and Honours (Special) B.Sc. degree of t he Uni-
versities, for other University Examinations of er,'livalent
standard, and for the Associateship of the Roy"l In: (itute of
Chemistry; also for the General Certificate of Edu' ltion at
Advanced Level, the Preliminary Scientific Ex. mil tion of
the Pharmaceutical Society, for the Ordinary .',nr; Higher
National Certificates in Chemistry, the various Sf:' i)larship
Examinations, and for general laboratory use. It hoped,
also, that the volume will be useful to practising 1 alytical
chemists.
The author wishes to record his indebtedness to Dr. A I Jlaassen
of Eindhoven for numerous suggestions; to Mr. C. Ky " RSc.,
for checking the new tests and procedures; to Dr. J. i .eioester
for the experimental work upon inorganic paper chromato-
graphy; to Messrs. W. T. Cresswell, B.Sc., and C. M. Ellis, B.Sc.,
and Drs. G. H. Jeffery and J. Leicester for reading tlie ga.ley
proofs and for helpful suggestions; and finally to lie. G. H.
Jeffery for his help and advice upon numerous occasions.
 Preface
The writer would be glad to hear from teachers, analytical
chemists and others of any errors which may have escaped his
notice; any suggestions whereby the book can be improved will
be welcomed.
A. I. VOGEL
Woolwich Polytechnic,
London, S.E.lS
September 1953
 CONTENTS

DHAPTER I
THE THEORETIC " r T OF QUALITATIVE A:r-._ .LYSIS
PAGE
I, 1. Electrolytes ru;d n,.n-electrolytos 2
I, 2. Electrolysi~ , 'n" 2
I, 3. Some 1''''' eoua qolutions 3
1,4. Re" 5
I, 5 .ures 6
'nation of ~. <q degree of
12
~tion of ions , X!l'..i.' 15
.lisation. Interiom, ry
~J.", 0 ...
nd Onsager 17
Tah~?,' )n . l
,w of mass action to solutio_.
0
;y coeffioient ,2
lnd bases . 26
ulybasic acids 28
..It 29
31
I solubility product relation 38
.gly soluble salts of weak acids in
l6
1,1~ r(,v'l)i~tiilt!n . 47
1,19. .t'reparation of s,'-tion " ·\9
1,20. CompleJt ion'l :n
1,21. Chemical f, 1'.'9
1,22. Chemical eq 60
1,23. Discussion 01 ,duction 61
1,24. The oxidati,...;. ·1 64
1,25. The ion-electron i. Ju 68
1,26. Typical oxidising aulI. reducing agents: summary 72
1,27. Concentration of reagents. Molar and normal solv' 76
1,28. Theory of oxidation and reduction 82
1,29. Electrode potentials 83
1,30. Calculation of electrode potentials 88
1,31. Concentration cells 90
1,32. Calculation of the e.m.f. of a voltaic cell 90
1,33. Oxidation-reduction cells 91
1,34. Calculation of the oxidation potential 93
1,35. Equilibrium constant of oxidation-reduction reactions 95
1,36. The ionic product of water 97
1,37. Hydrogen ion exponent (pH) . 99
1,38. Determination of the hydrogen ion concentration 101
• ix
 Oontents
PAGE
1,39. Buffer solutions 109
1,40. Hydrolysis of salts . . . . 114
1,41. Hydrolysis constant and degree of hydrolysis.. 117
1,42. Hydrolysis and the proton theory of acids and bases. 125
1,43. The distribution or partition law 13l
1,44. The colloidal state. 1:14

CHAPTER II
EXPERIMENTAL TECHNIQUE OF QUALITATIVE
INORGANIC ANALYSIS
TECHNIQUE OF MACRO ANALYSIS
II, 1. Dry reactions 1>3
II, 2. Wet reactions 154

TECHNIQUE OF SEMIMICRO ANALYSIS

II, 3. Semimicro apparatus and semimicro analytical operations 165

. TECHNIQUE OF MICRO ANALYSIS

II, 4. General iliscussion . . . . . 188
II, 5. Micro apparatus and micro analytical operations 189
II, 6. Apparatus required for spot test analysis . 1',}'

CHAPTER III
REACTIONS OF THE METAL IONS OR CATIONS
III, 1. The analytical classification of the metals 206

THE SILVER GROUP (GROUP I)

III, 2. Reactions of the lead ion 208
III, 3. Reactions of the mercurous ion 211
III, 4. Reactions of the silver ion . 21'
III, 5. *Analysis of the silver group (Group I); Table I and
Table SMI 217

THE COPPER AND ARSENIC GROUP (GROUP II)

III, 6. Reactions of the mercuric ion 219
III, 7. Reactions of the bismuth ion 221
III, 8. Reactions of the cupric ion . 223
III, 9. Reactions of the cadmium ion . . . . 229
111,10. *Analysis of the copper group (Group IlA); Table II :!33
Table IIA . 234:
Table SMIIA. . . . 235
1lI,11. Reactions of arsenious compounds 237
111,12. Reactions of arsenic compounds . 2'0
111,13. Special tests for small amounts of arsenic 2'2
• For elementary .,udenta.
 Oontents
PAGE
111,14. Reactions of antimonious compounds 247
111,15. Reactions of antimonic compounds 249
,111,16. Reactions of stannous compounds 252
111,17. Reactions of stannic compuunds . 254
111,18. *Analysis of the arsenic group (Group lIB): Table III 256
Table IlIA 257
Table SMIIIA. 258

THE IRON AND ZINC GROUP (GROUP Ill)

111,19. Reactions of the ferrous ion. 260
UI,20. Reactions of the ferric ion . 262
111,21. Reactions of the aluminium ion 267
111,22. Reactions of the chromic ion 272
111,23. *Analysis of the iron group (Group lIlA); Table I\T 277
Table SMIV . 278
111,24. Reactions of the cobaltous ion 279
111,25. Reactions of the nickel ion . :1 283
111,26. Reactions of the manganolls ion 288
111,27. Reactions of the zinc ion 292
111,28. *Analysis of the zinc group (Group IIIB); Table V. 297
Table SMV 298

THE CALCIUM GROUP

111,29. Reactions of the barium ion 299
111,30. Reactions of the strontium ion 302
111,31. Reactions of the calcium ion 303
111,32. *Analysis of the calcium group (Group IV); Table VI 307
Table SMVI 308
Table SMVIA . 309

THE ALKALI GIWUP (GROUP V)

111,33. Reactions of the magnesium ion 311
111,34. Reactions of the potassium ion 315
111,35. Reactions of the sodium ion 317
111,36. Reactions of the ammoniulU ion 318
111,37. *Analysis of the alkali group (Group V); Table VII 323
Table SMVII . 324

CHAPTER IV
REACTIONS OF THE ACID RADICALS OR ANIONS
IV, 1. Scheme of classification 325
IV, 2. Reactions of carbonates 326
IV, 3. Tests for bicarbonates. 328
IV, 4. Reactions of sulphites . 329
IV, 5. Reactions of thiosulphates 333
IV, 6. Reactions of sulphides. 335
IV, 7. Reactions of nitrites. . . . 338
IV, 8. Rd~tions of cyanides. . . . 340
IV, 9. I~ctions of cyanates . . . . 344
• For elementary >ltudenta .
•
xii Oontents

IV,10. Reactions of thiocyanates 3H'i

IV,ll. Reactions of ferrocyanides 3~8
IV,12. Reactions of ferricyanides
IV,13. Reactions of hypochlorites
IV,14. Reactions of chlorides.
IV,I5. Reactions of bromides.
IV,16. Reactions of iodides
IV,17. Reactions of fluorides .
IV,lS. Reactions of nitrates . :)1)3
IV,19. Reactions of chlorates . 3(,6
IV,20. Reactions of bromates . 3G9
IV,2t. Reactions of iodates
IV,22. Reactions of perchlorates :r,2
IV,23. Reactions of borates :li3
IV,24. Reactions of sulphates . :r77
IV,25. Reactions of persulphates :;;9
IV,26. Reactions of silicates . . 3131
IV,27. Reactions of silicofluorides (fluosilicates) :H,4
IV,28. Reactions of orthophosphates .. :1s5
IV,29. Reactions of pyrophosphates and of metaphosphates :;89
IV,30. Reactions of phosphites 390
IV,3t. Reactiolls of hypophosphites ::01
IV,32. Reactions of arsenites and of arserlates . :j92
IV,33. Reactions of chromates (and dichromates) :\03
IV,34. Reactions of permanganates . • :;\)5
IV,35. Reactions of acetates . :)tJ7
IV,36. Reactions of formates . -100
IV,37. Reactions of oxalates . 401
IV,3S. Reactions of tartrates. 404
IV,39. Reactions of citrates 407
IV,40. Reactions of salicylates .j09
IV,4t. Reactions of benzoates 410
IV,42. Reactions of succinates . ,H2
IV,43. Reactions of hydrogen peroxide - . 413
IV,44. Reactions of hydrosulphites (hyposulphites or dithionites) n5
IV,45. Special tests for mixtures of acid radicals 416

CHAPTER V
SYSTEMATIC MACRO QUALITATIVE INORGANIC
ANALYSIS FOR ELEMENTARY STUDENTS
V, 1. Abbreviated course of im~truction. .. 131
V, 2. Systematic analysis. General considerations . t3!
V, 3. Preliminary tests. .. 433
V, 4. Examination for acid radicals (anions) in solution 438
V, 5. Confirmatory tests for acid radicals (anions) 44.2
V, 6. Special tests for mixtures of acid radicals 4"
V, 7. Examination for metal ions (cations) in solution <148
V, 8. Separation of cations into groups; Table S 450
V, 9. Modification of the analysis in the presence of phosphate i54
V,10. Analysis of a liquid (solution) 455
 Oontents xiii
CHAPTER VI
INTRODUCTION TO SYSTEMATIC SEMIMICRO
QUALITATIVE INORGANIC ANALYSIS
PAGE
VI, 1. Preliminary discussion. 457
VI, 2. Abbreviated course of instruction. 458
VI, 3. Systematic analysis. General considerations . 460
VI, 4. Preliminary tests . 460
VI, 5. Examination for acid radicals (anions) in solution 467
VI, 6. Confinnatol'Y tests for acid radicals or anions. 471
VI, 7. Special tests for mixtures of acid radicals (anions) 475
VI, 8. Examination for metal ions (cations) in solution 479
VI, 9. Separation of cations into groups; Table SM.S 482
VI,IO. Modification of the analysis in the presence of phosphate,
etc. 486
VI,lI. Analysis of a liquid (solution) ./ 487

CHAPTER VII
SYST~MATIC QUALITATIVE INORGANIC ANALYSIS
VII, 1. Analysis of solid and non-metallic substances. . 489
VII, 2. Preliminary dry tests. 490
VII, 3. Preliminary tests for acid radicals (anions) 496
VII, 4. Preparation of a solution of the solid . 502
VII, 5. General scheme for the separation of the cations into
groups. 503
VII, 6. Separation of cations into groups; Table I 505
VII, 7. Phosphate separation table (zirconyl nitrate method);
Table II 511
VII, 8. Analysis of Group I (Silver Group); Table III 512
VII, 9. Analysis of Group II (Copper and Arsenic Groups).
Separation of Group IIA (Copper Group) and Group
lIB (Arsenic Group); Table IV, Method A . 513
Table IVA, Method B . 515
VII,IO. Analysis of Group IIA (Copper Group); Table V . 517
VII,l1. Analysis of Group IIB (Arsenic Group); Table VI,
Method A 519
Table VIA, Method B . 521
VII,12. Analysis of Group IlIA (Iron Group); Table VII . 523
VII,13. Analysis of Group IIIB (Zinc Group); Table VIII,
Method A 524
Table VIllA, Method B . . 527
VII,14. Analysis of Group IV (Calcium Group); Table IX,
Method A 529
Table lXA, Method B . 532
VII,IS. Analysis of Group V (Alkali Group); Table X 533
VII,16. Examination for acid radicals (anions) in solution. 534
VII,17. Confirmatory tests for acid radicals or anions 549
VII,IS. Analysis of a liquid (solution) 553
VII,19. Analysis of a metal or an alloy 15154
VII,20. Analysis of insoluble substances 1566
xiv Oontents
CHAPTER VIII
MODIFICATION OF THE SYSTEMATIC ANALYSIS WHEN
ORGANIC ACIDS, SILICATES, BORATES, FLUORIDES
AND PHOSPHATES ARE PRESENT
PAGE:
VIII, 1. Procedure for the removal of interfering acids in
systematic qualitative analysis f)(,6
VIII, 2. Analytical procedures in the presence of phosphates.
"Phosphate Separations" f,()7

CHAPTER IX
REACTIONS OF SOME OF THE .. RARER" ELEMENTS
IX, IA. Reactions ofthallous compounds 572
IX, lB. Reactions of thallic compounds. 573
IX, 2. Reactions of tungstates . . . 5'74
IX, 3. Analysis of Group I (Silver Group) in the presence of Tl
and W; Table I fi'76
IX, 4. Reactions of molybdates r, i 7
IX, 5. Reactions of auric compounds [,79
IX, 6. Reactions of chloroplatinates 5S1
IX, 7. Reactions of palladous compounds 583
IX, SA. Reactions of selenites 584
IX, SB. Reactions of selenatea 586
IX, 9A. Reactions of tellurites 587
IX, 9B. Reactions of tellurates . . . . .~S8
IX,IO. Analysis of Group II (Copper and Arsenic Groups) in the
presence of Mo, Au, Pt, Pd, Se and Te; Table II. 589
Analysis of Group IIA (Copper Group); Table III 590
Analysis of Group lIB (Arsenic Group); Table IV 591
IX,H. Reactions of vanadates 59!
IX,12. Reactions of beryllium compounds 595
IX,13. Reactions of titanic compounds .598
IX,14. Reactions of zirconium compounds 601
IX,15. Reactions of uranyl compounds 604
IX,16. Reactions of thorium compounds . 606
IX,17A. Reactions of cerous compounds . 607
IX,17B. Reactions of eerie compounds r,O!}
IX,IS. Analysis of Group lIlA in the presence of Ti, Zr, Ce, Th,
U and V; Table V . .- fill
IX,19. Notes on the precipitation and separation of Group IIIB
in the presence of "rarer" elements 612
IX,20. Reaotions of lithium oompounds ti 13
IX,21. Borax bead tests; Table VI . 615

CHAPTER X
PAPER CHROMATOGRAPHY
X, 1. Introduction. RF values 1:16
X, 2. Apparatus and general technique (;18
X, 3. Some typical group separations fi23
X, 4. Miscellaneous separations 627
 OO'ntents xv
APPENDIX
PAGE
A, 1. Atomic weights of elements (1952) . 632
A, 2. Reagents 633
A, 3. Test solutions 640
A, 4. Buffer solutions. . . . . 643
A, 5. Solubilities of salts and bases in water at 18 0 C. 647
A, 6. Logarithms . 648
A, 7. Antilogarithms 650
Index. 651
 CHAPTER I

THE THEORETICAL BASIS OF QUALITATIVE

ANALYSIS

ELEMENTARY TREATMENT
Qualitative analysis has for its object the identification of
the constituents of a substance, of mixtures of sulmtances or
of solutions, and the manner in which the component elements
or groups of elements are combined with one another. Quanti-
tative analysis is concerned with the methods of determining
the relative proportions of these constituents. It is evident
that rigid qualitative analysis must precede the quantitative
analysis; the former should give an approximate illdication of
the relative proportions of the constituents present and should
serve as a guide to the methods to be adopted in the latter.
In what follows, the principles underlying the separation of
the more commonly occurring elements will be considered. The
treatment will be an elementary one and is designed as an
introduction to the subject. By its aid it is hoped that the
student will be able to appreciate the significance of the opera-
tions commonly employed in qua.litative analysis. In addition,
a knowledge of the principal reactions of the elements and their
derivatives is necessary. Chapters III and IV deal with this
aspect of the subject. The molecular chemical equa.tions are
given throughout. The student should have no difficulty, after
studying Sections I, 24 and I, 25 in converting most of these
into "ionic equations."
The identification of a substance involves its conversion,
usually with the aid of another substance of known composition,
into a new compound which possesses characteristic properties.
This transformation is called a chemical reaction. The sub-
stance by means of which this transformation is brought about
is termed the reagent. One distinguishes between reactions in
the wet way (i.e. those in which a li.quid, usually water, is
present) and reactions in the dry way; the former are by far
the more important and will therefore be studied in greater
detail.
• 1+ 1
2 Qualitative Inorganic Analysis [I,

REACTIONS OF INORGANIC SUBSTANCES IN

AQUEOUS SOLUTION
The reactions employed in qualitative analysis are largely the
reactions of inorganic acids, bases and salts with each othlr in
aqueous solution. Other solvents are rarely employed ex cept
for special operations. It is therefore necessary to have a
general knowledge of the conditions that exist in such solutions.

THEORY OF ELECTROLYTIC DISSOCIATION

It 1. Electrolytes and Non-Electrolytes.-A solution is the
homogeneous product obtained when a substance is dissoi ,-ed
in water (or any other liquid); the dissolved substance is knuwn
as the solute, and the water (or other liquid) in which the solute
is dissolved is called the solvent. Substances can be divided
into two main classes according to the behaviour of 1. i wir
aqueous solutions to an electric current. In the first class one
has those which conduct the electric current and are decom-
posed thereby; the second class is composed of those wLich
yield non-conducting solutions. The former are termed electro.
lytes, and these include acids, bases and salts; the latter are
designated non-electrolytes, and are exemplified by cane sugar,
mannose, glucose, glycerine, ethyl alcohol and urea. It ll:llSt
be pointed out that a substance which is an electrolyte in witter, \
e.g. sodium chloride, may not yield a conducting solutic) in i

another solvent such as ether or hexane. Furthermore, electro-

lytic character is not confined to solutions; it is also manifested
by fused salts.
It 2. Electrolysis and Ions.-Pure water is a very poor con- i,

ductor of electricity but, as already stated, when acids, bases

or salts are dissolved in it, the resultant solution not (Jnly
conducts the electric current but is also simultaneously de-
composed. The decomposition is called electrolysis. Thus, if
an electric current from, say, a battery is passed through hydro-
chloric acid, the hydrogen chloride is split up into hydrogen and
chlorine. The hydrogen is liberated at the electrode by which
the current leaves the solution (the negative electrod, or
cathode) whilst the chlorine is liberated at the electrod by
which the current enters the solution (the positive elect, ode
or anode). This behaviour is a general one for electrolyto.:s-
for the present it is assumed that no secondary changes occur a.t
the electrodes-and it is obvious that the part of the electrolyte
3] The Theoretical Basis of Qualitative Analysi8 3
moving to the cathode must be positively charged and that
moving to the anode must likewise be negatively charged.
Faraday termed the charged components of the electrolyte
Source of Current
(Battery)
---11[1[1[1[1---

:--. . -: : + =--=~--=-
-- -e-- - :-. .--
- -~---
-- --
-- -- - - --&--
-- + ~----
- -
- --
-

Fig. I, 2, 1

ions; the positively and negatively charged ions were called

cations and anions respectively. A diagrammatic figure of
electrolysis is shown in Fig. I, 2, 1.
I, 3. Some Properties of Aqueous Solutions.-It has been
found experimentally that equimolecular quantities of non-
electrolytes, dissolved in the same weight of solvent, have the
same effect upon the lowering of vapour pressure, the depression
of freezing point and the elevation of boiling point. The deter-
mination of any of these quantities for a solution therefore
enables one to calculate the molecular weight of the dissolved
substance provided the change produced by one molecular
weight in a known weight of solvent is known. Thus the
freezing point of \vater is lowered by 1'86°0 by the molecular
weight of any non-electrolyte dissolved in 1000 grams; the
boiling point is similarly raised by 0·51 °0.
Abnormal results were obtained with electrolytes. Those of
the sodium chloride type gave a depression of freezing point
of about twice the expected or normal magnitude, whilst with
compounds of the type of calcium chloride or sodium sulphate
,the depression of freezing point was approximately three times
 Qualitative Inorganic Analy8i8 [I,
that produced by a non-electrolyte of the same molecular con-
centration.
It was to explain the abnormal vapour pressures, freezing
points and boiling points of aqueous solutions of electrolytes
that Arrhenius in 1887 put forward his theory of electrolytic
dissociation or ionisation. According to this theory, all electro-
lytes when dissolved in water are decomposed or dissociated
into charged atoms or groups of atoms (ions). The extent of
this dissociation or ionisation increases with dilution, and at
very great dilutions it is practically complete. For every I."on-
centration there is a state of equilibrium between the ulldis-
socia ted molecules and the ions; the process is a reversible une.
The ionisation of compounds may therefore be represented by:
NaCI ~ Na+ +
Cl-;
HCI ~ R+ + Cl-;
CaCl2 ~ Ca++ +2Cr;
Na2S04 ~ 2Na+ + S04--

The ions carry positive and negative charges and, since the
solution is electrically neutral, the total number of positive
charges must be equal to the total number of negative charges.
The number of charges carried by an ion is equal to the valency
of the atom or radical.
The abnormal results referred to above now receive a si tIlple
explanation if it be assumed that the effect of each ion upon
the vapour pressure, freezing point or boiling point is equivalent
to that of a molecule of a non-electrolyte. Sodium chll,ride
yields two ions in aqueous solution, so that the nearly double
depression of freezing point obtained in dilute solution wl)uld
appear to indicate considerable dissociation. The resul1 for
sodium sulphate and calcium chloride are similarly accounted
for. It is evident that precise measurements of this
"abnormality" may be employed to calculate the extent of
Ionisation or the degree of dissociation. Another metho, i for
determining this quantity, dependent upon the measurelllent
of electrical conductivity, will be discussed in a subseqllent
section.
The phenomena of electrolysis also receive a simple explana-
tion on the basis of the theory of electrolytic dissociation.
The conducting power of aqueous solutions of electrolyt""s is
due to the ions which transport the current through the
solution. Returning to the example of hydrochloric acid
already considered, it is clear that if two inert electrodes. say
 4] The Theoretical Basis of Qualitative Analysis 5
of platinum, connected to a source of current, be introduced
into the solution, the positively charged hydrogen ion H+ will
travel to the cathode from which it will take up one electron,
become converted into a neutral hydrogen atom and be dis-
charged. The negatively charged chlorine ion CC will be
attracted to the anode; here it will give up its charge, become
neutral and be liberated as the free gas. The discharge of the
ions is accompanied by a simultaneous dissociation of the
electrolyte in order to maintain the equilibrium.
The phenomenon is not always as simple as for hydrochloric
acid. The ions are not always discharged at the respective
electrodes; they may also react with the electrodes themselves
or with the electrolyte or if the potential required to discharge
either of the ions be greater than that necessary for the dis-
charge of the ions of water H+ and OH- (H 20 ~ H+ +
OH-),
either of the latter may be preferentially discharged. Thus in
the electrolysis of sodium chloride solution, chlorine is evolved
at the anode and the sodium initially formed at the cathode
reacts with the water liberating hydrogen; with a mercury
cathode, however, the sodium dissolves in the mercury and an
amalgam is formed. The electrolysis of a solution of sodium
sulphate (Na2804 ~ 2Na+ +
804--) results in the liberation
of hydrogen at the cathode and oxygen at the anode. The
latter arises from the circumstance that the sulphate ion
804 - - requires a higher potential for its discharge than does
the hydroxyl ion OH- and hence the latter is discharged in
accordance with the equation:
40H- = 440 + 2HzO + Oz
I, 4. Reactions of Ions.-Most of the wet reactions employed
in qualitative analysis are reactions of the ions. It is an
experimental fact that the compounds of most metals with
chlorine (chlorides), which are soluble in water, yield a white
precipitate of silver chloride when treated with a solution of
silver nitrate. This is because all chlorides give rise to the
chloride ion Cl- in aqueous solution, and this reacts with the
silver ion Ag+ originating from the silver nitrate solution. In
a similar manner all silver salts, which dissociate in aqueous
solution, will give the same precipitate when chloride ions are
added to their solutions. The reactions may be represented:
K+ + cr + Ag+ + N0 3 - =AgCI + K+ + N0 3-;
Na+ + cr + Ag+ + (CzHaOz)- = AgCI + Na+ + (CzH a0 2 )-;
, (II' 01- + Ag+ = AgCI
6 Qualitative Inorganic Analysis rl,
Thus the precipitation of the highly insoluble silver chlorid" is
due to the combination between silver and chloride i(>!ls.
These ions react independently of the other ions with wh; uh
they were originally associated in the solid state.
When a solution of potassium chlorate is added to one of
silver nitrate, no precipitate of silver chloride is obtain . d,
because potassium chlorate furnishes K+ ions and CIO a- j. "lS
in solution but no Cl- ions. Silver nitrate, dissolved in et. yl
alcohol, does not yield a precipitate with chlorobenz, 11e
CaH5CI or with carbon tetrachloride CCI.. in alcoholic soluti( i1,
although it does so with sodium chloride solution. The sodililU
chloride is dissociated to a small extent in alcoholic soluti(J tl;
the 'Chlorobenzene and carbon tetrachloride not at all.
I, 5. Theory of Acids and Bases.-An acid is most simply
defined (after Arrhenius) as a substance which, when dissoh,~d
in water, undergoes dissociation with the formation of hydrogt·n
ions as the only positive ions:
HOI ~H+ +01-
HNO a ~ H+ + NOa-
Actually hydrogen ions H + (or protons) do not exist in the frce
state in aqueous solution. Each proton is bound to one wa10r
molecule by coordination with a pair of free or lone electrons
on the oxygen of the water, H+ +- OH 2 or HaO+; its formatiun
is similar to that of the ammonium ion NH4 +, which is a co-
ordination of a proton with a pair of electrons on the nitrogen
in ammonia, H+ +- NH a. The HaO+ ion is termed the
hydroxonium, oxonium or hydronium ion: the first of the:-:e
names will be employed.
The experimental evidence for the existence of the hydroxonium ion
in aqueous solution includes the following:
(i) Liquid sulphur dioxide (at -30°) dissolves water to a small extent
and hydrogen bromide in larger quantity but neither of these solutions
alone forms a conducting solution. The solution of hydrogen bromide
in liquid sulphur dioxide will dissolve exactly one molecule of water
per molecule of hydrogen bromide giving a highly conducting solution.
These observations are readily accounted for by the reaction:
HBr + H 2 0 _,. Br- + HsO+
Furthermore, when the solution is electrolysed, bromine is liberated at
the anode and hydrogen is evolved at the cathode; also the solution
near the cathode gains one molecule of water for each hydrogen ion
deposited at the cathode:
2Br- -+ Br. + 2e
2H sO+ + 2e -+ HI + 2H.O
 5] The Theoretical Basis of Qualitative Analysis 7
(ii) X-r<1y examination of crystalline perchioric acid monohydrate
indicates that it fonus an ionic lattice [HaO+] [CIO, -]. i.e. f [30 .ClO, .-
HsO+ + ClOt -: it is isomorphous with ammoniwn perchlorate
[NH, +] [ClOt -].
The above equations are more accurately expressed by:
Hel + H 20? HsO+ + Cl-
HNOs + H 2 0 ~ HaO+ + NOs -
The dissociation may be attributed to the great tendency of the
free hydrogen ions H+ or protons to combine with water to
form hydroxonium ions. Hydrochloric and nitric acids are
almost completely dissociated in aqueous solution in accor-
dance with the above equations; this is readily detected by
freezing point measurements.
Polybasic acids dissociate in stages. In sulphuric acid, the
first hydrogen atom is almost completely ionised:
H 2SO, ~~ H+ + HSO,-,
or H 2SO, + H20 ~ HaO+ + HSO,-
The second hydrogen atom is only partially dissociated, except
in very dilute solution:
HSO,- ~ H+ + SO,--,
or HSO, - + H 20? HaO+ + SO,--
Phosphoric acid also dissociates in stages:
H aP04 ~ H+ + H 2 PO,- ~ H+ + HPO,-- ~ H+ + P04 - - - ;
or H SP04 + H 2 0 ~ HaO+ + H 2 PO, -,
H 2 PO, - + H 2 0 ~ HaO+ + HPO, --,
HPO,-- + H 2 0 ~ HaO+ + PO,---

The successive stages of dissociation are known as the primary,

secondary and tertiary dissociation respectively. As already
mentioned, these do not take place to the same degree. The
primary dissociation is always greater than the secondary, and
the secondary very much greater than the tertiary.
Acids of the type of acetic acid H. C2 H aO z, give an almost
normal freezing point depression in aqueous solution; the
extent of dissociation is accordingly small. It is usual, there-
fore, to distinguish between acids which are completely or
almost completely dissociated in solution and those which are
only slightly dissociated. The former are termed strong acids
(examples: hydrochloric, nitric and iodic acids, primary dis-
sociation of sulphuric acid) and the latter are called weak acids
•
 8 Qualitative Inorganic Analy8i8 (I,
(examples: acetic acid, secondary and tertiary ionisation of
phosphoric acid, carbonio acid, boric acid and hydrpr:en
sulphide). There is, however, no sharp division between these
classes. Methods for the measurement of the relative strengths
of acids are described in Section I, 12.
A base is most simply defined (after Arrhenius) as a substance
which, when dissolved in water, undergoes dissociation with, he
formation of hydroxide ions OH- as the only negative i( !lS.
Thus sodium hydroxide, potassium hydroxide and ot tier
metallic hydroxides are almost completely dissociated in
aqueous solution:
NaOH __ Na+ +OH-;
these aro strong bases. Aqueous ammonia solution, howe\ cr,
is a weak base. Only a small concentration of hydroxide i'illS
is produced in aqueous solution. Arrhenius assumed the intvr-
mediate formation of ammonium hydroxide by the parI ial
hydration of ammonia:
NHs + H 20 <? NH,OH <? NH,+ + OH-
It is more usual to write the reaction as:
NHs +H 0 2 ~ NH,+ + OH-
The above classical definitions of acids and bases proved 1iO
be of very limited application, although they suffice for mOllY
applications in qualitative inorganic analysis. These limi1 ;L-
tions are apparent, for example, in the field of non-aquee IS
solvents. Thus, if potassium hydroxide is dissolved in etJ·.\'}
alcohol, the solution will contain hydroxide ions, just as In
water: by dissolving potassium ethQxide in the same solvent,
a solution with stronger basic properties is obtained and this
contains ethoxide ions (OC2H5-) in place of hydroxide ions.
With ethyl alcohol as solvent, it would seem more logical to
define bases in terms of the ethoxide ion rather than in terms
of the hydroxide ion. Similarly, in liquid ammonia the
strongest bases are the metallic amides MeNH 2 , and the
characteristic basic ion is the amide ion NH2 -.
A more general definition of acids and bases was proposed
almost simultaneous and independently in 1923 by J. N. Bron-
sted and T. M. Lowry. They define an acid as any substance
(in either the molecular or ionic state) which donates protons
(H+), and a base as any substance (molecular or ionic) which
accepts protons. This can be expressed by the scheme:
A ~B+H+
 5] The Theoretical Basis of Qualitative Analysis 9
where A and B are termed a conjugate (or corresponding) acid-
base pair. It is important to realise that the symbol H+
in this definition represents the bare proton or unsolvated
hydrogen ion, and hence the new definition is independent of
the solvent. The equation expresses a hypothetical scheme for
defining the acid and base, and not a reaction which can actually
take place. The dissociation of an acid to yield H+ is con-
ditioned by the presence of a base, i.e. a substance capable of
accepting the liberated H+.
The Bronsted-Lowry definition of an acid includes:
(a) the uncharged molecules known as acids in the classical
dissociation theory, e.g. HCI, HN0 3, H 2 S04, CHa.COOH, etc.;
(b) anions like HS04-, H 2 P04- and HOOC.COO-, which
occur in acid salts;
(c) the ammonium ion by virtue of the tendency represented
by NH4+ ~ NH3 + H+, and the hydroxonium ion (HaO+ F
H 20 + H+)-these are examples of cation acids; and
(d) cations, like the hydrated aluminium and other metallic
ions
[Al(H 20)o]3+ <? [Al(H2 0)6(OH)]2+ + H+
For bases, the new definition is concerned with the ability of
accepting a proton and not with the production of the hydroxide
or some similar ion. The following are included:
(a) uncharged molecules (ammonia and the amines) by virtue
of the reaction RNH2 + H + <? RNHa +;
(b) metallic hydroxides, due to the production of the
hydroxide ion-OH- + H+ ~ H 2 0.
The hydroxide ion is one example of an anion base: other
examples are the anions of all weak acids. Thus the acetate
ion is a weak base:
CHa.COO- + H+ ~ CHa.COOH
It is important to note that the familiar strong bases according
to the classical definition, such as the alkali and alkaline earth
hydroxides, are invariably ionic in nature even in the solid
state. The basic nature of these strong bases is due to the
OH- ions which are always present in the solid state or in
aqueous solution, and interaction with the solvent is not an
essential preliminary as for weaker bases, such as those of the
ammonia (RNH 2) type:
RNH2 + H 20? RNHs + + OH-
Some substances can function both as acids and bases, and
• 1*
10 Qualitative inorganic AnalY8is [I,
are called amphoteric electrolytes or ampholytes: H 20, Het)3-
and H 2P04- are examples.
As already pointed out, the equation A ~ B + H+ does "ot
represent a reaction which can actually take place: othenl ise
expressed, the free proton, because of its small size and the
intense electric field surrounding it, will have a great affillity
for other molecules, especially those with unshared electn)fis
and therefore cannot exist as such to any appreciable ext<'nt
in an aqueous or other basic solvent. The acceptor of a pro! <m
is a base. Thus if one writes the two equations A 1 ~ B 1 + I {+
and B2 + H+ ~ A 2 , one obtains:
Al + B'}, .p A2 + BI
Acid l Base. Acid. Basel
This represents the transfer of a proton from Al to B2 and £rom
A2 to B 1 • Reactions between acids and bases are therehre
often called protolytic reactions. The conjugate acid and h, se
are designated by the same subscript.
It is of interest to examine the mechanism of the reaction wh l "h
occurs when strong and weak acids are dissolved in water as
illustrated by hydrochloric acid and by acetic acid respectively.
Hydrogen chloride in the gaseous or pure liquid state does J" It
conduct the electrio current, and possesses all the properties of
a covalent compound. When the gas is dissolved in water, the
resulting solution is found to be an excellent conductor ,)f
electricity and therefore contains a high concentration of iOll:>.
Evidently the water, behaving as a base, has reacted with the
hydrogen chloride to form hydroxonium and ohloride ions:
HOI + H 20 ~ HsO+ + or
The reaction proceeds almost entirely towards the right,
indicating that the ability of water to combine with protons
is very much greater than the tendency of chloride ions to
combine with H+, i.e. water is a stronger base than chloride
ion. When acetic acid is dissolved in water, the resultillg
solution has a comparatively low conductivity indicating that
the concentration of ions is relatively low. The reaction:
H.O'},HsO z + H 20 ~ HaO+ + 02H a0 2 -
proceeds only slightly towards the right, and it is evident ttat
the acetate ion has a more powerful attraction for protons than
the chloride ion, i.e. 02H302 - is a stronger base than 01-.
The ionisation of an acid thus depends upon the readiness with
which the solvent can take up protons as compared with the
anion of the acid. An acid, like hydrogen chloride, which gives
...
 5] The Theoretical Basis of Q'ualitative Analysis 11
up H+ readily to the solvent to yield a solution with a high
concentration of H30+ is termed a strong acid. An acid, like
acetic acid, which gives up its protons less readily affording a
Rolution with a relatively low concentration of H30+ is called
a weak acid. It is clear, therefore, that if the acid is strong,
its conjugate base must be we(tk; if the acid is weak, the con-
jugate base is strong, i.e. possesses a powerful tendency to
combine with H+.
Some examples of protolytic reactions are collected below:
Acid 1 Bases Acids Baf;A 1
__,..
H 2SO4 + H 2O ..,- __,..
H30 + + HS04 -
804- -
H804- + H 2 O ..,- H30 + +
CH 3·COOH + H 2O ~ H30 + + CH3·COO- (i)
CH 3·COOH + NH3
__,..
..,- NH4+ + CH 3·COO- (ii)
H 2O + CH 3. COO- ~ CH3. COOH + mr (iii) ,
NH4+ + H 2O ~ H30 + + NH3 (iv)
OH-
H 2O + NHs
HP0
~
__,..
NH 4+ +
OH-
(v)
H 2O + 4
-- ..,- H 2 P0 4- + (vi)
__,.. C H OH + 01-
HCI + C2H 5OH ..,- 2 5 2 + (vii)
Reaction (i) represents the dissociation of acetic acid in water;
(ii) the neutralisation of acetic acid by ammonia or the hydro-
lysis of ammonium acetate solution; (iii) the hydrolysis of an
alkali acetate solution or the neutralisation of acetic acid by an
alkali hydroxide; (iv) the hydrolysis of an ammonium salt or
the neutralisation of ammonia by a strong acid; (v) the dis-
sociation of ammonia in water; (vi) the hydrolysis of a secon-
dary phosphate or the neutralisation of a primary phosphate
with an alkali hydroxide; and (vii) ethyl alcohol functioning as
a base and yielding the conjugate acid C2H 5 0H 2+. Some of
these reactions are discussed in greater detail in Section I, 42.
Salts. The structure of numerous salts in the solid state has
been investigated by means of X-rays and by other methods,
and it has been shown that ions are actually present in the solid
state. Sodium chloride, for instance, is built up of sodium ions
and chlorine ions so arranged that each ion is surrounded sym-
metrically by six ions of the opposite sign; the crystal lattice is
held together by electrostatic forces due to the charges upon the
ions. It is not surprising, therefore, that when salts are dis-
solved in a solvent of high dielectric constant such as water,
they are completely dissociated. The complete dissociation of
salts in aqueous solution is the modern view and is now almost
• universally accepted. There are, however, some exceptions,
12 Qualitative Inorganic Analy8i8 [I,
and these have, in some cases, been supported by X r'ay
measurements. Feebly dissociated salts (weak electrol.)' es)
are exemplified by mercuric chloride, mercuric cyanide, lPad
acetate and the cadmium halides.
I, 6. Experimental Determination of the Approximate
Degree of Dissociation.-The degree of dissociation of ill
electrolyte in an aqueous solution may be computed (a:: er
Arrhenius) either from the freezing point or from the electll 'al
conductivity. Let us consider the freezing point method fj, .:t.
If 1 gram molecule of a binary electrolyte is dissolved in IlitI'< of
water and if a fraction IX of the gram molecule is dissociated, ; ite
solution will contain (1 - IX) gram molecule of the undissocia \ ud
electrolyte and 21X gram molecules of ions. 'fhe total cone. n-
tration of the solute will be (1 - IX) + 21X = (1+ IX) gr:rm
molecules. If L1 (theory) is the depression of freezing PCHllt
produced at this concentration by a non-electrolyte (i.e. w];"n
no dissociation occurs), and L1 (obs.) is the observed depress:, In
of freezing point, then
.tJ(obs.}/.tJ(theory) = (1 + 1X)/1 = i or IX = i - I
Similarly, if the molecule of the electrolyte gives rise to n ie.: IS
upon dissociation, the increase in the number of solute particles
in the solution will be in the ratio of {I + (n - 1)1X}/1, or
IX = (i - l)/(n - 1). Dissociation is complete when i = n.
Let us now study the conductivity method. The electric
current is transferred through the solution by means of the
ions, hence the conductance at any temperature, measured in
a definite way, will depend upon the degree of ionisation. The
specific resistance or resistivity p of a solution is the resistance
in ohms, measured between parallel faces, of a cube of 1 cent.i-
metre side. The reciprocal of the specific resistance or resis-
tivity is called the specific conductance or conductivity, and
is generally represented by the Greek symbol kappa (K). It is
measured in "reciprocal ohms" or mhos (mho = ohm written
backwards), K = IIp. For electrolytic solutions, it is more
convenient to employ the equivalent conductance or the
equivalent conductivity (frequently designated by the Gree 1rf
symbol lambda A) for purposes of comparison. The latter is
the conductance of a solution which contains 1 gram equivalent
of the solute between two electrodes of indefinite size, 1 centi-
metre apart. The specific conductance and equivalent con-
ductance are connected by the relation:
A = KV = K/C,
6] The Theoretical Basis of Q'ualitative Analysis 13
where V is the volume in c.c. containing 1 gram equivalent of
the solute and c is the concentration in gram equivalents per
cubic centimetre.
The discovery that the equivalent conductance of aqueous
solutions of electrolytes increases with dilution and ultimately
reaches a limiting value, was made by Kohlrausch. The
Arrhenius theory sought to account for this by assuming that
the degree of dissociation increases with. increase of dilution
until at very great dilutions dissociation is complete. The
limiting conductance corresponds to complete dissociation; it
is represented by ..10 (when referring to concentrations), or ..100
(when referring to dilutions). The degree of dissociation ~, at
any concentration c, is given by ex = AelAo, where Ac is the
equivalent conductance at that concentration. Some results
for the degree of dissociation ex, deduced from freezing point
and conductivity data, are collected in Table 1,6, I: it will be
noted that the agreement is only approximate up to about o·lN
and it may be stated that in more concentrated solutions the
two values differ considerably.
TABLE I, 6, 1. DEGREE OF DISSOCIATION OF ELECTROT.YTES BY
FREEZING AND BY CONDUCTIVITY METHODS

! Concentration cxfram cxfrom No. of ions

Substance G. freezing conduc- for one
equiv./litre point tivity molecule, n

KCI 0·01 0·946 0·943 2

0·02 0·915 0·924
0·05 0·890 0·891
0·10 0·862 0·864

BaCl2 0·001 0·949 0·959 3

0·01 0,903 0·886
0·10 0·798 0·754

K 2S04 0·001 0·939 0·957 3

0·01 0·887 0·873
0·10 0·748 0·716
It
Ka[Fe(CN)6] 0·001 0·946 0·930 4
0·01 0·865 0·822
0·10 0·715 -
The variation of equivalent conductance with concentration
or a
number of electrolytes at 25°0 is shown in Table I, 6, 2.
14 Qualitative Inorganic Analysis [J
TABLE 1, 6, 2. EQUIVALENT CONDUCTANCES AT 25°0

Conon. KCl NaCl HCl NaOH KOH Na. H.

C2 H s0 2 C2 Hl
- - -- - -- - -
0·0001 149·2 125·3 - - - - -
0·0002 - - - - - - 104·;
0·0005 148·3 124·3 422·2 246·5 270·1 89·4 64.;
0·001 147·5 123·5 421·1 244·7 268·2 88·7 48·~
0·002 146·5 122·2 419·2 242·5 266·2 87·7 35·'
0·005 144·2 119·8 414·9 238·8 262·1 85·7 22·,'
0·01 141·6 117·8 410·5 234·5 258·9 83·7 16·~
0 150·1 126·2 423·7 260·9 283·9 91·3 388,(
I J
Electrolytes which are largely ionised in solution are cajl"d
strong electrolytes, whilst those which are only slightly ioni, , d
are termed weak electrolytes. Table 1,6, 3 gives the deg: pe
of ionisation or fraction of electrolyte dissociated, 0(, ;,s
determined from the conductivity in o·IN solution.

TABLE 1,6, 3. APPARENT DEGREE OF IONISATION IN O'lN

AQUEOUS SOLUTIONS FROM CONDUCTIVITY DATA

Acids SaUs
Hydrochloric (H+, Cr) 0·92 Potassium chloride (K+, cr) 0'86
Nitric (H+, NO s-) 0'92 Sodium chloride (Na+, Cn 0·86
Sulphuric (H+, HSO.-) 0·61 Potassium nitrate (K+, NO s-) 0'82
Phosphoric (H+, HsPO.-) 0·28 Silver nitrate (Ag+, NO.-) 0'82
Hydrofluoric (H+, F-) 0·085 Sodiumacetate(Na+,CH •. COO-) 0'80
Acetic (H +, CH s . COO-) 0·013 Barium chloride (Ba++, 201-) 0·75
Carbonic (H+, HCO s-) 0·0017 Potassium sulphate (2K+, SO,-) 0·73
Hydrosulphuric (H +, HS-) 0·0007 Sodium carbonate (2Na+, CO.-) 0·70
Hydrocyanic (H+, CW-) 0·0001 Zinc sulphate (Zn + +, SO.-) 0·40
Boric (H+, H,BO s-) 0·0001 Copper sulphate (Cu++, SO,-) 0·39
Mercuric chloride (Hg++, 2Cl-) <0·01
Mercuric cyanide (Hg+ + ,2CN-) very
small
Basea
Sodium hydroxide (Na+, OIr) 0·91
Potassium hydroxide (K +, OIr)
Barium hydroxide (Ba + +, 20H-)
Ammonia (NR, +, OIr)
0·91
0·81
0·013
•
It should be mentioned that although the results for strong
electrolytes have been considerably modified (their ionisation
is now regarded as complete-see Section I, 8), the general
picture presented by the Table is still significant in so far a.s.
 7J . The Theoretical Basis of Qualitative Analysis 15
the broad difference between strong and weak electrolytes and
also between individual weak electrolytes are concerned.
For strong electrolytes, the limiting conductance .10 may be
determined by extending the measurements to low concentra-
tions and then extrapolating the conductivity-concentration
curve to zero concentration. For weak electrolytes, such as
acetic acid and ammonia, this method cannot be employed
since the dissociation is nowhere near complete at the lowest
concentrations at which measurements can be conveniently
made (ca. O·OOOIN). Another method is, however, available
for estimating ..1 0, This is described in the following section.

I, 7. The Independent Migration of Ions.-As a result of a

prolonged and careful study of the conductance of salt solutions
down to low concentrations, Kohlrausch found that the equi-
valent conductance of an electrolyte is made up of the sum of
the limiting equivalent conductances of the component ions.
This permits one to predict ..10 by adding together numbers
which are characteristic of the ions in the solution. The
relation is:
Ao =..\0., + .\0.,
where -'Oa and -'oc are the limiting conductances or mobilities
of the anion and cation respectively. The ionic mobilities are
computed from ..10 with the aid of transport numbers; these
represent the fraction of the current carried by the cation and
anion respectively, and are obviously proportional to their
respective speeds. (For a fuller discussion of transport num-
bers, the student is referred to text-books of physical chemistry.)
Thus for potassium chloride at 18°, ..10 = 130·1, n" the anion
transport number is 0·503 (after Kohlrausch and Maltby),
hence
AOa = -'or = 0·503 X 130'1 = 65'5,
and "0, = "Na+ = 0·497 X 130'1 = 64·6
When one pair of mobilities is known, others may be computed
from the relation, also discovered by Kohlrausch, that the dif-
ference between the values of ..10 for two anions is independent
of the cation and vice versa. In this manner, a table of
mobilities can be constructed. Some limiting ionic mobilities
at 18°0 and 25°0 are collected in Table I, 7, 1. This may
be utilised fo!' the determination of the limiting conductance of
• any electrolyte. Its particular value is for weak electrolytee
16 Qualiwtive Inorganic AnalY8i8 [If
TABLE 1, 7, 1. LIMITING IONIa MOBILITIES AT 18°0 AND 25°(

18°0 25°0
-H+------ -
H+ 317·0 OH- 174·0 348·0 on- 21"
Na+ 43·5 01- 65·5 Na+ 49·8 or 7(;
K+ 64·6 NO s- 61·8 K+ 73·4 103 - 4::~
Ag+ 54·4 Br- 67·7 Ag+ 61·9 C2H 30 2 - 4('
1/2 Ca++ 52·2 r 66·1
1/2 Sr++ 51·7 F- 46·8
1/2 BaH 55·0 010 3 - 55·0
1/2 Pb H 61·6 IO s- 34·0
1/2 Cd++ 46·5 C2H 3 0 2 - 32·5
1/2 Zn++ 46·0 1/280,,-- 68·3
1/2 Cu++ 45·9 1/202 0,-- 6J.l

where ..10 cannot be determined by direct extrapolation. Thus

for acetic acid at 25°,
Ao = ~2H302- + "n:+ = 40·6 + 348·0 = 388·6
The degree of dissociation at any concentration c can then be
calculated from the relation ~ = ..1./..10' where A. is the equi-
valent conductance at that concentration. A few typical
results, calculated in this manner, are collected in Table I, 7, 2.

TABLE I, 7, 2. DISSOCIATION OF ACIDS AT 25°0

Degree oj Dissociation I
- 0-5N O·OOIN

Strong Acids
Hydrochloric acid 0·862 0·993
I
Sulphuric acid (primary ionisation) 0·536 0-960
Nitric acid 0·862 0-997
Trichloroacetic acid 0·760 0·994

Weak acids
Acetic acid 0·006 0·126
Oarbonic acid 0·0008 0·017
Hydrocyanic acid 0·00005 O'OOll

It is evident that the degree of dissociation varies consider-

ably both with the nature of the acid and with the concentration.
8] The Theoretical Basi8 of Qualitative AnalyBi" 17
The strengths of acids can be rougldy compared in terms of
IX at any given concentration. This method of comparison
divides the acids into two main groups: strong acids, which are
largely dissociated, and weak acids, which are feebly dissociated
in aqueous solution. Considerable variations occur amongst
the weak acids, and more accurate methods for the comparison
of their strengths will be discussed under the law of mass
action (Section I, 9).
,
I, 8. Theory of Complete Ionisation. Interionic Attrac-
tion Theory of Debye, Huckel and Onsager.-It has already
been pointed out that strong electrolytes, particularly salts and
bases, are completely dissociated in aqueous solution. How
then is one to explain the increasing equivalent conductance
with decreasing concentration? We have seen that Arrhenius
ascribed this to the increasing degree of dissociation, the
mobilities of the ions at all concentrations being assumed con-
stant. This classical view can now no longer be held to possess
any significance for strong electrolytes. Debye and Huckel in
1923 and Onsager in 1925 accepted the complete dissociation
theory, and attributed the changes in conductance with dilution
(and also the associated changes in osmotic activity in dilute
solutions) to the electrical forces between the ions. Owing to
the interionic forces, each ion will build up an "atmosphere"
of ions of opposit,e sign. When an electromotive force is
applied, the ionic" atmosphere" will be unsymmetrical, for the
ion has to build up a new ionic "atmosphere" in front, whilst
the "atmosphere" behind the moving ion will be dispersed.
The dispersal of the ionic "atmosphere," however, requires a
certain amount of time ("time of relaxation"), and hence there
will always be, in the rear of the moving ion, an excess of ions
of opposite sign as a result of which the mobility will be
diminished. Further, the motion of, say, a positively charged
reference ion will be subject to a retardation by the movement
of the negative ions in the opposite direction, and the effect will
be that of a viscous electrical drag (" electrophoretic effect ").
In short, the speed of the ions will be diminished because of the
attractive forces exerted by the ions constituting the "atmo-
sphere" of opposite sign. The attractive forces will dearly be
greater the more concentrated the solution, since the ions are
brought closer together. Consequently the mobility of the ions
will decrease with increasing concentration. At extreme dilu-
tions the interionic forces will become negligibly small owing to
tee relatively great distance between the ions, and the mobilities
18 Qualitative Inorganic Analysis [I,
will approach a maximum value. The change in equiv:,lent
oonductivity is thus attributed, not as in the Arrhenius th, '>ry
to changes in the degrees of dissociation or to changes in the
number of ions, but to variations in the velocities of the il)llS
due to interionic forces. Debye, Huckel and Onsager lmve
deduced an expression which accounts satisfactorily for "he
variation of the equivalent conductance with concentratio I of i

strong electrolytes from the lowest concentration to about

O·002N: it may be expressed in the form that Ae is proporti/,nal
to the square root of the concentration. At higher concen! ."a-
tions deviations occur, and many, at present, empirical aSSU··lp-
tions are introduced to express the rela.tionship between lie
and the concentration over a larger concentration range. The
deviations may be regarded as due to some form of i, aic
association, such as the formation of ionic doublets which 1 ,ay
behave, in some respects, as unionised molecules. The exl"nt
to which this occurs will depend upon the interionic forces a ad
upon the chemical nature of the ions of the solvent, since many
ions possess a tendency to undergo solvation, i.e. to combine
with the molecules of the solvent.
It is important to realise that whilst complete dissociabm
occurs with strong electrolytes, this does not mean that : he
effective concentrations of the ions are the same at all concenl ra-
tions, for if this were the case, the osmotic properties of aque, illS
solutions could not be accounted for. The variation of OSm(,i ic
properties is ascribed to changes of the "activity" of the iom;
these are dependent upon the electrical forces between the io'ls.
Expressions for the variations of the activity or of rela!"d
quantities, applicable to dilute solutions, have also be"n
deduced from the Debye-Huckel-Onsager theory. Furt):!lr
consideration of the conception of "activity" will be given in
the following section.
The ratio 110/110 on the modern complete ionisation theory
no longer gives the degree of ionisation <X. for a strong electroly t e
(for which <X. = 1); it has been named the conductivity coeffi-
cient or conductance ratio. It does give the approxima te
degree of dissociation for weak electrolytes, but even here there
is a slight ion interaction and a correction may be applied wi t h
the aid of the Debye-Huckel-Onsager theory.

I, 9. THE LAW OF MASS ACTION

Goldberg and Waage in 1867 clearly stated the law of mass
action in the form; the velocity of a chemical reaction a~
9J The Theoretical Basis of Qualitative Analysis 19
constant temperature is proportional to the product of the
concentrations of the reacting substances. The concentrations
are usually expressed in gram molecules per litre. On applying
the law to homogeneous systems, i.e. to systems in which all
reacting molecules are present in one phase, for example in
solution, one can arrive at a mathematical expression for the
conditions of equilibrium in a reversible reaction.
Consider first the simple reversible reaction at constant
temperature:
A+B~O+D
The velocity with which A and B react is proportional to their
concentrations, or
"1 = kl X [AJ X [B],
where leI is a constant known as the velocity coefficient, and
the square brackets in heavy type indicate the molecular con-
centrations of the substance enclosed within the brackets.
Similarly, the velocity with which the reverse reaction occurs
is given by
"2 = k2 X [0] X [D]
At equilibrium, the velocities of the reverse and forward re-
actions will be equal (the equilibrium is a dynamic and not a
static one) and therefore VI = V2,
or kl X [A] X [B] = k2 X [0] X [D],

or [0] X [D] = kl = K
[AJ X [B] k2
K is the equilibrium constant; it will vary somewhat with the
temperature and pressure, but such variations are of relatively
little importance in qualitative analysis.
The expression may be generalised. For a reversible reaction
represented by:
PIAl + P2 A 2 + PaAs ~ q1B l + q2 B 2 + qsBa,
where PI, P2, Pa and ql, q2, qa are the number of molecules of
the reacting substances, the condition for equilibrium is given
by the expression:
r
[Bl]"l X [B 2 2 X [Barl = K
[Al]Pl X [A 2 ]P2 X [As 3 r
Expressing this in words, it may be stated: When equilibrium
isreached in a reversible reaction, at constant temperature,
 20 Qualitative Inorganic Analysis [1
the product of the molecular concentrations of the result ;LOts
(the substances on the right-hand side of the equation), di\ ided
by the product of the molecular concentrations of the reaCl .lUts
(the substances on the left-hand side of the equation), ,'ach
concentration being raised to a power equal to the number of
molecules of that substance taking part in the reactio' i, is
constant.

I, 10. Application of the Law of Mass Action to Solutions

of Electrolytes.-Attention has already been directed tCl !,he
fact that weak electrolytes, such as acetic acid and "ammOlI i 11m
hydroxide," undergo reversible dissociation when dissolved in
water. The equilibrium between the undissociated mole( i les
and the ions for such electrolytes can be investigated by m, ,tUs
of the law of mass action. The law cannot be applied to stl" ,ng
electrolytes, such as salts, where dissociation is complete, E'I' lce
there is little or no equilibrium between the ions and the ull,lis-
sodated molecules in solution.
The following equilibrium exists in a dilute aqueous solui ion
of acetic acid:
H.C 2H a0 2 + H 20 ~ HsO+ + C2H a0 2- *
Applying the law of mass action, we have for the equilibrillill
constant Kequil.:
[C2 H s0 2 -] X [HsO+]/[H. C2 H a0 2 ] X [H2 0] = K'PII.
The concentration of water [H 20] is so large as to rem, in
essentially constant, hence we may write:
[CllH a0 2-] X [HsO+]/[H.C2Ha02J = [H 20] X K,qull. = K.,
where Ka is the dissociation or ionisation constant at const:,nt
temperature. The term affinity constant is sometimes f'lil-
ployed for acids and bases. If 1 gram equivalent of 1 ite
electrolyte is dissolved in V litres of solution (V = llc, wh, '1'e
c is the concentration in gram equivalents per litre), and if c" is
the degree of dissociation at equilibrium, then the amount 'If
undissociated electrolyte will be (1 - cr.) gram equivalents, [l i\d
the amount of each of the ions will be cr. gram equivalents. The
• The equilibrium was formerly written:
H.C,HsO, ~ H+ + C.H.O J-
This leads to the same result for the dissociation constant, and here H+ is
understood to be the solvated proton or hydroxonium ion. This form of (l,e
equilibrium equation will be used frequently throughout the text for the BH.;e
of siInplicity: it should, however, be interpreted in the Bronst- ri T -~. ~~ •. ~d
as explained for acetic acid.
10] The Theoretical Ba8is of Qualitative .Analysis 21
concentration (gram equivalents per litre) of undissociated
acetic acid will therefore be (1 - IX)/V, and the concentrations
of each of the ions rx/V. Substituting in the equilibrium equa-
tion, one obtains the expression:
rx 2/(l - rx)V = K. {or 1X 2c/(1 - rx) = K.}
This is known as "Ostwald's dilution law." The agreement
of the "law" with experiment is illustrated by the following
results for acetic aeid at 25°0 (Table I, 10, 1).

TABLE I, 10, 1. EQUIVALENT CONDUCTANOE AND DISSOOIATION

CONSTANT OF ACETIC ACID A1' 25°0

Concn. X 104 Ac IX Ka X 105

1·873 102·5 0·264 1·78

5·160 65·95 0·170 1·76
9-400 50·60 0·130 1·83
24·78 31·94 0·080 1·82
38·86 25·78 0·066 1·83
56·74 21·48 0·055 1·84
68·71 19·58 0·050 1·84
92·16 16·99 0·044 1·84
112·2 15·41 0·040 1·84
0 388·6

The mean classical or Ostwald dissociation constant of acetio

acid at 25 ° is 1·82 X 10-5 • Similar results-the individual
variations may sometimes be slightly greater-are obtained for
other weak electrolytes.
The equilibrium in an aqueous solution of a weak base, e.g.
ammonia, may be discussed in a similar manner. According to
classical theory, the series of equilibria may be written:
NH g (gas) + Aqua ~NH3 (aq.) + H 2 0 ~NH40H ~NH.1+ + OH-
( dissolved)
The term aqua denotes solvent water as distinguished from
water reacting chemically: the hypothetical ammonium hy-
droxide was introduced in order to conform with the Arrhenius
definition of a base. The vapour pressure of NH3 above even
dilute solutions of ammonia indicates that the NH:) remains
largely in the form of dissolved gas. There appears to be little
direct evidence for the existence ofNH4 0H molecules. Indeed,
from the Lowry-Bronsted standpoint, there is little need to
.:
 22 Qualitative Inorganic Analysis [I,
postulate the existence of NH4 0H as the ions can be produced
directly by a protolytic reaction between ammonia and v. ,I ter:
NHa + H 20 ~ NH4+ + OH-
Bases Acid I Acids Basel,'"
The expression for the (concentration) equilibrium~tallt, is:
[NH4+] X [OH-]/[NHs1 = [H 2 0] X· Kequll. = Kb
Since [H 20] is large and may be considered constant, a Ilew
constant K b, the basic dissociation constant may be employed.
Some results for Kb (due to Ostwald, 1887) for ammonin at
25° are collected in Table 1, 10, 2. It may be noted that, in
general, for bases RNH2, the same numerical result is obk 'ned
if the hypothetical solvated base RNH2H. OH is employ! . i in
the calculations.

TABLE I, 10, 2. EQUIVALENT CONDUCTANCE AND DISSOCIATION

CONSTANT OF AMMONIA AT 25°

Dilution (litres) A 1000c K6 X 10

8 3·4 1·35 2·3
16 4·8 1·91 2·3
32 6·7 2·66 2·3
64 9·5 3·77 2·3
128 13·5 5·36 2·4
256 19·0 7·54 2·4
CXJ 252

I, 11. Activity and Activity Coefficient.-In our deduction

of the law of mass action, it was assumed that the effective
concentrations or active masses of the components could be
expressed by the stoichiometric concentrations. In solut ;ons
of electrolytes, this is not the case. Owing to the elect r I cal
forces acting between oppositely charged ions, the activit of
the ions is reduced, and hence the ions behave as if they \\ ere
of lower concentration than that calculated from the stoidtio-
metric concentration of the dissolved electrolyte. If, there-
fore, the law of chemical equilibrium is to be applied to a
reaction involving ions, each concentration must be multiplied
by a factor which will allow for the interionic attraction. This
factor is termed the activity coefficient because it givef' the
fraction of the total concentration which is effective in t ' tui-
librium reactions. If we represent the corrected concentr:. t ion
11] The Theoretical Ba8i8 of Qualitative AnalY8i8 23
or activity by a, the activity coefficient by f and the concentra-
tion by c, then
a =c xJ
The value of the activity approaches that of the molar con-
centration or molarity as the solution is progressively diluted,
since under these conditions the ions will be further apart and
the interionic attraction will consequently become smaller.
At infinite dilution the forces between the ions will be practically
zero - a = c and f = 1.
The concept of activity, a thermodynamic quantity, was
introduced by G. N. Lewis. According to modern thermo-
dynamics, the rigid equilibrium equation for, say, a binary
electrolyte:
AB ~A+ +B-
is a A + X aa-/aAB = KIA......
where a A +, a B - and a AB denote the activities of A+, B- and AB
respectively, and K therm . is the true or thermodynamic dis-
sociation constant. At any molar concentration
a A+ =fA+·[A+], aB- =fB-·[B-] and aAB =fAB·[AB],
where f refers to the activity coefficients, and the square
brackets to the molar concentrations. Substituting in the
above equation, one obtains:
fA+' [A+] X fB-' [B-] = [A+]. [B-] X fA+ X fB- = KIA
JAB' [AB] [AB] fAB ......
This is the rigorously correct expression for the law of mass
action as applied to weak electrolytes.
The activity coefficient varies with the concentration. For
ions, it varies with the valency, and has the same value for
all dilute solutions having the same ionic strength, the latter
being a measure of the electrical field existing in the solution.
The ionic strength, designated by the symbol I, was introduced
by Lewis and Randall in 1921, and is defined as equal to one-
half of the sums of the products of the total concentration of
each ion multiplied by the square of its valency, or I = 1/2
EC,Z,2, where Ci is the ionic concentration in gram moles per litre
of solution. An example will make this clear. The ionic
strength of 0·1 molar HN0 3 solution containing 0·2 molar
Ba(NO a)2 solution is given by:
1/2{0'1 (for H+) + 0·1 (for NO a-) + 0·2 X 22 (for Ba.++)
+ 0·2 X 2 (for NO.-)} = 1/2{ 1·4} = 0·7
24 Qualitative Inorganic Analysia [I,
Activity coefficients may be derived inter alia, by rna "ing
appropriate assumptions, from measurements of the e.m.,. of
suitably arranged concentration cells and also from freezing-
point data for solutions. * The Debye-Huckel theory of com-
plete dissociation (1923) has provided a theoretical solutio" of
the problem of calculating individual activities of ions in " ,)ry
dilute solution. The expression for the activity coefficiel,. of
an ion is:
log II = - AZ,2y'1"
where A is a constant, Zi is the valency of the ion and 1 is I he
ionic strength of the solution. A may be computed from:
A = N2 e3v'2tr/lOOO/2·303R3/2c;:3/2T3/2:
N is Avogadro's number; e the electronic charge; R the /as
constant ~ f! the dielectric constant (this is usually taken for

Fig. 1,11, 1 Fig. I, 11, 2

dilute solutions as that of the solvent); and T is the absoilite

temperature. The mean activity coefficient of a dilute aque l "lS
solution of a 8alt at 25 0 is given by:
log I = - O'509z+z_ y'I
where z+ and Z_ are the valencies' of the positive and negat; ,e
ions respectively. The expression is a limiting one and [8
applicable to solutions of low ionic strength (up to ab("lt
1 = 0'01). The mean activity coefficients (experiment :~l
values) of a number of typical electrolytes at round concentm-
• For details, _, for example, S. Glasstone, Text Book oj Phllaical Ohemistry,
Second Edition, 1947 (Macmillan).
11] The Theoretical Baais of Qualitative Analym 25
tions are collected in Table I, 11, 1. The activity coefficients,
in general, pass through a minimum and then rise gradually;
in some cases they exceed the value 1 in the region 1-4 molar.
Figs. I, 11, I and I, 11, 2 indicate graphically the change in

TABLE I, 11, 1. MEAN ACTIVITY COEFFICIENTS OF V ABIOU8

ELECTROLYTES

Molar 0·001 0'01 0·05 I 0·1 0·2 0·5 1·0 2·0

Concentration
- - - -- - - -- -- -
HCI 0·966 0·904 0·830 0·796 0·767 0·758 0·809 1·01
HBr 0·966 0·906 0·838 0'805 0·782 0·790 0·871 1-17
HNO. 0·965 0·902 0·823 0·785 0·748 0'715 0·720 0·78
HIO. 0·96 0·86 0·69 0·58 0·46 0·29 0·19 0·10
H.SO, 0·830 0·544 0·340 0·265 0·209 0·154 0·130 0·12
NaOH - - 0·82 - 0·73 0·69 0·68 0·70
KOH -. 0·90 0·82 0·80 - 0·73 0·76 0·89
Ba(OH). - 0'712 0·526 0·443 0·370 - - -
AgNO. - 0'90 0·79 0·72 0·64 0·51 0·40 0·28
Al(NO.). - - - 0·20 0·16 0·14 0·19 0·45
BaCl, 0·88 0·72 0·56 0·49 0·44 0·39 0·39 0·44
Ba(NO.). 0·88 0'71 0·52 0·43 0·34 - - -
CaCl, 0·89 0·73 0'57 0'52 0·48 0·52 0·71 -
Ca(NO.). 0·88 0'71 0·154 0·48 0·42 0·38 0·35 0·35
CdCI, 0·76 0·47 0·28 0·21 0·15 0·09 0·06 -
CdSO, 0·73 0·40 0·21 0·17 0·11 0·07 0·05 0·04
CuCI. 0·89 0·72 0'58 , 0'52 0·47 0·42 0'43 0·51
CUSO, 0'74 0·41 0·21 0·16 0·11 0·07 0·05 -
FeCla 0·89 0·75 0·62 0'58 0·55 0·59 0·67 -
KF - 0·93 0'88 0·85 0·81 0·74 0·71 0·70
KCI 0·965 0'901 0·815 0'769 0·719 0·651 0·606 0·576
KBr 0·965 0'903 0'822 0'777 0·728 0·665 0·625 0·602
KI 0·965 0'905 0·84 0·80 0·76 0·71 0·68 0·69
KCIO a 0·967 0·907 0·813 0'755 - - - -
KCIO, 0·965 0·895 0·788 - - - - -
K.SO, 0·89 0'71 0·52 0·43 0·36 - - -
K,Fe(CN). - - 0·19 0·14 0·11 0·67 - -
LiBr 0·966 0·909 0·842 0·810 0·784 0·783 0·848 1·06
Mg(NO.). d·88 0·71 0·55 0·51 0·46 0·44 0·50 0·69
MgSO, - 0·40 0·22 0·18 0·13 0·09 0·06 0·05
NH,Cl 0·96 0·88 0·79 0·74 0·69 0·62 0·57 -
NH,Br 0·96 0·87 0·78 o·n 0·68 0·62 0'57 -
NH,I 0·96 0·89 0·80 0'76 0·71 0·65 0·60 -
NH,NO. 0·96 0·88 0'78 0'73 0·66 0'56 0'47 -
(NH')2 S0 , 0·87 0·67 0·48 0·40 0·32 0·22 0·16 -
NaF - 0·90 0·81 0'75 0·69 0·62 - -
NaCl 0·966 0·904 0'823 0'780 0·730 0·68 0·66 0·67
NaBr 0·966 0·914 0·844 0'800 0·740 0·695 0·6H6 0·734
NaI 0·97 0·91 0'86 0·83 0·81 0·78 0·80 0·95
NaNO. 0·966 0·90 0'82 0'77 0·70 0·62 0·55 0·48
Na 2SO, 0·89 0·71 0·53 0·45 0·36 0·27 0·20 -
NaCIO, 0·97 0·90 0·82 0'77 0·72 0·64 0·58 -
Pb(N0 3 ). 0·88 0·69 0·46 0'37 0·27 0·17 0·11 -
ZnCI. 0·88 0'71 0·56 0'50 0'45 0·38 0·33 -
ZnSO, 0·70 0·39 - 0·15 0·11 0·07 0·05 0·04
 !
26 Qualitative Inorganic Analym [I,
activity coefficient with increasing concentration for a !"ew
selected electrolytes: f is plotted agamst the square root 0: (,he
concentration (g. mols. per 1,000 g. of solvent) c.
The activity coefficients of unionised molecules do not d llier
appreciably from unity. For weak electrolytes in which the
ionic concentration and therefore the ionic strength is S1" all,
the error introduced by neglecting the difference between ~he
actual values of the activity coefficients of the ions, fA + and (B-'
and unity is small «5%). Hence for weak electrolytes, the
true or thermodynamic expression reduces to
[A+] X [B-]/[AB] = K;
the constants obtained by the use of simple concentrations will
be accurate to 2-6%. Such values are sufficiently pr. ·ise
for purposes of calculation in qualitative analysis. It nl !lSt,
however, be pointed out that precision values for the dissoeia-
tion constants of weak electrolytes can be obtained by the
use of special methods; the discussion of these is outside the
scope of this volume.
For strong electrolytes, as well as for the more concentr! ·jed
solutions of weak electrolytes, activity coefficients shoul!! be
employed when precise results are required. Activity co-
efficients, particularly for solutions containing mixtures of ,. Llts
of various valence types such as are encountered in qualitn 1 ive
analysis, are difficult to determine. For this reason, we "Ilall
employ the molecular concentrations instead of activitk c in
this text. Strong electrolytes will be assumed to be comph' ely
dissociated and no correction for activity coefficients will
generally be made. Fortunately, in a large number of C:l'1es,
the errors thus introduced are not -very serious.
I, 12. Strengths of Acids and Bases.~It has already i ,nen
stated that the properties of acids are the properties of the
hydrogen ion H+ (or, more correctly, the hydroxonium ion
H30+). For any given total concentration of acid, the con-
centration of the hydrogen ions will depend upon the degrf'e of
dissociation IX; the strength of an acid will thus depend 1!! Ion
the value of IX at a given concentration. The dissocia t ion
constant gives a relationship between IX and the concentration,
and it accordingly also represents a measure of the strengt!; of
the acid or a measure of its tendency to undergo dissocia! 'on.
The properties of bases, according to the most elemen I :Lry
view, * depend upon the hydroxyl ion and the ionis:!: ion
constant will likewise be a measure of the strength of the ),,;,8e.
• See Section It 5 for Bronsted-LoWI'Y definition.
 , I
12] The Theoretical Basis of Qualitative Analysis 27

TABLE 1.12, L DISSOCIATION CONSTANTS AT 25°0

Monobasic Acids
-
Nitrous acid 4·6 X 10-' Monochloroacetic
Hydrocyanic acid 7·24 X 10- 10 acid 1·5 X 10-3
Formic acid 1·77 X 1O- 4 t Cyanoacetic acid 3·49 X 1O-3 t
Acetic acid 1·82 X 10- 5 Phenylacetic acid 4'88 X 1O- 5t
1·76 X 1O- 5t Benzoic acid 6·37 X 1O- 5t
Propionic acid 1·34 X 10- 5 o-Chlorobenzoic
Boric acid 5·8 X 10- 10 acid 1·20 X 1O- 3 t
o-Nitrobenzoic
acid 6·00 X 1O-'t
Hydrofluoric acid 6·9 X 10-'
Phenol 1,3 X 10- 10

Dibasic Acid8
---
Hydrogen
sulphide
{KK 9.1
I X 10-
1·2 X 10-
8
15 Oxalic acid {KK 5'9
I
6·4
1O- t
1O- 5t
X
X
2

Sulphurous
acid
2
{KK 1'7
1 X 10-
1'0 X 10-
2
7 Malonic acid {KK 2·20
2
11'40 X 1O- t
X 1O- t
3
6

Sulphuric acid Ka 1·15 X 1O-

2
t 2
{KK 2'54
2
6'63 1O- 5t X
Carbonic {KK 5·61
4'31 X 1O- t 7 Succinic acid 1
1O- t X 6

acid
I
2 X 1O- t 11 d-Tartaric
acid
{KKa 4·55
2
11'04 lo-at
lO-'t
X
X

Tribasic Acids

Phosphoric {KK 6·23

1 7'52 X 1O- t
X 1O- t
8
8 Citric acid
{KKa 2·69
19'20 X 1O-'t
1O- 5t X
acid
K35 XX 1O-
2

10-3t
13
Ka 1·34 1O- t X 6

Arsenic acid
{KKa 4·0
1 5'0
10- 5

K 6'0 XX 10-
3
10

--
Bases

Ammonia 1·8 X 10- 5 Diethylamine 1·2 X 10-8

1·79 X 1O- 5 t Triethylamine 6·4 X 10-'
Methylamine 4·38 X 1O- 4 t Aniline 4·0 X 10- 10
Dimethylamine 5·20 X 1O- 5t Pyridine 2·0 X 10- 8
Trimethylamine 1)·45 X 10-5t Quinoline 6·0 X 10- 10
Ethylamine 5·6 X 10-' Piperidine 1,3 X 10-8

t Figures marked with a dagger (tl are the true or thermodynamio dis-
sooiation oonstants (see Section It 11).
28 Qualitative Inorganic Analysis [I,
For very weak or slightly dissociated electrolytes, the e:- Pres-
sion ('J.2j(1 - ('J.)V = K reduces to ('J.'J. = KV or ('J. = '\ [{V,
since oc may be neglected in comparison with unity. ] i mce
for any two weak acids or bases at any given dilution !' (in
litres), one has OCI = VKIV and OCll = VK 2 V, or IXI '2 =
VKljVK;. Expressed in words, for !;tny two weak or sli iltly
dissociated electrolytes at equal dilutions, the degrees or dis-
sociation are proportional to the square roots of their dis" ,cia-
tion constants. Some values for the clissociation constal;' , at
25° for weak acids and bases are collected in Table 1, j , l.

I, 13. Dissociation of Polybasic Adds.-When a poly i . lsic

acid is dissolved in water, the various hydrogen atoms Ull< rgo
dissociation to different extents. For a dibasic acid H2A the
primary and secondary dissociation can be represented b.) the
equations:
H2A ~ H+ + H.t\- (1)
HA- ~H+ +A~- I I . (2)
If the dibasic acid is a weak electrolyte, the law of mass a( I ion
may be applied, and the following expressions obtained:
[H+] X [HA-]/[H 2 A] = Xl (1a)
[H+] X [A--]/[HA-1 = Xl! (2a)

K 1 and K 2 are known as the primary and secondary dis socia ! j on

constants respectively. Each stage of the dissociation pro· ,.~ss
has its own ionisation constant, and the magnitudes of t; ,)se
constants give a measure of the extent to which each ionisa T ion
has proceeded at any given concentrl1tion. The greater ,he
value of K J relative to K 2 , the smaller will be the secont; lry
dissociation, and the greater must be the dilution before i he
latter becomes appreciable .. It is therefore possible that, a
dibasic (or polybasic) acid may behave, 'so far as dissocial ion
is concerned, as a monobasic acid over a considerable con("'u-
tration range. This is indeed characteristic of many polyb<l,;ic
acids (see Table I, 12, 1).
A tribasic acid H3A (e.g. orthophosphoric acid) will simib dy
yield three dissociation constants, Kb K2 and Ea. which l;;,ty
be computed in an analogous manner:
HsA ~ H+ + H 2 A- (3)
H2A- I? H+ + HA-- (4)
(5)
14] The Theoretical Basi8 of Qualitative AnalyBil 29
We can now apply some of the theoretical considerations to
actual examples encountered in qualitative analysis. *
Example 1. To calculate the concentrations of HS- and S-- in
a saturated solution of hydrogen sulphide.
A saturated aqueous solution of hydrogen sulphide at 25°, at
atmospheric pressure, is approximately 0·1 molar. The primary and
secondary dissociation constants are 9·1 X 10- 8 and 1·2 X 10-15
respectively.
Thus [H+] X [HS-]/[H 2S] = 9·1 X 10- 8 (i)
and [H+] X [S--]/[HS-] = 1·2 X 10-15 (ii)
The very much smaller value of K 2 indicates that the secondary
dissociation, and consequently [S--] is exceedingly small. It
follows, therefore, that only the primary ionisation is of importance,
and [H+] and [HS-] are practically equal in value. Substituting
in equation (i): [H+] = [HS-] and [H 28] = 0·1, one obtains
[H+] = [HS-] = V9·1 X 10 8 X 0·1 = 9·5 X 10-5•
Both the equilibrium equations must be satisfied simultaneously;
by substitution of these values for [H+] and [HS-] in equation (ii)
one obtains 9·5 X 10-5 X [8--] = 1·2 X 10-15 X 9·5 X 10-5 , or
[S--] = 1·2 X 10-15 , which is the value for K 2 •
If one multiplies equations (i) and (ii) together and transposes:
[8--] = 1·1 X 1O-23/[H+]2
Thus the concentration of the sulphide ion is inversely proportional
to the square of the hydrogen ion concentration, i.e. if one, say,
doubles [H+] by the addition of a strong acid, the [8--] would be
reduced to 1/22 or 1/4 of its original value.
I, 14. Common Ion Effect.-The concentration of a parti-
cular ion in an ionic reaction can be increased by the addition
of a compound which produces that ion upon dissociation.
The particular ion is thus derived from the compound already
in solution and from the added reagent, hence the name
common ion. We shall confine our attention to the case in
which the original compound is a weak electrolyte in order that
the law of mass action may be applicable. The result is usually
that there is a higher concentration of this ion in solution than
jhat derived from the original compound alone, and new equi-
ibrium conditions will be produced. Examples of the calcula-
jion of the common ion effect are given below. In general, it
nay be stated that if the total concentration of the common
on is only slightly larger than that which the original com-
)ound alone would furnish, the effect is small; if, however, the
• For further examples the reader is referred to any of the numerous boob
on chemical calculations.
II
30 Qualitative Inorganic AnalY8i8 [I,
concentration of the common ion is very much increased if .g.
that produced by the addition of a completely dissociated s"lt),
the effect is very great and may be of considerable pract il!al
importance. Indeed, the common ion effect provide,- a.
valuable method for controlling the concentration of the j ins
furnished by a weak electrolyte.
Example 2. To calculate the sulphide ion concentration in a ()·25
molar hydrochloric acid solution saturated with hydrogen sulpl,ide.
This concentration has been chosen since it is that at whicl, che
sulphides of the metals of Group II are precipitated. The i tal
concentration of hydrogen sulphide will be approximately the ~'lme
as in aqueous solution, i.e. O·IM; the [H+] will be equal to that
of the completely dissociated HCI, i.e. 0·25M, but the [S--] will
be reduced below 1·2 X 10-15 •
Substituting in equations (i) and (ii) (Section I, 13), one find~:
8 X [H 2S] = 9·1 X 10-8 X 0·1 _ 3.6
[ HS-] = 9·1 X 10- [H+] 0.25 -
' -8
X 1.1
1·2 X 10-15 X [HS-] 1·2 X 10-15 X 3·6 X 10- 8
[H+] 0·25
= 1·7 X 10-zZ
Thus by changing the acidity from 9·5 X 1O-5M (that preser !; in
saturated H 2 S water) to 0·25M, the sulphide ion concentrati, 11 is
reduced from 1·2 X 10-15 to 1·7 X 10-22 •
Example 3. What effect has the addition of 0·1 gram mok"ule
(8.20 grams) of anhydrous sodium acetate to I litre of 0·1 It'!)lar
acetic acid upon the degree of ionisation of the acid 1
The dissociation constant of acetic acid at 25° is 1·82 X 11)-5.
The degree of dissociation 0: in O'IM solution (c = 0·1) rna, be
computed by solving the quadratic equation:
[Ht-] X [C2 H s 0 2-j ~ = 1.82 X 10- 5
[H.C zH s 0 2 ] (I - 0:)
For our purpose it is sufficiently accurate to neglect 0: in (I 0:),
since 0: is small:
:.0: = v'KfC = Vl·82 X 10 4=0·0135
Hence in O·IM acetic acid,
[H+] = 0·00135, [C2Ha02 -] = 0·00135 and [H. C2 H 3 0 2] = 0,' '')86.
The concentrations of sodium and acetate ions produced by the
addition of the completely dissociated sodium acetate are:
[Na+] = 0·1 and [C2Ha02 -] = 0·1 gram mole respectivelv.
The acetate ions from the salt will tend to decrease the ibnisatilJo of
the acetic acid since K is constant, and consequently the acetatp ion
15] The Theoretical Basi8 of Qualitative Analysi8 31
concentration derived from it. Hence we may write, [C 2 H a0 2- ] =
0·1 for the solution, if rx' is the new degree of ionisation,
[H+] = rx'c = O·lrx' and [H.C2 H aOz] = (1 - rx')c = 0'1,
since rx' is negligibly small.
Substituting in the mass action equation:
[H+] X [C zH a0 2-] = Q: lrx' ~0'1 = 1.82 X 10-5
[H. CZH S0 2 ] 0·1 '
or rx' = 1·8 X 10- 4
[H+] = rx'c = 1·8 X 10- 0
The addition of a tenth of an equivalent weight of sodium acetate
to a 0-1 molar solution of acetic acid has decreased the degree of
ionisation from 1·35 to 0·018 per cent, and the hydrogen ion con-
centration from 0'013;'3 to 0'000018.
Example 4. What effect has the addition of 0·5 gram molecule
(26·75 grams) of ammonium chloride to one litre of 0·1 molar
ammonia solution upon the degree of dissociation of the base?
(Dissociation constant of NHs = 1·8 X 10-5 )
In O'lM ammonia solution rx = vlc-·=8-X----"I'""0:--~5-c/~0-=·1 = 0·013.
Hence [OH-] = 0'0013, [NH4 +] = 0·0013 and [NHs] = 0·0987.
Let rx' be the degree of dissociation in the presence of the added
ammonium chloride. Then [OH-] = a'c = O·la' and [NHsJ =
(1 - a')c = 0·1, since a' may be taken as negligibly small. The
addition of the completely ionised ammonium chloride will of
necessity decrease the [NH4 +] derived from the base and increase
[NHs], since K is constant under all conditions. Now [NH4+] =
0·5, as a first approximation.
Substituting in the equation:
[NH4+] X [OH-] = 0·5 X O·la' = 1.8 10-5
[NHs] 0'1 X,
or rx' = 3·6 X 10- 5 and [OH-] = 3·6 X 10-6
The addition of half of an equivalent weight of ammonium
chloride to a 0·1 molar solution of ammonia has decreased the
degree of ionisation from 1·35 to 0·0036 per cent, and the hydroxyl
ion concentration from 0·0013 to 0·0000036.
I, 15. Solubility Product.-It was found as a result of experi-
ment that for sparingly soluble binary electrolytes (i.e. those
with solubilities less than 0·001 gmm molecules per litre), the
product of the total molar concentrations of the ions is constant
at constant temperature. This product Se is termed the solu-
bility product. For a binary electrolyte:
AB,.=A++B-
81. = [A+] X [B-1
32 Qualitative Inorganic Analysis
Nernst, about 1889, enunciated the solubility product prilldple
in the form: in a saturated solution of a sparingly S( llble
electrolyte, the product of the concentrations of the consti' .rent
ions for any given temperature is constant, the ion conCt' tra-
tion being raised to powers equal to the respective numb, '9 of
ions of each kind furnished bv the dissociation of one mol mle
of the electrolyte. (The c~ncentration of an ion rna be
changed by adding another electrolyte yielding an ion in om-
mon with the solid substance, but the solubility pr( .. iuct
remains the same: if, say, for a binary electrolyte, the con-
centration of one ion increases, that of the other ion decr tses
correspondingly.) Thus for an electrolyte A"Bo' which it,:jses
into pA+··· and qB-··· ions:
A"Bq r;p pA +... + qB-... f1.
SlJlB = [A+···]p X [B-···]·
This relationship can be derived as follows. For simp! ,jty,
let us consider a saturated solution of a slightly soluble b :tary
electrolyte in which excess of solid is present:
A+B- o? A+ + B-
(solid) (ions in solution)

The activities of the solid and the ions in solution m: " be

written as a AB , a A + and a B - respectively. The solid is :om-
pletely ionised in dilute solution. By applying the law Of nass
action in its most general form, we have:
0A+ X an-JOAB = K'fVu,

The activity of the solid may be taken as unity since it ;~ the

pure component. Its ability to lose ions to a solutioll may
depend upon the extent of its surface in contact wit', the
solution, but the tendency of the ions to crystallise ou also
depends upon the nature of this same surface and hence, 9 far
as equilibrium is concerned, the surface factor cancel out.
The amount of solid present has no effect upon the equili ,rium
provided a reasonable quantity is present. The expr· .,sion
for the equilibrium constant therefore reduces to:
0A+ X an- = Sln
where Sk is the activity product constant. Nowacth liy =
concentration X activity coefficient, hence:
[A+]./A+ X [B-]./.- = S~.
15] The Theoretical Ba8i8 of Qualitative AnalY8is 33
In very dilute solutions of the sparingly soluble salt, the
activity coefficients are close to unity and we may then write:
[A+] X [B-] = BAR
It is important to note that the solubility product relation
applies only to saturated solutions of slightly soluble electro-
lytes and with small additions of other salts, say, provided the
total salt concentration does not exceed 0·2-0·3 molar. In the
presence of large concentrations of salts, the ionic concentration
and therefore the ionic strength of the solution will increase.
This will, in general, lower the activity coefficients of both ions
(since log Ii = - Az,2v'1, Section I, 11). As a consequence
the solubility of the slightly soluble salt must increase since
24.--------·
M
~
x 20

'<;-8

SaCI Z

- -. - •••• _!_{_I_
°O~~O~.O~2~O~'O~4~O'~06~~O'~08~O~'I~O~0·'12---0'~14~O~'16
Normality of added salt

Fig. I, 16. I.-Influence of Various Salts on the Solubility of TICI

[A +] X [B-] .fA + X IB- must be kept constant. The effect of

electrolytes with no common ion upon the solubility is often
called the salt effect. The salt effect is illustrated by the
curves shown in Figs. 1, 15, 1 and I, 15, 2. In the former the
three salts with the common ion decrease the solubility of
TICI somewhat less than the solubility product predicts, whilst
the two salts with no common ion increase the solubility, the
divalent sulphate ion exerting the greater effect. In the latter
case excess of AgN0 3 decreases the solubility somewhat less
than simple theory predicts, MgS04 and K 2S04 decrease the
solubility only slightly, whilst KNO s and Mg(NOs)2 markedly
increase the solubility with the divalent magnesium ion causing
the greater increase. These effects, which are inexplicable on
thll~!asis of the classical theory of Arrhenius, can be readily
 34 Qualitative Inorganic AnalY8i8 [I, •
8or---------------__~

'"
~ 70
l<

50,-- added
(Calc.)

AgN03
" . Ag+ add«
10 0~--0~.~02~0-.0-4~0.....0-6-0....0-8---'0.10 (Calc.
Normality 0/ added salt
Fig. 1,15, 2.-Infiuence of Various Salts on the Solubilityof"Ag,"04

understood on the basis of the influence of the various ,<tIts

upon the activity coefficients. It will be observed that wllilst
the influence of a salt with a common ion is to depress the
solubility (the dotted curve indicates the solubility calcul. \I ed
from the simple solubility product relationship), this deCIdse
is often greatly modified by the salt effect: indeed, with Mg <04
the salt effect nearly cancels out the common ion effect.
The great importance of the conception of solubility pro.; (lOt
lies in its bearing upon precipitation from solution, which i., of
course, one of the principal operations of qualitative analysis.
The solubility product is the ultimate value which is attained
by the ionic product when equilibrium has been establi,' 'ed
between the solid phase of a difficultly soluble salt and the
solution. If the experimental conditions are such that the
ionic product is different from the solubility product, 1 i ,en
the system will attempt to adjust itself in such a manner I flat
the ionic and solubility products are equal in value. Thu,· if,
for a given electrolyte, the product of the concentration of
the ions in solution is arbitrarily made to exceed the solubi iity
product, as for example by the addition of a salt with a comJnon
ion, the adjustment of the system results in the precipita i ion
of the solid salt, provided supersaturation conditions are
excluded. If the ionic product is less than the solubi Ity
product or can arbitrarily be made smaller, as for exampl, by
complex salt formation or by the formation of weak eleNw-
15] The Theoretical Basis of Qualitative Analysis 35
lytes (see Section I, 20), then a further quantity of the solute
can pass into solution until the solubility product is attained,
or if this is not possible, until all the solute has dissolved.
The concentrations are expressed in gram moles pcr litre for
the calculation of solubility products. A few examples may
help the student to understand the subject fully.
Example 5. The solubility of silver chloride is 0·0015 grams per
litre. Calculate the solubility product.
The molecular weight of AgCl is 143·5.
The solubility is therefore 0·0015/143·5 = 1·05 X 10-5 moles per
litre. In a saturated solution the dissociation, AgCl ;p Ag+ Cl-, +
is complete; 1 mole of AgCl will give 1 mole each of Ag+ and 01-.
Hence [Ag+] = 1·05 10-5 and [Cl-]
X = 1·05 X 10- 5
SA.Cl=[Ag+] X [Cl-] = (1·05 X 10- 5) X (1·05 X 10-5 )
= 1·1 X 10- 10
Example 6. Calculate the solubility product of silver chromate,
given that its solubility is 2·5 X 10-2 grams per litre.
Ag2Cr04;P 2Ag+ + Cr04--.
The molecular weight of Ag 2CrO" is 332, hence the solubility
= 2·5 X 10-2/332 = 7·5 X 10-5 mole per litre.
Now 1 mole of Ag2Cr04 gives two moles of Ag+ and I mole of
Cr04 --, therefore
SA'2CrO, = [Ag+]2 X [Cro 4--]
= (2 X 7·5 X 10- 5 )2 X (7·5 X 10- 5 )
= 1·7 X 10-12
Example 7. The concentration of fluoride ion in a saturated
aqueous solution of CaF 2 is 0·0078 gram per litre. Calculate the
solubility product of calcium fluoride.
The dissociation can be written:
CaF2 ;p Ca++ 2F- - +
i.e. in a saturated aqueous solution the concentration of Ca++ is
half that of F-. The fluoride ion concentration is 0·0078/19 =
4·0 X 10-4 mole per litre, and the calcium ion concentration is
therefore 2·0 X 10-4 mole per litre.
SC.F2 = [Ca++] X [F-]2 = (2·0 X 10- 4) X (4·0 X 10- 4)2

= 3·2 X 10-11
Example 8. The solubility product of lead orthophosphate is
1·5 X 10-32 • Calculate the !lolu bility in grams per litre.
The dissociation is:
36 Qualitative Inorganic AnalY8i8 [I,
If x is the solubility in gram moles per litre, [Pb++] = 3.1 and
[P04 - - - ] = 2x.
SPb3(P0412 = [Pb++]3 X [PO"---]2
or 1·5 X 10-32 = (3x)3 X (2x)2
or x 5 = 1·5 X 10-32 /108
or x = ~13·9 X 10-35 = 1·70 X 10-7 mole per i;tre
The molecular weight of Pb S (P04 }2 is 358, hence the solubil i 1Y is
1·70 X 10-7 X 358 = 6·1 X 10-5 grams per litre
Example 9. Given that the solubility product of magne',1 um
hydroxide is 3·4 X 10- 11 , calculate the concentration of hydr(l \ ide
ions in a saturated aqueous solution.
Mg(OH}2 ~ Mg++ + 20H-
If 2x is the concentration of OH- in gram molecules per litre,
then [Mg++] = x.
SMv,(OHh = [Mg++) X [OH-P

or 3·4 X 10- 11 = X X (2x)2

or x 3 = 3·4 X 10-11/4
'lI~ ~~

or x = ~8'5 X 10-12 = 2·04 X 10-4 gram mole per I tre

or [OH-] = 2x = 4·08 X 10- 4 gram mole per litre
In order to explain many of the reactions of qualitat, ve
analysis in a clear and intelligent manner, the values of ! he
solubility products of the various sparingly soluble substall' 'es
are useful. Some of the most important figures are collecl, ,d
in Table I, 15, 1, and what appear to be most trustwort liy
values in the literature are given. The student is referred 1,0
text-books on physical chemistry' for a description of tile
methods for determining these quantities. Many of th, ':-ie
constants are obtained by indirect means, such as measure-
ments of electrical conductivity, of e.m.f. of cells, or frofU
thermodynamic calculations using thermal data. The variolls
methods, however, do not always give consistent results alld
this may be attributed to various causes, which include the
following. In some cases the physical structure, and hence the
solubility of the precipitate at the time of precipitation, is not
the same as that of an old or stabilised precipitate: this may
be due to the process known as "ripening", which is a sort of
recrystallisation, or it may be due to a real change of cryst ,1
structure. Thus for nickel sulphide three forms (0:., f1 and :.)
have been reported with solubility products of 3 X 1O-~ I,
1 X 10- 26 and 2 X 10- 28 respectively: another source gives one
15] The TheoretiCiil7Jdsis of Qualitative Analy8i8 37
value of 1·4 X 10-24 • The at-form is said to be that of the
freshly precipitated substance: the other forms are produced
on standing. For cadmium sulphide a value of 1·4 X 10-28
has been computed from thermal and other data (Latimer,
1938), whilst direct determination leads to a solubility product
of 5·5 X 10-25 (Belcher, 1949).

TABLE I, 15, 1. SOLUBILITY PRODUCTS AT THE LABORATORY

TEMPERATURE

Solubility Solubility
Substance Substance
product product

AgBr 7·7 X 10-13 FeS 4·0 X 10-19

Ag Br0 3 5·0 X 10-5 Hg 2 Br2 5·2 X 10-23
AgCNS 1·2 X 10-12 Hg 2Cl 2 3·5 X 10-18
AgCI 1·5 X 10-10 Hg 212 1·2 X 10-28
Ag2C20 4 5·0 X 10-12 Hg2S 1 X 10-45
Ag 2Cr04 2·4 X 10-12 HgS 4 X 10-54
AgI 0·9 X 10-16 K2!_PtC~) 1·1 X 10-"
AgI0 3 2·0 X 10- 8 MgC0 3 1·0 X 10-5
Ag3P04 1·8 X 10-18 MgC 2 0 4 8·6 X 10-5
Ag 2S 1·6 X 10-411 MgF2 7·0 X 10-11
Ag 2S04 7·7 X 10-5 Mg(NH4)P04 2·5 X 10-13
AI(OH)3 8·5 X 10-23 Mg(OH)z 3·4 X 10-11
BaCO a 8·1 X 10-11 l\fu(OH)2 4·0 X 10-14
BaC2O, 1·7 X 10-7 l\fuS 1·4 X 10-15
BaCr04 1·6 X 10-10 Ni(OH)2 8·7 X 10- 111
BaS04 9·2 X 10-11 NiS 1·4 X 10-24
BizS a 1·6 X 10-72 PbBr2 7·9 X 10-5
CaCOa 4·8 X 10-11 PbCl 2 2·4 X 10-4
CaC 20 4 2·6 X 10-1) PbCO a 3·3 X 10-14
CaF 2 3·2 X 10-11 PbCrO, 1·8 X 10-14
CaSO, 2·3 X 10-4 PbF 2 3·7 X 10- 8
CdS 1·4 X 10- 28 PbI 2 8·7 X 10-1)
Co(OH}z 1·6 X 10-18 Pb 3(P04 )2 1·5 X 10-32
CO(OH)3 2·5 X 10-43 PbS 0 X 10- 211
CoS 3 X 10- 26 PbS 0 4 2·2 X 10- 8
Cr(OH)a 2·9 X 10- 211 SrC0 3 1·6 X 10-11
CuBr 1·6 X 10- 11 SrC 2 0 4 0·0 X 10- 8
CuCI 1·0 X 10-6 SrS04 2·8 X 10-7
CuI 5·0 X 10-12 TICI 1·5 X 10-4
CuS 1 X 10-44 TIl 2·8 X 10- 8
CuSCN 1·6 X 10-11 Tl 2S 1 X 10-22
Fe(OH)z 4·8 X 10-16 Zn(OH)2 1 X 10- 17
Fe(OH)3 3·8 X 1O-a8 ZnS 1 X 10-28
 38 Qualitative Inorganic Analysis [I,
I, 16. Applications of the Solubility Product Relation ,-
In spite of its limitations (as outlined in the previous Sect:, lll)
the solubility product relation is of great value in qualitat ,ve
analysis, since with its aid it is possible not only to explain i ,ut
also to predict precipitation reactions. The solubility prod llct
is in reality an ultimate value which is attained by the i( ;lic
product when equilibrium has been established between I he
solid phase of a slightly soluble salt and the solution. If con-
ditions are such that the ionic product is different from t he
solubility product, the system will seek to adjust itself in Sli :h
a manner that the ionic product attains the value of the S(,ju-
bility product. Thus if the ionic product is arbitrarily mil' Ie
greater than the solubility product, for example by the addit,· 'n
of a small quantity of another salt with a common ion, l' ,e
adjustment of the system results in the precipitation of ilie
solid salt. Conversely, if the ionic product is made smaller
than the solubility product as, for instance, by diminishing the
concentration of one of the ions (see Section I, 17), equilibrium
in the system is attained by some of the solid salt passing into
solution.
As an example of the formation of a precipitate, let us con-
sider the case of silver chloride. The solubility product for
silver chloride is:

S~rcl = [Ag+] X [01-] = 1·5 X 10-10

Let us suppose that to a solution which is 0·1 molar in SilV"l'

ions we add enough potassium chloride to produce momentari: \'
a chloride concentration of 0·01 molar. The ionic product i,
then 0·1 X 0·01 = 1 X 10-3 • Since 1 X 10-3 > 1·5 X 10-] ",
equilibrium will not exist and precipitation will take plan'
(Ag+ + Cl- -+ AgCl) until the value of the ionic product h: :-l
been reduced to that of the solubility product, i.e. unl \l
°:
[Ag+] X [Cl-] = 1·5 X 10-1 at this point the rate of pr"-
cipitation is equal to the rate of solution of the precipitatl'.
If now, with a saturated solution of silver chloride as the initial
solution, we add either a soluble chloride or a soluble silver
salt in small quantity, a slight further precipitation of silver
chloride takes place: if, after equilibrium has been reache;
the concentrations of the respective ions are determined, ',e
find that, although the concentration of one ion has increased
and that of the other has decreased, the ionic or solubility pru-
duct is roughly constant. Some results, due to J ahn (1904),
clearly illustrate this point.
16] The Theoretical Basis of Qualitative AnalY8is 39
TABLE I, [tJ, 1
EFFEOT OF CHLORIDE IONS UPON THJ~ SOLUBILITY PRODUOT OF Agel

[KOl] [CZ-] x lOS [Ag+] X 108 BAgCI = [Ag+] . [Or] x 1010

0·00670 6·4 1·75 1·12
0·00833 7·9 1·39 1·10
0·01114 10·5 1·07 1'12
0·01669 15·5 0·74 1·14
0·03349 30·3 0·39 1·17

A simple example is instructive.

Example 10. What is the concentration of silver ion in gram
moles per litre remaining in solution after adding sufficient HOI to a.
solution of AgNO s to make the final chloride ion concentration
0·05 molad The solubility product of AgOI is 1·5 X 10- 10•
In the final solution
BAgCl = 1·5 X 10-10 = [Ag+] X [01-] = [Ag+] X 0·05
or [Ag+] = 1·5 X 10- 10/0.05 = 3·0 X 10-9 gram mole per litre
It should be pointed out that the solubility product defines a
state of equilibrium, but does not mention the rate at which
equilibrium is established. Whilst the solubility product must be
exceeded before precipitation can occur, this does not necessarily
imply that precipitation will take place immediately. Indeed,
in the formation of small amounts (say, up to 5 mg. in a volume
of 10-100 ml.) of a number of insoluble salts, such as BaSO",
eus and Mg(NH,,)P0 4 , precipitation is not complete (and there-
fore equilibrium is not attained) until after 12-48 hours.
Hence the statement so frequently made that precipitation
occurs when the solubility product is exceeded, must have the
qualification that for small amounts of precipitate some time
elapses before precipitation actually begins and then a further
period of variable duration must elapse before precipitation is
complete.
Attention must also be drawn to the fact that complete pre-
cipitation of a sparingly soluble electrolyte is impossible, because
no matter how much the concentration of one ion is arbitrarily
increased, the concentration of the other ion cannot be de-
creased to zero since the S.P. * has a constant value. The con-
centration of the ion can be reduced to a very small value:
in Example 10 the silver ion concentration is 3·0 X 10-9 X 108
• The abbreviation S.P. will be employed for solubility product.
40 Qualitative Ino,.ganic Analysu (I,
= 3·24 X 10-7 g. per litre, which is negligible for most practi,'al
purposes. It may be noted that in practice it is found tklt
after a certain point, further excess of precipitant does pot
materially increase the weight of the precipitate. Indeed a
large excess of precipitant may cause some of the precipitn Ie
to dissolve either as the result of increased salt effect (.'-e
Section I, 15) or as a result of complex ion formation with ,n
ion of the precipitate (see Section I, 20). Some results of
Forbes (1911), collected in the following Table, on the infiuelli'e
of excess of NaCI upon the solubility of AgCl illustrate tJ,is
point.
TABLlIl I, 16, 2. EJTECT OF NaCI UPON THlll SOLUBILITY OF AgCI

N aOl (molea/lit,.e) Ag (molea/litre) X 105

0·933 8·6
1·433 18·4
2·272 57·0
3·000 119·4
4·170 333·5
5·039 603·9

These results show why only a slight excess of the reagent i,

added in precipitation reactions.
Having completed a limited general discussion, we are no\\'
in a position to consider SOme direct applications to qualitath I,
analysis.
Precipitation of Sulphides. The solubility products of a nun!
ber of common sulphides are: HgS 4 X 10-54 , PbS 5 X 10-2 ".
CuSl X 10-44 ,CdS 1·4 X 10-28 (or 5·5 X 1O-25 ),MnS 1·4 X 10- 10
and ZnS 1 X 10-23 • When hydrogen sulphide is passed into :t
solution of the salts of these metals, precipitation will occm
when [M++] X [S--] exceeds the solubility product (M++ 1>1
the ion of the metal). In the usual course of qualitative
analysis, the concentration of the metallic ions cannot be
varied between wide limits since one is limited, on the OIll'
hand, by the solubility of the salt and, on the other hand, by
the necessity of obtaining sufficient precipitate to handle and
to use for qualitative tests. The concentration of the solution
is of the oJ'der 10- 1 to 1 molar. The sulphide ion concentratioll
can, however, be varied between wide limits. We have already
seen that in 0·25-0'3 molar hydrochloric acid (Section I, 14,
16] The Theoretical BasitJ oj Qualitative Analysis 4:1
Example 2), the concentration at which Group II is usually
precipitated, [8--] is 1·7 X 10-22 ; under these conditions only
the solubility products of HgS, PbS, CuS and CdS are exceeded,
,and these are therefore almost completely precipitated. * If the
concentration of the acid is much higher, then [S--] is reduced
still further, and it is not difficult to see that CdS will be either
not precipitated at all or incompletely precipitated. In a
saturated aqueous solution of hydrogen sulphide, [S--] is
1 X 10- 14, and under these conditions ZnS is partially preci-
pitated; precipitation ceases at a certain concentration, due
to the accumulation of hydrogen ions arising from the acid
produced in the reaction. The increased hydrogen ion con-
centration decreases the dissociation of the hydrogen sulphide
until [S--] is such that [Zn++] X [S--] is not in excess of the
solubility product. For the complete precipitation of zinc sul-
phide, the hydrogen ions must be removed or their concentra-
tion considerably reduced; this can be achieved by the addition
of sodium acetate. The latter gives rise to the feebly dis-
sociated acetic acid (C 2H a0 2- + H+ ,.:. H.C 2H a0 2 ), the [S--]
is maintained sufficiently high and precipitation is complete.
Another method is to employ a soluble sulphide, e.g. ammonium
or sodium sulphide, which gives a high concentration of sulphide
ions in solution; ZnS, MuS and related sulphides can then be
completely precipitated.
Example 11. Oalculate the maximum concentration of Od++ ions
and of Mn++ ions which will remain in solution after precipitation
by excess of H 2S in 0'25M HOI. (Solubility products: CdS =
5·5 X 10-26 ; MuS = 1·4 X 10-16 .)
The sulphide ion concentration [S--] in O'2aM HOI saturated
with H 2S is 1·7 X 10- 22 gram mole per litre.
Now [Od++] X [S--] = 5·5 X 10-25
[Od++] = 5·5 X 10-25 /1'7 X 10-22 = 3·2 X 10-8 gram mole
per litre
= 3·2 X 10-8 X 112·4 = 3·6 X 10-1 grams per litre
Thus H 2S will precipitate about 96% of the Od++ from a solution
of 0'25M HOI containing 10 mg. of Od.;..;. per ml.
For manganese sulphide, [Mu++] X [8--] = 1·4 X 10-15 ;
[Mn++] = 1·4 X 10- 15/1.7 X 10- 22 = 8·2 X 106 gram mole
per litre,
= 8·2 X 106 X 55 = 4·5 X 108 grams per litre
This figure clearly shows that no MnS will be precipitated in
0'25M HOI solution.
• A detailed caloulation is given at the end of this paragraph to illustrate
this point.
"2-
 42 Qualitative Inorganic Analysis [I,
Precipitation of Hydroxides.-Here also the hydroxyl I(JD
concentration of the precipitating agent is controlled, and The
method is employed to differentiate between hydroxides of
different solubility products. We have seen (Section I, 14,
Example 4) that the addition of ammonium chloride to ammo .ia
solution* reduces the hydroxyl ion concentration considera1lly.
The resultant [OH-] is sufficient to exceed the solubility pm-
ducts of iron, aluminium and chromium but not of cobalt,
nickel, manganese, zinc and magnesium hydroxides; the lat'!lr
therefore remain in solution, whilst the former are precipitated
when ammonium chloride and ammonia solution are added to
a solution of their salts.
A very instructive example of the application of the so'a-
bility product principle is the precipitation and solution (If
aluminium hydroxide. The addition of hydroxyl ions in 1 i,e
form of sodium, potassium or ammonium hydroxides to a
solution of an aluminium salt yields a white gelatinous pi cl-
cipitate of aluminium hydroxide, which possesses amphote1lc
properties. It will dissolve in solutions of caustic alku i is
forming solutions of alkali aluminates, and also in solutions "f
acids forming the aluminium salts of the acids. The dissocia-
tion of aluminium hydroxide in aqueous solution may be
expressed:
(a) Al+++ + 30H- ? Al(OH)3 ~ AJ0 2 - + H30+ (b)
Basic dis8ociation Acid dissociation
Let us now consider what will happen when excess of ;~
strong acid, i.e. H+ ions, is added to a suspension of aluminilliil
hydroxide. The acid dissociation (b) would be repressed on
account of the common ion effect, and the basic dissociation (a)
would be simultaneously enhanced, due to the combination of
the H+ ions with the OH- ions of the solution to form un-
dissociated water. Initially, the ionic product of water,
[H+] X [OH-] = I X 10-14, held, but with the addition of
excess of H+ ions, i.e. with a large increase of [H+], this wili
be momentarily greatly exceeded. In order that the ionic
product relation for water be maintained under the new experi-
mental conditions, it will be necessary for the hydroxyl ions
supplied by the aluminium hydroxide to combine with the
hydrogen ions of the acid to form water. The removal of
hydroxyl ions in this manner will necessitate the further dis-
• The terms ammonia solution 80lld ammonium hydroxide solution may be
used synonymously throughout this book and refer, of course, to the aqueous
solution of ammonia.
16] The Theoretiool Basis of Qualitative Analysis 43
sociation of the aluminium hydroxide according to (a) since the
solubility product relation
[Al+++] X [OH-P 0= SAl(OHI3
(the latter is very small) must hold simultaneously. Since
[H+] is very large, the further dissociation and consequent
solution of the aluminium hydroxide will continue until the
latter is completely dissolved.
The addition of a solution of a strong base, sodium or
potassium hydroxide, i.e. of a large hydroxyl ion concentration,
will similarly repress the basic dissociation (a) and increase the
acid dissociation (b), owing to combination with the hydrogen
ions derived from this dissociation. It is clear that in order to
maintain the ionic product of water and the solubility product
of aluminium hydroxide constant under the new conditions,
more Al(OH)s must dissociate in accordance with (b); in con-
sequence of the high hydroxyl ion concentration this process
will continue until all the aluminium hydroxide has passed into
solution.
The precipitation of Al(OH)a by treating its solution in strong
alkali (thus containing Al0 2- ions) with excess of ammonium
chloride solution and boiling, is readily interpreted. The effect
of a large concentration of ammonium ions is to decrease the
hydroxyl ion concentration owing to the formation of ammonia,
a weak base; the excess of the latter is removed by boiling as
ammonia gas.
NH4+ + OH- ~ NHs t + H 2 0
This reduction of hydroxyl ion concentration will promote the
reaction (a) and bring about the combination of HsO+ and
Al0 2 - to produce a concentration of AI(OH)a in excess of that
in a saturated solution. The excess of aluminium hydroxide
will then be precipitated.
The above is perhaps an over-simplified picture of the
behaviour of aluminium hydroxide as an amphoteric hydroxide.
The acid dissociation may also be written as:
Al(OHb + 2H 2 0 ~ [Al(OH)4r + HsO+
It will be noted that [AI(OH)4r is a hydrated form of [Al0 2 r,
i.e. [A10 2 .H 2 0r. The soluble salt Na[Al0 2]xH 20 has been
isolated. The formation of an aluminate can also be represented
as:
Al(OH)s +
OH- ~ [Al(OII)4r
An alternative explanation of the amphoterio charaoter of
</I
44 Qualitative Inorganic A nalyai8 [I,
certain metallic hydroxides (see Section I, 20) has been giv.'n
along the following lines. It will be illustrated by reference '0
aluminium hydroxide and zinc hydroxide. Some remarks
concerning the hydrolysis of the aluminium ion will be given
first. The aluminium ion is believed to be hydrated, i.e.
[Al(OH 2)6]+++ (compare Section I, 42) and this undergoes
hydrolysis in successive stages:
- [Al(OH2 )6]+++ + H 2 0 ~ [Al(OH2)s(OH)]++ + HsO+
[Al(OH2 )5(OH)]++ + H 20 ~ [Al(OH2)4(OH)2]+ + HsO+
[Al(OH2)4(OH)2]+ + H 20 ~ [Al(OH2)s(OH)s] + HaO+
Aluminium hydroxide
The dissolution of aluminium hydroxide in acids is merely a.
reversal of the hydrolysis. In basic solution, the OH- ion
withdraws a proton from the water molecules coordinated with
the aluminium atom and the hydrated aluminate ion [Al(OH)4r
is produced:
[Al(OH2 )s(OH)s] + OH- ~ [Al(OH2 MOH)4r + H 20 (i)
According to this scheme the precipitation of aluminium
hydroxide from a solution of an aluminium salt by a base may
be expressed as:
[Al(OH2)6]+++ + 3NHa ~ [Al(OH2 )s(OH)s] + 3NH4+
Aluminium hydroxide in water is both a proton donor (acid):
[Al(OH2)s(OH)s] + H 20 ~ [Al(OH2)2(OH)4r + HsO+ (ii)
and a proton acceptor (base):
[AI(OH2)s(OH)a] + 3HsO+ ~ [Al_(OH 2 )6]+++ + 3H 20 (iii)
The latter process can be expressed in three stages (as above)
since the aluminium hydroxide is a tri-acid base, but for sim-
plicity the three steps have been combined into one equation.
If aluminium hydroxide is treated with a strong acid, equi-
librium (iii) is displaced to the left, the substance dissolves
and the hydrated aluminium ion is formed. Upon adding,
say, sodium hydroxide solution to a suspension of aluminiUllt
hydroxide, the OH- ions of the solution combine with ttn
HsO+ ions thus displacing (ii) to the right, and the aluminatu
ion is produced: the ultimate reaction is expressed by (i).
The amphoteric character of zinc hydroxide, ·written as
Zn(OH 2 b(OH)2], is explained similarly:
[Zn(OH2 l2(OH)2] + 2H 20 ~ [Zn(OH)4r- + 2HsO+ (iv)
[Zn(OH2 MOH)2] + 2HaO+ "'" [Zn(OH2),]++ + 2H2 0 (v)
 16] The TheoreticatBasis of Qualitative AnalY8is 45
The over-all reaction for the dissolution of zinc hydroxide in a
solution of a strong base with the formation of zincate ion is
given by the following equation:
[Zn(OH zMOH)2] + 20H- ~ [Zn(OH)4r- + 2H zO (vi)
It will be noted that [Zn(OH)4r- may be regarded as the
hydrated zincate ion [ZnOz.2H20r-. The classical represen-
tation of the amphoteric character of zinc hydroxide is:
Zn++ + 20H- ~ Zn(OH)z ~ 2H+ + ZnOz--
Coprecipitation. The discussion in the previous paragraphs
gives the impression that precipitation is controlled by the
solubility product principle and that the resulting precipitates
are chemically pure. This, however, is not always the case.
Thus, if barium sulphate is precipitated in the presence of
potassium nitrate or of ferric (but not ferrous) sulphate, the
precipitate is contaminated by these salts and these otherwise
soluble salts cannot be removed by washing with water. The
contamination of a precipitate by a substance that is normally
soluble under the conditions of precipitation is termed co-
precipitation. Other examples include the dragging down of
Ni++ or [Ni(NHa)4]++ ions with ferric hydroxide or aluminium
hydroxide, of sodium oxalate or calcium hydroxide with
calcium oxalate, and of zinc hydroxide with ferric hydroxide.
If hydrogen sulphide is passed into a solution containing
Cu++ and Zn++ ions which is O·25-0·3M with respect to H+ ions,
the solubility product of CuS is soon exceeded and it is therefore
precipitated from solution. If the precipitate is examined
immediately after precipitation, it is found to be largely pure.
Upon standing, the precipitate becomes increasingly con-
taminated with ZnS notwithstanding the fact that the solubility
product of ZnS has not been attained under the conditions of
the experiment. In this case the primary precipitate separates
in a more or less pure form and a second phase of foreign
. substance, which is slightly soluble, slowly forms subsequently.
The entrainment of impurity after the precipitate of the desired
material has been formed is termed post precipitation. It is
usually difficult to draw a sharp line of demarcation between
coprecipitation and post precipitation, but both processes are
clearly responsible for the invalidation of the solubility product
principle in certain cases and therefore for errors in analytical
separations. Examples of post precipitation include the
following: zinc sulphide and of nickel sulphide in the presence
.9f the sulphides of mercury and of bismuth, of ferrous sulphide
46 Qualitative Inorganic Analysis [I,
with copper sulphide, and also of magnesium oxalate in the
presence of calcium oxalate.
There are many interpretations of the phenomena of co-
precipitation and post precipitation, but these cannot be dis-
cussed here in detail. They may be due to adsorption on tlw
surface of the precipitate, to mutual precipitation of colloidal
particles in suspension (compare Section I, 44), to occlusion
(mechanical trapping of the mother liquor containing foreign
iOlls in the precipitate), or to substitution of one ion for another
in the crystal lattice of the precipitate. The phenomena are
usually specific. Coprecipitation may be diminished by making
the concentration of the coprecipitated salt as small as is
practicable; if the precipitant itself is dragged down, it should
be diluted and added dropwise with rapid stirring. In some
cases (e.g. calcium oxalate in the presence of magnesium ions),
the contaminated precipitate is separated by filtration, partially
washed, dissolved and reprecipitated. This process is termed
double precipitation. The extent of contamination of the pre-
cipitate is a function of the concentration of the coprecipitatf'! I
substance: the second precipitate is produced in a solution ill
which the contaminants are present in much lower concen-
tration and thus the amount of coprecipitation is decreased
considerably.
1,17. Solubility of Sparin~ly Soluble Salts of Weak Acids
in Stron~ Mineral Acids.-The solubility product principle
enables one to give a simple explanation of this phenomenon,
which is of relatively frequent occurrence in qualitative analysis
Typical examples are the solubilities of barium chromate and of
calcium oxalate in dilute mineral acids, but not in acetic acid.
When dilute hydrochloric acid is added in excess to a suspensioll
of calcium oxalate in water, the following ionic equilibria will
be present in solution:
CaC 2 0 4 ~ Ca++ +
C2 0 4 - - (almost complete dissociation) (i i
H+ + C2 0 4- - ~ HC 20,- (li)
H+ + HC 2 0 4- ,.= H 2C2 0, (iii)
The primary and secondary dissociation constants of oxalic
acid are 5·9 X 10-2 and 6·4 X 10-5 respectively, i.e.
[H+] X [HC 2 0 4 -]/[H 2C2 0,] = 5·9 x 10-2 (iv)
[H+] x [C 2 0 4 --]/[HC2 0,-] = 6·4 x 10-5 (VI

It is evident from equation (v) that if [H+] is large, [C 20 4--]

must be correspondingly smail, and will be reduced from it."
18] The Theoretical Basis ojQualitative Analysis 47
initial value in a saturated solution of calcium oxalate by com-
bination with hydrogen ions to form first H0 2 0, - and sub-
sequently H 20 20,. Equilibrium (i) will thus be disturbed; in
order to maintain the solubility product equilibrium more cal-
cium oxalate will pass into solution to restore that removed
by reactions (ii) and (iij). If sufficient mineral acid is present,
the process will continue until the whole of the calcium oxalate
has dissolved.
When acetic acid is added, no reaction occurs. The ionisa-
tion constant of acetic acid,
[H+] X [02Hs02-]/[H.02Hs02], is 1·82 X 10- 5,'
and the hydrogen ion concentration thereby introduced is not
sufficiently great to influence the oxalate ion concentration in
equation (v).
Similarly with barium chromate, the addition of a large
excess of mineral acid reduces the chromate ion concentration
by the reaction:
20rO, -- + 2H+ ~ 2HOr04- ~ Or207 -- + H 20,
and consequently the substance passes into solution. (All di-
chromates are soluble in water.) Acetic acid, on the other
hand, introduces only a very small hydrogen ion concentration
and therefore has little effect. For this reason, tIle barium
carbonate precipitate in Group IV is dissolved in dilute acetic
acid, not in hydrochloric acid, before the addition of potassium
chromate solution.

I, 18. Fractional Precipitation.-The calculation as to which

of two sparingly soluble salts will be precipitated under a given
set of experimental conditions may be made with the aid of the
solubility product principle. An example of great practical
importance is the Mohr method for the estimation of halides.
In this process a solution of a chloride, i.e. 01-, is titrated with
silver nitrate solution, i.e. Ag+, a small quantity of potassium
chromate (Oro, --) being added to serve as an indicator. Here
two sparingly soluble salts may be formed, viz. silver chloride
and silver chromate, the solubility products of which are
1·5 X 10- 10 and 2·4 X 10- 12 respectively.
The following relations must be satisfied for equilibrium
between the two precipitates and their solutions:
[Ag+] X [01-] = 1·5 X 10-10 (i)
[Ag+]2 X [OrO,--] = 2·4 X 10-11 (ii)
 48 Qualitative Inorganic Analyaia [I,
From (i) and (ii), one obtains:
[Cr]2 (1'5 X 10-10)1 1
(iii)
[Cro, --] = 2·4 X 10-12 = 1·1 X 108
Silver chromate will therefore not precipitate until its COn-
centration, or more correctly the chromate ion concentration,
is in excess of that given by this equation. It is evident thll t
if the initial solution contains chloride and 8- chromate in equ i
valent proportions, and one adds a solution of silver nitrate
dropwise, silver chloride will be precipitated until [Oro, --] is
in excess of the ratio given in equation (iii); henceforth silver
chromate will be precipitated with traces of silver chloride, the
equilibrium ratio in (iii) being maintained in the supernatant
liquid. In actual practice, the chloride ion concentration j,.;
usually approximately 0·1 molar, the silver nitrate solutio!!
about 0·1 molar and the chromate ion concentration aboll:
2 X 10-3 molar (2 ml. of 0·1 molar potassium chromate solutio,
per 100 ml. of solution). It is clear, therefore, that precipitv
tion of silver chloride is almost complete before reaction occur
between the excess of silver ions and chromate ions to give th,
red silver chromate.
The following detailed calculations may prove instructive.
Example 12. A solution contains 0·1 gram mole 01- and 0·00:'
gram mole Oro,-- per litre. Deci-molar silver nitrate solution i
added gradually to this solution. Calculate: (i) whether AgCI (.c o

Ag 2CrO, will be precipitated first, (ii) the concentration of chlorid·

ion in solution when the Ag 2CrO, begins to precipitate, and (iii) tho
fraction of the orginal chloride ion concentration remaining ill
solution when Ag 2CrO, commences to precipitate.
(i) SAlOl =
1·5 X 10- 10 = [Ag+] X [cr]
= [Ag+] X 0·1
or [Ag+] = 1·5 X 10-1%'1 = 1·5 X 10-9 gram mole per li!_l!__
=
2·4 X 10-12 = [Ag+]2 X 0·002
SAg2Cr0 4

or [Ag+] = '\12'4 X 10 12/0'002 = 3·5 X 10-5 gram mole per litre

A smaller concentration of Ag+ is required to precipitate AgCI and
hence it will precipitate first.
(ii) The Ag+ concentration necessary to precipitate the Ag 2CrO.
is 3·5 X 10-6 gram mole per litre. The chloride ion concentration
will then be:
[Cl-] = 1·5 X 1O-1o/[Ag+] = 1·5 X 1O- l0 j3·5 X 10-5
= 4·3 X 10-~ gram mole per litre
19] The Theoretical Baaia of Qualitative Analyaia 49
(ill) The initial 01- oonoentration is 0·1 gram mole per litre, henoe
[01-] when Ag 2CrO, preoipitates is 4·3 X 10-6/0.1 = 4·3 X 10-5 =
0·0043 per cent of original chloride ion concentration.
Another example of some practical interest is the precipita-
tion of a solution containing Sr++ ions and Ba++ ions by S04--
ions. Which will be precipitated first1
The solubility products are given by:
[8r++] X [804--] = 2·8 X 10-7 (iv)
[Ba++] X [804--] = 9·2 X 10-11 (v)
These two expressions and also the relation:
[8r++] 2·8 X 10-7 3000
(vi)
[Ba++] = 9·2 X 10-11 = 1
must be satisfied for equilibrium between the two precipitates.
It follows therefore:
(a) if [Sr++] > 3000 [Ba++], and SO.-- is added, SrS04 will
be precipitated until [Sr++] = 3000 [Ba++];
(b) if [Sr++] < 3000 [Ba++] , and S04-- is added, BaS04
will be precipitated until [Sr++] = 3000 [Ba++].
Further addition of S04-- in either (a) or (b) will result in
the precipitation of a mixture of SrS04 and BaS04 in the ratio
of 3000 to I, the equilibrium ratio (vi) in the supernatant liquid
being maintained.
The student should carry out a similar calculation for SrS04
and CaS04 (solubility product = 2·3 X 10-4): this has an
important bearing upon the separation of Group IV metals
(see Sections III, 32, and VII, 15).
As previously pointed out, the values of many solubility
products are not known with any great accuracy: for this
reason considerable caution must be exercised in predicting
whether or not a given ion can be separated from one or more
ions on the basis of solubility product equations, particularly
when there is some doubt as to the exact magnitude of the
solubility products.
I, 19. Preparation of Solutions.-In order to prepare a
"solution" of a substance sparingly soluble in water, the process
of precipitation must be reversed, i.e. the action of the reagent
must be such as to reduce the concentration of one or both of
the ions of the slightly soluble substance. The concentration
of an ion can be reduced by one of the following methods:
(~ the formation of a weak electrolyte or of undissociated
60 Qualitative Inorganic Analysis [II
molecules; (b) the formation of a complex ion; (c) by ~,.11
deoomposition; and (d) by oxidation or reduotion. .~
The first method is applicable to eleotrolytes whioh arE
derivatives of weak acids (or bases), such as barium sulphite,
calcium phosphate, caloium carbonate and ferrous sulphide.
If any of these substances is treated with dilute hydrochlorio
aoid, solution occurs because of the formation of the we!! k
acids H 2SO a, H 2PO" -, H 2CO a and H 2S. These weak electT' ,-
lytes can exist in equilibrium with only a very small concentril-
tion of their ions, and the anion concentration is diminish('( L
still further by the presence of hydrogen ions from the COlll-
pletely dissociated hydrochloric acid. The ionic concentrati(lll
is thus reduced to so Iowa value that the solubility product j"
never exceeded, and the substance passes into solution in 11) 1
attempt to restore the solubility product equilibrium. Let 11,
consider a particular case in detail-the solution of ferrolh
sulphide in dilute hydrochloric acid. The ionic equilibTl'l
involved will be:
FeS ~ Fe++ + S-- (solubility product = 4·0 X 10-19 )
HOI ~ H+ + 01- (J' )
2H+ + S-- ~ H 2S (or H+ + S-- ~ HS- + H+ ~ H 2S) (iii!
and Fe++ + 201- ~ Fe012 (iv)

is disturbed.

Furthermore, manganous, zinc and magnesium hydroxide,~

dissolve in ammonium chloride solution owing to the formati~[1
20] The Theoretical Basis oj Qualitative Analysis 51
of the weak base, ammonia. The presence of a high concen-
tration of ammonium ions reduces the hydroxyl ion concentra-
tion to so Iowa value that the solubility products of the above
hydroxides cannot be attained (compare Example 4 in Section
I, 14) and they consequently pass into solution.
Numerous examples are available to illustrate method (b),
but only two will be mentioned now as the subject is treated
fully in Section I, 20. Silver chloride is soluble in ammonia
solution, due to the formation oUhe complex ion [Ag(NHa)2]+;
this yields so small a silver ion concentration, particularly in
the presence of excess of ammonia solution, that the solubility
product of silver chloride is not attained. In a similar manner
silver cyanide dissolves in potassium cyanide solution, the
complex ion [Ag(CNbr being formed.
In method (c), the product of the reaction is either another
insoluble substance or a substance which can be removed from
the system by virtue of some such property as ease of decom-
position or volatility. This procedure is exemplified when an
insoluble salt is heated with a large excess of a saturated
solution of sodium carbonate. Partial decomposition ensues
with the formation of the insoluble carbonate of the cation
and a solution containing the anion, together with the excess
of carbonate ions. Mter filtration, the residue may be dis-
solved in dilute hydrochloric acid, and a solution, containing
the cations, obtained. A specific example is the preparation
of a solution of barium sulphate; the initial aqueous extract
contains the sulphate ions, and the hydrochloric acid extract
the barium ions.
Process (d) may be illustrated by the dissolution of cupric
sulphide in nitric acid. The sulphide ion S-- is oxidised to
free sulphur So, the sulphide ion concentration is thereby
reduced below the solubility product of CuS and hence the
latter passes into solution.
I, 20. Complex Ions.-Reference was made in the previous
section to the increase of solubility produced by the formation
of complex ions. A complex ion is formed by the union of a
simple ion with either other ions of opposite charge or with
neutral molecules. Let us now examine a few examples in
some detail.
When potassium cyanide solution is added to a solution of
silver nitrate, a white precipitate of silver cyanide is formed
because the solubility product of silver cyanide.
• [Ag+] X [00-] = BArON ANGRAU Central Librar
Hyderabad
1 flhl
52 Qualitative Inorganic A 'natysis-'- [I,
is exceeded. The reaction is expressed:
K+ + CN- + Ag+ + NO a- = AgCN + K+ + NO a-,
or CN- + Ag+ = AgCN
This precipitate dissolves upon the addition of excess of potas-
sium cyanide, the complex ion [Ag(CNhr being produced:
AgCN ~ Ag+ + CN- + CN- ~ [Ag(CN)2r *
solid
(or AgCN + KCN = K[Ag(CNhJ-a soluble complex salt)
This complex ion dissociates to give silver ions, since 1 i Ie
addition of sulphide ions yields a precipitate of silver sulph!, Ie
(solubility product 1·6 X 10-49 ), and also silver is deposi1 "d
from the complex cyanide solution upoJ1 electrolysis. 'J i Ie
complex ion thus dissociates in accordance with the equati( 'n:
[Ag(CN)2r ~ Ag+ + 2mr (ii)
'By applying the law 01 mass action to \ii), one obtains the {l'lS-
sociation constant or instability constant of the complex ion:
[Ag+] X [CN-P = K (iii)
[{ Ag(CN)2} ]
The constant has a value of 1·0 X 10-21 at the ordinary tem-
perature. By inspection of this expression, and bearing in
mind that an excess of cyanide ions is present, it should i 'e
evident that the silver ion concentration Jllust be very sm;, II,
so small, in fact, that the solubility product of silver cyanide
is not exceeded.
The process of solution of the silver cyanide in the potasshl III
cyanide solution may be pictured as follows. Equations I i)
and (iii) control the silver ion concentrations in AgCN and 1 he
complex [Ag(CNhr respectively, the former being very mu,·h
greater than the latter. The concentration of silver iOllS
derived from the saturated solution of AgCN is much great or
than that permitted by equilibrium (ii); acoordingly, the excc'ss
of silver ions combine with cyanide ions to form the complex
[Ag(CN)2r. This will result in the low-ering of the ionic
product of AgCN, and more of the latter will pass into solutiun
in order to supply the silver ions removed in the formation I)f
the slightly dissociated complex ion. This process will contin ue
either until all the AgCN has dissolved or until practically the
• It is usual to employ square brackets to include the whole of a complex
ion. In order to avoid confusion with concentrations for which square
brackets are also widely used, concentrations will be expressed in heavy type
and complex ions either in lighter type or between braces.
20] The Theoretical Basis of Qualitative Analysis 53
whole of the OW- has reacted to form [Ag(ON)2r. It must be
remembered that the complex salt formed, K[Ag(ON)21 is very
soluble in water, and its solubility product is therefore never
exceeded under the ordinary experimental conditions. This
mechanism, viz. the formation of a feebly dissociated complex
ion from one of the ions of a completely dissociated, sparingly
soluble salt and another ion or neutral molecule is the basis of
all the reactions of the type that are being considered.
Let us consider now the solubility of silver chloride in
ammonia solution. The reactions are:
Ag+ + cr ~ AgCI;
AgCI ~ Ag+ + CI- + 2NHs ~ [Ag(NHs )2]+ + CI-,
solid
(or AgCI + 2NHs ~ [Ag(NHs)2]CI)
Here again, for reasons similar to those already given, silver
ions are present in solution. The dissociation of the complex
ion is represented by:
[Ag(NHS )2]+ ~ Ag+ + 2NHs (iv)
and the instability constant is given by:
[Ag+] X [NH sJ2 _ _. -8
[{Ag(NHsb}+] - K - 6 8 X 10 {v)

The magnitude of the instability constant clearly shows that

only a very small silver ion concentration is produced by the
dissociation of the complex ion. It is clear from the expression
for the instability constant that the concentration of Ag+ which
can exist in equilibrium with NH3 is inversely proportional to
the square of the concentration of ammonia. The greater the
concentration of the latter, the smaller will be the concentration
of silver ion. The concentration of Ag+ available from AgOI
is controlled by the solubility product relation:
SAgOl = [Ag+] X [Cr] (vi)
This [Ag+] is very much greater than can exist in equilibrium
with NH 3, hence the Ag+ combines with the NHs to form some
[Ag(NHs)2]+' The resulting lowering of [Ag+] will cause the
ionic product [Ag+] X [OC] to fall below the solubility product
of AgOI and more AgOI must dissolve. This process will con-
tinue until all the AgOI is dissolved or until practically all the
NH3 has been converted into the complex ion. Summarising,
we may say that AgOI dissolves in NH3 because [Ag+] con-
trolled by the SAgCl relationship is greater than that from the
instability constant expression (v) .
.J
54 Qualitative Inorganic Analysis [I.
Silver bromide is less soluble in water than silver ch10lide
and thus gives a smaller [Ag+]: for this reason AgBr dissoi' es
only slightly in dilute ammonia solution but to a larger ext; nt
in concentrated ammonia. The [Ag+] in a saturated aque: dIS
solution of AgBr is only slightly larger than the [Ag+] in liV)
and consequently only a little will dissolve. With concentra! :·d
ammonia solution, the value of [Ag+] in (iv) is so much redu, ,·d
that it is considerably lower than [Ag+] derived from Af: I \r
hence more AgBr passes into solution. Silver iodide is mwh
less soluble in water than silver bromide and hence it does }, It
dissolve appreciably even in concentrated ammonia solution.
The following experimental facts now have a reasonable
theoretical explanation:
1. Upon adding KBr to a dilute ammoniacal solution of
AgCI, AgBr is precipitated.
2. Upon adding KI to an ammoniacal solution of AgCI or ,f
AgBr, AgI is precipitated.
Another familiar example is the solution of ferrous cyanide
in potassium cyanide solution to yield potassium ferrocyanido
or the ferro cyanide ion:
Fe(CN)2 ~ Fe++ + 2CN- + 4CN- ~ [Fe(CN)6r---
solid
(or Fe(CN)2 + 4KCN ~ K 4[Fe(CN)6])
The further dissociation of the ferro cyanide ion:
[Fe(CN)6]---- ~ Fe++ + 6CN-.
is so small that no method at present known can detect eitht·r
the simple ferrous ion or the cyanide ion in solution: the con!
plex ion is an extremely stable one.
Other cyanide complex ions include the following
[Fe(CN)6]3-, [CO(CN}6]4-, [Co(CN}6P-, [Hg(CN}4J 2-, [Cu(CN).d3
[Cd(CN)4]2-, [Ni(CN)4P- and [Zn(CN)4]2-. The cuprous and
cadmium complexes are of especial interest since they an'
utilised in one method for the separation of Cu++ and Cdh .
. A solution containing these ions is treated with excess (d
ammonia solution and then with potassium cyanide solutiou
until the blue colour of the solution is just discharged (see
Section VII, 11). The resulting solution contains the com·
pletely ionised salts K 3[Cu(CN)4] (derived from cuprous copper)
and K 2[Cd(CN)4]' The instability constants of [CU(CN)4J3
and [Cd(CN)4]2- are 5·0 X 10-28 and 1·4 X 10- 17 respectively.
i.e. the former is much more stable than the latter and the[Cu+]
furnished by it is extremely small. When hydrogen sulphide
•
20] The Theoretical Basis of Qualitative Analysis 55
is passed into the solution CdS is precipitated (solubility pro-
duct 1·4 X 10-28 ) but no copper sulphide (solubility products,
CU2S 2 X 10-47 , CuS 1·0 X 10-44 ) in spite of the fact that the
solubility product is much smaller.
Some reference should be made to the so-called hydroxide
complex ions. When sodium hydroxide solution is added in
small quantities to a solution containing Zn++, a white pre-
cipitate of zinc hydroxide is formed: this dissolves in excess of
the reagent. A complex salt, sodium zincate Na2[Zn02]2H20
or Na2[Zn(OH)4], is formed. The reaction is perhaps best
represented as:
Zn(OH)2 + 20H- ? [Zn(OH)4r- (see Section I, 16);
the formation of this complex ion reduces the Zn++ concentra-
tion with the result that the ionic product [Zn++] X [OH-P is
less than the solubility product and the zinc hydroxide dissolves.
The complex Na 2[Cd(OH)4J is formed with difficulty and
requires the use of very strong alkali. A solution containing
aluminium ions behaves similarly to zinc towards sodium
hydroxide solution, the initial precipitate of aluminium hydrox-
ide dissolving in an excess of alkali to form an aluminate of
the type Na[Al0 2]xH 20 or Na[Al(OH)4J:
Al(OH)s + OH- ? [Al(OH)4r (see also Section I, 16)
Chromic hydroxide also behaves similarly and the complex ion
may be written (by analogy) as [Cr(OH)4r. Stannous salts
give initially a precipitate of stannous hydroxide, which dis-
solves in excess of alkali to form sodium stannite, variously
formulated as Na2[Sn02Jaq. or Na[SnO. OHJaq. The reaction
may be written:
Sn(OH)2 + OH- ~ [Sn(OH)sr
Stannic salts yield ultimately Na2[Sn03J3H20 or Na2[Sn(OH)6],
i.e.
Sn(OH), + 20H- ? [Sn(OH)er-
There is some evidence for the existence of the plumbite
[Pb(OH)ar and plumbate [Pb(OH)6r- ions. All the above
hydroxides are amphoteric.
The oxalate ion forms a fairly stable complex with the ferric
ion:

The [Fe+++] can be reduced (by the addition of sufficient

CtO, --) to so Iowa value that the solution does not give the

r \l'AU CEliTRAL L1I:SRP

I ,... / I
 56 Qualitative Inorganic Analysis [I,
red colour of the ferri-thiocyanate ion [Fe(SCN)J++ wit!. a
soluble thiocyanate; it does, however, yield a precipitat(' of
ferric hydroxide when treated with sodium hydroxide se,j u-
tion. Upon adding a strong acid the slightly ionised H0 2 , 14 -
is formed, leading to the ionisation of the complex ferri-oxaL te
ion to such an extent that Fe+++ can be detected with potassill rn
ferro cyanide or with potassium thiocyanate.
Certain non-volatile organic compounds containing hydro~ d
(OH) groups, such as tartrates, citrates, sugars and glycer. ,1,
form complex ions with various metals (Cu++, Fe+++, .Al+-t +,
Cr+++, etc.). In these the metal replaces the hydrogen in the
hydroxyl group. Thus in an alkaline solution of a tartrat("
the complex ion with Cu++ may be formulated thus:
000- 000- 000-
H6-0H Hb-O- Hb-O\
I + 20H- - 2H20 + I ~ I
HC-OH HC-O- HC-of Cil
I
UOO-
I
COO-
I
COO--
Tartrate ion Complex CUpl'<
tartrate ion
These complex ions are very stable and yield such low COl
centrations of the simple metal ions that they often fail to
respond to the simple tests of qualitative analysis. It is for
this reason that involatile organic matter is destroyed before
proceeding with the systematic detection of the metals.
Complex ions are formed by Cu++, Cd++, Ni++, Co+++ an':
Zn++ with NHa molecules, e.g.
00+++ + 6NHa ~ [Co(NHs)6]+++
Zn++ + 4NHa ~ [Zn(NHs),]++ II •
Many halide complex ions are known. These include
[HgCI4r-, [SnClar-, [SbClar--, [FeF6r--, [AlF6 r--,
[AUC4r and [PtClar-. These, and many others of different
types, will be referred to in connexion with the reactions of
the metallic ions.
The stability of complex ions varies within very wide limiti-
It is quantitatively expressed by means of the dissociation or
instability constant. The more stable the complex, the smaUer
is the instability constant. When the complex ion is very
stable, the common ionic reactions of the components are not
shown. A few seleoted values of these oonstants at the
ordina.ry temperature, determined by methods involving
L
20] The Theoretical Ba8ia of Qualitative A nalysil 57
potentiometric titration, are collected in Table I, 20, I; this is
instructive and also useful for reference purposes.
TABLE 1,20, 1. INSTABILITY CONSTANTS OF COMPLEX IONS

[Ag(NH s).]+ ~Ag+ + 2NHs 6'8 x 10- 8

[Ag(SzOslzr--? Ag+ + 2S I 0 3 - - 1·0 X 10- 18
[Ag(CN)zr ?Ag+ + 2CN- 1·0 x 10- 11
[Cu(CN),r-- ?Cu+ + 4CN- 5·0 x 10- 1S
[Cu(NH a),]++ ? Cu++ +4NH a 4·6 X 10-1&
[Cd(NH s),]++ ? Cd++ + 4NHs 2·5 x 10-7
[Cd(CN),r- ? Cd++ + 4CN- 1·4 x 10- 17
[CdI,r- ? Cd++ +4C 5 X 10-7
[HgCI,r- ?Hg++ +4Cr 6·0 x 10- 17
[HgI,r- ?Hg++ +4C 5·0 X 10-11
[Hg(CN),r- ?Hg++ +4CN-- 4·0 x 10-n
[Hg(SCN),r- ?Hg++ + 4SCN- 1·0 x 10- 11
[Co(NHs)o]+++ ? Co+++ + 6NH a 2·2 x 10-14
[Co(NHs)oJ++ ? Co++ + 6NH s 1'3 x 10-'
[Iar ?C + I, 1·4 X 10-1
[Fe(SCN)]++ ? Fe+++ + SCN- 3·3 x 10--
[Zn(NH s),]++ ? Zn++ +4NH a 2·6 X 10-10
[Zn(CN),r- ?Zn++ +4CN- 2 x 10- 17
I
Some examples of calculations involving complex ions should
assist the student in thoroughly understanding the subject.
Example 13. Aqueous ammonia solution is added to a precipi-
tate of silver chloride until its final concentration at equilibrium is
3 molar. Calculate the weight of AgCI per litre which will be
dissolved. (This is equivalent to calculating the solubility of AgCI
in 3M NHs.)
The reaction is AgCI + 2NHs = [Ag(NHs )2]+ + CI-; the in-
stability constant of the complex ion is 6·8 X 10- 8 ; SAlOl is
1·5 X 10-1 °. Two equilibria are involved in the prooess of solution,
viz.
AgCI (solid) ? Ag+ +
CI-, and
[Ag(NHs)2]+? Ag+ 2NHs+
At equilibrium the [Ag+] must be the same for both provided solid
AgCI and also [Ag(NHs)2]+ ions are present.
For each mole of AgCI dissolved, 1 mole of [Ag(NHs)2]+ and I
mole of CI- are formed. The small value of the instability constant
of the [Ag(NHs)2]+ ion indicates that the amount of dissociation of
the complex ion is small and consequently no appreciable error will
be introduced by assuming that [Ag(NHsh]+ = [CI-] = x, where
x is expressed in mole per litre. The value of [Ag+] at equilibrium
can be obtained from:
SAgGl = [Ag+] X [CI-] = 1·5 X 10-10
[Ag+] = 1·5 X 10-10/x
 38 Qualitative Inorganic Analyaia rT,
Substituting the approximate values in the instability constl'lIt
equation
[Ag+] X [NHIIJ2 _ . -8
[Ag(NHs)IlJ+ . - 68 X 10

we have (1·5 X 10- 10/x) X 31l = 6.8 X 10-8

x
whence x = 13·5 X 10- °/6.8 X 10-8 = 0·126 mole per litre
1

= 0·126 X 143·3 = 18·0 gram AgOl per litre

The molecular weight of AgCI is 143·3.
Example 14. Calculate the silver ion concentration in 0·1 mohr-
[Ag(NHa)2]+ solution in which (a) excess of NHs is absent alld
(b) the NHs concentration is 3 molar.
(a) The dissociation of the complex ion is:
[Ag(NHs)2]+ ~ Ag+ + 2NHs
Let [Ag+] = x, and hence [NHa] = 2x. Since the dissociation of
the complex ion is small, we may assume [Ag(NHsh]+ = 0·1. By
substituting these values in the instability constant equation, we
have:
x X (2x)2/0·1 = 6·8 X 10-8
or x = {"6·8 X 10-9/4 = 1·9 X 10-3 mole Ag+ per litre
(b) It is evident from the instability constant equation that
[Ag+] will be inversely proportional to [NHs]2 and therefore as
[NHsJ is increased [Ag+] will be considerably decreased. By sub-
stituting the new values for the various constants, we obtain:
x X (2x + 3)2/0·1 = x X 32 /0.1 = 6·8 X 10-8 (since 3 ~ x)
or x = 6·8 X 10-9/9 = 7·7 X 10-10 mole Ag+ per litre
Example 15. A 0·1 molar solution of [Cu(NHs),]++ is stirre'!
with an excess of potassium cyanide sufficient to convert all th,'
ammonia complex to the corresponding cuprocyanide comple.:.
[CU(CN)4r-- and in addition to provide the solution with aI,
excess of CN- equal to 0·2 molar. Show by calculation that whe!1
the final solution is treated with hydrogen sulphide, no precipitatiol1
of cuprous sulphide will occur.
For this calculation, let us assume that the sulphide ion con·
centration of the solution saturated with hydrogen sulphide i;;
0·001 mole per litre.* SOU2S is 2·0 X 10- 47 • The instability con·
• A saturated solution of H 2S in water is about O·IM: this may be regarde( i
as acting like O·lM K 2 S in the alkaline solution. The O·lM K 2 S is largel)
hydrolysed (see Example 22 in Section 1,41) and gives a [S--J of ca. O·OOIM.
The final conclusion regarding precipitation is unaffected even if the 8ulphid,·
ion concentration is taken as O·lM.
21] The Theoretical Basi8 of QUalitative AruJlysis 59
stant of the cuprocyanide ion is 5·0 X 10-28 • The cuprocyanide
complex ion dissociates thus:
[Ou(ON),)--- ~ Cu+ + 40N-
A O·IM [Ou(NH s),]++ solution will yield O'IM [Ou(ON),r--. If x
is the concentration of cuprous ions in moles per litre, we may
substitute in the equilibrium equation with [ON-] = 0·2:
[Ou+] X [CN-]4 28
X X (0·2)4
[Ou(ON)41 = 5·0 X 10- = 0.1
or x = 3·1 X 10- 26 mole per litre = [Ou+]
Now SCU2S = [Ou+]2 X [8--] = 2·0 X 10-47
The ionic product is (3'1 X 10-26 )2 X (1 X IO-S ) = 9·6 X 10-66 :
this value is less than the solubility product of OU28 and hence the
latter is not precipitated.

CHEMICAL EQUATIONS
The two fundamental laws of chemistry, the law of definite
proportions and the law of conservation of mo,ss, find their
chief expression in practice in the form of chemical formulae
and balanced equations. It is therefore of greo.t importance
that the student should be familiar with the methods of writing
formulae and balancing equations. If the atomic weights are
known, the percentage composition of a compound can be
calculated from its chemical formula; the ratio of the weights
in which substances interact and the relative weights of the
products can likewise be computed from the chemical equation
representing the reaction. These quantities find considerable
application in the calculations of both qualitative and quanti-
tative analysis.
It 21. Chemical Formulae.-The important principle to be
borne in mind when writing the more com1Jlon chemical
formulae is that the elements or radicals must be combined in
equivalent proportions. Thus univalent elements or radicals
combine (i) with other univalent elements or rttdicals in the
ratio of 1 : 1, e.g. NaCI, NH4 .C 2H 30 2 ; (ii) with bivalent atoms
or radicals in the ratio of 2 : 1, e.g. Na2S04, CaCI2• (NH4)2C20,;
(iii) with tervalent elements or radicals in the ratio of 3 : 1,
e.g. FeCI s, H SP0 4 ; and (iv) with tetravalent elements or radicals
in the ratio of 4: 1, e.g. SnCl" Pb(C2HsO~),. Bivalent
elements or radicals combine with other bivalent elements or
ra~icals in the ratio of 1 : 1, e.g. MgSO., CaC 2 0 4 ; with tervalent
60 Qualitative l1wrganic AnalY8i8 [It
radicals in the ratio of 3: 2, e.g., Ca3(PO,b, Al z(S04)a, ,tc.
These facts are sometimes expressed in the form of the foUm\ i ng
rule, which is applicable to normal salts: divide the least c, 'ill-
mon multiple of the valencies of the two ions by the val£'ilcy
of each ion, and use the resulting figures as subscripts to
denote the ratio in which the two ions aTe combined in the f- ·It.
A subscript of 1 need not be inserted. Thus in ferric sulph: ie,
the ferric ion has a valency of 3 and the sulphate ior· a
valency of 2. The least common multiple is 6 and the form', fa
is therefore Fe2(S04)a.
This rule implies a previous knowledge of the valenciei' !)f
the ions or radicals, and applies only to those salts wh' h
contain one kind of positive ion in combination with one kilid
of negative ion. When applied to more complex compoun' !~,
such as acid salts, basic salts and double salts, the rule mldt
be interpreted in the form that the sum of the valencies of l\le
positive radicals (valency multiplied by the subscript for enl'h
radical) must equal the sum of the valencies of the negati \ e
radicals. Thus in basic lead acetate, Pb(C2H a0 2b Pb(OH l2
or Pb 2(C 2H a0 2)2(OH)2' the total valency of the lead ions is 4
and the total valency of the acetate and hydroxyl radicals is
also 4. In iron alum, (NH4bSO" Fe2(SO,)a or (NH4 )Fe(S04l2,
the positive and negative valencies are both either 8 or 4.
I, 22, Chemical Equations.-To construct a chemical equa-
tion one must know the formulae of the reactants and of the
products of the reaction; the skeleton equation can then lIe
written down. In order to balance the equation, the Sa)i.)
principle as was employed in deducing the formulae of norD I· Ii
salts is utilised, that is, reagents interact with each other i'l
equivalent proportions. If the latter are known, the COl i -
pletion of the equation is a simple matter. The difficult·.,
however, is in determining the number of equivalents repr' '-
sented by the molecular formulae of the reactants. Metho, ie;
for determining these are described below.
It is convenient to divide equations into two groups (A)
those not involving oxidation-reduction and (B) those thnt
do involve oxidation-reduction (vide infra for definition of
oxidation and reduction).
(A) Equations not involving oxidation-reduction.-The mo"t
common reaction of this class is that involving double decorli'
position or metathesis, e.(/. the precipitation of barium sulpha1 e
by the action of barium chloride solution upon sulphurio aoid,
or the neutralisation of nitrio aoid with potassium hydroxido
23] The Theoretical Baaia of Qualitative Analyaia 61
solution. The following procedure will be found applicable to
most of the examples commonly encountered:
(i) Write down the formulae of the reactants and products
in the form of a skeleton equation.
(ii) Examine the formula of the main product (or of any
product more complex than the rest) to determine the reactants
from which its constituents are derived.
(iii) Utilise the coefficients for the corresponding reagents
that will supply these components in the correct ratio.
(iv) If one of the reactants supplies components for a second
product, deduce the amount required for this, and add that
amount to the coefficient required in (iii).
(v) Complete the equation by inspection.
As an example we may consider the balancing of the
equations:
(a) K4[Fe(CN)o] + FeCl s (excess);
(b) HgCl2 + KI (excess)
In (a) the products are ferric ferrocyanide Fe4[Fe(CN)6h and
KCl. The incomplete equation is:
FeCls + K4[Fe(CN)o] = Fe,[Fe(CN)o]s + KCI
The formula Fe4[Fe(CN)6h requires three [Fe(CN)6r-- and
four Fe+++ ions, hence at least three molecules of K 4[Fe(CN)6]
and four molecules of FeCls are required for this alone. The
components of the second product KCI are supplied by the two
reactants, and inspection shows that the equation is balanced
by using these coefficients alone:
4FeCIs + 3K4 [Fe(CN)6] = Fe4[Fe(CN)6]S + 12KCI
In (b) the products are the complex salt K2[HgI4] and KCI,
or HgC1 2 + KI = K2[HgI4] + KCI (incomplete)
The formula K2[HgI4] requires four atoms of iodine to one
of mercury, and the formula KCI one atom of potassium to one
of chlorine. The equation when written as
HgCl 2 + 4KI = K2[HgI4J + 2KCI
is balanced. If this were not the case, further adjustment of
the coefficients would be necessary.
(B) Equations involving oxidation-reduction.-These are
considered in Sections I, 24 and I, 25.
I, 23. Discussion of Oxidation-Reduction.-The simplest
and oldest conception of oxidation involves the taking up of
.
oxygen by an element or compound, as in the conversion of
62 Qualitative Inm-ganic Analysi8 [I,
CU20 into CUO or of FeO into Fe20a. Oxygen was the typical
oxidising agent. Now CuCI and FeCl 2 bear the same relatiun
to CuCl 2 and FeCl a respectively as do the corresponding oxides
to one another; it is customary, therefore, to regard the c()n-
version of CuCI and FeCl2 into CuCl 2 and :FeCla respectiv, ,y
as oxidations, i.e. in oxidation the positive valency of an elemellt
or radical is increased.
It may be noted that combination with a non-metaL,,)
element other than oxygen resembles combination with oxyg('!\.
Thus carbon burns in fluorine more vigorously than in oxyge'
C + 2F2 = CF4 , Iron burns in fluorine and, when heak:,
combines with chlorine and also with sulphur: 2Fe + 3F2
2FeF a ; 2Fe + 3Cl2 = 2FeCla ; Fe + S = FeS. Owing to tLn
similarity of these reactions to combinations with oxygen, thl'v
may clearly be regarded as a generalised sort of oxidation.
Reduction was formerly considered to be the process by whi('; I
oxygen was removed from a compound. Hydrogen Wit'
regarded as the typical reducing agent. The definition call
be logically extended to the process resulting in the decrea~('
of the positive valency of an element or radical. Thus tIw
conversion of Fe20a into FeO, of FeCl a into FeCI 2 , of CuCI"
into Cuel, are examples of reduction. It is evident that th,'
processes of oxidation and reduction are complementary:
whenever one substance is oxidised, another substance must
be correspondingly reduced.
Let us write the simple equation representing the oxidation
of ferrous chloride by chlorine in aqueous solution:
2FeC12 + C1 2 = 2FeC13 ,
or, expressed ionically, 2Fe++ + C1 2 ' 2~e~++ +2Cl-. ~h(
ferrous ion Fe++ is converted into the ferrIC Ion Fe+++ (oxlda
tion) and the neutral chlorine molecule into negatively charged
chloride ions Cl- (reduction). According to the electronic con
ception of the constitution of matter, the conversion of Fe+
into Fe+++ requires the loss of one electron, and the trans
formation of the neutral chlorine molecule into chloride ione
necessitates the gain of two electrons. This leads to the view
that, for reactions in solution, oxidation is a process involving
the loss of electrons, as in
Fe++ - e = Fe+++,
and reduction is the process resulting in the gain of electrons,
as in
23] The Theoretical Ba8is of (uulitative Analysis 63
In the actual oxidation-reduction process electrons are trans-
ferred from the reducing agent to the oxidising agent.
The following are more satisfactory definitions:
Oxidation is the increase in the positive valency of an element
or radical either by the addition of oxygen, or by the addition
of chlorine or some other atom or radical which can constitute
acid radicals or anions (electronegative radicals). Qualitative
analysis is largely concerned with reactions in solution. The
above definition may therefore be extended to ionic reactions
and expressed in the form: oxidation is the process which results
in the loss of one or more electrons by atoms or ions. An oxi-
disin~ a~ent is one that gains electrons and is reduced to a
lower valency condition. This electronic definition of oxida-
tion will apply, of course, to electrovalent compounds in the
solid state. Thus sodium is oxidised when it burns in chlorine
to form sodium chloride:
2Na + C12 _ 2Na+C1-
The oxidation of the metallic sodium is the process of removing
an electron from each sodium atom:
Na -e =Na+
Reduction is the decrease in positive valency (or increase of
the negative valency) either by the removal of oxygen or some
electronegative atom or radical, or by the addition of an atom
or radical which can constitute cations (electropositive radical).
The extension of this definition to ionic reactions is: reduction
is a process which results in the gain of one or more electrons
by atoms or ions. A reducin~ a~ent is accordingly one that
loses electrons and becomes oxidised to a higher valency
condition.
Examples of oxidising agents of importance in analytical
chemistry are: the halogens, potassium permanganate, potas-
sium dichromate, nitric acid and hydrogen peroxide. Examples
of reducing agents are: sulphur dioxide, hydrogen sulphide, the
metals, hydrogen, stannous chloride and hydriodic acid. A
detailed discussion of these is given below.
The principle referred to above, 'L'iz. that reagents react with
one another in equivalent proportiolls, is employed in balancing
oxidation-reduction equations. In all oxidation-reduction
processes (or redox* processes) there will be a reactant under-
going oxidation and one undergoing reduction, since the two
reactions are complementary to one another and occur simul-
taneously--one cannot take place without the ?ther. The
• The simple term "redox" is an abbreviation of reduction-oxidadon.
'"
 64 Qualitative Inorganic .AnalY8i8 [I,
reagent undergoing oxidation is termed the reducing agen t or
re~u.c~ant, and the reagent undergoing reduction is called (,he
oXIdismg agent or oxidant. It is necessary to deter) i' ine
th~ .r_ll~mber of equi,:"alents represented by one molecule 01 t.he
oXIdisJ?g and reducmg agent respectively, and then to as,;ign
co~:ffiClents to each such that the number of equivalents of the
oXIdant and of the reductant are equal. The equation 'an
then be completed by inspection. The number of equival, :Lts
represented by one molecule of the oxidant and the reduct, I nt
is determined by direct comparison. Two methods are c,,:u-
monly employed for this purpose; these are considered in the
two sections which follow:

I, 24. The Oxidation Number Method.-This procedure

was introduced by O. O. Johnson in 1880. It is a dir"ct
development of the view that oxidation and reduction il re
attended by changes of valency. The fundamental conceptll)n
is the state of oxidation of the elements in particular com-
pounds. Johnson expressed this by the term "positive or
negative bond." Other authors have used" valence," "chan i"~S
of valence," "valence number" and "oxidation number" ,,0
express the same quantity. The present writer prefers "oxida.-
tion number" as this term is less likely to cause confusion.
The quantity is not determined by reference to any theory of
atomio or molecular structure, and may be regarded ai' a
mathematical entity deduced from an examination of tiLe
formulae of the initial and final compounds in a reacti, ,n.
The oxidation number of an element is a number which, apph'd
to that element in a particular oompound, indicates 1 'le
amount of oxidation or reduction which is required to com· rt
one atom of the element from the free state into that in 1 ile
oompound. If oxidation is necessary to effect the change, t} Ie
oxidation number is positive, and if reduction is necessar'l,
the oxidation number is negative.
The following rules apply to the determination of oxidation
numbers:
(1) The oxidation number of the free or uncombined element
is zero. This may be written So, Ba 0, 01 2 0 , etc.
(2) The oxidation number of hydrogen in combination is,
+1
with few exceptions, * +1 (H) .
• The only exceptions are the hydrides of very electropositive metals, slloh
as those of lithium and sodium: the oxidation number of the metal is t 1
+1 -1
and that of hydropn is -1, •. g. Li B.
24] The Theoretical Basis of Qualitative Analysi8 65
(3) The oxidation number of oxygen in combination is
-2
normally -2 (0).*
(4) The oxidation number of a metal in combination is
usually positive. t
(5) The oxidation number of a radical or an ion is that of
its electrovalency with the correct sign attached, i.e. is equal
to its electrical charge.
(6) The oxidation number of a compound is always zero,
and is determined by the sum of the oxidation numbers of the
individual atoms each multiplied by the number of atoms of
the element in one molecule.
Let us consider a few simple applications of these rules.
(i) Oxidation number of Ou in OuO. To convert Cuo into
CuO, the copper undergoes two units of oxidation, hence the
oxidation number of the copper is +2. Alternatively, by
+2-2
rule 6, since oxygen is -2, copper in CUO must be +2.
(ii) 8 in H 28. Here H2 = +2, hence 8 is -2.
(iii) N in NH"pl. Consider NH3: H3 is +3, hence N is -3.
In HOI, H = +1, therefore Cl is -1. When NH3 and HCl
combine to form NH4 CI, the oxidation numbers of the elements
in the new compound remain the same. In NH4Cl, H4 = +4
and Cl = -1, hence N = -3.
(iv) N in HN0 3 • Here 0 3 = -6, H = +1, therefore
N=+5.
(v) Mn in KMn04' Here 0 4 = -8, K = +1, hence
Mn = +7.
(vi) 8 in 804--, Here Q, = -8, 804- - = -2, hence
-2 = -8 + 8, or 8 = +6.
(vii) 0 in 00 2 , Here O2 = -4, hence 0 = +4.
(viii) 0 in OH,. Here H, = +4, hence 0 = -4.

The following rules apply to the use of the oxidation number

method for the balancing of equations:
(1) Determine the numerical change in oxidation number of
a significant element in the oxidant.
(2) Repeat this for a corresponding significant element in
the reductant.
• The exceptions are: hydrogen peroxide and the true peroxides in which
+2-2 +2-2
oxygen is -1, e.g. HID. and NaIO I ; oxygen difluoride, in which the oxygen
+2-2
is combined with the only more electronegative element, fluo~OF •.
-4+4
t Exceptions are to be found in the compounds with hydrogen, e.g. GeH ••
><3+
 66 Qualitative Inorganic Analysis [I,
(3) Multiply each by coefficients which will make the total
change in oxidation number equal.
(4) Inspect the skeleton equation deduced from (3), awl
introduce the proper coefficients for the compounds or radiCH! 'l
which are not oxidised or reduced.
The application to a number of examples is given below.
Reaction I: action of nitric acid upon cadmium sulphid ...
CdS + HNO a = Cd(NOa)s + NO + S + H 20 (incomplete)
Nitric acid: HNO a: O.N.* of N = - (-6 + 1) = +5
Nitric oxide NO: O.N. of N = -( -2) = +2, i.e. in the reacti(",
nitrogen changes in O.N. from +5 to +2, or by 3 units of reductior:
Cadmium sulphide CdS: O.N. of S = -( +2) = -2.
Free sulphur: O.N. = O.
Since one molecule of HNO a undergoes 3 units of reduction all I
one molecule of CdS 2 units of oxidation, the two must react in tI"
ratio of three molecules of CdS to two molecules of HNO a. Further
more, Cd(NOah requires two nitrate radicals for each atom ('-
cadmium; six more molecules of HNO a will therefore be required
to balance the equation. The latter will be:
3CdS + 8HNO. = 3Cd(NO a). + 2NO + 3S + 4H,O
Reaction II: the reduction of potassium permanganate by ferrOl",
sulphate in the presence of dilute sulphuric acid.
KMnO, + FeSO, + HzSO,
= K.SO, + MnSO, + Fe 2 (SO,)a + H.O (incomplete)

The oxidant KMnO, is reduced to MnSO,:

+1+7-8 +2+6-8
KMnO, ..... MnSO"
i.e. the change in O.N. of manganese is from + 7i'O+ ~;or'by ;;
units of reduction.
The reductant FeSO, is oxidised to Fe2(SO,)a:
+2 -2 +6-6
Fe(SO,) ..... Fe.(SO,)a.
i.e. the change in O.N. of one atom of iron is from +2 to t( +6),
or by 1 unit of oxidation.
The KMnO, and FeSO, will therefore react in the ratio of 5 : 1.
Now Fe2(SO,)a contains two atoms of iron; the numbers ofmolecuks
in the ratio must accordingly be doubled, and are 10 : 2.
The equation becomes:
2KMnO, + IOFeSO, + xH1SO,
= 2MnSO, + K.SO, + 5Fe.(SO,)s + xH.O
The number of sulphate radicals (after making allowance for those
supplied by the FeSO,) required in the formation of the molecules
* The term oxidation number is abbreviated to O.N.
24] The Theoretical Ba8i8 of qUalitative AnalyBi8 67
of MnS04, K 2S04 and Fe2(804)s is estimated by inspection, and this
gives x = 8.
Reaction III: the interaction of potassium dichromate and potas-
sium iodide in the presence of dilute sulphuric acid.
K 2Cr Z0 7 + KI + H z80,
= Cr 2 (SO,ls + K s80 4 + 12 + H 20 (ineomplete)
The oxidant K ZCr Z0 7 is reduced to Or2(804)s:
+2+12-14 +6-6
Cr z(80,)s
K 2Cr l 0 7 ~

The change in O.N. of two atoms of chromium is from +12 to +6,

or by 6 units of reduction.
The reductant KI is oxidised to 12 :
+1-1 0
KI - I I
The change in O.N. of one atom of iodine is from -1 to 0, or by
1 unit of oxidation.
Since one molecule of K 2Cr 20 7 undergoes 6 units of reduetion and
one molecule of KI suffers 1 unit of oxidation, the two will react
with one another in the ratio of K2Cr207: 6KI.
The equation will thcrefore be:
K 2Cr Z0 7 + 6KI + ;eH SO, 2 = Crz(SO,la + 4K 280, + 31a + xH 20
Inspection shows that x must be 7 in order to account for the
number of molecules of Cr 2(S04Js and K 2 804 formed.
Reaction IV: the reduction offerric chloride by hydrogen sulphide.
FeCI s +H 2 S = FeCl s + 8 + HCI (incomplete)
The oxidant FeOls is reduced to FeCl 2:
+3-3 +2-2
FeCl a ~ FeCl s
The change in O.N. of iron is from +3 to +2, or by I unit of
reduction.
The reductant H 2S is oxidised to free S:
+2-2 0
H28~ S
The change in O.N. of the sulphur is from -2 to 0, or by 2 units of
oxidation.
Two molecules of FeOls therefore react with one molecule of H 28,
and this fact, coupled with inspection of the incomplete equation,
gives the balanced equation:
2FeCI a + HIS = 2FeCl 2 + 2HCI + 8
Reaction V: the action of concentrated hydrochloric acid upon
potassium permanganate.
KMnO, + HCI = KCl + MnCl 2 + CIs + H 20 (incomplete)
The oxidant KMn04 is reduced to MnCl z :
+1+7-8 +2-2
KMnO, ~ MnCI"
 68 Qualitative Inorganic Analy8i8 [I,
i.e. the change in O.N. of the manganese is from +7 to +2, or by
5 units of reduction.
The reductant HOI is oxidised to 01 2 :
+1-1 0
HCI-+ CIs,
i.e. the change in O.N. per atom of chlorine is from -1 to 0, or by
1 unit of oxidation.
The KMn04 and HOI will therefore react in the ratio of 5 1.
The molecule of chlorine contains two atoms; the number of
molecules in the ratio must accordingly be doubled, and are 10 : 2.
The equation becomes:
2KMn04 + (10 + xl HCI = 2KCI + 2MnCl + 5Cl + (5 + x/2) ] I 20
2 2

Inspection shows that x must be 6 in order to account for 1 he

formation of the correct number of molecules of KOI and MIJI.)12
derived from the KMn04 •

I, 25. The Ion-Electron Method.-This method, develo] "~,d

in some detail by Jette and La Mer in 1927, is based upon 111e
conception of oxidation as the loss of one or more electro'ls,
and of reduction as the gain of one or more electrons. 'fite
method is limited to ionic reactions in aqueous solutions bilt,
since nearly all the reactions encountered in qualitative analy,is
are ionic in character, the expression of chemical reactions .LS
interaction between the ions is, for many reasons, an advanta):t).
Furthermore, such ionic reactions can be readily converted into
the molecular equations and vice versa.
In order to balance an ionic equation by the ion-electron
method, the equation is divided into two balanced, partial
equations representing the oxidation and reduction respec-
tively. These may be regarded as corresponding to the two
half cells described in Sections I, 28 and I, 33 in connexion with
the theory of oxidation-reduction. It must be remembert"t
that the reactions take place in aqueous solution so that i!l
addition to the ions supplied by the oxidants and reductan1"
the molecule of H 20, H+ ions and OH- ions are also presenl,
and may be utilised in balancing the partial ionic equation,.
The unit change in oxidation or reduction is a change of OJJU
electron, which will be denoted bye. To appreciate the pri] \
ciples involved, let us study first the reaction between feIT!
chloride and stannous chloride in aqueous solution. Th
partial ionic equation for the reduction is:
Fe+++~Fe++ (a)
and for the oxidation is:
Sn++ -+ Sn++++ (b)
10.-
25] The Theoretical Basis of Qualitative Analysis 69
The equations must be balanced not only with regaru to the
number and kind of atoms but also electrically, that is, the
net electric charge on each side must be the same. Equation (a)
can be balanced by adding one electron to the left-hand side:
Fe+++ + e ~ Fe++ . (a')
Itnd equation (b) by adding two electrons to the right-hand
side:
Sn++ ~ Sn++++ + 2e (b')
These partial equations must then be multiplied by coefficients
which result in the number of electrons utilised in one reaction
being equal to those liberated in the other. Thus equation (a')
must be multiplied by two, and we have:
2Fe+++ + 2e ~ 2Fe++ (a W )
Sn++ ~ Sn++++ + 2e (b")
Adding (a") and (b"), we obtain:
2Fe+++ + Sn++ + 2e ~ 2Fe++ + Sn++++ + 2e,
l.nd by cancelling the electrons common to both sides, the
3imple ionic equation is obtained:
2Fe+++ + Sn++ = 2Fe++ + Sn++++
The following facts must be borne in mind. All strong
~lectrolytes are completely ionised; hence only the ions actually
baking part in or resulting from the reaction need appear in the
~quation. Substances which are only slightly ionised, such as
El 20, or which are sparingly soluble in water and thus yield
)nly a small concentration of ions, e.g. Agel and BaS04 , are, in
~eneral, written in the molecular form because most of the
substance is present in this state.
The complete rules for the application of the ion-electron
method may be expressed as follows:
(1) Ascertain the products of the reaction.
(2) Set up a partial equation for the oxidising agent.
(3) Set up a partial equation for the reducing agent in the
same way.
(4) Multiply each partial equation by a factor so that when
the two are added the electrons just compensate each other.
(5) Add the partial equations and cancel out substances
which appear on both sides of the equation.
A few detailed examples follow.
Reaction I: action of nitric acid upon cadmium sulphide.
One partial equation (reduction) is:
NO. - -+ NO (incomplete)
70 Qualitative hwrganic Analysis [I,
To balance this atomically one must write:
NO a- + 4H+ - NO + 2H 0 2
To balance the latter equation electrically, 3e must be adde<I, to
the left-hand side:
NO a- + 4H+ + 3e ~ NO + 2H 2 0
The second partial equation (oxidation) is:
CdS _ So
This must be written as:
CdS -+ So + Cd++,
to balance atomically, and as:
CdS ~ So + Cd++ + 2e,
to balance electrically. Thus one nitrate ion requires 3 electro" 'l,
and one molecule of cadmium sulphide liberates 2 electrons; ',!,e
two partial reactions will take place in the ratio of 2 : 3.
2(NOa - + 4H+ + 3e = NO + 2H 2 0)
3(CdS = So + Cd++ + 2e)
3CdS + 2NO a- + BH+ + 6e = 3Cd++ + 3S + 2NO + 4H 0 + 6(. 2
or 3CdS + 2NO s- + 8H+ = 3Cd++ + 3S + 2NO + 4H 0 2

Reaction II: the reduction of potassium permanganate by ferrolj"

sulphate in the presence of dilute sulphuric acid.
The first partiaJ equation (reduction) is:
MnO,- -+ Mn++
To balance this atomically one needs 8H+:
MnO, - + 8H+ - Mn++ + iliaO;
and to balance it electrically one requires 5e on the left-hand sick:
MoO,- + 8H+ + 5e ~ Mn++ + 4HaO
The second partial equation (oxidation) is:
Fe++ -+ Fe+++
To balance this electrically one must add one electron to the right-
hand side (or subtract one electron from the left-hand side):
Fe++ ~ Fe+++ +e
Now the gain and loss of electrons must be equal. One permaIl-
ganate ion uses 5 electrons, and one ferrous ion liberates I electron;
hence the two partial reactions take place in the ratio of I : 5.
MnO,- + 8H+ + 5e ~ Mn++ + 4H zO
5(Fe++ ~ Fe+++ + e)
or MoO, - + 8H+ + 5Fe++ = Mn++ + 5Fe+++ + 4H 2 0
Reaction III: the interaction of potassium dichromate and pota~­
sium iodide in the presence of dilute sulphuric acid.
Cr.0 7 - - -+ Cr+++;
Cr.O, -- + 14H+ -+ 2Cr+++ + 7H30
25] The Thwretical BaSM of Qualitative Analysis 71
To balance electrically, add 6e to the left-hand side:
Cr.O, -- + 14H+ + 6e ~ 2Cr+++ + 7HaO
The various stages in the deduction of the second partial equation
are:
r -+ II;
2r -+ II;
2r ~ II + 2e
One dichromate ion uses 6e, and two iodide ions liberate 2e; hence
the two partial reactions take place in the ratio of 1 : 3.
Crlo,-- + 14H+ + 6e .= 2Cr+++ + 7H sO
3(2r .= Is + 2e)
or Cr a0 7 - - + 14H+ + 6r = 2Cr+++ + 7HaO + 3Ia
Reaction IV: the reduction offerric chloride by hydrogen sulphide.
Fe+++ -+ Fe++;
Fe+++ + e >? Fe++
HIB -+ So;
HIB -+ SO + 2H+;
HIS ~ So + 2H + + 2e
Thus one ferric ion liberates I electron, and one molecule of hydrogen
sulphide uses 2 electrons. The partial reactions will therefore take
place in the ratio of 2 : 1.
2(Fe+++ + e ~ Fe++)
HaS ~ So + 2H+ + 2e
--------------------~-----
2Fe+++ + HIS = 2Fe++ + S + 2H+
Reaction V: the action of concentrated hydrochloric acid upon
potassium permanganate.
MnO,- -+ Mn++;
MnO,- + SH+ -+ Mn++ 4H.0; +
MnO,- + SH+ + 5e ~[Mn++ + 4H.0
cr -+ CIa;
2Cr -+CI.
2Cr ~ CIa + 2e
One permanganate ion utilises 5e, and two chloride ions liberate 2e,
hence the two partial reactions take place in the ratio of:.! : 5.
2(MnO,- + SR+ + 5e .= Mn H + 4R zO)
5(2CI- ~ CI + 2e) 2

2Mn0 4 - + 16R+ + lOCI = 2Mn++ + 5CI, + SHzO

72 Qualitative Inorganic A'naZy8i8 [I,
The advantages of the ion-electron method are:
(i) The final equation gives only the substances which r, 'lOt
and are produced in the redox reaction.
(ii) The method is free from hypothesis regarding the di~lri­
bution of the valency bonds among the individual atlllUS
constituting the oxidant and reductant. Thus with perm aU-
ganates, it is not heptavalent manganese Mn VII which is the
oxidant but the MnO( - ion, the concentration of which lliay
be experimentally determined and controlled.
(iii) The influence of the hydrogen ion (or hydroxonium 1 ,a)
concentration, while not apparent in the oxidation num Ler
procedure, is clearly emphasised.
(iv) The equations are not hypothetical: indeed, they hI! \'e
an experimental basis.
The student should experience little difficulty in balancing
the common equations by the ion-electron method and con-
verting them into molecular equations. A brief resume 'W' U
now be given of a few typical oxidising and reducing agel,' S
and the reactions which they undergo. This will be useLll
for reference purposes. The reader should' attempt to dedn"~
the ionic equations independently, and also to formulate tld~
corresponding molecular equations.

1,26. TYPICAL OXIDISING AND REDUCING

AGENTS: SUMMARY
OXIDISING AGENTS

Potassium permanganate. Its action depends upon the co;

version of the manganese into a manganese compound wiT i-
ll. lower valency or with a lower oxidation number. In ac', j
solution, the oxidation number of manganese changes from -l ;
to +2, or by 5 units of reduction. Expressed ionic all,
Mn04- is converted into Mn++; this involves a. gain of ,
electrons.
Mn04- + 8H+ + 5e ~ Mn++ + 4H 20
Some of the ionic reactions which potassium permanganal "
undergoes, are:
Mn04- + 5Fe++ + 8H+ = Mn++ + 5Fe+++ + 4H 20
2Mn04 - + lOr + 16H+ = 2Mn++ + 51 2 + 8H20
2Mn04 - + 5H2S + 6H+ = 2Mn++ + 5S + 8H20
In neutral or alkaline solution, the manganese in the per-
manganate is generally reduced to MnO z, i.e. by 3 units of ~
26] The Theoretical Basis of Qualitative Analysis 73
reduction. Ionically expressed, the change of Mn04 - into
Mn0 2 corresponds to a gain of 3 electrons. An example of
this is the oxidation of manganese salts to Mn0 2, to which the
permanganate ion is itself reduced.
2Mn04- + 3Mn++ + 2H'!v = 5Mn0 2 + 4H+
Potassium dichromate. Its action depends upon the con-
version of the chromium into a chromic compound. In acid
solution, the O.N. of two atoms of chromium changes from
+ 12 to +6, or by 6 units of reduction. Ionically expressed,
Cr207-- is converted into 2Cr+++, and this corresponds to a
gain of 3 electrons per atom of chromium.
Cr207-- + 14H+ + 6e ~ 2Cr+++ + 7H 20
Cr207-- + 6Fe++ + 14H+ = 2Cr++++ 6Fe+++ + 7H 2 0
Cr20 7-- +6r + 14H+ = 2Cr+++ + 312 + 7H20
Cr20 7-- + 3Sn++ + 14H+ = 2Cr+++ + 3Sn++++ + 7H 20
Cr207-- + 3H.CHO + 8H+ = 2Cr+++ + 3H.COOH + 4H 20
(formaldehyde) (formic acid)
Nitric Acid. The oxidising action is dependent upon the
reduction of the nitrogen. The nature of the reduction varies
with the concentration of the acid and with the compound to
be oxidised. The most common product is nitric oxide, but
nitrogen dioxide, nitrous oxide, nitrogen and ammonia are also
formed under different experimental conditions.
In the conversion of the nitrogen in nitric acid into nitric
oxide, the O.N. changes from +5 to +2, or by 3 units of
reduction. Expressed ionically, the transformation of N0 3-
into NO results in a gain of 3 electrons.
NO s- + 2H+ + e? N0 2 + H 20
NO s- + 4H+ + 3e ~ NO + 2H20
3CuS + 2NOs- + 8H+ = 3Cu++ + 3S + 2NO + 4H zO
3Fe++ + NOs - + 4H+ = 3Fe+++ + NO + 2H 20
3Ag + NO a- + 4H+ = 3Ag+ + NO + 2H20
The halogens. Here the action is dependent upon the
conversion of the neutral and free halogen into halogen ions
by accepting electrons.
C1 2 + 2e ~ 2CI-
2Fe++ + C1 2 = 2Fe+++ + 2C1-
The oxidising action of aqua regia may be ascribed to the
free chlorine which is liberated in the reaction:
+
HNOs 3HCI = NOCI + CIs + 2H, O
74 Qualitative Inorganic Analysis [I,
Hydrogen peroxide. This substance acts as both an oxidif'
ing and reducing agent. The former action, particularly iI'
acid solution, is usually attributed to the presence of one atoll i
of oxygen differing in its mode of attachment from the other
oxygen atom.
2Fe++ + H 20 + 2H+ = 2Fe+++ + 2H 20
2

REDUCING AGENTS
Sulphur dioxide or sulphurous acid. The reducing actio]·
is dependent upon the conversion of the sulphite ion into tb.
sulphate ion. Often the reagent is employed by adding sodiun
sulphite to the slightly acidified solution to be reduced. Tb··
O.N. of the sulphur changes from +4 to +6, or by two unit
of oxidation. Expressed ionically, the 80 3 - - ion passes int,·
the 804 - - ion, and this corresponds to a loss of 2 electrons pel
atom of sulphur.
803- - + H 20 ~ 804- - + 2H+ + 2e
80 3 - - + 2Fe+++ + H 20 = 804 - - + 2Fe++ + 2H +
80 3- - + 12 + H 20 = 804- - + 21- + 2H+
380 3 - - + Or207-- + 8H+ = 3804 - - + 2Cr+++ + 4H 20
80 3-_ + As04- - - = 804- - + As0 3- - -
Hydrogen sulphide. The action depends upon the conver-
sion of the sulphur with an O.N. of -2 into free sulphur with
an O.N. of zero, i.e. by 2 units of oxidation. Expresse( I
ionically, the change involves the loss of 2 electrons per molecuk
of hydrogen sulphide.
8-- ~ 8° + 2e
3H 28 + Cr 20 7- - + 8H+ = 38 + 20r+++ + 7H20
5H 28 + 2Mn04- + 6H+ = 5S + 2Mn++ + 8H 20
H 28 + 2Fe+++ = S + 2Fe++ + 2H +
H 28 + 01 2 = 8 + 2H+ + 201-
3H 28 + 2N0 3 - + 2H + = 38 + 2NO + 4H 20
Hydriodic acid. Here the iodine ion passes into free iodine.
the O.N. changes from -1 to 0, or by 1 unit of oxidation.
This is equivalent to the loss of 1 electron.
2r ~ 12 + 2e
2r + 2Fe+++ = 12+ 2Fe++ U
6r + +
Cr2 0 7-- 14H+ = 312+ 2Cr+++ + 7H20
lOr + 2MnO,- + 16H+ = 512+ 2Mn++ + 8H 20
26J The Theoretical Basis of Qualitative Analysis 75
TABLE 1,26, 1

COMMON OXIDIS1NG AGENTS

------
Substance
Radical or O.N.of
element "effective"
Redue-
tion New
O.N.
I Decrea8e
inO.N.
Gain in
eleetrona
involved element pTOduet
KMnO, (acid) MnO.- +7 Mn++ +2 5 5
KMnO, MnO.- +7 MuO. (or +4 3 3
(alkaline) Mn++++)
K.Cr.O, Cr.O,-- +6 Cr+++ +3 3 3
HNO. (dil.) NO.- +5 NO +2 3 3
HNO. (cone.) NO.- +5 NO. +4 I 1
CI. CI 0 cr -1 1 1
Hr, Br 0 Br- -1 1 1
I. I 0 r -1 1 1
3HCI: IHNO. Cl 0 cr
0--
-1 1 1
H 2O. 0 0 -2 2 2
Na.O, 0 0 0-- -2 2 2
KCIO, ClO.- +5 CI- -1 6 6
KBrO. BrO.- +5 Bt·- -1 6 6
KIO. 10 3- +5 r -1 6 6
NaOCI ocr +1 CI-
I -1 2 2

COMMON REDUCING AGENTS

Radical or O.N. of Oxida·
Substance element " effective" tion New
O.N.
Increa86i Loss in
in O.N . . electrona
invoh'ed element product

H.SO. or SO 3 - +4 SO.-- +6 2 I 2
Na.SO. I
H.S S- -2 So 0 '2 2
HI r -1 ro 0 1 1
SnCI. Sn++ +2 Sn++++ +4 2 2
Metals, e.g. Zn Zn 0 Zn++ +2 2 2
Hydrogen H 0 H+ +1 1 1
FeSO, (or any Fe++ +2 Fe+++ +3 1 1
ferrous salt) I
Na.AsO. AsO,--- +3 AsO.--- +5 2 2
H,C,O, I C.O.--- +3 CO. +4 1 I 1

Stannous chloride. The reducing action, which usually

occurs in acid solution, is dependent upon the facile conversion
of stannous ions into stannic ions; the change in O.N. is from
+2 to +4, or by 2 units of oxidation. This is equivalent to
the loss of 2 electrons.
Sn++ .= Sn++++ + 2e
Sn++ +
2Hg012 = Sn++++ + Hg201 2 + 201-
Sn++ +
Hg2C1 2 = Sn++++ + 2Hg + 201-
Sn++ +
01 2 = Sn++++ + 20r
Sn++ +
2Fe+++ = Sn++++ + 2Fe++
 76 Qualitative Inorganic Anaiyaia [I,
Metals and hydrogen. The use of metalE3 and of hydrogel I
as reductants is based upon the conversion of the metal an' I
of neutral hydrogen into cations. The change requires ai,
increase in O.N., or a loss of electrons, dependent upon th,
valency of the metal. With hydrogen, the increase in O.N. j
1 for each atom, and this corresponds to a loss of 1 electron
The reduction may take place in neutral, acid or alkalint
solution.
Zn ~Zn++ + 2e
4Zn + N0 3- + 70H- = 4Zn02 -- + ~H3 + H 2 0
2Al + 20H- + 2H20 = 2Al0 2 - + 3R2
Fe + 2H+ = Fe++ + H2
Zn + 2Fe+++ = Zn++ + 2Fe h
A useful summary of the common oxidiaing and reducini-'
agents, together with the various transformations which the.,
undergo, is given in Table I, 26, 1.

I, 27. Concentration of Reagents. Molar and Normal

Solutions.-In order to carry out an amtlysis in a truly
scientific manner, it is necessary to know not only the reactions
of the different anions and cations, but also the sensitiveness
of each reaction, that is, the smallest amount of substanct-
which can be detected under a standard set of experimental
conditions. One should be able to estimate from the size of a
precipitate the approximate amount of reacting ion which i,·
present in the original substance. This, of course, will onl~
be possible when the tests are carried out with known quanti tie"
of the reagent. For this reason, experiments are made witL
reagents of known strength. It is the purp()se of this section
to discuss the two important methods of expressing the con
centration of solutions .
. Molar Solutions. A molar solution is Olle which contain~
one gram molecular weight (or one mole) of solute per litre oi
solution. Thus a molar solution of potassium chloride con
tains 39 + 35·5 = 74·5 grams ofKCI per litre; a molar solutiOli
of sodium sulphate decahydrate contains 46 -+ 32 + 64 + 18(!
= 322 grams of Na2S04,lOH20 per litre.
This term is also applied to ions in soluti(m, since, as their
osmotic and other properties indicate, they possess some of
the properties of molecules. The gram molecular weights of
H+, Cl-, S04-- and P04--- ions are 1,35·5,96 and 95 grams
respectively. A molar solution of hydrogen . - - -- -
27) The 'l'heoretical13asis of Qualitative Analyai8 17
sulphate ions or phosphate ions contains respectively 1, 35·5,
96 and 95 grams per litre of solution.
Normal Solutions. A normal solution contains one gram-
equivalent weight of the solute per litre of solution. For
convenience of manipulation, the concentration of solutions
employed in qualitative analysis often contain multiples or
fractions of the equivalent weight per litre, e.g. five times
normal which is represented as 5N, or one-tenth normal, O·IN.
The gram equivalent weight is most simply defined as that
weight of substance which will react with or displace 1·008 grams
of hydrogen, 8 grams of oxygen, 35·5 grams of chlorine or that
quantity of any element which reacts with these weights of
hydrogen, oxygen and chlorine respectively. Usually the equi-
valent of an element is equal to its atomic weight d lvided by
its valency. The equivalent weight of a compound is that
weight which contains one gram equivalent weight of the com-
ponent taking part in the reaction under consideration. This
is generally the chief component. With acids, it is the ionisable
and replaceable hydrogen; with bases, it is the ionisable hy-
droxyl group, and with salts, it is generally the cation or anion.
The above statements apply to the simplest cases, that is,
those in which no oxidation or reduction occurs. In general,
the gram equivalent weight will depend upon the particular
reaction in which the substance takes part. It often happens
that the same compound will possess different equivalent
weights in different chemical reactions. The situation may
therefore arise in which a solution may have normal concentra-
tion when employed for one purpose, and a different normal
concentration when used in another chemical reaction.
The equivalent weight* of an acid is that weight of it which
contains one replaceable hydrogen atom, i.e. 1·008 grams of
hydrogen. The equivalent weight of a monobasic acid, such
as hydrochloric, hydrobromic, hydriodic, nitric or acetic acid,
is identical with the molecular weight. A normal solution of
a monobasic acid will therefore contain one gram molecular
weight (or 1 mole) in a litre of solution. The equivalent weight
of a dibasic acid (e.g. H 2S04 ) or of a tribasic acid (e.g. H 3P04 )
is likewise 1/2 and 1/3 respectively of the molecular weight.
The equivalent weight of a base is that weight of it which
contains one replaceable hydroxyl group, i.e. 17·008 grams of
ionisable hydroxyl. 17·008 grams of hydroxyl are equivalent
* Throughout this volume the terms equivalent weight and molecular weight
will be used synonymously with gram equivalent weight and gram molecular
w"}ght respectively.
78 Q'/,lalitative Inorganic Analysis [1,
to 1·008 grams of hydrogen. The equivalent weights c'!
NaOH, KOH and NH40H (or NH3-the Arrhenius definitiOli'
suffice for most purposes) are 1 mole, and of Ca(OHh, Sr(OH
and Ba(OH)2 1/2 nlole.
The equivalent weight of a normal salt is that weight of it
which contains one gram equivalent weight of the cation or
anion. This quantity will be the molecular weight of the salt
divided by the tota.l valency of the cation or anion. Thus the
equivalent weight of KCI is 1 mole, of Na2S04 1/2 mole, of
AICl3 1/3 mole, of SnCl4 1/4 mole and of Ca3(P04,)2 1/6 mole.
For acid and double salts, the equivalent weight may var,'
with the component to which the equivalent is referred. Thu·
for the salt Na2HAs04, 12H20, which yields the ions 2Na-t.
HAs04--, H+ and As04--- upon progressive ionisation th,·
equivalent will be 1/2 mole when referred to Na+ or HAs04--
I mole when referred to H+, and 1/3 mole when referred t,
As0 4---. With a double salt, like chrome alum K 2S04
Cr2(S04)a, 24H 20 the equivalent weight will be 1/2, 1/6 anO
1/8 mole respectively according as to whether the reacting com
ponent is K+, Cr+-J-+ or S04--. It must clearly be pointed
out that the above remarks apply only to the calculation 0 t
the equivalents of salts which do not function as oxidising 01
reducing agents. 'The equivalent weight of an acid or doubk
salt, which does not act as an oxidant or reductant, is the gran,
molecular weight divided by the total valency of the reactinf-:
constituent.
The equivalent weight of an oxidising agent is determine(l
by the change in oxidation number which the reduced element
experiences. It is that quantity of oxidant which involves 1\
change of one unit in the oxidation number.* Thus in th!
normal reduction of potassium permanganate in the presenc!
of dilute sulphuric II>cid to a manganous salt,
+1+7-8 +2+6-8
KMn04 ~ MnS04,
the change in oxidation numbers of the manganese is from +7
to +2, or by 5 units of reduction. The equivalent weight is
therefore 1/5 mole (compare Sections 1,24 and I, 26). Similarly
for the reduction of potassium dichromate in acid solution,
+2+12-14 +6-6
K 20r20 7 ~ Or2(S04)3,
• The standard of reference may be taken as the reaction:
+
H O .= H+ +
e, or 1/2H • .= H+ e
This involves unit change in oxidation number. Incidentally this equation
clearly shows the relation between the oxidation number method and the
ion· electron method for deducing equivalent weights. ..
 - - T
27] The Theoretical Basis of QUalitative Analysis 79
the change in O.N. of two atoms of chromium is from +12 to
+6, or by 6 units of reduction. The equivalent weight of
K2Cr207 is accordingly 1/6 mole. In order to find the equiva-
lent weight of an oxidising agent, one divides the molecular
weight by the total change in O.N. per molecule which some
element in the substance undergoes.
We may also employ the ion-electron method (Section I, 25).
The partial ionic equation in which the oxidising agent takes
part is first written down. For potassium permanganate in
acid solution, this is:
Mn04- + 8H+ + 5e ~ Mn++ + 4H 20
The equivalent weight of an oxidising agent in a particular
reaction is then that weight of the oxidant which is associated
with a gain of one electron in that reaction. In the example
under consideration 5 electrons are gained, hence the equivalent
weight is 1/5 mole. In general, to calculate the equivalent
weight of an oxidising agent for a particular reaction, one
divides the gram molecular weight by the number of electrons
per molecule indicated in the partial ionic equation as taking
part in the reaction.
The equivalent weight of a reducing agent is similarly
determined by the change in oxidation number which the
oxidised element suffers. Consider the conversion of ferrous
into ferric sulphate:
+2 -2 +6-6
2(Fe804) -+ Fe2(S04)S
Here the change in O.N. per atom of iron is from +2 to +3, or
by 1 unit of oxidation, hence the equivalent weight of ferrous
sulphate is 1 mole. The ion-electron method may also be
employed; the procedure is exactly analogous to that described
under oxidising agents. One example will be studied, viz. the
conversion of sodium sulphite into sodium sulphate. The
partial ionic equation is:
803- - + H 20 - 2e ~ S04-- + 2H+
Two electrons are lost per gram molecular weight of sodium
sulphite; the equivalent weight is accordingly 1/2 mole.
In general, it may be stated: (i) The equivalent weight of an
element taking part in an oxidation-reduction (redox) reaction
is the atomic weight divided by the change in oxidation
number. (ii) When an atom in any complex molecule suffers
a change in oxidation number (oxidation or reduction), the
eq~valent weight of the molect,tle is the molecular weight
80 Qualitative Inorganic An~lY8i8 [I,
divided by the change in oxidation number of the oxidise I
or reduced element. If more than one atom of the reacth I'

element is present, the molecular weight is divided by the tot:i i

change in O.N.
For convenience of reference the partial ionic equations for
a number of oxidising and reducing agents are collected in
Table I, 27, I (compare Table I, 26, 1).

TABLE I, 27, 1. IONIO EQUATIONS FOR USE IN THE CALOULATION OF

THE EQUIVALENT WEIGHTS OF OXIDISING AND REDUOING AGENTS

Sub8tance Partial Ionic Equation

OXIDANTS

Potassium permanganate MnO,- + 81I+ + 56 ~ Mn++ + 4H.O

(acid)
Potassium permanganate MnO,- + 2H 20 + 36 ~ MnO. + 40F
(neutral)
Potassium dichromate Cr.0 7- + 14H+ + 66 ~ 2Cr+++ + 7H.0
Ceric sulphate Ce++++ + 6 ~ Ce+++
Chlorine CII + 26 ~ 2Cr
Ferric chloride Fe+++ + 6 ~Fe++
Potassium iodate 10.- + 6H+ + 6e ~r + 3H O I
Sodium hypochlorite ClO- + H.O + 26 ~ cr + 20F
lIydrogenperoxide 1I.0. + 21I+ + 26 ~ 2H.0
Manganese dioxide MnO. + 41I+ + 26 ~ Mn++ + 2H, 0
Sodium bismuthate BiO.- + 6H+ + 26 ~ Bi+++ + 3H.0
Nitric acid (conc.) NO.- + 2H+ + e ~NO. + HIO
Nitric acid (dil.) NO.- + 4H+ + 36 ~ NO + 2H.0

REDUCTANTS

lIydrogen H. - 26 ~2H+
Zinc Zn - 2e ~Zn++
Hydrogen sulphide H.S - 26 ~ 2H+ +S
Hydrogen iodide 2HI - 26 ~I. + 2H+
Oxalic acid C.O,- - 26 ~ 2CO.
Ferrous sulphate Fe++ - e ~Fe+++
Sulphurous acid H.SO. + H.O - 26 ~ SO,- + 4H+
Stannous chloride Sn++ - 26 ~ Sn++++
Stannous chloride (in pre.
Bence of hydrochloric
acid) - 26 ~ SnCl.-
lIydrogen peroxide - 2e ~ 2H+ + 0.
Sodium thiosulphate - 26 ~ S,O.-

We are now in a position to understand more clearly why

the equivalent weights of substances vary with the reaction.
A normal solution of ferrous sulphate FeS04,7H 20 will have .
27) The Theoretical Ba8i8 of Qualitative Analym 81
an equivalent weight of 1 mole when employed as a reducing
agent and 1/2 mole when employed as a normal salt or pre-
cipitant. A solution of ferrous sulphate which is normal as a
salt will be N/2 as a reducing agent. A few other examples are
collected below.
Oxalic Acid. H 2C2 0 4 ,2H 20. This compound contains two
replaceable hydrogen atoms, hence a normal solution contains
1/2 mole per litre.
2H+ + 20H- = 2H 2 0,
or H 2C2 0 4 + 2KOH =K2C20 4 + 2H20
As a reducing agent, the partial ionic equation is:
C20 4-- - 2e ~ 2C0 2,
so that the equivalent weight is 1/2 mole.
Potassium hydrogen oxalate. KHC 20 4. This substance
has one replaceable hydrogen atom, hence, as an acid, the
equivalent is 1 mole:
KHC 2 0 4 + KOH = K 2C2 0 4 + H 2 0
When functioning as a reducing agent, the reducing power is
due to the C2 0 4--, and the equivalent is 1/2 mole.
Potassium tetroxalate. KHC204,H2C204,2H20. This salt
contains three replaceable hydrogen atoms, and its equivalent
weight is therefore 1/3 mole.
KHC204,H2C204,2H20 + 3KOH = 2K2~04 + 5H20
As a reducing agent, a gram molecular weight contains 2C 20 4--
and the equivalent weight is therefore 1/4 mole. A solution of
this salt which is 3N as an acid is 4N as a reducing agent.
Potassium permanganate. KMn04' As a salt, that is, as a
precipitant, the equivalent weight is 1 mole. We have already
seen (Section I, 26; Tables I, 26, 1 and I, 27, 1) that the
equivalent weight in acid solution is 1/5 mole, and in neutral
or alkaline solution 1/3 mole. A solution of KMn04 which is
O·IN as a precipitant, is o'5N as an oxidising agent in acid
solution, and O·3N as an oxidising agent in neutral or alkaline
solution.
Once the reader has grasped the above concepts as to the
calculation of equivalent weights he should experience no diffi-
culty in computing the exact amount of substance required in
the preparation of any solution required in qualitative analysis.
The strengths of the reagents employed, together with details
for their preparation, are collected in the Appendix (Section
A,2).
""
82 Qualitative Inorganic Analysis [I,
1,28. THEORY OF OXIDATION AND REDUCTION
Reference has already been made in Section I, 23 to the fll' t
that oxidation consists of the loss of electrons and reduction· ,f
the gain of electrons. Thus in the reduction of ferric chlorid,~
by stannous chloride:
2FeCls + SnCl z = 2FeCl z + SnC~,
or 2Fe+++ + Sn++ = 2Fe++ + 8n++++,
for every atomic weight (56 grams) of iron reduced 96,500
coulombs or 1 Faraday of electricity is lost by the iron, and
for every atomic weight (1l9 grams) of tin oxidised, the latter
has gained 2 X 96,500 coulombs or 2 Faradays.*
According to modern theory, an electric current is essentially
a flow of negative electrons. It should therefore be possible iu
V

NaG/

A B
Fig. I, 28, 1

obtain direct proof of the transfer of electrons in the oxidation-

reduction reaction under suitable experimental conditions.
This is clearly shown by the following experiment (Fig. I, 28, 1).
Solutions of stannous chloride and of ferric chloride, each
acidified with dilute hydrochloric acid to increase the con-
d>Jctivity, are placed in separate beakers A and B, and the
two solutions are connected by means of a "salt bridge" con-
taining sodium chloride. The latter consists of an inverted
U-tube filled with a solution of a conducting electrolyte, such
as sodium chloride, and stoppered at each end with a plug of
... It follows from Faraday's law that each gram equivalent weight of an ion
is associated with a charge of one Faraday of electricity. A change of charge
of one thus corresponds to the gain or loss of one Faraday per formula weight
of the 8ubstance. •
29] The Theoretical Basis of Qualitative AnalY8is 83
cotton wool to arrest mechanical flow. It connects the two parts
of the redox system while preventing mixing. The electrolyte
in solution in the salt bridge is always selected so that it does
not react chemically with either of the solutions which it con-
nects. Platinum foil electrodes are introduced into each of
the solutions, and the two electrodes are connected to a milli-
voltmeter V. When the circuit is closed, it will be found that
the current in the external circuit passes from the E'tannous
chloride solution to the ferric chloride solution. After a little
time, stannic ions can be detected in A and ferrous ions in B.
In the preceding experiment the flow of current is due to
the e.m.f. produced by the chemical changes in the redox
reaction. An electric current, according to modern theory,
consists of a flow of electrons and it would therefore be expected
to give rise to oxidation-reduction reactions. This can readily
be demonstrated as follows. In Fig. 1,28, 1, beaker A contains
ferrous ammonium sulphate solution acidified with dilute sul-
phuric acid, beaker B ferric chloride solution likewise acidified
with dilute acid, and the salt bridge dilute sulphuric acid, and
the millivoltmeter is replaced by a 6-volt battery with the
positive pole connected to A and the negative pole to B.
After some time ferric ions can be detected with putassium
thiocyanate solution in A, and ferrous ions with potassium
ferricyanide solution in B. At the anode (+ electrode) each
ferrous ion loses one electron and becomes a ferric ion: at the
cathode (- electrode) each ferric ion gains 1 electron and is
reduced to a ferrous ion:
Fe++ ~ Fe+++ + e (anode); Fe+++ + e ~ Fe++ (cathode)
It is a well-known fact that oxidants and reductants vary
considerably in strength. Information of a quantitative nature
as to the relative strengths (compare relative strengths of weak
acids and bases as expressed by their dissociation constants in
Table I, 12, 1) would be of considerable practical value. A
method which suggests itself at once is the measurement of the
e.m.f. of redox reactions under standard conditions. This is
indeed the method which is employed, but before this can be
understood by the student, it will be necessary to consider the
subject of electrode potentials.
I, 29. Electrode Potentials.-When a rod of zinc is partially
immersed in a solution of zinc sulphate, the metal becomes
negatively charged relative to the solution. To account for
this, Nernst (1888) introduced the idea of electrolytic solution
psessure. Just as a liquid passes into a vapour until the
84 ' ' 1 norgantc
Qual 'ttat'we . All
na . YSM [I,
pressure of the vapour has a definite value, so zinc wIlen pIa, ,·d
in a solution of one of its salts passes into solution as zinc ior ,s.
The zinc will consequently become negatively charged relat, \ e
to the solution; a potential difference therefore exists betwt', n
the metal and the solution. Owing to the comparatively lar. I~
charge which the ions carry, the ions do not move far aWn \r
from the metal but are held by electrostatic attraction aJ' l
form an "electrical double layer." The electrolytic soluti,,' I
pressure P of the metal will be opposed by the osmotic pressu !"
p of the ions in the solution, which tends to deposit them ".
the metal and the change soon stops (i.e. equilibrium is reache, 1,
when only a minute amount of zinc has passed into the ion I'
state. '1'he greater the concentration of zinc in the solution.
the greater is their osmotic pressure and the smaller is tl"
negative potential of the zinc.
H a rod of copper (a metal with only very small electrolyt!,
solution pressure) is immersed in a solution of copper sulphat,
a minute amount of copper ions deposits on the metal becam,
of their osmotic pressure and the metal consequently acquirt·
a positive charge, leaving the solution negatively charged.
The metal then attracts negative (S04 --) ions from the solutio! I

to form the "electrical double layer." The greater the con

centration of copper ions in the solution, the larger is th'
osmotic pressure, and the greater is the positive potential oj
the copper.
The potential difference established between a metal and II
solution of one of its salts, or the electrode potential, will bl
dependent upon the concentration of the ions of the metal ill
the solution and, of course, upon the metal itself. If P is the
electrolytic solution pressure of the metal and p the osmoti(
pressure of the ions in the solution, we have: (a) if P> p
(e.g. with zinc), the metal becomes negative in the solution:
(b) if P < p (e.g. with copper or silver), the metal becomes
positive in the solution; and (c) if P = p, the metal remains
uncharged in the solution. The convention will be adopted
in this book that the sign of the electrode potential is that of
the metal: thus when the metal is positive with respect to the
solution, it will be assumed to have a positive (+) potential.
Other authors, particularly in the U.S.A., use the opposite
algebraic sign.
• Only in solutions in which the concentration, and therefore the osmotic
pressure, of copper ions has been reduced to a very minute value (e.g.
by the addition of excess of KCN and the formation of the complex ion
[Cu(CN),]-) does metallic copper send ions into the solution and so becomes
negatively charged. J
29] The Theoretical BalJis of Qualitative Analysis 85
. The electrodes just referred to are reversible with respect to
the cation: one may also have electrodes which are reversible
with respect to an anion. Thus when silver, in contact with
solid silver chloride, is immersed in a solution of potassium
chloride, that is, when one has the electrode AgjAgCI (solid),
KClj, the potential will depend upon the concentration of the
chloride ion, and the electrode will be reversible with reference
to this ion. The calomel electrode, described in a later Section,
is also reversible with respect to the anion.
Nernst (1889) deduced the following expression for computing
the potential difference which exists between a metal and a
solution of its ions, that is, for the electrode potential E:
RT p
E = nF log ]5'
where R is the gas constant expressed in electrical units, F is
the quantity of electricity borne by one equivalent weight in
grams (one Faraday), n the valency of the ions and T the
absolute temperature. The expression reduces to:
0·0577 p 0·0591 P
E l8 0 = -n- log P volts, and E25 = -n- log P volts
0

at 18°0 and 25°0 respectively. The osmotic pressure p is

directly proportional to the concentration of the solution and
to the absolute temp~rature; the e.m.f. will therefore vary with
the concentration. If the concentration is increased tenfold,
the e.m.f. increases by 0·06 volt for a univalent ion, by 0,06/2
= 0·03 volt for a bivalent ion, etc. The electrolytic solution
pressure provides a measure of the tendency of the metal to
be converted into ions or, since the formation of ions constitutes
an oxidation, it is also a measure of the capacity of the metal
to undergo oxidation.
In order to determine the potential difference between an
electrode and a solution, it is necessary to have another electrode
and a solution, the potential difference between which is known.
These two electrodes can then be combined to form a voltaic
cell, the e.m.f. of which can be directly measured. The e.m.f.
of the cell is the algebraic difference between the two electrode
potentials; the value of the unknown potential can then
be calculated. In practice the standard electrode used
for comparative purposes is the molar or normal hydrogen
electrode. This consists of a piece of platinum foil, coated
with platinum black by an electrolytic process, and immersed
in }' solution of hydrochloric acid, molar with respect to
 ;
86 Qualitative Inorganic Analy8i8 [I
hydrogen ions (more correctly in a solution of hydrochloric acid
containing hydrogen ions of unit activity). Hydrogen gas :,1
a pressure of one atmosphere is passed over the foil throug I!
the side tube C (Fig. I, 29, 1) and escapes through the sma i I
openings B in the surrounding glass tube A; the foil is thl"
kept saturated with the gas. Connection between the platinUl'l
foil sealed into the tube D and an outer circuit is made wit i,
mercury in D. The platinum black has the remarkable pr;,
perty of adsorbing large quantities of hydrogen, and it permi: '
the change from the gaseous to the ionic form and the rever'
process to occur without hindrance; it therefore behaves ."
though it were composed entirely of hydrogen, that is, as "
hydrogen electrode. Under fixed conditions, viz. of atm,
spheric pressure and molar concentration of hydrogen ions j'l
the solution in contact with tIl\'
D
electrode, the hydrogen electro(J.
possesses a definite potential /, 1
all temperatures. By connectin~
the molar hydrogen electrode wit I j

A a metal electrode (a metal in COlI'

tact with a molar solution of it:,
ions) by means of[ a salt (sa,'>
=--=--- -= potassium chloride) bridge, th,·
-=----:::_---=---=
molar or standard electrod('
- -Molar·- potential of the metal may b"
--H+-
determined directly. Other ele<,
'ij_~-=--= trodes, particularly the calome J
electrode and the silver-silver
chloride electrode, the potential,
Fig. 1,29, 1 of which have been determine. I
by direct reference to the mola r
hydrogen electrode, are often used in practice owing to con
venience of manipulation. The former is referred to again ill
Section 1,38, but for a fuller treatment the student is referred
to text-books of physical chemistry. *
When a rod of zinc is immersed in a molar solution of ziw'
ions and this is coupled with a molar hydrogen electrode, the
resultant cell:

Zn I Zn++(M) " H+(M) I H 2 , Pt,

.. See, for example, S. Glasstone, Text Book oj PhY8ical Chemistry, Second

Edition, 1947 (Macmillan). A detailed account is also to be found in the
author's Text-Book oj Quantitative Inorganic Analysill; Theory and Practice,
Second Edition, 1951 (Longmans, Green & Co. Ltd.)., .,
29] The Theoretical Basis of Qualitative Analysis 87
has an e.m.f. of 0·76 volt. The two reactions which take place
are:
Zn ~ Zn++ + 2e, and H2 -- 2e ~ 2H+
The zinc pole is negative and therefore the zinc electrode is
0·76 volt more negative than the hydrogen electrode, or the
potential of the molar zinc electrode is -0,76 volt (the molar
hydrogen electrode is arbitrarily taken as equal to zero).
Further, if one employs a copper electrode immersed in a molar
solution of cupric ions, and couples this with a molar hydrogen
electrode, the cell has an e.m.f. of 0·34 volt~ The copper pole
is now positive; the potential of the molar copper electrode is
accordingly +0'34 volt.
The standard or molar electrode potential of an element may
therefore be defined as the e.m.f. produced when a half cell
consisting of the element immersed in a molar solution of its
ions (more correctly in a solution of its ions possessing unit
activity) is coupled with a molar hydrogen electrode, the
potential of which is assumed equal to zero. Tabl@ I, 29, I
gives a list of standard electrode potentials at 25 0 0; the sign
of the potential here adopted is that of the charge on the
electrode.
TABLE I, 29, 1. STANDARD ELECTRODE POTENTIALS AT 25°0

LijLi+ -3,045 CrjCr+++ -0·74

KjK+ -2·925 I Fe/Fe++ -0·440
NaJNa+ -2·714 Cd/Cd++ -0·403
BajBa++ -2·90 I
Co/Co++ -0·277
Sr/Sr++ -2·89 Ni/Ni++ -0·250
Ca/Ca++ -2·87 SnjSn++ -0·136
Ce/Ce+++ -2·48 Pb/Pb++ -0·126
MgjMg++ -2·37 Pt, (H 2)/H+ 0·000
ThjTh++++ -1·90 Cu/Cu++ +0·337
BejBe++ -1·85 2HgjHg2++ +0·789
V/V+++ -1·80 AgjAg+ +0·799
AljAl+++ -1·66 PdjPd++ +0'99
MnjMn++ -1·18 AujAu+++ +1'5
ZnjZn++ -0·763

When metals are arranged in the order of their tltandard

electrode potentials, the so-called electrochemical series of the
metals is obtained. The greater the negative value of the
potential, the greater is the tendency of the metal to pass into
the ionic state. A metal with a more negative potential will
..
88 Qualitative Inorganic Analysi8 [I,
displace any other metal below it in the series from solutions
of its salts. Thus magnesium, aluminium, zinc or iron will
displace copper from solutions of its salts; lead will displace
copper, mercury or silver; copper will displace silver or mercury.
The standard electrode potential is a quantitative expressi()n
of the readiness of the element to lose electrons. It is therefore
a measure of the strength of the element as a reducing agent;
the more negative the element, the more powerful its action as
a reductant.
I, 30. Calculation of electrode potentials.-The Nern"i
equation:
RT p
E = nF log. p
may be written in the form:
E = RT
-n F
log' p
RT
- - log P
nF e

At constant temperature the term !~ loge P is a constant ff'

a given metal; hence:
RT
E+ = nF log. p + constant
The gas laws may be written in the form p = RTc where '
is the concentration of the positive ions in the solution. Mor'
accurately, the expression should be p = RTa+ where a+ is th.
activity of the ions.
RT
Thus n log.
E+ = -F G+ + constant (Eo) 1

The equation can be simplified by substituting the kn~~~~i~ef'

of the constants and converting the logarithms to base 10; it
then becomes:
E - 0'0001982T I
+- n og G+
+ E0
For a temperature of 25°0 (T = 298°):
0·0591
E+ = - - loga+ +Eo (i)
n
Before the introduction of the activity concept, the concentra-
tion of the ions c!+ (in moles per litre) was used in place of the
activity:
0·0591
E+ = - - . log Ct+ + Eo
"
30] The Theoretical Basis of Qualitative Analy8i8 89
The latter expression is sufficiently accurate for most practical
purposes in qualitative analysis.
For a non-metal, which yields negative ions, equation (i)
becomes
0·0591
E _ =Eo - -n- log a _ ,
where a_ is the activity of the negative ions. For purposes of
calculation C1 may replace a_.
It will be seen that for a solution of unit activity, where
a+ or a_ is unity, E = Eo: thus Eo is the standard ~r molar
electrode potential of the element. Knowing the value of Eo,
the potential for any concentration can be calculated with the
aid of equation (i').
An interesting application of this equation is to the cal-
culation of equilibrium constants.
Example 16. Calculate the equilibrium constant of the reaction:
+
Zno Cu++ ~ Zn++ +
Cuo
This is the familiar displacement of cupric ions from solutions
by metallic zinc.
For the zinc electrode:
0·059
E zn = Eo + -2- log [Zn++],
= - 0·76 + 0·0295 log [Zn++]
For the copper electrode:
0·059 .
EOll = Eo+ -2- log [Cu++.1
= + 0·34 + 0·0295 log [Cu++],
At equilibrium E zn = Eeo
+
- 0·76 0·0295 log [Zn++] = + +
0·34 0·0295 log [Ou++],
[Zn++] 1·10
or log [Cu++] = ().0295 = 3'73,

or [Zn++] = () + 1037
[Cu++] w

The equilibrium constant is given by:

[Zn++] X [CUO] = K
[ZnO] X [Cu++]
Now [Cu O] and [ZnO] refer to the solid metallic condition and can
therefore be regarded as constant quantities. The equation thus
reduces to:
[Zn++] ,
[Cu++] = K
90 Qualitative Inorganic A nalysia [I,
The ratio of the ionic concentrations at equilibrium is shown abov"
to be 2 X 1037 , and this is the equilibrium constant of the reaction
In practice this means that when metallic zinc is added to a solutio;
containing cupric ions, reaction ceases when the ratio of the COl:
centration of the zinc ions produced to the concentration of th'
oopper ions remaining in solution is 2 X 1037 , that is, a practical]'.
negligible quantity of oupric ions. For all ordinary purposes th"
may be taken as the complete removal of cupric ions from solutioll,
I, 31. Concentration cells.-The electrode potential varif.-
with the concentration of the ions in solution. Hence b\
bringing two electrodes of the same metal but immersed i:;
solutions containing different concentrations of the ions of th.·
metal into contact, a cell may be formed. Such a cell is terme,
a concentration cell. The e.m.f. of the cell will be the algebrai
difference of the two electrode potentials. It may be calculate"
as follows. At 25 0 :
0·0591 0·0591
E = - - log
n
Cl + Eo - - - log
n
Cs - Eo,

= 0·0591
-n- Ct
log -, where
Cs
Cl > Cs
As an example we may consider the cell:
A \ AgNO a aq. II AgNO a aq.
g Ag+ = O·00475M Ag+ = O'043M
I Ag
EI El
Assuming no potential difference at the liquid junction:
0·0591 0·043
E = El - Es = - 1 - log 0.OM75 = 0·056 volt

Concentration cells have an obvious application in tht·

determination of the solubility of sparingly soluble salts.
I, 32. Calculation of the e.m.f. of a voltaic cel1.-0ne 01
the simplest of galvanic cells is the Daniell cell. This consist"
of a rod of zinc dipping in zinc sulphate solution and a strip of
copper in copper SUlphate solution; the two solutions art'
generally separated by placing one inside a porous pot and th(·
other in the surrounding vessel. The cell may be represented:
Zn I ZnSO, aq. II CuSO, aq. I Cu
At the zinc electrode, zinc ions pass into solution leaving an
equivalent negative charge on the metal. Copper ions are
deposited at the copper electrode, rendering it positivel)
cha.rged. By completing the external circuit, the curren1
33] The Theoretical Basis of Qualitative Analysis 91
(electrons) passes from the zinc to the copper. The chemical
reactions in the cell are as follows:
(a) zinc electrode-
Zn ~ Zn++ + 2e,
(b) copper electrode-
+ 2e ~ CU
Cu++
The net chemical reaction is:
Zn + Cu++ = Zn++ + Cu
The potential difference at each electrode may be calculated
by means of equation (i'), and the e.m.f. of the cell is the
algebraic difference of the two potentials, the correct sign being
applied to each.
As an example, we may calculate the e.m.f. of the Daniell cell
with molar concentrations of zinc ions and cupric ions.
E = Bo(ou) - EO(Znl = + 0·344 - ( - 0·762) = 1·106 volts
The small potential difference produced at the contact between the
two solutions (the so-called liquid-junction potential) is neglected.
I, 33. Oxidation-reduction cells.-Redustion is accompanied
by a gain of electrons and oxidation by a loss of electrons. In
a system containing both an oxidising agent and its reduction
product, there will be an equilibrium between them and
electrons. If an inert electrode, such as platinum, is placed in
a redox system, for example one containing ferric and ferrous
ions, it will assume a definite potential indicative of the position
of equilibrium. If the oxidation tendency predominates, the
system will take .electrons from the platinum leaving the latter
positively charged; if, however, the system has reducing pro-
perties, electrons will be given up to the metal, which will then
acquire a negative charge. The magnitude of the potential
will thus be a measure of the oxidising or reducing power of
the system.
To obtain comparative values of the" strengths" of oxidising
agents it is necessary, as in the case of the electrode potentials
of the metals, to measure under standard experimental con-
ditions the potential difference between the platinum and the
solution relative to a standard of reference. The primary
standard is the molar or normal or standard hydrogen electrode,
and its potential is taken as zero. The standard experimental
conditions for the redox system are those in which the ra.tio
of the concentrations of the oxidant to the reductant is unity.
_.
92 Qualitative Inorganic Analysis [I,
Thus for a ferrous-ferric chloride electrode, the redox cell would
be:
Pt I~:::+ II I
H+ H 2(Pt) \
The potential measured in this way is called the standard
oxidation potential. A selection of these is given in Tabl
I, 33, 1. The sign of the potential is that of the electrode.

TABLE I, 33, 1. STANDARD OXIDATION POTENTIALS AT 25°0

EO
Electrode
Co'+,Oo=+/Pt
I 003+ Electrode reaction
e .= OoH +1·84
+
Pb'+,Pb'+/Pt Pb'+ + 2e .= Pb H +1·75
MnO,-,MnO./Pt MnO,- + 4H+ + 36 .= MnO. + 2H.O +1-59
MnO,-,Mn3+/Pt MnO,- + 8H+ + 56 <"Mn2+ + 4H.O +1·51
Ce'+,Ce3+/Pt Ce'+ + e .= Cel+ +1-45
BrO.-,Br./Pt 2BrOa- + 12H+ + 10e .= Br. + 6H.O +1-45
Cl.,2cr/Pt Cl, + 2e.= 2cr +1·36
Cr.0 7 i1-,2Cr3+/Pt Cr.0 7 i1- + 14H+ + 6e? 2Cr8+ + 7H.0 +1-36
IO,-,I./Pt 210,- + 12H+ + 10e .= I. + 6H.0 +1-20
Br.,2Br-/Pt Br. + 2e.= 2Br- +1·07
FeS+,FeH/Pt FeH + 6.= Fe H +0'77
HaAsO"HaAsO./Pt HaAsO. + 2H+ + 2e .= H aAs0 3 + H 2 O +0·56
1.,2r/pt II + 26.= 2r +0'53
[Fe(CN)s]3-,
[Fe(CN).]'-fPt Fe(CN).3- + 6 .= Fe(CN).'- +0'36
CuI+,Cu/Pt Cul+ + 2e .= Cu +0'35
Sn'+,SnH/Pt Sn H + 26 ?Sn H +0·15
H+,H./Pt 2H+ + 26.= H t 0·00
Ti'+,TiS+/Pt TiH + e .= TiS+ -0·04
Cr3+,Cr2+IPt Cr3+ + e .= Cr'-t- -0·41
SO,SO-/Pt So + 2e? SiI- -0·48
Znl+,Zn Znl+ + 26 ?Zn -0·76
I

These oxidation potentials enable one to predict which iom<

will oxidise or reduce other ions at molar concentrations. The
most powerful oxidising agents are at the upper end of the
Table and the most powerful reducing agents at the lower end.
Thus permanganate ions can oxidise CI-, Br-, I-, Fe++ and
Fe(CN)6---- ions; ferric ions can oxidise As0 3---, r-, but not
Cr 20 7- - or CI- ions. It must be emphasised that oxidation
potentials do not give any information as to the velocity of the
reaction; in some cases, the presence of a catalyst is necessary
in order that the reaction may proceed with reasonable velocity.
In order to understand fully the significance of oxidation-
reduction potentials and their application in calculations, it is
advisable to consider that in all solutions of oxidants, some of the
reduced form is always present: the concentration of the latter may
34] The Theoretical Basia of Qualitative AnalyaU 93
vary from a significant measurable quantity to an amount so small
that it cannot be detected by any known method. A similar con-
ception of reductants should be visualised. Thus in solutions con-
taining ferric ion, there is always present some ferrous ion, and
vice versa. In the quantitative study of oxidation-reduction re-
actions, both forms must always be considered, because, as we shall
see in the following Section, it is their relative effective concentra-
tions which determine the oxidising power or the oxidation potential
of an oxidant. Examples of pairs include I 2 ,2r-; Mn04 -,Mn++;
Fe+++,Fe++; and Cr207 --,2Cr+++. When, therefore, we speak
of the oxidant Cr Zo7--, the pair or system CrZ07 --,2Cr+++ is
understood, notwithstanding the fact that chromic ion concentra-
tion may be infinitesimally small.

I, 34. Calculation of the oxidation potential.-A reversible

oxidation-reduction reaction may be written in the form
(oxidant = substance in oxidised state, reductant = substance
in reduced state):
Reductant ~ Oxidant + ne
'----v----' '-----v--'
Red Ox

The electrode potential which is established when an inert or

unattackable electrode is immersed in a solution containing
both oxidant and reductant is given by the expression:

E p-- EO + RT Iog.-
-
aoz. (i)
nF aR,d.

where ET is the observed potential of the redox electrode

at TO, EO is the standard oxidising potential, n the number of
electrons or negative charges gained by the oxidant on being
converted into the reductant, and a o.,. and a Red. are the activities
of the oxidant and reductant respectively. Since activities
are often difficult to determine directly, they may be replaced
by concentrations; the error thereby introduced is usually of
no great importance. The equation therefore becomes:

E p-- EO + RT
- o1 g .oz-. C (i/)
nF CRedo

Substituting the known values of Rand F, and changing from

natural logarithms to common or Briggsian logarithms (by
multiplying by 2·303), we have for a temperature of 25°0
T = 298°):
E = EO + O·059! I [Ox.] (i' )
25' n og [Red.]
94 Qualitative Inorganic Anaiyau [I,
If the concentrations (or more accurately the activities) of th,·
oxidant and reductant are equal, E260 = EO, i.e. the standar,:
oxidation potential. It follows from this expression that, fOi
example, a tenfold change in the ratio of the concentration
of the oxidant to the reductant produces a change in th,·
potential of the system of O'0591/n volts.
A simple example will illustrate the application of thi"
formula. Consider the cell:

Pt I~:::+(~~t[1) II H+(IM),H21 Pt
The e.m.f. is given by (the liquid junction potential between
the acid and salt solutions is neglected):
0·0591 [Fe+++]
E = EO + -1- log [Fe++] ;
0·1
= + 0·75 + 0·059 log 0,001 ;
= + 0·75 + 0·118 = 0·87 volt
The application of standard oxidation potentials to th,'
calculation of equilibrium constants of simple ionic reaction-:
is illustrated by the following example.
Example 17. Calculate the equilibrium constant of the reaction:
01 2 + 2Fe++ ~ 201- +
2Fe+++
The equilibrium constant is given by:
[01-]2 X [Fe+++]2
[Cl21 X [Fe++]2 =K
The reaction may be regarded as taking place in a voltaic cell, the
two half cells being a CI 2,2C1- electrode and a Fe++, Fe+++ electrodp
The reaction is allowed to proceed to equilibrium; the total volta~,·
or e.m.f. of the cell will then be zero, i.e. the potentials of the t""
electrodes will be equal.
0,059 [C12 ] 0·059 [Fe+++]
+
EOCl1•2CI - -2- log [C1-]2 = EO Fe ++.Fe +++ + -1- log [Fe++]
Now EOC12.2C1- = 1,36 volts and EOF .++. F .+++ = 0·77 volt,
. [Fe+++J2 X [C1-]2 0·59
.. log [Fe++]2 X [C1 ] = 0.0295 = 20·00 = log K,
2
K = 1·0 X 1020
The large value of the equilibrium constant signifies that the reaction
will proceed from left to right almost to completion. This is III
harmony with the practically complete oxidation of a ferrous sait
by chlorine, and the stability of a ferric chloride solution.
35] The Theoretical Basis of Qualitative Analysis 95
1,35. Equilibrium Constant of Oxidation-Reduction Re-
actions.-The general equation for an oxidation-reduction
electrode may be written:
pA + qB + rC ...... + ne ~ sX + tY + uZ + ..... .
The potenti8J is given by:
E = EO + RT
_ Ioge.a' A' ~".
n!!.. acr ••••••
nF ax. ay.az I"
......
,

where a refers to activities, and n to the number of electrons

involved in the oxidation-reduction reaction. This expression
reduces to the following for a temperature of 25°0 (concentra-
tions are substituted for activities in order to permit of its
facile application in practice):
- EO
E - 0·0591 1 c~ .eI!_._:ccc__._._._._
••
+-- n
og.
cA.CY,C
I ..
Z ••••••

It is, of course, possible to calculate the influence of change

of concentration of certain constituents of the system by the
use of the latter equation. Consider, for example, the per-
manganate reaction:
MnO,- + 8H+ + 5e ~ Mn++ + 4H20
E = EO + 0·0591
5
I [Mn0
og
X [H+]
4- ]
[~In++]
8 * ( t 250C)
a.

The concentration (or activity) of the water is taken as constant,

since it is assumed that the reaction takes place in dilute
solution, and the concentration of the water does not change
appreciably as a result of the reaction. The equation may be
written in the fonn:
E = EO + 0.0591 [Mn04- ] + 0.0591 1 [H+] 8
5 1og [Mn++] 5 og
This enables one to calculate the effect of change in the ratio
[Mn04 -] / [Mn++] at constant hydrogen ion concentration, or
to compute the effect of change in the hydrogen ion concentra-
tion, other factors being maintained constant. In this parti-
cular case difficulties are experienced in the latter calculation
owing to the fact that the reduction products of the perman-
ganate ion vary at different hydrogen ion concentrations. In
* More accurately, e.ctivities should be employed. The square brackets in
heavy black (bold) type denote molecular concentrations.
96 Qualitative Inorganic AnalysM [I,
other cases no such difficulties arise, and the calculation I"ay
be employed with confidence. Thus in the reaction:
HsAs04 + 2H+ + 2e ~ HsAsOs + H 2 0,

E = EO + 0·0591 I [HsAs041 X [H+]2 ( t 2500)

2 og [HsAs04] a ,

or E = EO + 0·0591 I [HsAs 04] + 0·0591 I [H+]2

2 og [HsAsOs] 2 og

The calculation of equilibrium constants of more com}, lex

oxidation-reduction reactions (compare Example 17, Sec' Ion
I, 34) is best illustrated by an actual example.
Example 18. Calculate the equilibrium constant of the reaction:
Mn0 4- + 5Fe++ + 8H+ ~ Mn++ + 5Fe+++ + 4HzO
The equilibrium constant K is given by:
[Mn++] X [Fe+++]5
K=~~~~~~~~~~=
[MnO, ] X [Fe++]5 X [H+]8
The term 4H 2 0 is omitted since the reaction is carried out in <L" lte
solution and the water concentration may be assumed consh nt.
The hydrogen ion concentration is taken as molar.
The complete reaction may be divided into two half-cell react Ins
corresponding to the partial equations:
MnO,- + 8H+ + 5e :? Mn++ + 4HzO (i)
and Fe++ ~ Fe+++ +e (ii)
For (i) as an oxidation-reduction electrode, one has:
E = EO + 0·059 I [&0,-] X [H+]8 i
5 og [Mn++]
= 1.51 + 0·059 I [MnO,-] X [H+]8
5 og [Mn++]
The partial ionic equation (ii) may be multiplied by 5 in order to
balance (i) electrically:
5Fe++ ~ 5Fe+++ + 5e (ii')
For (ii') as an oxidation-reduction electrode:
0·059 [Fe+++]5
E = EO + -5- log [Fe++]Ii'

0·059 [Fe+++]5
= 0·77 + -5- log l'Fe++15
36] The Theoretical Basis of Qualitative Analysu 97
Combining the two electrodes into a cell, the e.m.f. will be zero when
equilibrium is attained:

J.e. 1.51 + 0·059

5
I [l\In0 4-] X [H+r
og [Mn++]
_. 0·059 [Fe+++]5
- 0 77 + ~5- log [Fe++]6
[Mn++] X [Fe+++]6 5(1,51 - 0·77)
or log [MnO" ] X [Fe++]5 X [H+]8 = 0.059 = 62·7

[Mn++] X [Fe+++]6
62
K = [MnO" ] X [Fe++]5 X [H+]8 = 8·5 X 10
This result clearly indicates that the reaction proceeds to completion.

1,36. The Ionic Product of Water.-Kohlrausch and Heid-

weiller (1894) found that the most highly purified water that
can be obtained possesses a small but definite electrical con-
ductivity. Water must therefore be slightly ionised in accor-
dance with the equation:
HzO ?H+ + OH- *
Applying the law of mass action to this equation, one obtains,
for any fixed temperature:
ag+ X tJOH- [H+] . [OH-] fH+ ·foH- ta t
= [H 0] X -1-- = a cons D,
~20 Z . H20

where aX) [xl, and f. refer to the activity, <lOncentration and

activity coefficient respectively of the species x. Since water
is only slightly ionised, the ionic concentrations will be small
and their activity coefficients may be regarded as unity; the
activity coefficient of the unionised molecules may also be
taken as unity. The expression thus becomes:
[H +] X [OH-] = & constant
[HzO]
* Strictly speaking the hydrogen ion exists in wate:r as the hydroxonium
ion H.O+. The electrolytic dissociation of water should therefore b" written:
2H.O ? H.O+ + OH-
On the Lowry-Bronsted hypothesis, water may be rflgarded as undergoing
ionisation as an acid donating a proton to another molecule of water
functioning as a base:
H.O + nlo ? H.O+ + OH-
Acldl Bue2 Acid2 Basel
For the sake of simplicity, the more familiar symbol H+ will be retained,
particularly as in the subsequent discussion the term pH and not p{H.O) ia
employed.
4'4-
 !
98 Qualitative Inorganic Analysis [,

In pure water or in dilute aqueous solutions, the co~ln'ral i'Jn

of the undissociated water may be considered constant. HeJ, --e:
[R+] X [OR-] = K ..
Kw is the ionic product of water. It must be pointed out ti:at
the assumption that the activity coefficients of the ions -, re
unity and that the activity coefficient of water is const ,It
applies strictly to pure water and to very dilute solutions (i(, ic
strength ;:j> 0'01); in more concentrated solutions, i.e. in
solutions of appreciable ionic strength, the electrical envil '1-
ment affects the activity coefficients of the ions and also - 'le
activity of the unionised water. The ionic product of w[,' ~r
will then not be constant, but will depend upon the k ,ic
environment. It is, however, difficult to determine the acti, y
coefficients, except under specially selected conditions, so to Lt
in practice the ionic product K II" although not strictly constant,
is employed.
The ionic product varies with the temperature, hut UD' i lr
ordinary experimental conditions (at about 25°) its value D' ly
be taken as I X 10- 14 with concentrations expressed in gr" n
ions per litre. This is sensibly constant in dilute aque, ,s
solution. If the product of [H+] and [OR-] in aqueous so .t-
tion momentarily exceeds this value, the excess ions will imDiu-
diately combine to form water. Similarly, if the product <If
the two ionic concentrations is momentarily less than 1O-! 4,
more water molecules will dissociate until the equilibrium val!le
is attained. .
The hydrogen and hydroxyl ion concentrations are equal . '1
pure water; therefore:
[R+] = [OR-] = ...;x:_ = 10-7 gram ions per litre at about 2['
A solution in which the hydrogen and hydroxyl ion concenti ,-
tions are equal is termed an exactly neutral solution. If [H ]
is greater than 10-7 , the solution is acid, and if less than 10 "
the solution is alkaline (or basic). It follows that at ordina \'
temperatures [OH-] is greater than 10-7 in alkaline soluti 'l
and less than this value in acid solution.
In all cases the reaction of the solution can be quantitativ£ '.'
expressed by the magnitude of the hydrogen ion (or hydro, .
onium ion) concentration, or less frequently of the hydrox '" I
ion concentration, since the following simple relations betwef '\
[R+] and [OR-] exist:

[R+] = [O~-]' and [OR-] = [~:l

37] The Theore#cal Ba8i8 of Qualitative AnalY8i8 99
The variation of Kw with temperature is shown in Table
I, 36, 1.

TABLE I, 36, 1. IONIC PRODUCT OF W A'l'ER AT VARIOUS TEMPERATURES

Temp. (°0) K .. X 10-14 Temp. (°0) Ko. X 10-14

0° 0·12 35° 2·09
5° 0·19 40° 2·92
10° 0·29 45° 4·02
15° 0·45 50° 5·48
20° 0·68 55° 7·30
25° 1·01 60° 9·62
30° 1·47

1,37. Hydrogen Ion Exponent (pH).-For many purposes,

especially when dealing with small concentrations, it is cumber-
some to express concentrations of hydrogen and of hydroxyl
ions in terms of gram equivalents per litre. A very convenient
method was proposed by Sorensen (1909). He introduced the
hydro~en ion exponent pH defined by the relationships:
1
pH = -lOglO [H+] = PH
log [H+]' or [H+] = lO-

The quantity pH is thus the logarithm of the reciprocal of the

hydrogen ion concentration, or is equal to the logarithm of the
hydrogen ion concentration with negative sign. * This method
has the advantage that all states of acidity and alkalinity
between those of solutions molar (or normal) with respect to
hydrogen or hydroxyl ions, can he expressed by a series of
positive numbers between 0 and 14. Thus a neutral f'olution
with [H+] = 10-7 has a pH of 7; a solution with a molar (or
[lormal) concentration of hydrogen ions has a pH of 0 (= 10°);
~nd a solution molar with respect to hydroxyl ions has
[H+] = Kw / [OH-] = 10- 14/10° = 10- 14 and possesses apH of
14. A neutral solution is therefore one in which pH = 7, an acid
301ution one in which pH < 7, and an alkaline solution one jn
which pH > 7. The greater the hydrogen ion concentration,
ihe smaller is the pH. An alternative definition for a neutral
* Strictly speaking pH should be defined in terms of activity, i.e.
pH = - log aH+ or all+ = l()--pH
3ecause of uncertainties relating to single ion activities, it is usual in approxi-
nate calculations to employ the concentration rather than the activity of the
lydrojen ion when definina: pH. Similar remarks apply to pOH.
 100 Qualitative Inorganic Analys£s [I,
solution is one in which the hydrogen ion and hydroxyl ion
concentrations are equal. In an acid solution the hydrogen
ion concentration exceeds the hydroxyl ion concentration,
whilst in an alkaline or basic solution the hydroxyl ion ('on-
centration is the greater.
Example8.-(i) Find the pH of a solution of which [H +] = 4·0 X
10-6 •
Log 4·0 = 0·602, hence log 4·0 X 10-5 is
5·602 = 0·602 - 5 = - 4·398 11 •
(the decimal part or mantissa of the logarithm is always positiyo).
pH = - log [H+] = - ( - 4·398) =4·398
(ii) Find the hydrogen ion concentration corresponding to
pH = 5·643.
pH = -log [H+] = 5·643; .'. log [H+] = - 5·643
This must be written in the usual form containing a negative charac·
teristic and a positive mantissa:
log [H+] = - 5·643 = 6·357
Referring to a table of antilogarithms, the number corresponding
to the logarithm 0·357 is 2·28; the number corresponding to the
logarithm 6·357 is accordingly 2·28 X 10-6 •
[H+] is therefore 2·28 X 10- 6
(iii) Calculate the pH of a 0·01 molar solution of acetic acid I t he
degree of dissociation is 12·5 per cent).
The hydrogen ion concentration is 0·125 X 0·01 -= 1·25 XIII 3.
Now log 1·25 = 0·097;
:. pH = - ( - 3 + 0·097) = 2·903
The hydroxyl ion concentration may be expressed ill a
similar way:
pOH = - IOglO [OH-] = log [O~-]' or [OH-] = 10-poa
If one writes the equation:
[H+] X [OH-] = Kw = 10-14 ,
in the form:
log [H+]+ log [OH-] = log K .. = -14
then pH + pOH = pK.. = 14.
This relationship should hold for all dilute solutions at ab. ,'It
25°,
38] 'The Theoretical Basi8 of Qualitative AnalY8i8 101
Fig. I, 37, 1 will serve as a useful mnemonic for the relation
between [H+], pH, [OH-] and pOH in acid and alkaline
solution.
The logarithmic or exponential method has also been found
useful for expressing other small numerical quantities which
arise in qualitative analysis. These include (i) dissociation
1 2 8 7 9 10 12 13 14
[H+] 1(10°) 10 10 103 1()4 165 10 10 lOB 10 16 10"10 10 10

'"Ii iiiii liii'iiii

pOH 14 13 12 11 10 9 8 7 6 6 4 3 2 0
[ow] 1014 10-13 1012 10" 1010 10 9 las 107 106 lc;& 104 163 102 101 1(10°)
_ _ _t _ _
Acid 1 Alkaline
Neutral
Fig. I, 37, 1

constants, (ii) other ionic concentrations, and (iii) solubility

products.
(i) For any acid with a dissociation constant of Ka:
1
pK. = -log K. = log
Similarly for any base with dissociation constant Kb:
.
K

1
pKb = -log Kb = log Kb
(ti) For any ion I of concentration [I]:
1
pI = -log [I] = log [1]
Thus for [Na+] = 8 X 10-5 , pNa = 4·1
(iii) For a salt with solubility product S:
1
pS = -log S = log S
I, 38. Determination of the Hydrogen Ion Concentration.
-The hydrogen ion concentration of a solution is of great
importance both in pure and in applied chemistry. Two
methods are commonly employed for its estimation, (a) the
colorimetric method and (b) the electrometric method.
The Colorimetric Method. In this method one employs
what are known as indicators. An indicator is a Bubstance
 102 Qualitative Inorganic Analysis [I,
which varies in colour according to the hydrogen ion con<' 'n-
tration. It is generally a weak organic acid or base all< I is
employed in very dilute solution. The change in colou! is
usually due either to the production of different tautoill' ic
forms of the original substance or to the formation of coloTI "d
ions; the formation of these takes place over a small I iIt
definite pH range. The hydrogen ion concentrations at wI; ·h
different indicators exhibit their colour change have b 'n
determined by direct electrometric methods; the pH ra·· ~e
over which the indicator is applicable is thus known. Ta le
I, 38, 1 summarises the pH values of a number of the ill' ·~·e
common indicators.
There are two methods for the determination of the pH (.: a
solution calorimetrically.
A. Buffer Solution Method. The approximate pH of : e
solution must be found first with the aid of a multiple-raj :fe
indicator solution (for example, the B.D.H. "universal" indi, l,-
tor*), by the systematic use of a number of indicators, or "y
the use of indicator test papers.t A "wide range" or "U.il-
versal" test paper, covering pH 1-2 to 10, is marketed, as ",·n
as anum ber of "narrow range" indicator test papers wh i 11
cover most of the pH range in steps of 1,5-2 pH units. Colo, 1-
matching charts are supplied by the manufacturers to show ti Ie
change in colour at 0·3 pH intervals. The test papers are b(,,,t
used, and their accuracy is greatest, by dipping the papers irl i <)
the fluid: if the test solution is "spotted" on the indicator paper
the colour shade of the spot produced may vary from tllC
centre outwards and some difficulty may be experienced in
deciding which shade to consider as showing the actual pH.
The test papers tend to deteriorate with storage. For tl,o
average observer, it is doubtful whether the test papers pern :'.
the determination of pH closer than to 0,5-1 pH unit, but tI, .
suffices for many purposes.
A series of buffer solutions (Sections I, 39 and A, 4) is selecte·\,
differing successively in pH by about 0·2, covering the p t !
* A "universal" indicator may be prepared, after Bogen, by dissolvi,
0·2 g. of phenolphthalein, 0·4 g. of methyl red, 0·6 g. of dimethylaminoa>
benzene, 0·8 g. of bromothymol blue and 1·0 g. of thymol blue in 1 litre
absolute ethyl alcohol. Dilute sodium hydroxide solution is added dropw, '
until the colour changes to the yellow corresponding to the neutral regie,.
The colours over the pH scale are:
pH 2 4 6 8 10 12
Colour red orange yellow green blue purple
t Manufactured in Great Britain by British Drug Houses Ltd., Poo'
Dorset, and by Johnsons of Hendon Ltd., Hendon Way, London, N.W.,
Equivalent test papers are available in the U.S.A.
38J The Theoretical Ba8is of Qualitative A nalY8is 103
range of the solutions under investigation; the range of buffer
solutions required will be indicated by the preliminary pH

TABLE I, 38, 1. COLOUR CHANGES AND pH RANGE OF SOME

INDICATORS

IColour in Colour in pH
180~;!n
Ohemical f'I41'M alkaline range
8olution
1-----------1-----------------
BrillilLD.t oresyl Amino-diethylamino- II' Red- Blue O-()-l-Q
blue (acid) methyl diphenazonium orange
chloride
IX-Naphthol- Colour- Yellow 0·1)-0·8
benzein (acid) less
Methyl violet Pentamethyl p-rosanilin" Yellow Blue- 0-0..-1-8
hydrochloride green
Cresol red o-Cresolsulphone- Red Yellow 1-2-2'8
(acid) phthalein
'rhymol blue Thymol-suIphone- Red Yellow 1·2-2·8
(acid) phthalein
Meta oresol m-Cresolsulphone- Red Yellow ]-2-2'8
purple phthalein
Bromo-phenol Tetrabromophenol- Yellow Blue
blue sulphone phthalein
Methyl orange Dimethylamino-azo- Red Yellow 3·1-4·4
benzene-sodium
sulphonate
Congo red Diphenyl-bis-azo-IX- Violet Red 3·()-5·0
naphthylamine-4-
sulphonic acid
Bromo-oresol Tetrabromo-m-cresol- Yellow Blue 3·8-5-4
green sulphone-phthalein
Methyl red o-Carboxybenzene-azo- Red Yellow 4·2-6·3
dimethylaniline
Chloro-phenol Dichlorophenol- Yellow Red 4·8-6'4
red sulphone-phthalein
Azolitmin Red Blue 5'()-8'0
(litmUB)
Bromo-thymol Dibromo-thymol- Yellow Blue 6·()-7·6
blue sulphone-phthalein
Diphenol o-Hydroxy-diphenyl- Yellow Violet 7·()-8·6
purple sulphone-phthalein
Cresol red o-Cresol-sulphone- Yellow Red 7·2-8·8
(base) phthalein
IX-Naphthol- ex-Naphthol-phthalein Yellow Blue 7·3-8·7
phthalein
Thymol blue Thymol-sulphone- Yellow Blue 8·()-9·6
(base) phthalein
IX-Naphthol- Yellow BIue- 8·2-10·0
benzein (base) green
Phenol- Phenol-phthalein Colour- Red 8·3-10·0
phthalein less
Thymol- Thymol-phthalein Colour- Blue 9'3-10'5
phthalein loss
BrillilLD.t cresyl (See above) Blue Yellow 10·8-12·0
blue (baBe)

L
104 Qualitative Inorganic Analysi8 [I,
determination. Equal volumes, say 5 or 10 mI., of the bu:ff~ ,
solutions differing successively in pH by about 0·2 are placf :
in test-tubes of colourless glass and having approximately tl '
same dimensions, and a small quantity of a suitable indicat(, i
for the particular pH range is added to each tube. A series of
different colours corresponding to the different pH values i"
thus obtained. An equal volume (say 5 or 10 m!.) of the test
solution is treated with an equal volume of indicator to th;; t
used for the buffer solutions, and the resulting colour is con,
pared with that of the individual coloured, standard buff.
solutions. When a complete (or almost complete) match
found, the test solution and the corresponding buffer soluti(, , I
,I have the same pH within 0·2 p! 1
I 1== , ~I
I-
unit. For matching the colour
the buffer solutions may be arrangE· ;
I I I I
AI I c Il I in the holes of a test-tube stand i '
I I I order of increasing pH; the te,.
I I
,I ,I I I
solution is then moved from hoi,
=-_ =
,
~ -=
-=='
to
is
hole until the best colour mate II
obtained. Special stands and
,~ I I -
I I I I standards for making the com-
B I , I DI I parison are available commercially
I
I I
I I (e.g. from The British Drug Houses
I I Ltd.). The commercial standards,
I I
,, I ,
I I I I prepared from buffer solutions, are
~, , I ,= not permanent and must be checked
I I I 1
L LIGHT _ _ ) every six months.
For turbid or slightly coloured
Fig. I, 38, 1 solutions, the direct-comparison
method given above can no longer
be applied. The interference due to the coloured substance
can be eliminated in a simple way by a device due to
H. Walpole (1916). In Fig. 1, 38, I, A, B, C and D are glass
cylinders with plain bottoms standing in a box, which is
painted dull black on the inside. A contains the coloured
solution to be tested (here the test solution + indicator), H
contains an equal volume of water, C contains a solution uf
known strength for comparison (here the standard buffer
solution + indicator), whilst D contains the same volume of
the solution to be tested as was originally added to A. The
colour of the unknown solution is thus compensated for.
B. Comparator (or Permanent Colour Standard) Method.
In this procedure comparison is made with a series of per-
manent glass colour standards. Nine glass colour standards
38] The Theoretical Basis of Qualitative Analysis 105
are fitted into a disc, and the latter is inserted into a comparator,
which is furnished with four compartments to receive small
test-tubes or rectangular glass cells, and is also provided with
an opal glass screen. The disc can revolve in the comparator,
and each colour standard passes in turn in front of an aperture
through which the solution in the cell (or cells) can be observed.
As the disc revolves, the pH value of the colour standard
visible in the aperture appears in a special recess. The Lovi-
bond comparator* is shown in Fig. I, 38, 2: this may be used
with 13·5 mm. test-tubes or 13·5 mm. rectangular cells. The
comparator is employed with B.D.H. indicators. The colour
discs available include cresol red (acid and base range) thymol
blue (acid and base range), bromophenol blue, bromocresol

y,l!lltIm.Il1'dtJ'IJttll'io.'JH'" 1tti'IIlt.'1llJdf"UII.
~UIfIIJ' l];i'ftt,lJt} I1.llrl/l1 H~ IItU1i1rllIHIl'
I'll ~II(~ I(I~I ""nl jlllIllOt1!1'II\'JIlI.lJltlfll

Fig. 1, 38, 2

blue, bromocresol green, methyl red, chlorophenol red, bromo-

cresol purple, bromothymol blue, phenol red, diphenol purple,
cresol red, thymol blue and the B.D.H. "universal" indicator
-the pH ranges for these indicators are given in Table I, 38, 1.
A determination of the approximate pH of the solution is
first made with a "universal" or "wide range" indicator or
with indicator test papers (see under A), and then a suitable
disc is selected. Ten m}. of the unknown solution is placed
in the glass test-tube or cell, the appropriate quantity of
indicator (usually 0'5 m!.) is added, and the colour is matched
against the glass disc. Provision is made in the apparatus for
• Manufactured by 'The Tintometer Ltd., Milford, Salisbury, England. A
similar apparatus is marketed by Hellige, Inc., of Long Island City 1, N.Y.,
U.S.A.: this utilises Merck's (U.S.A.) indicators. The glass discs in the two
instruments are not interchangeable.
-4*
 I
I
106 Qualitative Inorganic AnalY8i8 [I,
the application of the Walpole technique-by the insertion ',f
a "blank" containing the solution. It is claimed that resu i! s
accurate to 0·2 pH unit can be obtained.
The Electrometric Method. The e.m.f. of a concentrn-
tion cell at 25 0 is given by (Section I, 31):
E = 0·0591 log'l
n C2

It a hydrogen electrode (Section I, 29) is immersed in til(~

solution the pH of which is to be measured, and this half c(·11
coupled with a molar (or normal) hydrogen electrode by mea!
of a potassium chloride solution bridge in order to eliminat
liquid junction potential, the e.m.f. of the resulting cell:
Pt I H 2 , H+ II H 2 , H+ I Pt,
a=1 a=x
may be measured.
0·0591 1 0
Here E = - 1 - log [H+] (at ca. 25 )
=0·0591 pH 1
:. pH = EjO·0591
The use of the molar hydrogen electrode as "a standar,:
electrode or half cell presents certain practical difficulties. I,
is usual to employ some form of the calomel electrode as ;,
secondary standard half cell. A calomel electrode is one iJ;
which mercury and calomel are covered with a potassiun,
chloride solution of definite concentration; this may be O·IN
N, 3'5N or saturated. The potassium chloride solution musi
be saturated with calomel. The potential of, say, the saturated
calomel electrode (i.e. that prepared with saturated potassiurr,
chloride solution) must first be determined with reference k
the molar hydrogen electrode. Let this value be designated
Ecal (sat.). For the measurement of hydrogen ion concentration
one then employs the cell:
Hg I Hg 2 C1 2 , KCl(satd.) II H+, Hzl Pt
Let the resultant e.m.f. be E obs. One then has at 25°:
E ..,. = E"",. (••'.) -0·0591 log [H+],
pH = E obI,
-E . .I. (Ial.)

0·0591
The value of E co1. (sat.) is 0·246 volt at 25°. The corresponding
figures (at 25°) for the decinormal and normal calomel electrodes
are 0·337 and 0·285 volt respectively.
38] The Theoretical Ba.9is of Qualitative Analysis 107
A simple form of calomel electrode suitable for elementary
work is illustrated in Fig. I, 38, 3. It consists of a glass vessel
provided with a bent side tube A and another side tube B,
over the end of which a piece of rubber tubing is placod which
can be closed by a spring or screw clip. Electrical connexion
with the electrode is made by means of a platinum wire, sealed
through a glass tube C; the latter contains a little pure mercury
into which an amalgamated copper wire dips. To set up the
electrode a saturated solution of analytically pure potassium
chloride containing some solid salt is first prepared. Pure
mercury to a depth of about 0·5 cm. is placed in the bottom
of the dry electrode vessel; the mercury is then covered with
a layer of calomel paste. The latter is
prepared by rubbing pure calomel,
mercury and saturated potassium chloride
solution together in a mortar; the
supernatant liquid iR poured off and the
rubbing process repeated twice with
fresh quantities of saturated potassium
chloride solution. The rubber stopper
carrying the glass tube and platinum wire A
is then inserted, care being taken that
the platinum wire dips into the mercury.
The vessel is then filled with a saturated
solution of potassium chloride (previously
saturated with calomel by shaking "\vith
the solid salt) by drawing in the solution
through the bent tube A and then closing
the rubber tube B with a clip. The
electrode is then ready for use.
The preparation of reproducible Fig. 1, 38, 3
hydrogen electrodes is a comparatively
tedious process. The electrode cannot be employed in the
presence of reducible substances or of ions which have
positive electrode potentials (see Table I, 33, 1), such as
copper, silver and gold. Biilmann (1921) introdllced the
quinhydrone electrode; this renders the determination of pH
a rapid and simple process and does not involve the use of
hydrogen gas. The underlying theory is as follows. Let us
consider the reversible reduction of quinone to quinhydrone in
acid solution:
C6H 40 2 + 2H+ + 2e ~ C(lH,(OH)z
This is a reversible o~idation-reduction system and the potential
•
 !
108 Qualitative Inorganic Analysis fl,
of an inert electrode, such as platinum, immersed in the system
is given by:
E =EO +RT I aQ.~+
2F oge n_ ,
-.tl2Q

--EO + RT a RT
2Flog. - +y log.~+,
Cht
Q

2Q

where a Q , lZ:H+, fl:s:2Q are the activities of the quinone, hydrog(,rt

ions and hydro quinone respectively, and EO is the standa! l
potential referred to the molar hydrogen electrode. If til,
solution contains equi-molecular amounts of quinone and hydr ,-
quinone, the ratio of the activities may be regarded as unity:
RT
E = EO + Flog. Cht+ (i)

The sparingly soluble substance quinhydrone is a moleculil r

compound of quinone and hydro quinone, C6H402.C6H4(OH I ,
and dissociates into the two components when dissolved I' 1
water; it follows, therefore, that in the pH range over which
this compound is stable, equation (i) holds. It may therefore
be employed for the determination of pH. EO has been
determined in the usual manner by direct reference to the
molar (or normal) hydrogen electrode, and has a value of 0·704
volt at ISO and 0·699 volt at 25°. By making the usual sub-
stitution for the known values of the constants in equation (i),
one obtains at 25°:
E = 0·699 + 0·0591 log ~+
Thus the potential of the quinhydrone electrode changes with
the hydrogen ion activity in a manner which is exactly similar
to that of the hydrogen electrode.
To determine the pH of a solution, the quinhydrone electrode
may be combined with a calomel electrode, thus forming the
cell:
Hg I Hg 2C1 2 , KCI (satd.) II Solution, quinhydrone I Pt
The potential of the saturated calomel electl-ode, Eeal._ (aat,i'
against the molar hydrogen electrode is 0·246 volt at 25°.
Hence
= 0·699 + 0·0591 log [H+] - 0·246.
= 0·453 + 0·0591 log [H+]
+ _ _ 0·453 - E ok.
-log [H ] - pH - 0.0591
39] The Theoretical Basis of Qualitative Analysis 109
To carry out the determination of the hydrogen ion con-
centration of a solution, about 1 gram of quinhydrone per
100 ml. of the solution is added, and the solution stirred. A
bright platinum electrode is immersed in the solution and the
quinhydrone electrode combined in a cell with a saturated
calomel electrode; a saturated solution of potassiulll chloride
m.1y be used as the salt bridge. The e.m.f. of the cell is
determined and the pH calculated. The e.m.f. is measured by
the potentiometer method based upon the Poggendorff com-
pensation principle; details of this will be found in text-books
of physical chemistry*. It must be pointed out that the quin-
hydrone electrode cannot be employed in alkaline solutions
in which the pH is greater than 8, for the ra,tio of quinone to
hydro quinone is no longer unity"!".
Determinations of pH can be rapidly made with the aid of a
glass electrode and a pH meter: a description of these is outside
the scope of this volume. *
I, 39. Buffer Solutions.-A solution of O·OOOIM hydrochloric
acid should give a pH equal to 4, but the solution is extremely
sensitive to traces of alkali from the glass of the containing
vessel and to ammonia from the air. Likewise a O'OOOIM
solution of sodium hydroxide, which should have a pH of 10,
is sensitive to traces of carbon dioxide from the atmosphere.
Aqueous solutions of potassiulll chloride and of ammonium
acetate have a pH of about 7. The addition of I mI. of molar
hydrochloric acid to 1 litre of the solution results in a change
of pH to 3 in the former case and in very little change in the
latter. The resistance of a solution to changes in hydrogen
ion concentration upon the addition of acid or alkali is termed
buffer action; a solution which possesses such properties is
known as a buffer solution. It is said to possess "reserve
acidity" and "reserve alkalinity. " Solutions of which the pH
values (determined by reference to the hydrogen electrode) are
known, which can be readily prepared and which are unaffected
by small additions of alkali or acid, are required for the colori-
metric determination of hydrogen ion concentration and for
other purposes.
Buffer mixtures usually consist of solutions containing a
mixture of a weak acid or base and its salt. In order to
• A detailed account is also given in the author's Terxt Book of Quantitative
buwganic AnalY8ia: Theory and Practice, Second Edition, 1951 (Longmans,
Green & Co. Ltd.).
t This is partly due to the facile oxidation of hydroquinono in alkaline
solution and partly to the ionisation of hydro quinone as a weak dibasic acid.
The effect of the latter is reduoed in buffered solutions.
<II
 [
110 Qualitative Inorganic Analysis (I,
understand buffer action, let us study first the equilibril,! '1
between a weak acid and its salt. The dissociation of a we" I~
acid HA is given by: \
HA~H++A-,

and its magnitude is controlled by the value of the dissociati'lll

constant Ka:
/Zn+ X a A -
artA
= K., or ag+ = 1ZnA~'.
- X K. :t'. ' .
aA- " ' "
.
Il)

where ax refers to the activity ofthe species X. The expressi(, '

may be approximated by writing concentrations for activiti,'s
(strictly speaking, it will be recalled (Section I, 11), activity.
concentration X activity coefficient):
+ _ [HA]
[H ] - [A-] X K. (ii)

This equilibrium applies to a mixture of an acid HA and it"

salt, say, :MA. If the concentration of the acid be Ca and th;,;
of the salt be c., then the concentration of the undissociate,l
portion of the acid is ca - [H +]. The solution is electricalh'
neutral, hence [A-] = CB +
[H+] (the salt is completely di,,-
sociated). Substituting these values in the equilibrium equa
tion (ii):
+ _ c. - [H+]
[H ] - c + [H+] X K. (iii)

This is a quadratic equation for [H +], and may be solved ill

the usual manner. It can, however, be simplified by intn·
ducing the following approximation. In a mixture of a weai
acid and its salt, the dissociation of "the acid is repressed b\
the common ion effect, and [H +] may be taken as negligibL
small by comparison with Ca and Cg • Equation (iii) then reduce·
to:
[H+] -- 9· K
c,· ., or
[H+] - [Acid] K
- [Salt] X • (iv)

[Salt]
or pH = pKa + log [Acid] (v)

Similarly for a mixture of a weak base of dissociation con

stant Kb and its salt with a strong acid:

[OH-] = [ts:::l X Kb (vi

[Salt] (vu·· I,
or p OH = p K b + Iog [Base]
39] The Theoretical Ba8i8 of Q1:alitative Analysis HI
A simple example is a mixture of ammonia and ammonium
chloride solution: the OH- concentration has a small value,
which is sufficient to precipitate the hydroxides of the Group
IlIA metals with small solubility products but not those of
the metals of the later Groups.
Let us confine our attention to the case in which the con-
centrations of the acid and its salt are equal, i.e. of a half
neutralised acid. Then pH = pKa. Thus the pH of a half
neutralised solution of a weak acid is equal to the negative
logarithm of the dissociation constant of the acid. For acetic
acid Ko. = 1·82 X 10-5,pKo. = 4·74; a half neutralised solution
of, say, O·l1}I acetic acid will have a pH of 4·74. If one adds
a small concentration of H + ions to such a solution, the former
will combine with the acetate iOIlS to form undissociated acetic
acid.
H + + C2H a0 2 - ;:=-~ H. C2H s0 2
Similarly, if a small concentration of hydroxyl ions be added,
the latter will combine with the hydrogen ions arising from the
dissociation of the acetic acid and form unionised water; the
equilibrium will be disturbed and more acetic acid will dis-
sociate to replace the hydrogen ions removed in this way. In
either case, the concentrations of the acetic acid and acetate
ion (or salt) will not be appreciably changed. It follows from
equation (v) that the pH of the f'olution will not be materially
affected.
The solution containing equal concentrations of acid and
salt, or a half neutralised solution of the acid, has the maxi-
mum buffer capacity. Other mixtures also possess consider-
able buffer capacity, but the pH will differ slightly from the
half neutralised acid. Thus in a quarter neutralised solution
of acid, [Acid] = 3 [Salt] :
pH = pKa + log 1/3 = pE. + 1'52,
=pKa -0·48
For a three-quarter neutralised acid, [Salt] = 3[Acid]:
pH = pJ{. + log 3,
=pK. +0·48
In general, it may be stated that the buffering capacity is
maintained for mixtures within the range I acid: 10 salt and
10 acid: 1 salt. The approximate pH range of a weak acid
buffer is:
pH =pK. ± 1;
112 Qualitative Inorganic AnalY8i8 [I,
the concentration of the acid is usually of the order 0·05-0·:!
molar. Similar remarks apply to weak bases.
The preparation of a buffer solution of a definite pH is a
simple process if the acid (or base) of appropriate dissociation
constant is found; small variations in pH are obtained by
variations in the ratio of the acid to the salt concentratioll.
One example is given in Table I, 39, 1.

TABLE I, 39, 1. pH OF ACETIC ACID-SonHJM: ACETATE BUFFER

MIXTURES

10 ml. mixtures of x mI. of O' 2M acetic acid and y m!. of O' 2M

sodiwn acetate

Acetic Acid (x rol.)

I
Sodium Acetate (y ml.) pH I
-I
9·0 1·0 3·72
8·0 2·0 4·05
7·0 3·0 4·27
6·0 4·0 4·45
5·0 500 4·63
4·0 6·0 4·80
3·0 7·0 4·99
2·0 800 5·23
100 9·0 5·57 !
l
i

Before leaving the subject of buffer solutions it is necessary

to draw attention to a possible erroneous deduction from
equation (v), namely that the hydrogen ion concentration of
a buffer solution is dependent only upon the ratio of the con-
centrations of acid and salt and upon K .. , and not upon the
actual concentrations; otherwise expressed, that the pH of such
buffer mixture should not change upon dilution with water.
This is approximately although not strictly true. In deducing
equation (ii) concentrations have been substituted for activities,
a step which is not entirely justifiable except in dilute solution.
Theoretically, the expression controlling buffer action is:

~+ =
aru.
- X
cJ. X K •
K • = ----:r- (viii)
aA - C"'A-

where a and f refer to activities and activity coefficients

respectively of the species indicated in the subscript. The
activity coefficient f .. of an undissociated acid is approximately
~
39] The Theoretical Ba8is of Qualitative AnalY8is 113
unity in dilnte aqueous solution. Expression (viii) thus be-
comes:
[Acid]
tJn+ = [Salt] X fA.- X K. (ix)

or pH = pKa + log [Salt]/[Acid] + log fA.- (x)

The activity coefficient of the ion fA- generally increases with
decreasing ion concentration, so that when a buffer solution is
diluted fA- increases and consequently ~+ will decrease (or pH
will increase). For most practical purposes the change is
small, but for precise measurements the change must be taken
into account. * Thus it has been calculated that if a buffer
solution containing O'IN acetic acid and O·IN sodium acetate
is diluted with an equal volume of water, the pH changes from
4·52 to 4·58. The addition of neutral salts to a buffer mixture
results in a change of the ionic strength of the solution: this
will affect the activity coefficients of the ions and therefore the
pH of the solution. The results (due to R. P. Bell, 1952) for
the pH at 20° of a formate buffer at various ionic strengths I
clearly illustrate this point. The ratio [HCOOH] / [HCOO-]
was maintained at 2·96 throughout.

[HCOOH] [HCOO-] [NaCl] I pH

0·0296 0·0100 - 0'01l 2'18
0·1480 0·0500 - 0·050 2·10
0·2960 0·1000 - 0·100 2·03
0·1776 0·0600 0·0400 0·100 2·03
0·0987 0·0300 0·0667 0·100 2·03

Unless K'M,..,.. is known and activity coefficients are taken

into account, it is advisable for accurate work to check the
pH of the buffer solution by means of the hydrogen electrode.
The following standard buffer solutions have been proposed,
the pH values refer to 25°: O·IM KHC204,H2C204' 2H 20,
pH 1'48; saturated potassium hydrogen tartrate, pH 3·57;
0'05M potassium hydrogen phthalate, pH 4·00; O·IM
CHaCOOH +
O'llJf CHaCOONa, pH 4·64; 0'005M Na2B407,
10H 20, pH 9·18 (see also Section A, 4).
A number of examples of calculations involving buffer
solutions are given below and should be useful to the student.
Interionic effects are not taken into account.
• For- a more detailed discussion, see the author's Text Boole of Quantitative
Inorganic Analysis: Theory and Practice, Second Edition. 195]; R. P. Bell.
Acid8 and Basu. 1952 (Methuen).

"
114 Qualitative Inorganic AfULlysis rr,
Example 19. Calculate the pH in a solution which is O·IM 111
acetic acid and 0·2M in sodium acetate. (Ka = 1·82 X 10-5 )
To a first approximation, equation (v):
+
pH = pK. log [Salt] I [Acid]
= 4·74 + log 2/1 = 4·74 + 0·30
= 5·04
The hydrogen ion concentration in O'lM acetic acid is 1·35 X 10-3 g.
ion per litre (Section I, 14, Example 3), i.e. the solution has a 1) I [
of 2·87.
Example 20. Given a solution which is O'lM in acetic acid all,l
O'lM in sodium acetate, calculate the pH when (a) 1 m!. of lOX
hydrochloric acid and (b) 2 ml. of 5N sodium hydroxide is added to
1 litre of the buffer solution. (The change in volume of the solutiolt
may be neglected.)
The pH of the solution, computed from equation (v), is 4'7!
(a) The hydrochloric acid is completely ionised: it gives a [H+]
10/1,000 = 0·01 g. ion per litre. The 0·01 mole of hydrogen ior
will combine with 0·01 mole of acetate ions to yield 0·01 mole ' :
practically undissociated acetic acid. Hence [C 2H a0 2-] = 0·10
0·01 = 0·09, and [H.CzHa02] = 0·10 + 0·01.
[H+] = K. X [H. C2Ha02]/[C2Ha02 -] = 1·82 X 10-5
X (0·11/0·0(1
= 2·22 X 10-1i
i.e. pH = 4·66
Thus the change in pH upon adding the strong acid is from 4·7 i
to 4·66 only. If the strong acid were added to 1 litre of wak'
(pH = 7·0), the pH change would be from 7·0 to -log (0·01) ,
2·0, i.e. by 5 units. (b) The 2 ml. of 5N sodium hydroxide solutiol!
in 1 litre of water gives a concentration of 0·01 g. mole of NaOJ I
per litre. The 0·01 mole of NaOH will neutralise 0·01 mole of aceti,
acid to form 0·01 mole of acetate ion. Hence [C zH a0 2-] = 0·10 -!
0·01 = 0·11 and [H.0 2H a0 2] = 0·10 - 0·01.
[H+] = 1·82 X 10- 5 X (0·09/0'11) = 1·49 X 10- 5
or pH = 4·83
Thus the change in pH upon adding strong alkali to the acetak
buffer is from 4·74 to 4·83. If the sodium hydroxide solution wer::
added to 1 litre of water, [H+] = Kw / [OH-] = 10- 14 /0.01 =
1·0 X 10-12 , or pH = 12: thus the change in pH is from 7·0 to 12,
i.e. by about 5 pH units.
1,40. HYDROLYSIS OF SALTS
Salts may be divided into four main groups:
I, those derived from the strong acids and strong bases, e,g.
potassium chloride; .
40] The Theoretical Basis of Qualitative Analysis ll5
II, those derived from weak acids and strong bases, e.g.
sodium acetate;
III, those derived from strong acids and weak bases, e.g.
ammonium chloride; and
IV, those derived from weak acids and weak buses, e.g.
ammonium formate or aluminium acetate.
When any of these is dissolved in water, the solution, as is
well known, is not always neutral in reaction. Interaction
occurs with the ions of water and the resultant solution may
be neutral, acid or alkaline according to the nature of the salt.
With an aqueous solution of a salt of group I, neither the
anions have any tendency to combine with hydrogen ions nor
the cations with the hydroxyl ions of water. The equilibrium
between the hydrogen and hydroxyl ions in water:
H 20 ~ H+ + OH- (i)
is therefore not disturbed and the solution remains neutral.
Consider, however, a salt MA derived from a weak acid HA
and a strong base MOH of the conventional or Arrhenius type
(group II). The salt is completely dissociated in aqueous
solution:
MA ~Mt +A-
A very small concentration of hydrogen and hydroxyl ions,
originating from the small but finite ionisation of 'vater, will
be present initially. HA is a weak acid, that is, it is ionised
only to a small degree; the concentration of A - ions which can
exist in equilibrium with H + ions is accordingly small. In
order to maintain the equilibrium the large initial concentration
of A-ions must be reduced by combination with H + ions to
form unionised HA:
H+ +A- ~HA (ii)
The hydrogen ions required for this reaction can be obtained
only from the further dissociation of the water; this dissociation
produces simultaneously an equivalent quantity of hydroxyl
ions. The hydrogen ions are utilised in the formation of HA,
consequently the hydroxyl ion concentration of the solution
will increase and the solution will react alkaline. The net result
is that the anions of the salt react with the hydrogen ions of
water yielding the weak acid HA, and there is an increase in
the concentration of hydroxyl ions over that present in water.
It is usual in writing equations involving equilibria between
completely dissociated and slightly dissociated or sparingly
t
116 Qualitative Inorganic AnalY8i8 [I,
soluble substances to employ the ions of the former and t I if]
molecules of the latter. The reaction is therefore written:

This equation can also be obtained by combining (i) and (ii)

since both equilibria must coexist.
This interaction between the ion (or ions) of a salt and ti"l
ions of water is called hydrolysis. Formerly the chemi(';d
reaction was written:
MA + H 20 ~MOH +HA,
or as:
Salt + Water ~ Base + Acid
The reaction of the solution was clearly dependent upon tL"
relative strength of MOH and HA. This led to the origin" i,
but now obsolete, definition of hydrolysis as the decompositi( d\
of a salt by water into an acid and a base.
Let us now study the salt of a strong acid and a weak ba,·
(group III). The two types of weak bases commonly e"
countered are metallic hydroxides (such as ferric, aluminiu! I,
or cupric hydroxides) and ammonia or primary amines RNH~.
The ultimate ionisation of the former is:
M(OH)n ~ Mn+ + nOH-
The basic character of ammonia and of amines is be,.;!
represented as:
RNH2 + H 20 ~ RNHs+ + OH- ___ _ _
The alternative formulation:
RNH2 + H 20 ~ RNHs.OH ~ RNHs+ + OH-
is regarded as less probable, owing to the doubtful existence of
RNH3 . OH; it leads, however, to the same result. Since those
metallic hydroxides which are weak bases are usually poly-
acidic and therefore can ionise in stages, it will simplify the
discussion if we confine our attention to weak organic bases
of the type RNH 2 , where R = H, alkyl or aryl. We may
represent such bases by the symbol B. A salt of such a weak
base and a strong acid may be formulated (BH)A: an example
is ammonium chloride (NH3H)CI or NH4Cl. In an aqueous
solution of a salt (BH)A, the initial high concentration of
cations BH+ will be reduced by interaction with the hydroxyl
ions of water to form the weak base B (or BH . OH, its hydrated
form) until the equilibrium,
BR+ + OH- ~ B + H 20 (= BR.OH) (iv)
41] The Theoretical Basis of Qualitative Analysis 117
is attained. The hydrogen ion concentration of the solution
will thus be increased and the solution will have an acidio
reaction. The hydrolysis is here represented by:
BH+ + H 20 ~ B + H30+ (v)
or, less probably but possibly more clearly, by:
BH+ +H 20 ~ EH.OH + H+
For salts of group IV in which both the acid and the base
are weak, two reactions will occur simultaneously:
A- + H 20 ~ HA + OH- (vi)
BH+ + H 2 0 ~B + HaO+ (vii)
The acidic or basic reaction of the solution will clearly depend
upon the relative strengths or dissociation constants of the
acid and base. If they are equal in strength, the solution will
be neutral; if Ka> K b , it will be acidic; and if Ku > K a, it
will be basic or alkaline.
Having considered the possible cases, we are now in a
position to give a more general definition of hydrolysis.
Hydrolysis is the interaction between the ion (or ions) of a.
salt and the ions of water with the production of (a) a weak
acid or a weak base or (b) of both a weak acid and a weak base.
I, 41. Hydrolysis Constant and Degree of Hydrolysis.
Case 1. Salt of a Weak Acid and a Stron~ Base. The equi-
librium in solution of a salt MA may be represented by:
M+ + A- + H 2 0 ~ M+ + OH- + HA,
or by A- + H 20 ~ OH- + HA (i)
Applying the law of mass action, one obtains:
aOH - X ~A = [OH-] . [HA] X IOH-. IRA = Kh (ti)
aA - [A ] J...-
where a, f and [] refer to activities, activity coefficients and
concentrations respectively, and Kh is the hydrolysis constant.
The solution is assumed to he dilute; the activity of the
unionised water may be then taken as constant. In dilute
solutions, the ionic strength is small, and the approximation
that the activity coefficient of the unionised acid is unity and
also fOH- IfA - = 1 may be introduced. Equation (ii) then
reduces to:
(iii)
lIS Qualitative bwrganic Analysi8 [I,
This is often written in the form:
X _ [Base] X [Acid] (iv)
h - [Unhydrolysed Salt]
the free strong base and the unhydrolysed salt are completely
ionised and the acid is very little dissociated.
The degree of hydrolysis is the fraction of each gram molecule
hydrolysed at equilibrium. If c is the concentration of the
salt in gram moles per litre and x is the degree of hydrolysis,
then the concentrations of the various species in gram moles OJ"
gram ions per litre are:
[OH-] = xc; [HA] = xc; and [A -] = (I - x)c
The substitution of these values in (iii) gives: Ij j
X = [OH-] X [HA] = xc X xc = ~ (v)
h
[A ] (I - x)c (I - x)
The expression enables one to calculate the degree of hydrolysi~
x from the value of the hydrolysis constant Kh and the COli
centration c. It is evident that as the concentration is d( >

creased (i.e. the dilution is increased), the degree of hydrolysl '

x must increase. The expression (v) is a quadratic equatioJ!
for x and the solution is:
x = _ Xl>
2c
+JKh 2 + X h
4c 2 C
(vi)

If x is small « 2-5 per cent), (v) reduces to Kb = x 2c

and x = vi Kb/c (vii)
The two equilibria:
H 2 0 ~H+ + OH-,
and HA =H+ +A-,
must coexist with the hydrolytic equilibrium:
A- +H 2 0 ~HA + OH-
Hence the two relationships:
[H+] X [OH-]=Kw
and [H+] X [A-] / [HA] = K.,
must hold in the same solution as:
[OH-] X [HA] / [A-] = Xb
B t K .. = [H+] X [OH-] X [HA] _ [OH-] X [HA] = K
U K. [H+] X [A ] - [A ] b,

therefore K.,. / K. = Kb {viii\

or pKb = pK... - pK.
41] The Theoretical Basis oj (!talitative Analysis 119
The hydrolysis constant is thus related to the ionic product of
water and the ionisation constant of the acid. Since K", varies
slightly and Kw varies considerably with temperature, Kh and
consequently the degree of hydrolysis will be largely influenced
by changes of temperature.
The hydrogen ion concentration of a solution of a hydrolysed
salt can be readily computed. The amounts of HA and OH-
ions formed as a result of hydrolysis are equal, therefore in a
solution of the pure salt in water [HA] = [OH-].
If the concentration of the salt is c gram moles per litre, then:
[HAl X [OH-] _ [Qlr-]~ _ K _ Kw
[A ] - c - b - K:
and [OH-] = J~'K.Kw (x)

or [H+] = JK...~K:, since [H+] = K ... /[OH-] (xi)

:. pH = tpKw + ~pKa + t log c * (xii)

It follows, therefore, that the pH of the solution increases with
increasing concentration of the salt, although the degree of
hydrolysis decreases.
Equation (xii) can be employed for the calculation of the
pH of a solution of a salt of a weak acid and strong base.
Thus the pH of a O,o5M solution of sodium benzoate is given
by:
pH = 7·0 2·10 + +
:!(--I'30) = 8·45
(Benzoic acid: Ka = 6·37 X 10-5 ; pK. = 4·20)
Such a calculation will provide useful information as to the
indicator which should be employed in the titration of a weak
acid and strong base. An explanation is thus given for the
use of phenolphthalein (pH range 8-3 - 10'0) in the titration
of benzoic (or acetic) acid with strong bases.
Example 21. Calculate (1) the hydrolysis constant, (2) the degree
of hydrolysis and (3) the hydrogen ion concentration of a 0-1 molar
solution of sodium acetate at the laboratory temperature.
Kb = Kw / K. = 1·0 X 10- 14 /1.82 X 10-5 = 5·5 X 10- 10
The degree of hydrolysis x is given by Kb = x 2c / (1 -
x). Sub-
stituting for Kb and c, and solving the quadratic equation for x,
one obtains x = 7·5 X 10-5 or 0-0075 per cent.
* To be consistent one should write p. = -log c.
120 Qualitative Inorganic Analysis r I,
Alternatively, x may be deduced by substituting in equations i \ i)
or (vii)
C2H a0 2 - + H 2 0 ~ H.C2 H 3 0 2 + OH-
I mole 1 mole 1 mole
If the solution were completely hydrolysed, the concentration "f
acetic acid produced would be O·IM. But the degree of hydrol,} ,s
is 0·0075 per cent, therefore the concentration of acetic acid ;8
7·5 X 10- 6 M. This is also equal to the hydroxyl ion concentrati, '11
produced, i.e. pOH = 5·13.
pH = 14·0 - 5·13 = 8·87
The pH may also be computed from equation (xii):
pH = !pKw + ipK. +
t log c
= 7·0 + 2·37 + !( - 1) = 8·87
If the degree of hydrolysis is calculated for a O'OIM solution, ,I'
sodium acetate, it is found to be 0·0235 per cent, and the pH is 8·3·~.
Example 22. Calculate (1) the degree of hydrolysis and (2) tl
pH of a 0·1 molar solution of sodium sulphide at the laboratof .
temperature. (For H 2S: Kl = 9'1 X lO-8; K2 = 1·2 X 10-15 .)
The hydrolysis of the sulphide ion takes place in two steps:
S-- +
H 2 0 ~ HS- +OH-
and HS- + H 20 ~ H 2S +
OH-
The contribution of the OH- ions from the second step is negligibJ \
small and hence only the primary hydrolysis need be considere( j
The HS- is effectively the weak acid in this reaction, hence tb
secondary ionisation constant (K2 = [S--] X [H+] / [H2S]) j
employed in the calculation of the hydrolysis constant.
Kh =K... / K. = 1·0 X 10-14 /1·2 X 10-15 = 8'~

Let x be the degree of hydrolysis, then: -

K = 8.3 = [HS-] X [OH-] =~ = 0'lx 2
h [S] (1 - x) (1 - x)
i.e. x2 +83x - 83 = 0
or x = 0·99 or 99 per cent
The sulphide ion concentration = (1 - x)c = 0·01 X 0·1 = 0·00 I
mole per litre. Since the solution is almost completely hydrolysed
the hydroxyl ion concentration will be almost 0·1 mole and the pH
accordingly 13.
Example 23. (a) Calculate (1) the degree of hydrolysis and (2)
the pH of a 0·1 molar solution of sodium carbonate; also (b) calculate
the pH of a 0·1 molar solution of sodium bicarbonate at the labora-
tory temperature. (For H 2C03 : Kl = 4·31 X 10-7 ; K2 = 5·61 X
10-11 .)
41] The Theoretical Basis of Qualitative AnalY8i8 121
(a) The hydrolysis of the carbonate ion takes place in two stages
COs-- + ~O ~ HCO a- + OH- (il
and HCOa- + H 2 0 ~ H 2 00S + OH- (ii)
The contribution of the OH- ions from the second step is very
small since H 2C0 3 is not so weak an acid as H00 3- and also the
OH- ions produced in (i) will tend to diminish the hydrolysis of
HCO s- in (ii), hence only the primary hydrolysis need be considered.
Kb = K" / Ka = 1·0 X 10-14 / 5·61 X 10- 11 = 1·79 X 10- 4
Let x = degree of hydrolysis, then:
Kb = 1.79 X 10-4 = tHCOs -] X [OH-] = x 2 X 0·1
[COs ] (1 - x)
or x = 0·0414 or 4·14 per cent
The value of x deduced from the approximate expression x =
\I' Kh / C is 0·0423. i
pH = IpK" + IpK, + ~ log c .
= 7·0 -+- 5·13 + t( -
1) = 11·62
(b) The hydrolysis of the bicarbonate ion may be written:
HCOs- + H 20 ~ H 2 C03 + OH- (iii)
The ionisation of the bicarbonate ion itself must also be taken into
account:
HCOs- ~ CO a-- H+ + (iv)
this is, in fact, th~ secondary ionisation of carbonic acid. Since the
equilibrium:
H+ + OH- ~ H 2 0 (v)
coexists with (iii) and (iv), we may write:
2HOOs- ~ H 2 COs COs-- + (vi)
Upon combining the equations for the primary and secondary dis-
sociation constants for carbonic acid, we obtain:
[H+] X [HCOs-] [H+] X [C03 - - ] [H+]2 X [COs--]
[H 2COa] .• . [HCO ]
s
--[H 2 CO S] - -
= KI X K2 = 2·42 X 10 -17 (vii)
Now [H 2 CO S] = [C03 - - ] by equation (vi), hence:
[H+]2 = KI X K2 = 2·42 X 10- 17
[H+] = \1'2·42 X 10- 17 = 4·91 X 10-9 gram ions per litre
or pH = 8·31
The experimental value obtained by glass electrode measurements
is pH = 8'18, indicating that the cal culation is sUbstantially correct.
Case 2. Salt of a Strong Acid and a Weak Base. For the
sake of simplicity we will consider the salt (BH)A derived from
122 Qualitative Inorganic Analysis [I.
a weak organic base B and a strong acid HA (see Section I, 40.
The hydrolytic equilibrium is represented by:
BH+ + H 20 ~ B + HsO+ (xiii)
By applying the law of mass action along the lines of Oase I.
the following equations are obtained:
K _ [HsO+] X [B] _ [Acid] X [Base] Kw (xiv)
b - [BH+] - [Unhydrolysed Salt] = Kb
x 2c
(xv',
(1 - x)
The dissociation constant of the base

-'
.... },
Furthermore, since [B] and [HsO+] are equal {equation (xiii)
K _ [HsO+] X [B] _ [HsO+]2 _ [HsO+]2 _ K.., (xvi)
h - [BH+] - (1 - x)c - c - Kb
It is assumed that x is small «2-5 per cent)

Hence [HsO+] = JKK~C (xvii)

or pH = lpK.., - lpKb - 1 log c (xviii)

It is evident from equation (xv) that the degree of hydroly:,;"l
x increases with dilution and with decreasing strength of baf' ;
also that the pH of the solution must be less than !pKw = "
i.e. the solution has an acidic reaction.
Equation (xviii) can be applied to the calculation of the l' I [
of solutions of salts of strong acids and weak bases. Thus L·(j
pH of a 0'2M solution of ammonium chloride is:
pH = 7·0 - 2·37 - H-0·70) = 4·98
(Ammonia: Kb = 1·8 X 10-6 ; pKb = 4·74)
Example 24. Calculate (1) the degree of hydrolysis and (2) 1 fie
pH of a 0·1 molar solution of ammonium chloride at the laborat( , y
temperature.
The hydrolysis may be written as :
NH, + + H 2 0 ~ NHs + HsO+
Kb = Kw / Kb = 1·0 X 10-14 /1·8 X 10- 6 = 5·6 X 10-10
Now Kb = x 2 c i (1 - x), where x is the degree of hydroly~i.'.
Substituting for Kb and c, and solving the quadratic equation for .c,
we find
x = 7·5 X 10-6 or 0·0075 per cent
41] The 'l'heoretical Basis of Qualitative Analysis 123
Alternatively x may be calculated from the relation x = V Kh / c.
The concentration of hydrogen ion = xc = 7·5 X 10-5 X 0·1 =
7·5 X 10-6 g. ion per litre, or pH = 5·13.
Oase 3. Salt of a Weak Acid and a Weak Base. The hydro-
lytic equilibrium in a solution of a salt (BH)A, derived from a
weak organic base B and a weak acid HA, is expressed by the
equation:
BH+ + A- + 2H2 0 ~ H30+ + OH- + B + HA (xix)
Since the normal equilibrium 2H 2 0 ~ H30+ +
OH- exists in
any case, this may be subtracted from (xix); the result may be
represented:
BH+ + A- ~~ B + HA (xx)
The equilibrium constant is given lIy:
Kh = !La X aHA = [B]_:_ [H~L X }B ·fRA (xxi)
a BH + X aA - [BH+] . [A-] JSH+ .JA-
By making the usual approximations, that is, by assuming
that the solution is dilute so that the activity coefficients of
the unionised molecules and, less justifiably, of the ions may
be taken as unity, the following approximate form of (xxi) is
obtained:
[B] X [HA]
Kh = [BH+] X [A --] (xxii)

[Base] >< [Acid]

(xxiii)
= [Unhydrolysed Salt]2
If x is the degree of hydrolysis in a solution of concentration
c gram mols per litre, the individual concentrations are:
[B] = [HA] = xc ; [BH+] = [A-] = (1 - x)c
By substituting these values in (xxii), we obtain:
K _ __ xc X xc _ X2
(xxiv)
h - (1 _ x)c X (1 - x)c (1 - x)2
Furthermore, as in Oase 1, the expressions: Kw = [H +] X
[OH-], Ka = [H30+] X [A-]/[HA], and Kb = [BH+]
X [OH-] I [B], hold simultaneously with equation (xxi) for
the hydrolytic equilibrium. By substitution in (xxi) it can
be readily shown that:
Kh = Kw / (K. X K b ) (xxv)
The solution of equation (xxiv) for the degree of hydrolysis
x is:
x = VKh / (1 + VE".) (xxvi)
•
 I
124 Qualitative Inorganic AnAlysis [I.
If Kh is small in comparison with unity, then:
v
x = Y Kh = K.., I (K. X K b ) (xxvii)
'rhis expression, and also (xxv), enable one to calculate x froll]
the dissociation constants of the acid and the base.
The hydrogen ion concentration of the hydrolysed solutilill
is computed in the following manner:
[HsO+] =K. X [HA] I [A -] =K. X xci (1 - x)c = K. X xl (1 - /)
By equation (xxiv) xj(l - x) = yKh , thus:
[HsO+] = K. X yKb = YK.., X K. I Kb (xxvi;.
or pH = fpK.., + ipK. - tpKb (xxix)
It follows from equations (xxiv) and (xxix) that the degree /
hydrolysis and the pH are independent of the concentration of ti, ,
salt; the weaker the acid and the base, the greater will be the extf" ,
of hydrolysis. This is strictly true only if [BH+] = [A-] al l
[B] = [HA] as assumed above: this condition will be realised t
K. = Kb or at least are approximately equal. If the acid BI-I"-
and the base A-have different strengths, they will intereact with
water to different extents (see Section I, 40) and consequently ,t
equilibrium [BR +] and [A -] are not necessarily equal; simi! c
remarks apply to the equilibrium concentrations of Band B '.
Fortunately, except in very dilute solution, no significant errors 1., )
introduced unless K. and Kb differ by several powers of 10.
If the dissociation constants of the acid and the base fi' 'l
equal, that is, K .. = K b , pH = tpKw = 7·0 and the soluti,,'l
is neutral although hydrolysis may be considerable. i f
K .. > K b , pH < 7 and the solution is acidic; when Kb > JI "
pH > 7 and the solution reacts basic or alkaline.
The pH of a solution of ammonium acetate is given by:
pH = 7·0 + 2·37 - 2·37 = 7·0,
i.e. the solution is approximately neutral. On the other hand,
for any solution of ammonium formate:
pH = 7·0 + 1·88 - 2·37 = 6·51,
(Formic acid: K. = 1·77 X 10- 4; pK. = 3·75)
i.e. the solution reacts slightly acid.
Example 25. Calculate the degree of hydrolysis of a 0·1 J[
solution of ammonium acetate at the laboratory temperature.
The hydrolytic reaction is:
NH4 + + C2 H s 0 2 - ? NHs + H. C2 H s0 2 - {cf. equation (xx)}
Kb = [NHs] X [H . C2 H s 0 2] I [NH4 +] X [C2H s0 2-]
= K."I (K. X E t,)
= 1'0 X 10-a / (1'82 X 10--6 X 1·8 X 10-6) = 3·1 X 10-6
42] The 'l'heoretical Basi8 of Qualitative AnalY8i8 125
Kh is clearly small in comparison with unity and we may therefore
use equation (xxvii):
x = VK h = Y=3-C::·1- x---=1=O-:'-6 = 5·5 X 10-3 or 0·55 per cent
I, 42. Hydrolysis and the Proton Theory of Acids and
Bases.-If the BrOnsted-Lowry definitions of acids and bases
(see Section I, 6) are adopted consistently, the term hydrolysis
loses much of its original significance. The older and, indeed,
firmly established definitions of hydrolysis are merely examples
of acid-base reactions when considered in the light of the proton
transfer theory of acids and bases.
Before discussing the subject in detail, it is desirable to deal
more fully with the subject of acid and conjugate base. The
relationship is:
A (acid) ~ H+ (proton) + B (base); i
the acid A and the base B, which differ by a proton, are said
to be conju~ate to one another. Every acid must, in fact,
have its conjugate base and every base its conjugate acid.
The interaction of an acid Al of one system with a base B2
of another system may be represented by:
Al + B2 ~ BI + A2,
Acid l Base. Basel Acid 2
where Al and BI are the conjugate acid and base of anyone
system, and A2 and B2 are those of the other system. Free
protons, because of their great reactivity and small size, do not
exist to any extent in solution, and hence the acidic or basic
functions of any molecule or ion cannot become manifest unless
the solvent molecules can act as proton acceptors or donors
respectively, i.e. the medium itself must have basic or acidic
properties. Solvents are divided roughly into three categories
according as the molecules are (I) proton acceptors, i.e. basic
or protophilic; (2) proton donors, i.e. acidic or protogenic; or
(3) neither acceptors nor donors, i.e. aprotic. A solvent, such
as water or an alcohol, which is both protophilic and protogenic
is said to be amphiprotic. We will confine our attention to
water: the conjugate acid and base can function simultaneously
and we will study their relative dissociation constants in a
given medium.
Water can combine with a proton to give the hydroxonium
ion HaO+, or it can lose a proton to form the hydroxyl ion OH-.
The equilibria between the solvent (water) and (a) the acid HA
and (b) its conjugate base A- may be written:
(a) HA + H 2 0 ~H30+ +A- and (b) A- + H20~HA + OH-
(,
126 Qualitative Inorganic Analy&i8 (I,
The dissociation constants of acid and conjugate base in WE' t'lr
are:
K. = lln30+ X ac / ~ and Kb = alIA X a on - / a A- (i)
The solvent (water) can itself function as an acid and a a
base, thus leading to the equilibrium
H 2 0 + H 2 0 ~ HaO+ + OH-;
if the activity of the solvent is assumed to be unity in dib t e
solution, then:
Kl( = lln30+ X a on - (ii)
The quantity Kw is, of course, the ionic product of watt']'.
Upon combining equations (i) and (ii), we obtain the relatioll-
ship: .
(iii)
that is, the dissociation constant of an acid is inversely P")-
portional to' that of its conjugate base, and vice versa, in wa!· r
(an amphiprotic medium). Otherwise expressed, if the acid is
strong, the conjugate base will be weak; if the acid is we: I.,
the conjugate base will be strong.
The question of strengths of bases is usually treat· 1
separately from acids, but on the proton theory of acids alili
bases this is really unnecessary, since any protolytic reacti')l1
involving an acid must also involve its conjugate base. Tid)
older method of evaluating basic strength depended upon tf I)
OH- concentration produced in an aqueous solution of a ba- '.
Thus the basic dissociation constant of ammonia (NH3 +
HI)
~ NH4 + + OH-) was given by:
Kb = [NH4+] X [OH-:] / [NH a] *
The acid dissociation of the ammonium ion may be writt, i\
as:
NH4+ ~ NHa + H+ (i v)
this is an abbreviation of:
NH4+ + H 2 0 ~ NHa + HaO+ (v)
* The symbol [NH 31 represents the total concentration of undissociat. d
ammonia, irrespective of whether it is present as NH3 or as NH.OH. The tv.. )
species are related by the equilibrium NH3 + H 2 0"" NH.OH: since wakr
is present in large excess, the ratio [NH 31 I [NH.OH] will be the same in i l
dilute solutions at the same temperature, hence the form of any equilibril . l
expression will not be affected by taking into account partial hydration :'
the undissociated ammonia. If the equilibrium is written NH•. OH . ~
NH.+ + OH-, the numerical value for Kb will be the same order sin,·,·
[NH.OH] is always taken as equal to the activity (or concentration) of t!
whole of the ammonia which is not ionised. In actual fact, it is doubt!
whether the true NH.OH exists: it may be a loose hydrogen.bonded compl, .
between ammonia and a water molecule.
42] The Theoretical Basi8 of Q~litative Analysis 127
The acid dissociation constant of the ammonium ion is:
K B.L . = [NHg] X [H+] / [NH4+] (vi)
Since, to a first approximation, Kw = [H +] X [OH-], we have:
Kb = Kw/ KB .L . (vii)
This expression enables one to express the "conventional"
basic dissociation constant in terms of its conjugate acid.
Neutralisation, in the classical sense, may be described as
the reaction between equivalent amounts of acid and base
(both defined according to Arrhenius) with the production of
a salt and water:
HA + MOH = l\IA + H 20
If the terms acid and base are employed in the Br<:>nsted-Lowry
sense, the product is not necessarily described as a si1lt and
water. The general expression for an acid-base reaction is, as
we have already seen in Section I, 6, an example of a proton-
transfer or protolytic reaction:
HA + B = BH+ + A-
Acid l Basel Acid, Basel
The products of such a reaction are the conjugate acid and the
conjugate base of the reactants. If the acid HA and a con-
ventional strong base MOH are neutralised, we may write the
reaction:
HA + M+ + OH- = M+ + A- + H 20
Acid l Basel Basel Acid l
The anion of the acid is thus regarded as a base.
A displacement reaction between the salt of a weak acid and
between a strong acid is a neutralisation from the Bronsted-
Lowry standpoint. A simple example is:
HCI + Na+ + C2H s0 2- ~ Na+ + Cl- + H.C 2H s0 2
Acid l Base, Basel Acid.
The neutralisation of ammonia or a primary amine by an acid
may be expressed:
HA + RNH2 ~ A- + RNHs+
Acid l Base, Basel Acid g
The displacement reaction involving the salt of a wenk base
and a strong base can also be regarded as a neutralisation, for
example:
NH4+ + CI- + Na+ + OH- ~ NH3 + H 2 0 + Na+ + or
Acid l Base. Basel Acid g
The extent to which a neutralisation reaction (HA B ~ +
+
BH + A -) proceeds will depend, not only upon the relative
c
128 Qualitative Inorganic Analysis
strengths of the two acids concerned, but also upon the nat,., e
of the solvent. We are primarily concerned with water, ,n
amphiprotic solvent, which can act as an acid and a base !t
may interact with the neutralisation products in two ways:
(a) BH+ + H 20 ~ B + HsOT
Acid l Base. Basel Acid.
and (b) A- + H 20 ~ HA + OH-
Basel Acid. Acid l Base.
In (a) the original base is reformed, whereas in (b) the origj d
acid is produced. Hence, in addition to primary neutral, L-
tion, further interaction may occur with the solvent wh h
leads to the partial reversal of the neutralisation. The la1: ,)r
is an example of a general phenomenon known as solvoly~is:
when the solvent is water, it is termed hydrolysis.
The strength of an acid or a base is, according to equat;.n
(vii), inversely proportional to that of its conjugate form. If
the acid HA (e.g. Hel) is strong, its conjugate base A - (e.g. ( -)
will be very weak and hydrolysis (b) occurs to a negligli'le
extent. If the base used for neutralisation is also strong ( g.
Na+OH- or, effectively, OH-), the conjugate acid (e.g. H ,))
will be very weak and consequently reaction (a) will be of Ii· . Ie
importance. It is clear, therefore, that neutralisation betw· ·m
a strong acid and a strong base in aqueous solution will proc, !)d
to completion and no hydrolysis will occur. A necesf" ry
corollary is that the salt of a strong acid and a strong base ' ill
not be hydrolysed in aqueous solution. When the salt is
derived from a weak acid or a weak base or from both a w. ILk
acid and a weak base, the corresponding conjugate form :)r
forms will be strong, and appreciable hydrolysis will ensue.
The three cases to be considered are those involving (1) a weak
acid, (2) a weak base and (3) both a weak acid and a weak base.
Each of these will be studied in detail.
Let us first consider the hydrolysis of the salt MA (e.g.
sodium acetate) of a weak acid HA and a strong base (" 'y,
M+OH-) from the Br5nsted-Lowry standpoint. The acid iiA
is weak, consequently the conjugate base A- is reason8' ,Iy
strong. We have the equation (the ions of the metal ai, ,m
play no part in the reaction):
A - + H 2 0 ~ HA + OH- (viii)
Basel Acid. Acid I Base.
This equation for the hydrolysis reaction is identical with that
given in Section I, 41, although the terminology is different.
42] The Theoretical Basis of Qualitative Analy8i8 129
The expression for the equilibrium oonstant of this reaotion,
previously termed the hydrolysis constant, might more suitably
be called an acid-base equilibrium constant K B•L .; its magnitude
is, however, the same irrespective of its name.
The case of the salt (BH)A of a strong acid HA and a weak
base B may be treated similarly. '1'0 avoid misunderstanding
of the general case, let us consider first the specific case of
ammonium chloride. This salt may be regarded as derived
from the weak base ammonia and the strong acid, hydrochloric
acid. ':'".1.ld weak base NHs will have NH.t + as its conjugate
acid and the latter will have appreciable strength: this is, in
fact, the ion derived from the completely dissociated ammonium
chloride. The hydrolytic equilibrium is therefore represented
as:
NH,+ + H 20 ~ NHs + HsO+ (ix)
For the general case of the salt {BH+)A-, the equilibrium may
be written:
(x)
(The anion, e.g. chloride or nitrate, has no appreciable acidic
or basic properties sinee it has no detectable tendency to react
with the solvent, and therefore will not take part in the equi-
librium.) The equilibrium expression for (ix) may be written:
K - [NHaJ X [HaO+] (xi)
B.L. - [NH,+]
where K B.L . is the equilibrium constant; it is identical with
the acid dissociation constant for the ammonium ion { equation
(vi) }. The equilibrium constant for (x) is given by:
K _ [B] X [HsO+]
B.L. - [BH+] (xii)

_ [Base] X [Acid]
(xiii)
- [Unhydrolysed Salt]
This expression is identical with that deduced on the basis of
classical theory in the previous Section.
When considering a salt constituted from a weak acid HA
and a weak base B, it will be realised that the respective con-
jugate base A-and conjugate acid BH+ have appreciable
strength, and so both react with the solvent thus:
A- + H 20 ~ HA + OH- (xiv)
BH+ + H 20 r? B + HsO+ (xv)
By combining both equations, we have:
BH+ + A- + 2H O ~ HsO+ + OH- + B + HA
j (xvi)
130 Qualitative Inorganic Analys'" [I,
Since the equilibrium 2H 2 0 ~ H30+ + OH- exists in any ( lse,
we may subtract it from (xvi):
BH+ + A- ~ B + HA (xvii)
Unhydrolysed salt Free base Free acid
The approximate equilibrium constant is given by:
K _ [B] X [HA] (x,iii)
B.L. - [BH+] X [A ]
This expression for the equilibrium constant, deduced on the
basis of the proton theory of acids and bases, is identical" t,h
that obtained in Section It 41 {equation (xxii)}.
Metallic Hydroxides as Weak Bases. Hydrolysis of
Metallic Ions.-Many metallic hydroxides, for example tJ" ,se
of aluminium, iron, zinc and copper, are weak bases:
Al(OH)s ~ Al+++ + 30H-
There is a considerable volume of evidence that these metallic
ions are hydrated (e.g. [Al(H 2 0)6]+++ and [Cu(H 2 0)4]++) and
these hydrated ions are therefore regarded as the conjufIate
acids of the corresponding weak bases. The conjugate at ids
of these weak bases will have appreciable strength {comJ"lre
equation (iii)}. The primary hydrolysis of the hydra! ed
metallic ions may be represented as:
[M(HzO)",]n+ + H 20 ~ [M(H 2 0)a:-l(OH)Jn-l)+ + HsO+;
further hydrolysis may occur under suitable conditions lead lUg
ultimately to the precipitation of the metallic hydrm. ide
M(OH)". Comparatively few quantitative data are at pretl·nt
available for the acid dissociation constants of the hydra i ed
metallic ions {compare acid dissociation constant of \ he
ammonium ion in equation (vi)}. A value of 1·4 X lO-5 J :as
been given for the dissociation constant of the reaction:
[Al(H ZO)6]S+ + H 20 ~ [Al(H ZO)5(OH)]2+ + HsO+,
and this may serve as a basis for the following illustra t 1ve
calculation.
Example 26. Calculate the pH of a 0·1 molar solution of ,: iu-
minium chloride [Al(H 20)6]3+CI ss-.
Let y = [HsO+] = [Al(H ZO)5(OH)]2+
~~~"K = [HsO+] X [AI(H zO)5(OH)]2+ = y2 = 1'4 10-6
[Al(H 2 0)6]S+ 0'1 X
(compare E;r,ample 3 in Section I, 14).
y2 =.: 1·4 X 10-6, Y = 1·18 X lO-s g. ions per litre,
or pH =: 2·93
43] The Theoretical Ba8i8 of Qualitative A nalyaia 131
I, 43. Thb Distribution or Partition Law.-It is a well~
known fact that certain substances are more soluble in some
solvents than in others. Thus iodine is very much more soluble
in carbon disulphide, chloroform or carbon tetrachloride than
it is in water. Furthermore, when certain liquids sllch as
carbon disulphide and water, and also ether and water, are
shaken together in a vessel and the mixture allowed to stand,
the two liquids separate out into two layers. Such liquids are
said to be immiscible (carbon disulphide and water) or partially
miscible (ether and water), according as to whether they are
almost insoluble or partially soluble in one another. If iodine
is shaken with a mixture of carbon disulphide and water and
then allowed to settle, the iodine will be found to be distributed
between the two solvents. A state of equilibrium exists
between the solution of iodine in carbon disulphide and the
solution of iodine in water. It has been found that when
the amount of iodine is varied, the ratio of the concentrations
is constant at any given temperature. That is:
Concentration of iodine in carbon disulphide = O2 = K
Concentration of iodine in water 01 d

The constant Kd is known as the partition or distribution

coefficient. Some early (and therefore approximate) experi-
mental results at 18° are collected below.

Grams of iodine in Grams of iodine in O

K d = -2
10 mI. of OS2 (0 2 ) 10 mI. of H 20 (0 1 ) 01

1·76 0·0041 420

1·29 0·0032 400
0·66 0·0016 410
0-41 0·0010 410

It is important to note that the ratio O2 /0 1 is constant only

when the dissolved substance has the same molecular weight
in both solvents. The distribution or partition law may be
formulated: when a solute distributes itself between two
immiscible solvents, there exists for each molecular species, at
a given temperature, a constant ratio of distribution between
the two solvents, and this distribution ratio is independent of
any other molecular species which may be present. The value
of the ratio varies with the nature of the two solvents, the
nature of the solute, and the temperature.
132 Qualitative Inorganic Analysis
The distribution law has a number of applications in analyc;i3.
(a) Removal of bromine and of iodine from aqueolls
solution. When an aqueous solution of iodine is sha],"n
with carbon disulphide, the concentration of iodine in the re-
sulting carbon disulphide layer is about 400 times that in
water. The carbon disulphide layer may be removed with lite
aid of a separatory funnel and the process repeated. In 1]; is
way the concentration of iodine in the aqueous solution may he
reduced to a very small value, although theoretically it Canll()t
be removed completely. The distribution coefficients at i lie
laboratory temperature for iodine in OHOl3 /H 2 0 and 0014/ B:O
are 109 and 85 respectively.
Example 27. Ten mg. of iodine are suspended in 12 m!. of water
and then shaken with 2 m!. of carbon tetrachloride until equilibri Il III
is reached. Calculate the weight of iodine remaining in the aque, 'lIS
layer.
Let x be the weight (mg.) of iodine in the aqueous layer at e<l'I[-
librium: the concentration will therefore be x/12. The quantit) I)f
iodine (mg.) extracted by the CC14 will be (10 - x) and its c, >!l-
centration (10 - x) 12.
Kd = 85 = {(10 - x) 12} 1 (x /12)
or x = 0·66 mg.
If the CCl4 layer is now withdrawn with the aid of a separatnry
funnel, and the residual aqueous layer (12 m!.) shaken with a
further 2 m!. of CCl4 until equilibrium is attained, the quantit,\ y
of iodine remaining in the aqueous layer can be computed froffl:
Kd = 85 = {(0·66 - y) / 2} / (y / 12)
Y = 0·043 mg.
It can easily be shown that upon wi"thdrawttl of the COl4 layer,
followed by a further extraction with 2 m!. of the same solvellt,
the weight of iodine in the aqueous layer is reduced to 0·0028 llIg.
If instead of three successive extractions with 2 m!. portions of
CCI" the original 10 m!. of the aqueous suspension were trea 1, ,.j
with 6 m!. of CCI4 , the weight of iodine remaining in the aque, '! S
layer would be reduced to 0·23 mg., as can be shown by a calculatll!n
similar to the above. This is a simple illustration of the fact tJ,.,t
in performing extractions, it is more efficient and also more eco,,,)-
mical to carry out a number of successive e~tractions with sn, ,II
portions of the solvent rather than a single extraction with a lal .'e
quantity.
Use is made of the partition principle in the detection, ,f
bromides (Section IV, 15, reaction 5), of iodides (Section IV, I ii,
reaction 4) and in the detection of bromides and iodides in 1 ',e
presence of each other (Section IV, 44, reaction 8).
 43J 'llhe Theoretical Basis of Qualitative Analysis 133
(b) Various tests in qualitative analysis. (i) "Perchromic
acid" (Section IV, 33, reaction 4) is more soluble in amyl
alcohol (or in ether) than in water; by shaking the dilute
aqueous solution with amyl alcohol (or with ether), a con-
centrated solution in the latter solvent is obtained, and the
presence of chromate or of hydrogen peroxide is indicated by
the blue colour.
(ii) The compound ammonium eobaltothiocyanate, (NH4k
[CO(CNS)4], .1roduced by the action of a concentrated solution
of ammoniUl..l thiocyanate upon a cobaltous salt (see Section
III, 24, reaction 6), is more soluble in amyl alcohol than in
water; the blue coloration of the amyl alcohol layer, due to the
formation of a concentrated solution of this compound, is a
sensitive and characteristic test for cobalt.
(c) Study of hydrolysis. In the hydrolysis of a salt of a
weak base and a strong acid or of a weak acid and a strong
base, there is an equilibrium between the salt, the free aoid
and the free base. The hydrolysis, for our present purpose,
may be written:
Salt + Water? Acid + Base (see Sections I, 40-1, 42)
The concentration of the weak acid or of the weak ba,se can
be determined by distribution between water and another
solvent, such as benzene or ohloroform; the partition coeffioient
of the acid or base between the water and the other solvent
must, of course, be known. The degree of hydrolysis may then
be calculated from the concentration of the salt and the deter-
mined concentration of the weak acid or base. An example of
such a salt is aniline hydrochloride. This is partially hydro-
lysed into aniline and hydrogen chloride. Upon shaking the
aqueous solution with benzene, the aniline will distribute itself
between the water and benzene in the ratio of the distribution
coefficient. The initial concentration of aniline hydrochloride
is known, the concentration of the free aniline in the aqueous
solution can be computed from that found in the benzene
solution, and from this the total concentration of aniline, pro-
duced by hydrolysis, is deduced. Sufficient data are then
available for the calculation of the degree of hydrolysis.
(d) The determination of the constitution of complex halide
ions. Iodine is much more soluble in an aqueous solution of
potassium iodide than it is in water; this is due to the formation
of potassium tri-iodide KIa. The following equilibrium exists
in such a solution:
KI + I. <F KIa or III + r .= 13-
134 Qualitative Inorganic Analysis [I,
If the solution is titrated with standard sodium thiosulphat"
solution, the total concentration of the iodine, both as free]
and combined as KIa (or I a-), is obtained since, as soon as som"
iodine is removed by interaction with the thiosulphate, a fres:
amount of iodine is liberated from the tri-iodide in order t,
maintain the equilibrium. If, however, the solution is shakel,
with carbon tetrachloride, in which iodine alone is appreciabh
soluble, then the iodine in the organic layer is in equilibriuIr I
with the free iodine in the aqueous solution. By determinin.:'
the concentration of the iodine in the carbon tetrachloridt·
solution, the concentration of the free iodine in the aqueou·
solution can be calculated from the known distribution coeffi
cient, and therefrom the total concentration of the free iodin,
present at equilibrium. Subtracting this from the total iodine
the concentration of the combined iodine (as KIa) is obtained
by subtracting the latter value from the initial concentratiOlI
of potassium iodide, the concentration of the free KI is deduced.
The equilibrium constant:
K = [KI] X [1 2] or
[KIa]
is then computed.
A similar method has been used for the investigation of the
equilibrium between bromine and bromides:
Brz + KBr ~ KBra, or Brz + Br- ~ Bra-
Distribution measurements have also been used to prove
the existence of the cuprammonium ion [Cu(NH 3)4]++ in an
aqueous ammoniacal solution of copper sulphate, the partition
of the free ammonia being studied between chloroform and
water:
[Cu(NHs)4]++ ~ Cu++ + 4NHa
I, 44. The Colloidal State.-It sometimes happens in quali-
tative analysis that a substance does not appear as a preoipitate
when the reactants are present in such concentrations that the
solubility product of the substance is greatly exceeded and
precautions are taken against supersaturation of the resulting
solution. Thus when hydrogen sulphide is passed into a
cooled solution of arsenious oxide, no precipitate is discern-
ible when one looks through the resulting mixture. The
solution, however, has acquired a deep yellow colour and when
viewed by reflected light shows a marked opalescence. If a
powerful beam of light is passed through the solution and the
"J The Theoretical BaN of Q'Il.ahtative A nalY8ia 135
latter viewed through a microscope at right angles to the
incident light, a scattering of light (bright spots of light against
fI, dark background) is observed, evidently due to the light

reflected by the particles in suspension in the solution. The

gcattering of light is called the Tyndall effect, whilst the
I1rrangement of viewing the Tyndall beam in a microscope is
termed the ultramicroscope. True solutions, i.e. those with
particles of molecular dimensions do not exhibit a Tyndall
~ffect, and are said to be "optically empty." Clearly the
reaction has taken place forming arsenious sulphide but
particles are in such a fine state of division that they do not
'tppear as a precipitate. They are in fact in the colloidal
state or in colloidal solution. Other colloidal solutions which
may be encountered in qualitative analysis include ferric,
chromic and aluminium hydroxides, cupric, manganous and
nickel sulphides, silver chloride and silicic acid.
Further examination of the colloidal solution of arsenious
mlphide brings to light other peculiar properties. When an
II.ttempt is made to filter the solution, the particles are
found to pass right throurh the filter paper. Also, when the
colloidal solution is ano ved to stand for a long time, no
I1ppreciable settling takes place; no precipitation takes place
upon shaking with solid arsenious sulphide, thus ruling out
the possibility of supersaturation. The addition of, say, alu-
minium sulphate solution brings about immediate precipitation
of arsenious sulphide, although there is no apparent reaction
between the AI+++ or S04-- and any ion in the solution.
Potassium chloride solution produces the same effect but con-
siderably more of it must be added. Any electrolyte, in fact,
causes precipitation, i.e. coagulation or flocculation of the
colloidal material. Heating the solution also favours coagula-
tion. It is evident that the colloidal state must be avoided in
qualitative analysis, and a more detailed account of the pheno-
menon will therefore be given. '
The colloidal state of matter is distinguished by a certain
range of particle size, as a consequence of which certain
characteristic properties become apparent. Before discussing
these, mention must be made of the various units which are
employed in expressing small quantities. The most important
of these are:
1 micron = 1 I-' = 10-3 mm. = 10-6 m.
1 milli-micron = 1 ml-' = 11-'1-' = 10-6 mm.
1 Angstrom unit = 1 A = 10-10 m. = 10-7 mm. = 0-1 ml-'
136 Qualitative Inorganic Analysis [I,
Colloidal properties are, in general, exhibited by substance
of particle size ranging between 0·2 IL and 5 mIL. Ordinar.,
qualitative filter paper will retain particles up to a diameter
of 1-2 X 10-2 mm. or 10-20 IL, so that colloidal solutions iJ,
this respect behave like true solutions (the size of molecules j
of the order 0·1 mIL or 10- 8 cm.). The limit of vision unde.
the microscope is about 0·2 IL, whilst that of the ultra-micro
scope is about 5-10 mIL. Colloidal solutions are not tru,
solutions. Close examination shows that they are not homo
geneous, but consist of suspensions of solid or liquid particle
in a liquid. Such a mixture is known as a disperse system
the liquid (usually water in qualitative analysis) is called th,
dispersion medium and the colloid the disperse phase.
An important consequence of the smallness of the size 0:
the particles in a colloidal solution is that the ratio of th,·
surface to the volume is extremely large. Phenomena whicl
depend upon the size of the surface, such as adsorption, will
therefore play an important part.
The effect of particle size upon the area of the surface will be
apparent from the following approximate caloulations. The tota I
surfaoe area of 1 m!. of material in the form of a oube of 1 om
side is 6 sq. om. When it is divided into oubes of 10-6 cm. siz,
(whioh approximates to many oolloidal systems), the total area ot
the same volume of material is 6 X 106 sq. om.
Although colloidal parth les cannot be separated from thosl'
of molecular dimensions by the use of ordinary filter papers-
the best quantitative filter papers retain particles larger thaJ I
about IlL in diameter-separation can be effected by the use ot
special devices. The procedure known as dialysis utilises tht·
fact that substances in true solution,- provided the molecule,
are not too large, can pass through membranes of parchment
or collodion, while colloidal particles are retained. Tht·
separation can also be effected by ultra-filtration. Filter paper,-
are impregnated with collodion, or with gelatin subsequently
hardened by formaldehyde, thereby making the pores small
enough to retain particles of colloidal dimensions. The ulti-
mate size of the pores depends upon the particular paper used
and upon the concentration of the solution employed to
impregnate it. The solution is poured on the filter and the
passage of the liquid is accelerated by suction or by pressure.
It may be mentioned that other factors (e.g. rates of diffusion
and adsorption) in addition to pore size determine whether
particles of a given size will pass through an ultra-filter or not.
Colloidal systems, in which a liquid is the dispersion medium,
44] The Theoretical Basis of Qualitative Analysis 137
are often termed sols to distinguish them from true solutions:
the nature of the liquid is indicated by the use of a prefix, e.g.
aquasols, alcosols, etc. The solid produced upon coagulation
or flocculation of a sol was originally described as a gel, but
the name is now generally restricted to those cases in which
the whole system sets to a semi-solid state without any super-
natant liquid initially. Some authors employ the word gel to
include gelatinous precipitates, such as aluminium and ferric
hydroxides, formed from sols, whereas others refer to them as
coagels. The process of dispersing a flocculated solid or gel
(or coagel) to form a colloidal solution is called peptisation.
Colloidal solutions may be divided roughly into two main
groups, designated as lyophobic (Greek: solvent hating) and
lyophilic (Greek: solvent loving): when water is the di;:;persion
medium, the terms hydrophobic and hydrophilic are employed.
The chief properties of each class are summarised in tho follow-
ing Table, * but it must be emphasised that the distinction is
not an absolute one since some, particularly sols of metallic
hydroxides, exhibit intermediate properties.
It may be mentioned that negatively-charged colloids include
the sols of metals, sulphur, metallic sulphides, silicic acid,
stannic acid, silver halides, gums, starch and certain acid dye-
stuffs, whilst sols of metallic hydroxides and of certain basic
dyestuffs usually carry a positive charge.
The stability of a colloidal solution is intimately associated
with the electrical charge on the particles. Thus in the forma-
tion of an arsenious sulphide sol by precipitation with hydrogen
sulphide in faintly acid solution, sulphide ions are primarily
adsorbed (since every precipitate has a tendency to adsorb its
own ions), and in order to maintain the electro-neutrality of
the solution, an equivalent quantity of hydrogen ions is secon-
darily adsorbed. The hydrogen ions or other ions which are
secondarily adsorbed have been termed counter ions. Thus
the so-called electrical double layer is set up between the
particles and the solution. If the electrical double layer is
destroyed, the sol is no longer stable, and the particles will
flocculate since the concentration is in excess of the Holubility
product. Thus if barium chloride solution is added, barium
ions are preferentially adsorbed by the particles; the orientation
of the surface is disturbed and the charge disappears. Mter
flocculation, it is found that the dispersion medium is acid
* For a more detailed account S66, for example, H. B. Weiser, A Text Book
of OoUow Ohemi8try, Second Edition, 1949 (J. Wiley), or the appropriate
sections in S. Glasston!!, TtUd Book oj Physteal Ohemi8try, Sscond Edition, 1946.
s:
138 Qualitative Inorganic Analysis [I,

HYDROPHOBIC SOLS HYDROPHILIC SOLS

1. The viscosity of the sols is 1. The viscosity is very much

similar to that of the medium. higher than that ofthe medium;
Examples: sols of the metals, they set to jelly-like masses,
silver halides, metallic hydrox- often termed gels (or coagels).
ides and barium sulphate. Examples: sols of silicic acid,
stannic oxide, gelatin, starches
and proteins.
2. A comparatively minute 2. Small quantities of eleotro-
quantity of an electrolyte lytes have little effect: large
results in flocculation. The amounts may cause precipita-
change is, in general, irrever- tion, "salting out." The
sible; water has no effect upon change is, in general, reversible
the flocculant. upon the addition of water.
3. The particles, ordinarily, 3. The particles change their
have an electric charge of charge readily, e.g. they are
definite sign, which can be positively charged in acid
changed only by special medium and negatively charged
methods. The particles in a basic medium. Uncharged
migrate in one direction in an particles are also known. The
electric field (cataphoresis or particles may migrate in either
eleetrophoresis) . direction or not at all in an
electric field.
4. The ultramicroscope 4. Only a diffuse light is
reveals bright particles in exhibited in the ultramicro-
vigorous motion (Brownian scope.
movement).
5. The surface tension is 5. The surface tension is
similar to that of water. often lower than that of water:
foams are often produoed
readily.

owing to the liberation of the hydrogen counter ions. It

appears that ions of opposite charge to those primarily adsorbed
on the surface are necessary for coagulation. The minimum
amount of electrolyte necessary to cause flocculation is called
the flocculation or coagulation value. It has been found that
the latter depends upon the valency of the ions of the opposite
charge to that on the colloidal particle, the higher the valency
the smaller the coagulation value; the nature of the ions has
some influence also. If two sols of opposite charge are mixed
(e.g. ferric hydroxide and arsenious sulphide), mutual coagula-
tion usually occurs because of the neutralisation of charges.
The above remarks apply largely to hydrophobic BOls •
..
44] The Theoretical Basis of Qualitative Analysis 139
Hydrophilic sols are generally much more difficult to floeculate
than hydrophobic sols. If a small amount of a hydrophilic sol
(preferably, but not necessarily, with the same charge), e.g.
gelatin, is added to a hydrophobic sol, e.g. of gold, then the
latter appears to be strongly protected against the flocculating
action of electrolytes. It may be that the particles of the
lyophilic sol are adsorbed by the lyophobic sol and impart their
properties to the latter. The hydrophilic substance is known
as a protective colloid. An explanation is thus provided of
the relative stability of the otherwise unstable gold (or other
noble metal) sols produced by the addition of a little gelatin or
of the salts of protalbic or lysalbic acids (the latter are obtained
by the alkaline hydrolysis of albumin). For this reason organic
matter, which might form a protective colloid, is gcnerally
destroyed before proceeding with an analysis.
During the flocculation of a colloid by an electrolyte, the ion
of opposite sign to that of the colloid is adsorbed to a varying
degree on the surface; the higher the valency of the ion, the
more strongly is it adsorbed. In all cases, the precipitate will
be contaminated by surface adsorption. Upon washing the
precipitate with water, part of the adsorbed electrolyte is
removed, and a new difficulty may arise. The electrolyte con-
centration in the supernatant liquid may fall below the coagula-
tion value, and the precipitate will pass into colloidal solution
again. This phenomenon is known as peptisation. It can be
prevented by washing the precipitate with a suitable electrolyte.
The adsorptive properties of colloids find some application in
analysis, e.g. (i) in the removal of phosphates by hydrated
stannic oxide in the presence of nitric acid (compare Section
VIII, 2), and (ii) in the formation of coloured lakes from col-
loidal metallic hydroxides and certain soluble dyes (see tests
for Aluminium in Section III, 21, and for Magnesium in Section
111,33). There is, however, some evidence that lake formation
may be partly chemical in character.
Precipitates thrown down from dilute or very concentrated
solutions are often in the form of very fine crystals. These
fine precipitates will generally become filterable if allowed to
stand for some time in contact with the mother liquor, pre-
ferably, if the solubility permits, near the boiling point of the
solution. The addition of macerated filter paper, in the form
of a WOOtman filtration accelerator or as the Schleicher and
Schuell (U.S.A.) filter pulp No. 289, is beneficial; the latter is
particularly valuable for assisting the filtration of. colloidal
precipitates. The macerated filter paper increases the speed
•
140 Qualitative Inorganic Analysis [I,
of filtration by retaining part of the precipitate and thus pre
venting the clogging of the pores of the filter paper. Whell
the precipitation has taken place from concentrated solution
the crystals are formed so rapidly that they are imperfect
On standing the crystals tend to perfect themselves: very small
particles have a greater solubility than larger particles, hen Ct·
they dissolve and are deposited upon the larger crystals.
Occasionally the precipitate first formed is a metastable modifi·
cation which is changed on standing into a more stable and lesi<
soluble state. The process of ageing of precipitates is spoken
of as digestion.
When a precipitate separates from a solution, it is not always
perfectly pure: it may contain varying amounts of impurities
dependent upon the nature of the precipitate and the conditions
of precipitation. The contamination of the precipitate by sub-
stances which are normally soluble in the mother liquor is
termed coprecipitation (see also Section 1,16). Two important
types of coprecipitation must be distinguished. The first is
-concerned with adsorption at the surface of the particles exposed
to the solution, and the second relates to the occlusion of foreign
substances during the process of crystal growth from the
primary particles. Surface adsorption is, in general, greatest
for gelatinous precipitates and least for those of pronounced
macro-crystalline character.
Some precipitates are deposited slowly and the solution is in
a state of supersaturation for a considerable time. Thus, when
calcium oxalate is precipitated in the presence of a high con-
centration of magnesium ions, the precipitate is practically
pure at first, but if it is allowed to remain in contact with the
solution, magnesium oxalate forms slowly and the presence of
the calcium oxalate precipitate tends to accelerate the forma-
tion of the magnesium oxalate. This precipitation (magnesium
oxalate) which occurs on the surface of the first precipitate
(calcium oxalate) after its formation is termed post-precipita-
tion. It is often encountered with sparingly soluble substances
which form super-saturated solutions; they usually have an ion
in common with the primary precipitate. Another example is
the precipitation of copper or mercuric sulphide in O·3N hydro-
chloric acid solution in the presence of zinc ions; zinc sulphide
is slowly post-precipitated.
 CHAPTER II

EXPERIMENTAL TECHNIQUE OF
QUALITATIVE INORGANIC ANALYSIS

BEFORE the student attempts to carry out the analytical

reactions of the various cations and anions detailed in Chapters
III and IV, he should be familiar with the operations commonly
employed in qualitative analysis, that is, with the lahoratory
technique involved. It is assumed that the student has had
some training in elementary practim11 chemistry, such as that
given in the author's manual*; he should be familiar with such
operations as solution, evaporation, crystallisation, distillation,
'precipitation, filtration, decantation, bending of gla8s tubes,
preparation of ignition tubes, boring of corks and con8truction
of a wash bottle. These will therefore be either very briefly dis-
cussed or not described at all in the following pages.
Qualitative analysis may be carried out on various scales.
In macro analysis the quantity of the substance employed is
0·5-1 gram and the volume of solution taken for the analysis
is about 20 ml. In what is usually termed semimicro analysis,
the quantity used for analysis is reduced by a factor of 0·1-
0·05, i.e. to about 0·05 gram and the volume of solution to.
about 1 ml. For micro analysis the factor is of the order of
0·01 or less. There is no sharp line of demarcation between
semimicro and micro analysis: the former has been called centi-
gram analysis and the latter milligram analysis, but these
terms indicate only very approximately the amounts used in
the analysis. It will be noted that only the scale of the
operations has been reduced; the concentrations of the ions
remain unchanged. Special experimental techniques have
been developed for handling the smaller volumes and amounts
of precipitate, and these will be described in some detail.
For routine analysis by students, the choice lies between macro
and semimicro analysis. There are many advantages in adopt-
ing the semimicro technique; these include:
(i) Reduced consumption of ehemicals and the consequent
considerable saving in the laboratory budget.
(ii) The greater speed of the analysis, due to working with
smaller quantities of materials and the saving of time in
• Elementary Practical Ohemistry, 1936 (Blackie & Son Ltd.).
• 141
 142 Qualitative Inorganic Analysis [II,
carrying out the various standard operations of filtration,
washing, evaporation, saturation with hydrogen sulphide, etc.
(iii) Increased sharpness of separation, e.g. washing of pre-
cipitates can be carried out rapidly and efficiently when a
centrifuge replaces a filter.
(iv) The amount of hydrogen sulphide used is eonsiderably
reduced.
(v) Much space is saved both on the reagent shelves and
more especially in the lockers provided immediately below the
bench for the housing of the individual student's apparatus;
the latter merit may be turned to good use by reducing the
size of the bench lockers considerably and thus effectively
increasing the accommodation of the laboratory.
(vi) The desirability of securing a training in the manipula-
tion of small amounts of material.
For these, and also other, reasons many laboratories now
employ semimicro analysis, particularly for the elementary
courses. Both macro and semimicro procedures will be given
separately in this book in order that the requirements of all
types of students may be met. Nevertheless, when the semi-
micro technique is adopted, students are recommended to read
the Sections dealing with macro technique. It may be said
that when the general technique of semimicro analysis has been
mastered and appreciated, no serious difficulty should be en-
countered in adapting a macro procedure to the semimicro
,scale. Apart from drop reactions, few applications of the micro
technique will be described in the text.
Qualitative analysis utilises two kinds of tests, dry reactions
and wet reactions. The former are applicable to solid sub-
stances and the latter to substances in solution. Most of the
dry reactions to be described can be used with only minor
modifications for semimicro analysis. Dry tests appear to have
lost their popularity in certain quarters; they do, however,
often provide useful information in a comparatively short time
and a knowledge as to how they are carried out is desirable for
all students of qualitative analysis. Different techniques are
employed for wet reactions in macro, semimicro and micro
analysis.
 TECHNIQUE OF MACRO ANALYSIS
II, 1. DRY REACTIONS
1. Action of heat. The substance is placed in a small
ignition tube (bulb tube), prepared from soft glass tubing, and
heated in a Bunsen flame, gently at fIrst and then more strongly.
Small test-tubes, 2!-3 inches X !--i inch, which are readily
obtainable and are cheap, may also be employed. Sublimation
may take place, or the material may melt or may decompose
with an attendant change in colour, or a gas may be evolved
which can be recognised by certain characteristic properties
(see Chapter V, Section VII, 2, Preliminary Dry Tests, Test i).
2. Blowpipe tests. A luminous Bunsen flame (air holes
completely closed), about 2 inches long, is employed for these

Fig. II, 1, 1

tests. A reducing flame is produced by placing the nozzle of

a mouth blowpipe just outside the flame, and blowing gently
so as to cause the inner cone to play on the substanee under
examination. An oxIdising flame is obtained by holding the
nozzle of the blowpipe about one-third within the fhme and
blowing somewhat more vigorously in a direction parallel with
the burner top; the extreme tip of the flame is allowed to play
upon the substance. Fig. II, 1, 1 illustrates the oxidising and
reducing flames.
The tests are carried out upon a clean charcoal block in
which a small cavity has been made with a pen-knife or with
a small coin. A little of the substance is placed in the cavity
and heated in the oxidising flame. Decrepitation will occur
with crystalline salts; deflagration indicates the presence of
~ M3
 f
144 Qualitative Inorganic Analysi8 [II,
an oxidising agent (nitrate, nitrite, chlorate, etc.). More fr(·
quently the powdered substance is mixed with twice its bu]:.
of anhydrous sodium carbonate or, preferably, with "fusio',
mixture" (an equi-molecular mixture of sodium and potassim)
carbonates; this has a lower melting point than sodium cal
bonate alone) in the reducing flame. The initial reaction COli
sists in tbe formation of the carbonates of the cations presen:
and of the alkali salts of the anions. The alkali salts are largel)
adsorbed by the porous charcoal, and the carbonates are, for
the most part, decomposed into the oxides and carbon dioxide.
The oxides of the metals may further decompose, or be reduced,
to the metals or they may remain unchanged. The final pro-
ducts of the reaction are therefore either the metals alone,
metals and their oxides, or oxides. The oxides of the noble
metals (silver and gold) are decomposed without the aid of th(,
charcoal into the metal, which is often obtained as a globule
and oxygen. The oxides of lead, copper, bismuth, antimony
tin, iron, nickel and cobalt are reduced either to a fused metalli,'
globule (Pb, Bi, Sn and Sb) or to a sintered mass (Cu) or t('
glistening metallic fragments (Fe, Ni and Co). The oxides oj
cadmium, arsenic and zinc are readily reduced to the metal
but these are so volatile that they vaporise and are carrie( I
from the reducing to the oxidising zone of the flame, wher.·
they are converted into difficultly volatile oxides. The oxide~
thus formed are deposited as an incrustation round the cavit:
of the charcoal block. Zinc yields an incrustation which i.·
yellow while hot and white when cold; that of cadmium i·
brown and is moderately volatile; that of arsenic is white and
is accompanied by a garlic odour due to the volatilisation 01
the arsenic. A characteristic incrustation accompanies th,
globules of lead, bismuth and antimony.
The oxides of aluminium, calcium, strontium, barium and
magnesium are not reduced by charcoal; they are infusible ant I
glow brightly when strongly heated. If the white residue 0)
white incrustation left on a charcoal block is treated with 11
drop of cobalt nitrate solution and again heated, a bright bhw
colour, which probably consists of either a compound or a solid
solution of cobaltous and aluminium oxides (Thenard's blue)
indicates the presence of aluminium, * a pale green colour.
probably of similar composition (Rinmann's green), is indicativ(
of zinc oxide, and a pale pink mass is formed when magnesium
oxide is present (see Chapter VII, Section VII, 2, Preliminary
Dry Tests, Test iii).
*A blue colour is also given by phosphates, arsenates, silicates or borates.
I<
1) Experimental Technique of Inorganic Analysia 145
3. Flame tests. In order to understand the operations
involved in the flame colour tests and the various bead tests
to be described subsequently, it is necessary to have some
knowledge of the structure of the non-luminous Bunsen flame
(Fig. II, 1, 2).
The non-luminous Bunsen flame consists of three parts:
(i) an inner blue cone ADB consisting largely of unburnt gas;
(ii) a luminous tip at D (this is only visible when the air holes
are slightly closed); and (iii) an outer mantle ACBD in which
complete combustion of the gas occurs. The principal parts of
the flame, according to Bunsen, are clearly indicated in Fig.
II, 1,2. The lowest temperature is at the base of the flame (a);
this is employed for testing c
volatile substances to determine
whether they impart any colour
to the flame. The hottest part 'Upper OXidising Zone (d)
of the flame is the fusion zone
at (b) and lies at about one-
third of the height of the flame
and approximately equidistant /Upper Reducing Zone (e)
from the outside and inside of
/Hottest Portion oj Flame (b)
the mantle; it is employed for
testing the fusibility of sub-
stances, and also, in conjunction
- - -Lower Reducing Zone (f)
with (a), in testing the relative
volatilities of substances or of --low Temperature Zone (a)
a mixture of substances. The B
lower oxidising zone (c) is
situated on the outer border
of (b) and may be used for the
oxidation of substances dis- Fig. II, 1, 2
solved in beads of borax, sodium
carbonate or microcosmic salt. The upper oxidising zone (d)
consists of the non-luminous tip of the flame; here a large
excess of oxygen is present and the flame is not so hot as at (c).
It may be used for all oxidation processes in which the highest
temperature is not required. The upper reducing zone (e) is
at the tip of the inner blue cone and is rich in incandescent
carbon; it is especially useful for reducing oxide incrustations
to the metal. The lower reducing zone (j) is situai ed in the
inner edge of the mantle next to the blue cone and it is here
that the reducing gases mix with the oxygen of the air; it is a
less powerful reducing zone than (e), and may be employed for
the reduction of fused borax and similar beads .
.
 !
I

146 Qualitative Inorganic Analysis [II,

We can now return to the flame tests. Compounds of certai i,
metals are volatilised in the non-luminous Bunsen flame an.!
impart characteristic colours to the flame. The chlorides aT.
amongst the most volatile compounds, and these are prepare! I
in situ by mixing the compound with a little concentrate. i
hydrochloric acid before carrying out the tests. The procedur.·
is as follows. A thin platinum wire* about 5 cm. long an.l
0,03-0·05 mm. in diameter, fused into the end of a short pier,
of glass tubing or glass rod which serves as a handle, j
employed. This is first thoroughly cleaned by dipping it int,
concentrated hydrochloric acid contained in a watch glass ani!
then heating it in the fusion zone (b) of the Bunsen flame; th,·
wire is clean when it imparts no colour to the flame. The wir,
is dipped into concentrated hydrochloric acid on a watch glasf'
then into a little of the substance whereby a little adheres t.,
the wire. It is then introduced into the lower oxidising zon,
(0), and the colour imparted to the flame observed. Lese
volatile substances are heated in the fusion zone (b); in thi~'
way it is possible to make use of the difference in volatilitiec;
for the separation of the constituents of a mixture.
A table showing the colours imparted to the flame by saltt'
of different metals is given in Chapter V, Section VII, 2
Preliminary Dry Tests, Test (ii). Carry out flame tests with the
chlorides of sodium, potassium, calcium, strontium and barium
and record the colours you observe. Repeat the test with a
mixture of sodium and potassium chlorides. The ye11o>\
coloration due to the sodium masks that of the potassium.
View the flame through two thicknesses of cobalt glass; the
yellow sodium colour is absorbed and the potassium flame
appears crimson.
Potassium chloride is much more volatile than the chlorides
of the alkaline earth metals. It is therefore possible to detect
potassium in the lower oxidising flame and the calcium, stron-
tium and barium in the fusion zone.
After all the tests, the platinum wire should be cleaned with
concentrated hydrochloric acid. It is a good plan to store the
wire permanently in the acid. A cork is selected that just fits
into a test-tube, and a hole bored through the cork through
which the glass holder of the platinum wire is passed. The
test-tube is about half filled with concentrated hydrochloric
,. If a platinum wire is not available, a short length of chromel (or nichrome)
wire, bent into a small loop at one end and inserted into a cork (to serve as a
handle) at the other, may be used. This is not as satisfactory as platinum
wire and is not recommended.
•
1] Experimental Technique of Inorganic AnalY8i8 147
acid so that when the cork is placed in position, the platinum
wire is immersed in the acid.
A platinum wire sometimes acquires a deposit which is removed with
difficulty by hydrochloric acid and heat. It is then best to employ
fused potassium hydrogen sulphate. A coating of potassium hydrogen
sulphate is made to adhere to the wire by drawing the hot wire across
a piece of the solid salt. Upon passing the wire slowly through a flame,
the bead of potassium pyrosulphate which forms travels along the wire,
dissolving the contaminating deposits. When cool, the bead is readily
dislodged. Any small residue of pyrosulphate dissolves at once in
water, whilst the last traces are usually removed by a single moistening
with concentrated hydrochlorio acid, followed by heating. The result·
ing bright clean platinum wire imparts no colour to the flame.

4. Spectroscopic tests. Flame spectra. The only trust-

worthy way to employ flame tests in analysis is to resolve the
light into its component tints and to identify the cations present

Fig. II, 1, 3

by their characteristic sets of tints. The instrument employed

to resolve light into its component colours is called a spectro-
scope. A simple form is shown in Fig. II, 1, 3. It consists
of a collimator A which throws a beam of parallel rays on the
prism B, mounted on a turn-table; the telescope C through
which the spectrum is observed; and a tube D, which contains
148 Qualitative Inorganic Analysis [II,
a scale of reference lines which may be superposed upon th,'
spectrum. The spectroscope is calibrated by observing th,
spectra of known substances, such as sodium chloride, pota~
sium chloride, thallium chloride and lithium chloride. Th<
conspicuous lines are located on a graph drawn with wav£'
lengths as ordinates and scale divisions as abscissae. Th,
wave-length curve may then be employed in obtaining th,
wave-lengths of all intermediate positions and also in establish
ing the identity of the component elements of a mixture.
To adjust the simple table spectroscope described abov, ,
(which is always mounted on a rigid stand), a lighted Bunsell
burner is placed in front of the collimator A at a distance or
about 10 cm. from the slit. Some sodium chloride is intro
duced by means of a clean platinum wire into the lower pari
of the flame, and the tube containing the adjustable slit rotate' I
until the sodium line, as seen through the telescope C, is in "
vertica.I position. (If available, it is more convenient to employ
an electric discharge "sodium lamp," such as is marketed b.\
the General Electric Company: this constitutes a high intensit.\
sodium light source.) The sodium line is then sharply focused
by suitably adjusting the sliding tubes of the collimator aU! I
the telescope. Finally, the scale D is illuminated by placing ;}
small electric lamp in front of it, and the scale sharply focused
The slit should also be made narrow in order that the position
of the lines on the scale can be noted accurately.
A smaller, relatively inexpensive and more compact instru
ment, which is more useful for routine tests in qualitativ,
analysis, is the direct vision spectroscope with comparisOl J
prism,* shown in Fig. II, 1, 4.
The light from the "flame" source passes through the centra I
axis of the instrument through the slit, which is adjustable by :t
milled knob at the side. When the comparison prism is interposed.
half the length of the slit is covered and thus light from a source iJ J

a position at right angles to the axis of the instrument will fall on

one·half of the slit adjacent to the direct light which enters thp
other half. This light passes through an achromatic objective lem,
and enters a train of five prisms of the 60 0 type, three being of
crown glass and the alternate two of flint glass. The train 01
prisms gives an angular dispersion of about 11 between the red and
0

the blue ends of the spectrum. The resulting spectrum, which can
... The instrument illustrated is the wave.length prism spectroscope (with
comparison prism) manufactured by R. and J. Beck Ltd., 69 Mortimer Street,
London, W.l. A similar instrument ("hand spectroscope") is manufactured
by R. Winkel, G.m.b.H., KOnigsallee 17-21, Giittingen, Germany: it possessE',
8 number of additional features, which render it very convenient to use for
flame and other tests.
1] Experimental Technique of Inorganic Analysis 149
be focused by means of a sliding tube adjustment, is observed
through the window. There is a subsidiary tube adjacent to the
main tube: the former contains a graticule on a glass disc, which is
illuminated either from the same source of light as that being
observed or from a small subsidiary source (e.g. a flash lamp bulb).
It is focused by means of a lens system comprising two achromatic
combinations between which is a right angle prism. This prism
turns the beam of light so that it falls on the face of the end prism
(of the train of five prisms) and is reflected into the observer's eye,
where it is seen superimposed upon the spectrum. An adjusting
screw is provided to alter the position of the right angle prism in

Window

Focussing adjustment jor scale

Fig. II, 1,4

order to adjust the scale relative to the spectrum. The scale is'
calibrated directly into divisions of 100 angstroms and has also an
indication mark at the D-line: it is "calibrated" by means of a
sodium source, and the adjusting serew is locked into position by
means of a locking nut. The instrument can be mounted on a
special stand.

If a sodium compound is introduced into the colourless

Bunsen flame, it colours it yel1ow; if the light is examined
by means of a spectroscope, a bright yellow line is visible. By
narrowing the s1it, two fine yellow lines may be seen. The
mean wave-length corresponding to these two lines is 5893 X
10-7 mm. Wave-lengths are generally expressed in Angstrom
units; one Angstrom unit (or 1 1) = 10- 8 cm. = 10-10 m.;
 ,
150 Qualitative Inorganic Analysis [II,
sometimes the unit /-tfJ. or mfJ. (milli-micron) is employed to
express 10- 6 mm. or 10-9 m. The mean wave-length of the
two sodium lines is therefore 5893 Aor 589·3 m/-t. The elements
which are usually identified by the spectroscope in qualitative
analysis are: sodium, potassium, lithium, thallium and, less
frequently, because of the comparative complexity of their
spectra, calcium, strontium and barium. The wave-lengths 01
the brightest lines, visible through a good-quality direct visioJI
spectroscope, are collected in the following table. As alread~
stated, the spectra of the alkaline earth metals are relativel)
complex and consist of a number of fine lines; the wave-length"
of the brightest of these are given. If the resolution of thl'
spectroscope is small, they will appear as bands.

Element Description of line(s) Wave-length in A

'.
Sodium Double yellow 5890,5896
Potassium Double red 7665, 7699
Double violet 4044,4047
Lithium Red 6708 1 ,
Orange (faint) 6103
Thallium
Calcium

Strontium
Green
Orange band
Yellowish. green
Violet (faint)
Red band
Orange
Blue
5350
6182-6203
5554
4227
6744, 6628
6060
4607
J.
Barium Green band 5536, 5347, 5243, 5137
Blue (faint) - 4874
I
The spectra of the various elements are shown diagrammatic-
ally in Fig. II, 1,5; the positions of the lines have been drawn
to scale.
A more extended discussion is outside the scope of thi~
volume, and the reader is referred to the standard works on
the subject. *
5. Borax bead tests. A platinum wire, similar to that
referred to under flame tests, is used for the borax bead test",
The free end of the platinum wire is coiled into a small loop
... See, for example, W, A. Brode, Ohemical Spectro8copy, 1943 (J. Wiley;
ChE'''''' ............................... ...:1 Un,l1\. l\.r u 'l\.Tn"'l-.. ..... ~""h P_;/VI",,'_l ...
ft ........ ~ D""' ....
_4 ..• __ .... "o_-.",o~

chej
1] Experimental Technique of Inorganic AnalY8i8 151

RED
~l~i
~::H GREEN ··
: BLUE VIOLET

I I I
g:~:
, . ···I I

Nal - T-'~---r--r--,..u..-J'""'T"---r----r---'----:-l~
Kil III
Li I--r--I ~r ---l.;--r --.-----.-------r------ll
Tllr~-r~__8~ ,___~ ,~I__~__~__~~__~1
Ca ~-,-uir......,.-----..glil----,--r--~~II
I -t~
~~
I w

g
,._

Sr I I III I ~,~, • 1 ~.
Bai"""""II",,,,,,,,,llF J,
000000
000000
o·
0
I 'I0
0
0
0
I
~ ~ ~ ~ g :8 ~ ~ i,
Fig. II, 1.5
 I
152 Qualitative Inorganic A nitlysia [IT.
through which an ordinary match will barely pass. The 10' ! I
is heated in the Bunsen flame until it is red hot and th. ,
quickly dipped into powdered borax Na2B407,lOH20. TL"
adhering solid is held in the hottest part of the flame; tL"
salt swells up as it loses its water of crystallisation and shrinL.;
upon the loop forming a colourless, transparent, glass-like beH'!
consisting of a mixture of sodium metaborate and boric all
hydride:*
Na2B407 = 2NaB02 + B2 0 a
The bead is moistened (this may be done with the tongue) a)1l 1
dipped into the finely powdered substance whereby only ,
minute amount of the substance will adhere to the bead. It i .
important to employ a minute amount of substance as othc
wise the bead will become dark and opaque in the subsequelll
heating. The bead and adhering substance is heated first ! I,
the lower reducing flame, allowed to cool and the colom
observed. It is then heated in the lower oxidising flam,
allowed to cool and the colour observed again.
Characteristic coloured beads are produced with salts "I'
copper, iron, chromium, manganese, cobalt and nickel. Tj,,·
student should carry out borax bead tests with salts of the,,·
metals and compare his results with those tabulated III
Chapter V, Section VII, 2, Preliminary Dry Tests, Test (iv), all,l
also in Chapter IX, Table VI.
Mter each test, the bead is removed from the wire by heatul:.!
it again to fusion, and then jerking it off the wire into a vess(' I
of water. The borax bead also provides an excellent meth(" I
for cleaning a platinum wire; a borax bead is run backwarl I..
and forwards along the wire by suitably heating, and is the It
shaken off by a sudden jerk.
The coloured borax beads are due to the formation (, f
coloured borates; in those cases where different coloured bea( 1-
are obtained in the oxidising and the reducing flames, borak;
corresponding to varying stages of oxidation of the metal aJ"!'
produced. Thus with copper salts in the oxidising flame, OIl"
has:
Na2B,,07 = 2NaB0 2,B20 a;
CuO + B 2 0 a = CU(B0 2)2 (cupric metaborate).
• Some authors do not recommend the use of a loop on the platinum wi rR
as it is considered that too large a surface of the platinum is thereby exposE" i
According to their procedure, the alternate dipping into borax and heati,<
is repeated until a bead 1·5-2 mm. in diameter is obtained. The danger··(
the bead falling off is reduced by holding the wire horizontally. It is ti",
present author's experience that the loop method is far more satisfactory.
especially in the hands of beginners, and is less time· consuming.
1] Experimental Technique oJ Inorganic Analysis 153
The reaction:
CuO + NaB0 2 = NaCuBOa (orthoborate),
probably also occurs. In the reducing flame (i.e. in the pre-
sence of carbon), two reactions may take place: (i) the coloured
cupric salt is reduced to colourless cuprous meta borate-
20u(B0 2)2 + 2NaB0 2 + 0 = 2CuB02 + Na2B,07 +00;
(ii) the cupric borate is reduced to metallic copper, so that the
bead appears red and opaque-
2Cu(B0 2b + 4NaB0 2 + 2C = 2Cu + 2Na2B407 + 200
With iron salts Fe(B02b and Fe(B0 2)a are formed in the
reducing and oxidising flames respectively.
Some authors assume that the metal metaborate may com-
bine with sodium metaborate to give complex borates of the
type Na2[Cu(B02),], Na2[Ni(B02)4] and Na2[Co(B02)4]:
Cu(B0 2}2 + 2NaB0 2 = Na2[Cu(B02}4]
6. Phosphate or microcosmic salt bead tests. The
bead is produced similarly to the borax bead except that
microcosmic salt, Na(NH4)HP04 ,4H 20, is used. The colour-
less, transparent bead contains sodium metaphosphate;
Na(NH 4 ) HPO, = NaPOa + H 2 0 + NHa
This combines with metallic oXides forming orthophosphates,
which are often coloured. Thus a blue phosphate bead is
obtained with cobalt salts:
NaPOa + CoO = NaCoPO,
The sodium metaphosphate glass exhibits little tendency to
combine with acidic oxides. Silica, in particular, is not dis-
solved by the phosphate bead. When a silicate is strongly
heated in the bead, silica is liberated and this remains sus-
pended in the bead in the form of a semi-translucent mass;
the so-called silica" skeleton" is seen in the bead during and
after fusion. This reaction is employed for the detection of
silicates:
CaSiOs + NaPOa = NaCaP0 4 + Si02
It must, however, be pointed out that many silicates dis-
solve completely in the bead so that the absence of a silica
"skeleton" does not conclusively prove that a silicate is not
present.
In general, it may be stated that the borax beads are more
viscous than the phosphate beads. They accordingly adhere
better to the platinum wire loop. The colours of the phos-
phates, whioh are generally similar to those of the borax beads,
154 Qualitative Inorganie Analysis [II,
are usually more pronounced. The various colours of the
phosphate beads are collected in the following table.

Oxidising flame Redueing flame Metal

Green when hot, blue Colourless when hot, Copper

when cold. red when cold.
Yellowish- or reddish- Yellow when hot, Iron
brown when hot, colourless to green
yellow when cold. when cold.
Green, hot and cold. Green, hot and cold. Chromium
Violet, hot and cold. Colourless, hot and cold. . Manganese
Blue, hot and cold. Blue, hot and cold. Cobalt
Brown, hot and cold. Grey when cold. Nickel
Yellow, hot and cold. Green when cold. Vanadium
Yellow when hot, Green, hot and cold. Uranium
yellow-green when
cold.
Pale yellow when hot, I Green when hot, blue* Tungsten
colourless when cold. when cold.
Colourless, hot and Yellow when hot, Titanium,
cold. violet* when cold.

• Blood red when fused with a trace of ferrous sulphate.

7. Sodium carbonate bead tests. The sodium carbonate

bead is prepared by fusing a small quantity of sodium carbonate
on a platinum wire loop in the Bunsen flame; a white, opaque
bead is produced. If this is moistened, dipped into a little
potassium nitrate and then into a small quantity of a man-
ganese compound, and the whole heated in the oxidising flame,
a green bead of sodium manganate is formed:
MnO + Na2COS + O2 = Na2Mn04 + CO 2
A yellow bead is obtained with chromium compounds, due to
the production of sodium chromate:
2Cr20 S + 4Na2COS + 302 = 4Na2Cr04 + 4C0 2
11,2. WET REACTIONS
These tests are made with substances in solution. A re-
action is known to take place (a) by the formation of a pre-
cipitate, (b) by the evolution of a gas or (c) by a change of
colour. The major number of the reactions of qualitative
analysis are carried out in the wet way and details of these are
given in later chapters. The following notes upon the methods
2] Experimental Technique of Inorganic AnalY8is 155
to be adopted in carrying out the tests will be found of value
and should be carefully studied.
1. Test-tubes. The best size for general use is 6 inches X
! inch. It is useful to remember that 10 m!. of liquid fills a
test-tube of this size to a depth of about It inches. Smaller
test-tubes are sometimes used for special tests. For heating
moderate volumes of liquids a somewhat larger tube, about
7 inches X 1 inch, the so-called "boiling tube," is recom-
mended. A test-tube brush should be available for cleaning
the tubes.
2. Beakers. Those of 50, 100 and 250 m!. capacity and of
the Griffin form are the most useful in qualitative analysis.
Clock glasses of the appropriate size should be provided. For
evaporations and chemical reactions which are likely to become
vigorous, the clock glass should be supported on the rim of
the beaker by means of V -shaped glass rods.
3. Conical or Erlenmeyer flasks. These should be of
50, 100 and 250 m!. capacity, and are useful for decompositions
and evaporations. The introduction of a funnel, whose stem
has been cut off, prevents loss of liquid through the neck of the
flask and permits the escape of steam.
4. Stirrin~ rods. A length of glass rod, of about 4 mm.
diameter, is cut into suitable lengths and the ends rounded
in the Bunsen flame. The rods should be about 20 em. long
for use with test-tubes and 8-10 cm. long for work with basins
and small beakers. Open glass tubes must not be used as
stirring rods. A rod pointed at one end, prepared by heating
a glass rod in the flame, drawing it out when soft as in the
preparation of a glass jet and then cutting it into two, is
employed for piercing the apex of a filter paper to enable one
to transfer the contents of a filter paper by means of a stream
of water from a wash bottle into another vessel.
A rubber-tipped glass rod or "policeman" is employed for
removing any solid from the sides of glass vessels. A stirring
rod of polythene (polyethylene) with a thin fan-shaped paddle
on each end is available commercially* and functions as a
satisfactory "policeman" at the laboratory temperature: it
can be bent into any form.
• "Police rod" from New York Laboratory Supply Co. Inc., 76 Varick
Street, New York, N.Y.13, U.S.A., A similar "police rod" is supplied by
Rediweld Ltd., 15/17 Crompton Way, Crawley, SU88eX, England.
"r--,,-, A-T-T-r-):1--.r-T-JI-A-'-'-T-I,>
 156 Qualitative Inorganic AnalY8i8 [II,
6. Wash bottle. This may consist of a 500 m!. flat
bottomed flask, and the stopper carrying the two tubes shoul'l
be preferably of rubber (compare Fig. II, 3, 9, a). It is reconl
mended that the wash bottle be kept ready for use filled wit!,
hot water as it is usual to wash precipitates with hot water
this runs through the filter paper rapidly and has a great!·,
solvent power than cold water, so that less is required fl l!
efficient washing. Asbestos string or cloth should be woun, i
round the neck of the flask in order to protect the hand.
A rubber bulb may be attached to the short tube as in Fig.
II, 3, 9, b: this form of wash bottle is highly convenient and I ;
more hygienic than the type requiring blowing by the moutl:
6. Precipitation. When excess of a reagent is to be USI 1
in the formation of a precipitate, this does not mean that a II
excessive amount of it should be employed. In most case·
unless specifically stated, only a moderate amount over th,,!
required to bring about the reaction is necessary. This 1-
usually best detected by filtering a little of the mixture aJl<!
testing the filtrate with the reagent; if no further precipitati, >II
occurs, a sufficient excess of the reagent has been added. I t
should always be borne in mind that a large excess of tk
precipitating agent may lead to the formation of complex iOt i i
and consequent partial solution of the precipitate; furth("
more, an unnecessary excess of the reagent is wasteful aJI,i
may lead to complications at a subsequent stage of the analysi:<.
7. Precipitation with hydro~en sulphide. This operl'
tion is of such importance in qualitative analysis that it meri I"
a detailed discussion. One method, which is sometim,:'1
employed, consists in passing a stream of gas in the form "f
bubbles through the solution contained in an open beak!"
test-tube or conical flask, this procedure is sometimes term' ,1
the "bubbling" method. The efficiency of the metbod is 10\\ ,
particularly in acid solution; absorption of the gas takes pIa tl i

at the surface of the bubbles and, since the gas is absorb, ,1

slowly, most of it escapes into the air of the fume chamber aI, 11
is wasted. It must be remembered that the gas is high iv
poisonous. The" bubbling" method i8 not recommended alld
8hould not be used for macro analysis. The most satisfacto!.'f
procedure (the "pressure" method) is best described with the
aid of Fig. II, 2, 1, a. The solution is contained in a small
conical flask A, which is provided with a stopper and lead-in
tube: B is a wash bottle containing water and serves to
remove any hydrochloric acid spray that might be ca.rried
2] Experimental Technique of Inorganic AnalY8is 157
over from the Kipp's apparatus in the gas stream: C is a
stopcock which controls the flow of gas from the generator,
whilst stopcock D* provides an additional control for the gas
flow. The conical flask is connected to the wash bottle by a
short length of rubber tubing. The stopper is first loosened
in the neck of the flask and the gas stream turned on (C first,
followed by D) so as to displace most of the air in the flask:
this will take not more than about 30 seconds. With the gas
flowing, the stopper is inserted tightly and the flask is gently
shaken with a rotary motion: splashing of the liquid on to the
H 2S delivery tube should be avoided. In order to ensure that
all the air has been expelled, it is advisable to loosen the
stopper in A again to sweep out the gas and then to tightly
c

(6) !
Fig. II, 2, I

stopper the Bask. Passage of the gas is continued with gentle

rotation of the flask until the bubbling of the gas in B has
almost ceased. t At this point the solution in A should be
saturated with hydrogen sulphide and precipitation of the
sulphides should be complete: this will normally require only a
few minutes. Complete precipitation should be tested for by
separating the precipitate by filtration, and repeating the pro-
cedure with the filtrate until the hydrogen sulphide produces
no further precipitate. Occasionally a test-tube replaces the
'" Stopcock D is optional; it prevents diffusion of air into the wash bottle
and thus ensures an almost immediate supply of H.S.
t It must be borne in mind that the gas may contain a small proportion
of hydrogen, due to iron usually present in the commercial ferrous sulphide.
Displacement of the gas in the flask (by loosening the stopper) when the
bubbling has diminished considerably will ensure complete precipitation.
158 Qualitative Inorganic Analys·is [II,
conical flask; it is shown (with the stopper) in (b). Tb,'
delivery tube mu.st be thoroughly cleaned after each precipita
tion. The advantages of the "pressure" method are; (i) .I
large surface of the liquid is presented to the gas and (ii) i!
prevents the escape of large amounts of unused gas.

8. Filtration. The purpose of filtration is, of course, in

separate the mother liquor and excess of reagent from Hl"
precipitate. A moderately fine-textured filter paper is generalJ \
employed. The size of the filter paper is controlled by tIl<
quantity of precipitate and not by the volume of the solutim;
The upper edge of the filter paper should be about 1 cm. fro I J I

the upper rim of the glass funnel. It should never be mOIl'

than about two-thirds full of the solution. Liquids COl,·
taining precipitates should be heated before filtration exce]"
in special cases, such as those containing lead chloride whi('})
is more soluble in hot than cold water. Gelatinous precipl
tates, which usually clog the pores of the filter paper and thlJ~
considerably reduce the rate of filtration, may be filterc,!
through fluted filter paper or through a pad of filter paper.,
resting on the plate of a Buchner funnel (Fig. II, 2, 4, B or C) :
tbis procedure may be used when the quantity of the precipita1,'
is large and is to be discarded (compare Section III, 20, I,·,
action 8). The best method is to add a little filter paper pulp
to the solution and then to filter in the normal manner. Til,:
filter paper pulp may consist of (a) filter paper clipping ..
ashless grade, (b) a filtration "accelerator" or "ash1ess tablet"
(Whatman), or (c) "dry-dispersed," ash-free, analytical fi11.-[·
paper pulp (Schleicher and Schuell, U.S.A.). All the vario'I:i
forms of pure filter paper pulp increase the speed of filtrati')11
by retaining part of the precipitate and thus preventing ti,t)
clogging of the pores of the filter paper.
When a precipitate tends to pass through the filter paper. it
is often a good plan to add an ammonium salt, such ciS
ammonium chloride or nitrate, to the solution; this will h,'!p
to prevent the formation of colloidal solutions. The additi"n
of a Whatman filtration "accelerator" may also be advtlll-
tageous.
A precipitate may be washed by decantation, as much 'tS
possible being retained in the vessel during the first two Jr I

three washings, and the precipitate then transferred to llie

filter paper. 1'his procedure is unnecessary for coarse, erys! ,d-
line, easy filterable precipitates as the washing can be carn·d
out directly on the filter paper. This is best done by direct! ilg
2] Experimental Technique of Inorganic Analyaia 159
a stream of water from a wash bottle first around the upper
rim of the filter and following this down in a spiral towards
the precipitate in the apex; the filter is filled about one-half to
two-thirds full at each washing. The completion of washing,
i.e. the removal of the precipitating agent, is tested for by
chemical means; thus if a chloride is to be removed, with silver
nitrate solution. If the solution is to be tested for acidity or
alkalinity, a drop of the thoroughly stirred solution, removed
upon the end of a glass rod, is placed in contact with a small
strip of "neutral" litmus paper or of "wide range" or "uni-
versal" test paper (Section I, 38) on a watch glass. Other test
papers are employed similarly.
9. Removal of the precipitate from the filter. If the
precipitate is bulky, sufficient for examination can be removed
with the aid of a small nickel or stainless steel spatula. If the
amOlmt of precipitate is small, one of two methods may be
employed. In the first, a small hole is pierced in the base of
the filter paper with a pointed glass rod and the precipitate
washed into a test-tube or a small beaker with a stream of
water from the wash bottle. In the second, the filter paper is
removed from the funnel, opened out on a clock glass and
scraped with a spatUla.
It is frequently necessary to dissolve a precipitate completely.
This is most readily done by pouring the solvent, preferably
whilst hot, on to the filter and repeating the process, if neces-
sary, until all the precipitate has passed into solution. If it is
desired to maintain the volume of the liquid small, the filtrate
may be poured repeatedly through the filter until all the pre-
cipitate has passed into solution. When only a small quantity
of the precipitate is a,vailable, the filter paper and precipitate
may be heated with the solvent and filtered.
10. Aids to filtration. The simplest device is to use a
funnel with a long stem, or better to attach a narrow-bored
glass tube, about 18 inches long and bent as shown in Fig.
II, 2, 2, to the funnel by means of rubber tubing. The lower
end of the tube or of the funnel should touch the side of the
vessel in which the filtrate is being collected in order to avoid
splashing. The speed of filtration depends inter alia upon the
length of the water colunm.
Where large quantities of liquids and/or precipitates are to
be handled, or if rapid filtration is desired, filtration under
diminished pressure is employed: a metal or glass water pump
may be used to provide the redueed pressure. A filter flask
 ,
160 Qualitative Inorganic Analysis [II,
of 250-500 ml. capacity is fitted with a two-holed rubber bUii~:
a long glass tube is passed through one hole and a short gl 1S
tube, carrying a glass stopcock at its upper end, through: Ite
other hole. The side arm of the flask is connected by me;, '1S
of thick-walled rubber tubing (" pressure" tubing) to anot! .'lr
flask, into the mouth of which a glass funne i is
fitted by means of a rubber bung. Upon apldv-
ing suction to the filter paper fitted into 'ite
funnel in the usual way, it will be punctured dr
sucked through, particularly when the volume ,)f
the liquid in the funnel is small. To SurmOl; I1t
the difficulty, the filter paper must be support"d
in the funnel. For this purpose either a Whatnun
filter cone (No. 51) made of a specially hardeJ",d
filter paper, or a Schleicher and Schuell (U.S. \.)
filter paper support (No. 123), made from a
muslin-type of material which will not ret;· I'd
filtration, may be used. Both types of supp, ,et
are folded with the filter paper to form the non', ILl
type of cone (Fig. II, 2, 3). After the filter pal 'or
has been supported in the funnel, filtration D'" Y
be carried out in the usual manner under I r te
partial vacuum created by the pump, the stope, "k
T being closed. When filtration is complete, i i te
Fig. II, 2, 2 stopcock T is opened, air thereby entering lite
apparatus which thus attains atmospheric pr '3-
sure: the filter funnel may now be removed from the fil; llr
flask (Fig. II, 2, 4, a).
For a large quantity of precipitate, a small Buchner funnel
b in Fig. II, 2, 4, shown enlarged for the sake of clarity) is

Fig. II, 2, 3

employed. This consists of a porcelain funnel in whicl; a

perforated plate is incorporated. Two thicknesses of w"il-
fitting filter paper cover the plate. The Buchner funnel is
fitted into the filter flask by means of a cork. When 1 :te
volume of liquid is small, it may be collected in a test-ti.lile
2) Experimental Technique of Inorganic Analy8i8 161
placed inside the filter flask. The Jena "slit sieve" funnel, *
shown in c, is essentially a transparent Buchner funnel; its
great advantage over the porcelain Buchner funnel is that it
is easy to see whether the funnel is perfectly clean.
Strongly acidic or alkaline solutions cannot be filtered
through ordinary filter paper. They may be filtered through
a small pad of glass wool or of asbestos placed in the apex of

(0) (b)

(0) (d)
Fig. II, 2, 4:

a glass funnel. A more convenient method, applicable to

strongly acidic and mildly basic solutions, is to employ a
sintered glass funnel (Fig. II, 2, 4, d): the filter plate, which is
available in various porosities, is fused into a resistance glass
(borosilicate) funnel. Filtration is carried out under reduced
pressure exactly as with a Buchner funnel.
11. Evaporation. The analytical procedure may specify
evaporation to a smaller volume or evaporation to dryness.
Both operations can be conveniently carried out in a porcelain
evaporating dish or casserole: the capacity of the vessel should
be as small as possible for the amount of liquid being reduced
• A Pyrex "slit sieve" funnel, with 65 mm. disc. is available commeroially.
6+
•
 162 Qualitative Inorganic Analysis [II.
in volume. The most rapid evaporation is achieved by heatm:!
the dish directly on a wire gauze. For many purposes a wat(
bath (a beaker half-filled with water maintained at the boilin.
point is quite suitable) will serve as a source of heat; the rai
of evaporation will of course be slower than by direct heatin.
with a flame. Should corrosive fumes be evolved during tb,
evaporation, the process must be carried out in the fum,
cupboard. When evaporating to dryness, it is frequent1'
desirable, in order to minimise spattering an
bumping, to remove the dish whilst there is still
little liquid left; the heat capacity of the evaporB
ting dish is usual1y sufficient to complete tbt'
operation without further heating.
The reduction in volume of a solution may als\)
be accomplished by direct heating in a small
beaker over a wire gauze or by heating in a wide
test-tube ("boiling-tube"), held in. a holder, by a
-10m, free flame; in the latter case care must be taken
T that the liquid does not bump violently. A useful
Fig. II, 2, 5 anti-humping device, applicable to solutions froll
which gases (hydrogen sulphide, sulphur dioxid(
etc.) are to be removed by boiling, is shown in Fig. II, 2, r
It consists of a length of glass tubing sealed off about 1 crr,
from one end, and is inserted into the solution. The devie,
must not be used in solutions that contain a precipitate.
12. Drying of precipitates. Partial drying, which J
sufficient for many purposes, is accomplished by opening ou
the filter, laying it upon several dry filter papers and aUowin.
them to absorb the water. More complete drying is obtained
by placing the funnel containing the filter paper in a "drying
cone" (a hol1ow tinned-iron cone or cylinder), which rests eithe;
upon a sand bath or upon a wire gauze and is heated by mean
of a small flame. The funnel is thus exposed to a current (
hot air, which rapidly dries the filter and precipitate. GreB
care must be taken not to char the filter paper. A safer bv
slower method is to place the funnel and filter paper, or tb,
filter paper alone resting upon a clock glass, inside a stear
oven.
13. Cleaning of apparatus. The importance of usin
clean apparatus cannot be too strongly stressed. All glasl
ware should be put away clean. A few minutes should b
devoted at the end of the day's work to "cleaning up"; tb,
student should remember that wet dirt is very much easier t, '
2] Experimental Technique of Inorganic AnalY8is 163
remove than dry dirt. A test-tube brush is provided to clean
test-tubes and other glass apparatus. Test-tubes may be in-
verted in the test-tube stand and allowed to drain. Other
apparatus, after rinsing with distilled water, should be wiped
dry with a "glass cloth," that is, a cloth which has been
washed at least once and contains no dressing.
Glass apparatus which appears to be particularly dirty or
greasy is cleaned by soaking in "chromic acid mixture" (con-
centrated sulphuric acid in which sodium dichromate is dis-
solved; say, 70 g. Na2Cr207,2H20 per litre), followed by a
liberal washing with tap water, and then with distilled water.

14. Some working hints. (1) Always work in a tidy,

systematic manner. Remember a tidy bench is indict1tive of
a methodical mind. A string duster is useful to wipe up
liquids spilt upon the bench. All glass and porcelain apparatus
must be scrupulously clean.
(2) Reagent bottles and their stoppers should not be put
upon the bench. They should be returned to their correct
places upon the shelves immediately after use. If a reagent
bottle is empty, it should be returned to the store-room for
filling.
(3) When carrying out a test which depends upon the forma-
tion of a precipitate, make sure that both the solution to be
tested and the reagent is absolutely free from suspended par-
ticles. If this is not the case, filter the solutions first.
(4) Do not waste gas or chemicals. The size of the Bunsen
flame should be no larger than is absolutely necessary. It
should be extinguished when no longer required. Avoid using
unnecessary excess of reagents. Reagents should always be
added portion -wise.
(5) Pay particular attention to the disposal of waste.
Neither strong acids nor strong alkalis should be thrown into
the sink; they must he largely diluted first, and the sink flushed
with much water. Solids (corks, filter paper, etc.) should be
placed in the special boxes provided for them in the laboratory.
On no account may they be thrown into the sink.
(6) All operations involving (a) the passage of hydrogen
sulphide into a solution, (b) the evaporation of concentrated
acids, (c) the evaporation of solutions for the removal of
ammonium salts and (d) the evolution of poisonous or dis·
agreeable vapours or gases must be conducted in the fume
chamber.
(7) All results, whether positi ve, negative or inconclusive,
 I
I
164 Qualitative Inorganic Analysis [II,
must be recorded neatly in a notebook in ink at the time they
are made. The writing up of experiments should not be post-
poned until after the student has left the laboratory. Apart
from inaccuracies which may thus creep in, the habit of per-
forming experiments and recording them immediately is one
that should be developed from the very outset.
(8) If the analysis is incomplete at the end of the laboratory
period, label all solutions and precipitates clearly. It is a gOt III
plan to cover these with filter paper to prevent the entran,,,
of dust, etc.
3J Experimental Technique of Inorganic Analysis 1&5

TECHNIQUE OF SEMIMICRO ANALYSIS

II, 3. Semimicro apparatus and semimicro anaJytical
operations.-The essential technique of semimicro analysis
does not differ very greatly from that of macro analysis.
Since volumes of the order of 1 m!. are dealt with, the scale of
the apparatus is reduced; it may be said at once that as soon
as the simple technique has been acquired and mastered, the
student will find it just as easy to manjpulate these small
volumes and quantities as to work with larger volumes and
quantities in ordinary test-tubes (150 X 20 mm.) and related
apparatus. The various operations occupy less time and the
consumption of chemicals and glassware is reduced consider-
ably; these two factors are of great importance when time and
money are limited. Particular care must be directed to having
both the apparatus and the working bench scrupulously clean.
1. Test-tubes and centrifuge tubes. Small Pyrex test-
tubes (usually 75 X 10 mm., 4 ml.; sometimes 100 X 12 mm.,

Ii
Ii
~~-+
1:2

~
Ii
~
1
~
~ x
E
:2 ""
:2 ~
x
x
<0
'""- "-

I 4 mI.
j
omI. 20 mI.
j
3 mi.
(a) (b) (0) (d)
Fig. 11, 3, I
8 m!.) are used for reactions which do not require boiling.
When a precipitate is to be separated by centrifuging, a test-
tube with a tapered bottom, known as a centrifu~e tube
(Fig. II, 3, 1, d) is generally employed; here, also, the contents
•
166 Qualitative Inorganic Analysis [II,
cannot be boiled as "bumping" will occur. Various sizes are
available; the 3 ml. centrifuge tube is the most widely usui
and will be adopted as standard throughout this book. For
rapid concentration of a solution by means of a free flame, tllo
semi micro boiling tube (60 X 25 mm." Pyrex; Fig. II, 3, I, ' )
will be found convenient.
2. Stirring rods. Solutions do not mix readily in sen·!-
micro test-tubes and centrifuge tubes: mixing is effected 1,\,

(a) (b)
Fig. II, 3, 2

means of stirring rods. These can readily

be made by cutting 2 mm. diameter glass
rod into 12 cm. lengths. A handle may
1
be formed, if desired, by heating about I
cm. from the end and bending it back at
an angle of 45° (see Fig. II, 3, 2, b). The
sharp edges are fire-polished by heating
momentarily in a flame. In washing a 1
precipitate with water or other liquid,
it is essential to stir the precipitate so
that every pa,rticle is brought in contact
with as large a volume of liquid as
i
~
possible: this is best done by holding ""
the tube almost horizontal, to spread
the precipitate over a large surface, and 1 (a) (b)
then stirring the suspension (Fig. II, 3,
2, b). Fig. II, 3, 3
3. Droppers. For handling liquids in semimicro analysi,
a dropper (also termed a dropper pipette) is generally employe( j,
Two varieties are shown in Fig. II, 3, 3, a and b. The former
finds application inter alia WIth 30 or 60 ml. (lor 2 fluid
ounce) reagent bottles and may therefore be called a reagen t
3] Experimental Technique of Inorganic Analyaia 167
dropper; the capillary of the latter (b) is long enough to reach
to the bottom of a 3 ml. centrifuge tube, and is used for re-
moving supernatant liquids from test-tubes and centrifuge tubes
and for the quantitative addition of reagents. Dropper b will
be named a capilJary dropper.
Whilst both types of dropper may be purchased, it is quite a simple
operation (and excellent practice) to make them from gla"l tubing.
To make a capillary dropper, take a piece of glass tubing about 20 cm.
long and of 7 rom. bore and heat it near the middle in a Bunsen or
blowpipe flame, rotating slowly all the time. When the centre is soft,
allow the glass to thicken slightly by continuing the heating an,1 rotating
whilst exerting a gentle inward pressnre from the ends. Remove the
tube from the flame and Blowly draw out the softened portion to form
a fairly thick.walled capillary about 20 cm. long and 2 rom. diameter.
When cold, cut the capillary at the mid.point with a file. :Fire-polish
the capillary ends by rotating in a flame for a moment or two. In
order that a rubber bulb (teat) may fit securely on the wide end, heat
it cautiously in a flame until just son, and whilst rotating slowly open
it up with a file or gls.ss.worker's triangular "reamer"; alternatively,
the softened end of the tube may be quickly pressed down on an
asbestos or uralite sheet or upon some other inert surface. A reagent
dropper is made in a similar manner except that it is unneeessary to
appreciably thicken the middle of the tube before drawing out.
Before use the droppers must be calibrated, i.e. the volume
of the drop delivered must be known. Introduce some distilled
water into the clean dropper by (lipping the capillary end into
some distilled water in a beaker and compressing and then
releasing the rubber teat or bulb. Hold the dropper vertically
over a clean dry 5 ml. measuring cylinder, and gently press the
rubber bulb. Count the number of drops until the meniscus
reaches the 2 m!. mark. Repeat the calibration until two
results are obtained which do not differ by more than 2 drops.
Calculate the volume of a single drop. The dropper should
deliver between 30 and 40 drops per m!. Attach a small label
to the upper part of the dropper giving the number of drops
per m!.
The standard commercial form of medicine dropper, with a
tip of 1·5 mm. inside diameter and 3 mm. outside diameter,
delivers drops of dilute aqueous solutions about 0·05 m!. in
volume, i.e. about 20 drops per ml. This dropper is somewhat
more robust than that shown in Fig. 11, 3, 3, a as it has a
shorter and thicker capillary: this may be an advantage for
elementary students, but the size of the drop (ca. 20 per ml.)
may be slightly too large when working with volumes of the
order of 1 m!. However, if this dropper is used, it should be
calibrated as described in the previous paragraph.
•
 I
168 Qualitative Inorganic Aruily8i8 [II,
It must be remembered that the volume of the drop delivered b:y .•
dropper pipette depends upon the density, surface tension, etc., of t' "
liquid. If the dropper delivers 20 drops of distilled water, the num1\,1'
of drops per ml. of other liquids will be very approximately as follows: :j
dilute aqueous solutions, 20-22; concentrated hydrochloric acid, 23-2 I ;
concentrated nitric acid, 36-37; concentrated sulphuric acid, 36-3
acetic acid, 63; and concentrated ammonia solution, 24-25.

4. Reagent bottles and reagents. A semi micro reagenl

bottle may be easily constructed by inserting a reagent dropP"i'
through a cork or rubber stopper that fits a 30 or 60 ml. (1 ,,,
2 fluid ounce) bottle-as in Fig. II, 3,4, a. One or two oun·
dropping bottles (Fig. II, 3, 4, b) may be purchased* and a

l,

(0) (b) (c) (d)

Fig. II, 3, 4

inexpensive: the stoppers of these bottles a're usually made "f

a hard rubber or plastic composition, and this as well as tJ '
rubber teat (or bulb) are attacked by concentrated inorgam
acids. A dropping bottle of one ounce capacity with an inter-
changeable glass cap (Fig. II, 3, 4, c) is also marketed.t TIlt'
bottles a and b cannot be used for concentrated acids and oth, '('
corrosive liquids because of their action upon the stopper,.:
The simplest containers for these corrosive liquids are 30 ,),
60 ml. T.K. dropping bottles (Fig. II, 3, 4, d).
Each student should be provided with a solid wooden stand
* The manufacturers of one satisfactory grade of dropping bottle v
Beatson, Clark & Co. Ltd., Rotherham, Yorks; the commercial name
"Bakelite-capped, amber, round eye drops with bulb end pipettes." TJ ..
firm also supplies the "Stoppered white T.K. dropping bottles."
t Quickfit and Quartz Ltd., "Quickfit" Works, Stone, Staffs.
3J Experimental Technique of Inorganic Analysis 169
housing a set of reagents in 30 mI. or, preferably, 60 mI. bottles.
The following are used in the author's laboratory.

Reagent Bottles Fitted with Reagent Droppers

(Fig. II, 3, 4, a or b)
Sodium hydroxide 5N Acetic acid, dil. 5N
Ammonium sulphide 6N Ammonia solution, conc. 15N
Potassium hydroxide 2N Ammonia solution, dil. 5N
Barium chloride O·5N Potassium ferro cyanide 0'5N
Silver nitrate O·IN Potassium chromate 0'5N
Ferric chloride 0'5N Ammonium carbonate 4N
T.K. Drappel' Bottles
Hydrochloric acid, conc. 12N Hydrochloric acid, dii. 5N
Sulphuric acid, conc. 36N Sulphuric acid, dil. 5N
Nitric acid, conc. 16N Nitric acid, dil. 5N

Some may prefer to have the Ammonia solution, conc. in a

T.K. bottle, and the dilute mineral acids in the reagent bottles
fitted with reagent droppers. Others may like to have the
Hydrochloric acid, dil. of 2'5-3N strength. These are
questions of personal preference, and the decision will rest
with the teacher.
The other reagents, which are used less frequently, are kept
in 60 or 125 ml. dropping bottles (30 ml. for expensive or
unstable reagents) on the reagent shelf (side shelf or side rack
reagents); further details of these will be found in the Appendix
(Section A, 2). Two sets of these bottles should be available
in each laboratory. When using these side shelf reagents,
great care should be taken that the droppers do not come into
contact with the test solutions, thus contaminating the re-
agents. If accidental contact should be made, the droppers
must be thoroughly rinsed with distilled water and then dried.
Under no circumstances should the capillary end of the dropper
be dipped into any foreign solution.
5. The centrifuge. The separation of a precipitate from
a supernatant liquid is carried out with the aid of a centrifuge.
This is an apparatus for the separation of two substances of
different density by the application of centrifugal force: the
latter may be several times that of gravity. In practice, the
liquid containing the suspended precipitate is placed in a semi-
micro centrifuge tube. The tube and its contents, and a
similar tube containing an equal weight of water are placed in
diagonally opposite buckets of the centrifuge, and the cover is
6*
~
170 Qualitative Inorganic Analysis [IT,
placed in position; upon rotation for a short time, allowing tJ .
buckets to come to rest and removing the cover, it will 1,,·
found that the precipitate has separated at the bottom of th
tube. This operation (centrifugation) replaces filtration j "
macro analysis. The supernatant liquid can be readily re-
moved by means of a capillary dropper; the clear liquid rna \'
be called the centrifugate or "centrate. "
The advantages of centrifugation are: (i) speed, (ii) tb
precipitate is concentrated into a small volume so that sma!
precipitates are observed readily and their relative magnitudp
estimated, (iii) the washing of the precipitate can be carrie, i
out rapidly and efficiently, and (iv) concentrated acids, bas(
and other corrosive liquids can be manipulated easily.
The theory of the centrifuge is given below. The rate of settling I,
(cm./sec.) of spherical particles of density dp and of radius a (em.) in .
medium of viscosity 7J (c.g.s. units) and of density dm is given by Stoke,
law:
2a Zg(dp -- dm } (I')
r, = 97]
where g is the acceleration due to gravity (981 cm./sec. D). It is evidenl.
from the equation that the rate of settling is increased by: (a) aI,

Fig. 11,3,5

increase in the size of the particles a; (b) an increase in difference

between the density of the particles dp and that of the medium d m ;
(o) a decrease in the viscosity 7J of the medium; and (d) an increase in
the acceleration due to gravity g. Fine crystalline particles tend to
increase in size when allowed to stand in the liquid in which they are
precipitated, particularly when the solution is maintained at elevated
temperatures and shaken occasionally. The coagulation of colloidal
and gelatinous precipitates is also accelerated by high temperatures
and stirring, and also by the addition of certain electrolytes. Moreover,
an increase in temperature reduces the viscosity and also increases the
difference (dp - - dm)' This explains why centrifuge tubes or test-tubes
3J Experimental Technique of Inorganic Analysis 171
in which precipitates are formed are usually placed in a hot water
bath and shaken from time to time before separation of the mother
liquor. The effect of these factors iR. however, comparatively small.
To accelerate greatly the rate of settling, the force on the particle g
(acceleration due to gravity) must be changed. This is readily and
conveniently achieved with the aid of a centrifuge.
The relative rates of settling in a centrifuge tube and in a stationary
test-tube may be derived as follows. The centrifugal force 1", upon a
particle of effective mass m (grams) moving in a circle of diameter r (em.)
at n revolutions per second is given by:
mv 2 m(2m-n) 2
= rna = -
Fe - - - - - = m.47r 2rn 2 ,
r =r
where a is the acceleration (cm./sec. 2 ), v is the velocity (cm./sec.), and
1T = 3·1416. The gravitational force F, on a particle of mass m is
given by:
F, = m.g
F. m.47r 2rn 2 41T2rn 2
F.= -mg- = -g-
Expressing rotations per second n in rotations per minute N, and
substituting for 1T, we have:
F, _ 47r 2rN2 _ . -5 N2
Fg - 9S1 X 602 - 1 118 X 10 r (2)
Thus a centrifuge with a radius of 10 cm. and a speed of 2000
revolutions per minute has a comparative centrifugal force of
l'llS X 10- 5 X 10 X (2000)2 = 447, say, 450 times the force of
gravity. A precipitate which settles in, say, 10 minutes by the force
of gravity alone will settle in 10 X 60/450 or in 1·3 seconds in such a
centrifuge. The great advantage of a centrifuge is thus manifest.
Several types of centrifuge are available for somimicro
analysis. These are:
A. A small 2-tube hand centrifuge with protecting bowl and
cover* (Fig. II, 3, 6 and Fig. II, 3,23); if properly constructed
it will give speeds up to 2-3000 r.p.m. with 3 m!. centrifuge
tubes. The central spindle should be provided with a locking
screw or nut: this is an additional safeguard against the possi-
bility of the head carrying the buckets flying off-an extremely
rare occurrence. The hand-driven centrifuge is inexpensive
and is satisfactory for elementary courses.
B. An inexpensive constant speed, electrically-driven centri-
fuge (see Figs. II, 3, 22 and II, 3, 23) is marketedt and has a
working speed of 1450 r.p.m. It is supplied with a dual-
purpose head. The buckets can either "swing out" to the
* An excellent model is manufactured by Moseley Centrifuge and Engineer-
ing Co. of 119 Copenhagen Street, London, N.!.
t "Micro" centrifuge from Measurllig and Scientific Equipment Ltd.,
Spenser Street, London, S.W.I, or from International Equipment Company,
1284 Soldiers Field Road, Boston 35, Mass., U.S.A.

•
 172 Qualitative Inorganic Analysis [II,
horizontal position or, by means of a rubber adapter, he
buckets can be held at a fixed angle of 45° (l\LS.E.) or ,1 0
(International); in the latter case, the instrument acts af: m
" angle" centrifuge. This is an alternative to the hand cer, "1-
fuge.
C. A variable speed, electrically-driven centrifuge (see l'ig.
II, 3, 23) with speed indicator* is the ideal instrument ',)r
centrifugation, but is relatively expensive. It is recommenl' d
Removable Lid Llftinq handles for lid

Fig. II, 3, 6

that at least one of these should be available in every laboratory

for demonstration purposes.
When using a hand-driven centrifuge, the following points
iti~ould be borne in mind:
bet'I) The two tubes should have approximately the same size
(0) a weight.
the aL f
increas~he tube should not be filled beyond I cm. rom the top.
precipit~ may corrode the buckets and produce an unbalanced
temperat
and geiat,
and stirrin§_' centrifuge from Measuring and Scientific Equipment Ltd.,
an increase inical model" centrifuge from International Equipment Com.
difference (d" Controlled speeds to a maximum of about 4000 r.p.m.
3) Experimental Technique of Inorganic Analysis 173
(3) Before centrifuging a precipitate contained in a centrifuge
tube, prepare a balancing tube by adding sufficient distilled
water from a dropper to an empty tube of the same capacity
until the liquid levels in both tubes are approximately the same.
(4) Insert the tubes in diametrically opposite positions in the
centrifuge; the head (sometimes known as a rotor) will then be
balanced and vibration will be reduced to a minimum. Fix
the cover in place.
(5) Start the centrifuge slowly and smoothly, and bring it to
the maximum speed with a few turns of the handle. Maintain
the maximum speed for 30-45 seconds, and then allow the centri-
fuge to come to rest of its own accord by releasing the handle.
Do not attempt to retard the speed of the centrifuge with the
hand. A little practice will enable one to judge the exact time
required to pack the precipitate tightly at the bottom of the
tube. It is of the utmost importance to avoid strains or
vibrations as these may result in stirring up the mixture and
may damage the apparatus.
(6) Before commencing a centrifugation, see whether any
particles are floating on the surface of the liquid or adhering to
the side of the tube. Surface tension effects prevent surface
particles from settling readily. Agitate the surface with a
stirring rod if necessary, and wash down the side of the centri-
fuge tube using a capillary dropper and a small volume of
water or appropriate solution.
(7) Never use centrifuge tubes with broken or cracked lips.
The instructions for use of constant speed, electrically-driven
centrifuges are similar to those given above with the addition
of the following:
(8) Never leave the centrifuge while it is in motion. If a
suspicious sound is heard, or you observe that the instrument
is vibrating or becomes unduly hot, turn off the current at
once and report the matter to the teacher. An unusual sound
may be due to the breaking of a tube; vibration suggests an
unbalanced condition.
(9) If a variable speed, electrically-driven centrifuge is
employed, switch the current on with the resistance fuUy in
circuit: gradually move the resistance over until the necessary
speed is attained. (For most work, it is neither necessary nor
desirable to utilise the full speed of the centrifuge.) After
30-45 seconds, move the slider (rheostat arm) back to the
original position: make certain that the current is switched off.
Allow 30 seconds for the centrifuge to come to rest, then raise
the lid and remove the tubes .
•
174 Qualitative Inorganic Analysis [II,
Most semimicro centrifuges will accommodate both sen,
micro test-tubes (75 X 10 mm.) and centrifuge tubes (up 'J
5 m!. capacity). The advantages of the latter include (a) easi
removal of the mother liquor with a droPP( .
and (b) with small quantities of solids, t):·,
precipitate is more clearly visible (and ti
relative quantity is therefore more easi
estimated) in a centrifuge tube (Fig. 11,3, ';
To remove the supernatant liquid, it,
capillary dropper is generally used. TIw
centrifuge tube is held at an angle in tJ "
left hand, the rubber teat or nipple of tj, .
capillary dropper, held in the right hand, "

"", Precipitate
/
Fig. II, 3, 7
compressed to expel the air and the capillal'
end is lowered into the tube until it is ju 1
below the liquid (Fig. II, 3, 8). As tJ.·
pressure is very slowly released the liqu:,;
rises in the dropper and the latter is lowered further into t} ,
liquid until all the liquid is removed. Great care should 1,
taken as the capillary approaches the bottom of the centrifu!_ '
tube that the tip does not touch the precipitate. The solution
in the dropper should be perfectly clear: it can be transferred j 0

Fig. 11,3,8

another vessel by merely compressing the rubber bulb. In diffi-

cult cases, a little cotton wool may be inserted in the tip of tL··
dropper and allowed to protrude about 2 mm. below the glasc\
tip; any excess of cotton wool should be cut off with scissor..;,
6. Washing of precipitates. It is essential to wash HI!
precipitates in order to remove the small amount of soluti() I I
3] Experimental Technique of Inorganic AnalY8i8 175
present in the precipitate, otherwise it will be contaminated
with the ions present in the centrifugate. It is best to wash
the precipitate at least twice, and to combine the first washing
with the centrifugate. The wash liquid is a solvent which does
not dissolve the precipitate but dilutes the quantity of mother
liquor adhering to it. The wash liquid is usually water, but
may be water containing a small amount of the precipitant
(common ion effect) or a dilute solution of an electrolyte (such
as an ammonium salt) since water sometimes tends to produce
colloidal solutions, i.e. to peptise the precipitate.
To wash a precipitate in a centrifuge tube, 5-10 drops of
water or other reagent are added and the mixture thoroughly
stirred (stirring rod or platinum wire); the centrifuge tube is
then counterbalanced against another similar tube containing
water to the same level and centrifuged. The supernatant
liquid is removed by a capillary dropper, and the washing is
repeated at least once.
7. Wash bottles. For most work in semimicro analysis a
30 or 60 m!. glass-stoppered bottle is a suitable container for

(a) (b) (c)

Fig. II, 3,9

distilled water: the latter is handled with a reagent dropper.

Alternatively, a bottle carrying its own dropper (Fig. II, 3, 4, a
or b) may be used. A small conical flask (25 or 50 ml.) may
be used for hot water. For those who prefer wash bottles,
various types are a.vailable (Fig. II, 3,9); a is a 100 or 250 m!.
flat-bottomed flask with a jet of 0,5-1 mm. diameter, and is
mouth-operated; b is a hand-operated wash bottle (flask, 125
m!.; rubber bulb, 50 ml.); and c is a Pyrex 50 ml. graduated
wash bottle.
 176 Qualitative Inorganic Analysis [II,
8. Transferring of precipitates. In some cases precipi
tates can be transferred from semimicro test-tubes with a sma!
spatula (two convenient types in nickel or monel metal* ar'
shown in Fig. II, 3, 10). This operation is usually difficul1
particularly for centrifuge tubes. Indeed
~ in semimicro analysis it is rarely neces
'<:l E;'
-E; sary to transfer actual precipitates fron,
r one vessel to another. If, for somt
. reason, transfer of the precipitate i:
~ essential, a wash liquid or the reagen1
~I itself is added, the mixture vigorousl)
stirred and the resulting suspensioII
transferred to a reagent dropper, and
the contents of the latter ejected intv
the other vessel; if required, the liquid
is removed by centrifugation.
If the precipitate in a test-tube is to
be treated with a reagent in an evapora-
ting dish or crucible, the reagent is added
first, the precipitate brought into suspen-
sion by agitation with a stirring rod, and
5 ;;: the suspension is then poured iuto the
mm. mm open dish or crucible. The test-tube
(a) (b) may be washed by holding it in an
Fig. II, 3, 10 almost vertical (upside down) position
with its mouth over the receptacle and
directing a fine stream of solution or water from a capillary
dropper on to the sides of the test-tube.
9. Heating of solutions. Solutions in semimicro centri-
fuge tubes cannot be heated over a free flame owing to the
serious danger of "bumping" (and consequent loss of part or
all of the liquid) in such narrow tubes. The "bumping" or
spattering of hot solutions may often be dangerous and lead to
serious burns if the solution contains strong acids or bases.
Similar remarks apply to semimicro test-tubes. However, by
heating the side of the test-tube (8 ml.) and not the bottom
alone with a micro burner, as indicated in Fig. II, 3, 11, and
withdrawing from the flame periodically and shaking gently,
"bumping" does not usually occur. The latter heating
operation requires very careful manipulation and should not
be attempted by elementary students. The mouth of the
test-tube must be pointed away from the students nearby.
• Type b, with slightly modified dimensions, is obtainable from Wilkens
Anderson Co., 4525 W. Division Street, Chicago 51, Illinois, U.S.A.

•
3] Experimental Technique of lnor(Janic Analysis 177
The danger of "bumping" may be considerably reduced by
employing the anti-bumping device shown in Fig. 11, 2, 5;
the tube should be about 1 cm. ](.nger than the test-tube to
facilitate removal.
On the whole it is--Setter to resort to safer methods of heating.
The simplest procedure is to employ a small water bath. This
may consist of a 250 m!. Pyrex beaker, three-quarters filled
with water and covered with a lead or galvanised iron plate
(Fig. II, 3, 12) drilled with two holes to accommodate a test-
tube and a centrifuge tube. It is a good plan to wind a thin

Fig. II, 3, 11 Fig. II, 3, 12

rubber band about 5 mm. from the top of the tube; this will
facilitate the removal of the hot tube from the water bath
without burning the fingers and, furthermore, the rubber band
can be used for attaching small pieces of folded paper con-
taining notes of contents, etc.
A more elaborate arrangement which will, however, meet
the requirements of several students, is Barber's water bath
rack (Fig. II, 3, 13). The dimensions of a rack of suitable
size are given in Fig. II, 3, 14. This rack will accommodate
four centrifuge tubes and four semimicro test-tubes. The
apparatus is constructed of monel metal, stainless steel, a
plastic material which is unaffected by water at 100°, or of
brass which is subsequently tinned. The brass may be tinned
by boiling with 20 per cent sodium hydroxide solution con-
taining a few lumps of metallic tin.
10. Evaporations. Where rapid concentration of a liquid
is required or where volatile gases must be expelled rapidly.
I i
~ 178 Qualitative Inorganic Andlysis
the semimicro boiling tube (c in Fig. II, 3, 1) may be employe' I
Two useful holders, constructed of a light metal alloy, a'

"OBmm.

4mm.

Fig. II, 3, 13 Fig. II, 3, 14

shown in Fig. II, 3, 15; b is to be preferred as the boiling tube

cannot fall out by mere pressure on the holder at the point

'.
, .._,_.--~ ..

O~(b)O- a

Fig. II, 3, 15

where it is u1:!ually held. * Slow evaporation may be achieved

by heating in a test-tube, crucible or beaker on a water bath.
• A SIIlall wooden clothes-peg (spring type) may also be used for holding
semiroioro test-tubes.
3] Experimental Technique of Inorganic Analysis 179
If evaporation to dryness is required, a small casserole (ca.
6 ml.) or crucible (3-8 ml.) may be employed. This may be
placed in an air bath consisting of a 30 ml. nickel crucible and
supported thereon by an asbestos or uralite ring (Fig. II,
3, 16, a), and heated with a semimicro burner. Alternatively,
a small Pyrex beaker (say, of 50 or 100 ml. capacity) may be
used with a silica or nichrome triangle to support the ('rucible
or casserole (Fig. II, 3, 16, b): this device may also be applied
for evaporations in semimicro beakers.
Evaporation to dryness may also be accomplished by direct

(a) (6)
Fig. II, 3. 16
.
intermittent heating with a micro burner of a crucible (sup-
ported on a nichrome or silica triangle) or of a semimicro
beaker (supported on a wire gauze). A little practice is
required in order to achieve regular boiling by intermittent
heating with a flame and also to avoid "bumping" and spat-
tering: too hot a flame should not be used. In many cases
the flame may be removed whilst a little liquid remains: the
heat capacity of the vessel usually suffices to complete the
evaporation without further heating. If corrosive fumes are
evolved, the operation should be conducted in the fume cup-
board.
11. Dissolving of precipitates. The reagent is added
and the suspension is warmed, if necessary, on the water bath
until the precipitate has dissolved. If only partial solution
occurs, the suspension may be centrifuged.
12. Precipitations with hydrogen sulphide. Various
automatic generators of the Kipp type are marketed, and may
be employed for groups of students. Owing to tho highly
poisonous and very obnoxious character of hydrogen mlphide,
these generators are always kept in a fume cupboard (draught
chamber or hood). A wash bottle containing water should
ISO Qualitative Inorganic Analysis l' f,
always be attached to the generator in order to remove a(
spray (compare Fig. II, 2, I, a). The tube dipping into t,
liquid in the wash bottle should preferably be a heavy-wall.
capillary: this will give a better control of the gas flow and "\\
also help to prolong the life of the charge in the H 2S generat( ,
Precipitation may be carried out in a centrifuge tube, but
semimicro test-tube or 10 m!. conical flask is generally pI'
ferred; for a large volume of solution, a 25 ml. Erlenmey,
flask may be necessary. The delivery tube is drawn out to
thick-walled capillary (1-2 mm. in diameter) and carries at tJ
upper end a small rubber stopper which fits the semi micro tef
tube * (Fig. II, 3, 17) or conical flask. The perfectly clet,
delivery tube is connected to the source of hydrogen sulphi( ,
as in Fig. II, 2, I and a slow str«;lam of gas is passed thro~~
the liquid for about 30 seconds in order 1
expel the air, the cork is pushed into positio,
and the passage of hydrogen sulphide is COl
tinued until very few bubbles pass through tl
liquid; the vessel is shaken gently from time 1
time. The tap in the gas generator is the!,
turned off; the delivery tube is disconnecte,;
and immediately rinsed with distilled wate
If the liquid must be warmed, the stopper j
loosened, the vessel placed in the water baL
for a few minutes, and the gas introduce i
again.
Fig. II, 3, 17 If an individual generator is desired, ,!
Pyrex test-tube (150 X 20 mm.) charged wit},
"Aitch-tu-ess" or an equivalent mixture (essentially an irl
timate mixture of a solid paraffin hydrocarbon, sulphur an'
asbestos) is utilised: this yields hydrogen sulphide whCl
heated by a micro burner and the evolution of gas cease,
(but not usually abruptly) when the source of heat is re
moved. The test-tube type of generator is depicted in Fig
II, 3, IS, a. The small hole (vent) is covered with the fingel
during the passage of the gas. Since the hydrogen sulphid,
evolution does not cease abruptly with the removal of th,
flame, an absorption bottle (Fig. II, 3, 18, b) is generall:
employed to absorb the unused gas. It consists of a 60 ml.
bottle containing 10 per cent sodium hydroxide solution: the
lower end of the longer 6 mm. tube is just above the surface
'" For a 3 ml. centrifuge tube or a 4 ml. test-tube, the top part of the rubber
teat (bulb) from a dropper makes a satisfactory stopper: a small hole is made
in the rubber bulb and the delivery tube is carefully pushed through it.
3] Experimental Technique of Inorganic Analysis 181
of the solution. When saturation of the solution with the
gas is completed, the capillary pipette and cotton wool bulb
are removed and the absorption bottle is attached. The

(a)
Fig. II, 3, 18

method is not strongly recommended because "pressure"

precipitation (compare Section II, 2, 7) is difficult and, if
attempted, introduces an element of danger.
13. Identification of gases. Many anions (e.g. carbonate,
sulphide, sulphite, thiosulphate and hypochlorite) are usually
identified by the volatile decomposition products obtained

(b) (c)

Fig. II, 3, 19

with the appropriate reagents. Suitable apparatus for this

purpose are shown in Fig. II, 3, 19. The simplest form a
consists of a s~imicro test-tube with the accompanying" filter
 182 Qualitative Inorganic A nalysi8 (II.
tube"*: a strip of test paper (or of filter paper F ':ld win
the necessary reagent) about 3-4 mm. wide is Stl in tI"
"filter tube." In those cases where spray is likel~ ~ct tlJ.
test paper, a loo8e plug of cotton wool should Ge placed H t
the narrow end of the" filter tube." Apparatus b is employe,!
when the test reagent is a liquid. A short length of wide-bon,
rubber tubing is fitted over the mouth of a semimicro test-tub.

(a) (b)
I·'i.
jt:

Fig. II, 3, 20

with about 1 cm. protruding over the upper edge. The chemical
reaction is started in the test-tube and a "filter tube" con-
taining a tightly-packed plug of cotton wool is inserted through
the rubber collar, the filter plug again packed down with a
4 mm. glass rod, and 0·5-1 ml. of the reagent introduced. An
'" Test.tubes (75 x 10 mm. and 100 X 12 mm,) together with the matching
"filter tubes" (55 X 7 mm. and 80 X 9 mm.) are standard Pyrex products;
they are inexpensive and therefore eminently suitable for elementary and
other students. The smaller size is satisfactory for most purposes.
t
3J Experimental Technique of Inorganic Analysis 183
alternative apparatus for liquid reagents is shown in c; it is a
type of absorption pipette and is attached to the 4 m!. test-
tube by a rubber stopper or a tightly-fitting paraffined cork.
A drop or two of the liquid reagent is introduced into the
absorption tube. The double bulb ensures that all the ovolved
gas reacts, and it also prevents the test reagent from
being sucked back into the reaction mixture. All tho above
apparatus, a-c, may be warmed by placing in the hot water
rack (e.g. Fig. 11, 3, 13). They will meet all normal require-
ments for testing gases evolved in reactions in qualitative
analysis.
When the amounts of evolved gas are likely to be small, the
apparatus of Fig. 11, 3, 20 may be used: all the evolved gas
may be swept through the reagent by a
stream of air introduced by a rubber
bulb of 3-4 fluid ounces capacity. *
The approximate dimensions of the
essential part of the apparatus are given
o
in a, whilst the complete assembly is
depicted in b. The sample under test is
placed in B, the test reagent is intro-
duced into the "filter tube" A over a
tightly-packed plug of cotton wool (or
other medium), and the acid or other
liquid reagent is added through the
"filter tube" C. The rubber bulb is in-
serted into C, and by depressing it gently
air is forced through the apparatus, thus
sweeping out the gases through the test
reagent in A. The apparatus may be
warmed by placing it in a hot water
bath.
14. Cleaning of apparatus. It is
essential to keep all apparatus scrupu-
lously clean if trustworthy results are to Fig. II, 3, 21
be obtained. All apparatus must be
thoroughly cleaned with cleaning mixture (a solution of
sodium dichromate in concentrated sulphuric acid, say 70 g.
Na2Cr207,2H20 per litre) or with a brush and cleaning powder.
The apparatus is then rinsed several times with tap water, and
repeatedly with distilled water. Special brushes (Fig. II, 3,21)
are available for semimicro test-tubes and centrifuge tubes; the
• The bulb of a commercial rectum or ear syringe is satisfactory.

l
 184 Qualitative Inorganic Analysis [II.
commercial "pipe cleaners" are also satisfactory. The tub,
may be allowed to drain in a special stand or else they may 1"
inverted in a small beaker on the bottom of which there a, -
several folds of filter paper or a filter paper pad to absorb tl-
water. Larger apparatus may be allowed to drain on a clea
linen towel or glass cloth. Droppers are best cleaned by first f<
moving the rubber bulbs or teats and allowing distilled water t-
run through the tubes; the teats are cleaned by repeatedly fiUin
them with distilled water and emptying them. When cleal-
they are allowed to dry on a linen glass cloth. At the end ( ,
the laboratory period, the clean apparatus is placed in a bo,
with cover, so that they may remain clean until required.
15. Spot plates. Drop reaction paper. These aT'
employed chiefly for confirmatory tests (see Section II, 6 fo;
a full discussion). Spot plates with a number of circula
cavities are marketed, either black or white. The former ar'
employed for white or light-coloured precipitates, and th,
latter for dark-coloured precipitates. Transparent spot plate;
(e.g. Jena) and combination black and white spot plates (wit}
line of demarcation between the black and white runnin!:
exactly through the centres of the depressions) are also avail-
able commercially. Spot plates are useful for mixing small
quantities of reagents, and also for testing the pH of a solution
colorimetrically.
Drop reaction or spot test paper (e.g. Whatman, No. 120) if
a soft variety of pure, highly porous paper which is used for
reactions that result in highly coloured precipitates. The pre-
cipitate does not spread very far into the paper because of the
filtering action of the pores of the paper; consequently the spot
test technique is employed in highly sensitive identification
tests, the white paper serving as an excellent background for
dark or highly coloured precipitates, and incidentally provid-
ing a permanent record of the test.
Semi-quantitative results may be obtained by the use of the
Yagoda "confined-spot-test" papers (Schleicher and Schuell,
U.S.A., Nos. 211Y and 597Y): these are prepared with a
chemically inert, water-repelling barrier which constricts the
spot reaction to a uniform area of fixed dimensions.
16. Calculation of the volume of precipitating reagents.
This type of calculation is instructive, for it will assist the
student to appreciate fully the significance of the quantities of
reagent employed in semimicro analysis. Let us assume that
a sample contains 1 mg. of silver ions and 2 mg. of mercurous
3] Experimental Technique oj Inorganic Analysis 185
ions, and that the precipitating agent is 5N hydrochloric acid.
To calculate the volume of the precipitating agent required,
the number of equivalents of the ion or ions to be precipitated
and the number of equivalents per ml. of the precipitating
agent must be ascertained. In the present sample there will
be (1 X 10-3)/107.9 = 9·3 X 10-6 equivalents of silver ion and
(2 X 10-3)/200.6 = 1 X 10-5 equivalents of mercurous ion, i.e.
the total concentration of cation is 1·93 X 10-5 equivalents.
Now 1 ml. of 5N hydrochloric acid contains 5 X 10-3 equi-
valents of chloride ion, so that the volume of acid required
will be (1·93 X 10-5 )/(5 X 10-3 ) = 0·0039 ml. The capillary
dropper delivers a drop of about 0·03 ml. (30-40 drops per mI.),
hence 1 drop of 5N hydrochloric acid contains sufficient chloride
ions to precipitate the silver and mercurous ions and also to
provide a large excees to reduce the solubility of the sparingly
soluble chlorides (common ion effect).
In practice, the weights of the ions in a solution of the sample
are usually not known, so that exact calculations cannot be
made. However, if the weight of sample employed is known,
the maximum amount of precipitating agent required can be
easily calculated. This is one of the reasons for taking a
known weight (weighed to the nearest milligram) of the sample
for analysis. Let us consider an actual example. \Ve may
assume that 50 mg. of the solid sample or, for solutions, such
a volume as will yield 50 mg. of solid upon evaporation to
dryness, is taken for analysis and that the maximum quantity
of all the metal ions present in the sample is 35 mg. It is
evident that the smaller the equivalent of a given ion, the
greater will be the number of equivalents contained in a given
weight of it and hence the larger the volume of hydrochloric
acid required for precipitation. III Group I, lead has the lowest
equivalent (103·5). The number of equivalents for 35 mg. of
lead is 35/(103·5 X 1000) = 3·38 X 10-4 equivalents or 0·338
milli-equivalents. Now 1 m!. of 5N hydrochloric acid contains
5 X 10-3 equivalents or 5 milli-equivalents. Hence the exact
volume of this acid required for complete precipitation is
0·338/5 = 0·0676 ml. = 2 drops, and the addition of 3-4 drops
will suffice for complete precipitation (common ion effect) and
also to prevent the precipitation of bismuth and antimony
oxychlorides.
17. Some practical hints (compare Section II, 2, 14): .
(1) Upon commencing work, arrange the more common and
frequently used apparatus in an orderly manner on your bench.
I.
 i
186 Qualitative Inorganic Analysis [II,
Each item of apparatus should have a definite place so that i r,
can be found readily when required. All apparatus shoul'
have been cleaned during the previous laboratory period.
(2) Weigh the sample for analysis (if a solid) to the nearef'
milligram: 50 mg. is a suitable quantity.
(3) Read the laboratory directions carefully and be certaii!
that you understand the purpose of each operation-additio; I

of reagents, etc. Examine the label on the bottle before addin:.'

the reagent. Serious errors leading to a considerable loss (I;
time and, possibly, personal injury may result from the use ("
the wrong reagent. Return each reagent bottle to its prope;'
place immediately after use.
(4) When transferring a liquid reagent with a reagent drop
per, always hold the dropper just above the mouth of tho
vessel and allow the reagent to "drop" into the vessel. n '
not allow the dropper tip to touch anything outside the reagen'
bottle; the possible introduction of impurities is thus avoided
Similar remarks apply to the use of T.K. dropper bottles.
(5) Never dip your own dropper into a reagent. Pour"
little of the reagent (e.g. a corrosive liquid) into a small clea1'
vessel (test-tube, crucible, beaker, etc.) and introduce you,
dropper into this. Never return the reagent to the bottle; j
is better to waste a little of the reagent than to take the riS!
of contaminating the whole supply.
(6) Do not introduce your spatula into a reagent bottle t"
remove a little solid. Pour or shake a little of the solid on t, ,
a clean, dry watch glass, and use this. Do not return the soli•.
reagent to the stock bottle. Try to estimate your require
ments and pour out only the amount ;necessary.
(7) All operations resulting in the production of fumes (acid
vapours, volatile ammonium salts, etc.) or of poisonous or dis
agreeable gases (hydrogen sulphide, chlorine, sulphur dioxide
etc.) must be performed in the fume chamber.
(8) Record your observations briefly in your note-book it
ink immediately after each operation has been completed.
(9) Keep your droppers scrupulously clean. Never plac(
them on the bench. Rinse the droppers several times wit}.
distilled water after use. At the end of each laboratof\
period, remove the rubber teat or cap and rinse it thoroughli
(10) During the course of the work place dirty centrifug'
tubes, test-tubes, etc., in a definite place, preferably in iI
beaker, and wash them at convenient intervals. This task cal!
often be done while waiting for a solution to evaporate or for II
precipitat,e to dissolve while being heated on a water bath.
3] Experimental '1'echnique of Inorganic Analysis 187
(11) Adequately label all solutions and precipitates which
must be carried over to the next laboratory period.
(12) When in difficulty, or if you ~mspect any apparatus (e.g.
the centrifuge) is not functioning efficiently, consult the
teacher.
18. Semimicro apparatus. The plates (Figs. II, 3, 22
and II, 3, 23) show all the general npparatus required for
semimicro analysis. Other apparatus of specialised character
will be described in the text.
The apparatus suggested for each student is listed below (see
plate, Fig. II, 3, 22). (The liquid reagents recommended for
each student are given in Section II, 3, 4.)
1 beaker, Pyrex, Griffin form, 250 ml.
1 hot water rack constructed of tinned copper (Fig. 11,3,13-14) or
1 lead cover (Fig. II, 3, 12) for water bath.
1 beaker, Pyrex, 5 mI.
1 beaker, Pyrex, 10 ml.
1 conical flask, Pyrex, 100 mI., and one 50 m!. rubber bulb (for
wash bottle, Fig. II, 3, 9, b).
2 conical flasks, Pyrex, 10 m!.
1 conical flask, Pyrex, 25 ml.
6 test-tubes, Pyrex, 7:-' X 10 mm.,* 4 mi., with rim.
2 test-tubes, Pyrex, 75 X 10 mm.,* 4, mI., without rim.
2 "filter tubes," Pyrex, 55 X 7 mIll. * (Fig. II, 3, 19, a).
1 gas absorption pipette (with 75 X 10 mm. test-tube and rubber
stopper, Fig. II, 3, 19, c).
4 centrifuge tubes, Pyrex, 3 m!. (Fig. II, 3, I, d).
2 semimiero boiling tubes, Pyrex, 60 X 25 mm., 20 m!.
1 wooden stand (to house test-tubes, "fi1t·er tubes," gas ab~orption
pipette, conical flasks, etc.).
2 medicine droppers, complete with rubber teats (bulbs).
2 reagent droppers (Fig. II, 3, 3, a).
2 capillary droppers (Fig. II, 3, 3, b).
I stand for droppers.
2 anti-bump tubes (Fig. II, 2, 5).
1 crucible, porcelain, Royal Worcester, 3 ml. (23 X 15 mm.).
1 crucible, porcelain, Royal Worcester, 6 ml. (28 X 20 mm.).
I crucible, porcelain, Royal Worcester, 8 ml. (32 X 19 mm.).
3 rubber stoppers (one i X i inch, two! X t inch, to fit 25 ml.
conical flask, test-tube and gas absorption pipette).
30 CID. glass tubing, 4 mID. outside diameter (for H 2S apparatus).
* Semimicro test-tubes (Pyrex, 100 X 12·5 mm., S ml.) and the appropriate
"filter tubes" (Pyrex, SO X 9 rom.) are marketed, and these may lind appli-
cation in analysis. The smaller 4 ml. te8t·tubes will generally Bulnce: their
great advantage is that t.hey can be used dirently in a semimicro centrifuge
in the buckets provided for the 3 ml. centrifuge tubes.
 \
188 Qualitative Inorganic Analysis
10 cm. rubber tubing, 3 mm. (for H 2S apparatus).
5 cm. rubber tubing, 5 mm. (for" filter tubes ").
30 cm. glass rod, 3 mm. (for stirring rods, Fig. II, 3, 2)-:-
1 measuring cylinder, 5 ml.
I watch glass, It inch diameter.
2 cobalt glasses, It X It inches.
2 microscope slides.
I platinum wire (5 cm. of 0·3 mm. diameter).
I forceps, 4 inches.
I semimicro spatula (Fig. II, 3, 10, a or b).
I semimicro test-tube holder (Fig. II, 3, 15).
I semimicro test· tube brush (Fig. II, 3,21).
I pipe cleaner.
I spot plate (6 cavities).
1 wide-mouthed bottle, I ounce, filled with cotton wool.
I wide-mouthed bottle, 1 ounce, filled with strips (2 X 2 cm.) "f
drop reaction paper.
I dropping bottle, labelled DISTILLED WATER.
I packet blue litmus paper.
1 packet red litmus paper.
1 triangular file (small).
1 tripod and wire gauze (for water bath).
1 retort stand and one iron ring (3 inches).
1 wire gauze (for ring).
I triangle, silica.
I triangle, nichrome.
I burner, Bunsen or Tirrill.
I semimicro burner.

TECHNIQUE OF MICRO ANALYSIS

II, 4. General Discussion.-In micro analysis the scale of oper,,·
tions as compared with macro analysis is reduced by a factor of 0·01
Thus whereas in macro analysis the weights and volumes for analysi,
are 0·5-1 g. and about 10 mi., and in semimicro analysis 50 mg. alii I
I m!. respectively, in micro analysis the corresponding quantitifh
are about 5 mg. and 0·1 ml. Micro analysis is sometimes termed
milligram analysis to indicate the order of weight of the sampl.
employed. It must be pointed out that whilst the weight of th,
sample for analysis has been reduced, the ratio of weight to volum,
has been retained and in consequence the concentration of th.·
individual ions, etc., are maintained. A special technique must b"
used for handling such small quantities of materials. There is no
sharp line of demarcation between semimicro and micro analysis
and much of the technique described for the former can, witb
suitable modifications to allow for the reduction in scale by about
one-tenth, be utilised for the latter. Some of the modifications,
involving comparatively simple apparatus, will be described. No
5] Experimental Technique of Inorganic Analysis 189
attempt will be made to deal with operations centered round the
microscope (magnification up to 250) as the specialised technique is
outside the scope of this volume. *
The small amounts of material obtained after the usual systematic
separations can be detected, in many cases, by what is commonly
called spot analysis, i.e. analysis which utilises spots of solutions
(about 0·05 ml. or smaller) or a fraction of milligram of solids. Spot
analysis has been developed as a result of the researches of numerous
chemists: the names of Tananaeff, Krumholz, Wenger, van Niewen-
burg, Gutzeit and, particularly, Feigl and their collaborators must
be mentioned in this connexion. In general, spot reactions are
preferable to tests which depend upon the formation and recognition
of crystals under the microscope, in that they are easier and quicker
to carry out, less susceptible to slight variations of experimental
conditions, and can be interpreted more readily. Incomplete
schemes of qualitative inorganic analysis have been proposed which
are based largely upon spot tests: these cannot, however, be
regarded as entirely satisfactory for very few spot tests are specific
for particular ions and also the adoption of such schemes will not,
in the long run, help in the development of micro qualitative
analysis. Furthermore, such schemes, when considered from the
point of view of training of students in the theory and practice of
analysis, are pedagogically unsound. It seems to the writer that
the greatest potential progress lies in the use of the common macro
procedures (or simple modifications of them) to effect the pre-
liminary separations for which the specialised micro technique is
adopted, followed by the utilisation of spot tests after the group or
other separation has been effected. Hence the following pages will
contain an account of the methods which can be used for per-
forming macro operations on a micro scale and also to a discussion
of the technique of spot analysis.
II, 5. Micro Apparatus and Micro Analytical Operations.-
It is assumed that the reader is familiar with the account of semi-
micro technique given in Section II, 3.
Micro centrifuge tubes (Fig. 11, 5, 1) of 0·5-2 ml. capacityt
replace test-tubes, beakers and flasks for most operations. Two
types of centrifuge tubes are shown: b is particularly useful when
• For a detailed account, see E. M. Chamot and C. W. Mason, Handbook
of Chemical Micr08copy, Volume I (1938) and Volume II (1940) (J-. Wiley;
Chapman and Hall); also A. A. Benedetti-Pichler, Introduction to the Micro-
technique of Inorganic AnalY8is (1942) (J. Wiley; Chapman and Hall).
t The dimensions given ensure that the C'entrifuge tubes fit into tho buckets
of a semimicro centrifuge. The dimensions for other capacities are: Type a:
0·5 mL, 60 X 6·3 mm. (ext.); 2 mL, 68 X 1l·25 mm. (ext.); 3 mL, 76 X 11·25
mm. (ext.). Type b: 0·5 mL, 63 rom., 8'5 mm. (ext.), 2·5 rom. (int.).
All the dimensions have been extractod from B.S. 1428, 195:;, Micro-
chemical Apparatus, Part E3, Micro-centrifuge Accessories, and are repro-
duced by kind permission of British Standnrds Institution, 24 Victoria Street,
London, S.W.I.

•
 190 Qualitative Inorganic AnalY8i8 [II,
very small amounts of precipitate are being handled. Cent, ,fuge
tubes are conveniently supported in a rack consisting of a WI.' den
block provided with 6 to 12 holes, evenly spaced, of § inch dial ,~ter
and t inch deep.
Solutions are separated from precipitates by centrifuging. ,"·,'rni-
micro centrifuges (Section II, 3, 5), either hand-operate. I or
~ electrically - driven, can be ' ;ed.
:t Adapters are provided inside the
~ buckets (baskets) in order to ac lm-
modate micro centrifuge tubes . ith
narrow open ends.
Precipitations are usually ca, led
out in micro centrifuge tubes. J ter
centrifuging, the precipitate col "ts
in the bottom of the tube. • he
supernatant liquid may be rem( . ed
either by a capillary dropper (Fig. fl,
%~ 3, 3) or by means of a tran;,fer
';;; E;

1! ~ capillary pipette. The latter .' n-

sists of a thin glass tube (inte. :al
Iml. I mi. diameter about 2 mm.: this can be
prepared from wider tubing) 20 to
(b)
25 cm. in length with one end dr:' 'In
} Fig. II, 5, 1 out in a micro flame to a tip wit' aI

j: fine opening. The correct method qf

,ransferring the liquid to the capillary pipette will be evident fI" 'm
!fig. II, 5, 2. The centrifuge cone is held in the right hand: ,d
,he capillary pipette is pushed slowly towards the precipitate 0
,hat the point of the capillary remains just below the surface ,f
,he liquid. As the liquid rises in the pipette, the latter is graduD 'y
owered, always keeping the tip just below the surface of the Jiq],;' I

11-:_ _ _ s:::=»
'(

Fig. II, 5, 2

until the entire solution is in the pipette and the tip is about I mIll.
above the precipitate. The pipette is removed and the liquid blo" ';
or drained out into a clean dry centrifuge tube.
Another useful method for transferring the centrifugate to, say.
another centrifuge tube will be evident upon reference to Fig. II, 5,~;
The siphon is made of thermometer capillary and is attached t"
the capillary pipette by means of a short length of rubber tubin'
5] Expe1'imental Technique of Inorganic Analysis 191
of 1 mm. bore. The small hole A in the side tube permits of perfect
control of the vacuum; the side arm of the small test-tube is situated
near the bottom so as to reduce spattering of the liquid in the centri-
fuge tube inside the teBt-tube when the vacuum is released. Only

A
~~~==~~==~~
pump

Fig. II, 5, 3

gentle suction is applied and the 9pening A is

closed with the finger; upon removing the finger,
the action of the capillary siphon ceases immedi-
ately.
For the washing of precipitates the wash
solution is added directly to the precipitate in the
centrifuge tube and stirred thoroughly either by 0'3 em.
a platinum wire or by means of a micro stirrer, bore
lOem.
such as is shown in Fig. II, 5, 4; the latter can
readily be made from thin glass rod. The mixture
is then centrifuged, and the clear solution removed
by a transfer capillary pipette as already des-
cribed. It may be necessary to repeat this
operation two or three times to ensure complete
washing.
The transfer of precipitates is comparatively
rare in micro qualit.c'1tive analysis. Most of the 0·' em. i

Il
operations are usually so designed that it is only bore1 4 em
necessary to transfer solutions. However, if
transfer of a precipitate should be essential and 0'2 em. .
the precipitate is crystalline, the latter may be
dia. _.
sucked up by a dry dropper pipette and trans-
ferred to the appropriate vessel. If the precipitate Fig. II. 6, 4

•
 UJZ Qualitative Inorganic Analysis [II,
is gelatinous, it may be transferred with the aid of a narrow glass,
nickel, monel metal or platinum spatula. The centrifuge tube mli4 be
of type a (Fig. II, 5, 1) if most of the precipitate is to be rem(! ed.
The heating of solutions in centrifuge tubes is best carrie. 'out
by supporting them in a suitable stand (compare Figs. II, 3, 1. 13)
and heating on a water bath. When higher temperature, are

Fig. II, 6, 5 Fig. II, 6, 6

required, as for evaporation, the liquid is transferred to a D i :oro

beaker or micro crucible; this is supported by means of a nicm, i me
wire triangle as indicated in Fig. II, 5, 5. Micro beakers rna \ be
heated by means of the device shown in Fig. II, 5, 6, whi('h is
laid on a water bath.

flubber stopper

t-
Clamp

Fig. II, 6, 7 Fig. II, 6, 8

Another valuable method for concentrating solutions or ev, 110-

rating to dryness directly in a centrifuge tube consists in condu( , ng
i

the operation on a water bath in a stream of filtered air sUPI ed

through a capillary tube fixed just above the surface of the liq [d.
The experimental details will be evident by reference to Fig. II, 7.
!,
5] Expertmental Technique of Ihorganic Analysis 193
Micro centrifuge tubes are cleaned with a feather, "pipe cleaner"
or small test-tube brush (compare Fig. II, 3, 21). They are then
filled with distilled water and emptied by suction as in Fig. II, 5,8.
Mter suction has commenced and the liquid removed, the tube is
filled several times with distilled water without removing the suction
device. Dropper pipettes are cleaned by re-
peatedly filling and emptying them with distilled
water, finally separating rubber bulb and glass
tube, and rinsing both with distilled water from
a wash bottle. A transfer capillary pipette is
cleaned by blowing a stream of water through it.
The passage of hydrogen sulphide into a 'i "'\
solution in a micro centrifuge tube is carried Puriflea
out by leading the gas through a fine capillary cotton wool
tube in order not to blow the solution out of the
tube. The delivery tube may be prepared by
drawing out part of a length of glass tubing of
6 mm. diameter to a capillary of 1-2 mm. bore
and 10-20 cm. long. A plug of pure cotton wool
is inserted into the wide part of the tubing, and
then the capillary tube is drawn out by means of
a micro burner to a finer tube of 0,3-0·5 mm. bore Fig. II, 5, 9
and about 10 cm. long. The complete arrange-
ment is illustrated in Fig. II, 5, 9. Such a fine capillary delivers
a stream of very small bubbles of gas: large bubbles would throw
the solution out of the micro centrifuge tube. The flow of the
hydrogen sulphide must be commenced before introducing the point
of the capillary into the centrifuge cone. If this is not done, the
solution will rise in the capillary and when
hydrogen sulphide is admitted, a precipitate will
form in the capillary tube and clog it. The point
of saturation of the solution is indicated by an
increase in the size of the bubbles; this is usually
after about two minutes.
The identification of gases obtained in the
reactions for anions may be conducted in an
Erlenmeyer (or conical) flask of {) or 10 ml.
capacity; it is provided with a rubber stopper
.which carries at its lower end a "wedge point"
pin, made preferably of nickel or monel metal
Fig. II, 5, 10 (Fig. II, 5, 10). A small strip of impregnated
test paper is placed on the loop of the pin. The
stoppered flask, containing the reaction mixture and test paper is
placed on a water bath for five minutes. An improved apparatus
consists of a small flask provided with a ground glass stopper
on to which a glass hook is fused (compare Fig. II, 6, 12):
the test paper is suspended from the glass hook. If the evolved
gas is to be passed through a liquid reagent, the apparatus
7+
•
 194 Qualitative Inorganic Analysis [II,
of Fig. II, 3, 19, b or c, proportionately reduced, may bl em-
ployed.
Confirmatory tests for ions may be carried out either on ,trop
reaction paper or upon a spot plate. The technique of spot I ests
is fully described in Section II, 6.
The following micro apparatus* will be found useful:
(I) Micro porcelain, silica and platinum crucibles of 0·5 to _ ml.
capacity.
(2) Micro beakers (5 ml.) and micro conical flasks (5 ml.).
(3) Micro centrifuge tubes, (0·5, 1·0 and 2·0 ml.).
(4) Micro test-tubes (40-50 X 8 mm.).
(5) ]'\'licro volumetric flasks (I, 2 and 5 ml.).
(6) Micro nickel, monel or platinum spatula, 7-10 cm. in kngth
and flattened at one end.
(7) Micro burner.
(8) Micro agate pestle and mortar.
(9) Magnifying lens, 5 X or 10 X.
(10) A pair of small forceps.
(11) A small platinum spoon, capacity 0·5-1 ml., with h:ll,dle
fused into a glass tube. (This may be used for fusions.)
II, 6. Apparatus required for Spot Test Analysis.-The term
"spot reaction" is applied to micro and semimicro tests for I,lm-
pounds or for ions. In these chemical tests manipulation ',ith
drops (macro, semimicro and micro) play an important part. ";JOt
reactions may be carried out by any of the following processes
(i) By bringing together one drop of the test solution and 01 'he
reagent on porous or non-porous surfaces (paper, glass or porcel 'm).
(ti) By placing a drop of the test solution on an appropr Lte
medium (e.g. filter paper) impregnated with the necessary reag, ,ts.
(iii) By subjecting a strip of reagent paper or a drop of th, re-
agent to the action of the gases liberated from a drop of the )st
solution or from a minute quantity of the solid substance.
(iv) By placing a drop of the reagent on a small quantity oj 'he
solid sample, including residues obtained by evaporation or igni' ,'Ill.
(v) By adding a drop of the reagent to a small volume I ;Iy,
0·5-2 ml.) of the test solution and then extracting the rear Ion
products with organic solvents.
The actual" spotting" is the fundamental operation in spot ,'st
analysis, but it is not always the only manipulation invol, 'd.
Preliminary preparation is usually necessary to produce the cor' ct
reaction conditions. The preparation may involve some of flO
operations of macro analysis on a diminished scale (compare Sec: m
II, 5), but it may also utilise certain operations and appar: : lIS
peculiar to spot test analysis. An account of the latter forms 1 ile
subject matter of the present Section.
Before dealing with the apparatus required for spot test reactii" IS,
• All glaas apparatus must be of resistance (e.g. Pyrex) glaas.
6) Experimental Technique of Inorganic Analysis 195
it is necessary to define clearly the various terms which are em ployed
to express the sensitivity of a test. The limit of identification is
the smallest amount recognisable, and is usually expressed in micro
grams (ftg.) or gamma (y), one micro gram or one gamma being
one·thousandth part of a milligram or one-millionth part of a gram.
1 J1-g. == 1y = 0·001 mg. = 10- 8 g.
Throughout this text the term sensitivity ",ill be employed synony-
mously with limit of identification. The concentration limit is
the greatest dilution in which the test gives positive results; it is
expressed as a ratio of substance to solvent or solution. For these
two terms to be comparable, a standard size drop must be llsed in
performing the test. Throughout this book, unless otherwise :otated,
sensitivity will be expressed in terms of a standard drop of 0·05 ml.
The removal and addition of drops of test and reagent
solutions is most simply carried out by using glass
tubing, about 20 cm.long and 3 mm. external diameter;
drops from these tubes have an approximate volume
of 0·05 ml. The capillary dropper (Fig. II, 3, 3, b)
may also be employed. A useful gl"ss pipette, about
20 cm. long, may be made from 4 mm. tubing and
drawn out at one end in the flame (l!'ig. II, 6, 1); the
drawn-out ends of these pipettes may be made of
varying bores. A liberal supply of glass tubes and
pipettes should always be kept at hand. They may be
stored in a beaker about 10 cm. high with the con-
stricted end downwards and resting upon a pad of pure
cotton wool; the beaker and pipettes can be protected
against dust by covering with a she'et of cellophane.
Pipettes which are used frequently may be supported
horizontally on a stand constructed of thin glass rod.
Mter use, they should be immersed in beakers filled
with distilled water: interchanges are thus prevented Fig. II, 6,1
and subsequent thorough cleaning is facilitated. OIle-third
Very small and even-sized drops can be obtained by actllal size
means of platinum wire loops; the size of the loop
can be varied and by calibrating the various loops (by weighing
the drops delivered), the amount of liquid delivered from eauh loop
is known fairly accurately. A number of loops are made b~T bend-
ing platinum wire of suitable thickness; the wires should be at,tached
in the usual manner to lengths of glass rod or tubing to act as
handles. They are kept in Pyrex test-tubes fitted with corks or
rubber stoppers and labelled with particulars of the size I)f drop
delivered. It must be pointed out that new smooth platinllm wire
allows liquids to drop off too readily, and hence it is essential to
roughen it by dipping into chloroplatinic acid solution, followed by
heating to glowing in a flame; this should be repeated several
times. Micro burettes sometimes find application for the delivery
of drops.
 1
196 Qualitative Inorganic A'nalysUJ Ill,
Reagent solutions can be added from dropping bottles of 2;, 30
ml. capacity (see Section II, 3, 4). A stock bottle for water . nd
for solutions which do not deteriorate on keeping, is show! III
Fig. II, 6, 2; it permits the facile addition in drops. This S 'ck
bottle is constructed from a Pyrex flask into which a tube wi .l a
capillary end is fused; a small rubber bulb is placed over the dr:, '.'U-
out neck, which has a small hole to admit air.
Digestion of solid samples with acid or solvent may be perfOJ .: led
in small crucibles heated on a metal hot plate, or in an air :. cth
(Fig. II, 5, 5), or in the glass apparatus illustrated in Fig. II, 3.
The last-named is heated over a micro burner, and then rotak,: so
that supernatant liquid or solution may be poured off drop- 1\ ise
without danger or loss.
Spot tests may be performed in a number of ways : on a spot pi lte,

Fig. II, 6, 2 Fig. II, 6, 3

One-third actual size Actual size

in a micro crucible, test tube or centrifuge tube, Or on filter p:~ per.

Gas reactions are carried out in special apparatus.
The commercial spot plates are made from glazed porcelain .md
usually contain 6 to 12 depressions of equal size that hold (I , to
1 mI. of liquid. It is advisable, however, to haye several spot l' ,tes
with depressions of different sizes. The white porcelain LICk-
ground enables very small colour changes to be fleen in reactions
that give coloured products; the colour changes are more re;dlily
perceived by comparison with blank tests in adjacent cavities of
the spot plate. Where light-coloured or colourless precipitat('.~ or
turbidities are formed, it is better to employ black spot pb tes.
Transparent spot plates of resistance glass (e.g. Jena) are ;,lso
available; these may be placed upon glossy paper of suitable CO:qur.
The drops of teet solution and reagent brought together on a spot
6] Experimental Technique of Inorganic Analysis 197
plate must always be mixed thoroughly: a glass stirrer (Fig. 11,5,4)
or a platinum wire may be employed.
Traces of turbidity and of colour are also readily distinguished in
micro test-tubes (50 X 8 mm.) or in micro centrifuge tubes. As a
general rule, these vessels are employed in testing dilute solutions
so as to obtain a sufficient depth of colour. The liquid in a micro
centrifuge tube or in a test-tube may be warmed in a special stand
immersed in a water bath (compare Figs. II, 3, 12-13) or in the
apparatus depicted in Fig. II, 6, 4. The latter is constructed of
thi..'1 aluminium or nickel wire; the tubes will slip through the
openings and rest on their collars. The wire holder is arranged to
fit over a small beaker, which can be filled with water at the appro-
priate temperature.
For heating to higher temperatures (>lOOO) micro porcelain
crucibles may be employed: they are immersed in an air bath
(Fig. II, 5, 5) and the latter heated by a micro
burner, or they can be heated directly on an
asbestos mat. Small silica watch glasses also
find application for evaporations.
It must be emphasised that all glass and
porcelain apparatus, including spot plates and
crucibles, must be kept scrupulously clean. It is
a good plan to wash all apparatus (particularly
spot plates) immediately after use. Glassware
and porcelain crucibles are best cleaned by im- Fig. II, 6, 4
mersion in a chromic acid-sulphuric acid mixture
or in a mixture of concentrated sulphurio acid and hydrogen peroxide,
followed by washing with a liberal quantity of distilled water, and
drying. The use of chromic acid mixture is not reoommended for
spot plates.
The great merit of glass and porcelain apparatus is that they can
be employed with any strength of acid and base: they are also
preferred when weakly coloured compounds (especially yellow) are
produced or when the test depends upon slight colour differences.
Filter paper, however, cannot be used with strongly acidic solutions
for the latter cause it to tear, whilst strongly basic solutions produce
a swelling of the paper. Nevertheless, for many purposes and
especially for those dependent upon the application of c;1pillary
phenomena, spot reactions carried out on filter paper possess
advantages over those in glass or porcelain: the tests generally have
greater sensitivity and a permanent (or semi-permanent) record of
the experiment is obtau1ed.
Spot reactions upon filter paper are usually performed with
Whatman drop reaction paper No. 120, but in some cases Whatman
No. 3MM is utilised: the Schleicher and Schuell (U.S.A.) equivalents
are Nos. 601 and 598. These papers possess the desirable property
of rapidly absorbing the drops without too much spreading, as is
the case with thinner papers. Although impurities have been
 198 Qualitative Inorganic Analysis flI,
reduoed to minimum values, they may oontain traoes of iron "ond
phosphate: spot reactions for these are better made with qu: tlti-
tative filter paper (Whatman No. 42 or, preferably, the hard, lied
variety No. 542). The paper should be out into strips 6 X 2 :m.
or 2 X 2 cm., and stored in petri dishes or in vessels with tig :!Iy-
fitting stoppers.
Spot test papers are marketed in which the spot reaction is )ll-
fined to a uniform area of fixed dimensions, produced by SurrOUl, : ing
the area by a chemically inert, water-repelling barrier. '] iiese
papers were developed by H. Yagoda and may be employed for
semi-quantitative work. The Schleicher and Schuell (U.S.A.) ~o.
211Y "confined spot test" paper is intended for use with s; gle
drops of solution, and No. 597Y for somewhat larger volv les.
They are often referred to as Yagoda test papers.
Spot reactions on paper do not always involve interaction bet .., een
a drop of the test solution and one of the reagent. Sometime, she
paper is impregnated with the reagent and the dry impreg:r;,:ted
reagent paper is spotted with a drop of the solution. Special tre
must be taken in the choice of the impregnating reagent. Or f nic
reagents, that are only slightly soluble in water but dissolve re, dily
in alcohol or other organic solvents, find extensive applica ,In.
Water-soluble salts of the alkali metals are frequently not . '3ry
stable in paper. This difficulty can often be surmounted bJ ,he
use of sparingly soluble salts of other metals. In this waJ !;he
concentration of the reactive ion can be regulated automati, ,lIy
by the proper selection of the impregnating salt, and the speci1 I ity
of the test can be greatly improved by thus restricting the nm 'Jer
of possible reactions. Thus potassium xanthate (see under M(" rb-
denum, Section IX, 4, reaction 8) has little value as an impregn; mg
agent since it decomposes rapidly and is useless after a few (i :ys.
When, however, cadmium xanthate is used, a paper is obtll i led
which gives sensitive reactions only with copper and molybde' , 1m
and it will keep for months. Similarly the colourless zinc f. ro-
cyanide offers parallel advantages as a source of ferro cyanide , IS:
it provides a highly sensitive test for ferric ions. A further exa' pIe
is paper impregnated with zinc, cadmium or antimony sulph os:
such papers are stable, each with its maximum sulphide ion 'm-
centration (controlled by its solubility product) and henoe only 1 ')se
metallic sulphides are precipitated whose solubility produots ,tre
sufficiently low. Antimonious sulphide paper precipitates onl.) .\g,
Cu and Hg in the presence of Pb, Cd, Sn, Fe, Ni, Co and Zn. It
might be expected that the use of "insoluble" reagents w, 'lId
decrease the reaction rate. This retardation is not significant len'I
paper is the medium because of the fine state of division and ! he
great surface available. Reduction in sensitivity becomes a}'I,re-
I. ciable only when the solubility products of the reagent and the
~ reaotion product approach the same order of magnitude. ThO', is
naturally avoided in the selection of the reagents.
6] Experimental Technique oj lrwrganic Analysis 199
Filter paper may be impre~nated with reagents by the following
methods:
(i) For reagents that are soluble in water or in organic solvents,
strips of filter paper are bathed in the solutions contained in beakers
or in dishes. Care must be taken that the strips do not stick to
the sides of the vessel or to one another, as this will prevent a.
uniform impregnation. The immersion should last about 20 minutes
and the solution stirred frequently or the vessel gently rotated to
produce a swirling of the solution. The strips are removed from
the bath, allowed to drain, pinned to a string (stretched horizontally)
and allowed to dry in the air. Uniform drying is of great impor-
tance.
Alternatively, the reagent may be sprayed on to the filter paper.

/'" A
~~. -Ouler lube 3·5mm. diam.
'i)~

'/
--:r-~'
Outer lube 10 mm. diam.
I
-Inner lube 2 mm. diam.
20mm.
C

#016:- tubing of 1mm. wall

Fig. II, 6, 5

The all-glass spray shown in Fig. II, 6, 5 (not drawn to scale) gives
excellent results. A rubber bulb is attached at C; the cork is fitted
into a boiling tube or small flask charged with the impregnating
solution. The paper is sprayed first on one side and then on the
other.
(ii) For reagents that are precipitated on the paper, the strips
are soaked rapidly and uniformly with the solution of one of the
reactants, dried and then immersed similarly in a solution of the
precipitant. The excess reagents are then removed by washing,
and the strips dried. The best conditions (concentration of solu-
tions, order in which applied, etc.) must be determined by experi-
ment. In preparing highly impregnated papers, the precipitation
should never be made with concentrated solutions as this m::ty lead
to an inhomogeneous precipitation and the reagent will tend to fall

•
200 Qualitative Inorganic AnalVN [II,
off the paper after it is washed and dried. It is essential to ,'arry
out the soaking and preoipitation separately with dilute sol, : ions
and to dry the paper between the individual precipitations. i" 'me-
times it is preferable to use a reagent in the gaseous form, e.g.
hydrogen sulphide for sulphides and ammonia for hydroxides; 'here
is then no danger of washing away the precipitate.
The reactions are carried out by adding a drop of the test so' ,tion
from a capillary pipette, etc., to the centre of the horizontal rf' :~ent
paper resting across a porcelain crucible or similar vessel: an un-
hindered capillary spreading follows and a circular spot n ,tits.
With an impregnated reagent paper, the resulting change in (:lour
may occur almost at once, or it may develop after the appli, cion
of a further reagent. It is usually best not to place a drop ( the
test solution on the paper but to allow it to run slowly fr 'n a
capillary tip (0'2-1 mm. diameter) by touching the tip 0) the
paper. The test drop then enters over a minute area, precipi1 ',ion
or adsorption of the reaction product occurs i.J the
immediate surrounding region, where it remains ixed
in the fibres whilst the clear liquid spreads ra ,'tlly
outwards by capillarity. A concentration oj the
coloured product, which would otherwise be sl,read
over the whole area originally wetted by the' test
drop, is obtained. thus rendering minute quan' ,ties
distinctly visible. A greater sensitivity is i hus
obtained than by adding a free drop of the test
solution. Contact with the fingers should be av ,led
in manipulation with drop-reaction papers: a c ',ner
of the strip should be held with a pair of clean for' <lps.
Fig. II, 6, 6 The problem of separating solid and liquid ph'.Ises
Actual size either before or after taking a sample drop or t'l I) of
the test solution frequently arises in spot test anah sis.
When there is a comparatively large volume of liquid and the ,Iolid
matter is required, centrifugation in-a micro centrifuge tube j1'ig.
II, 5, 1) may be employed. Alternatively, a micro sintered iass
filter tube (Fig. II, 6,6), placed in a test-tube of suitable size, 'ilay
be subjected to centrifugation: this device simplifies the wa: ing
of a precipitate. If the solid is not required, the liquid ma, be
collected in a capillary pipette by sucking through a small Pi: : of
purified cotton wool placed in the capillary end; upon rem{ , lUg
the cotton wool and wiping the pipette, the liquid may be deli, i:ed
clear and free from suspended matter.
A useful filter pipette is shown in Fig. II, 6,7. It is constru, ted
of tubing of 6 mm. in diameter. A rubber bulb is attached to the
short arm A; the arm B is ground fiat, whilst the arm C is drawn
out to a fine capillary; a short piece of rubber tubing is fitted over
the top of B. For filtering, a disc of filter paper of the same dia-
meter as the outside diameter of the tube (cut out from filter p ,per
by means of a sharp cork borer or by a hand punch) is placed on
6] Experimental Techn£que of Inorganic Analysia 201
the flat ground surface of B, the tube F placed upon it and then
held in position by sliding the rubber tubing just far enough over

D
=

B F

c::>E

eo
D
c

Fig. II, 6, 7
the paper to hold it when the tube F is removed. The filter pipette
may be used either by placing a drop of the solution on the filter
disc or by immersing the tube end B into the
crucible, test-tube or receptacle containing the
solution to be filtered. The bulb is squeezed
by the thumb and middle finger, and the dropper
point closed with the fore-fmger thus allowing
the solution to be drawn through the paper
when the bulb is released. To release the drops
of filtered liquid thus obtained, th6 filter pipette
is inverted over the spot plate, etc., in an in-
clined position with the bulb uppermost.
Manipulation of the bulb again forces the
liquid in the tip on to the spot plate, etc. The
precipitate on the paper can be withdrawn for
any further treatment by simply sliding the
rubber tubing D down over the arm B.
Another method involves the use of an Emich
filter stick fitted through a rubber stopper
into a thick-walled suction tube; the filtrate is
colleoted in a micro test-tube (Fig. II, 6, 8).
The filter stick has a small pad of purified
asbestos above the constriction.
The apparatus illustrated in Fig. II, 6, 9 may Fig. II, 6, 8
be employed when the filter paper (or drop Two-thirds actual
reaction paper) must be heated in steam; the size
filter paper is placed on the side arm support.
By charging the flask with hydrogen sulphide solution, ammonia
solution, chlorine or bromine water, the apparatus can be used for
treating the filter paper with the respective gases or vapours.
7·
•
 I
{JuaUtative Inorganic A halysiB rH,
Fusion and solution of a melt may be conducted either i i a
platinum wire loop or in a platinum spoon (0·5-1 ml. capa( f y)
attached to a heavy platinum wire and fused into a glass hoI i lr.
Gas reactions may be performed in spec; ,Ily
devised apparatus. Thus in testing for .r-
bonates, sulphides, etc., it is required to ab 'rb
the gas liberated in a drop of water or rea,: nt
solution. The apparatus is shown in Fig. II, 6 10,
and consists of a micro test-tube of about I al.
capacity, which can be closed with a small grG rJ.d
glass stopper fused to a glass knob. The rea nt
and test solution or test solid are placed in he
bottom of the tube, and a drop of the rea nt
for the gas is suspended on the knob of 'he
stopper. The gas is evolved in the tub. if
Fig. II, 6, 9 necessary, by gentle warming, and is absorbed by
One-quarter the reagent on the knob. Since the apparatl " is
actual size closed, no gas can escape, and if sufficient I; me
is allowed it is absorbed quantitatively by ,he
reagent. A drop of water may replace the reagent on the stop I (~r;
the gas is dissolved, the drop may be washed on to a spot pIal' or

I
Fig. 11, 6, 10 Fig. II, 6, 11 Fig. II, 6, 12
7 Actual size Actual size Actual size

into a micro crucible and treated with the reagent. The appar, '!lS,
shown in Fig. II, 6, 11, which is closed by a rubber stopP(' is
sometimes preferable, particularly when minute quantities of ga, .re
 6] Experimental Techn{que 0.1 Inorganic A nalY8i8 203
concerned; the glass tube, blown into a small bulb at the lower
end, may be raised or lowered at will, whilst the change of colour
and reaction products may be rendered more easily visible by filling
the bulb with gypsum or magnesia powder. In some reactions, e.g.
in testing for ammonia, it may be desirable to suspend a small strip
of reagent paper from a glass hook fused to the stopper as in Fig.
II, 6, 12. When a particular gas has to be identified in the pre.
sence of other gases, the apparatus shown in Fig. II, 6, 13 should
be used; here the stopper for the micro test-tube consists of a small
glass funnel on top of which the impregnated filter paper is laid in
order to absorb the gas. The impregnated filter paper permits the
passage of the indifferent gases and only retains the gas to be tested
by the formation of a non-volatile compound that can be identified
by means of a spot test. Another useful apparatus is shown in

Fig. II, 6, 13 Fig. II, 6, 14 Fig. II, 6, 15

Actual size Actual size Actual size

Fig. II, 6,14; it consists of a micro test-tube into which is placed a

loosely-fitting glass tube narrowed at both ends. The lower capillary
end is filled to a height of about 1 mm. with a suitable reagent
solution; if the gas liberated forms a coloured compound with the
reagent, it can easily be seen in the capillary.
Where high temperatures or glowing are necessary for the evolu-
tion of the gas, a simple hard glass tube supported in a circular hole
in an asbestos or "uralite" plate (Fig. II, 6, 15) may be used .
. The open end of the tube should be covered by a small piece of
reagent paper and kept in position by means of a glass cap.
Micro distillation is sometimes required, e.g. in the chromyl
chloride test for a chloride (see Section IV, 14, reaction 5). The
apparatus depicted in Fig. II, 6, 16 is suitable for the distillation
of very small quantities of a mixture. A micro crucible or a micro
centrifuge tube may be employed as a receiver.
204: Qualitative Inorganic Analysis [II,
In Chapters III, IV and IX the experimental details are gi'.'(ln
for the detection of a number of elements or radicals by spot te-. t s.
These tests are set out in small (9 point) type as distinct from; he
other reactions which are in larger type: they can thus be read:ly
distinguished and this is further facilitated by the use of a dagger t)
preceding the small type. The sensitivities given are, as a gen, ['al
rule, for a solution containing only
the ion in question. It must be
remembered that this is the Dlt)St
favourable case, and that in act Iial
practice the presence of other j<>rlS
usually necessitates a modifica1 t, on
of the procedure, which is I.' e·
quently indicated, and which, m· ,re
often than not, involves a I, dS
of sensitivity. Almost with, '\It
exception each test is subject to

UU
Fig. II, 6, 16
interference from the presence· of
other ions, and the possibility of
these interferences occurring mist
Actual size be taken into consideration wi,nn
a test is applied. Furtherml,re,
the sensitivities when determined upon drop-reaction paper \\ ill
depend upon the type of paper used. The figures given in the t, d
have been obtained largely with the Schleicher and Schuell Sl,ot
paper: substantially similar results are given by the equivalent
Whatman papers. For purposes of reference the following equi.
valent papers are tabulated:

Schleicher and Schuell paper WOOtman paper

No. 601, "spot paper." Drop-reaction paper, No. 120,

double thickness.
No. 598. No.3 MM., 1st quality.
No. 589. No. 42 or No. 542.

It is important to draw attention to the difference between 1 he

terms "specific" and "selective" when used in connexion "i 1b
reagents or reactions. Reactions (and reagents), which under 111e
experimental conditions employed are indicative of one substalJ"e
(or ion) only are designated as specific, whilst those reactions (1' 'Id
reagents) which are characteristic of a comparatively small numi!()r
of substances are classified as selective. Hence we may descfl be
reactions (or reagents) as having varying degrees of selectivity;
however, a reaction (or reagent) can be only specific or not specific.
 CHAPTER III

REACTIONS OF THE METAL IONS OR CATIONS

III, 1. The Analytical Classification of the Metals.-The

common metallic ions may be divided, for purposes of qualita-
tive analysis, into a number of groups which are distinguished
by the fact that the metals of any group are precipitated by
a particular group reagent. Thus by the addition of a slight
I
Group Formftla of Distinguishing
Group reagent lona
I precipitate featureB
I Dilute HCI Ag+,Pb++, AgCI, PbCl!, Chlorides in-
(Silver Hg.++ HgaCl l soluble in cold
group) dilute HCI.
II H.S in pre- Hg++, HgS, PbS, Sulphides in-
(Oopper sence of Pb++, Bi.S., CuS, soluble in dilute
and dilute HCl Bi+++, CdS, SnS, HCI (ca. 0·3N)
arsenic Cu++, As.S.,
groups) Cd++, Sb 2 S., SnS.
Sn++,
As+++,
Sb+++,
Sn++++

IlIA Aq. Nil a in Al+++, Al(OH)., Hydroxides

(Iron presence Cr+++, Cr(OH)., pptd. by
group) ofNH,Cl Fe+++ Fe(OH). aq. Nil. in
presence of
excess of
Nil,Cl.
lIIB H.S in pre- N·++
1 , NiS, CoS, Sulphides pptd_
(Zinc sence of Co++, MnS, ZnS by H.S in pre-
group) aq. NHa l\fu++, sence of aq.
and Zn++ NH. and
Nil,C! Nil,Cl.
IV (NH,).CO a Ba++, BaCO., Carbonates
(Oalcium in presence Sr++, SrCO., pptd. by
group) ofaq. NBs Ca++ CaCO. (NH,).CO.
andNH.Cl in presence of
NH,Cl.
V No particu- Mg++, Na+, Mg++, Na+, Ions not pptd.
(Alkali lar reagent K+,NH.+ K+, NH,+, in previous
group) in solution groups.

205
206 Qualitative Inorganic Analysis [Ill,
excess of dilute hydrochloric acid to a solution containing (U
the common metallic ions, a precipitate is obtained consistj,:g
of the chlorides of silver, lead and mercurous mercury. Th(',e
metal ions are therefore classed together in Group I; th'lr
chlorides are insoluble in cold, dilute hydrochloric acid ( I.
O·3N). Similarly by the use of the appropriate group reagen, ,
the remaining metallic ions are separated into different groul' .
In general, it may be stated that the classification is based up ,,}
the varying solubilities of the chlorides, sulphides, hydroxilh!
and carbonates.
The various groups are summarised in the table on 1, e
previous page.
Ammonium is detected in the original substance by boili 1<5
a small portion with sodium hydroxide solution before carryi: c5
out the separation of the metal ions into groups.
It is assumed in the above table that the group reagents v ' ,}
added systematically to the solutions from which the ions ' f
the earlier groups have been removed. Thus dilute hyffi, ,_
chloric acid is added to the original solution, hydrogen sulphi, (~
is passed into the filtrate from Group I, ammonium chlori,le
and aqueous ammonia solutions are added to the filtrate frO',l
Group II, and so on.
A knowledge of the reaction of the various ions is neceSSal,\'
in order to understand the processes involved in the separati: '11
of the members ~f the various groups and generally to appl' -
ciate the subject of qualitative analysis. A systematic accou:, t;
of the more common metal ions arranged in order of the grou f ''1
is given in the following pages.
The reactions will be expressed larg~ly as molecular equation,
Many of these should, of course, be written as ionic equation_:
the student is therefore recommended to rewrite, where appb
able, the molecular ~quations in their ionic forms, and tIll"
should be regarded as an essential part of the study of tli(;
reactions of the various cations and anions. The so-calk I
ammonium hydroxide reagent is a solution of ammonia gas I: I
water and it is doubtful whether the undissociated ba','
NH40H has any actual existence (see Sections I, 5 and I, 42:
the reagent will be termed ammonia solution in the text. ! I
will be appreciated that the basic character of ammon,:l
solution (NHa + H 2 0 ~ NH4 + + OH-) is readily understo(,,!
on the Lowry-Bronsted theory (see Section I, 42). For tL
sake of simplicity, the unhydrated hydrogen ion H + will }",
employed in equations for the hydroxonium ;lln H _() +. 1"
aqueous solution it is, of course, the hydrated
1] Reactions of the M etaZ Ion8 or Oation8 207
the free proton that is present (soo Section I, 5). Mention
should also be made of the fact that a solution of hydrogen
sulphide in aqueous ammonia contains mainly ammonium
hydrosulphide NH.HS; the existence of the normal sulphide
(NH.)2S in aqueous solution is very doubtful and, in any case,
would be almost completely hydrolysed (compare Example 22
in Section I, 40).
When carrying out the various reactions of cations and
anions, the student may adopt either the macro or semimicro
technique. For the former test-tubes (150 X 19 mm.), beakers,
conical flasks (50 mI.), etc., are employed: the student should
always aim to keep the volumes and quantities of reagents as
small as possible. The advantages of the semimicro technique,
especially from the viewpoint of economy of chemkals and
apparatus (see paragraphs before Section II, 1), are so great
that it must be strongly recommended to all. Reactions are
performed in 4 m!. test-tubes (75 X 10 mm.) or 3 m!. centri-
fuge tubes, the precipitates are separated from the super-
natant liquids by centrifugation, evaporations are conducted
in either 5-8 m!. porcelain crucibles or in 20 m!. boiling tubes,
etc. (see SectIOn II, 3). Alternative tables of separation for
macro and semimicro work will be provided.
As an illustration of the eoonomy of chemicals and of time on the
semimicro scale, details will be given as to how reaction 1 for lead
and silver ions (Sections III, 2 and III, 4) may be carried out.
To 2 drops of the test solution ofPb++ contained in a 3 ml. centrifuge
tube add 2 drops of dilute hydrochloric acid. Observe the nature,
size and colour of the precipitate. Centrifuge the mixture: remem-
ber to balance the test-tube with aaother similar tube containing
the same volume of water. Remove the supernatant liquid, called
the centrifugate, by means of a capillary dropper to another centri-
fuge tube, test it with another drop of dilute hydrochloric acid to
ensure complete precipitation, and t,hen reject the solution. Treat
the precipitate, termed the residue, with 2 drops of distilled water,
stir and centrifuge. Remove the liquid, called the washings, and
reject it. Add 5 drops of distilled water to the residue, stir and place
the tube in a boiling water bath. Stir while heating: note that the
precipitate dissolves completely. To the solution add 1 drop of
dilute acetic acid and 1 drop of potassium chromate solution. A
yellow precipitate of lead chromate separates.
To 2 drops of the test solution of Ag+ contained in a 3 ml. centri-
fuge tube add 2 drops of dilute hydrochloric acid. Observe the
nature, colour and size of the precipitate. Centrifuge and discard
the centrifugate. Wash the precipitate by adding 2 drops of
distilled water, stir and centrifuge: discard the washing,;. Treat
208 Qualitative Inorganic A nalys'is [III,
the residue of silver chloride with 5 drops of dilute aqueous ammon ia
and stir until complete solution takes place. Now add dilute ni1 "c
acid, drop by drop, stirring the mixture after each addition, Ul 1 il
acid (test by removing a drop of the stirred mixture on to b 'Ie
litmus paper). Observe the formation of a white precipitate of
silver chloride.

THE SILVER GROUP (GROUP I)

LEAD, MEROURY (QUS) AND SILVER
The oompounds of these metals are charaoterised by their preoipitation as
ohlorides by dilute hydroohlorio acid or by a soluble ohloride. Lead ohloride
is slightly soluble in water and hence is not completely precipitated as
ohloride in this group; it is therefore also found in Group II, where it is pre·
oipitated as the highly insoluble sulphide.
LEAD,Pb
Lead is a bluish-grey metal with a density of 11·48. It is rea dily
dissolved by dilute nitric acid:
3Pb + SHNO a = 3Pb(NOsh + 2NO + 4H 0 2
With concentrated nitric acid, a protective film of lead nii rate,
which is insoluble in this acid, prevents complete solution. ] lJ(ute
hydrochloric acid and dilute sulphuric acid have little action'· ,ving
to the formation of protective films of lead chloride and SUlphate
respectively.

111,2. REACTIONS OF THE LEAD ION, Pb++

Use a solution of lead nitrate, Pb(N0 3)2, or of lead a(', tJate,
Pb(C 2H a0 2 b,3H 2 0 (abbreviated to PbA 2,3H 2 0), acidified with
a little acetic acid H.C 2 H 30 2 (or HA).*
1. Dilute Hydrochloric Acid: white precipitate Of lead
chloride PbCI 2 , formed only in cold and not too dilute solution:
Pb(NOa)2 + 2HCI = PbCl2 + 2HNO a
The precipitate is soluble in hot water (33·4 g. and 9·9 .l!;. per
litre at 100 0 and 20 0 respectively), but separates out apin in
needles when the solution is cooled. It is also soluble I! leon-
centrated hydrochloric acid and in concentrated alkali c! loride
solutions owing to the formation of complex compound- (co~­
pare Section I, 19); these are decomposed on dilutic"! with
water with the separation of lead chloride:
PbC1 2 + HCI ~ H[PbClaJ; PbC1 2 + 2HCI ~ H 2 [PbCLd
• It is recommended that the test solutions employed in the study of th~
reactions of the cations and anions described in Chapters III OJ,· j IV bE
prepared as detailed in the Appendix (Section A, 3). These contain l(
milligrams of the cation or anion per ml

-,
\
 2] Reactions of the Jfetal 10na or Oations 209
2. Potassium Iodide Solution: yellow precipitate of lead
iodide PbI 2 , moderately soluble in boiling water to yield a
colourless solution from which it separates on cooling in golden
yellow plates. It is also soluble in excess of potassium iodide
solution forming a complex salt, which is decomposed on
dilution with deposition of lead iodide.
Pb(NOa)2 + 2KI = PbI 2 + 2KNO s
PbI 2 + 2KI .= K 2[PbI,]
3. Dilute Sulphuric Acid: white precipitate of lead sul-
phate PbSO" insoluble in excess, but soluble in a concentrated
solution of ammonium acetate (due to the formation of lead
acetate, which is little ionised in the presence of excess of
acetate ions; see Common Ion Effect, Section I, 14) or in an
ammoniacal solution of ammonium tartrate.
Pb(NO a)2 + H 2S04 = PbS04 + 2HNO s
PbSO, + 2NH,. C2H a0 2 = Pb(C 2 H a0 2 )2 + (NH')2S0,
4. Potassium Chromate Solution: yellow precipitate of
lead chromate PbCrO" insoluble in acetic acid and in ammonia
solution, but soluble in alkali hydroxides and in nitric acid.
Lead chromate is quantitatively precipitated from an ammo-
nium acetate solution of lead sulphate (reaction 3).
Pb(NOa)2 + K 2 CrO, = PbCr04 + 2KNOs
PbCrO, + 4NaOH = Na2[Pb02] + Na2CrO, + 2H20
5. Hydrogen Sulphide: black precipitate of lead sulphide
PbS. The precipitate is often red in the presence of hydro-
chloric acid; this is due to the initial formation of lead
sulphochloride Pb 2SCI 2 , which is decomposed on dilution and
by passage of excess of hydrogen sulphide forming black lead
sulphide.
Pb(N0 3 )2 + H 2S = PbS + 2HNO s
2PbCI 2 + H 2S = Pb 2SCl 2 + 2HCI
The precipitate of lead sulphide is very slightly soluble in
solutions of alkali polysulphides, insoluble in alkali mono-
sulphides, but soluble in hot dilute nitric acid:
8PbS + 8HNO s = 8Pb(NO ah + 2NO + 4H 2 0 + 88
It is converted into white lead sulphate PbSO, on treatment
with hydrogen peroxide:
PbS + 4H 2 0 2 = PbSO, + 4H 2 0
The great insolubility of lead sulphide in water (4·9 X 10- 11 g. per litre)
explains why hydrogen sulphide is such a sensitive reagent for the detection
208 Qualitative Inorganic Analysi8 [III,
the residue of silver chloride with 5 drops of dilute aqueous ammonia
and stir until complete solution takes place. Now add dilute nil "lc
acid, drop by drop, stirring the mixture after each addition, TIl, lil
acid (test by removing a drop of the stirred mixture on to L! \Ie
litmus paper). Observe the formation of a white precipitate of
silver chloride.

THE SILVER GROUP (GROUP I)

LEAD, MEROURY (QUS) AND SILVER
The compounds of these metals are characterised by their precipitati(Jll lIB
ohlorides by dilute hydrochloric acid or by a soluble chloride. Lead chl()ride
is slightly soluble in water and hence is not completely precipitated lIB
ohloride in this group; it is therefore also found in Group II, where it iH pre-
oipitated lIB the highly insoluble sulphide.
LEAD,Pb
Lead is a bluish-grey metal with a density of 11·48. It is re;lilily
dissolved by dilute nitric acid:
3Pb + 8HNO a = 3Pb(NO s)2 + 2NO + maO
With concentrated nitric acid, a protective film of lead nil rate,
which is insoluble in this acid, prevents complete solution. ) .'Ilute
hydrochloric acid and dilute sulphuric acid have little action" ving
to the formation of protective films of lead chloride and sulphate
respectively.

111,2. REACTIONS OF THE LEAD ION, Pb++

Use a solution of lead nitrate, Pb(N0 3)2' or of lead a(', tate,
Pb(C 2H s0 2 )2,3H 20 (abbreviated to PbA 2,3H 20), acidified with
a little acetic acid H.C 2H 30 2 (or HA).*
1. Dilute Hydrochloric Acid: white precipitate of lead
chloride PbCI 2, formed only in cold and not too dilute sollltion:
Pb(NO s)2 + 2HCl = PbCl 2 + 2HNO s
The precipitate is soluble in hot water (33·4 g. and 9·9 g. per
litre at lOOo and 20° respectively), but separates out a;_r Lin in
needles when the solution is cooled. It is also soluble ;: l con-
centrated hydrochloric acid and in concentrated alkali c! loride
solutions owing to the formation of complex compound, (co~­
pare Section I, 19); these are decomposed on dilutiC1\ with
water with the separation of lead chloride:
PbCl2 + HOI ~ H[PbCI 3 ] ; PbCl 2 + 2HCI ~ H 2[PbCI 4]
• It is recommended that the test solutions employed in the study of the
reactions of the cations and anions described in Chapt,ers III w)·j IV be
prepared as detailed in the Appendix (Section A, 3). These contain 10
milligrams of the cation or anion per ml
 2] Reaction8 of the j-fetal Ions or Oations 209
2. Potassium Iodide Solution: yellow precipitate of lead
iodide PbI 2 , moderately soluble in boiling water to yield a
colourless solution from which it separates on cooling in golden
yellow plates. It is also soluble in excess of potassium iodide
solution forming a complex salt, which is decomposed on
dilution with deposition of lead iodide.
Pb(N0 3 h + 2KI = PbI 2 + 2KNO s
PbIz + 2KI ~ K z[PbI4]
3. Dilute Sulphuric Acid: white precipitate of lead sul-
phate PbS0 4, insoluble in excess, but soluble in a concentrated
solution of ammonium acetate (due to the formation of lead
acetate, which is little ionised in the presence of excess of
acetate ions; see Common Ion Effect, Section I, 14) or in an
ammoniacal solution of ammonium tartrate.
Pb(NOah + H 2 S04 = PbS04 + 2HN03
PbS04 + 2NH4 . C2H a0 2 = Pb(C2 H a0 2 )z + (NH4)2S04
4. Potassium Chromate Solution: yellow precipitate of
lead chromate PbCr04, insoluble in acetic acid and in ammonia
solution, but soluble in alkali hydroxides and in nitric acid.
Lead chromate is quantitatively precipitated from an ammo-
nium acetate solution of lead sulphate (reaction 3).
Pb(N0 3 )2 + K2Cr04 = PbCr04 + 2KNO s
PbCr04 + 4NaOH = Na2[Pb02] + Na2Cr04 + 2H20
5. Hydrogen Sulphide: black precipitate of lead sulphide
PbS. The precipitate is often red in the presence of hydro-
chloric acid; this is due to the initial formation of lead
sulphochIoride Pb 2SCI2 , which is decomposed on dilution and
by passage of excess of hydrogen sulphide forming black lead
sulphide.
Pb(NOah + H 2S = PbS + 2HNO s
2PbCl 2 + H 2S = Pb 2SC12 + 2HCl
The precipitate of lead sulphide is very slightly soluble in
solutions of alkali polysulphides, insoluble in alkali mono-
sulphides, but soluble in hot dilute nitric acid:
3PbS + 8HN0 3 = 3Pb(N0 3 h + 2NO + 4H 2 0 + 38
It is converted into white lead sulphate PbS0 4 on treatment
~th hydrogen peroxide:
PbS + 4H 2 0 2 = PbS04 + 4H20
The great insolubility of lead sulphide in water (4·9 X 10-11 g. per litre)
explains why hydrogen sulphide is such a sensitive reagent for the detection
21-0 Qualitati'IJe Inorganic Analyai8 [III,
of lead, and why it can be detected in the filtrate from the separation of tha
sparingly soluble lead chloride in dilute hydrochloric acid.
Note.-Hydrogen sulphide is a highly poisonous gas, and 11'1
operations with the gas must be conducted in the fume chamb, .
Every precaution must be observed to prevent the escape of hydrog. I

sulphide into the air of the laboratory.

6. Sodium Hydroxide Solution: white precipitate of lel;'!
hydroxide Pb(OHh, soluble in excess of the reagent to fOfl!'
sodium plumbite:
Pb(NOs)2 + 2NaOH = Pb(OH)2 + 2NaNOs ;
Pb(OH)2 + 2NaOH = Na2[Pb02] + 2H20
Hydrogen peroxide or a solution of a pefsulphate precipitate"
brown lead dioxide Pb0 2 from a solution of sodium plumbit!
Ammonia solution yields the white lead hydroxide, insolubi('
in excess of precipitant.
t7. Tetramethyldiamino-diphenylmethane (or" Tetra-base ,.
Reagent

a blue oxidation product {hydrol: -CHz -+ -CH(OH)} is formed under

the conditions given below.
Place 1 ml. of the test solution in a 5 ml. centrifuge tube, add 1 ml.
of 2N potassium hydroxide and 0·5-1 ml. of 3 per cent hydrogen
peroxide solution. Allow to stand for 5 minutes. Separate the pre
cipitated lead plumbate by centrifugation, and wash once with cold
water. Add 2 ml. of the reagent, shake and centrifuge. The super-
natant liquid is coloured blue.
Pb(OH), + 2KOH + HIO I = KzPbO a + 3H IO
The ions of Bi, Ce, Mn, TI, Co and Ni give a similar reaction: Fe and
large quantities of Cu interfere.
Concentration limit: 1 in 10,000.
The reagent is prepared by dissolving 0·5 g. of the "tetra-base" ill
a mixture of 20 m!. of glacial acetic acid and 80 ml. of 96 per cent
ethyl alcohol.
t8. Benzidine Reagent

the so-called "benzidine blue" is produced upon oxidation with lead

dioxide. The ions of Bi, Ce, Mn, Co, Ni, Ag and TI give a similar
reaction, but by performing the test in an alkaline extract (i.e. with a
plumbite solution), only TI interferes. Oxidation is conveniently
2] Reactions of the M etaZ I ans or OationA 211
carried out by sodium hypobromite; the excess oftbe latter is dest.royed
by ammonia: 2NHa + 3NaOBr = Nt + 3NaBr + 3H,O.
Place a drop of the test solution upon drop-reaction paper, and treat
successively with 2 drops of 3N sodium hydroxide and 1 drop of
saturated bromine water. Add 2 drops of 1 : l-ammon:a solution;
remove the excess of ammonia by waving the paper over a small Bame.
Add 2 drops of the reagent: a blue colour develops.
Sensitivity: 1 fLg. Pb. Concentration limit: 1 in 50,000.
The reagent is a 0·05 per cent solution of benzidine in 10 per cent
acetic acid.
t9. Gallocyanine Reagent
HOOC

( (yN'lli
bH
o
,f'~~'-...o/ ~"-..
N(CH')3' HCI
):
deep violet precipitate of unknown composition. The test is applicable
to finely-divided lead sulphate precipitated on filter paper.
Place a drop of the test solution upon drop-reaction paper, followed
by a drop each of 1 per cent aqueous pyridine and the gallocyanine
reagent (blue). Remove the excess of the reagent by placing several
filter papers beneath the drop-reaction paper and adding drops of thG
pyridine solution to the spot until the wash liquid percolating through
is colourless; move the filter papers to a fresh position aftor each
addition of pyridine. A deep violet spot is produced.
Sensitivity: 1-6 fLg. Pb. Concentration limit: 1 in 50,000.
In the presence of silver, bismuth, cadmium or copper, proceed
as follows. Transfer a drop of the test solution to a drop-reaction paper
and add a drop of 2N -sulphuric acid to fix the lead as lead sulphate.
Remove the soluble sulphates of the other metals by washing with
about 3 drops of 2N-sulphuric acid, followed by a little rectified spirit.
Dry the paper on a water bath, and then apply the test as detailed above.
The reagent consists of a 1 per cent aqueous solution of gallocyanine.
tlO. Dipbenylthiocarbazone (or Dithizone) Reagent
/NH.NHC.H,).
( SC"-..N=NC.H, •

brick-red complex salt in neutral, ammoniacal, alkaline or alkali.

cyanide solution.
Place 1 mI. of the neutral or faintly alkaline solution in a micro
test-tube, introduce a few small crystals of potassium cyanide, and then
2 drops of the reagent. Shake for 30 seconds. The green colollr of the
reagent changes into red.
Sensitivity: 0·1 fLg. Pb (in neutral solution). Concentration limit:
1 in 1,250,000.
Heavy metals (Ag, Hg, Cu, Cd, Sb, Ni, Zn, etc.) interfere, but this
effect may be eliminated by conducting the reaction in the presence of
212 Qualitative Inorganic AruilY8i8 [III,
much alkali cyanide: excess of KOH solution is &lso required for Zn.
The reaction is extremely sensitive, but it is not very selective.
The rea~ent is prepared by dissolving 2-5 mg. of dithizone in 100 ITt i,
of carbon tetrachloride or chloroform. It does not keep well.

Dry Tests
(i) Blowpipe test.-When a lead salt is heated with alkali
carbonate upon charcoal, a malleable bead of lead (which 1,;
soft and will mark paper), surrounded with a yellow incrustH'
tion of lead monoxide, is obtained.
(ii) Flame test.-Pale blue (inconclusive).

MERCURY Hg
Mercury is a silvery-white, liquid metal at the ordinary temper!.
ture and has a density (d~:) of 13·595. It is unaffected by treat
ment with dilute hydrochloric or dilute sulphuric acid, but react,
readily with nitric acid. Cold dilute nitric acid and excess (If
mercury yield mercurous nitrate, whilst with excess of the hOT
concentrated acid mercuric nitrate is produced:
6Hg + 8HNO a = 3Hg a(NO a). + 2NO + 4H.O;
Hg + 4HNO s = Hg(NOa)a + 2NO a + 2H.O
With hot concentrated sulphuric acid, mercurous or mercuric su]
phate is formed according as the metal or the acid is present in excess
2Hg + 2H aSO, = HgaSO, + SO. + 2HaO;
Hg + 2H.SO, = HgSO, + SO. + 2H.0
Mercury forms two series of salts: the mercurous compound~.
corresponding to mercurous oxide 'HgzO and containing the bivalen 1
mercurous group Hg z ++ (-Hg-Hg-), and the mercuric com
pounds, corresponding to mercuric oxide and containing the bivalent
ion Hg++.

111,3. REACTIONS OF THE MERCUROUS ION, Hg 2 +.

Use a solution of mercurous nitrate, Hg 2 (N0 3 )2,2H 20. *
1. Dilute Hydrochloric Acid: white precipitate of mer
curous chloride (calomel) Hg 2C1 2 , insoluble in hot water and
in cold dilute acids, but soluble in aqua regia, whereby it is
converted into mercuric chloride.
Hg2 (NO a)2 +
2HCI = Hg 2Cl 2 2HNO s +
The precipitate becomes black when ammonia solution ic
poured over it, due to the production of amino-mercuri(
chloride (" infusible white precipitate") and finely divided
• Use suffioient oold, dilute nitrio acid to produce 8 olear solution.
3] Reactiona of the M etallona Vf Oationa 213
mercury (black); this black mixture is soluble in aqua regia
with the formation of mercurio chloride:
Hg2C12 + 2NHa = Hg(NH2)Cl + Hg + NH,Cl
2. Potassium Iodide Solution: yellowish-green preoipitate
of mercurous iodide Hg 212, which yields soluble potassium
mercuri-iodide K 2[HgI4] and black finely divided mercury with
excess of the reagent.
Hg2 (NO a)z + 2KI = Hg 212 + 2KN08 ;
Hg 2I z + 2KI = K 2[HgI4] + Hg
3. Potassium Chromate Solution: brown amorphous
precipitate of mercurous chromate Hg2Cr04 in the cold, which
is converted into a red crystalline form on boiling.
Hg 2(NO a)2 + K2Cr04 = Hg2Cr04 + 2KNO s
4. Hydrogen Sulphide: immediate black precipitate of
mercuric sulphide HgS and mercury (difference from mercuric
salts).
Hg2 (NO a)2 + H 2S = 2HNOa + HgS + Hg
5. Sodium Hydroxide Solution: black precipitate of
mercurous oxide Hg 2 0, insoluble in exoess of the precipitant.
Hg 2 (NO a)2 + 2NaOH = Hg 20 + 2NaNO a + H 20
6. Ammonia Solution: black precipitate, consisting of a
mercuric amino salt and finely divided mercury.
Hg
/'-.
2Hg.(NO')2 + 4NH3 + H 20 = 0 NH •. N0 3 + 2Hg + 3NH.NO.
'-./
Hg
7. Stannous Chloride Solution: grey, finely-divided mer-
cury is obtained with excess of the reagent.
Hg2 (NO a)2 + SnCl z + 2HCl = 2Hg + SnC4 + 2HNOa
8. Potassium Nitrite Solution: meroury separates as a.
dark grey (or black) precipitate (distinotion from mercurio
salts).
t The spot test technique is as follows. Place a drop of the faintly
acid test solution upon drop-reaction paper and add a drop of concen-
trated potassium nitrite solution. A black (or dark grey) spot is
produced. The test is highly selective. Coloured ions yield a brown
ooloration which may be washed away, leaving the black spot.
...
 I
214 Qualitative Inorganic Analysis [III,
Dry Tests
See under Mercuric Ion, Section III, 6.
\
SILVER Ag
Silver is a white, malleable and duotile metal. It is insoluble in
dilute hydrochlorio and sulphurio aoids, but dissolves readily ! 11
nitrio acid (2: 1) and in boiling ooncentrated sulphuric iLcid:
Ag + 2HNO a = AgNO a + NOg + H 20;
2Ag + 2H 2S04 = Ag 2S0 4 + S02 + 2H 20
111,4. REACTIONS OF THE SILVER ION, A~+

Use a solution of silver nitrate, AgN0 3.

1. Dilute Hydrochloric Acid: white, curdy precipitate ,,f
silver chloride Agel, which darkens on exposure to light. TJ ,n
precipitate is insoluble in water (solubility, 1·5 X 10-3 g. pel'
litre) and in acids (including nitric acid), but is soluble in dilute
ammonia solution owing to the formation of the complex ion.
[Ag(NH3hJ+ (see Section I, 20). It is precipitated from th
ammoniacal solution by the addition of dilute nitric acid; silv, \
iodide is precipitated with potassium iodide solution.
AgN0 3 +HCI = AgCI + HNO a ;
AgCI +2NH3 = [Ag(NHa)2]CI;
[Ag(NHa)2]CI + 2HN0 3 = AgCI + 2NH4NO a ;
[Ag(NH a)2]Cl + KI = AgI + KCl 2NHa+
Silver chloride is also soluble in potassium cyanide solutic'! 1
(highly poisonous) and in sodium thiosulphate solution:
AgCI + 2KCN = + KC}
K[Ag(CN)2]
2AgCI + 3Na2S20a = Na4[Ag2(S20a)a] + 2NaCI
t A useful spot test, which may be applied to a silver chloride pr(1.
cipitate, makes use of the reaction with manganous salts and alkaL,
2Ag+ + Mn++ + 40H- = MoOg + 2Ag + 2H g O
A stain of AgCI is thus coloured black. Mercurous and mercuric
mercury, stannous tin and the noble metals interfere.
Place a drop of dilute HCI, followed by a drop of the test solution
upon filter or drop reaction paper. Then add a drop of 2 per cell t
MnS04 or Mn(NOs)a solution and a drop of 10 per cent KOH solution,
A black stain is produced.
Sensitivity: 2 fLg. Ag. Concentration limit: 1 in 25,000.
2. Potassium Iodide Solution: yellow precipitate of silver
iodide AgI, insoluble in concentrated ammonia solution, bUI
4] Reactions of the Metal 10M or Catiom 215
readily soluble in solutions of potassium cyanide and of sodium
thiosulphate.
AgNO a + KI = AgI + JL.'\WS;
AgI + 2KCN = K[Ag(CN)2J + KI
3. Potassium Chromate Solution: red precipitate of silver
chromate Ag2Cr04' insoluble in dilute acetic acid, but soluble
in dilute nitric acid and in ammonia solution.
2AgNO s + K 2 Cr04 = AgzCrO, + 2KNO s
t The spot technique is as follows. Place a drop of the test solution
on a watch glass or on a spot plate, add a drop of ammonium carbonate
solution and stir (this renders any mercurous mercury or lead ions un-
reactive by precipitation as the highly insoluble carbonates). Remove
one drop of the clear liquid and place it on drop-reaction paper together
with a drop of the potassium chromate reagent. A red ring of silver
chromate lli obtained.
Sensitivity: 2/Lg. Ag. Concentration limit: 1 in 25,000.
Altematively, the reaction with the clear solution may be earned out
on a spot plate, when red silver chromate lli precipitated.
The reagent consllits of a 1 per cent solution of potassium chromate
in N -acetic acid.
4. Hydro~en Sulphide: black precipitate of silver sulphide
Ag 2 S, insoluble in water (solubility, 1 X 10-11 g. per litre) and
in ammonia solution, but soluble in hot dilute nitric acid.
2AgNOs + H 2S = Ag2S + 2HNOs
3Ag 2S + 8HNO s = 6AgNO s + 2NO + 3S + 4H 20
5. Sodium Hydroxide Solution: brown precipit ate of
silver oxide Ag 20, insoluble in excess of the precipitant.
2AgNOs + 2NaOH = Ag20 + 2NaNOs + H 20
6. Ammonia Solution: white precipitate at first which
quickly passes into brown silver oxide Ag 20, soluble in excess
of the precipitant.
Ag2 0 + 4NHs + H 2 0 = 2[Ag(NH s )2]OH
t7. para-Dimethylamino-benzylidene-rhodanine Reagent

86",-,.. / d=OH -r)-

HN--CO )
N(CH,)s :
( ,=-
"
red-violet salt (Ag replaces II of liN group) in faintly acid wlution.
Mercury, cuprous copper, gold, platiuum and palladium salts form
similar compounds and therefore interfere.
 I
216 Qualitative Inorganic Analy8i8 rIll,
Spot the test solu~ion upon drop reaction paper, add 1 drop "f N
nitric acid, followed by a drop of the reagent. A red- violet precipita' " or
stain is formed according to the silver content of the test solutio!!.
Alternatively, the test may be performed on a spot plate or 'I a
semimicro test-tube; in the latter case the excess of the reageI,t is
extracted with ether or amyl alcohol when violet specks of the f'. ver
complex will be visible under the yellow solvent layer.
Sensitivity: 0'02 p.g. Ag. (in 0·2N nitrio acid).
Concentration limit: 1 in 2,500,000.
If mercury is present, treat a drop of the test solution eithflr on
drop reaction paper or on a spot plate with a. drop of 5 per cent p' ; as-
sium cyanide solution, followed by a drop of the reagent and a drql of
2N nitrio acid. The silver rhodanine complex is precipitated: the
mercury is held in solution as undissociated mercuric cyanide.
If gold, platinum and palladium are present (copper mw, be
absent since cuprous copper gives a violet precipitate in acid soluti!m),
mix on a spot plate 1 drop of the test solution with a drop of 10 per cent
potassium cyanide solution and a drop of the reagent. Stir and actrlify
with 3N nitric acid. A red colour is obtained in the presence of 2·;", JLg,
of silver.
The reagent consists of a 0·03 per cent solution of p-dirnethylan 'lUO-
benzylidene-rhodanine in acetone or in alcohol.
To detect Ag in a mixture ofPbCl 1 , Hg1CI, and AgCl (Group I), Ghe
mixture is treated with 5 per cent potassium cyanide solution wher!)by
Hg(CN)2 + Hg as well as K[Ag(CN)s] are formed: after filtratiOl.l (or
centrifugation), a little of the clear filtrate is treated on a spot plate
with a drop of the reagent and 2 drops of 2N nitric acid. A red col.mJ,-
tion is formed in the presence of Ag in weakly acid solution.

Dry Tests
Blowpipe test.-When a silver salt is heated with alkali
carbonate on charcoal, a white malleable bead without an
incrustation of the oxide results; this is readily soluble in nl: ric
acid. The solution is immediately precipitated by ru;llte
hydrochloric acid, but not by very dilute sulphurio acid \,lif-
ference from lead).

DETEOTION AND SEPA.RA.TION OF METALS IN TlIE SILVER GROUP

(GROUP I)
When the student has worked through the reactions of the mt"Lals
in this group, he should attempt to identify the members of the
group both singly and when present in a mixture in the solutions
supplied to him by the teacher. With the aid of the follo'wing
simplified table which is directly based upon the reactions already
studied, this should prove a comparatively simple task. A more
detailed table will be given when all the metals have been stud led.
It is important that the student should a.cquire the habit of
recording his results in tabular form.
5J Reactions of the M etaZ lona or Oati0n8 217
III, 5. Table I. Analysis of the Silver Group (Group I)

To the given solution (or to the solution of the substance in water). add
dilute HCI in excess and filter. Discard t.he filtrate. (T)· Wash the
precipitate. which may contain PbCI •• AgCI and Hg.Cl •• with a little
very dilute HCI (ca. 0·5N). Boil the precipitate with 5-10 mi. of water
and filter hot.
"---
Residue. May contain Hg.Cl. and AgCI. I Filtrate. May contain
Wash the ppt. thoroughly with hot water PbCl •. Divide into two
until the extract gives no ppt. with K.OrO. parts:
solution. thus ensuring the complete removal (i) Add a little ammo-
of lead; reject the washings. nium acetate solution fol-
Pour 3-4 mi. of warm dilute NHs solution lowed by K.OrO, solution.
over the ppt. on the filter." Yellow ppt. of PbCrO,.
(ii) Cool und{lr tap.
White crystalline ppt. of
Residue. Black. Filtrate. May contain PbCl •.
Hg + Hg(NH.)Cl. [Ag(NH.).]Cl. Lead present.
Mercury Acidify with dilute
present. HNO,.
White ppt. of AgCI.
Silver present.

III, 5. Table SMI. Analysis of the Silver Group (Group I)

To 1 mi. of the given solution in a 3 ml. oentrifuge tube (or a 4 mi.
test-tube). add 3-4 drops (1) of dilute RCl. Stir. Centrifuge. Remove
the centrifugate with a dropper pipette to another tube. and test for
completeness of precipitation with 1 drop of dilute HCI; if no ppt. forms,
discard the solution. Wash the ppt. with 3 drops of dilute HCI, stir, and
centrifuge. Remove and discard the washings. (T) '" The residlle may
contain PbCl., AgCI and HgsCI.. Add 1 mi. of hot water to the ppt.,
place the tube in a boiling water bath for 1-2 minutes, and stir con-
tinuously. Centrifuge rapidly: separate the solution from the residue
with a capillary pipette and transfer the clear solution to a centrifuge tube.
--------------------------------~---------------
Residue. May contain HgaCl. and Agel, and Centrifugate. May
also some undissolved PbCl.. To remove the contain PbC].. Add
latter, add 1·0 mi. of water, place the tube in a 2 drops of ammonium
boiling water bath for 1 minute; centrifuge and acetate solution and
reject the supernatant liquid. Treat the residue 1 drop of K.CrO,
with 0·5 mi. of warm dilute aqueous NH s• stir and solution.
centrifuge. Yellow ppt. of
PbCrO,.
Residue. Black. Lead present.
CentrHugate. May con-
Hg+Hg(NH.)CI. tain [Ag(NH.).]Cl. Add dilute
Mercury HCl or dilute HNO. tmtil
present. acid (2).
White ppt. of Agel.
Silver present.

• The symbol (T) refers to the point at which the group separation is
commenced in connexion with Table S (Section V. 8) and Table SM.S
(Section VI. 9) respectively.
218 Qualitative Inorganic Analysia [III,
Notes.-(l) For the sake of uniformity throughout the text, a dr()!>
is intended to mean 0·05 mI.-the volume of the drop deliver!,:
by the common medicine dropper. If the instructions require tL
addition of 0·5 mI., this quantity can either be measured out in :
small measuring cylinder or from a calibrated pipette, or 10 dr0l
can be added directly from a reagent dropper provided, of cours
that a drop from the latter does not differ appreciably from 0·05 Ir
(see, however, Section II, 3,3). It is recommended that all droppel
be calibrated as follows. The dropper pipette is almost filled wil "
water by alternately compressing and releasing the bulb whilst tL
capillary end is dipped into a small beaker containing distilled wate:
The dropper is held vertically over a clean, dry measuring cylinder
the bulb gently pressed and the number of drops counted until tl.
meniscus reaches the 2 mI. mark. This process is repeated uni:'
two results are obtained which do not differ by more than two drop
A small label, stating the number of drops per mI., should L,·
attached to the upper part of the dropper.
(2) As a rule, when a solution is to be rendered acidic or basi,
an indicator test paper, such as litmus, should be used. Tb
indicator test paper is placed on a watch glass. The solution
treated with acid or base dropwise and with stirring until the WI' i
stirring rod when brought into contact with a dry spot on tI: .
indicator paper causes the appropriate change in colour. In tI,
present instance, the addition of a micro drop of phenolphthalei i;
t,o the liquid in the tube is satisfactory.

THE COPPER AND ARSENIC GROUP (GROUP II)

MEROURY (10), LEAD, BISMUTH, OOPPER,
OADMIUM, ARSENIO, ANTIMONY AND TIN
The compounds of these elements are characterised by their precipitati(!1
as sulphides by hydrogen sulphide from O·3N hydrochloric acid solutiOl
The sulphides of arsenic, antimony and tin are soluble in both ammoniUl' I
sulphide and in potassium hydroxide solution, whilst those of the remainin
metals are practically insoluble. It is therefore usual to sub·divide this grOD'
into the copper group or Group IIA, comprising mercury, lead, bismut},
copper and cadmium, and the arsenic group or Group lIB, comprising arsenic,
antimony and tin.

THE COPPER GROUP (GROUP IIA)

MERCURY, Hg
Mercury forms two series of compounds, the mercurous and
mercuric, which may be regarded as derived respectively from th"
oxides Hg 2 0 and HgO. The reactions for the former have alread:
been described (Section III, 3); those for the latter are detailed belo"
It may be mentioned that mercuric chloride is only slightly dif-
sociated in aqueous solution. Mercuric cyanide is soluble in water
and practically undissociated; it will give a precipitate only witi
hydrogen sulphide.
6] Reactions of the Metal Ions or Cations 219
111,6. REACTIONS OF THE MERCURIC ION, Hg++
Use a solution of mercuric chloride, HgCl 2 (highly po£sonous).
1. Hydrogen sulphide: initially a white, then yellow,
brown and finally a black precipitate of mercuric sulphide
HgS. In all cases, excess of hydrogen sulphide gives the black
mercuric sulphide. The white precipitate is the chloro-
sulphide Hg 3S 2Cl 2 (or HgCI 2,2HgS), which is decomposed by
hydrogen sulphide.
3HgC1 2 + 2H zS = Hg 38 2Cl 2 + 4HCl;
HgsS 2 C1 2 + H 2 S = 2HCI + 3HgS;
The net result is: HgCl z + H z8 = Hg8 + 2HCI
Mercuric sulphide if) practically insoluble in water, hot dilute
nitric acid, and in solutions of alkali hydroxides and of colour-
less ammonium sulphide. The precipitate is appreciably
soluble in sodium sulphide solution and can be reprecipitated
by adding ammonium chloride solution: it dissolves also in
aqua regia and in a mixture of sodium hypochlorite solution
and dilute hydrochloric acid.
3Hg8 + 2HNO + 6HCl =
g 3HgCl z + 2NO + 38 + 4HzO
2. Stannous Chloride Solution: a white precipitate of
mercurous chloride Hg 2Cl 2 is first obtained, which is reduced
by excess of the reagent to grey-black metallic mercury.
2HgCl z + SnC1 2 = ~nC14 + Hg 2 C1 2 ;
Hg 2C1 2 + SnC1 2 = SnC4 + 2Hg
3. Sodium Hydroxide Solution: initial reddish-brown
precipitate oi basic chloride, converted by excess of alkali
into yellow mercuric oxide.
HgCl z + 2NaOH = HgO + 2NaCl + H 20
4. Ammonia Solution: white precipitate of amino mer-
curic chloride (NHz)HgCl, known as "infusible white precipi-
tate" for it volatilises without molting.
HgCl 2 + 2NHa = Hg\NH 2 )CI + NH4CI
The precipitate is soluble in a large excess of aqueous ammonia
and ammonium chloride.
5. Potassium Iodide Solution: red (initially yellowj pre-
cipitate of mercuric iodide HgT2' soluble in exces~~ of the
220 Qualitative Inorganic AnalY8i8 [111,
preoipitant owing to the formation of the complex salt, pota
sium mercuri-iodide K2[HgI4] (compare Sections I, 19 and 1,20
HgCl 2 + 2KI = HgI 2 + 2KCI;
HgI 2 + 2KI = K2[HgI4]
6. Copper: when a piece of bright copper foil, cleansed-if
necessary-by rubbing it with emery paper or by dipping it
into concentrated nitric acid, is immersed into the mercur:'
chloride solution, it becomes coated with a grey film of mercur.\ .
which acquires a silvery appearance on rubbing (see Electro(;,'
Potentials, Section I, 29).
HgCl 2 + Cu = Hg + CuCl2
7. Ethylenediamine Reagent: a dark blue-violet precipi
tate of the complex [Cu en2] [HgI4J is formed when a mercurJ,
salt in neutral or faintly ammoniacal solution is treated wit
excess of 2 per cent potassium iodide solution, followed by tIl,'
ethylenediamine reagent.
HgCl 2 + 4KI = K2[HgI4] + 2KCl;
K2[HgI4] +[Cu en2]804 = [Cu en2] [HgI4J + K 280 4
(NH 2. CH2. CH 2. NH2 = en)
The reaction is a sensitive one, but cadmium ions, which form
a similar complex [Cu en2] [CdI4], interfere.
The reagent is prepared by treating a solution of cupric sulphate
with an aqueous solution of ethylenediamine (5-6 times the theo-
retical quantity) until the dark blue-violet coloration, due to tlH'
[Cu en2]++ ion, appears and does not increase in intensity upc,'
further addition of the base. The presence of excess of the latter
in the reagent has no harmful influence.
t8. Stannous Chloride-Aniline Test.-Mercuric salts are reduce, i
to grey or black metallic mercury. The aniline adjusts the pH of tJ,,·
medium so that the similar reaction of Sb + + + does not occur. Lar,:.
amounts of Ag interfere as do Au and Mo: Bi and Co are without effec
Treat a drop of the test solution upon drop reaction paper or upon
spot plate with a drop of the stannous chloride solution and a drop ,
aniline. A brown or black stain of Hg is produced.
Sensitivity: 1 p.g. Hg. Concentration limit: 1 in 50,000.
The rea~ent consists of a 5 per cent solution of stannous chloride HI
lON hydrochloric acid.
t9. Diphenylcarbazone Reagent
/N ... N.C.H5 )
( CO"NH.NH.C.H.
 Reactions of the Metal Ions or Oations 221
,lue to violet inner complex salt. The sensitivity of the test depends
.pon the pH of the solution. decreasing with increasing acidity. In
·2N nitric acid, the test is highly selective provided chromates and
:lOlybdates (which give coloured compounds) are absent. Chromates
lay be reduced with sulphurous acid or with hydrogen peroxide to
.on-reacting chromic salts: molybdates may be rendered inacdve by
dding 5 per cent oxalic acid solution when a Mo-oxalic acid complex
! produced.
Place a drop of the test solution and a drop of 0·2N nitric acid upon
rop reaction paper, which has been moistened with the reagent. A
iolet or blue coloration appears.
Sensitivity: 1 fLg. Hg. Concentration limit: 1 in 50,000.
The reagent consists of a I per cent solution of diphenylcarbazone
1 90-100 per cent ethyl alcohol.

tlO. Cobalt Acetate-Ammonium Thiocyanate Reagent.--When

solution of a mercuric salt is treated with a concentrated solution of
obalt acetate and a little solid ammonium thiocyanate, a dpep-blue
rystalline precipitate of cobaltous mercuri-thiocyanate Co[Hg(CNS)4]
! formed. Crystallisation is sometimes slow, but may be accelerated
y scratching the interior of the vessel with a glass rod.
Place a drop of the test solution on a spot plate, add a small crystal
f ammonium thiocyanate followed by a little solid cobalt acetate. A
lue colour is produced.
Sensitivity: 0'5 (-tg. Hg. Concentration limit: I in lCO,OuO.
)ry Test
All compounds of mercury when heated with a large excess
7-8 times the bulk) of anhydrous sodium carbonate in a small
ry test-tube yield a grey mirror, consisting of fine drops of
lercury, in the upper part of the tube. The globules coalesce
rhen they are rubbed with a glass rod.
Note.-Mercury vapour is extremely poisonous, and not more
than 0·1 gram of the substance should be used in the test.

BISMUTH, Bi
Bismuth is a brittle, crystalline and reddish-white metal. It is
insoluble in hydrochloric acid, but dissolves in hot concentrated
sulphuric acid and in aqua regia. The best solvent is nitric acid.
2Bi + 6H aSO, = Bi a(80 4)a + 6H 20 + 380.
2Bi + 8HNO s = 2Bi(NO a)a + 4HaO + 2NO
The salts of bismuth may be regarded as derived from the sesqui-
oxide Bi2 0 3. The hydroxide Bi(OH)3 is a weak base; the salts are
accordingly hydrolysed by much 'Water (see Hydrolysis of Salts,
Section I, 40) yielding insoluble basio (usually bismuthyl, i.e. con-
taining the radical BiO-) BaIts.
BiCl. + RIO "'" BiOCl + mOl.
 I

222 Qualitative Inorganic Analysi8 I fIl,

III, 7. REACTIONS OF THE BISMUTH ION, Bi' ++
Use a solution of bismuth nitrate, Bi(NO a)a,5H 20, to v. 'Jich
just sufficient nitric acid has been added to produce a lear I

solution.
1. Hydrogen Sulphide: brown precipitate of bisliluth
sulphide Bi 2S 3 , insoluble in cold dilute acids and in ammonium
sulphide solution, but soluble in hot dilute nitric acid ali'i in
boiling concentrated hydrochloric acid.
2Bi(NO ah + 3H2S = Bi 2Sa + 6HNO a
2. Sodium Hydroxide Solution: white precipitate 0: bis-
muth hydroxide Bi(OH)a in the cold, very slightly soluL:.1 in
excess of the reagent (2-3 mg. Bi in 100 ml. N NaOH solution),
soluble in acids. It becomes yellow on boiling, due to p i,ial
dehydration.
Bi(NOgh + 3NaOH = Bi(OH)s + 3NaNOg
Bi(OHh = BiO. OR + H 2 0
If hydrogen peroxide be added to the solution containin.: the
white or yellowish-white precipitate in suspension, browli bis-
muthic acid HBiO a is formed:
BiO.OH + H 2 0 2 = HBiO a + H 2 0
3. Ammonia Solution: a white basic salt, of va, lble
composition, is precipitated. The precipitate is insolu' •3 in
excess of the reagent (distinction from copper and cadn lm).
4. Potassium Iodide Solution: dark brown precipit:: I e of
bismuth tri-iodide, readily soluble in excess of the reag! '. t to
give a yellow solution of the complex salt K[BiI4 ]. The om-
pIe x is decomposed upon dilution giving first a precipit •. e of
the tri-iodide and then an orange-coloured precipitate (,(' the
basic bismuthyl iodide (BiO)I.
Bi(NOah + 3KI = BiIa + 3KNO a ;
BiIs + KI = K[BiI4J;
Bils + H 2 0 ;0=: 2HI + (BiO)I
5. Sodium Stannite Solution: black precipitate of linely
divided bismuth in the cold. The reagent is prepaI" l by
adding sodium hydroxide solution to a solution of sta., nous
chloride until the initial white precipitate of stannous h: lrox-
ide just dissolves.
Sn(OH)2 + 2NaOH = Na2[Sn02J + 2H 20;
2Bi(NO a)s + 6NaOH + 3Na2[Sn02]
= 2Bi + 3Na2[SnOa] + 6NaNO a -1 'm2o
7] Reactions of the Metal Ions or Oations 223
t The test is rendered more sensitive by making use of the f!lct that
the slow reaction between lead hydroxide or sodium plumbite and
sodium stannite is greatly accelerated by the separation of even minute
quantities of bismuth:
Pb(OH)2 + Nu 2[Sn0 2] = Pb + Na 2[SnO S] + HaO
Silver, copper and mercury interfere: copper is rendered innOCllOUS by
the addition of a little potassium cyanide.
On a spot plate, mix a drop of the test solution, a drop of saturated
lead chloride solution, a drop of 5 per cont potassium cyanide l'olution
and 2 drops of sodium stannite solution. A brown to black coloration
appears.
Sensitivity: 0·01 ftg. Bi. Concentmtion limit: 1 in 5,000,000.
The sodium stannite reagent is prepared by mixing just before
use equal volumes of the two solutions a and b: (a) a solution (If 0·5 g.
of stannous chloride in 0'5 ml. of concentrated hydrochloric acid,
diluted to 10 ml. with di,~tilled water; (b) 25 per cent sodium hydroxide
solution.

6. Water. When a solution of a bismuth salt is noured

into a large volume of water, a white precipitate of tile cor-
responding basic salt is produced, which is soluble in dilute
mineral acids, but is insoluble in a solution of tartaric acid
(distinction from antimony) and in solutions of alkali hydrox-
ides (dlstinction from tin).
Bi(NOa)a +
H 20 ~ (BiO)NOa + 2HNO s ;
2Bi(NOsh + 3H2 0 ~ (BiO)2(OH)NOs + 5HNO a (very
large excess of water);
BiOla + H 20 ~ (BiO)Cl + 2HOl
7. Pyrogallol Reagent {I : :{ : 5-trihydroxybenzene,
C6H s (OH)a }: the addition of a slight excess of a concentrated
solution of the reagent to a hot solution of a bismuth salt
faintly acid with dilute hydrochloric acid or nitric acid, yields
a yellow precipitate of the complex Bi(C6H s03). It is best to
add ammonia solution until the solution is alkaline to litmus
paper and then dilute nitric acid until just acid. The test is a
very sensitive one. Antimony interferes and should be absent.
The reagent is prepared as required: a suitable concentrntion is
0'5 gram of pyrogallol in 5 rol. of water.

8. Sodium Phosphate or Sodium Arsenate Solution:

white crystalline precipitate of BiP04 or BiA.sO" api1ringly
soluble in dilute mineral acids (distinction from mercurie, lead,
IlOpper and oadmium. salts).
224 Qualitative Inorganic Analysis [lIT ,
t9. Cinchonine-Potassium Iodide Rea~ent: orange-red coloTd
tion or precipitate, due to bismuth-cinohonine iodide (BiI 3 , cinchoniw,
HI), in faintly acid solution.
Moisten a piece of drop-reaction paper with the reagent and placf'
drop of the slightly acid test solution upon it. An orange-red spot
obtained.
Sensitivity: 0·15 JLg. Bi. Concentration limit: 1 in 350,000.
The test may also be carried out on a spot plate.
Lead, copper and mercury salts interfere because they react with the
iodide. Nevertheless, bismuth may be detected in the presence of salts
of these metals as they diffuse at different rates through the capillaries
of the paper, and are fixed in distinct zones. When a drop of the tef't,
solution containing bismuth, lead, copper and mercury ions is placo(i
upon absorbent paper impregnated with the reagent, four zones can bo
observed: (i) a white central ring, containing the mercury; (ii) an oran .
ring, due to bismuth; (iii) a yellow ring oflead iodide; and (iv) a bro,"
ring of iodine liberated by the reaction with copper. The thickness",
of the rings will depend upon the relative concentrations of the vario",
metals.
Sensitivity: 10-15 JLg. Bi.
The rea~ent is prepared by dissolving 1 g. of cinchonine in 100 n •
of hot water containing a few drops of nitric acid; after cooling, 2 g. ,,(
potassium iodide are added.
tJO. Thiourea Rea~ent (NH •.CS.NH.): intense yellow oolorati,,,,
in the presence of dilute nitric aoid. The test may be carried out (·fl
drop.reaction paper, on a spot plate, or in a micro test-tube.
Sensitivity: 6 JLg. Bi. Concentration limit: 1 in 30,000.
Mercurous mercury, silver, antimony, ferric iron and chromates intN,
fere and should therefore be absent.
The rea~ent oonsists of a 10 per cent aqueous solution of thiourea

Dry Test
Blowpipe test.-When a bismuth -compound IS heated Oil
charcoal with sodium carbonate in the blowpipe flame, a brittj,
bead of metal, surrounded by a yellow incrustation of th"
oxide, is obtained.

COPPER, au
Copper is a light red metal, which is soft, malleable and ductilp
It is unaffected by hydrochloric acid and by dilute sulphurio acid.
but is readily attacked by dilute nitric acid and by warm concen
trated sulphuric acid:
3Cu + SHNO. = 3Cu(NO a). +4H.0 +
2NO;
Cu + 2H.SO, = CuSO, +SO. +
2H.0
Some cuprous sulphide CU2S is also formed probably in accordance
with the equation:
6Cu + 6H SO,
I = 4:CuSO, + CutS + SO, + 6R 0 I
8] Reactions of the M etallons or Cations 225
There are two series of copper compounds: those which may be
regarded as derived from cuprous oxide CU20 (red), known as
cuprous compounds and containing the ion Cu +, and those similarly
derived from cupric oxide CuO (black), known as the cupric com-
pounds and giving rise to the ion Cu ++. The cuprous compounds,
e.g. CuCI, are colourless, insoluble in water and comparatively un-
stable, being readily oxidised to the cupric compounds; they dissolve
readily in concentrated solutions of halogen acids, forming colourless
solutions which contain complex acids, such as H[CuCI 2]. Cupric
salts, when dissolved ill water, yield blue or green solutions; the
anhydrous salts are white or yellow.

III, 8. REACTIONS OF THE CUPRIC ION, Cu++

Use a solution of cupric sulphate, CuS04,5H20. (Aqueous
solutions of cupric salts are blue, due to the ion [Cu(H 2 0 )4] + +;
the latter is usually written as Cu ++.)
1. Hydrogen Sulphide: a black precipitate of cupric sul-
phide CUS is obtained in neutml or preferably acid (HCI)
solutions. The precipitate is soluble in hot dilute nitric acid
and in potassium cyanide solution; in the latter case a complex
salt, potassium cupro-cyanide K 3 [Cu(CN)4] is formed. Cupric
sulphide is insoluble in boiling dilute sulphuric acid (distinction
from cadmium); it is also insoluble in potassium hydroxide
solution, in alkali monosulphide solution and very slightly
soluble in alkali polysulphide solution.
CuSO, + H 2S = CuS + H 2S04
3CuS + 8HN0 3 = 3Cu(N03 )2 4H 20 + + 2NO + 3S
Cupric sulphide tends to form a colloidal solution and pass through filter
paper. This is avoided by carrying out the precipitation in the presence of
hydrochloric acid or some other electrolyte. It also tends to oxidise to the
soluble sulphate when exposed to the air in the moist state: this is prevented
by washing the precipitate with acidulated hydrogen sulphide water.
2. Sodium Hydroxide Solution: blue precipitate of cupric
hydroxide Cu(OHh, insoluble in moderate excess of the re-
agent, and converted on boiling into black cupric oxide.
CuSO, + 2NaOH = CU(OH)2 +
NazSO,
CU(OH)2 = CuO + HllO
In the presence of a solution of tartaric acid or of citric acid, cupric hydroxide
is not precipitated by solutions of caustic alkalis, but the solution is coloured
an intense blue. If the alkaline solution is treated with certain reducing
agents, such as hydroxylamine, hydrazine, glucose and acetaldehyde. yellow
cuprous hydroxide is precipitated from the warm solution, which is converted
into red cuprous oxide CU.O on boiling. The alkaline 8olution of cupric salt
containing tartaric acid is usually known as Fehling'/! 8olution; it oontains the
complex salt Na.[(OOC.CHO).Cu].
8+
 226 Qualitative Inorganic Analysis [III,
3. Ammonia Solution: pale blue precipitate of basic salt.
soluble in excess of the precipitant with the formation of a dee I'
blue solution containing the complex salt, tetra-ammine cuprj,
sUlphate [Cu(NHa)4]S04.
2CuS04 + 2NHs + 2H 20 = CuS04,Cu(OHh + (NH4)2S04,;
CuS04,Cu(OH)2 + (NH4)2S04 + 6NH s = 2[Cu(NHs)4]S04 + 2H 2( I
4. Potassium Ferrocyanide Solution: reddish-brown pre
cipitate of cupric ferro cyanide CU2[Fe(CN)6] from neutral Oi
acid solutions. It is insoluble in dilute acids, but dissolves iJ:
aqueous ammonia forming a blue solution. The precipitate i,.
decomposed by solutions of alkali hydroxides with the separa
tion of blue cupric hydroxide.
2CUS04 + K 4[Fe(CN)6] = CU2[Fe(CN)6] + 2K2SO,
5. Potassium Cyanide Solution (highly poisonous): yello"
precipitate of cupric cyanide Cu(CNh, which quickly decom
poses into cuprous cyanide CuCN and cyanogen (CNh. Th,
cuprous cyanide dissolves in excess of the reagent forming "
colourless solution of a complex salt, potassium cuprocyanidc
K 3[Cu(CN)4], in which the concentration of copper ions is so
small that it is insufficient to give a precipitate with hydrogel
sulphide (distinction from cadmium) (for detailed explanatioll
see Complex Ions, Section I, 20).
2CuSO, + 4KCN = 2Cu(CN)2 + 2K2SO,;
2Cu(CN)2 = (CNh + 2CuCN
CuCN + 3KCN = Ka[Cu(CN),]
6. Potassium Iodide Solution: cupric iodide CuI 2 is first
precipitated; this immediately decomposes into white cuproue-
iodide CuI and free iodine. The latter dissolves in the exces~
of the potassium iodide solution and colours the solutiOJ i
brown.
CuSO, + 2KI = CuI2 + K 2SO,
2Cu12 = 2Cu1 + 12;
or CuSO, + 4K1 = 2KzSO, + 2CuI + I z
7. Potassium or Ammonium Thiocyanate Solution'
black precipitate of cupric thiocyanate CU(SCN)2, which passel
slowly, or immediately upon adding sulphurous acid solution
into white cuprous thiocyanate CuSCN. The latter is in
soluble in water and in dilute sulphuric and hydrochloric acids
CuSO, + 2NR,SCN = Cu(SCNb + (NH')2S0,
2Cu(SCN)z + RISO. + HIO = 2CuSCN + 2RSCN + RIlSO,
8] Reaction8 of the Metal I0n8 or Oation8 227
8. Iron. If a clean iron nail or the Olade of a pen-kllife is
immersed in a solution of a cupric salt, a red deposit of copper
is obtained (see Electrode Potentials, Section I, 29):
CuS04 + Fe = FeS04 + Cu
t9.
ex-Benzoin Oxime (or Cupron) Reagent
{C8H&.CHOH.C(= NOH).C8Hd:
green precipitate of copper benzoin oxime Cu(C U H ll 0 2N), insoluble in
dilute ammonia solution. In the presence of metallic salts which are
precipitated by ammonia solution, their precipitation can be prevented
by the addition of sodium potassium tartrate. The reagent is specific
for copper in ammoniacal tartrate solution. Large amounts of am-
monium salts interfere Hud should be removed by evaporation and
heating to glowing: the residue is then dissolved in a little dilute
hydrochloric acid.
Treat some drop-reaction paper with a drop of the weakly acid test
solution and a drop of the reagent, and then hold it over ammonia
vapour. A green coloration is obtained.
Sensitivity: 0'1 f.Lg. Cu. Concentration limit: 1 in 500,000.
lf other ions, precipitable by ammonia solution, are present, a drop of
10 per cent Rochelle salt solution is placed upon the paper before the
reagent is added.
The reagent is prepared by dissolving f:i g. of ex-benzoin oxime in
100 ml. of 95 per cent alcohol.
tlO. Salicylaldoxime Reagent

(CX:~NOH ),
greenish-yellow precipitate of copper salioylaldoxime Cu(C 7H e0 2N)a in
acetic acid solution, soluble in mineral acids. Only palladium Hnd gold
give precipitates {Pd(C7H o0 2N)2 and metallic gold respectively} in acetic
acid solution and should therefore be absent.
Place a drop of the test solution, which has been neutralised and then
acidified with acetio acid, in a micro test-tube and add a dron of the
reagent. A yellow-green precipitate or opalescence (according to the
amount of copper present) is obtained.
Sensitivity: 0·5 fLg. Cu. Concentration limit: 1 in 100,000.
The reagent is prepared by dissolving 1 g. of salicylaldoxime in
5 ml. of cold alcohol and pouring the solution dropwise into 95 ml. of
water at a temperature not exceeding 80°0; the mixture is shaken until
clear, and filtered if necessary.
tll. Rubeanic Acid (or Dithio-oxamide) Reagent
H2N-C-C--NH. )
( ""
S S :
black precipitate of copper rubeanate Cur C( = NH)S}z from ammo-
niacal or weakly acid solution. The precipitate is formed in the
228 Qualitative Inorganic AnalY8i8 [Ill,
presence of alkali tartrates, but not in alkali-cyanide solutions. 01': V
nickel and cobalt ions react under similar conditions yielding blue al"l
brown precipitates respectively. Copper may, however, be detecl ,I
in the presence of these elements by utilising the capillary separat ,~
method upon filter paper. Mercurous mercury should be absent a8 t
gives a black stain with ammonia.
Place a drop of the neutral test solution upon drop-reaction pap,".
expose it to ammonia vapour and add a drop of the reagent. A blu<"i;:
or greenish-black spot is produced.
Sensitivity: 0·01 J.Lg. Cu. Concentration limit: 1 in 2,500,000.
Traces of copper in distilled water give a positive reaction, hence ,
blank test must be carried out with the distilled water.
In the presence of nickel, proceed as follows. Impregnate dr, J)
reaction paper with the reagent and add a drop of the test soluti ' l
acidified with acetic acid. Two zones or circles are formed: the cent, .[
olive green or black ring is due to copper and the outer blue-violet rio ,
to nickel.
Sensitivity: 0'05 J.Lg. Cu in the presence of 20,000 times amount ofNi,
Concentration limit: I in 1.000,000.
In the presence of cobalt, the central green or black ring, due ,
copper, is surrounded by a yellow-brown ring of cobalt ;ubeanate.
Sensitivity: 0·25 J.Lg. Cu in the presence of 2,000 times amount of Co.
Concentration limit: I in 200,000.
The reagent consists of a 0·5 per cent solution of rubeanic acid ill
95 p~r cent ethyl alcohol. It does not keep well and should be prepare, I
as required.
t12. Ammonium Mercuri-thiocyanate Reagent
{ (NH,) z[Hg(SCN),] }:
deep violet, crystalline precipitate in the presence of zinc or cadroiwl!
ions. Cobalt and nickel interfere since they yield green or blue pr.·
cipitates of the corresponding mercuri-thiocyanates X[Hg(SCN),]; t}"
interference of ferric iron is avoided by carrying out the precipitatioi'
in the presence of alkali fluorides or oxalates.
Place a drop of the acid test solution upon a spot plate, add I drop ( r
1 per cent zinc acetate solution and I drop of the reagent. The precip
tated zinc mercuri-thiocyanate is coloured violet due to coprecipitatio"
of the copper complex: it may be regarded as Zn[Hg(SCN),-
Cu[Hg(SCN),].
Sensitivity: 0·1 J.Lg. Cu. Concentration limit: 1 in 500,000.
(The addition of copper ions to a precipitate of zinc mercuri-thiocyanate,
already formed, has no influence.)
The reagent is prepared by dissolving 9 g. of ammoniwn thiocyanat "
and 8 g. of mercuric chloride in 100 mI. of water.
t13. Catalytic Effect upon the Ferric Iron-Thiosulphate Re
action.-Ferric salts react with thiosulphates in accordance with tho
equations:
Fe+++ + 2S,0,-- = [Fe(S.O,)s]- (violet complex ion) (1
[Fe(S.O.).r +Fe+++ => 2Fe++ +
8,0.-- (ii)
 9J Reactions of the M etatIons or Cations 229
Reaction (i) is fairly rapid; reaction (ii) is a slow one, but is enormously
accelerated by traces of copper salts. If the reaction is carried out in
the presence of a thiocyanate, which serves as an indicator for the
presence of ferric iron and also retards reaction (ii), then the reaction
velocity. which is proportional to the time taken for complete decolorisa-
tion, may be employed for detecting minute amounts of cupric ions.
Tungsten and, to a lesser extent, selenium cause a catalytic acceleration
similar to that of copper: they should therefore be absent.
Upon adjacent cavities of a spot plate place a drop of the test solution
and a drop of distilled water. Add to each 1 drop of the forric thio-
cyanate reagent and 3 drops of O'IN -sodimu thiosulphate solution. The
decolorisation of the copper-free solution is complete in 1'5-2 minutes:
if the test solution contains 1 I-'g. of copper, the decolorisation is
instantaneous. For smaller amounts of copper, the difference in times
between the two tests is still appreciable.
Sensitivity: 0'02 I-'g. Cu. Concentration limit: 1 in 2,500,000.
The "ferric thiocyanate" rea~ent is prepared by dissolving 1·5 g.
offerric chloride and 2·0 g. ofpotassiwn thiocyanate in 100 mI. of water.

Dry Tests
(i) Blowpipe test.-When copper compounds are heated with
alkali carbonate upon charcoal, red metallic copper is obtained,
but no oxide is visible.
(ii) Borax bead.-Green while hot and blue when cold after
heating in the oxidising flame; red in the reducing flame, best
obtained by the addition of a trace of tin or by moistening with
stannous chloride solution.
(iii) Flame test.-Green especially in the presence of halides,
e.g. by moistening with concentrated hydrochloric acid before
heating.
CADMIUM, Cd
Cadmium is a silver-white, malleable and ductile metal. It dis-
solves slowly in dilute hydrochloric and sulphuric acids with the
evolution of hydrogen. The best solvent for the metal is nitric acid.
Only one series of salts, derived from the oxide CdO, is of importance
in qualitative analysis.

III, 9. REACTIONS OF THE CADMIUM ION, Cd++

Use a solution of cadmium sulphate, 3CdS04 ,8H 20.
1. Hydro~en Sulphide: yellow precipitate of cadmium
sulphide CdS from solutions acidified with a little hydrochloric
acid (strength approximately 0'3 molar). The precipitate is
soluble in hot dilute nitric acid and also in hot dilute sulphuric
acid (distinction from copper), but is insoluble in potassium
cyanide solution (difference from copper). No precipita.tion
230 Qualita,tive Inorganic A ruilysis [III,
takes place in strongly acid solutions owing to the reversibilii \
of the reaction:
CdSO, + H 2S ~ CdS + H 2SO,
(for a detailed discussion of the reaction see Section I, 16).
2. Sodium Hydroxide Solution: white precipitate of ca'!
mium hydroxide Cd(OHb insoluble in excess of the reagen
CdSO, + 2NaOH = Cd(OH)z + Na ZS04
3. Ammonia Solution: white precipitate of cadmium h'
droxide, soluble in excess of the precipitant (distinction fro 1,:
lead and bismuth); the soluble complex salt, tetra-ammiJ,
cadmium sulphate [Cd(NH 3 ),]SO" is formed (see Compl<
Ions, Section I, 20).
CdSO, +
2NHs + 2HzO = Cd(OH)z + (NH4)zS04;
Cd(OH)2 +
(NH')2S0, + 2NHs = [Cd(NHs ),]S04 +
2H20
4. Potassium Cyanide Solution: white precipitate , i
cadmium cyanide Cd(CNb soluble in excess of the reagent ' )
yield the complex, potassium cadmi-cyanide K 2[Cd(CN),]. \
sufficiently high concentration of cadmium ions is produced J \
the dissociation of the complex ion to give a precipitate, 'i
yellow cadmium sulphide with hydrogen sulphide.
CdS04 + 2KCN = Cd(CN)2 + K ZS04;
Cd(CN)z +
2KCN = K z[Cd(CN)4J;
K z[Cd(CN)4] + HzS = CdS + 2KCN + 2HCN
The marked difference in the values of the instability constants of j: "
complex ions [Cd(CN),r- and [Cu(CN),r-- serves as the basis for one :'
the methods for the separation of copper ~d cadmium (for discussion, ~",
Section I, 20).

5. Ammonium Thiocyanate Solution: no precipita l

"

(distinction from copper).

to. Dinitro-p-diphenylcarbazide Reagent
/NH.NH.C,H,.NO.(4)) .
( CO"NH.NH.C H •. NO.(4) .
s
Cadmium hydroxide is coloured brown by the reagent, which rapidl,"
becomes greenish·blue with formaldehyde.
Place a drop of the acid, neutral or ammoniacal test solution or: 'L
spot plate and mix it with 1 drop of 10 per cent sodium hydroxl l l
solution and 1 drop of 10 per cent potassium cyanide solution. Int) ,.
duce 1 drop of the reagent and 2 drops of 40 per cent formaldehj d
solution. A brown precipitate is formed, which very rapidly becom,';
greenish-blue. The reagent alone is red in alkaline solution and "
coloured violet with formaldehyde, hence it is advisable to compare tl Ii)
9] Reactions of the M etaZ Ions or OatioruJ 231
colour produced in a. blank test with pure water when searehing for
minute amounts of cadmium.
Sensitivity: O'S fLg. Cd. Concentration limit: 1 in 60,000.
In the presence of considerable amounts of copper, 3 drops eaeh of the
potassium cyanide and formaldehyde solution should be used; the
sensitivity is 4 fLg. Cd in the presence of 400 times the amount of Cu.
The r~agent consists of a 0'1 per cent solution of dinitro-p-Jiphenyl-
carbazide in alcohol.
t7. 4-Nitronaphthalene-diazoamino-azobenzene ("Cadion 2B")
Reagent

(O'NS N-N-NH-Q-N-N-Q )
Cadmium hydroxide forms a red-coloured lake with the reagent, which
contrasts with the blue tint of the latter.
Place a drop of the reagent upon drop reaction paper, add one drop
of the test solution (which should be slightly acidified with acetic acid
containing a little sodium potassium tartrate), and then onn drop of
2N potassium hydroxide. A bright pink spot, surrounded by a blue
circle, is produced.
Sensitivity: 0·025 fLg. Cd.
The interference of Cu, Ni, Co, l!"e, Cr and Mg is prevented by adding
sodium potassium tartrate to the test solution: only Ag (removed as AgI
by the addition of a little KI solution) and Hg then interfere. Mercury
is best removed by adding a little sodium potassium tartrate, a few
crystals of hydroxylamine hydrochloride, followed by KOH solution
until alkaline; the mercury is precipitated as metal. Stannous chloride
is not suitable for this reduction since most of the cadmium is adsorbed
on the mercury precipitate.
The reagent is prepared by dissol ving 0·02 g. of "cadion 2B" in
100 ml. of ethyl alcohol to which 1 ml. of 2N-KOH is added. The
solution must not be warmed. It is destroyed by mineral acid.

Dry Tests
Blowpipe test.-All cadmium compounds when heated with
alkali carbonate on charcoal give a brown incrustation of
cadmium oxide CdO.
Ignition test.-Cadmium salts are reduced by sodium oxalate
to elementary cadmium, which is usually obtained as a metallic
mirror surrounded by a little brown cadmium oxide. Upon
heating with sulphur, the metal is converted into yellow cad-
mium sulphide.
Place a little of the cadmium salt mixed with an equal weight
of sodium oxalate in a small ignition tube, and heat. A mirror
232 Qualitative Inorganic Analysia (IIr,
of metallic cadmium with brown edges is produced. AIl()\\'
to cool, add a little Bowers of sulphur and heat again. T:·,
metallic mirror is gradually converted into the orange-colour; ,l
sulphide, which becomes yellow after cooling. Do not confu ..
this with the yellow sublimate of sulphur.
DETECTION AND SEPARATION OF THE METALS IN THE COPPER
GROUP (GROUP ITA)
The foregoing reactions of the metals of the copper group furni,· !,
the facts upon which the table of separation is based (Tables .1 )
or IIA}. The student should use the test solution provided, or el·
prepare a solution of the chlorides of the metals and work throuf
the table. The sulphides of the metals of this group, and also tho,
of arsenic, antimony and tin (Group IIB), are precipitated by hydr.
gen sulphide in the presence of dilute hydrochloric acid. TIl
reactions of the Group IIB metals will be studied later, but for tb,
present it will suffice to state that the sulphides of the Group II. \
metals are best separated from those of Group IIB by the solubilit,
of the latter in warm yellow ammonium sulphide solution or iIi
hot 2N potassium hydroxide solution.

[TABLES, pp. 233-235.

.... v J

III, 10. Table II. Analysis of the Copper Group

(Group IIA)
The ppt. obtained with H 2S in the presence of dilute HCI (ca. 0·3N)
may contain the sulphides HgS, PbS, Bi.S., CuB, CdS and also SnS, SnS 2 ,
Sb.S, and As.S.. (T) Pierce the point of the filter with a small glass rod,
wash the ppt. into a beaker with a small quantity of water. Add 5 ml.
of yellow ammonium sulphide solution, heat to 50-60° for 2-3 minutes,
and filter. Wash the rt\sidue with a little dilute (1 : 100) (NH,)aS. solution.
Residue. May contain HgS, PbS, Bi.S., CdS and Filtrate. May
CuS. Transfer the ppt. to a beaker or porcelain basin, oontain metals
add ca. 5 ml. of dilute HNO" boil for a few minutes, of Group lIB.
filter and wash with a little water. (See Table
III.)
Residue. Filtrate. May contain Pb(NO.lz,
Black: HgS. Bi(NO.)., Cu(NO.). IIoIld Cd(NO.) •.
Warm the ppt. Test a small portion for Pb by adding
with conc. HCl, dilute H.SO. and alcohol: a white ppt.
add bromine indicates Pb. IfPb is present, add dilute
water dropwise H.SO. and ooncentrate in the fume
until most or chamber until thick white fumes
all of ppt. dis- appear. Cool, dilute with 10 ml. of
solves. Boil off water, and filter. Wash with a little
any excess cold water.
of bromine.
Filter if neces- Residue. Filtrate. May oontain Bi+++,
sary, dilute White: PbSO,. Cu++ and Cd++. Add NHs
with IIoIl equal Pass 2 mI. of solution in excess, and filter.
volume of ammonium
water, and add acetate solution Residue. Filtrate. May
SnCI. solution. throngh the White: Bi(OH),. contain
White ppt., filter several Wash well, pour [Cu(NH.),]++
turning grey or times. Treat sodium sta.nnite and
black. filtrate with a solution on [Cd(NH.).]++.
Hg present. few drops of filter. Blacken- If colourless, Cu
Alternatively, dilute acetic ing ofppt. is absent; test
dissolve the acid and then Bi present. then directly for
ppt. in NaOCI- with K,CrO, Alternatively, Cd with H.S
HCl, etc., as solution. dissolve the (see below). If
detailed in Yellow ppt. of white ppt. in blue, Cu pre-
Table IIA. PbCrO,. dilute HNO. sent.
Pb present. or in dilute HCl, Divide the solu-
and add a little tion into two
thiourea solu- unequal parts.
tion. SmaUer portion
Yellow (1). Add
coloration. K,[Fe(CN).J
Bi present. solution and
acetio acid.
Reddish-brown
ppt.
Cu present.
Large,. portion.
Add KCN solu-
tion dropwise
until solution is
decolorised.
PIIM HIS for
10-20 IeOOnda.
YelloW' ppt. of
CdS.
Cd preHat (2).

Notes to Table II on page 236.

III, 10. Table IIA. Analysis of the Copper Group
(Group IIA)

The ppt. obtained with HaS in the presence of dilute HOI (ca. 0·31\
may contain the sulphides HgS, PbS, Bi.S., CuS, CdS and also As.S
Sb.S. and SnS. (1). (T) Pierce the point of the filter with a small glaE
rod, wash the ppt. into a beaker with a 8mall quantity of water. Ad"
10 mi. of 2N-potassium hydroxide and boil with constant 8tirring for 2-,
minutes (CAUTION,' see Note 2). Add 2 mi. offreshly-prepared saturate,
H.S water: stir and filter (preferably through a double filter). Wash tho
residue twice with a little water and collect the washings with the filtrat<'

Residue. May contain HgS, PbS, Bi.S., CdS and Filtrate.

CUS. Transfer the ppt. to a small beaker or porcelain May contain
basin, add ca. 5 mi. of dilute RNO., boil gently for a few metals of
minutes, filter and wash with a little water. Group lIB.
(See Table
III, Section
Residue. Filtrate. May contain Pb(N0 3 )., III,18.)
Black: HgS. Bi(NO.)., Ou(NO.). and Cd(NO.) •. ~
Dissolve in a Add excess of concentrated NH. solu-
mixture of 2·5 tion until precipitation is complete.
mi. of 10% Filter.
N aOOI solution
and 0·5 ml. of
dilute ROI. Residue. May oontain Filtrate. May con-
Add 1 mi. of Bi(OH). and Pb(OH) •. Warm tain [Cu(NH 3 ),J ++
dilute HCl, with 5 mi. of NaOH solution and [Od(NH 3 ).J++.
boil off excess and filter. If colourless, Cu is
of CI. and cool. --------------~-----------I absent; test then
Add SnOI, directly for Cd by
Residue. May Filtrate. passing H.S for 10-
solution. be Bi(OH) •. May con-
White ppt. 20 seconds into the
Wash with a tainsodium ammoniacal solu-
turning grey or little water. Pour plumbite
black. tion.
sodium stannite Na.[PbO.]. Yellowppt.ofCdS.
Hg (ic) solution over Acidify
present. Cd present.
filter. with dilute If blue, Cu pre-
Blackening of acetic acid sent. Divide the
ppt. and add solution into two
Bi present. KaCrO, unequal parts.
Alternatively, solution. Smaller portion.
dissolve a little Yellowppt. Acidify with dilute
of the ppt. in 2-3 of PbCrO •. acetio acid and add
drops of dilute Pb present. K,[Fe(CN).J solu-
RNO.; place 1 tion.
drop of this solu- Reddish-brown ppt.
tion upon filter Cu present (3).
paper moistened Larger portion. Add
with cinchonine- KCN solution drop-
potassium iodide wise until solution
reagent. is decolourised. Pass
Orange-red spot. H.S for 10-20
Bi present. seoonds.
Immediate yellow
ppt. of CdS.
Cd present (4).

Notes to Table IIA on page 236.

10] Reactions of the Metal Ions or Oati0n8 235
111,10. Table SMIIA. Analysis of the Copper Group
(Group IIA)
The ppt. obtained with H.S in the presence of dilute HCI (ea. 0·3N)
may contain the sulphides HgS, PbS, Bi.S., CuS and CdS. and also As.S 3 •
Sb,S. and SnS. (1). Treat the ppt. with 1·5 ml. of 2N KOH solution.
and heat in a boiling water bath for 3 minutes with occasional stirring
{CAUTION: see Note 2}. Add 4 drops of freshly-prepared s[lturated
H.S water; stir and centrifuge.
Residue. May contain HgS, PbS, Bi.S., CuS and Centrifugate.
CdS. Wash the residue once with 0·5 ml. of water and May contain
combine the washings with the first centrifugate. Treat metals of
the ppt. with 1-1·5 mi. of dilute HNO.: place in a. boiling Group HE.
water bath, and heat for 2-3 minutes with stirring. (See Table
Centrifuge. SMIIIA. Sec-
-------:----------------! tion III, 18.)
Residue. Centrifugate. May oontain ~
Black: HgS. Pb(N0 3 la, Bi(NO.)., Cu(NO.). and ~
Wash with 0·5 Cd(NO,).. Add excess of concentrated ~
ml. of water NH. solution, and centrifuge. ~
and discard the
washings. Residue. May contain Centrifugate.
Treat the ppt. Bi(OH)a and Pb(OH).. Add May contain
with 5 drops 1 ml. of NaOH solution, place [Cu(NH.),](NO.).
of 10% NaOCI in the boiling water rack for 2 and
solution and 1 minutes, and centrifuge. [Cd(NH.),](N0 3 ) ••
drop of dilute If colourless, Cu is
. HCI. Heat on Residue. May Centrifu- absent: test then
the water bath be Bi(OH) •. gate. May directly for Cd by
for 1 minute. Wash with 0·5 contain passing HIS for 10
To the clear mI. of water and Na.(PbO I ]· seconds into the
solution, add reject washings. Acidify with ammoniacal solu.
1-2 drops of Add 1 mi. of dilute acetic tion. Yellow ppt.
SnCl, solution.sodium stannite acid, add 2 ofCdS.
White ppt., reagent (3) to the drops of Cd present.
turning grey orppt. K.CrO. If blue, Cu is pre.
black. Immediate black· solution. sent. Divide into
Hg (ic) present. ening of ppt. Yellowppt. two unequal parts.
Bi present. of PbCrO,. Smaller portion (4).
Alternatively, Ph present. Acidify with acetic
dissolve a little acid and add 1 drop
of the ppt. in 1-2 of K,[Fe(CN)8J
drops of dilute solution.
HNO.. Place 1 Reddish-bro\'ln ppt.
drop of the solu- on standing for 2-3
tion upon filter minutes.
paper moistened Cu present.
with cinchonine. Larger portion. Add
potassium iodide KCN solution drop-
reagent. wise. with stirring,
Orange-red spot. until the blue colour
Bi present. is discharged. Pass
H.S for 30-40
seconds.
Yellowppt.o[ CdS.
Cd present.
Confirm Cd by
ignition test with
Na.C,O., etc.
(Section III, 9).

Notes to Table SMIIA on page 236.

 236 Qualitative Inorganic AnalY8i8 [III,

NOTES TO TABLE II
Notea. (1) Alternatively, just acidify a few drops of the solution "ith
dilute sulphuric acid. Add one drop of the acid solution to a few drol ' of
zinc sulphate or acetate solution, and then add a little a.rnmonium me! tri.
thiocyanate reagent. A violet precipitate confirms Cu. If a little " llyl
alcohol is added, the precipitate collects in and colours the organic layer
(2) Cadmium may be confirmed, if desired, by the ignition test with SOdltlID
oxalate, etc. (see Section III, 9, Dry Tests).

NOTES TO TABLE IIA

Notea. (1) Stannous sulphide SnS is not completely solubte in 2N K,' FI.
If tin is present in the stannous state, it is necessary to oxidise it with H ~ I j 2:
a limited amount of arsenious arsenic may be oxidised at the same time.
(2) Potassium and sodium hydroxides are extremely dangerous 8ubstal,' os
because of their destructive effects upon the eyes. Precipitates, when he,. :' ld
with KOH solution, tend to bump. To avoid any possibility of the mixl '; 1'e
spurting into the eyes with a consequent likely loss of sight, it is essell' 'al
(a) to conduct the operation in a fume chamber, (b) to stir the mixture ( "1·
stantly and (c) to avoid bringing the face over the beaker. It is recommen, :,·d
that goggles be worn during this and similar operations.
I (3) Alternatively, just acidify a few drops of the solution with dilute;, I.
phuric acid. Add 1 drop of the acidic solution to a few drops of zinc sulpl, " e
or acetate solution, and then introduce a few drops of the a.rnmonium mere", i.
thiocyanate reagent. A violet precipitate confirms Cu. If a little 111","1
alcohol is added, the precipitate collects in and colours the organic lay"!,.
It is recommended that this test be performed even if the solution is aim"st
colourless. A blue solution indicates that copper is present in quantity.
(4) Cadmium may be confirmed, if desired, by the ignition test with sodium
oxalate, etc. (see Section III, 9, Dry Test8).

NOTES TO TABLE SMIIA

Notes. (1) Stannous sulphide is not completely soluble in 2N KOH
solution. For this reason H.O. is employed in the Group Separation Table
SM.S (Section VI, 9); any stannous tin is oxidised to the stannic state, leadill!.i
ultimately to snS" which dissolves readily in warm 2N KOB.
(2) Great care should be taken in heating the KOB mixtur·e. The mixtw
should be stirred constantly with a stirring rod: the face should not be broug'"
directly over the heated tube. Potassium hydroxide solution is a dangero, ,~
substance because of its destructive action upon the eyes.
(3) The sodium stannite solution is prepared by treating 1-2 drops
SnCl. solution with NaOH solution dropwiso until the initial precipitate
Sn(OH), dissolves completely. Cooling is desirable.
(4) Alternatively, acidify with dilute H 2SO" add a drop or two of ZnS( "
solution, followed by a few drops of ammonium mercuri-thiocyanate reagen'
A violet precipitate confirms Cu. The precipitate is rendered readily visib\<'
by adding a few drops of amyl alcohol and stirring; it collects in and colou,,,
the organic layer.
llJ Reactions of the Metal 10M or Oations 237
THE ARSENIC GROUP (GROUP IIB)
ARSENIC, As
Arsenic is a steel-grey, brittle solid with a metallic lustre. It
sublimes on heating, and a characteristic, garlic-like odour is
apparent; on heating in a free supply of air, arsenic burns with a
blue flame yielding white fumes of arsenious oxide As4 0 6 • All
arsenic compounds are poisonous. The element is insoluble in
hydrochloric acid and in dilute sulphuric acid: it dissolvps readily
in dilute nitric acid yielding arsenious oxide, and in coneentrated
nitric acid or in aqua -regia or in sodium hypochlorite solution
forming arsenic acid.
As, + 4HNO a (dil.) = As,O. + 4NO + 211,0
3As, + 20HNO. (cone.) + 8R aO = 20NO + 12H aAsO,
As, + lONaOCl + 6H O = I 4H aAsO, + lONaCl
Two series of compounds of arsenic are commonly encountered:
(a) The arsenious compounds may be regarded as derived from the
amphoteric arsenious oxide As40 6 , which yields salts with strong
acids, e.g. arsenious chloride AsCI 3 , and with strong bases, e.g.
sodium arsenite NaAs0 2 • (b) The arsenic compounds corresponding
to the pentoxide As Z0 5 ; they are usually salts of the tribasic ortho-
arsenic acid, e.g. NaH 2As04, Na2HAs04 and Na3As04'

III, 11. REACTIONS OF ARSENIOUS COMPOUNDS

Use a solution of arsenious oxide* in hydrochloric acid, or a
solution of sodium arsenite, NaAs0 2 •t
1. Hydrogen Sulphide: yellow precipitate of arsenious
sulphide As 2S a in acid (hydrochloric) solution.
2AsCI s + 3H zS = AszS s + 6Hel
2NasAsO s +6HCI +
3H zS = AszS s 6NaCI +
6H 2 0 +
* Arsenious oxide is sparingly soluble in water yielding a solution containing
the weak arsenious acid; the oxide, however, is recovered upon concentrating
the solution.
As,O. + 6H.O ~ 4H sAsO a ~ 4HAsO. + 4H.O
t The solid salt has the formula NaAsO.; i.e. sodium meta-arsenite. It is
considerably hydrolysed in solution:
No,AsO. + H.O ~ NaOH + HAsO.;
RAsO s + H 2 0 ~ HaAsO s
There is some evidence (e.g. the production of silver ortho-arsenit" Ag.AsO s )
that the AsO a--- is present in solution. For simplicity, the reactions of
arsenites will be represented as derived from the ortho-arsenite ion AsO.---
or, when written as molecular equations, from Na 3 AsO.. It should, however,
be borne in mind that the meta-arsenito ion AsO.- may also be present in
solution.
Similarly, the meta-thioarsenite (AsS.-) and ortho-thioarsenite (AsS.---)
ions appear to exist in solution. The subject requires re-investigation.
 238 Qualitative Inorganic Analysis [III,
The precipitate is insoluble in concentrated hydrochloric acj, i
(distinction and method of separation from Sb 2S a and SnS 2), b"t
dissolves in hot concentrated nitric acid:
3As zS g + 20HNOg + 4H zO = 6H sAsO, + 9HzSO", + 20NO
It is also readily soluble in solutions of alkali hydroxide,.
ammonia and ammonium sulphide:
ASzS g + 6KOH = 3H zO + KgAsOg + KgAsSg
(potassium thioarsenit·
As 2S S + 6NHs + 3H20 = (NH",)aAsO s + (NH,)aAsS a
As 2 S S + 3NH4HS + 3NHs = 2(NH4)aAsSs
Upon acidifying the above solutions thioarsenious aci,:.
H 3AsS 3, is set free: this acid is unstable in the free state aI' t
decomposes immediately into arsenious sulphide and hydrog{' I'
sulphide. Hence, upon treating a mixture of an arsenite an,!
thioarsenite or a thioarsenite with dilute hydrochloric acid,
a.rsenious sulphide is precipitated:
2(NH,hAsS3 + 6HCI = 6NH4 CI + 2HsAsSs;
2HgAsS a = As 2 SS + 3H2S
KgAsO s + KSAsSg + 6HCI = As 2Sg + 6KCI + 3H zO
The formation of soluble thio-salts explains the non-precipi
tation of arsenious sulphide from solutions of arsenites i:,
neutral or alkaline solution; for complete precipitation of arseni .
as the trisulphide, sufficient free mineral acid must be presen!
in the solution to prevent the formation of soluble thio-saltE<.
NaaAsOa + 3H2S ~ NaaAsSa + 3H20
Arsenious sulphide dissolves readily in yellow ammoniun,
sulphide solution (NH4)2S", forming first ammonium thio
arsenite (NH4)aAsS a, which is then oxidised to the thio
arsenate (NH4)aAsS4 by excess of sulphur. Upon acidifyin~'
the solution arsenic pentasulphide AS 2S5 is precipitated.
together with a little sulphur, produced by the decompositiOJ;
of the excess of the ammonium polysulphide by the acid.
As 2S a + 3(NH4)2S2 = 2(NH4)aAsS4 + S;
2(NH4 )aAsS, + 6HCI = 3H2S + As 2S5 +
6NH,CI
2. Silver Nitrate Solution: yellow precipitate of silver
arsenite Ag3AsOa from neutral solu~ions (dis~inct~o~ from
arsenates), soluble in ammonia solutIOn and ill rutnc acid
(compare Section I, 19).
NasAsOs + 3AgNO a = AgsAsOa + 3NaNOa
11] Reactions of the lYIetal ]0nIJ or OatioTUl 239
3. Ma~nesia Mixture (a solution containing MgC1 2 ,
NH,CI and a little NHs): no precipitate (distinction from
arsenate).
A similar result is obtained with the magnesium nitrate
reagent (a solution containing Mg(N0 3 )2 , NH,NO s and a little
NH 3 )·
4. Copper Sulphate Solution: green precipitate of copper
arsenite (Scheele's green), variously formulated as CuHAs0 3
and Cu 3 (As0 3 h.xH 20, from neutral solutions, soluble in acids,
and also in ammonia solution forming a blue solution. The
precipitate also dissolves in sodium hydroxide solution; upon
boiling, cuprous oxide is precipitated.
5. Solution of Iodine in Potassium Iodide Solution: de-
colourised, owing to the formation of hydriodic and arsenic
acids.
H3AsOs 12+ +H 2 0 ~ H 3AsO, 2H1 +
The reaction is not a quantitative one because of the reducing
character of the hydrogen iodide formed; in the presence of excess
of sodium bicarbonate solution, which neutralises the hydriodic acid
as formed, the reaction is quantitative. Sodium carbonate cannot
be employed as this reacts with the iodine.
NaaAsO a + 13 + 2NaHCO a = Na aAs0 4 + 2NaI + 2CO. + HsO
3NazCO s + 31. = NaIO. + 5NaI + 3CO.
6. Stannous Chloride Solution and Concentrated
Hydrochloric Acid (Bettendorff's Test).-A few drops of
the arsenite solution are added to 2 m!. of concentrated hydro-
chloric acid and 0·5 ml. of saturated stannous chloride solution,
and the solution gently warmed; the solution becomes dark
brown and finally black, due to the separation of elementary
arsenic.
Na3AsOs + 6HOl = Asel s + 3NaOI + 3H 20;
+
2As013 38n012 = 2As +38nOl,
If the test be made with the sulphide precipitated in acid solution,
then only mercury will interfere; by converting the arsenic into
magnesium ammonium arsenate and heating to redness, the pyro-
arsenate Mg 2 As 2 0 7 remains and any Inercury salts present are
volatilised. This forms the basis of a delicate test for arsenious and
arsenic arsenic.
t Mix a drop of the test solution in a micro-crucible with 1-2 drops
of concentrated ammonia solution, 2 drops of ': 20-volum?" hydro.gan
peroxide. and 2 drops of 10 per cent magneslum chlorlde 8olutlOn.
 . I ~"..-- _._" [III,
240 Qualitative Inorganic Analysis"
Evaporate slowly and finally heat until fuming ceases. Treat the
residue with 1-2 drops of a solution of stannous chloride in concentrated
hydrochloric acid, and warm slightly. A brown or black precipitate
or coloration is obtained.
Sensitivity: 1 p.g. As. Concentration limit: I in 150,000.

III, 12. REACTIONS OF ARSENIC COMPOUNDS

Use a solution of sodium arsenate, Na2HAs04,,12H20 or :L
solution of arsenic pentoxide As 20 5, containing some dilu 1()
hydrochloric acid.
1. Hydrogen Sulphide: no immediate precipitate in tJ "
presence of dilute hydrochloric acid. If the passage of tl,.
gas is continued, a mixture of arsenious sulphide As 28 a aJ·j
sulphur is slowly precipitated. Precipitation is more rapid ; i i
hot solution.
HaAs04 + H 2S = H 2 0 + HsAs03S (thioarsenic acid);
HaAsOsS = S + HaAsOa (arsenious acid);
2HaAsOa +-3H2S = As 2SS + 6H2 0
If a large excess of concentrated hydrochloric acid is preser! I
and hydrogen sulphide is passed rapidly into the cold solutiOlI
yellow arsenic pentasulphide As 285 is precipitated; in the hOi
solution, the precipitate consists of a mixture of the tri- and
penta-sulphides.
2HsAs04 + 5H~ = AS 2S5 + 8H20
Arsenic pentasulphide, like the trisulphide, is readily solubll"
in solutions of caustic alkalis, ammonia, ammonium sulphid·
or polysulphide and ammonium carbonate, but is insoluble ill
boiling concentrated hydrochloric acid:
As 2Sr; + 6KOH = 3H20 + KaAsS4 + KsAsOsS;
As 2Sr; + 3NH4HS + 3NH s = 2(NH4)sAsS4
As 2S5 + 3(NH4)200a = 300 2 + (NH 4)sAsS4 + {NH4)aAsOs8
Upon acidifying these solutions with hydrochloric acid, arsenic
pentasulphide is precipitated:
2(NH4)sAsS4/+ 6HOI = 3H2S + AS 2S5 + 6NH40l
For the rapid precipitation of arsenic from solutions of arsenates
without using a large excess of hydrochloric acid, sulphur dioxide
may be passed into the slightly acid solution in order to reduce the
arsenic to the tervalent state and then the excess of sulphur dioxide
is boiled off; upon oonducting hydrogen sulphide into the warm
12) Reaction8 of the Metal Ions or Oationa 241
reduced solution, immediate precipitation of a,rsenic trisulphide
occurs:
RgAs04 + R~SOa = RsAsO s + RISO,
The precipitation can be greatly accelerated by the addition of
small amounts of an iodide, say, 1 ml. of a 10 per cent solution, and
a little concentrated hydrochloric acid. The iodide acts as a catalyst
in that it reduces the arsenic acid thus:
AsO,--- + 21- + 2H+ .=AsO a--- + I, + HIO,
and the iodine liberati:'d is converted into iodide ions by the hydro-
gen sulphide:
Is + HsS .= 2HI +S
2. Silver Nitrate Solution: brownish-red precipitate of
silver arsenate Ag3As04 from neutral solutions (distinction
from arsenite and phosphate which yield yellow precipitates),
soluble in acids and in ammonia solution but insoluble in acetic
acid.
NasAs04 + 3AgNOs = AgsAsO, + 3NaNOs
t This reaction may be adapted as a delicate test for arsenic in the
following manner. The test is applicable only in the absence of
chromates, ferro- and ferri-cyanides, which also give coloured silver
salts insoluble in acetic acid.
Place a drop of the test solution in a micro-crucible, add a few drops
of concentrated ammonia solution Bnd of "20-volume" hydrogen
peroxide, and warm. Acidify with acetic acid and add 2 drops of
1 per cent silver nitrate solution. A brownish-red precipitate or
coloration appears.
Sensitivity: 6 fLg. As. Concentration limit: 1 in 8,000
3. Magnesia Mixture (see Section III, 11, reaction 3):
white, crystalline precipitate of magnesium ammonium
arsenate Mg(NH4)As04 ,6H 2 0 from neutral or ammoniacal
solution (distinction from arsenite).
Na 2HAs04 + MgCl2 + NHa = Mg(NH.,)As04 + 2N<~Cl
For some purposes (e.g. the detection of arsenate in the pre-
sence of phosphate), it is better to use the magnesium nitrate
reagent (a solution containing Mg(N0 3 b, NH4CI and a little
NH 3 )·
Upon treating the white precipitate with silver nitmte solu-
tion containing a few drops of acetic acid, red silver arsenate
is formed (distinction from phosphate) :
Mg(NH 4 )As04 + 3AgNOs = Ag 3 As04 + Mg(NO a)2 + NH4NO a
4. Ammonium Molybdate Solution: when the reagent and
nitric acid are added in considerable excess to a solution of
242 Qualitative Inorganic Analysis [III,
an arsenate, a yellow crystalline precipitate of ammonim"
arsenomolybdate, (NH4h[AsMoI2040] is obtained on boiliJl'.'
(distinction from arsenites which give no precipitate, and fro I I
phosphates which yield a precipitate in the cold or upon gent!
warming). The precipItate is insoluble in nitric acid, b:!1
dissolves in ammonia solution and in solutions of caust,,·
alkalis.
Na2HAs04 + 12(NH4 hl\Io04 + 23HNO s
= (NH4MAsl\:[012040] + 21NH4N0 3 + 2NaNO s + 12H2 0
5. Potassium Iodide Solution: in the presence of COli
centrated hydrochloric acid, iodine is precipitated; UpOI!
shaking the mixture with 1-2 ml. of chloroform or of CarbOl!
tetrachloride, the latter is coloured blue by the iodine. Thl~
reaction may be used for the detection oj arsenate in the presence;
of arsenite; oxidising agents must be absent.
HsAs04 + 2HI ~ HsAsOs + 12 + H 2 0
6. Uranyl Acetate Solution: light yellow, gelatinous pre
cipitate of uranyl ammonium arsenate U0 2 (NH4 )As04 ,xH 2 ()
in the presence of excess of ammonium acetate, soluble iJ,
mineral acids but insoluble in acetic acid. If precipitation i,·
carried out from a hot solution of an arsenate, the precipitate
is obtained in granular form. This test provides an excellent
method of distinction from arsenites, which do not give H
precipitate with the reagent (an approximately O·IN solutioll
of uranyl acetate).
Na2HAs04 + U0 2(C 2 H 3 0 2)2 + NH3
= U0 2 (NH4)As04 + 2Na.C 2H sO,

111,13. SPECIAL TESTS FOR SMALL AMOUNTS OF

ARSENIC
The following tests are applicable to all arsenic compounds.
(i) Marsh's Test.-This test, which must be carried out in the
fume chamber, is based upon the fact that all soluble compound!'
of arsenic are reduced by "nascent" hydrogen in acid solution te,
arsine AsHs, a colourless, extremely poisonous gas with a garlic-like
odour. If the gas, mixed with hydrogen, be conducted through a
heated glass tube, it is decomposed into hydrogen and metalli(;
arsenic, which is deposited as a brownish-black "mirror" just
beyond the h~ated part of the tube.
On igniting the mixed gases, composed of hydrogen and arsine
(after all the air has been expelled from the apparatus), they burn
with a livid blue flame, and white fumes of arsenious oxide are
13J Reactions of the j}JetaZ Ions or Oations 243
evolved; if the inside of a small porcehdn dish be pressed down upon
the flame, a black deposit of arsenic is obtained on the cool fiurface,
and the deposit is readily soluble in sodium hypochlorite or bleaching
powder solution (distinction from antimony).
AS,06 + 12Zn + 12H aSO, = 4AsHa + 12ZnSO, + 6H zO
HaAs04 + 4Zn + 4H aSO, = AsH a + 4ZnSO, + 4H 20
4AsH a = AS 1 + 6H 2 (heat)
4AsH a + 60 2 = AS~06 + 6H aO
As, + lONaOCl + 6H zO = 4H aAsO, + lONaCl
The Marsh test is best carried out as follows. The apparatus is
fitted up as shown in Fig. Ill, 13, 1. A conical flask of about
125 ml. capacity is fitted with a two-holed rubber stopper carrying
a thistle funnel reaching nearly to the bottom of the flask and a
5-7 mm. right-angle tube; the latter is attached by a short piece of

A B c

0las8 wool moistened

with Pb (CrlHa02)'.2 solution

-Zn and dilute H 2 S04

Fig. III, 13, 1

"pressure" tubing to a U-tube filled with glass wool moistelled with

lead acetate solution to absorb any hydrogen sulphide evoh'ed (this
may be dispensed with, if desired, as its efficacy has been questioned),
then to a small tube containing anhydrous calcium chloride of about
8 mesh, then to a hard glass tube, ca. 25 cm. long and 7 mm. dia-
meter, constricted twice near the middle to about 2 mm. diameter,
the distance between the constrictions being 6-8 cm. The drying
tubes and the tube ABC are securely supported by means of clamps.
All reagents must be arsenic-free. Place 15-20 grams of arsenic-free
zinc in the flask, add dilute sulphuric acid (1 : 3) until hydrogen 18
vigorously evolved. The purity of the reagents is tested by passing
the gases, by means of a delivery tube attached by a short piece of
rubber tubing to the end of C, through silver nitrate soilltion for
several minutes; the absence of a black precipitate or suspension
proves that appreciable quantities of arsenic are not present.
6AgNO a + 3H 0 + AsHa
2 = HaAsOa + 6Ag + 6HN0 3
244 Qualitative Inorganic Analysis
I [HI,
The solution containing the arsenio compound is then added 'n
small amounts at a time to the contents of the flask. If m; h
arsenic is present, there will be an almost immediate blackenini-' ,)f
the silver nitrate solution. Disconnect the rubber tube at C. B, Lt
the tube at A to just below the softening point; a mirror of ars( LC
is deposited in the cooler, less constricted portion of the tube. A
second flame may be applied at B to ensure complete decomposit" ,n
(arsine is extremely poisonous). 'When a satisfactory mirror bs
been obtained, remove the flames at A and B and apply a light at C.
Hold a cold porcelain dish in the flame, and test the solubility of
the black or brownish deposit in sodium hypochlorite solution.
The arsenic in the silver nitrate solution is present as arseni"ns
acid and can be detected by the usual tests, e.fI. by hydro,l'I'n
sulphide after removing the excess of silver nitrate with dill! te
hydrochloric acid, or by neutralising and adding further silH)r
nitrate solution, if necessary.
Filter paper moistened .. I l\1f~ars h test 'mvoI YI' d
Th e ongma
W 'th A NO 80 I t·
I g 3 U IOn b '
urnmg an d d eposltlOn
. . 0f' i He
Cotton wool arsenic upon a cold surface. Now:,-
days the mirror test is usu[lily
applied. The silver nitrate react' 'n
(sometimes known as Hofman: s
test) is very useful as a confirmatory
test.
(ii) Gutzeit's Test. - This IS'
essentially a modification of Marsl,'s
_oJ.---U"'U'~ H2 S04 test, the chief difference being tjJ,tt
only a test-tube is required and the
arsine is detected by means of silycr
nitrate or mercuric chloride. Place
Fig. III, 13, 2 1-2 grams of arsenic-free zinc in a
test-tube, add 5-7 m!. of dilute sul-
phuric acid, loosely plug the tube with purified cotton wool a I:d
then place a piece of filter paper moistened with 20 per cent sil, r
nitrate solution on top of the tube (Fig. III, 13, 2). It may ',13
necessary to warm the tube gently to produce a regular evolutJ "1
of hydrogen. At the end of a definite period, say 2 minut, "
remove the filter paper and examine the part that covered t i ,()
test-tube; usually a light-brown spot is obtained owing to j I.e
traces of arsenic present in the reagents. Remove the cotton-w(Jol
plug, add 1 m!. of the solution to be tested, replace the cotton wool
and silver nitrate paper, the latter displaced so that a fresh portion
is exposed. Mter 2 minutes, assuming that the rate of evoluti, 'n
of gas is approximately the same, remove the filter paper and
examine the two spots. If much arsenic is present, the secolld
spot (due to metallic silver), will appear black.
AsH. + 6AgNO. + 3H I O = 6Ag + 6HNO. + HaAsO a
13] Reactions of the M etaZ Ions or Cations 245
Hydrogen sulphide, phosphine PHs and stibine SbHs give a similar
reaction. They may be removed by means of a purified cotton-wool
plug impregnated with cuprous chloride.
The use of mercuric chloride paper, prepared by immersing
filter paper in a 5 per cent solution of mercuric chloride in alcohol
and drying in the atmosphere out of contact with direct sunlight,
constitutes an improvement. This is turned yellow by a little arsine
and reddish-brown by larger quantities. Filter paper, impregnated
with 1 per cent aqueous solution of "gold chloride" HAuCI4 ,2H2 0,
may also be employed when a dark-red to blue· red stain is produced.
A blank test must be performed with the reagent in all cases.
2AuCI a + AsH a + 3H zO = 2Au + 6HCI + HaAsOa
The test may be performed on the semimicro scale with the aid of
the apparatus shown in Fig. III, 13, 3. Place 10 drops of the test
solution in the semimicro test-tube, add a few
granules of arsenic-free zinc and 1 m}. of dilute sul-
phuric acid. Insert a loose wad of pure cotton wool
moistened with lead nitrate solution in the funnel,
and on top of this place a disc of drop reaction
paper impregnated with 10 per cent silver nitrate
solution; the paper may be held in position by a
watch glass or microscope slide. Warm the test-
tube gently (if necessary) on a water bath to
accelerate the reaction, and allow to stand. Examine
the silver nitrate paper after about 5 minutes. A
grey spot will be obtained; this is occasionally yellow,
due to the complex Ag 3 As,3AgN0 3 •
For minute quantities of arsenic, it is convenient to
use the apparatus depicted in Fig. II, 6, 13. Mix a
drop of the test solution with a few grains of zinc and
a few drops of dilute sulphuric acid in the micro test- Fig. III, 13, 3
tube. Insert the funnel with a flat rim, and place a
small piece of drop-reaction paper moistened with 20 per cent silver
nitrate solution on the flat surface. A grey stain will be obtained.
Sensitivity: 1 fLg. As. Concentration limit: 1 in 50,000.
A more sensitive test is provided by drop reaction paper impregnated
with gold chloride reitgent (a 1 per cent solution of HAuCl,,2H zO).
Perform the test as described in the previous paragraph: It blue to
blue-red stain of metallic gold is obtained after standing for 10-15
minutes. It is essential to perform a blank test with the reagents to
confirm that they are arsenic-free.
Sensitivity: 0'05 lug. As. Concentration limit: 1 in 100,000.
(iii) Fleitmann's Test.-This test depends upon the fact that
nascent hydrogen generated in alkaline solution, e.g. from aluminium
or zinc and sodium hydroxide solution, reduces arsenious compounds
to arsine, but does not affect antimony compounds. A method of
distinguishing arsenic and antimony compounds is thus provided.
 I

246 Qualitative Inorganic Analysis [III.

Arsenates must first be reduced to the arsenious condition ber, Ire
applying the test. The modus operandi is as for the Gutzeit t,· ct,
except that zinc or aluminium and sodium hydroxide solution repL, <Je
zinc and dilute sulphuric acid. It is necessary to warm the solutk! S.
A black stain of silver is produced by the action of the arsine.
The apparatus of Fig. III, 13, 3 may be used on the semim). 1'0
scale. Place I m!. of the test solution in the test· tube, add SOI'le
pure aluminium turnings and I ml. of 2N potassium hydrox',ie
solution. Gentle warming is usually necessary. A yellow or gr, y
stain is produced after several minutes.
(iv) Reinsch's Test.-If a strip of bright copper foil be boil, d
with a solution of an arsenious compound acidified with at Ie ,t
one·tenth of its bulk of concentrated hydrochloric acid, the arselllC
is deposited upon the copper as a grey film of copper arsem Ie
CU5As2' Antimony, mercury, silver and other metals are precii I·
tated under similar conditions. It is therefore necessary to test hr
arsenic in the deposit in the dry way. The strip is washed wi i h
distilled water, dried between filter paper and then gently heabi
in a test.tube; a white crystalline deposit of arsenious oxide is
obtained. The latter is identified by examination with a hand Ie]' "
when it will be seen to consist of colourless octahedral and teb I·
hedral crystals; it may also be dissolved in water and tested j 'r
arsenic by Fleitmann's or Bettendorff's test.
Arsenates are also reduced by copper, but only slowly even on
boiling.
Dry Tests
(i) Blowpipe test.-Arsenic compounds when heated up, 'Tl
charcoal with sodium carbonate give a white incrustation ,f
arsenious oxide, and an odour of garlic is apparent while hi'!'
(ii) When heated with excess of potassium cyanide and If I

anhydrous sodium carbonate in a dry bulb tube, a black min'l,r

of arsenic, soluble in sodium hypochlorite solution, is produced
in the cooler part of the tube.
ANTIMONY, Sb
Antimony is a lustrous, silver· white metal. It is insoluble :Ii
hydrochloric acid and in dilute sulphuric acid, is slowly attack,·,!
by hot concentrated sulphuric acid yielding unstable antimonio'H
Bulphate, and is converted into antimony trio or pentoxide by nib II)
acid, depending upon the amount and the concentration of the aci' i.
The best solvent for antimony is aqua regia; a solution of antimOlI ,\'
trio or penta· chloride is formed.
2Sb + 6H sSO, = Sb s(80,)a + 6H sO + 380 2
4Sb + 4HNO a = Sb,O, + 4NO + 2H,0
6Sb + IOHNO a = 3Sb,06 + IONO + 5H,O
Sb + HNO. + 3HCI = SbCI. + NO + 2H.Q
14] Reactions of the .J/etalIons or Oations 247
Two series of salts are known, the antimonious and alltimonio
corresponding respectively to the oxides Sb40 a and Sb40 lO , the
former being the more important. Antimonious compounds react
with water similarly to bismuth salts forming compounds containing
the antimonyl group SbO- (compare Hydrolysis of Salts, Section
1,40).
SbCl a + HIO ~ SbO.Cl + 2HCl
An important antimonyl compound is tartar emetic, potassium
antimonyl tartrate K(SbO). C4H 40 6 ,O'5H 20; it is prep:lred by
interaction between antimonious oxide and potassium hydrogen
tartrate.
Sb,Oa + 4KH.C,H,Os = 4K(SbO).C,H,Os + 2H.O
The solubility of antimonyl compounds in solutions of tartario acid
or of tartrates is due to the formation of compounds of this type.
The addition of dilute hydrochloric acid to an aqueous solution of
tartar emetic gives a white precipitate of antimonyl chloride, soluble
in excess of acid:
K(SbO).C,H,Os + 2HCl = H 2 • C,R,O. + SbO.Cl + KCl
III, 14. REACTIONS OF ANTIMONIOUS
COMPOUNDS
Use a solution of antimony trichloride, SbCl a, prepared by
dissolving either the solid trichloride or antimonious oxide,
Sb4 0 a, in dilute hydrochloric acid.
1. Hydrogen Sulphide: orange-red precipitate of antimony
trisulphide Sb 2S a from solutions which are not too acid. The
precipitate is soluble in warm concentrated hydrochloric acid
(distinction and method of separation from arsenious sulphide
and mercuric sulphide), in ammonium polysulphide (forming a
thioantimonate), and in alkali hydroxide solutions (forming
antimonite and thioantimonite).
Sb 2Sa + 6HCI ~ 2SbCIs + 3H 2S
Sb2Sa + 3(NH4hS2 = 2(NH4 )aSbS4 + S
2Sb zSa + 4KOH = KSb0 2 + 3KSbS z + 2H20
Upon acidification of the solution of the thioantimonate
solution with hydrochloric acid, antimony pentasulphide is
precipitated initially but usually decomposes partially into the
trisulphide and sulphur:
2(NH4 )aSbS 4 + 6HCl = Sb 2S& + 6NH4CI + 3HzS
Sb ZS6 = SbzS a + 2S
Acidification of the antimonite-thioantimonite mixture leads
to the precipitation of the trisulphide:
KSb0 2 + 3KSbS 2 + 4HCI = 2Sb 2Sa + 4KCI + 2H.O
248 Qualitative Inorganic Analysis [III,
2. Water: when the solution is poured into water, a whii ()
precipitate of antimonyl chloride SbO. Cl is formed, soluble 'n
hydrochloric acid and in tartaric acid solution (difference fre"ll
bismuth). With a large excess of water the hydrated oxi, i'l
Sb4 0 6,xH 2 0, is produced.
3. Sodium Hydroxide or Ammonia Solution: whil ()
precipitate of the hydrated antimonious oxide Sb406,xH(I~,
soluble in concentrated solutions of caustic alkalis formil,,~
antimonites.
4SbCI s + 12NaOR = Sb4 0 6 + 12NaCl + 6H 2 0;
Sb4 0 6 + 4NaOR = 4Na[Sb0 2] + 2H 2 0
4. Zinc: a black precipitate of antimony is produced. 1r
a little of the antimony trichloride solution is poured up, ! l
platinum foil and a fragment of metallic zinc be placed on tl."
foil, a black stain of antimony is formed upon the platinUl,! :
the stain (or deposit) should be dissolved in a little warm dilu' ,
nitric acid and hydrogen sulphide passed into tbe solution afl ;'
dilution; an orange precipitate of antimony trisulphide will till
obtained.
2SbCls + 3Zn = 2Sb + 3ZnClll
Some stibine Sblia may be evolved when zinc is used; it is pI<
ferable to employ tin. '
A modification of the above test is to place a drop of the solution
containing antimony upon a genuine silver coin and to touch the coin
through the drop with a piece of tin or zinc; a black spot will form
on the coin.
5. Iron Wire: black precipitate of antimony. This may
be confirmed as described in reaction_ 4.
6. Potassium Iodide Solution: yellow coloration owing to
the formation of a complex salt.
t7. Rhodamiue-B (or Tetraethyl-rhodamine) Reagent
EtsNyY0Y'r.1"'NEtl+

~~
C

CXo- •
violet or blue coloration with quinquevalent antimony. Tervale, i
antimony does not respond to this test, hence it must be oxidised wi;"
potassium or sodium nitrite in the presence of strong hydrochloric aci :
In Group IIB SbCl a is always formed together with SnCl 4 when ti ,e
 15] Reaction., of the Metal Iona or Oations 249
precipitate is treated with hydrochlorio acid: by oxidising Sb (III) to
Sb (V) with a little solid nitrite, an excellent means of testing for Sb
in the presenoe of a large excess of Sn is available. Mercury, gold,
thallium, molybdates, vanadates and tungstates in acid solution give
similar oolour reactions.
The test solution should be strongly acid with hydrochloric acid
and the antimoniollS antimony oxidised by the addition of a little solid
sodium or potassium nitrite: a. large excess of nitrite should be avoided.
Place 1 ml. of the reagent on a spot plate and add 1 drop of the test
solution. The bright red colour of the reagent changes to blue.
Sensitivity: O·Sp.g. Sb and applioable in the presenoe of 12,500 times
the amount of Sn.
Conoentration limit: 1 in 100,000.
The reagent is prepared by dissolving 0·01 g. of rhodamine·B in
100 ml. of water. A more ooncentrated reagent is obtained by dis-
solving 0·05 g. of l'hodamine-B in a 15 per cent solution of potassium
chloride in 2N hydroohlorio acid.
t8. Phosphomolybdic Acid Reagent (Hs[PMollO,o]aq.): "molyb-
denum blue" is produoed by antimonious salts. Of the ions in Group
II, only stannous tin interferes with the test. The test solution may
consist of the filtered solution obtained by treating the Group IIB
precipitate with hYdrochloric aoid: the antimony is present as SbCI s
and the tin as SnCI" which has no effeot upon the reagent.
Plaoe a drop of the test solution upon drop reaotion paper which has
been impregnated with the phosphomolybdic acid reagent and hold the
paper in steam. A blue ooloration appears within a few minutes.
Sensitivity: 0·2p.g. Sb. Conoentration limit: 1 in 250,000.
Alternatively, place 1 mI. of the test solution in a semimioro tf'st-tube,
add 0'5--1 mI. of the reagent, and heat for a short time. The reagent is
reduced to a blue oompound, which can be extracted with amyl aloohol.
Stannous ohloride reduces not only the reaotive phosphomolybdic
acid but also its relatively unreactive (e.g. ammonium or potassium)
salts to "molybdenum blue." However, antimonious salts do not
reduce ammonium phosphomolybdate: Sn + + may thus be detected in
the presenoe of Sb -I- + +.
Impregnate drop reaction paper with a solution of phosphomolybdic
acid and then hold it for a short time over ammonia. gas to form the
yellow, spa.ringly soluble ammonium salt; dry. Plaoe a drop of the
test solution on this paper: a blue spot appeal'S if stannous tin is present.
Sensitivity: 0·03p.g. Su. Concentration limit: 1 in 650,000.
The reagent consists of a 5 per cent aqueous solution of phospho-
molybdic aoid. It does not keep well.

111,15. REACTIONS OF ANTIMONIC COMPOUNDS

Use a solution of antimony pentoxide in concentrated hydro-
chloric acid, or of potassium antimonate, KH 2SbO,.
Sh 20 5 + IORel = 2SbC15 + 5RzO
1. Hydrogen Sulphide: orange-red precipitate of antimony
pentasulpbide Sb 2S5 in moderately acid solutions. The pre-
 250 Qualitative Inorganic Analysis '~-on,
cipitate is soluble in ammonium sulphide solution (yielding L
thio-antimonate), in alkali hydroxide solutions, and is a; )
dissolved by concentrated hydrochloric acid with the forni'-
tion of antimony trichloride and the separation of sulph l " .
The thio-salt is decomposed by acids, the pentasulphide hei' ~
precipitated.
2SbCl5 +
5H2S = Sb 2S5 + IOHCl;
Sb2 S5 + 6HCI = 2SbCla + 2S + 3H2S
8b 2S5 + 3(NH4)28 = 2(NH4)a8b84 ;
2(NH4)sSbS4 + 6HCI = Sb 2S5 + 6NH4Cl + 3H 2S
Sb 2S5 +
6KOH = Ks8bSO s + +
K sSb84 3H zO;
KsSbSO s + +
K sSbS4 6HCl = Sb28 6 + 6KCI + 3H 2 0
2. Water: white precipitate of basic salt.
3. Potassium Iodide Solution: iodine separates out fr01U
. a hydrochloric acid solution (difference from antimonious COlll-
pounds).
2SbC15 + 2KI = I2 + 2SbCIs + 2KOI
4. Zinc or Tin: black precipitate of antimony in the prt~­
sence of hydrochloric acid (see antimonious compounds). SO!i'e
stibine (SbHa) is produced with zinc.
to'. Rhodamine-B Reagent: see uncleI:' Antimonious Compound"

SPECIAL TESTS FOR SMALL AMOUNTS OF ANTIMO:" Y

(i) Marsh's Test.-This test is carried out exactly as descrilltd
for arsenic. The stibine SbHs (mixed with hydrogen) which's
evolved burns with a faintly bluish-green flame and produces a (/,ill
black spot upon a cold porcelain dish held in the flame; this dep()~it
is insoluble in sodium hypochlorite or bleaching powder solutil 'fl,
but is dissolved by a solution of tartaric acid (difference fr' '!ll
arsenic).
The gas is also decomposed by passage through a tube heated 10
dull redness. A lustrous mirror of antimony is formed in a sim) hr
manner to the arsenic mirror, but it is deposited on both sides of i ile
heated portion of the tube because of the greater instability of I lie
stibine. This mirror may be converted into orange-red antimlily
trisulphide by dissolving it in a little boiling hydrochloric acid ;,. ,d
passing hydrogen sulphide into the solution.
When the stibine-hydrogen mixture is passed into a solution 'If
silver nitrate (Hofmann'S test), a black precipitate of silver aJ,' i-
monide SbAg3 is obtained; this is decomposed by the excess ',f
silver nitrate into silver and antimonious oxide:
SbHs + 3AgNO s = AgaSb + 3HNO a ;
4AgaSb + 12AgNO. + 6H,O = 24Ag + Sb,O. + 12HNO a
 15] Reactions of the M etaZ Ions or Oation8 251

It is best to dissolve the precipitate in a solution of tartaric acid and

to test for antimony with hydrogen sulphide in the usual manner.
(ii) Gutzeit's Test.--A brown stain is produced which is soluble
in 80 per cent alcohol, provided the antimony concentration of the
solution is not too high.
(iii) Fleitmann's or BettendorfI's Tests.-Negative results
are obtained when these are applied to antimony com pounds
(distinction from arsenic).
(iv) Reinsch's Test.-A grey to black deposit is formed upon
the copper. Ignition of this deposit in a dry test-tube gives a non-
crystalline sublimate of antimonious oxide, soluble in potassium
hydrogen tartrate solution; hydrogen sulphide precipitates orange-
red antimony sulphide from this solution, acidified with hydro-
chloric acid.

Dry Test
Blowpipe test.-When antimony compounds are heated with
sodium carbonate upon charcoal, a brittle metallic bead, sur-
rounded by a white incrustation, is obtained.

TIN, Bn
Tin is a silver-white metal, which is malleable and ductile at
ordinary temperatures, but at low temperatures it becomes brittle,
due to transformation into an allotropic modification. The metal
dissolves slowly in dilute hydrochloric and sulphuric acids with the
liberation of hydrogen and the formation of stannous salts; it is
readily dissolved by the hot concentrated acids. Dilute nitric acid
dissolves tin slowly without any evolution of gas, stannous nitrate
and ammonium nitrate being formed; with concentrated nitric arid,
a vigorous reaction occurs, a white solid, usually formuhted as
hydrated stannic oxide SnOz,xHzO and sometimes known as meta-
stannic acid, being produced. Solution takes place readily with
aqua regia; stannic chloride is the sole product.
Sn + 2HCI (dilute and cone.) = SnCl. + HI
Sn + H 2S0 4 (dilute) = SnS04 + H2
Sn + 4H 2SO, (cone.) + +
= Sn(SO')2 2S0 2 4H 20
4Sn + lOHNO a (dilute) = 4Sn(NO a )2 + NH,NO a + 3H 20
3Sn + 4HNO s + (x - 2)H 2 0 = 4NO + 3Sn0 2,xH 2 0
3Sn + 4HNO s + 12HCl = 4NO + 3SnCl, + 8H i O
Tin forms two oxides: stannous oxide SnO and stannic oxide
Sn02 from which the stannous and sbnnic salts respectively may be
regarded as derived. Both oxides are amphoteric, the stannic
compound to the greater degree.
252 QWllitative Inorganic Analysis [III,
III, 16. REACTIONS OF STANNOUS COMPOUND '"
Use a solution of stannous chloride, SnCI2,2H 20, in dilutll
hydrochloric acid.
1. Hydro~en Sulphide: brown precipitate of stannou,
sulphide SnS from not too acid solutions (say in the presen ','
of O·25-0·3M hydrochloric acid or pH ca. 0·6 {compare Secti('ll
I, 37}). The precipitate is soluble in concentrated hydrn,
chloric acid (distinction from arsenious sulphide and mercUI','
sulphide); it is also soluble in yellow {(NH4)2S",}, but not •
colourless {NH4HS}, ammonium SUlphide solution to form l
thiostannate. Treatment of the solution of ammonium thi·,
stannate with an acid yields a yellow precipitate of stann '"
sulphide SnS2'
SnClz + H 2S = SnS + 2HCI;
SnS + (NH')2S2 = (NH')2SnSa;
(NH,)zSnSa + 2HCI = SnS2 + 2NU,CI + H 2S
Stannous sulphide is practically insoluble in solutions of caustic alkalh.
hence, if potllBsium hydroxide solution is employed for separating Group IJ \
and Group lIB, the tin must be oxidised to the stannic state with hydrog. ;,
peroxide before precipitation with hydrogen sulphide.

2. Sodium Hydroxide Solution: white precipitate of sta]·

nous hydroxide, soluble in excess of alkali forming Bodim r;
stannite Na2[SnOZ]'
SnClz + 2NaOH = Sn(OH)2 + 2NaCI;
Sn(OH)2 + 2NaOH = Na2[Sn02] + 2H 20
With ammonia solution, white stannous hydroxide is preCi
pitated, but this is not appreciablY'soluble in excess of tb"
reagent.
3. Mercuric Chloride Solution: white precipitate of mer
curous chloride Hg 2C1 2. If the stannous chloride solution J
present in excess, the precipitate tmns grey, especially Or,
warming, owing to further reduction to metallic mercury.
SnCl2 + 2HgCl2 = SnC4 + Hg 2C1 2;
SnCl2 + Hg 2Cl 2 = SnC4 + 2Hg
4. Bismuth Nitrate Solution and Sodium Hydroxidt·
Solution: black precipitate of metallic bismuth (see under
Bismuth, Section III, 7, reaction 5).
5. Metallic Zinc: spongy tin is deposited which adheres tu
the zinc. If the zinc rests upon platinum foil, as described
16) Reacti0n8 of the Metal IOn8 or Oation8 253
under antimony (Section III, 14, reaction 4), and the solution
is weakly acid, the tin is partially deposited upon the zinc in
a spongy form but does not stain the platinum. The precipi-
tate should be dissolved in concentrated hydrochloric achl and
the mercuric chloride test applied.
t6. Dimetbylglyoxime-Ferric Chloride Test.*-No coloration is
produced when ferric salts are mixed with the dimethylglyoxime re-
agent and a little ammonia solution, but if a trace of a ferrous salt is
present (produced by reduction with stannous ions), a deep red colora-
tion, due to a ferrous dimethylglyoxime complex, is formed. If tin is
present in the Sn (IV) state, it is reduced to Sn (II) by treatment with
aluminium or magnesium filings and hydrochloric acid and the solution
is filtered. This procedure may be be used with the Group IIB precipi-
tate after treatment with hydrochloric acid.
Vanadium, uranyl, titanium, cobalt and nickel ions give a similar
reaction; the ions of copper, chromium, manganese, gold, palladium,
platinum, selenium and tellurium interfere, as do also molybdates and
tungstates: reducing agents, which affect ferric chloride, must be absent.
Place 0·2 ml. of the test solution containing stannous tin (this may
consist of the solution obtained from the Group IIB precipitate, roduced
with magnesium) in a micro test-tube, acidify (if necessary) with dilute
hydrochloric acid, add 0·2 ml. of O'IN ferric chloride solution, followed
by 0·3 ml. of 5 per cent tartaric acid solution (to prevent the formation
of ferric hydroxide), 3 drops of the dimethylglyoxime reagent and about
0'5 ml. of 4N ammonia solution. A red coloration is produced.
Sensitivity: 0·05 ftg. Sn. Concentration limit: 1 in 1,250,000.
The reagent consists of a. 1 per cent solution of dimethylglyoxime in
ethyl alcohol.
t7. Cacotbeline Reagent (a nitro-derivative of brucine, C IlH 21 0 7N .):
violet coloration with stannous salts. The test solution should be acid
(2N HCl), and if tin is in the Sn (IV) state, it should be reduced pre-
viously with aluminium or magnesium, and the solution filtered.
The following interfere with the test: strong reducing agents (hydro-
gen sulphide, dithionites (hyposulphites), sulphites and selenites); V, U,
Te, Hg, Bi, Au, Pd, Se, Te, Sb, Mo, W, Co and Ni. The reaction is not
selective, but is fairly sensitive: it can be used in the analysis of the
Group lIB precipitate. Since ferrous salts have no influence on the
test, it may be applied to the tin solution which has been reduced
with iron wire.
Impregnate some drop reaction paper with the reagent and, before
the paper is quite dry, add a drop of the test solution. A violet spot,
surrounded by a less coloured zone, appears on the yellow paper.
Alternatively, treat a little of the test solution in a micro test-tube
with a few drops of the reagent. A violet (purple) coloration is
produced.
Sensitivity: 0·2 ftg. Sn. Concentration limit: 1 in 250,000.
The reagent oonsists of a 0·25 per oent aqueous solution of caoo-
theline.
• For formulae, Bee under Niokel, Section III, 25, reeotion 8.
 254 Q-ualitative 1norganie A nalysi8 [III,
t8. Diazine Green Reagent (dyestuff formed by coupling diazotifw,j
safranine with dimethyl-aniline).-Stannous chloride reduceS! the bJ ,,1
diazine green to the red safranine, hence the colour change is blue
violet __,. red. Titanous chloride reacts similarly, but ferrous salts all I
similar reducing agents have no effect. The reagent is therefore usei ,l
in testing for tin in the mixed sulphides of antimony and tin obtain, l
in routine qualitative analysis. The solution of the sulphides in hydr .
chloric acid is reduced with iron wire, aluminium or magnesium powd,.,.
and a drop of the reduced solution employed for the test.
Mix 1 drop of the test solution on a spot plate with 1 ml. of tJ
reagent. The colour changes from blue to violet or red. It is advisab:
to carry out a blank test.
Sensitivity: 2/Lg. Sn. Concentration limit: 1 in 25,000.
The reagent consists of a 0·01 per cent aqueous solution of diazir",
green.
t9. 4-MethyI-I : 2-dimercapto-.benzene (or" DithioI") Reagent

(<(H}
SH

red precipitate when warmed with stannous salts in acid solution. The
following interfere: silver, lead, mercury, cadmium, arsenic and anti·
mony (yellow precipitates); copper, nickel and cobalt (black precipi-
tates); bismuth (red precipitate); colloidal organiC substances (starch.
etc.); phosphates and nitrites. The hydrochloric acid concentration oj
the solution should not exceed 15 per cent.
Place 2 drops of the test-solution, acidified with dilute hydrochloric
acid, in a micro crucible and add 3 drops of the reagent_ Warm (not
above 60°0): a red colour or precipitate develops.
Concentration limit: 1 in 500,000.
The reagent is prepared by dissolving 0·2 g. of 4-methyl-l : 2-
dimercapto-benzene in 100 ml. of 1 per cent sodium hydroxide solution
and adding 0,3-0'5 g. of thioglycollic acid. The use of the latter in
the reagent is not imperative, but it serves to facilitate the reduction
of any stannic salt present. The reagent is discarded if a white precipi-
tate of the disulphidEl forms.

III, 17. REACTIONS OF STANNIC COMPOUNDS

Use a solution of stannic chloride, SnCl4 ,5H 20, in dilute
hydrochloric acid (this probably contains hexachlorostannic
acid:
SnC14 + 2HC1 ~ H2[SnC~] ~ 2H + + [SnC~r-
~ 2H+ + Sn++++ + 6C1-),
or of ammonium stannichloride, (NH4 MSnC4].
17J Reactions of the M etaZ Ions or Oations 255
1. Hydrogen Sulphide: yellow precipitate of stannic sul-
phide SnS2 from dilute acid solutions (::}O·3N). The precipitate
is soluble in concentrated hydrochloric acid (distinction from
arsenious and mercuric sulphides), in solutions of alkali
hydroxides, and also in colourless (NH4HS) and yellow
{(NH4)zS",} ammonium sulphide solutions. Yellow stannic
sulphide is precipitated upon acidification.
H z[SnC16 ] + 2H 2S ? SnS2 + 6HCl
SnS2 +
NH4SH +
NHs = (NH4}2SnSS (thiostannate);
(NH4)2SnSa +
2HCI = SnSz + 2NH4Cl + H 2S
3SnS2 +
6KOH = K2SnOa + 2K2SnSS + 3H 20;
K2SnOa +
2K2SnSs +
6HCl = 3SnS2 + 6KCI + 3H20
No precipitation of stannic sulphide in the presence of oxalic acid, due to
the formation of the stable complex ion of the type [Sn(C.O.).(H 20)2r---;
this forms the basis of a method of separation of antimony and tin.

2. Sodium Hydroxide Solution: gelatinous white precipi-

tate of stannic hydroxide Sn(OH)4, soluble in -excess of the
precipitant forming sodium stannate Na2[Sn03]'
+
SnC14 4NaOH = Sn(OH)4 + 4NaCl;
Sn(OH)4 + 2NaOH = 3H zO +
Naz[SnO s]
With ammonia and with sodium carbonate solutions, a similar
precipitate is obtained which, however, is insoluble in excess of
the reagent.
3. Mercuric Chloride Solution: no precipitate (difference
from stannous compounds). ,
4. Metallic Iron: reduces stannic salts in hydrochloric acid
solution to the stannous condition; filter and test the filtrate
with mercuric chloride solution (ferrous salts do not reduce the
latter). Similar results are obtained on boiling the solution
with copper or antimony.
H2[SnC~] + Fe = SnCII! + FeCl2 + 2HCI
Dry Tests
(i) Blowpipe test.-All tin compounds when heated with
sodium carbonate, preferably in the presence of potassium
cyanide, on charcoal give white, malleable and metallic globules
of tin which do not mark paper. Part of the metal is oxidised
to stannic oxide, especially on strong heating, which forms a ...
white incrustation upon the charcoa!.
256 Qualitative Inorganic Analysis [III,
(il) Borax bead test.-A borax bead which has been coloured
pale blue by a trace of copper salt becomes a clear ruby red in
the reducing flame if a minute quantity of tin is added.

DETECTIQN AND SEPARATION OF THE METALS ill THE ARSENIC GROUP

(GROUP IIB)
The foregoing reactions of the metals of this group provide the
facts upon which the following simple table of separation is based.
Alternative and more comprehensive schemes are given in Section
VII. 12. The student should prepare, or obtain from the teacher,
a solid mixture soluble in hydrochloric acid, or a solution containing
these elements, and work through the table in order to familiarise
himself with it,
The sulphides are precipitated in the presence of hydrochloric
acid and then separated from those of Group IIA by warming for
a few minutes with yellow ammonium sulphide solution (Table III)
or with 2N potassium hydroxide solution (Table IIlA), the filtrate
being employed for the tests. If no metal1:l of Group IIA are
present, the ammonium 1:lulphide or potassium hydroxide treatment
is, of course, unnecessary.

III, 18. Table III. Analysis of the Arsenic Group

(Group lIB)
The filtrate from the Copper Group (Group lIA) may contain the
thio-salts (NH,)aAsS" (NH,hSbS, and (NH')2SnS.. Dilute with a little
water, add dilute HCI in slight exoess (i.e. until (l.cid to litmus), warm,
filter and wash with a little H 2S water. Reject the filtrate. The residue
upon the filter may contain As,S" As,S., SbIS" Sb,S., SuS. and S.'"
Boil the precipitate gently with 5-10 mi. of con()entrated hydroohlorio
acid, dilute with a little water, and filter.

Residue. :May oontain As.S, Filtrate. May oontain H[SbCI,]

(and/or As.S.). and H,,[SnCI.].
Dissolve the ppt. in 3-4 mi. of Divide into two parts:
warm dilute NBs, filter (if neces- Firat p01'tion.-Make just alkaline
sary), add 3-4 mI. of 3% H,O. and with dilute lSR, solution, add 1-2
warm to oxidise any arsenite to g. of o:x:alio &.lid, boil and p88B H,S
arsenate. Add a few mI. of the for 1 minute. __
Mg(NOsls reagent. Stir and allow Orange ppt. of Sb.S,.
to stand.
White, orystalline ppt. of
Mg(NH,)AsO,,6H.O.
Sb present.
Second portion.-Partially
neutralise the liquid, add about 15
I
As present. cm. of clean iron wire, hoat for 5 ,
Confirm as follows: filter off the
ppt., and pour 1 mi. of AgNO s solu-
minutes to reduce the SnCI, to
SnCI., and filter into a solution of
I
tion containing a few drops of dilute HgCl •.
acetio o.oid on to the residue on the White ppt. of Hg.Cl. or grey ppt. I
filter.
Brownish-red residue of Ag,AsO,.
ofHg.
Sn present.
I
I
* If Group IIA absent, commence here.
18] Reactions of the M etall OM or Oati0n8 257

III, 18. Table IliA, Analysis of the Arsenic Group

(Group liB)

The filtrate from the Copper Group (Group IIA) may contain KAsO.,
KAsS., KSbO., KSbS., K.SnO. or K.[Sn(OH).], and K.SnS., and a little
KHgS,. Add concentrated HCI cautiously (drop wise and with constant
stirring) until the solution is distinctly acid to litmus paper. Treat with
H.S for 2-3 minutes to ensure complete precipitation of the sulphides.
The formation of a precipitate indicates the possible presence of HgS,
As.S a, Sb.S. and SnS.. Filter, wash the precipitate with a little water,
and discard the filtrate and washings. * Transfer the precipitate to a small
conical flask, add 5-10 ml. of concentrated HCl, heat to boiling [FUME
OUPBOARD] and maintain the mixture near the boiling point over a
low flame with constant stirring for 5 minutes. Dilute with a little
water, and filter.

Residue. May contain HgS and AsIS •. Filtrate. May contain

If yellow, only As.S. present. Wash with H[SbCI,] and H.[SnCI.].
water. Pour 5 mI. of dilute NH. through Divide into three parts.
the filter: run filtrate again through filter. (i) Render just alkaline
with aq. NH., add 1-2 g. of
oxalic acid, boil and pass
Residue. If Filtrate. Add dilute H,S for ca. 1 minute into
dark-coloured HNO, until distinctly the hot solution.
(HgS). acid. Orange ppt. of Sb.S •.
Hg present. Yellow ppt. of As.S •. Sb present.
Confirm as in As present. (ii) To 2 drops of the
Table IIA, if Confirm by redissolving solution on a spot plate,
Hg not found in in warm aq. NH., warm add 1 minute crystal of
Group IIA. for a few minutes with NaNO., stir and add 2
3% H.O. to oxidise drops of Rhodamine-B re-
arsenite to arsenate, add agent.
Mg(NO.). reagent, stir Violet coloration or ppt.
and allow to stand. Sb present.
White ppt. of Mg(NH.)- (iii) Partially neutralise
AsO.,6H.O. Filter and the liquid, add 10-15 cm.
wash with a little water. of clean iron wire to 1 ml.
Pour on to the filter 1 mI. of the solution, warm gently
of AgNO. solution con- to reduce tin to the stan-
taining a few drops of nous state, and filter into a
dilute acetic acid. solution of HgOl •.
Brownish-red residue of White ppt. of Hg.CI. or
Ag,AsO,. grey ppt. of Hg.
Sn present. t

• If Group IlA absent, commence here.

t If the proportion of Sb is large, it is better to reduce with Mg turnings or
powder and dilute HOI.

8+ t
208 Ciual$tatwe lnorgan$C AnatY818 LIll,
III, 18. Table SMIIIA. Analysis of the Arsenic Group
(Group liB)
The centrifugate from the Copper Group (Group IIA) may contain
KAsO., KAsS., KSbO., KSbS., K.SnO. or K.[Sn(OH).], K,SnS. and a
little KHgS.. Transfer to a small conical flask, add concentrated HCI
dropwise and with stirring until the mixture is distinctly acid to litmus
paper. Treat with H.S for 30-60 seconds to ensure complete precipita-
tion of the sulphides. The formation of a precipitate indicates the
possible presence of HgS, As,S., Sb.S. and SnS.. Centrifuge about
2'0 mi. of the mixture, remove the supernatant liquid with a dropper
pipette and discard it. Transfer the remainder of the mixture in the
flask to the centrifuge tube, centrifuge, remove the solution and discard
it: wash the residue with a little water, completely remove the washings
and reject them. * Treat the precipitate with 0·5-1 mi. of concentrated
HCI, place in the hot water bath for 2-3 minutes and stir frequently.
Centrifuge: remove the centrifugate to a 4 mi. test-tube; wash residue
with 0·3 m!. of dilute HCI and add washings to the contents of the
test-tube.
Residue. May contain HgS and Centrifugate. May contain
As.S.. If yellow, only As.S. pre- H[SbCI.] and H.[SbCI.].
sent. Wash residue with 5 drops of Divide into two parts.
water: discard washings. Treat (i) Either-Render just alkaline
residue with 0'5 mi. of dilute aq. with concentrated NH. solution,
NH., stir well, and centrifuge. add 0·3 g. of oxalic acid, and pass
H.S for 20-30 seconds.
Orange ppt. of Sb.S 3 •
Residue. Centrifugate. Add Sb present.
If dark- dilute HNO. until acid. Or-To 2 drops of the solution
coloured Yellow ppt. of As.S •. on a spot plate, add a minute
(HgS). As present. crystal of NaNO., stir, and add 2 i
Hg Confirm thus: centri- drops of Rhodamine-B reagent. '
present. fuge and reject wash- Violet coloration.
Confirm ings. Dissolve the ppt. Sb present.
as in in 0·5 mi. of warm dilute (ii) Either-Introduce 2 cm. of
Table NH., add 0·25 mi. of clean iron wire or 20 mg. of iron
SMIIA, 6% H 2 0. and heat on filings, and heat on 8 water bath
if Hg not a water bath ,for 3 for 3-5 minutes. Centrifuge, and
found in minutes (to oxidise treat the clear centrifugate with
Copper arsenite to arsenate). 2 drops of HgCI. solution.
Group. Add 4 drops ofMg(NO.). White ppt. of Hg.CI. or grey
reagent and stir. White, ppt.ofHg.
crystalline ppt. of Sn present. t
Mg(NH,)AsO,,6H.O. Or-Treat 0·2-0·3 mi. of the
Centrifuge and reject solution with 5-10 mg. of Mg
centrifugate. Add 2 powder, add 2 drops of FeCI.
drops of AgNO. solution solution, 2-3 drops of 5% tartaric
and 1 drop of dilute acid solution, 1-2 drops of di-
acetic acid. Brownish- methylglyoxime reagent, and then
red residue of Ag.AsO,. dil. NH. solution until basic.
Red coloration.
Sn present.

* If Group IIA absent, commence here.

t If the proportion of Sb is large, 8 deposit of Sb is found on the iron wirt
which tends to slow down the reduction considerably. It is then better t
use Mg turnings or powder for the reduction. Alternatively, the solutio
(conta.ining Sb and Sn) may be added dropwise to the iron wire reacting i
dilute HOl.
18] ReactwnB oJ u/,e .Metal Ions or uations 259
Note -With Table Sl\HIIA as a guide, the student should
have no difficulty in adapting Table III (Section III, 18) to
the semimicro scale.

THE IRON AND ZINC GROUP (GROUP III)

IRON, ALUMINIUM, OHROMIUM, NIOKEL,
OOBALT, MANGANESE AND ZINO
The metals of this group are not precipitated by the group reagents for
Groups r and II, but are 811 precipitated, in the presence of ammoniwn
chloride, by hydrogen sulphide from their solutions made alkaline with
ammonia solution. The metals, with the exception of alwniniwn and
chromium which are precipitated as the hydroxides owing to the complete
hydrolysis of the sulphides in aqueous sollltion, are precipitated as tho suI.
phides. Iron, aluminium and chromium (often accompanied by a little
manganese) are also precipitated as the hydroxides by ammonia solution in
the presence of ammonium chloride, whilst the other metals of the group
remain in solution and may be precipitated as sulphides by hydrogen sulphide.
It is therefore usual to subdivide the group into the iron group (iron,
aluminium and chromium) or Group IlIA and the zinc group (nickel, cobalt,
manganese and zinc) or Group IIIB.

THE IRON GROUP (GROUP IlIA)

Fe
IRON, •
Pure iron is a silver.white, tenacious and ductile metal. The
commercial metal is rarely pure and usually contains small quan tities
of the carbide, silicide, phosphide and sulphide of iron, and a little
graphite. Iron dissolves in dilute and concentrated hydrochloric
acid and in dilute sulphuric acid with the evolution of hydrogen
and the formation of ferrous salts; with hot concentrated sulphuric
acid, sulphur dioxide and ferric sulphate are produced. Ferrous
and ammonium nitrates are obtained with cold dilute nitric acid,
whilst a more concentrated acid yields a ferric salt and either nitrous
oxide or nitric oxide depending upon the experimental conditions.
Cold concentrated nitric acid renders iron passive; in this state it
does not react with dilute nitric acid nor does it displace copper
from an aqueous solution of a copper salt.
Fe + 2HCI = FeCl z + Hs;
Fe + H 2SO, (dilute) = FeSO, + H 2 ;
2Fe + 6H 2 SO, (cone.) = Fe 2 (SO,)a + 6H 2 0 + 380,;
4Fe + !OHNO a (cold, dilute) = 4Fe(NO s)2 + NH,NO a + 3lI 20;
<1Fe + lOHNO a (warm, dilute) = <1Fe(N0 3 ), + NtO + 5H,O;
Fe + <1HNO a (s.g. > 1'12) = Fe(NOala + NO + 2H,0
Iron forms two important series of salts: the ferrous salts which
may be regarded as derived from ferrous oxide FeO in which the metal
is divalent, and the ferric salts, which may be regarded as derived
from ferric oxide Fe20s and containing trivalent iron.
,
-
260 Qualitative Inorganic Analysis [III.
111,19. REACTIONS OF THE FERROUS ION, Fe++
Use a freshly prepared solution of ferrous ammonium sui·
phate, FeS04,(NH4)2S04,6H20, acidified with a little dilute
sulphuric acid. (Solutions of ferrous salts are pale green due
to the presence of the [Fe(H 20 )6] + + or Fe + + ion.)
1.. ~'O~\.--un:.. v;,.~~~<::)·h~~~ ~\.~~\.~~'. 'V.~\.~ ~~"'_('3~\..~~~~ n.r_
ferrous hydroxide Fe(OH)2 in the complete absence of air,
insoluble in excess, but soluble in acids. Upon exposure to [l "
ferrous hydroxide is rapidly oxidised, yielding ultimatt V
reddish-brown ferric hydroxide. Under ordinary conditiom t
appears as a dirty green precipitate; the addition of hydrog. n
peroxide immediately oxidises it to ferric hydroxide.
FeS04 +
2NaOH = Fe(OH)2 + Na2S04;
4Fe(OH)2 +
2H 20 +
O2 = 4Fe(OH)s
2. Ammonia Solution: precipitation of ferrous hydroxide
occurs as in reaction 1. In the presence of excess of ammonium
ohloride solution, the common ion effect (Section I, 14) of the
ammonium ions lowers the concentration of the hydroxyl ions
to such an extent that the solubility product of ferrous hydrox-
ide Fe(OH)2 is not attained and precipitation does not occur.
Similar remarks apply to the other divalent elements of Group
III, nickel, cobalt, zinc and manganese and also to magnesium.
3. Hydrogen Sulphide: no precipitation takes place in
acid solution since the sulphide ion concentration, [S--], is
insufficient to exceed the solubility product of ferrous sulphide
(see Sections I, 15 and I, 16). If the hydrogen ion concentra-
tion is reduced, and the sulphide ion concentration correspo]l(i-
ingly increased, by the addition of sodium acetate solutiun,
partial precipitation of black ferrous sulphide FeS occurs.
4. Ammonium Sulphide Solution*: black precipitate of
ferrous sulphide FeS, readily soluble in acids with evolution ,>f
hydrogen sulphide. The moist precipitate becomes bro·. n
upon exposure to air, due to its oxidation to basic ferric ~,d­
phate Fe20(S04h.
FeS04 + NH4HS + NHs = FeS +(NH4)2S04;
FeS + 2HCI = +
FeCl2 H 2S
5. Potassium Cyanide Solutiont: yellowish-brown P'")-
oipitate of ferrous cyanide Fe(CNb, soluble in excess of 1 'le
• Colourless ammonium sulphide should be used for this teat: it may ')e
readily prepared by P888ing H 2S into dilute Nfla solution.
t Very poiaonous; in acid solution the volatile and highly poisonous hydr.},
gen oyanide HCN is produced.
 19] Reactions of the M etallons or Cations 261
precipitant forming a yellow solution of potassium ferro-
cyanide K 4 [Fe(CN}6]'
FeS04 + 2KCN = Fe(CN)2 + K 2SO,;
Fe(CN)2 + 4KCN = K,[Fe(CN)6]
Potassium ferro cyanide is a complex salt, and does not give the
typical ferrous ion reactions with ammonium sulphide or sodium
hydroxide solutions (compare Section 1,20); the iron present may
be detected by first decomposing the compound by boiling with
concentrated sulphuric acid (caution: poisonous carbon monoxide
is evolved).
K,[Fe(CN).] + 6H aO + 6H SO, 2
= FeSO( + 2K SO, + 3(NH,)sSO. + 6CO
2

6. Potassium Ferrocyanide Solution: in the complete

absence of air, a white precipitate of potassium ferrous ferro-
cyanide, K2Fe[Fe(CN)6J, is produced. Under ordinary atmo-
spheric conditions a pale blue precipitate is obtained; partial
oxidation to potassium ferric ferro cyanide, KFeIll[FeII (CN}6];
occurs.
FeSO, + K 4[Fe(CN)6] = K2Fe[Fe(CN)6] + KzSO,
7. Potassium Ferricyanide Solution: a dark blue pre-
cipitate is produced. This was formerly termed Turnbull's
blue and was formulated as potassium ferrous ferricyanide,
KFeII[FeIll (CN}6]' It is now considered to be identical with
Prussian blue, i.e. potassium ferric ferrocyanide, KFeIll-
[FeII (CN)6]'
FeSO, + Ks[Fe(CN)61 = KFe[Fe(CN)61 KzSO, +
The precipitate is decomposed by sodium or potassium hydrox-
ide solution, ferric hydroxide being precipitated.
8. Ammonium Thiocyanate Solution: no coloration is
obtained with pure ferrous salts (distinction from ferric Baits).
t 9. a;a;' -Dipyridyl Reagent

deep red complex bivalent cation [Fe(C,H,N)s] + + with ferrous salts in

mineral acid solution. Ferric iron does not react. Other metallic ions
react with the reagent in acid solution, but the intensities of the resulting
colours are so feeble that they do not interfere with the test for iron
provided an excess of the reagent is employed. Large amounts of
halides and sulphates reduce the solubility of the ferrous-dipyridyl
complex and a red precipitate may be formed.
202 'luat~tatwe lnorgan~c AnalysUl lUI,
Treat a drop of the faintly acidified test solution with 1 drop of th.,
reagent on a spot plate: a red coloration is obtained. Alternatively,
treat drop-reaction paper (Whatman No.3 MM., 1st quality) whicl
has been impregnated with the reagent and dried, with a drop of thE>
the test solution: a red or pink spot is produced.
Sensitivity: 0·3/Lg. Fe++. Concentration limit: 1 in 1,666,000.
If appreciable quantities of ferric salts are present and traces of ferrou,
salts are sought, it is best to carry out the reaction in a micro crucible
lined with paraffin wax and to fix the ferric iron as [FeFs]--- by the
addition of a few drops of potassium fluoride solution.
The rea~ent is prepared by dissolving 0·01 g. of cc cc' -dipyridyl in
0-5 ml. of alcohol or in 0-5 ml. of 0-IN -hydrochloric acid.
tiO. Dimethylglyoxime Reagent: soluble red ferrous dimethyl-
glyoxime in ammoniacal solution. Ferric salts give no coloration, but
nickel, cobalt and large quantities of copper salts interfere and must be
absent. The test may be carried out in the presence of potassium
cyanide solution in which nickel dimethylglyoxime (compare Section
III, 25) dissolves.
Mix a drop of the test solution with a small crystal of tartaric acid;
introduce a drop of the reagent, followed by 2 drops of ammonia solu-
tion. A red coloration appears.
Sensitivity: 0·04/Lg. Fe++. Concentration limit: 1 in 125,000.
The coloration fades on standing owing to the oxidation of the ferrous
complex.
If it is desired to detect ferric iron by this test, it must first be reduced
by a little hydroxylamine hydrochloride.
The reagent consists of a 1 per cent solution of dimethylglyoxime in
alcohol.
tIl. o-Phenanthroline Reagent

red coloration, due to the complex cation [Fe(C12HsN 2)3] + + in faintly

acid solution. Ferric iron has no effect and must first be reduced to
the ferrous state with hydroxylamine hydrochloride if the reagent is to
be used in testing for iron.
Place a drop of the faintly acid test solution on a spot plate and add
1 drop of the reagent. A red colour is obtained.
Concentration limit: 1 in 1,500,000.
The reagent consists of a 0'1 per cent solution of o-phenanthroline
in water.

III, 20. REACTIONS OF THE FERRIC ION, Fe+++

Use a solution of ferric chloride, FeCI 3 ,6H 20. (All ferric
solutions are yellowish-red or yellowish-brown; the ferric ion,
[Fe(H 2 0)6]+++ or Fe+++, is pale violet in oolour; hydrolysis
20] Reactions oj the Metal lona or Oations 263
occurs in aqueous solution leading to yellow or brown com-
plexes:
Fe+++ + H 20 ¢ Fe(OH)++ + H+).
1. Ammonia Solution: reddish-brown, gelatinous precipi-
tate of ferric hydroxide Fe(OH)s, insoluble in excess of the
reagent, but soluble in acids.
The solubility product offerric hydroxide is so small (1·1 X 10 --36)
that complete precipitation takes place even in the presence of
ammonium salts (distinction from ferrous iron, nickel, cobalt,
manganese, zinc and magnesium). Precipitation does not occur in
the presence of certain organic acids (see reaction 8 below). Ferric
hydroxide is converted on strong heating into ferric oxide; the
ignited oxide is soluble with difficulty in dilute acids, but dissolves
on vigorous boiling with concentrated hydrochloric acid.
FeCl a + 3NH a + 3H I O= Fe(OH)s + 3NH,CI;
2Fe(OH)a = FesO a + 3H aO
2. Sodium Hydroxide Solution: reddish-brown precipitate
of ferric hydroxide, insoluble in excess of the reagent (distinction
from aluminium and chromium).
3. Hydrogen Sulphide: reduced to ferrous salt in the
presence of acid, with separation of sulphur.
2FeCl s + H 2S = 2FeCl2 + 2HCl + S
4. Ammonium Sulphide Solution"': black precipitate,
consisting of ferrous sulphide and sulphur, from acid solutions.
From alkaline solutions, a black precipitate of ferric sulphide
Fe?,S3 is formed; this is readily soluble in dilute hydrochloric
acid forming ferrous chloride and sulphur.
2FeCl a + 3NH4HS + 3NH3 = Fe2Sa+ 6NH4Cl;
Fe2Sa + 4HCI = + S + 2H2S
2FeCl2
5. Potassium Ferrocyanide Solution: intense blue pre-
cipitate of potassium ferric ferro cyanide (Prussian blue).
FeCl s + K 4[Fe(CN)6J = KFe[Fe(CN)6J + 3KCI
The precipitate is insoluble in dilute hydrochloric acid, but
dissolves in oxalic acid solution, in concentrated hydrochloric
acid, and also in a large excess of the precipitant with the
production of a blue solution. It is decomposed by solutions
of caustic alkalis with the formation of ferric hydroxide and a
ferrocyanide.
• Use colourless ammonium sulphide: see Section III. 20, reaction 4.
264 Qualitative Inorganic Analyat8 [III,
6. Potassium Ferricyanide Solution: a brown coloratiOl
is produoed, due to ferrio ferricyanide Fe[Fe(CN)6] (distinctiOl
fmm ferrous salts).
FeOls + K 3[Fe(ON)6] = Fe[Fe(CN)6] + aKCl
Upon adding hydrogen peroxide or a little stannous chloridE'
solution, a blue solution or precipitate (Prussian blue) i~,
obtained: probably the ferricyanide is reduced to ferrocyanid<
and this then reacts with the ferric iron.
7. Sodium Phosphate Solution: yellowish-white precipi
tate of ferric phosphate FeP04 , readily soluble in mineral acids,
but insoluble in acetic acid.
FeCl s + NazHP04 = FeP04 + HCI + 2NaOI (i)
HOI + Na2HP04 = NaH2P04 + NaOI (ii)
FeCl s + 2Na zHP04 = FeP04 + 3NaCI + NaH 2P04 (iii)
It is evident from the equations that for the complete precipita-
tion of iron as phosphate it is necessary to use excess of the reagent
to react with the liberated hydrogen chloride. This is avoided by
the addition of excess of sodium acetate solution, since acetic acid
is produced {equation (iv)} in which ferric phosphate is insoluble,
and precipitation is quantitative.
Na.C.HaO. + HCI = H.C.HaO. + NaCI (iv)
The net result is:
FeCl a + Na.HPO, + Na.C.HaO. = FePO, + H.C.HaO. + 3NaCl
8. Sodium Acetate Solution: reddish-brown coloration,
attributed variously to ferric acetate Fe(C 2H sOzh or to the
complex ion [Fe(OC 2H s0 2)6r-- or to colloidal ferric hydrox-
ide; upon largely diluting and boiling the solution, the iron is
precipitated as basic ferric acetate Fe(OH)2' C2H s0 2 •
FeCls + 3Na.C2H sOz = 3NaCI+ Fe(C2H s0 )s; 2

Fe(C2 H s Oz)s + 2H20 = Fe(OH)2' C2H sOz + 2H .CzHaOz

Reaction.s 7 an.d 8 are combined for the removal of the phosphate radical
fro~ solutions in which it interferes with the normal course of analysis (see
SectIOn VIII, 2); they are also affected by the presence of organic acids
(tartario, citrio, sulphosalicylic and malic acids) and by polyhydric alcohols
(Il.g. glycerol, mannitol, various sugars), and special procedures must be
adopted in the ordinary oourse of analysis when these are present (see
Chapter VIII).

9. Cupferron Rea~ent {the ammonium salt of nitroso-

phenyThydroxylamine, C6H5N (NO )ONH4 }: reddish-brown
precipitate in the presence of hydrochloric acid. No precipi-
tate is given by the salts of aluminium and chromium under
 20) Reactions of the M etallona or Oati0n8 265
these conditions, i.e. in strongly acid solution. The precipi-
tate is soluble in ether, is insoluble in acids, and on treatment
with aqueous ammonia solution is converted into ferric hy-
droxide. 1I
FeCla + 3C6H 6N(NO)ONH4 = 3NH4 CI + [C6H6N(NO)O]aFe
The reagent is prepared by dissolving 2 grams of the solid in 100
ml. of distilled water, but does not keep well. It is recommended
that a piece of ammonium carbonate be placed in the stock bottle;
this enhances the stability.
10. Ammonium Thiocyanate Solution: deep red eolora-
tion (difference from ferrous salts). The coloration was formerly
attributed to undissociated ferric thiocyanate, but is now
known to be due to the ferri-thiocyanate ion, [Fe(SCN)] ++.
The reaction is a reversible one and hence the sensitivity is
increased by the addition of excess of the reagent. The ferri-
thiocyanate ion is more soluble in ether and in amyl alcohol
than in water; accordingly upon shaking with either of these
solvents the red colour passes into the organic layer. Phos-
phates, arsenates, borates, iodates, 8ulphates, acetates, oxa-
lates, tartrates, citrates and the corresponding free acids
interfere with the test.
The organic acids form complex ions of the type:
Fe + + + + 3C,O,-- ~ [Fe(C10,)a]---;
Fe+++ + 3C,H,O.-- ~ [Fe(C,H.O.l.r--

Fluorides and mercuric chloride bleach the colour because of

the formation of the ferrifluoride [FeF6 r--
ion and the slightly
dissociated mercuric thiocyanate Hg(SCN)2 respectively.
Fe+++ + SCN- ..= [Fe(SCN)]++
2[Fe(SCN)]++ + HgOls"= 2Fe+++ + Hg(SON)s + 20r
The presence of nitrites should be avoided, for in acid solution
they form nitrosyl thiocyanate NO. SON which yields a red
colour, disappearing on heating, similar to that with ferric iron.
t The reaction is well adapted as a spot test and may be carried out
as follows. Place a drop of the test solution on a spot plate and add
1 drop of 1 per cent ammonium thiocyanate solution. A deep red
coloration appears.
Sensitivity: 0·25p.g. Fe+++. Concentration limit: 1 in 200,000.
Coloured salts, e.g. those of copper, chromium, cobalt and nickel, reduce
the sensitivity of the test.
9*
 Qualitative Inorganic AnalY8is [III,
tll 7-Iodo-8-hydroxyquinoline-5-sulphonic Acid (or Ferron)
Rea~ent .
\

\ J

green or greenish-blue coloration with ferric salts in faintly acid solution

(pH 2'5-3·0). Ferrous iron does not react: only copper interferes.
Place a few drops of the slightly acid test solution in a micro test· tube
and add 1 drop of the reagent. A green coloration appears.
Sensitivity: 0-5 fLg. Concentration limit: 1 in 1,000,000.
The reagent consists of a 0·2 per cent aqueous solution of 7-iodo-8-
hydroxyquinoline-5-sulphonic acid.

Reduction of ferric to ferrous compounds.-This may

be accomplished by nascent hydrogen (e.g. from zinc and dilute
hydrochloric or sulphuric acid), hydrogen sulphide, sulphur
dioxide, stannous chloride, hydriodic acid, hydroxylamine
hydrochloride or hydrazine sulphate.
FeCla + H = FeClz + HCI;
2FeC13 + SOz + 2H zO = 2FeC12 + H ZS04 + 2HOI;1
,~ ~;
2Fe013 + Sn012 = 2FeCIz + Sn0l4 ; .'1

2FeCI s + 2H1 = 2FeCl 2 + 12 + 2HCI

Oxidation of ferrous to ferric compounds.-Oxidation

occurs slowly upon exposure to air. Rapid oxidation is effected
by concentrated nitric acid, hydrogen peroxide, concentrated
hydrochloric acid and potassium chlorate, aqua regia, potas-
sium permanganate, potassium dichromate and ceric sulphate
in acid solution.
3FeC12 + 3HOl + HN03 = 3FeCl3 + 2H20 + NO;
2KMn04 + lOFeSO, + 8H2SO,
= 5Fe2(S04)S + K 2SO. + 2MnSO, + 8H20 i
"K.'!.(Jr'l.()'l -\- ~"£~~()&. -\- ~\l~(')~
= 3"Fe2,SO,)s + 2.KRSO, + Cr 2(S04,)s + 7HzO
Distinctive tests for ferrous and ferric salts.-These
are summarised in the following table. The solution should
be slightly acid with hydrochloric acid.
 21] Reactions of the Metal Ions or Oations 267

ReG{Jent Ferrous salt Ferric salt

Potassium ferro. White or pale-blue Deep-blue precipita te
cyanide solution. precipitate. (Prussian blue).
Potassium ferri- Deep-blue precipi- No precipitate;
cyanide solution. tate. brown coloration.
Ammonium thio. No coloration in Deep-red coloration,
cyanate solution. complete absence of discharged by mer-
ferric salts. curic chloride solu·
tion.
Ammonia solu. White to greenish. Reddish-brown pre-
tion. white precipitate. cipitate.

Dry Tests
(i) Blowpipe te8t.-When iron compounds are heated on
charcoal with sodium carbonate, grey metallic particles of iron
are produced; these are ordinarily difficult to see, but can be
separated from the charcoal by means of a magnet.
(ii) Borax bead test.-With a small quantity of iron, the bead
is yellowish-brown while hot and yellow when cold in the
oxidising flame, * and pale green in the reducing flame.
, ALUMINIUM, Al
Aluminium is a white, ductile and malleable metal; the powder
is grey. The metal is little affected by cold dilute sulphuric acid,
but dissolves readily in the hot concentrated acid with the evolution
of sulphur dioxide. Nitric acid renders the metal passive; this
may be due to the formation of a protective film of oxide. It is
readily soluble in hydrochloric acid (dilute and concentrated) with
the evolution of hydrogen. Very pure aluminium, however, dis-
solves slowly in concentrated hydrochloric acid, but solution can be
accelerated by adding a little mercuric chloride solution. With
caustic alkalis a solution of an aluminate is formed,
2Al + 4H aSO, = Al,(SO,)s + SO, + 2H 10;
2Al + 6HCl = 2AlCl a + 3H.;
2Al + 2NaOH + 2H zO = 2Na[AlO.J + aHa
Aluminium forms only one series of salts derived from the oxide
hl'l.()'1>'
Ill, 11. REA.C'1'IONS OF THE 1\.LUMINHJM ION, h\+++
Use a solution of aluminium sulphate, A1 2 (S04)a,18H!1 0 ,
or of potash alum, K ZS04 ,Al 2 (S04h,24,H zO. ~All aq~e.o~s
* With large quantities of iron, the bead is reddIsh-brown ill the oXIdismg
flame.
 Qualitative Inorganic Analysis [III,
"til 7-Iodo-8-hydroxyquinoline-5-sulphonic Acid (or Ferron)
Reagent '
\
\

green or greenish-blue coloration with ferric salts in faintly acid solution

(pH 2'5-3·0). Ferrous iron does not react: only copper interferes.
Place a few drops of the slightly acid test solution in a micro test· tube
and add I drop of the reagent. A green coloration appears.
Sensitivity: 0'5 p.g. Concentration limit: 1 in 1,000,000.
The reagent consists of a 0·2 per cent aqueous solution of 7-iodo-8-
hydroxyquinoline-5-sulphonic acid.

Reduction of ferric to ferrous compounds.-This may

be accomplished by nascent hydrogen (e.g. from zinc and dilute
hydrochlorio or sulphurio acid), hydrogen sulphide, sulphur
dioxide, stannous ohloride, hydriodio acid, hydroxylamine
hydrochloride or hydrazine sulphate.
+ H = FeOl2 + HOI;
FeOla
2FeCI s + S02 + 2H 20 = 2FeCl2 + H 2S04 + 2HOl",
2FeCls + SnCl2 = 2FeCl2 + SnCl4 ; i
2FeCI s + 2HI = 2FeOl2 + I2 + 2HOI

Oxidation of ferrous to ferric compounds.-Oxidation

occurs slowly upon exposure to air. Rapid oxidation is effected
by conoentrated nitrio acid, hydrogen peroxide, ooncentrated
hydrochloric acid and potassium ohlorate, aqua regia, potas-
sium permanganate, potassium dichromate and eerie sulphate
in acid solution.
+ 3HCl + HNOa = 3FeOIs + 2H 20 + NO;
3FeC12
2KMn04 + lOFeS04 + 8H2S04
= 5Fe2(S04)s + K 2SO. + 2MnSO, + 8H 20;
K 2Cr2 0 7 + 6FeS04 + 8H2SO.
= 3Fe2(S04)s + 2KHS04 + Cr2 (SO,)s + 7HzO
Distinctive tests for ferrous and ferric salts.-These
are summarised in the following table. The solution should
be slightly acid with hydrochloric acid.
 21] Reactions of the Metal Ions or Oations 267

Rea{/ent Ferrous salt Ferric salt

Potassium ferro· White or pale-blue Deep. blue precipita te

cyanide solution. precipitate. (Prussian blue).
Potassium ferri· Deep-blue precipi- No precipitate;
cyanide solution. tate. brown coloration.
Ammonium thio· No coloration in Deep-red coloration,
cyanate solution. complete absence of discharged by mer·
ferric salts. curic chloride solu-
tion.
Ammonia solu· White to greenish- Reddish -brown pre.
tion. white precipitate. cipitate.

Dry Tests
(i) Blowpipe test.-When iron compounds are heated on
charcoal with sodium carbonate, grey metallic particles of iron
are produced; these are ordinarily diffioult to see, but can be
separated from the charcoal by means of a magnet.
(ii) Borax bead test.-With a small quantity of iron, the bead
is yellowish-brown while hot and yellow when cold in the
oxidising flame, * and pale green in the reducing flame.
, ALUMINIUM, Al
Aluminium is a white, ductile and malleable metal; the powder
is grey. The metal is little affected by cold dilute sulphuric acid,
but dissolves readily in the hot concentrated acid with the evolution
of sulphur dioxide. Nitric acid renders the metal passive; this
may be due to the formation of a protective film of oxide. It is
readily soluble in hydrochloric acid (dilute and concentrated) with
the evolution of hydrogen. Very pure aluminium, however, dis-
solves slowly in concentrated hydrochloric acid, but solution can be
accelerated by adding a little mercuric chloride solution. With
caustic alkalis a solution of an aluminate is formed,
2AI + 4H 2SO, = AI 2 (SO,)s + SOa + 2R sO;
2AI + 6RCl = 2AICl s + 3R t ;
2AI + 2NaOR + 2RaO = 2Na[A10.] + 3R a
Aluminium forms only one series of salts derived from the oxide
Al 2 0 S '
111,21. REACTIONS OF THE ALUMINIUM ION, Al +++
Use a solution of aluminium sulphate, A1 2 (S04h,18H 2 0,
or of potash alum, K 2S04,Al 2 (S04h,24H 2 0. (All aqueous
. • With large quantities of iron, the bead is reddish-brown in the oxidising
flame, .
268 Qualitative Inorganic AnalY8i8 [III.
solutions of aluminium salts are colourless, due to the colourlesfl
[AI(H20}6J +++ or AI +++ ion.}
1. Ammonia Solution: white gelatinous precipitate of
aluminium hydroxide Al(OH)a, slightly soluble in excess of th!
reagent. The solubility is decreased in the presence of ammo
nium salts owing to the common ion effect (Section I, 14). A
small proportion of the precipitate passes into solution a~
colloidal aluminium hydroxide (aluminium hydroxide 8ol): th(
80l is coagulated on boiling the solution or upon the additiOl,
of soluble salts (e.g. ammonium chloride) yielding a precipitate
of aluminium hydroxide, known as aluminium hydroxide gel
To ensure complete precipitation with ammonia solution, the
aluminium solution should contain excess of ammonium
chloride, the ammonia solution is added in slight excess and the
mixture boiled until the liquid has a slight odour of ammonia
When freshly precipitated, it dissolves readily in strong acid~
and bases, but after boiling it becomes difficultly soluble.
AI 2 (S04h + 6NHa + 6H20 = 2Al(OH)a + 3(NH4hS04
2. Sodium Hydroxide Solution: white precipitate oj
aluminium hydroxide AI(OH)a, soluble in excess of the reagent
with the formation of sodium aluminate Na[A10 2 ].
AI(OH)a + NaOH ~ Na[Al0 2] + 2H20
The reaction is a reversible one (compare Section I, 16), and
any reagent which will reduce the hydroxyl ion concentration
sufficiently should cause the reaction to proceed from right to
left with the consequent precipitation of aluminium hydroxide.
This may be effected with a solution of ammonium chloridt-
(the hydi.-oxyl ion concentration is reduced owing to the forma-
tion of the weak base ammonia, which can be readily removed
as ammonia gas on heating) or by the addition of acid; in the
latter case a large e~cess of acid causes the precipitated hydrox-
ide to re-dissolve. -
Na[Al0 2] + NH401 + H 20 = Al(OH)a + NHa + NaOl;
Na[Al0 2] +
lIOl + H 20 = Al(OH)a + NaOl;
Al(OB)3 + 3HOl ~ AlOIa + 3H20
The precipitation of aluminium hydroxide by solutions of sodium hydroxidB
and ammonia does not take place in the presence of tartaric acid, citric acid
sulphosalicylic acid, malic acid, sugars and other organic hydroxy compounds.
due to the formation of soluble complex salts. These organio substance,.
must therefore be decomposed by gentle ignition or by evaporating wit!.
concentrated sulphurio or nitrio acid before aluminium can be precipitated
in the ordinary oourse of qualitative analysis.
21] Reactions of the M etaZ Ions or Cations 269
3. Ammonium Sulphide Solution*: white precipitate of
aluminium hydroxide. The sulphide of aluminium is com-
pletely hydrolysed in the presence of water (compare Section
I, 40); it exists only in the dry condition.
2AICl a + 3NH4HS + 3NHs + 6H zO
= 2AI(OHh + 3HzS + 6NH4CI
AlzS s + 6H 0 = 2AI(OH)a + 3HzS
2

4. Sodium Acetate Solution: no precipitate is obtained

in cold neutral solutions, but on boiling with excess of the
reagent, a voluminous precipitate of basic aluminium acetate
Al(OHh. CZH 30 Z is formed.
Al Z(S04)s + 6Na.C2H a0 2 = 2Al(C2Ha02h + 3Na2S04;
Al(CzHaOz)s + 2H 2 0 ~ Al(OH)z. CzH a0 2 + 2H. CzH a0 2
5. Sodium Phosphate Solution: white gelatinous precipi-
tate of aluminium phosphate AIP0 4 , insoluble in acetic acid,
but soluble in mineral acids and in solutions of caustic alkalis.
AI 2 (S04)s + 2NazHP04 =2AIP04 + 2Na2S04 + H 2S04;
H 2S04 + 2NazHP04 =2NaH zP04 + Na2S04;
Al Z (S04)a + 4Na zHP04 = 2AlP04 + 3NazS04 +
2NaHzP04
+
AlP04 4NaOH = Na[AIOz] + Na aP04 + 2H zO
6. Sodium Carbonate Solution: white precipitate of
aluminium hydroxide, soluble in excess of the precipitant.
This is usually attributed to the complete hydrolysis of
the initially formed aluminium carbonate, but may be also
explained as due to the hydroxyl ions produced by the hydro-
lysis of the alkali carbonate.
+
A1 2 ( S04}a 3NazCOa = Alz(C0 3 )a + 3NazS04;
AI 2 (CO a)s+ 6H zO = 2Al(OH)s + 3HzCOa
2Al(OH)s + NazCOs = 2Na[AIO z]+ +
CO 2 3H zO
7. "Aluminon" Reagent (a solution of the ammonium
salt of aurine tricarboxylic acid, Cz2 H 1409 t): this dyestuff is
• Use colourless ammonium sulphide: see Section III, 19, Note 4.
t The constitutional formula of "aluminon " is:
COONH'
H,NOOC

HOO";:5
-
f 'OH

- n=o "'=ZcOONH&
270 Qualitative Inorganic Analysis [III.
strongly adsorbed by aluminium hydroxide giving a bright red
adsorption complex or "lake." The test is applied to the
precipitate of aluminium hydroxide obtained in the usual
course of analysis, since certain other elements interfere.
Dissolve the aluminium hydroxide precipitate in 2 m!. of JI
hydrochloric acid, add 2 ml. of 3M ammonium. acetate solutj,m
and 2 ml. of 0·1 per cent aqueous solution of the reagellG.
Shake, allow to stand for 5 minutes, and add excess of
ammoniacal ammonium carbonate solution to decolourise tile
excess of the dyestuff and lakes due to traces of chrOlll i c
hydroxide and silica. A bright red precipitate (or coloration),
persisting in the alkaline solution, is obtained.
Iron interferes with the test and should be absent. Chromium forms a
similar lake in acetate solution, but this is rapidly decomposed by the additi, ,n
of the ammoniacal ammonium carbonate solution. Beryllium gives a lake
similar to that formed by aluminium. Phosphates, when present in conaWrr.
able quantity, prevent the formation of the lake. It is then best to precipitn:"
the aluminium phosphate by the addition of ammonia solution; the resulta',\,
precipitate is redissolved in dilute acid, and the test applied in the usual WI!

a
The reagent is prepared by dissolving 0·25 grams of "aluminon
in 250 ml. of water.

((yew ):
t8. Alizarin Reagent

~/V
CO
red lake with aluminium hydroxide.
Soak some quantitative filter (or drop·reaction) paper in a saturate. i
alcoholic solution of alizarin and dry it. Place a drop of the acid tes i
solution on the paper and hold it over ammonia fumes until a viole,
colour (due to ammonium alizarinate) appears. In the presence 0'
large amounts of aluminium, the colour is visible almost immediately
It is best to dry the paper at 100° when the violet colour due to ammo
nium alizarinate disappears owing to its conversion into ammonia anti
alizarin: the red colour of the alizarin lake is then clearly visible.
Sensitivity: 0·15 ",g. AI. Concentration limit: I in 333,000.
Iron, chromium, uranium, thorium, titanium and manganese inter·
fere, but this may be obviated by using paper previously treated with
potassium ferrocyanide. The ions are thus "fixed" on the paper a.'i
insoluble ferrocyanides, and the aluminium solution diffuses beyond as
a damp ring. Upon adding a drop of a saturated alcoholic solution of
alizarin, exposing to ammonia vapour and drying, a red ring of the
alizarin-aluminium lake forms round the precipitate. Uranium ferro-
cyanide, owing to its slimy nature, has a tendency to spread outwards
from the spot and thus obscure the aluminium lake; this difficulty is
surmounted by dipping the paper after the alizarin treatment in
ammonium carbonate solution which dissolves the uranium ferrocyanide.
21] Reactions of the Metal Ions or Cations 271
t9. Alizarin-S (or Sodium Alizarin Sulphonate) Reagent

(CXX(.J'
red precipitate or lake in ammoniacal solution, which is fairly stable to
dilute acetic acid. •
Place a drop of the test solution (which has been treated with just
sufficient of N sodium hydroxide solution to give the aluminate ion
[AlOaJ-) on a spot plate, add I drop of the reagent, then drops of acetic
acid until the violet colour just disappears and 1 drop in excess. A red
precipitate or coloration appears.
Sensitivity: 0·7 fLg. AI. Concentration limit: 1 in 80,000.
A blank test should be made on the sodium hydroxide solution. Salts
of Cu, Bi, Fe, Be, Zr, Ti, Co, Ce, rare earths, Zn, Th, U, Co., Sr and
Ba interfere.
The reagent consists of a 0·1 per cent aqueous solution of alizarin-So
tl0. Quinalizarin (or 1 :2: 5: 8-Tetrahydroxy-anthraquinone)
Reagent

red precipitate or coloration under the conditions given below.

Place a drop of the test solution upon the reagent paper; hold it for
a short time over a bottle containing concentrated ammonia solution
and then over glacial acetic acid until the blue colour (ammonium
quinalizarinate) first formed disappears and the unmoistened paper
regains the brown colour of free quinalizarin. A red-violet or red spot
is formed.
Sensitivity: 0·005 fLg. Al (drop of 0·1 ml.).
Concentration limit: I in 2,000,000.
The reagent paper is prepared by soaking quantitative filter paper
in a solution obtained by dissolving 0·01 g. of quinalizarin in 2 mI. of
pyridine and then diluting with 20 m!. of acetone.

Dry Tests
(i) Blowpipe test.-Aluminium compounds when heated with
sodium carbonate upon charcoal in the blowpipe flame give a
white infusible solid, which glows when hot. If the residue be
moistened with one or two drops of cobalt nitrate solution and
272 Qualitative I rwrganic A nalyail [III,
again heated, a blue infusible mass (Thenard's blue, or cobalt
meta-aluminate) is obtained. It is important not to use a';
excess of cobalt nitrate solution since this yields black cobal l
oxide Co a0 4 upon ignition, which masks the colour of th,·
Thenard's blue.
2Al 20 a + 2Co(NO ah = 2COAl 20 4 + 4N02 + O2
An alternative method for carrying out this test is to soal
some ashless filter paper in aluminium salt solution, add a drO}'
or two of cobalt nitrate solution and then to ignite the filte!
paper in a crucible; the residue is coloured blue.
I
CHROMIUM, Cr
Chromium is a white crystalline metal and is not appreciably
ductile or malleable. The metal is soluble in hydrochloric acid
yielding the blue chromous chloride CrCl 2 if air is excluded, other-
wise chromic chloride CrClg is formed; hydrogen is evolved. Dilute
sulphuric acid reacts similarly forming chromous sulphate CrS04 in
the absence of air, and chromic sulphate Cr 2(S04)a in the presence
of air. Concentrated sulphuric acid, dilute and concentrated nitrie
acid induce passivity.
The normal oxide of chromium is the green aeaquioxide Cr 2 0 S '
from which the chromic salts may be regarded as derived.
Chromous salts, corresponding to 'the oxide Cro, are extremely
readily oxidised in air to chromic salts; the former are rarely en-
countered in elementary qualitative analysis and will therefore not
be considered here. An acidic oxide, chromium trioxide CrOg,
forming red deliquescent crystals, is known: this gives rise to the
coloured chromates (e.g. K 2 Cr04 or K20,CrOs) and dichromates (e.g.
K 2Cr 20 7 or K 20,2Cr0 a), which are discussed in Section IV, 33.

III, 22. REACTIONS OF THE CHROMIC ION, Cr+++

Use a solution of chromic chloride, CrCI 3 ,6H 20, or of chrome
alum, K2S04,Cr2(S04)s,24H20. (Chromic salts are either
green or violet in solution. *)
1. Ammonia Solution: grey-green to grey-blue gelatinous
precipitate of chromic hydroxide Cr(OH)a, slightly soluble in
excess of the precipitant in the cold forming a violet or pink
solution containing complex chrome-ammines; upon boiling
the solution, chromium hydroxide is precipitated. Hence for
complete precipitation of chromium as the hydroxide, it is
• Acid solutions, other than chlorides, contain the violet ion [Cr(H.O)6]+++
or Cr+++. Solutions of chromic chloride are green, due to the formation of
such complex ions as [Cr(H,O),CI]++ and [Cr(H.O),CI.]+.
22] Reactiona of the Metal lona or Oatiom 273
essential that the solution be boiling and excess of aq ueOU8
ammonia solution be avoided.
CrCls + 3NHs + 3H20 = Cr(OH)s + 3NH.Cl
Cr(OHla + 6NH3 = [Cr(NH3)6](OH)s
In the presence of acetate ions and the absence of other tri-
valent metal ions, chromic hydroxide is not precipitated. The
precipitation of chromic hydroxide is also prevented by tar-
trates and by citrates.
2. Sodium Hydroxide Solution: precipitate of chromic
hydroxide, readily soluble in acids and also in excess of the
precipitant in the cold forming a green solution containing
sodium chromite Na[Cr02]. Upon boiling the latter solution,
hydrolysis occurs and the chromium is almost quantitatively
re-precipitated as the hydroxide (distinction from aluminium).
Cr(OH)s + NaOH ~ Na[CrOz] + 2H zO
If hydrogen peroxide is added to the sodium chromite solution,
a yellow solution of sodium chromate is produced, which may
be identified by the" perchromic acid" reaction (Section IV, 33,
reaction 4; reaction 6 below) or by the diphenyl-carbazide
reagent (Section IV, 33, reaction 9).
2Na[Cr0 2 ] + 3Hz0 2 + 2NaOH = 2Na2[CrO,] + 4H2 0
3. Ammonium Sulphide Solution or Sodium Carbonate
Solution: precipitate of chromic hydroxide. The explanation
is similar to that given under Aluminium (Section III, 21,
reactions 3 and 6). Chromium sulphide is completely hydro-
lysed in aqueous solution.
4. Sodium Acetate Solution: no precipitate even on
boiling the solution.
In the presence of considerable amounts of iron and aluminium salts, the
precipitate of basic acetates obtained on boiling contains the basi3 acetate
Cr(OH) •. C.HaO.. If the chromium is present in excess, only a fraction of all
the metals will be precipitated as basic acetates, whilst some aluminium, iron
and chromium will remain in the filtrate. The basic acetate method of
separation (see Section VIII, 2) is therefore uncertain in the presence of a
large concentration of chromium.
The precipitation of chromic hydroxide is prevented by the presence of
certain organic compounds in solution (see under Aluminium, Section 111,21,
·reaction 6).

5. Sodium Phosphate Solution: green precipitate of

chromium phosphate Crpo4 , soluble in mineral acids, but
practically insoluble in cold dilute acetic acid.
CrCls + 2NazHPO. = Crpo4 + 3NaOl + NaHzPO.
 274 Qualitative inorganic Analysis [III,
6. Oxidation to Chromate Test.-A yellow solution of a
- chromate is produced by adding excess of sodium hydroxide
solution to a. solution of a. chromic salt, followed by a few ml.
of 6 per cent (" 20-volume") hydrogen peroxide, and then
boiling the resulting mixture for 2-3 minutes. Alternatively,
the oxidation may be conducted by adding a little solid sodium
perborate NaB0 3,4H 20 and boiling for a few minutes.
2CrCI s + 3H2 0 Z + lONaOH = 2Na2CrO~ + 6NaCI + 8HzO
NaBOs + H 20,.: NaB0 2 -I- H 2 0 2
The chromate is identified:
(a) By adding 2-3 ml. of amyl alcohol, acidifying with dilute
sulphuric acid, and then adding a little hydrogen peroxide
when it will be found that the organic layer is coloured blue,
due to the dissolution of the unstable chromic peroxide (often
erroneously called "perchromic acid"). Long usage, however,
appears to have established the use of the term "perchromic
acid" in the hydrogen peroxide test.
H 2CrZ0 7 + 4Hz0 2 ~ 2Cr06 + 5H2 0
(b) By acidifying with acetic acid and adding barium chloride
and sodium acetate solution when a yellow precipitate of
barium chromate is formed.
Note.-Formerly sodium peroxide was employed to effect the
oxidation. The sodium peroxide must be added to the cold solution:
in hot solution it reacts almost explosively. The use of sodium
peroxide is not recommended.
t7. Test with Diphenylcarbazide Rea~ent after Conversion into
Chromate.-Chromic chromium may be converted into chromate:
(i) by oxidation with bromine water in the presence of alkali (i.e. by
hypobromite); the excess of bromine is rendered inactive by the
addition of phenol which gives tribromophenol-
2Cr+++ + 30Br- + 100H- = 2CrO,-- + 3Br- + 5H,O
(ii) by heating in acid solution with an alkali persulphate in the
presence of a trace of a silver salt, which acts as a catalyst in accelerating
the oxidation-
2Cr+++ + 38 20 8- - + SHIO = 2CrO,-- + 16H+ + 6S0,-
Large quantities of halides must be absent as they prevent the catalytic
action of the silver ions.
(iii) As detailed in reaction 6.
Solutions of chromates in dilute mineral acids give So soluble violet
compound with the diphenylcarbazide rea.gent.
22] Reactions of the M etaZI ons or Oations 275
Place a drop of the test solution in mineral acid on a spot plate,
introduce a drop of saturated bromine water followed by 2-3 drops of
2N-potassium hydroxide (the solution must be alkaline to litmus).
Mix thoroughly, add a crystal of phenol, then a drop of the diphenyl-
carbazide reagent, and finally 2N-sulphuric acid dropwise until the red
colour (from the reaction between diphenylcarbazide and alkali) dis-
appears. A blue-violet coloration is obtained.
Sensitivity: 0·25 }Lg. Cr. Concentration limit: 1 in 2,000,000.
Copper, manganese, nickel and cobalt salts interfere in this procedure
because of their precipitation by the alkali.
Alternatively, mix a drop of the acidified test solution on a. spot
plate with a drop of saturated potassium persulphate solution and a
drop of 2 per cent silver nitrate solution, and allow to stand for 2-3
minutes. Add a drop of the diphenylcarbazide reagent. A violet or
red colour is formed.
Sensitivity: 0·8 fLg. Cr. Concentration limit: 1 in 600,000.
Manganese ions interfere (oxidised to permanganic acid) as do also
mercuric salts, molybdates and vanadates, which give blue to violet
compounds with the reagent in acid solution. The influence of molyb-
dates can be eliminated by the addition of saturated oxalic acid solution
thereby forming the complex H z[Mo0 3 (C 2 0,)].
The reagent consists of a 1 per cent solution of diphenylcarbazide in
alcohol.
t8. 1 : 8-Dihydroxynaphthalene-3 : 6-disulphonic Acid (or
Chromotropic Acid) Reagent

red coloration (by transmitted light) with an alkali chromate in the

presence of nitric acid. Chromic salts may be oxidised with hydrogen
peroxide and alkali to chromate, and then acidified with nitric acid
before applying the test. The nitric acid serves to eliminate the
influence of Fe, U and Ti, which otherwise interfere.
Place a drop of the test solution in a semimicro test-tube, add a
drop of the reagent, a drop of dilute nitric acid (1 : I), and dilute to
about 2 mI. Chromates give a red coloration: this is best observed
with a white light behind the tube.
The reagent consists of a saturated solution of chromotropic acid in
water.
Concentration limit: 1 in 5,000.

Dry'!ests
(i) Blowpipe test.-All chromium compounds when heated
with sodium carbonate on charcoal yield a green infusible mass
of chromium sesquioxide Cr20,.
 276 Qualitative Inorganic Analysis [III.
(ii) Borax bead test.-The bead is coloured green in both the
~ oxidising and reducing flames, but is not very characteristic.
(iii) Fusion with sodium carbonate and potassium nitrate in
a loop of platinum wire or upon platinum foil or upon the lid
of a nickel crucible results in the formation of a yellow mass
of alkali chromate.
Cr2(S04)a + 5Na2COa + 3KNOs
= 2Na2Cr04 + 3KN02 + 3Na2S04 + 5C02
DETECTION AND SEPARATION OF THE METALS IN THE IRON GROUP
(GROUP IDA)

In the following table it is assumed that the metals of Groups I

and II, if present, have been removed as already described, or that
only metals of Group IlIA are present; in the former case, it will be
necessary to boil off any hydrogen sulphide present (test fumes with
lead acetate paper). As in previous instances, the student should
make up for himself, or procure from the teacher, a solution con-
taining some or all of the metals of the group. Phosphates, borates,
silicates and organic acids are assumed to be absent. For satis-
factory precipitation with the group reagent aq. NHs and NH4Cl,
all of the three metals must be present as trivalent cations. It is
therefore necessary to test the so1ution for ferrous iron with potas-
sium ferricyanide solution and, if this is present, it must first be
oxidised to the ferric state by boiling the solution with a little
concentrated nitric acid.
It should be mentioned that manganese (a member of Group
IIIB; for reactions, see Section III, 26), when present in the man·
ganous state, should not be precipitated in Group IlIA by excess
of NHa solution in the presence of excess of NH4Cl: in practice,
however, the manganous ion is slightly oxidised by exposure of the
solution to air and accordingly some manganese may be precipitated
as the hydrated dioxide Mn0 2 ,xH2 0 by the group reagent. For
this reason, provision is usually made for the detection of Mn in
Group IlIA as well as in Group IIIB.

TABLES, pp. 277, 278.

23] Reactions of the Metal Ions or Oations 277
III, 23. Table IV. Analysis of the Iron Group (Group IlIA)
• Add 1-1·5 graIDll of solid ammonium chloride for each 10 ml. of
solution, heat to boiling and add dilute NH. solution slowly until the
solution smells of ammonia, boil for 1-2 minutes, filter rapidly and wash
with a little 1 % NH,Cl solution.
------------------------------------------------~---------
Residue. (T) May contain Fe(OH)" AI(OH).. Cr(OH). Filtrate.
and a little MnO.,xH.O.t Pierce a hole in the filter paper Reject.
with a glass rod and wash it into a small evaporating basin or
into a small beaker with the aid of about 10 m!. of water.
Treat the suspension with about 2 grams of sodium perborate
NaBO.,4H,0 (or with excess of NaOH solution, followed by
5 ml. of 3% H.O. solution). Boil gently lmtil the evolution
of 0. ceases (2-3 minutes). Filter and wash with a little hot
water or 2% ~1I,N03 solution.
Residue. May contain :B'e(OH). Filtrate. May contain Na.CrO,
and MnO •. xH,O. (yellow) or NaAlO, (colourless).
Either-Dissolve a small portion If colourless, Cr is absent and need
of the ppt. in 1 m!. of dilute HN0 3 not be considered further. If the
(1 : 1) with the aid, if necessary, solution is yellow, Cr is indicated.
of 3-4 drops of 3% H,O. or of 1 Divide the liquid into three
drop of saturated H.SO. solution. parts. (Use test (i) or (ii).)
Boil (to decompose H 2 0.), cool (i) Acidify with acetic acid, and
thoroughly, add 0·02 gram of add lead acetate solution.
NaBiO., shake and allow the solid Yellow ppt. of PbCrO,.
to settle. Cr present.
Violet solution of HMnO,. (ii) Acidify 2 m!. with dilute
Mn present. H::'{O., cool well, add 1 mI. of amyl
Or-Dissolve a little of the ppt. alcohol, and then 4 drops of 3%
in 2--3 mI. of dilute HNO. (1 : 1) H 2 0. solution. Shake well and
with the aid of a few drops of 3 % allow the two layers to separate.
H 2 0" if necessary. Add 0·5 gram Blue upper layer (containing
of Pb.O" boil gently for 2 minutes "perchromic acid"; it does not
and allow to settle. keep well).
Violet solution of HMnO,. Cr present.
Mn present. (iii) Acidify with dilute HCI (test
Dissolve another portion of the with litmus paper), then add dilute
ppt. in a little dilute HCI (filter, if NJI. solution until just alkaline.
necessary). Heat to boiling. Filter.
Either-Add a few drops of White gelatinous ppt. of
KSCN solution. AI(OH)a'
Deep red coloration. AI present.
Fe present. Confirm AI thus: dissolve a small
Or-Add K,[Fe(CN)sJ solution. portion of the ppt. in I ml. of dilute
Blue ppt. HCl. Cool, add 1 ml. of 10%
l<) present. ammonium acetate solution and
The origmal solution or sub. O· 5 ml. of the" aluminon .. reagent.
stance should be tested with Stir the solution and render basio
K,[Fe(CN)sJ and with KSCN to with ammonium carbonate solu·
determine whether Fe + + or tion. A red ppt. confirms the
Fe+++. presence of AI.

• If a ferrous salt is known to be present, it must first be oxidised to the

ferric state by warming with a little RN0 3 , otherwise the precipitation of
iron will be incomplete.
t Small quantities of manganese, if present, are often precipitated at this
stage. It is therefore best to provide for the identification of Mn in Group
IlIA 8B well 8B in Group nIB.
 278 Qualitative Inorganic Analysis
III, 23. Table SMIV. Analysis of the Iron Group
(Group IlIA)
* Add 0·2 gram of solid NH,CI (or 1 ml. of 20% NH.CI solutior
followed by dilute NH. solution until precipitation seems complete ar
the solution is ammoniacal, and then add a further 0·5 ml. Warm on
water bath with stirring for 1-2 minutes. Centrifuge.
Residue. (T) Wash with a little dilute aq. NRa and Centrifu·
reject the washings. The ppt. may contain Fe(OH)., gate.
Al(OH)s, Cr(OH). and a little MnO •. xH 2 0. Transfer the Reject.
ppt. to a semimicro boiling tube with the aid of 2 ml. of
NaOH solution: add I ml. of 3% H.O. solution or ca. 0·2
gram of sodiwn perborate, NaBO.,4H.O. Boil gently
until the evolution of 0. ceases (about 1 minute). Trans·
fer the mixture with the aid of a little water to a centrifuge
tube. Centrifuge.
Residue. May contain Fe(OH). Centrifugate (A). May contain I
and MnO.,xH,O. Wash with a NaAlO. and Na.CrO,: the latter is
few drops of hot water or 2% indicated by the yellow colour of
NR.NO. solution and add wash- the solution. Divide the solution
ings to A. into 2 parts.
Dissolve the ppt. in 0·5 ml. of (i) Either-Acidify with dilute
dilute HNO. and, if necessary, 2 acetic acid and add 1 drop of lead
drops of 3% H.O. solution or acetate solution.
1 drop of saturated H 2SO. solu- Yellow ppt. of PbCrO,.
tion. Warm on water bath to Cr present.
decompose excess of H 2 0 •. Or-Acidify with dilute HNO •.
Divide the solution into 2 parts. Cool: add 0,3-0·5 ml. of amyl
(i) Add 1 drop of K.[Fe(CN).] alcohol and 2 drops of 3% H.O.
solution. solution. Shake and allow the two
Blue ppt. layers to separate.
Fe present. Blue coloration of "perchromic
The original solution or sub. acid" in upper layer.
stance should be tested with Cr present.
K.[Fe(CN).] or KSON to deter- The blue colour does not last
mine whether Fe++ or Fe+++. long as the compound is unstable.
(ii) Dilute with 1 ml. of water, (ii) Acidify with dilute HCl
cool, add 10 mg. of NaBiO •• shake (litmus paper test) and then render
and allow solid to settle. just basio with dilute aq. NH., and
Violet solution of HMnO,. add 1 drop in excess. Heat on a
Mn present. water bath for 1 minute.
White gelatinous ppt. of AI(OH) •.
Al present.
Confirm Al thus: centrifuge,
wash with a few drops of water,
dissolve the ppt. in dilute HOI,
add 0·3 ml. of ammoniwn acetate
solution and 1 drop of the" alwni·
non" reagent. Mix, allow to stand
for 30 seconds, and render alkaline
with ammoniacal ammoniwn car.
bonate solution. A red ppt. con·
firms AI.

* If a ferrous salt is known to be present, it must be oxidised first to the

ferric state by warming with a few drops of HNO a. otherwise the precipitation
of iron will be incomplete.
24] Reactions of the Metal Ions or Oations 279

THE ZINC GROUP (GROUP IIIB)

COB4LT,CO
Cobalt is a steel.grey, magnetic solid. It dissolves slowly in warm
dilute hydrochloric or sulphuric acid, and more rapidly in nitric acid
forming cobaltous compounds, which may be regarded as derived
from cobaltous oxide CoO. Two other oxides exist: cobaltic oxide
C0 20 S, corresponding to the extremely unstable cobaltic compounds,
and cobaltous cobaltic oxide C08 0 4 • All the oxides of cobalt dis-
solve in acids yielding cobaltous salts.
Co.O s + 6RCI = 2CoCI 2 + CI + 3H 0;
B 1

C0 30, + SRCI = 300CI 2 + 01. + 4RaO

Many stable complex compounds containing trivalent cobalt, e.g.
potassium cobaltinitrite K s[Co(N0 2 )6] and potassium cobalti-
cyanide K s[Co(CN)6]' are known.

111,24. REACTIONS OF THE COBALTOUS ION, Co++

Use a solution of cobalt nitrate, Co(NO ab,6H 20. (All
aqueous solutions of cobaltous salts are pink, due to the
presence of the [Co(H 20)6J ++ or Co++ ion.)
1. Sodium Hydroxide Solution: a blue basic salt is pre-
cipitated in the cold; upon warming with excess of alkali
(sometimes merely upon addition of excess of the reagent),
the basic salt is converted into pink cobaltous hydroxide
Co(OHh but a small amount passes into solution. 'l'his hy-
droxide is transformed into the brownish-black cobaltic
hydroxide Co(OH)a on exposure to the air, or by prolonged
boiling of the aqueous suspension; the change takes place
rapidly if an oxidising agent, such as sodium hypochlorite
solution or hydrogen peroxide, is added. Cobaltous hydroxide
is readily soluble in concentrated solutions of ammonium salts
owing to the formation of complex salts; solutions of alkali
hydroxides do not, therefore, precipitate cobaltous hydroxide
from ammoniacal solution of cobalt salts nor from solutions
containing citrates or tartrates.
Co(NOsl2 + NaOH = Co(OH)NOs + NaNOs;
Co(OH)NOs + NaOH = CO(OH)2 + NaNOs;
2Co(OH)2 +
H 20 +
0 = 2Co(OH)s
Cobaltous hydroxide is slightly soluble in a large excess of concen-
trated sodium hydroxide solution, but cobaltic hydroxide is insoluble.
2. Ammonia Solution: precipitate of blue basic salt as in
reaction 1, readily soluble in excess of the precipitant and in
 280 Qualitative Inorganic Analysis [III,
solutions of ammonium salts. The brownish-yellow amme'
niacal solution turns red on exposure to air, more rapidly UpOll
addition of hydrogen peroxide; this is due to the formation of
complex salts (cobalt-ammines). These are unaffected by
alkali hydroxide solution.
\
4Co(OH)NOs + 28NHs + 6HzO + O2 ,

=4[Co(NHs)o](OH)3 + 4NH4NO;
The precipitation of cobaltous hydroxide does not take place in the presenc>
of certain organic acids and organic hydroxy compounds, as in the case oj
aluminium (Section III, 21, reaction 2).
3. Ammonium Sulphide Solution*: black precipitate of
cobalt sulphide CoS from neutral or alkaline solutions, in-
soluble in excess of the reagent, in acetic acid and in very
dilute hydrochloric acid (ca. N), but is readily soluble in hot
concentrated nitric acid and in aqua regia with the separation
of sulphur.
CO(NOS )2 + NH4HS + NHs = CoS +
2~N03
3CoS + 8HNOs = 3Co(NOs)z 2NO + + 3S + 4HzO
4. Potassium Cyanide Solution: reddish-brown precipi-
tate of cobaltous cyanide Co(CNh, soluble in excess of the
reagent to form a brown solution containing potassium cobalto-
cyanide K,,[Co(CN)6], analogous to potassium ferrocyanide
~[Fe(CN)6]' When the cob alto cyanide solution is treated
in the cold with dilute hydrochloric acid, cobaltous cyanide is
precipitated.
On prolonged boiling of the brown solution, preferably after
the addition of a few drops of hydrogen peroxide or of sodium
hypochlorite or of sodium hypobromite solution, it assumes a
yellow colour, due to oxidation to potassium cobalticyanide
K3[CO(CN)6J, analogous to potassium ferricyanide K 3[Fe(CN)6]'
The cobalticyanide solution gives no precipitate with acids
(distinction from nickel) nor with ammonium sulphide.
Co(NOs)z +
2KCN = Co(CN)z 2KNO s ; +
CO(CN)2 +
4KCN = ~[CO(CN)6];
~[CO(CN)6] +
2H20 +
O2 = 4Ks[Co(CN)6] 4KOH +
K.[CO(CN)6] +
4HCl = Co(CN)2 4HCN +
4KCI +
5. Potassium Nitrite Solution: yellow precipitate of
potassium cobaltinitrite K 3[Co(N0 2 )6],3H zO when added in
excess to a concentrated solution of a cobalt salt acidified
• Colourless ammonium sulphide solution may be used for this test: it may
be readily prepared by passing H.S into dilute NH. solution.
24] Reactiona of tke Metal IOn8 or Oatio'IUI 281
with acetic acid (distinction from nickel). In dilute solution,
the precipitate appears only after standing for several hours,
or more rapidly on shaking.
Co(NO)s + 2KNO z = Co(N0 2 )z + 2KNO.;
CO(NO Z)2 + 2KN0 2 + 2H. C2H s0 2 =
Co(NOz)s + 2K. C2H sOz + NO + HzO;
Co{N02 la + 3KN02 = K s[Co{N02 )6]
Co(NOs)z + 7KN02 + 2H. C2H s0 2 = K s[Co(N0 2 )8]
+2KNOs + 2K.CzH sOz + NO + H 2 0
6. Ammonium Thiocyanate Solution: a blue solution,
due to the cobalti-thiocyanate ion [CO(SCN)4r -, is produced
by adding concentrated NH4SCN solution (it is best to add a
few crystals of the solid salt to the test solution); if amyl
alcohol be added and the solution shaken, the blue colour
passes into the alcohol layer (distinction from nickel).
The free acid H,[Co(SCN),] is much more soluble in ether and in
amyl alcohol than its salts, hence it is best to strongly acidify the
solution with concentrated HCI: the test is thus rendered much more
sensitive.
Co(NO s).+ 4HSCN = H.(Co(SCN),] + 2HNO s
The disturbing effect of Fe + + + is overcome by the addition of a.
fluoride solution, thereby forming the highly stable ferri-fluoride ion
[FeFer--; alternatively, a little solid Na 2S SO a may be added and the
mixture vigorously shaken whereby Fe + ++ is reduced to Fe + + and
Na 2 S,Os is produced.
t The reaction may be employed as a spot test as follows. Upon a
spot plate, mix 1 drop of the test solution with 5 drops of a saturated
solution of ammonium thiocyanate in acetone. A green to blue colora-
tion appears.
Sensitivity: 0·5/Lg. Co. Concentration limit: 1 in 100,000.
If iron is present mix 1-2 drops of the slightly acid test solution
with a few milligrams of ammonium or sodium fluoride on a spot plate
and then add 5 drops of a 10 per cent solution of ammonium thio-
cyanate in acetone. A blue coloration is produced.
Sensitivity: l/Lg. Co in the presence of 100 times the amount of Fe.
Concentration limit: I in 50,000.
7. oc-Nitroso-,8-naphthol Reagent

reddish-brown precipitate of slightly impure cobalti-nitroso-,8-

naphthol CO(ClOH602N)a (an inner oomplex salt) in solutions
282 Qualitative Jnorganic Analysis [III.
acidified with dilute hydrochloric acid or dilute acetic acid;
the precipitate may be extracted by carbon tetrachloride to
give a claret-coloured solution. Precipitates are also given by
iron (Fe + + and Fe + + +), nickel and uranyl salts in Group III.
The nickel complex is soluble in dilute hydrochloric acid; ferric
iron is rendered innocuous by the addition of sodium fluoride;
the uranyl ion may be removed, as uranyl phosphate, by
ammonium phosphate solution. Copper, mercuric mercury,
palladium and many other metals interfere. The reaction
may, however, be used as a confirmatory test for cobalt in the
Group IIlB precipitate after the separation of the manganese
and zinc.
The reagent consists of a I per cent solution of oc-nitroso-(1-
naphthol in 50 per cent acetic acid, or in ethyl alcohol, or in
acetone.
t The technique for using the reaction as a spot test is as follows.
Place a drop of the faintly acid test solution on drop reaction paper,
and add a. drop of the reagent. A brown stain is produced.
Sensitivity 0·05 flog. Co. Concentration limit: 1 in 1,000,000.
8. Sodium I-Nitroso-2-hydroxynaphthalene-3: 6-di-
sulphonate (Nitroso-R-salt) Reagent

Co,;xX:.J,
deep red' coloration. The test is applicable in the presence
of nickel; tin and iron interfere and should be removed; the
coloration produced by iron is prevented by the addition of
an alkali fluoride.
t Place a. drop of the neutral test solution (buffered with sodium
acetate) on a spot plate, and add 2-3 drops of the reagent. A red
coloration is obtained.
Concentration limit: 1 in 500,000.
The reagent consists of 8 I per cent solution of nitroso-R-salt in
water.
t9. Rubeanic Acid (or Dithio-oxamide) Reagent
HaN-C-C-NH. )
( II II :
S S
yellowish-brown precipitate. Under similar conditions nickel and
copper salts give blue and black precipitates respectively (see under
25] Reactions of the Metal Ions or Oations 283
Copper, Section III, 8). Large quantities of ammoniwn salts reduce
the sensitivity.
Place a drop of the test solution upon drop-reaction paper, hold it in
ammonia vapour, and then add a drop of the reagent. A brown spot
or ring is formed.
Sensitivity: 0·03 p.g. Co. Concentration limit: I in 660,000.
The reagent consists of a I per cent solution of rubeanic acid in
alcohol.

Dry Tests
(i) Blowpipe test.-All cobalt compounds when ignited with
sodium carbonate on charcoal give grey, slightly metallic beads
of cobalt. If these are removed, placed upon filter paper and
dissolved by the addition of a few drops of dilute nitric acid, a
few drops of concentrated hydrochloric acid added and the
filter paper dried, the latter is coloured blue by the cobalt
chloride produced.
(ii) Borax bead test.-This gives a blue bead in both the
oxidising and reducing flames. Cobalt meta-borate Co(B0 2 h,
or the complex salt Na 2[Co(B0 2)4], is formed see (Section II, 1).
The presence of a large proportion of nickel does not interfere.

NICKEL, Ni
Nickel is a hard, silver-white metal; it is ductile, malleable and
very tenacious. Hydrochloric and sulphuric acids, both dilute and
concentrated, attack it slowly; dilute nitric acid dissolves it re:tdily,
but the concentrated acid induces passivity.
Only one stable series of salts, the nickelous salts, which may be
regarded as derived from the green nickelous oxide NiO, is known.
A brownish-black nickelic oxide Ni 2 0 3 exists, but this dissolves in
acids forming nickelous compounds.
Ni:aO a + 6HCl = 2NiCI I + 3H 10 + Cl.
III, 25. REACTIONS OF THE NICKEL ION, Ni + +
Use a solution of nickel sulphate, NiS04 ,7H 20, or of nickel
chloride, NiCI 2 ,6H 2 0. (Solutions of nickelous salts are green,
due to the presence of the [Ni(H20 )6] + + ion; this is usually
written as Ni++.)
1. Sodium Hydroxide Solution: green precipita1e of
nickelous hydroxide Ni(OHh, insoluble in excess of the re-
agent. No precipitation occurs iu the presence of tartrate or
citrate. The precipitate dissolve>; in ammonia solution or in
solutions of ammonium salts forming greenish-blue solutions
_L" __ ~ ___ 1 _ _ _ _ ~_1 _1 • n ,- T ..,,1Ik\ J1
 1
284 Qualitative I norganic Ana~ysis

solutions are not oxidised on boiling with free exposure to air

or upon the addition of hydrogen peroxide (difference fro); I
cobalt). Nickelous hydroxide is oxidised by sodium hypo-
chlorite solution to black nickelic hydroxide Ni(OH)s.
NiS04 +
2NaOH = Ni(OH)2 + Na2S04;
4Ni(OH)2 + 2H20 + O2 = 4Ni(OH)s
2. Ammonia Solution: green precipitate of basic salj.
soluble in excess of the reagent forming complex nickel ammirw
compounds.
NiC1 2 + NHs + H 20 = Ni(OH)Cl + NH4Cl;
Ni(OH)CI + 7NHs + H 20 = [Ni(NHs )6](OH)2 + NH4Cl
No precipitation takes place with ammonia solution in th,'
presence of ammonium salts; this is because the concentratiOJ I
of hydroxyl ions is so reduced that the solubility product 01
neither Ni(OH)Cl nor Ni(OHh is attained (see Sections I, 15
and I, 10).
3. Ammonium Sulphide Solution*: black precipitate 0 1
nickel sulphide NiS from neutral solutions, slightly soluble il
excess of the reagent forming a dark-brown, colloidal solutio})
which runs through the filter paper. If the colloidal solution
is boiled or if it is rendered slightly acid with acetic acid and
boiled, the colloidal solution (hydrosol) is coagulated and can
then be filtered. The presence of large quantities of ammonium
chloride usually prevents the formation of the sol. Nickel
sulphide is practically insoluble in cold dilute hydrochloric
acid, sp. gr. 1·02 (distinction from the sulphides of manganese
and zinc) and in acetic acid, but dissolves in hot concentrated
nitric acid and in aqua regia with the separation of sulphur.
+ NH HS + NHa = NiS + 2NH Cl
NiC1 2 4 4
3NiS + 8HNO s = 3Ni(N0 3 )2 + 2NO + 3S + 4H 20
3NiS + 2HNOa + 6HCl = 3NiCI2 + 2NO + 3S + 4H 20
4. Hydro~en Sulphide: only part of the nickel is slowly
precipitated as nickel sulphide from neutral so)utions; no pre-
cipitation occurs from solutions containing mineral acid or
much acetic acid. Complete precipitation occurs, however,
from solutions made alkaline with ammonia solution, or from
solutions containing excess of alkali acetate slightly acid with
acetic acid (compare Section I, 16).
NiCl 2 + H 2S ~ NiS + 2HCI
• Use colourleSl! ammonium sulphide: see Section III, 24. reaction 2.
25] Reaction3 of the Metal Ions or Oations 285
5. Potassium Cyanide Solution: green precipitate of
nickelous cyanide Ni(CNb, readily soluble in excess of the
reagent forming the complex salt, potassium nickelocyanide
K 2[Ni(CN)4] (compare Section I, 20). If this solution be
warmed with sodium hypobromite solution (prepared in situ
by adding bromine water to sodium hydroxide solution), the
complex cyanide is decomposed and a black or brown precipi-
tate is formed (difference from cobalt); the precipitate is
variously formulated as Ni(OH)a or Ni0 2 • Excess of potas-
sium cyanide solution should be avoided since the bromine
water will first react with the excess of cyanide forming cyano-
gen bromide CNBr; hence it is best to add potassium cyanide
solution drop by drop until the initial precipitate is just
dissolved.
Careful addition of dilute hydrochloric acid to the solution
of potassium nickelocyanide precipitates nickel cyanide.
NiCl z + 2KCN = Ni(CN12 + 2KCI;
+ 2KCN = K 2[Ni(CN)4];
Ni(CNh
2K 2[Ni(CN)4] + 9NaOBr + 4NaOH + H 2 0
= 2Ni(OH)a + 4KCNO + 4NaCNO + 9N"aBr;
KCN + Brz = CNBr + KBr;
Kz[Ni(CN)4] + 2HCl = Ni(CN)z + 2HCN + 2KCI
6. Potassium Nitrite Solution: no precipitate is produced
in the presence of acetic acid (difference from cobalt).
7. Ci - Nitroso - ~ - naphthol Rea~ent {C 1oH 6 (NO)OH}:
brown precipitate of composition Ni(C 10H 6 0 2N)2, soluble in
dilute hydrochloric acid (difference from cobalt, which gives a
reddish-broVi'll. precipitate, insoluble in dilute hydrochloric
acid).
8. Dimethyl~lyoxime Reagent (C4H s0 2N z): red precipi-
tate of nickel dimethylglyoxime in solutions just alkaline with
ammonia solution or containing sodium acetate.
OH
I
°
t
CHs·C=NOH CH •. C=N'\,. /N=C.CH s
2 I
CHs.C=NOH
+ NiSO, + 2NH,OH = , I
CHs.C=N
/Ni, '.
N=C.CH.
b dH
+ (NH')2S0 ,+2H 0 2

Ferrous iron (red coloration; compare Section III, 19), bismuth

(yellow precipitate), and cobalt whon present in large excess (brown
286 Qualitative Inorganic AnaZyaM [III,
coloration) interfere in ammoniacal solution. The influence of
interfering elements (Fe++ must be oxidised to Fe+++, say, by
hydrogen peroxide) can be eliminated by the addition of a tartr., reo
When large quantities of cobalt salts are present, they react", th
the dimethylglyoxime and a special procedure must be adopT "d
(see below). Oxidising agents must be absent. Palladium, p]:lli-
num and gold give precipitates in acid solution.
The reagent is prepared by dissolving 1 g. of dimethylg!y-
oxime in 100 m!. of rectified spirit.
t The spot test technique is as follows. Place a drop of the t,·~t
solution on drop-reaction paper, add a drop of the above reagent !11td
hold the paper over ammonia vapour. Alternatively, place a. drop of
the test solution and a drop of the reagent on a spot plate, and add a
drop of dilute ammonia solution. A red spot or precipitate (or colol:l.
tion) is produced.
Sensitivity: 0·16 p.g. Ni. Concentration limit: 1 in 300,000.
Detection of traces of nickel in cobalt salts. The solution Con·
taining the cobalt and nickel is treated with excess of concentrat,,,l
potassium cyanide solution, followed by "lO-volume" hydrogt!l
peroxide whereby the complex cyanides Ka[Co(CN)s] and Ka[Ni(CN' 11
respectively are formed. Upon adding 40 per cent formaldehy(",
solution the potassium cobalticyanide is unaffected (and hence remaik'
inactive to dimethylglyoxime) whereas the potassium nickelocyanide ,e
decomposed with the formation of nickel cyanide, which reacts imm("
diately with the dimethylglyoxime.
K 2[Ni(CN),) + 2H.CHO = Ni(CN)a + 2CH (CN)OK
2

Ni(CN)a + 2C,H sO aN a = + 2HCN

Ni(C,H 70 aN 2)a
t9. ~-Furil-dioxime Reagent
C.H 3 0- =NOH) :
Y
( C.H 0-C=NOH
3

red precipitate in slightly ammoniacal solution.

Place a few drops of the slightly ammoniacal test solution in a micr"
test-tube and add a few drops of the reagent. A red precipitate or
coloration is formed. Alternatively, the reaction may be carried out
on a spot plate.
~ensitivity: 0·02 p.g. Ni. Concentration limit: I in 6,000,000.
The reaction is not disturbed by silver or copper, or by ferrio iron,
ohromium or aluminium in the presence of ammoniacal tartrate solu-
tion; if zino is present, ammonium chloride should first be added;
cobaltous ions repress the sensitivity and should be oxidised to the
cobaltic state with hydrogen peroxide; ferrous iron interferes and
should be oxidised and alkaline tartrate solution added before applying
the test.
The reagent consists of a 10 per oent solution of ~·furil·dioxime in
alcohol.
25] Reacti0n8 of the Metal IOnIJ or CationIJ 287
tlO. Rubeanic Acid Reagent {(CS.Nlis)s}: blue or violet precipi-
tate or coloration in ammoniacal solution. Copper and cobalt. as well
as iron, salts interfere with the reaction and should be absent.
Place a drop of the test solution upon drop-reaction paper. hold it
over ammonia vapour, and add a. drop of the reagent. A blue or blue-
violet spot is obtained.
Sensitivity: 0'03 p.g. Ni. Concentra.tion limit: I in 1,250,000.
The reagent consists of a I per cent solution of rubeanic acid in
alcohol.

Dry Tests
(i) Blowpipe test.-All nickel compounds when heated with
sodium carbonate on charcoal yield grey, slightly magnetic
scales of metallic nickel. If these are placed upon a strip of
filter paper, dissolved by mean" of a few drops of nitric acid,
a few drops of concentrated hydrochloric acid added and the
filter paper dried by moving it back and forth in the flame or
by placing it on the outside of a test-tube containing water
which is heated to the boiling point, the paper acquires a green
colour owing to the formation of nickelous chloride. On
moistening the filter paper with ammonia solution and adding
a few drops of the dimethylglyoxime reagent, a red colour is
produced.
(ii) Borax bead test.-This is coloured brown in the oxidising
flame, due to the formation of nickel meta-borate Ki(B02h
or of the complex meta-borate Na2[Ni(B02)4] (see Section
11,1), and grey, due to metallic nickel, in the reducing flame.

MANGANESE, Mn
Manganese is a greyish-white metal, similar in appearance to cast
iron. It reacts with warm water forming manganous hydroxide
and hydrogen. Dilute mineral acids and also acetic acid dissolve
it with the production of manganese salts and hydrogen. Sulphur
dioxide is evolved with hot concentrated sulphuric acid.
Six oxides of manganese are knuwn: MnO, Mn 20 a, Mn a0 4 , Mn0 2 •
MnO s and Mn 2 0 7 • The most important compounds, the manganous
salts, may be regarded as derived from manganous oxide l\'lnO; the
manganic salts, related to Mn 2 0 3 , which correspond to the ferric
salts, are unstable and do not exist under ordinary analytical con-
ditions. All the oxides dissolve in warm hydrochloric acid and
hot concentrated sulphuric acid forming manganous salts, tbe higher
oxides being reduced with the evolution of chlorine and oxygen
respectively.
The two unstable acidic oxides Mn0 s and Mn 2 0 7 are related to
the manganates, e.g. K 2MnO, or K 20,MnOa, and permanganates,
288 Qualitative lnorgan~c Anaty~ LJ.·l.l,

e.g. K 2Mn 2 0 S or K 2 0,Mn 20 7 respectively. These 3!re discussed 1'1

Section IV, 34.
Mn + 2HCI = MnCI I + HI;
MnO. + 4HCl = MoCl. + Cl. + 2H_0;
MnaO, + SHCI = 3MnCI. + CIa + 4B t O;
2MnaOa + 4H aSO, = 4MnSO, + O. + 4IlaO;
2Mn aO, + 6H aSO, = 6MnSO, + O. + 6Il.0;
2MnO. + 2H.SO, = 2MnSO, + O. + 2I1aO

111,26. REACTIONS OF THE MANGANOUS ION, Mn -+ .

Use a solution of manganous chloride, MnC1 2 ,4H 20, or (.r
manganous sulphate, MnS04 ,5H 20. (Manganous compoun<:"
are usually pink in aqueous solution, due to the [Mn(H 20)6]-+
or Mn ++ ion.)
1. Sodium Hydroxide Solution: white precipitate (,:
manganous hydroxide Mn(OH)2, insoluble in excess of tj",
~eagent. Th.e precipitate ~apidl~ oxi<iiBes on e~:po!iiu.re to air,
becoming brown; the brown compound is either manganic
hydroxide, Mn(OH)a, or hydrated manganese dioxide Mn0 2 ,
xH 20.
+
MnCl 2 2NaOH = Mn(OH)2 + 2NaC) ,
4Mn(OH)2 + 2H 2 0 + O2 = 4Mn(OH)s
The addition of a little hydrogen peroxide conV'erts the mar:
ganous hydroxide rapidly into hydrated manganese dioxide:
Mn(OHh + HzOz = Mn0 2 + 2H20
2. Ammonia Solution: partial, precipitation of whit"
manganous hydroxide Mn(OH)2, soluble in solutions of amme
nium salts.
No precipitation takes place in the presence of ammonium salts owing t"
the lowering of the hydroxyl ion concentration and the COD,l3equent failure t"
attain the solubility product ofMn(OH)t (compare Section 1,16). On exposUl"
to air, brown manganic hydroxide or hydrated manganese dioxide is precir,
tated from the ammoniacal solution. This is important in connexion with tb"
separation from the Group IlIA metals. In precipitating iron, aluminiw"
and chromium, the solution should contain a large exceSS of arnmoniw"
chloride, and be boiled to expel most of the dissolved air, then a slight exce""
of ammonia solution added and the precipitate filtered as quickly as p088ibl,
Under these conditions very little manganese will be precipitated.
MnCl 2 + 2NHs + 2HzO <? Mn(OH)2 + 2l'ffi.Cl
3. Ammonium Sulphide Solution.: pink (flesh-coloured)
preoipitate of hydrated manganous sulphide MnS, readily
• Use colourleslI ammonium sulpbide: see Section In, 24, reaction I.
26] Reactions of the Metal Ions or Catio'lUl 289
soluble in dilute acids (distinction from nickel and cobalt) and
in acetic acid (distinction from nickel, cobalt and zinc). The
presence of ammonium chloride assist,s precipitation since the
sulphide when first formed is colloidal (compare Nickel, Section
III, 25, reaction 3). The precipitate turns brown on exposure
to air owing to oxidation. Boiling with excess of ammonium
sulphide solution converts the pink hydrated form into the less
hydrated green sulphide 3MnS,H 20.
MnCI 2 + NH4HS + NHs = MuS + 2NH4CI
The precipitate dissolves readily in dilute hydrochloric acid
(ca. N) (distinction from nickel and cobalt).
4. Sodium Phosphate Solution: flesh-coloured precipitate
of manganese ammonium phosphate Mn(NH4 )P04 ,7H 20 in the
presence of excess of ammonia solution.
MnC1 2 + NH40H + Na2HPO, + 6H20
=Mn(NH4)P04,7H 2 0 + 2NaCI
5. Lead Dioxide and Concentrated Nitric Acid.-On
boiling a dilute solution of a manganous salt, free from hydro-
chloric acid and chlorides, with lead dioxide (or red lead, which
yields the dioxide in the presence of nitric acid) and a little
concentrated nitric acid, diluting somewhat and allowing the
suspended solid containing unattacked lead dioxide to settle,
the supernatant liquid acquires a violet-red (or purple) colour
due to permanganic acid. The latter is decomposed by hydro-
chloric acid hence chlorides should be absent.
5Pb02 + 2MnSO, + 6HNOs
. = 2HMn04 + 3Pb(NOs )2 + 2PbSO, + 2H20
6. Ammonium or Potassium Persulphate.-When the
solid is boiled with a solution of a manganous salt in dilute
sulphuric acid in the presence of a little silver nitrate 8olution
(which acts as a catalyst), a reddish-violet solution of per-
manganic acid is formed. The unstable silver peroxide is
probably intermediately formed and this acts as the oxidising
agent.
5(NH4)2S20S + 5H20 = 5(NH4)2S04 + 5H2 S04 + 50;
lOAgNO s + 50 + 5H2 0 = 5Ag2 0 2 + 10HNOs ;
2MnS04 + 5Ag20 2 + lOHNOs
=2HMn04 + lOAgNO s + 2H2 S04 + 2H 2 0
The gross reaction may be written:
2MnSO, + 5(NR')IlSZ0B + BRzO
= 2HMnO, + lONH,HSO, +2H sSO,
10+
ililllU L......... ,

7. Sodium Bismuthate (NaBiOa).-WheI1 this solid is

added to a cold solution of a manganous salt in dilute ni, i ic
acid (sp. gr. 1·13) or in dilute sulphuric acid, the mixture stir 'ld
and the excess of the reagent filtered off (preferably thrOl, ~h
asbestos or glass wool or a sintered glass funnel), a solutior, of
permanganic acid is produced.
5NaBiO a + 2MnS04 + 16HNOs
= 2HMn04 + 5Bi(NO a)a + NaNO a + 2:Na2S04 + 71i ~O
t The spot-test technique is as follows. Place a drop of the ' st
solution on a spot plate, add a drop of concentrated nitric acid "ad
then a little sodium bismuthate. The purple colom' of permang' "io
acid appears. If the solution is so dark that the 13010ur cannot ')EI
detected, dilute the mixture with water until the colour appears.
Sensitivity: 25 fLg ]\in (in 5 ml.)_ Concentration linlit: 1 in 200,0' ,,).
8. Potassium Periodate (KI04).-The manganous c ,1-
phate solution is rendered strongly acid with sulphuric or nil I ic
acid or (best) phosphoric acid, 0,2-0,3 gram of potassi ,:n
-periodate added, and the solution boiled for 1 minute. A
solution of permanganic acid is formed.
Chlorides must be absent; if present, they must be remo~ed by evapora' ., m
with sulphuric or nitric acid before applying the test.
2MnS04 + 5KI04 + 3H 20 = 2HMn04 + 5KIOs + 2H2S04
t9.Potassium Periodate-"Tetrabase" Test.-A solution of lhe
"tetrabase" (tetramethyl-diamino-diphenylmethane) in chloroforn is
employed as a sensitive test to identify very small tLmounts of II} '1-
ganese as permanganic acid. The latter oxidises the "tetrabase" t< m
intensely blue compound. Chromium salts should be absent for t ,y
are oxidised by periodates to chromates, which yield a similar colour
with the "tetrabase."
Place a drop of the test solution on a Bpot plate, followed by a drop
of saturated potassium periodate solution and 2 drops of a 1 per cent
solution of the "tetrabase" in chloroform. A deep blue colow is
formed.
Sensitivity: 0·001 fLg. l\in. Concentration limit: 1 in 50,000,000
tlO. Ammonium Persulphate Test.-Manganelle salts in di] 'r,e
sulphuric or nitric acid solution react only on warming with persulphl1 '3S
with the formation of hydrated manganese dioxide. If, however, te
solution contains some silver ions as catalyst, oxidation proceeds to . :te
permanganate state:
2l\in++ + 58.0.-- + 8H.0 = 2l\in0,-+ 1080,~- + 16H+
Chlorides, bromides, iodides and other salts that precipitate sil" \)r
should be absent, as should also compounds which will react w, i h
permanganic acid_
Place a drop of the test solution in a micro-crucible, add 1 drop )f
ooncentrated sulphuric acid and 1 drop of O'lN -silver nitrate soluti, ,1,
26] Reactions of the M etallons or Oations 291
and stir. Introduce a few milligrams of solid ammonium persulphate
and heat gent/;y. The characteristic colour ofperroanganic acid appears.
Sensitivity: 0'1 fLg. Mn. Conc0ntration limit: 1 in 500,000.
tll. Formaldoxime Reagent (HCH = NOH): red coloration with
alkaline solution of manganous salts. Copper gives a blue-violet
coloration, but the interference can be overcome by the use of alkali
cyanide. Iron is best removed before applying the test (e.g. with a
suspension of zinc hydroxide or as the basic acetate), although it may
be rendered inactive by the addition of a tartrate. Chromium, cobalt
and nickel salts give colorations with the reagent and must therefore
be absent.
Place 2 ml. of the test solution, which has been rendered just alkaline
with 4N -sodium hydroxide, into a semimicro test-tube and add 1 drop
of the reagent. A red coloration is obtained.
Sensitivity: 0·25 p.g. (in 5 mI.). Concentration limit: 1 in 20,000,000.
The reagent consists of a 2·5 per cent solution of formaldoxime in
water.
; Ii
Dry Tests
(i) Borax bead test.-The bead produced in the oxidising
flame by small amounts of manganese salts is violet whilst
hot and amethyst-red when cold; with larger amounts of
manganese the bead is almost brown and may be mistaken
for that of nickel. In the reducing flame the manganese bead
is colourless whilst that due to nickel is grey.
(ii) Fusion test.-Fusion of any manganese compound with
sodium carbonate and an oxidising agent (potassium chlorate
or potassium nitrate) gives a green mass of alkali manganate.
The test may be carried out either by heating upon a piece of
platinum foil with potassium nitrate and sodium carbonate (if
platinum foil is not available, a piece of broken porcelain may
be employed), or by fusing a bead of sodium carbonate with a
small quantity of the manganese compound in the oxidising
flame and dipping the fused mass while hot into a little
powdered potassium chlorate or nitrate and reheating (coml,are
Section II, 1).
Mn804 + 2KNO a + 2Na2COS
= Na2Mll04 + 2KN02 + Na2S04 + 2C0 2
3Mn804 +
2KClO g +
6Na2COg
= 3Na2l\1n04 + 2KCI + 3Na2S04 + 6C0 2
ZINC, Zn
Zinc is a bluish-white metal; it is fairly malleable and ductile
at 110-150°. The pure metal dissolves very slowly in acids and in
alkalis; the presence of impurities, or contact with platinum or
292 Qualitative Inorganic Analysis [III,
copper, produced by the addition of a few drops of the solution, of
the salts of these metals, accelerates the reaction. This expllns
the solubility of commercial zinc. The latter dissolves readil.' in
dilute hydrochloric and in dilute sulphuric acid, with the evolu' <)n
of hydrogen. Solution takes place with very dilute nitric acid, i Jut
no gas is evolved; with increasing concentration of acid, nib .us
oxide or nitric oxide is evolved, depending upon the concentrati n;
concentrated nitric acid has very little action owing to the \ ry
slight solubility of zinc nitrate. Sulphur dioxide is evolved " Lh
hot concentrated sulphuric acid. Zinc also dissolves in solution·· of
caustic alkalis with the evolution of hydrogen and the formatiOl' of
zincates.
Zn + H 2SO, = ZnSO, +Hz:
4Zn + IOHNO a = 4Zn{NO a)1 +NH,NO a +
3HaO;
4Zn + IOHN0 3 = 4Zn{NO a)z +NzO +5H IO:
3Zn + 8HN0 3 = 3Zn(NO ah + 2NO + 4H 20:
Zn + 2H zSO, = ZnSO, + SOl + 2H zO;
Zn + 2NaOH = Na2[Zn02] + HI
Only one series of salts is known; these may be regarded as
derived from the oxide ZnO.

111,27. REACTIONS OF THE ZINC ION, Zn ++

Use a solution of zinc sulphate, ZnS04,7H 20. (Zinc com-
pounds are usually colourless in aqueous solution: the j·,n
[Zn(H 20 )4] + + or Zn + + is colourless.)
1. Sodium Hydroxide Solution: white gelatinous precil,i-
tate of zinc hydroxide Zn(OH)2' readily soluble in excess of
the reagent with the formation of sodium zincate (distinction
from manganese). The precipitate also dissolves in dilute acids
and is therefore amphoteric.
ZnS04 + 2NaOH = Zn(OH)2 + Na2S04;
Zn(OH)2 + 2NaOH ~ Na2[Zn02] + 2H2 0
2. Ammonia Solution: white precipitate of zinc hydroxid,·,
readily soluble in excess of the reagent and in solutions ,f
ammonium salts owing to the production of complex COl,)-
pounds. The non-precipitation of zinc hydroxide by ammon ia
solution in the presence of ammonium chloride is due to tho
lowering of the hydroxyl ion concentration to such a vailio
that the solubility product of Zn(OHh is not attained (compa) II
Section I, 16).
ZnS04 + 2NHs + 2H2 0 ~ Zn(OHh + (NH4)2S04;
Zn(OH)2 + 4NHs ~ [Zn(NHs)4](OH)2
27] Reactions of the Metal Ions or Gationa 293
3. Ammonium Sulphide Solution*: white precipitate of
zinc sulphide ZnS from neutral or alkaline solutions; it is
insoluble in excess of the reagent, in acetic acid and in solutions
of caustic alkalis, but dissolves in dilute mineral acidE-. The
precipitate thus obtained is partially colloidal; it is difiicult to
wash and tends to run through the filter paper, particularly
on washing. To obtain the zinc sulphide in a form which can
be readily filtered, the precipitation is conveniently canied out
in boiling solution in the presence of excess of ammonium
chloride, and the precipitate washed with dilute ammonium
chloride solution containing a little ammonium sulphide.
ZnS04 + NH4HS + NHa = ZnS + (NH4)2S04
4. Hydrogen Sulphide: partial precipitation of zinc sul-
phide in neutral solutions; when the concentration of acid
produced is about 0·3 . M (pH about 0·6), the sulphide ion con-
centration derived from the hydrogen sulphide is depressed so
much by the hydrogen ion concentration from the acjd that
it is too low to exceed the solubility product of ZnS, and con-
sequently precipitation ceases. Upon the addition of alkali
acetate to the solution, the hydrogen ion concentntion is
reduced because of the formation of the feebly dissociated acetic
acid, the sulphide ion concentration is correspondingly in-
creased, and precipitation is almost complete (compare Section
I, 16). Zinc sulphide is precipitated from solutions of alkali
zincates by hydrogen sulphide.
ZnS04 + H 2S ~ ZnS + H 2S04
2Na.C 2H sOz + H 2S04 = 2H.C2Ha02 + Na2S04
Na2[Zn02] + H 2S ~ ZnS + 2NaOH
5. Sodium Phosphate Solution: white precipitate of zinc
ammonium phosphate Zn(NH4 )PO, in the presence of ammo-
nium chloride; the precipitate is soluble in ammonia solution
and in dilute acids.
ZnS04 + NH4CI + 2Na zHP04
~ Zn(NH4)P04 + NaH2P0 + Na S04 + NaCI
4 Z

6. Potassium Ferrocyanide Solution: white precipitate

of zinc ferrocyanide Zn 2[Fe(CN)6]' which is converted by excess
of the reagent into the less soluble zinc potassium ferrocyanide
ZnaK2[Fe(CN)6]z.
2ZnS04 + ~[Fe(CN)6] = Zn2[Fe(CN)6] + 2KllSO <1
3Zn2[Fe(CN)6] + ~[Fe(CN}6] = 2ZnaKz[Fe(CN)a]z
• Use colourless BIllmonium sulphide: _ Section III, 24, reaction 2.
294 Qualitative Inorganic Analysis [III,
The precipitate is insoluble in dilute acids, but dissolves in
solutions of caustic alkalis: \
Zn2[Fe(CN)6] + 8NaOH = 2Na2[Zn02] + Na4[Fe(CN)6] + 4H2 0
7. Quinaldinic Acid Reagent (Quinoline-oc-carboxylic at' '1,
C9H6N. C0 2H).-Upon the addition of a few drops of the ,<)-
agent to a solution of a zinc salt which is faintly acid Wi h
acetic acid, a white precipitate of the zinc complex f:, I.t
Zn(CloH6N02)2,H20 is obtained. The precipitate is solui :e
in ammonia solution and in mineral acids, but is reprecipitai . d
on neutralisation. Copper, cadmium, uranium, iron a.d
chromium ions give precipitates with the reagent and Shal d
be absent. Cobalt, nickel and manganese ions have no effe ',.
This is an extremely sensitive test for zinc ions, and is a use: 'il
confirmatory test for zinc isolated from the Group IUB sepal j-

tion. The reagent is, however, expensive. The reaction is

best carried out on the semimicro scale or as a spot test.
The reag,ent is prepared by neutralising 1 gram of qui ,-
aldinic acid with sodium hydroxide solution and diluting \ \)
100 m!.
8. Ammonium Mercuri-thIocyanate-Copper Sulphate
Test.-The faintly acid (sulphuric acid or acetic acid) solutil·a
is treated with 0·5 m!. of 0·1 per cent copper sulphate solutio:"
followed by 2 m!. of the ammonium mercuri-thiocyanate 1"-
agent. A violet precipitate is obtained. The test is render.', l
still more sensitive by boiling the mixture for 1 minute, cooliJ, ~~
and shaking with a little amyl alcohol: the violet precipita: oj

collects at the interface. Iron salts produce a red coloratioJ; .

this disappears when a little alkali fluoride is added.
Copper salts alone do not give a precipitate with the amm(:·
nium mercuri-thiocyanate reagent, whilst zinc ions, if present
alone, form a white precipitate of zinc mercuri-thiocyanate:
Zn++ + [Hg(SCN)4r- = Zn[Hg(SCN)4]
In the presence of copper ions, the copper complex coprecip
tates with that of zinc, and the violet (or blackish-purpl( I
precipitate consists of mixed crystals of Zn[Hg(SCN)4] -i-
Cu[Hg(SCN)4]'
The ammonium mercuri-thiocyanate reagent is prepared by
dissolving 8 grams of mercuric chloride and 9 grams of ammo-
nium thiocyanate in 100 m!. of water.
t Place a drop or two of the test solution, which is slightly acid
(preferably with sulphuric acid), on a spot plate, add 1 drop of 0'1 pM
27] Reacticrn8 of the M etallons or Oatiom 295
cent copper sulphate solution and I drop of the ammonium mercuri-
thiocyanate reagent. A violet (or blackish-purple) precipitate appears.
The reaction may also be conducted in a semimicro test-tube: here
0'3-0·5 ml. of amyl alcohol is added. The violet precipitate collects at
the interface.
Concentration limit: 1 in 10,000.
9. Ammonium Mercuri-thiocyanate-Cobalt Sulphate
Test.-This test is similar to that described under 8, except
that a minute amount of a dilute solution of a cobalt salt
(sulphate, acetate or nitrate) is added. Coprecipitation of the
cobalt mercuri-thiocyanate gives a blue precipitate composed
of mixed crystals of Zn[Hg(SCN)4] +
Co[Hg(SCN),]. Ferric
salts give a red coloration (due to the ferri-thiocyanate ion
[Fe(SCN)J++) but this can be eliminated by the addition of a
little alkali fluoride (colourless [FeF6 r--
ions are formed).
Copper salts should be absent.
t Place a drop of the test solution (which should be slightly acid,
preferably with dilute sulphuric acid), a drop of 0·02 per cent cobalt
sulphate solution, and a drop of the ammonium mercuri-thiocyanate
reagent on a spot plate or in a micro crucible. A blue precipitate is
formed.
The reaction may also be carried out in a semimicro test-tube in the
presence of 0,3-0'5 ml. of amyl alcohol.
Sensitivity: 0'2-0·5 p.g. Zn. Concentration limit: 1 in 100,000.
tIO. Potassium Ferricyanide-p-Phenetidine Test_-Potassium
ferricyanide oxidises p-phenetidine (4-ethoxyaniline) and other aromatio
amines slowly with change of colour and the formation of potassium
ferrocyanide. If the ferrocyanide formed is removed by zinc ions as
the sparingly soluble, white zinc ferrocyanide, the oxidation proceeds
rapidly: the white zinc ferrocyanide is deeply coloured by the adsorption
of the coloured oxidation products.
Prepare the reagent by mixing 6 drops of 2 per cent potassium ferri-
cyanide solution, 2 drops of N sulphuric acid, and 6 drops of 2 per cent
p-phenetidine hydrochloride solution.
To 0'1 ml. of the freshly-prepared reagent on a spot plate, add a
drop of the test solution. A purple to blue coloration or precipitate
appears in the presence of zinc. A blank test is desirable.
Sensitivity: 1 p.g. Zn. Concentration limit: 1 in 100,O()0.
The test is especially useful in the presence of Cr, Al and Mg: cations
(Cu + +, Co + +, Ni + +, Fe + +, etc.) which give coloured precipitates with
potassium ferrocyanide should be absent.
tIl. Rinmann's Green Test.-The test depends upon the produc-
tion of Rinmann's green (largely cobalt zincate CoZnO z) by heating the
salts or oxides of zinc and cobalt. An excess of cobaltous oxide must
be avoided for it leads to a red-brown coloration: oxidation to cobaltic
oxide produces a darkening of colour. Optimum experimental con-
ditions are obtained by converting the zinc into the cobalticyanide:
Ka[Co(CN)6] + Zn++ = KZnrCo(CN).] + 2K+
 296 Qualitative Inorganic A nalym [III,
Ignition of the latter leads to zino oxide and cobaltous oxide in the
correct proportion for the fOl'IIl8.tion of cobalt zincate, whilst ca,! )on
- from the filter paper (see below) prevents the formation of cob, ltic
oxide. All other metals must be removed.
Place a few drops of the neutral (litmus) test solution upon POtasf: !lm
cobalticyanide (Rinmann'B green) test paper. Dry the paper ov, l' a
flame and ignite in a small crucible. Observe the colour of the ,sh
against a. white background: part of it will be green.
Sensitivity: 0·6 p,g. Zn. Concentration limit: 1 in 3,000.
The potassium cobalticyanide test paper is prepared by soa], I ng
drop reaction paper or quantitative filter paper in a solution contaiJ· 'lg
4 grams of potassium cobalticyanide and 1 gram of potassium chIO! :te
in 100 ml. of water, and drying at room temperature or at 100°. The
paper is yellow and keeps well.

Dry Tests
Blowpipe test.-Compounds of zinc when heated upon
charcoal with sodium carbonate give an incrustation of t1le
oxide, which is yellow when hot and white when cold. 'I,0
metal cannot be isolated owing to its volatility and subsequc' ,t
oxidation. If the incrustation is moistened with a drop ·,f
cobalt nitrate solution and again heated, a green mass (Rill-
mann's green), consisting largely of cobalt zincate CoZn02 l:'l
obtained.
An alternative method is to soak a piece of ashless filtt "
paper in the zinc salt solution, add one drop of cobalt nitra! '
solution and to ignite in a crucible or in a coil of platinum wir! .
The residue is coloured green.

DETECTION AND SEPARATION OF THE METALS IN THE ZINC GROU"

(GROUPIDB) .
As in previous groups, the student should obtain from the teacher.
or prepare for himself, a mixture of some or all of the simple solubJ(·
salts of the metals of this group. It is assumed that all the metal,
of the earlier groups are either absent or have been removed. Add
excess of ammonium chloride solution or 1-2 grams of solid ammo-
nium chloride, heat to boiling, add ammonia solution until alkaline
and then 1 ml. in excess, and pass hydrogen sulphide, pre·
ferably under pressure (Fig. II, 2, 1), for 30-60 seconds. Filter
immediately; the addition of a little filter paper pulp (e.g. as a
portion of a Whatman filtration accelerator) is beneficial. Test the
filtrate for complete precipitation. Wash the precipitate with 1 per
cent ammonium chloride solution containing a little saturated
hydrogen sulphide water. On occasion, the filtrate is dark-coloured
due to the production of colloidal nickel sulphide, which passes
through the filter. This is generally prevented by the use of
28) Reactions of the M etaZ Ions or Cations 297
macerated filter paper, but if it should occur, the filtrate must be
acidified with acetic acid and boiled for 30 seconds to coagulate
the nickel sulphide: the latter is filtered, washed and combined with
the main Group lIIB precipitate.

111,28. Table V. Analysis of the Zinc Group (Group IIIB)

The precipitate may contain CoS, NiS, MnS and ZnS. Wash the ppt.
with 1 % NH,el solution containing a little satur9ted HaS water. (T)
Transfer the ppt. to a small beaker and stir with cold dilute HOI (I volume
of concentrated acid: 11 volumes of water; ca. N) for 2-3 minutes.
Filter.
- -_ _._______ - - - - - - - - - - - - - - - - - - - - - - - - I

Residue. If black, Filtrate. May contain MnOl s and ZnCI.

may contain OoS and (plus, possibly, traces of CoCl s and NiOl s )' Boil
NiS. Test residue with until HIS removed (teat with lead acetate
borax bead. paper), cool, add excess of NaOH solution, 1
Blue bead. mI. of 3% H,Os solution, boil for 3 minutes
Co present. and filter.
Dissolve residue in a
mixture of 1·5 ml. of
10% NaOCI sol~ion Residue. Dark- Filtrate. May con-
and 0·5 ml. of "dilute coloured. May contain tain Na.[ZnO.].
HOI. Add 1 mI. of MnO s,xHsO (plus Divide into 2 parts.
dilute HOI and boil traces of Co(OH), and (i) Acidify with
until Ols is expelled. Ni(OH)s)' Dissolve the dilute acetic acid and
0001 and dilute to about ppt. in 5 mI. of dilute pass HsS,
4 ml. Divide into 2 HNO. with the addi- White ppt. of ZnS.
equal parts. tion of a few drops of Zn present.
(i) Add 1 mI. of amyl 3% HIO. solution. (ii) Just acidify
alcohol, 2 grams of solid Boil to decompose the with dilute HISO,.
NH,SON, and shake. excess ofR.O I . Then: Use 0·5 mI. of the
Amyl alcohol layer Either--Add 1 gram solution. Add 0·2
coloured blue. of Pb.O, and 3 mI. of mI. of dilute Co(NO.l.
Co present. concentrated HNO., solution and 0·5 mI.
(ii) Add 0'5 mI. of boil for 1 minute and of the ammonium
NH,CI solution, NH, allow to Bottle. mercuri-thiocyanate
solution until faintly Purple solution of reagent and stir.
alkaline, and then a HMnO,. Pale blue ppt.
little dimethylglyoxime Mn present. Zn present.
reagent. Or-To cold solution,
Red ppt. add 0·05-0·1 gram of
Ni present. NaBiO., shake and
allow to settle.
Purple solution of
HMnO,.
Mn present.

10*
 \
298 Qualitative Inorganic Analyau [III,
111,28. Table SMV. Analysis of the Zinc Group
(Group IIIB)
:------------------------
The ppt. may contain CoS, NiS, MnS and ZnS. it is not blat
If
CoS and NiS are absent. Wash the ppt. with 1% NH.Cl solution
which a little saturated H.S water has been added. (T) Stir the ppt.
the cold with 1 ml. of N-HCl (1 volume of concentrated acid: 10-12 pal'
of water) for 1-2 minutes. Centrifuge.

Residue. If black, Centrifugate. May contain MnCl. OJ 1

may contain CoS and ZnCl. (plus, possibly, traces of CoCl. OJ"l
NiS. Test residue with NiCI.).
borax bead. Transfer to a semimicro boiling tube, boil to
Blue bead. expel H.S (test with lead acetate paper), return
Co present. liquid to semimicro centrifuge tube, cool, add
Add 10-15 drops of excess of NaOH solution (0'5-1 mI.) and 4
dilute HCl and 5 drops drops of 3% H 20. solution; heat on a water
of 10% NaOCI solution, bath for 3 minutes. Centrifuge.
stir and place in a hot
water bath for 1-2
minutes. Transfer the Residue. Dark- Centrifugate. Me:
liquid with the aid of
1 ml. of water to a semi-
micro boiling tube and
coloured. May contain
MnO.,xH.O (plus
traces of Co(OH), and
contain Na.[ZnO.J.
Divide into 2 parts.
(i) Pass H.S.
I
boil gently to expel Cl •.
Divide the solution into
Ni(OH).). Dissolve the White ppt. of ZnS I
ppt. in 0·5 ml. of dilute Zn present.
2 parts. HN0 8 and a drop or Use either test (ii
(i) Add 0·5-1 ml. of two of 3% H 2 0. solu- or (iia).
amyl alcohol and 50 tion. Warm on a water (ii ) Just acidify with
mg. of solid NH,SCN, bath for 2-3 minutes dilute H.SO" add 5
and shake. to decompose excess of drops of 0·1 % CuSO.
Blue coloration in the H 20,; cool. Add 50 solution, and 5 drops
alcohol layer. mg. of NaBiO., shake of ammonium mer-
Co present.
(ii) Add 1 drop of
NH.CI solution, render
and allow to settle.
Purple solution of
HMnO,.
curi-thiocyanate re-
agent, and stir.
Violet ppt.
I
fa.intly alkaline with
NHa solution, and add
3-5 drops of dimethyl-
Mn present.
Alternatively, _dis-
solve the ppt. in 0·5 mI.
Zn present.
(iia) Just acidify
with dilute H.SO,.
I
glyoxime reagent. of dilute HNO. with add a drop of dilute
Red ppt. the addition of 1-2 cobalt acetate or
Ni present. drops of3% H 2 0. solu- nitrate solution, 0·5
tion. Transfer to a mI. of ammonium
semimicro boiling tube mercuri-thiocyanate
with the aid of 0·5 ml. reagent, and stir.
of water, and boil to Pale blue ppt.
decompose excess of Zn present.
H.O t • Cool, add 0·5
ml. of concentrated
HNO, and 250 mg. of
Pb.O,. Boil for 1
minute and allow to
stand.
Purple solution of
HMnO,.
Mn present.
29] Reactions of the Metal Ions or Oationa 299
THE CALCIDM GROUP (GROUP IV)
BARIUM, STRONTIUM AND OALOIUM
This group comprises the three alkaline earth metals; they are distinguished
from the metals of the preceding groups by the fact that their salts are not
precipitated by the group reagents for Groups I, II, IlIA and IIIB, and are
characterised by their precipitation with ammonium carbonate solution in the
presence of moderate concentrations of ammonium chloride and ammonia
solutions.
BARIUM, Ba
Barium is a silver-white, malleable and ductile metal, which is
stable in dry air. It reacts with water at the ordinary temperature
forming barium hydroxide and liberating hydrogen. The metal is
soluble in acids with the evolution of hydrogen.

111,29. REACTIONS OF THE BARIUM ION, Ba++

Use a solution of barium chloride, BaCl 2 ,2H 2 0.
1. Ammonia Solution: no precipitate of barium hydroxide
because of its relatively high solubility. * If the alkaline solu-
tion is exposed to the atmosphere, some carbon dioxide is
absorbed and a turbidity, due to barium carbonate, is pro-
duced.
2. Ammonium Carbonate Solutiont: white precipitate
of barium carbonate, soluble in acetic acid and in dilute mineral
acids.
BaCl2 + (NH4)2COS = BaCOs +
2NH4Cl
The precipitate is slightly soluble in solutions of ammonium salta
of strong acids: this is because the ammonium ion, being a strong
acid, reacts with- the base, the carbonate ion COs --, leading to the
formation of the bicarbonate ion HCO s-, and hence the carbonate
ion concentration of the solution is decreased:
NH,+ + CO a-- F NHs + HCO a-
or NH,+ + BaCO a F NHa + HCO s- + Ba++
If the amount of barium carbonate precipitate is very small, it may
well dissolve in high concentrations of ammonium salts.
3. Ammonium Oxalate Solution: white precipitate of
barium oxalate BaezO" slightly soluble in water (0'09 g. per
litre; S.P. 1'7 X 10-7 ), but readily dissolved by hot dilute
acetic acid (distinction from calcium) and by mineral acids.
BaClz + (NH4)2C204 = BaC20 4 + 2NH4CI
• A slight turbidity is due to small amounts of ammonium carbonate often
present in the reagent.
t Or a solution of any soluble carbonate.
300 Qualitative Inorganic Analyaia [III,
4. Dilute Sulphuric Acid: heavy, white, finely-divid!H!
precipitate of barium sulphate BaS04, practically insoluble ii'
water (2'5 milligrams per litre; S.P. 1·2 X 10- 10), almost il
soluble in dilute acids and in ammonium sulphate solution, an 1
appreciably soluble in boiling concentrated sulphuric acid. B \
precipitation in boiling solution or preferably in the presew
of ammonium acetate, a more readily filterable form is obtaine( I
BaCl2 + H 2S04 = BaS04 + 2HCl
BaS04 + H 2S04 (conc.) ~ Ba(HS04)2
If barium sulphate is boiled with a concentrated solution of sodium car-
bonate, partial transformation into the less soluble barium carbonate OCCU/'6
in accordance with the equation:
BaSO, + Na.CO s ~ BaCO s +Na.SO,
Owing to the reversibility of the reaction, the transformation is incompletc'.
If the mixture is filtered and washed (thus removing the sodium sulphate".
and the residue boiled with a fresh volume of sodium carbonate solution, mor,
of the barium sulphate will be converted into barium carbonate. By repetl
tion of this process, practically all of the sulphate can be converted into th,
corresponding carbonate. The carbonate may be dissolved in acids; thi
process therefore provides a method for bringing insoluble sulphates int,
solution. A more expeditious method of obtaining the same result is to fus·
the barium sulphate with 4--6 times its weight of anhydrous sodium carbonate.
the maximum concentration of carbonate is thus obtained and the reactiOl
proceeds almost to completion in one operation (compare Law of Mass Action
Section I, 9). The melt is allowed to cool, extracted with boiling water an"
filtered; the residue of barium carbonate can then be dissolved in the appro
priate acid. It has been stated that by boiling barium sulphate with at leas!
15 times its equivalent weight of I-2M sodium carbonate solution, 99 pel
cent is converted into barium carbonate in 1 hour.
5. Saturated Calcium Sulphate Solution: immediate
white precipitate of barium sulphate. A similar but more
trustworthy result is obtained with saturated strontium sul-
phate solution.
CaSO, + BaC12 = BaS04 + CaC12
6. Potassium Chromate Solution: yellow precipitate of
barium chromate BaCrO" practically insoluble in water (3'8
milligrams per litre; S.P. 2·3 X 10-1 °) and in dilute acetic acid
(distinction from strontium and calcium), but readily soluble
in mineral acids (compare Sections I, 17 and IV, 23).
+
K 2C'r04 BaCl2 = BaCr04 2KCl +
The addition of acid to potassium chromate solution causes the
yellow colour of the solution to change to reddish-orange due to
the formation of dichromate: '
2CrO,-- + 2H+ ~ 2HCrO,- ~ Cr 20 7- - + HIO
Upon adding a base (e.g. OH- ions) to a dichromate, the H+ ions
will be removed, the reaction will proceed from right to left, i.e.
 29] Reactions of the Metal Ions or Oations 301
chromate will form. In the presence of a large concentration of
hydrogen ions, the chromate ion concentration wil] be reduced to
such a value that the solubility product of BaCrO, will not be
attained. Hence to precipitate Ba ++ ions as BaCrO" strong acids
must be removed or neutralised. The addition of sodium acetate
acts as a buffer by reducing the hydrogen ion concentration and
complete precipitation of BaCrO, will take place.
The solubility products for SrCrO, and CaCrO, are much larger
than for BaCr04 and hence they require a larger CrO, -- ion con-
centration to precipitate them. The addition of acetic acid to the
K2Cr04 solution lowers the Cr04-- ion concentration sufficiently to
prevent the precipitation of SrCrO, and CaCr04 but is miLintained
high enough to precipitate BaCrO,.
t7. Sodium Rhodizonate Reagent
CO-Co-o.ONa)
I II
( CO-CO-C.ONa :

reddish-brown precipitate of the barium salt ofrhodizonic acid in neutral

solution. Calcium and magnesiwn salts do not interfere: strontium
salts react like those of barium, but only the precipitate due to the
former is completely soluble in dilute hydrochloric acid. Other
elements, e.g. those precipitated by hydrogen sulphide and by ammo-
nium sulphide, should be absent. The reagent should be confined to
testing for elements in Group IV (calcium group).
Place a drop of the neutral or faintly acid test solution upon drop-
reaction paper and add a drop of the reagent. A brown or reddish-
brown spot is obtained.
Sensitivity: 0·25 fLg. Ba. Concentration limit: 1 in 200,000.
The reagent consists of a 0'5 per cent aqueous solution of sodium
rhodizonate. It does not keep well so that only small quantities should
be prepared at a time.
In the presence of strontium the reddish-brown sta.in of barium
rhodizonate is treated with 0'5N -hydrochloric acid; the strontium
rhodizonate dissolves, whilst the barium derivative is converted into
the brilliant red acid salt. The reaction is best carried out on drop-
reaction paper as above.
Treat the reddish-brown spot with a drop of 0'5N hydrochloric acid
when a bright red stain is formed if barium is present. If barium is
absent, the spot disappears.
Sonsitif7'tr: 0-.7(£g. Ba in the pJ'[>~«eDce oj' [>0 times the amount of Sr.
Concentration limit: 1 in 90,000.

Dry Test II
Flame coloration.-Barium salts, when heated in the non-
luminous Bunsen flame, impart a yellowish-green colour to the
flame. Since most barium salts, with the exception of the
chloride, are non-volatile, the platinum wire is moistened with
concentrated hydrochloric acid before being dipped into the
302 Qualitative Irwrganic AnalY8i8 fIll,
substance. The sulphate is first reduced to the sulphide in t,he
reducing flame, then moistened with concentrated hydrocM ,ric
acid, and re-introduced into the flame.

STRONTIUM, Sr
Strontium is a silver-white, malleable and ductile metal. Its
properties are similar to those of barium.

III, 30. REACTIONS OF THE STRONTIUM ION, S1' f- +

Use a solution of strontium chloride, SrCI 2 ,6H 20.
1. Ammonia Solution: no precipitate.
2. Ammonium Carbonate Solution: white precipitate of
strontium carbonate SrCO a, less soluble in water than barilJ m
carbonate. Its slight solubility in ammonium salts of str( ng
acids is similar to that of BaCO a (see Section III, 29, reaction !).
3. Dilute Sulphuric Acid: white precipitate of strontium
sulphate SrS04' very sparingly soluble in water (0'1l0 g. J>{~r
litre; S.P. 3·6 X 10-7 ), insoluble in ammonium sulphate SO't-
tion even on boiling (distinction from calcium) and sligh' Y
soluble in boiling hydrochloric acid. It is almost complett :y
converted into the corresponding carbonate by boiling with 1
concentrated solution of sodium carbonate.
SrS04 + Na2COa ;;:= SrCOa + Na2S04
4. Saturated Calcium Sulphate Solution: white precipi-
tate of strontium sulphate, formed slowly in the cold but more
rapidly on boiling (distinction from barium).
5. Ammonium Oxalate Solution: white precipitate of
strontium oxalate, sparingly soluble in water (0'66 g. per litr\' ;
S.P. 1·4 X 10-7 ) and in acetic acid, but soluble in mineral acid,.
6. Potassium Chromate Solution: yellow precipitate of
strontium chromate SrCr04 from concentrated solutions; the
precipitate is appreciably soluble in water (1·2 grams per litre)
and in acetic acid. No precipitation therefore occurs in dilute
solutions nor from concentrated solutions containing acetic:
acid (distinction from barium; see Section III, 29, reaction 6).
t7. Sodium Rhodizonate Reagent: reddish·brown precipitate of
strontium rhodizonate in neutral solution. The test is applied to the)
elements of Group IV (calcium group). Barium reacts similarly and a
method for the detection of barium in the presence of strontium ha~
already been described (Section III, 29, reaction 7). To detect stron-
tium in the presence of barium, the latter is converted into the insoluble
31] Reactio'M of the Metal lona Of" Oation8 303
barium ohromate. Barium ohromate does not react with sodium
rhodizonate, but the more soluble strontium ohromate reacts normally.
If barium is absent, plaoe a drop of the neutral test solution on
drop-reaction paper or on a spot plate, and add a drop of thll reagent.
A brownish.red coloration or precipitate is produced.
Sensitivity: <1 f-Lg. Sr. Concentration limit: 1 in 13,000.
If barium is present, prooeed as follows. Impregnate some quanti'
tative filter paper or drop-reaction paper with a. saturated solution of
potassium chromate, and dry it. Place a drop of the test solution on
this paper and, after a minute, place 1 drop of the reagent on the
moistened spot. A brownish-red spot or ring is formed.
Sensitivity: 4 f-Lg. Sr in the presence of 80 times the amount of Ba.
Concentration limit: 1 in 13,000.
For further details of the reagent, see under Barium, Section III, 29,
reaction 7.

Dry Test
Flame coloration.-Volatile strontium compounds, especially
the chloride, impart a characteristic carmine-red colour to the
non-luminous Bunsen flame (see remarks under Barium).
CALCIUM, Ca
Calcium, like the other elements of this group, is a silver-white
metal and possesses similar properties. It is, however, only slightly
attacked by concentrated nitric acid.

111,31. REACTIONS OF THE CALCIUM ION, Ca ++

Use a solution of calcium chloride, CaCI 2 ,6H 20.
1. Ammonia Solution: no precipitate. The result is
similar to that for barium ions.
2. Ammonium Carbonate Solution: white amorphous
precipitate of calcium carbonate CaC0 3 , which becomes
crystalline on boiling. The precipitate is soluble in water
containing excess of carbonic acid, due to the formation of
the soluble bicarbonate. This remark applies also to the car-
bonates of strontium and barium.
CaCO a + H 20 + CO2 ~ Ca(HCOs )2
Calcium carbonate is slightly soluble in solutions of ammonium
salts of strong acids {compare BaC0 3 , Section 111,29, reaction
2}.
3. Dilute Sulphuric Acid: white precipitate of calcium
sulphate CaS04,2H 2 0 from concentrated solutions (see re-
action 10 below). The precipitate is appreciably soluble in
I II
304 Qualitative Inorganic AnalY8i8 [III,
water (2'0 grams per litre at 25°; S.P. 2·3 X 10-4 ), is more
soluble in acids than either strontium or barium sulphates,
and is readily soluble in hot concentrated ammonium sulphat n
solution owing to the formation of a complex salt (distinctiOlI
from strontium).
CaSO, + (NH4)2S04 = (NH4 MCa(SO')2J
4. Saturated Calcium Sulphate Solution: no precipitate
(difference from strontium and barium).
5. Ammonium Oxalate Solution: white precipitate of
calcium oxalate CaC 2 0 4 ,H 20, immediately from concentrated
solutions and slowly from dilute solutions. Precipitation b
facilitated by making the solution alkaline with ammoni"
solution. The precipitate is practically insoluble in water (~,
milligrams per litre at 20°; S.P. 3-8 X 10-9 ), insoluble in aceti!
acid, but readily dissolved by mineral acids (compare Secti01
I, 17).
6. Potassium Chromate Solution: no precipitate in dilut(
solutions (solubility 23 grams per litre) nor from concentrated
solutions containing free acetic acid (compare Section III, 29,
reaction 6).
7. Potassium Ferrocyanide Solution: white precipitate
of calcium potassium ferro cyanide CaK 2[Fe(CN)o] is produced
by excess of the reagent. The test is more sensitive in the
presence of excess of ammonium chloride solution; a white
precipitate of calcium potassium ammonium ferrocyanide of
variable composition is formed (distinction from strontium).
Large amounts of barium and of magnesium interfere, since
they give a similar reaction.
CaCl 2+K 4[Fe(CN)6] = CaK 2 [Fe(CN)6] 2KCI +
t8. Sodium Dihydroxytartrate Osazone Reagent
Ca H 6. NH - N =C-COONa) :
( CaH6.NH-N=~-COONa
yellow sparingly-soluble precipitate of the calcium salt. All other
metals, with the exception of alkali and ammonium salts, must be
absent. Magnesium does not interfere provided its concentration does
not exceed 10 times that of the calcium.
Place a drop of the neutral test solution on a black spot plate or upon
a. black watch glass, and add a tiny fragment of the solid reagent. If
calcium is absent, the reagent dissolves completely. The presence of
calcium is revealed by the formation over the surface of the liquid of a
white film which ultimately separates as a dense precipitate.
Sensitivity: 0·01 /Lg. Ca. Concentration limit: I in 5,000.000.
31) Reaction8 of the Metal Iona or Oations 305
The reagent is useful inter alia for the rapid differentiation between
tap and distilled water: a positive result is obtained with a mixture of
I part of tap water and 30 parts of distilled water.
t9. Picrolonic Acid (or I-p-Nitrophenyl-3-methyl-4-nitro-5-
pyrazolone) Reagent

characteristic rectangular crystals of calcium picrolonate

Ca(C 1oH7 0 6N 4) 2,8H 20
in neutral or acetic acid solutions. Strontium and barium give pre-
cipitates but of different crystalline form. Numerous elements, includ-
ing copper, lead, thorium, iron, aluminium, cobalt, nickel and barium,
interfere.
Place a drop of the test solution (either neutral or acidified with acetic
acid) in the depression of a warm spot plate and add 1 drop of a saturated
aqueous solution of picrolonic acid. Characteristic rectangular crystals
are produced.
Sensitivity: 100 fLg. (in 5 mI.). Concentration limit: 1 in 50,000.
The sensitivity is 0·01 fLg. (in 0·01 mI.) under the microscope.
tlO. Calcium Sulphate DIhydrate (Microscope) Test.--This is
an excellent confirmatory test for calcium in Group IV; it involves
the use of a microscope (magnification about 110 x). The salts should
preferably be present as nitrates.
Evaporate a few drops of the test solution on a watch glass to dryness
on a water bath, dissolve the residue in a few drops of water, transfer
to a microscope slide, and add a minute drop of dilute sulphuric acid.
(It may be necessary to wann the slide gently on a water bath until
crystallisation just sets in at the edges.) Upon observation through a
microscope, bundles of needles or elongated prisms will be visible if
calcium is present.
Concentration limit: 1 in 6,000.
It may be noted that barium and strontium nitrates are practically
insoluble in absolute ethyl alcohol and also in 83 per cent nitric acid,
whilst calcium nitrate is very soluble in absolute alcohol and fairly
soluble in the concentrated nitric acid. The best method for S(lparating
Sr and Ca makes use of 83 per cent nitric acid (see the various Group IV
separation tables).
Dry Test
Flame coloration.--Volati1e calcium compounds impart a
yellowish-red colour to the Bunsen flame (see remarks under
Barium).
306 Qualitative Irwrganic Analysis [HI,
DETECTION AND SEPARATION OF THE METALS IN THE CALCIUM QR ,op
(GROUP IV)
It is assumed that the metals of Groups I to lIIB have ken
removed as already described, or that only metals of the alkali ne
earth group are present. As in previous group separations, ; ile
student should prepare or obtain from the teacher a solution c,'n-
taining some or all of the simple salts of the metals of Group [V.
The filtrate from Group HIB, if employed, should be evapora ! nd
to dryness (moist paste) in an evaporating dish [FUME Gl 'P-
BOARD], allowed to 0001, and about 4 ml. of concentrated nil ric
acid added slowly and in such a manner as to wash down the ve-
oipitate on the sides to the bottom of the dish. Evaporation is
then continued cautiously until dry and then more strongly Ul. I il
no more fumes of ammonium chloride are evolved. The residw IS
allowed to cool, dissolved in a little dilute hydrochloric acid, tra '';'
ferred to a test-tube, and a little ammonium chloride solution add 11.
The clear solution may then be treated with ammonia solution Ulilil
alkaline and Group IV precipitated with ammonium carbonate
solution.
The reason for the above operation is that the filtrate from Group
lIIB contains a very high concentration of ammonium salts-far
higher than is necessary to prevent the precipitation of magnesium
hydroxide. The excessive concentration of ammonium ions will
lower the COg -- ion concentration of the solution (when ammonium
carbonate solution is added) to such an extent that appreciable
amounts of the carbonates of Ba, Sr and Ca may not be precipitated:
CO s-- + NH, + ~ NHa + HCO a-
The effect is due to the acidic properties of the ammonium ion, which
acts as a donor of protons to the carbonate ion. For this reason, it
is recommended that practically all the ammonium salts be elimina-
ted with concentrated nitric acid:
NH, + + NOs - ? NH,NO a = N sO + 2HaO
The latter reaction takes place at a lower temperature than thil (
necessary to remove ammonium salts by sublimation.
It may be noted that the precipitation with ammonium carbonat"
takes place in hot solution, due to the fact that the carbonates al I'

thus obtained in a more granular form and are therefore more easil\
filtered and washed. The solution must not be boiled as th I "
decomposes the reagent and may result in some redissolution of tIl'
car bonates:
(NH,)aCOa = 2NHa + COs + H 20
BaCO s + 2NH,CI = BaCIa + 2NHa + CO 2 + HaO
When reprecipitating SrCO s and/or CaCO s in the subsequent
separation, it is probably better to use a little Na2COa thaI.
(NH')2 CO a'
32] Reactions of the Metal Ions or Oations 307

111,32. Table VI. Analysis of the Calcium Group

(Group IV)
Add 1-2 mI. of NH,CI solution, NH3 solution until just basic, followed
by (NH.).CO. solution lmtil precipitation is complete. Heat on a water
bath, with stirring, at 60-70 0 G for 5 minutes. Filter, wash with a little
hot water and discard the filtrate and washings.
The residue may contain BaCO., 8rCO. and CaCO.. (T) Dissolve
the ppt. in 5 mi. of hot 2N acetic acid by pouring the acid repl·atedIy
through the filter paper. Test 1 mI. for barium by adding J".CrO,
solution dropwise to the nearly boiling solution. A yellow ppt. indicates
Ba.
Ba present.-Heat the remainder of the solution almost to boiling,
and add a slight excess of K.CrO. solution (i.e. until the solution assumes
a yellow tint). Filter and wash tho ppt. (G) with a little hot water.
Render the hot filtra.te and washings basic with NHs solution and add
an excess of (NH.l.Cv 3 solution or, better, a little solid Na.CO.. A
white ppt. indicates the presence of 8rC0 3 and/or CaC0 8 • Wash the
ppt. with hot water, and dissolve it in 4 mI. of warm 2N.acetic acid:
boil to remove excess of CO. (solution A).
Ba absent.-Discard the portion used in testing for barium, and
employ the remainder of the solution (B), after boiling for 1 minute to
expel CO 2, to test for strontium and calcium.
Residue (G). Solution A or Solution B. The volume
Yellow: BaCrO•. should be about 4 ml.
Wash well with hot Either-To 2 ml. of the cold solution, add 2 ml.
water. Dissolve the of saturated (NII,).SO. solution, followed by 0·2
ppt. in a little con- gram of sodimD thiosulphate, heat in a b ..aker of
centrated HCl, evapo- boiling wster for 5 minutes, and allow to stand
rate almost to dry. for a short time. Filter.
ness, and apply the Or-To 2 ml. of the solution, add 2 mi. of trio
flame test. ethanolamine, 2 ml. of saturated (NH,).SO,
Green (or yellowish. solution, heat on a boiling water bath with
green) flame. vigorous stirring for 5 minutes, and allow to stand
Ba present. for 1-2 minutes. Dilute with an equal volume
(Use spectroscope, of water and filter.
if available.) - - - - - ----_._;------_._---
Residue. Largely Filtrate. May
81'80,. Wash with a little contain Ca complex.
water. Transfer ppt. and (If 81' absent, use
filter paper to a small 2 ml. of solution A
crucible, heat until paper or E.) Add a little
has charred (or burn filter (NH')2C20, solution*
paper and ppt., held in a and warm on a water
Pt wire, over a crucible), bath.
moisten ash with a few White ppt. of
drops of concentrated CaC 20,.
HCI and ap}'ly the flame Ca present..
test. Confirm by flame
Crimson flame. test on ppt.-brick-
Sr present. red flame.
(Use spectroscope, if (Use spectroscope,
available.) if available.)

* When triethanolamine has been employed in the separation of Sr and Ca,

the addition of a little acetic acid (i.e. until the solution is faintly acid) may
uasist the precipitation of the CaG.O,.
308 Qualitative Inorganic Analysis [lIT,
111,32. Table SMVI. Analysis of the Calcium Group
(Group IV)
Add a few drops of NH.CI solution, render alkaline with concentrated
NHa solution and add, with stirring, 0·5 ml. of (NH.).CO s solution (1). II
Heat on a water bath to 60-70°0, with stirring, for several minutes.
Centrifuge. I
Residue. May contain BaCO a, SrCO a and CaCO a. !' Centrifugate.
Wash with a little hot water and reject washings. (T) Discard. I

Treat the ppt. with 0·5 mi. of dilute acetic acid and stir. I

Place in a hot water bath until the ppt. has dissolved. ~

Dilute with 0·5 mi. of water. Test 3-4 drops of the hot '
solution for barium by adding a drop or two of K.CrO,
solution. A yellow ppt. (BaCrO.) indicates Ba present.
Ba present.-To the remainder of the hot solution add a slight excess
of K.CrO. solution (i.e. until the solution acquires an orange tint), and
separate the ppt. of BaCrO, (0) by centrifugation. Render the centri·
fugate alkaline with NHa solution, and add excess of (NH,).CO a
solution or, better, a little solid Na.CO a. Place the tube in the hot
water bath. A white ppt. indicates SrCO a and/or CaCO a. Centrifuge
and wash with a little hot water. Dissolve the ppt. in 0·5-1 mi. of
dilute acetic acid, and place the tube in a hot water bath to remove
the excess of CO 2 (solution A).
Ba absent.-Discard the portion used in testing for barium, and
employ the remainder of the solution (B) in testing for strontium and
calcium after heating on a water bath for a few minutes to expel CO 2 ,
Residue (0). Solution A or Solution B. Adjust volume
Yellow: BaCrO,. to 2 ml. (solution D) by evaporation or dilution
Wash with hot as necessary.
water. Dissolve in a Either-To 1 mi. of solution, add 1 mi. of
few drops of concen- saturated (NH.).SO. solution followed by 0·1
trated HCI, evaporate gram of sodium thiosulphate, heat on a water
almost to dryness in bath for 5 minutes, and allow to stand for a
a small crucible, and short time. Centrifuge.
apply the flame test. Or-To 1 mI. of solution, add 1 ml. of tri-
Green( or yellowish- ethanolamine and 1 ml. of saturated (NH.).SO,
green) flame. solution, heat on a w~ter bath with stirring for
Ba present. 5 minutes, and allow to stand for 1-2 minutes.
(Use spectroscope, Centrifuge.
if available.)
Residue. Largely Centrifugate.
SrSO.. Wash with a May contain Ca com·
little water. Stir the plex. (If Sr absent,
ppt. with 3-4 drops of use 1 ml. of solution
water, transfer the sus· D.) Addafewdrops
pension by means of a of (NH.).C.O. solu·
capillary dropper to 1 tion (2) and warm
sq. cm. of quantitative on a water bath.
filter paper contained in White ppt. of
a 5 mI. crucible. Ignite CaC,O •.
until paper has charred, Ca present.
add 1-2 drops of con- Confirm by flame
centrated HCI, and test-brick·red
apply the flame test. flame.
Crimson flame. (Use spectroscope,
Sr present. if available.)
(Use spectroscope if
available.)

Notes to Table SMVI on page 310.

32] Reactions of the M eta,l 10m or Oations 309
111,32. Table SMVIA. Analysis of Calcium Group
(Group IV)
Add a few drops of NH,Cl solution, make alkaline with concentrated
NH. solution and add, with stirring, 0·5 ml. of (NH,).CO. solution (1).
Heat on a water bath to 60-70°0, with stirring, for several minutes.
Centrifuge.
Residue. May contain Ba00 3, 81'00. and OaOO •. Centrifugate.
Wash well with a little hot water and reject washings. Discard.
(T) Treat the ppt. with 0·5 ml. of dilute acetic acid, place \
in a hot water bath and stir until dissolved. Dilute with

~
0·5 m!. of water. Test 3-4 drops of the hot solution for
barium by adding a drop or two of K 2 CrO, solution. A
yellow ppt. (BaCrO,) indicates Ba present.
Ba present.-To the remainder of the hot solution add a slight
excess of K.CrO, solution (i.e. until the solution just assumes an orange
tint), and centrifuge the ppt. ofBaCrO, (C). Transfer the centrifugate
(solution A) by means of a capillary dropper to another centrifuge tu be:
wash the ppt. with 0·5 ml. of water and combine the washings with
solution A.
Ba absent.-Discard the portion used in testing for barium, and
employ the remainder of the solution (B) in testing for strontium and
calcium after heating on a water bath for a few minutes to expel CO •.
Residue (0). Solution A or Solution B. Render alkaline
Yellow: BaOrO,. with NlI. solution, and add excess of (NlI,).CO.
Dissolve in a solution or, better, a little solid Na 2 00.. Place the
few drops of con- tube in a hot water bath. A white ppt. indicates
centrated ROI, the presence of SrCO. and/or CaC0 3 • Centri-
evaporate to dry- fuge: discard centrifugate. Wash with 0·5 m!. of
ness in a small hot water and centrifuge: remove the supernatant
crucible and liquid as completely as possible with a capillary
apply the flame dropper. Add 4 drops of 83% RNO. (2), and cool
test. Green (or in a stream of cold water from the tap. Add
yellowish-green) further 4-5 drop portions of 83% RNO., with
flame. stirring, from aT. K. dropping bottle until 2 mI. (3)
Ba present. are introduced. 8tir for 3-4 minutes, and centri-
(Use spectro- fuge.
scope, if avail-
able.) Residue. Centrifugate (D). May conteJ-n
White: Oa(~03)2' Transfer m08t of the
Sr(NO.) •. liquid to a semimicro boiling tube or a
Srpresent. small crucible, and evaporate almost
Confirm by to dryness (FUME CUPBOARD).
flame test. Transfer to a centrifuge tube with
Crimson the aid of 0·5-1 ml. of water,
flame. render alkaline with NH. solution,
(Use and add excess of (NR.).O.O.
spectro. solution (4). Allow to stand in a hot
scope, if water bath for 2-3 minutes.
available.) White ppt. of CaO,O,.
Ca present.
Centrifuge, and confirm Ca in the
ppt. by the flame test-brick-red
flame.
(Use spectroscope, if available.)
Alternatively, confirm Ca by the
OaSO.,2H.O (microscope) test (5).

Notes to Table SMVIA on page 310.

;uu 4!ualUatwe 1 norgantc A nalYSZ8 LI1J,

NOTES TO TABLE SMVI

Notes. (1) If the filtrate from Group IIIB is employed, it is necessary t
remove the excess of ammonium salts. Evaporate to a moist paste in ,
small crucible, allow to cool, add 1 ml. of concentrated RNO. (by means of "
dropper) around the walls of the crucible so as to wash most of the adheriL:
salt to the centre. Reat (FUME CUPBOARD) cautiously at first and the',
more strongly until no further fumes of ammonium salts are evolved. AlIo,
to cool, add 5 drops of dilute RCI and 15 drops of water, transfer the soluti(,,,
to a centrifuge tube, rinse the crucible with 10 drops of water and combiJ,,'
the rinsings with the solution in the tube. To the clear solution add a fe "
drops of NR,CI solution, render alkaline with concentrated ammonia solutio: ,
and add 0·5 ml. of (NR,).CO. solution with stirring. Reat on a water bath,
with stirring, at 60-70°0 for a few minutes. Centrifuge.
(2) If triethanolamine has been employed in the separation of Sr and Co.,
the addition of a little acetic acid until faintly acid may assist the precipitation.

NOTES TO TABLE SMVIA

Notes. (1) See Note 1 to Table SMVI.
(2) The 83 per cent RNO. (in which Sr(NO.). is almost insoluble) is preparpoi
by adding 100 grams (68·0 mI.) of concentrated RNO. (sp. gr. 1·42: ca. 70~"
to 100 grams (66·2 mI.) of fuming RNO. (sp. gr. 1·5: ca. 95%).
(3) The T.K. bottle, charged with 83 per cent RNO., should be calibrated.
The acid should be added dropwise to a clean 5 mI. measuring cylinder unt ,i
the 2 mi. mark is reached and the number of drops counted. It is advisab! ..
to place a small label on the T .K. bottle stating the number of drops per m'
(4) The addition of dilute acetic acid until faintly acid may assist tl·
precipitation of the CaO.O,.
(5) Place 1 drop of the centrifugate D on a microscope slide and add 1 dro:'
of dilute R.SO.. Concentrate by placing the slide on a micro crucible an l
warming gently until crystallisation just commences. Examine the crysta i,
in a microscope (magnification: ca. X 100). Bundles of needles or elongated
prisms confirm Ca.

THE ALKALI GROUP (GROUP V)

MAGNESIUM, SODIUM, POTASSIUM AND
AMMONIUM
The metals of this group are not precipitated by the earlier group reagent'
Sodium and potassium belong to the alkali metal group; ammonium '
included in this group since its compounds resemble those of the alkali metal·
particularly those of potassium. Magnesium, although associated with tl.
alkaline earths in the periodic table, is incorporated in this group becam
its carbonate is not precipitated by ammonium carbonate solution in tL
presence of ammoniwn chloride.

l\UGNESIUM, Mg
Magnesium is a white, malleable and ductile metal which burn"
in air or oxygen with a brilliant white light, forming the oxide Mg( I
and a little nit:ide MgsN 2 • The metal is slowly decomposed b.'
water at the ordinary temperature but rapidly at 100°. It is readily
soluble in acids liberating hydrogen. The salts may be regarde;!
as derived from the basic oxide MgO.
 33]
.~ ~)'!:; Pl_il_
Reactions of the Metal Ions or Oations 311

111,33. REACTIONS OF THE MAGNESIUM ION, Mg ++

Use a solution of magnesium sulphate, MgS04 ,7H 20.
1. Ammonia Solution: partial precipitation of white,
gelatinous magnesium hydroxide Mg(OH)2, very sparingly
soluble in water (12 milligrams per litre; S.P. 3·4 X 10- 11 ),
but readily soluble in solutions of ammonium salts.
MgSO" + 2NH3 + 2H zO ~ Mg(OH)z + (NH")zSO,,
As the reaction progresses, the concentration of the ammonium ions, due
to the dissociation of the completely ionised ammonium salt, increnses and
consequently the concentration of the hydroxyl ions decreases owing to the
common ion effect (compare Section I, 14). The small hydroxyl ion conaen-
tration, already low, is decreased still further so that much of the magnesium
salt remains in solution. In the presence of a sufficient concentration of
ammonium salts, the hydroxyl ion concentration is reduced to such an extent
that the solubility product ofMg(OH). is not exceeded (compare Sectic,n 1,15);
hence magnesiwn is not precipitated by ammonia solution in the prt'sence of
ammonium chloride or other ammonium salts.

2. Sodium Hydroxide Solution: white precipitate of mag-

nesium hydroxide, insoluble in excess of the reagent, but
readily soluble in solutions of ammonium salts.
3. Ammonium Carbonate Solution: white precipitate of
basic magnesium carbonate, often only on boiling or on long
standing. No precipitate is obtained in the presence of ammo-
nium salts of strong acids, since the high concentration of
ammonium ions will lower the C0 3 - - ion concentration of the
solution when ammonium carbonate is added to so low 11 value
that the solubility product of MgCO a (2·6 X lO-5) is not
attained:
• NH,,+ + C0 3- - ~ NHa + HCO s-
4. Sodium Carbonate Solution: white voluminous pre-
cipitate of basic carbonate 4MgCO a,Mg(OHh,5H 20 or
[Mg(MgCOa),,](OHh, insoluble in solutions of bases, but soluble
in acids and in solutions of ammonium salts.
5MgS04 + 5NazCOs + H 20
= 4MgCO a,Mg(OH)2 + 5NazSO, + CO 2

5. Sodium Phosphate Solution: white orystalline precipi-

tate of magnesium ammonium phosphate Mg(NH,)P0 4 ,6H zO
in the presence of ammonium chloride (to prevent the precipita-
tion of magnesium hydroxide) and ammonia solutions; the pre-
oipitate is sparingly soluble in water, soluble in acetio acid and
312 Ct!ua£~tatt.Ve 1 norgamc .ti naly8~8 111J.,
in mineral acids. The normal solubility of Mg(NH 4 )P04 ,6H 2 0
is increased by its hydrolysis in water:
Mg(NH4)P04 + H 20": Mg++ + HP0 4- - + NH g + H 20
this tendency is reduced by moderate amounts of ammonia (it
isfound that the compound is very sparingly soluble in 2'5 per
cent ammonia solution). The precipitate separates slo\\'ly
from dilute solutions because of its tendency to form su 'or-
saturated solutions; this may usually be overcome by coo mg
and by rubbing the test-tube or beaker beneath the surfac, of
the liquid with a glass rod.
A white flocculent precipitate of magnesium hydrogen plll)s-
phate MgHP0 4 is produced in neutral solutions.
MgS04 + Na zBP04 + NBs = Mg(NB4)P04 + Na2S04
MgS04 + Na zHP04 = MgBP04 + NazSO,
6. Diphenyl-carbazide Rea~ent (C6Ho.NH.NH.CO.~ 1[.-
NH.C6Ho).-The magnesium salt solution is treated ",th
sodium hydroxide solution-a precipitate of magnesium lly-
droxide will be formed-then with a few drops of the diphellyl-
carbazide reagent and the solution filtered. On washing ! he
precipitate with hot water, it will be seen to have acquit!, 1 a
violet-red colour, due to the formation of a complex salt OJ an
adsorption complex. Metals of Groups II and III interfere
and should therefore be absent.
The reagent is prepared by dissolving 0'2 gram of diphej,y]-
carbazide in 10 ml. of glacial acetic acid and diluting to i 00
ml. with rectified spirit.
7. 8-Hydroxy-quinoline or "Oxine" Rea~ent

(W}
When a solution of a magnesium salt, containing a lltlile
ammonium chloride, is treated with 1-2 ml. of the rea~"nt
which has been rendered strongly ammoniacal by the addil, Ion
of 3-4 ml. of dilute ammonia solution and the mixture hell! ed
to the boiling point, a yellow precipitate of the complex ,alt
Mg(C 9 H 6N.Ob,4H 2 0 is obtained. All other metals, ex, "pt
sodium and potassium, must be absent.
The reagent is prepared by dissolving 2 grams of oxine in
100 ml. of 2N acetio acid.
33J Reactions of the M etaZ Ions or Oations 313
8. para-Nitrobenzene-azo-resorcinol (or Magneson I)

Reagent.-This test depends upon the adsorption of the

reagent, which is a dyestuff, upon Mg(OHh in alkaline E<olution
whereby a blue lake (compare Section I, 43) is produced.
Two ml. of the test solution, slightly acid with hydrochloric
acid, is treated with 1 drop of the reagent and sufficient N
sodium hydroxide solution to render the solution f'trongly
alkaline, say 2-3 ml. A blue precipitate appears. This is an
excellent confirmatory test in macro analysis, but it is essential
to perform a blank test with the reagents, which frequently
yield a blue coloration. For this reason a blue precipitate
should be looked for. All metals, except those of the alkalis,
must be absent. Ammonium salts reduce the sensitivity of
the test by preventing the precipitation of Mg(OH hand
should therefore be eliminated.
The reagent (for macro analysis) consists of a 0'5 per cent
solution of p-nitrobenzene-azo-resorcinol in 0'25N sodium
hydroxide.
t The spot-test technique is as follows. Place a drop of the test
solution on a spot plate and add 1-2 drops of the reagent. It is essential
that the solution be strongly alkaline; the addition of 1 drop of N
sodium hydroxide may be advisable. According to the concentration
of magnesium a blue precipitate is formed or the reddish-violet reagent
assumes a blue colour. A comparative test on distilled water should
be carried out.
Sensitivity: 0'5 p.g. Mg. Concentration limit: 1 in 100,000.
Filter or drop-reaction paper should not be used.
The reagent is prepared by dissolving 0·001 gram of the dyestuff
in 100 ml. of N sodium hydroxide.
An alternative agent is para-nitrobenzene-azo-IX-naphthol or
Magneson II

It yields the same colour changes as Magneson I, but has the advantage
that it is more sensitive (sensitivity: 0'2 p.g. Mg; concentration limit:
1 in 250,000) and its tinctorial power is less so that the blank test is not
so deeply coloured. Its mode of use and preparation are identical with
that described above for Magneson r.
.11
·1
31<l Q'u.alitati'IJe InoTganic Anal,!/sis tIll,.
t9. Titan Yellow Reagent.-Titan yellow (also known as Clayt'l'l
Yellow and Thiazole Yellow) is a water-soluble yellow dyestuff. It,
adsorbed by magnesium hydroxide producing a deep red colour .('
precipitate_ Barium and calcium do not react but intensify the r,' I
colour. All elements of Groups I to lIIB should be removed befc",'
applying the test.
Place a drop of the test solution on a spot plate, introduce a drop. ,f
reagent and a drop of O'IN sodium hydroxide. A red colour or precip i·
tate is produced.
An alternative technique is to treat 0·5 ml. of the neutral or slight I\
acidic test solution with 0·2 ml. of the reagent and 0·5 ml. of O· L\'
sodium hydroxide solution. A red precipitate or coloration is produce,!
Sensitivity: 1·5 f.Lg. Mg. Concentration limit: 1 in 33,000,
The reagent consists of a 0·1 per cent aqueous solution of titan yellow.
tJO. Quinalizarin* Reagent: blue precipitate or cornflower·blll,'
coloration with magnesium salts. The coloration can be readily distill
guished from the blue-violet colour of the reagent. Upon the additio,
of a little bromine water, the colour disappears (difference from beryl
lium). The alkaline earth metals and aluminium do not interfere unde;
the conditions of the test, but all elements of Groups I to lIIB shoul, i
be removed. Phosphates and large amounts of ammonium salt
decrease the sensitivity of the reaction.
Place a drop of the test solution and a drop of distilled water jJ:
adjacent cavities of a spot plate and add 2 drops of the reagent to each
If the solution is acid, it will be coloured yellowish-red by the reagent,
Add 2N sodium hydroxide until the colour changes to violet and "
further excess to increase the volume by 25 to 50 per cent. A blue
precipitate or coloration appears. The blank test has a blue-viole1
colour.
Sensitivity: 0·25 f'g. Mg. Concentration limit: I in 200,000.
The reagent is prepared by dissolving 0·01-0·02 gram of quinalizarin
in 100 ml. of alcohol. Alternatively, a 0·05 per cent solution in O·IN
sodium hydroxide may be used.

Dry Test
Blowpipe test.-All magnesium compounds when ignited on
charcoal in the presence of sodium carbonate are converted
into white magnesium oxide, which glows brightly when hot.
Upon moistening with a drop or two of cobalt nitrate solution
and reheating strongly, a pale pink mass is obtained.
K
POTASSIUM,
Potassium is a soft, silver-white metal. It remains unchanged
in dry air, but is rapidly oxidised in moist air, becoming covered
first with a blue film. The metal decomposes water violently.
evolving hydrogen and burning with a violet flame. Potassium is
usually kept under solvent naphtha. The salts are derived from
the normal oxide K 2 0.
• For formula, see under Aluminium, Section III, 21, reMtion 10.
 34] Reactionll of the Metal Ions or Cations 316

III,34. REACTIONS OF THE POTASSIUM ION, K +

Use a solution of potassium chloride, KCl.
1. Sodium Cobaltinitrite Solution (Nas[Co(N02)61):
yellow precipitate of potassium-sodium cobaltinitrite K 2Na
[CO(N0 2)6], insoluble in dilute a.cetio acid solution. Tho preci-
pitate forms immediately in concentrated solutions and slowly
in dilute solutions; precipitation may be acoelerated by warming.
Ammonium salts give a similar preoipitate and must therefore
be completely eliminated before applying the test. In alkaline
solutions, a brown or black precipitate of cobaltic hydroxide
Co(OH)a is obtained. Iodides and other reducing agent8 inter-
fere and should be removed before applying the test.
Na3[Co(N02)6] (excess) + 2KCl = K 2Na[Co(N0 2 )6] + 2NaCI
Na3[Co(N02)6] + 3KCl (excess) = K a[Co(N02)6] + 3NaCl
2. Tartaric Acid Solution (H 2 • C4 H 4 0 6 )*: white crystalline
precipitate of potassium acid tartrate KH. C4H 4 0 6 from con-
centrated solutions. The precipitate is slightly soluble in water
(3·2 grams per litre; S.P. 3·0 X 10-4 ), insoluble in 50 per cent
alcohol, soluble in mineral acids, and also in solutions of alkalis
with the formation of the normal salts, e.g. K 2 .C4H 4 0 6 . Pre-
cipitation is accelerated by vigorous agitation of the solution,
by scratching the sides of the vessel with a glass rod and by
adding alcohol. Ammonium salts yield a similar pre(;ipitate
and must be absent.
KCI + H 2.C4H 40 6 = KH.C4 H 4 0 6 + HCI;
KCI + NaH.C4 H 40 6 = KH.C4 H 40 6 + NaCl
3. Perchloric Acid Solutiont (HCl04 ): white crystalline
precipitate of potassium perchlorate KCI04 from not too dilute
solutions. The precipitate is slightly soluble in water (3·~ grams
and 198 grams per litre at 0° and 100° respectively) and
practically insoluble in absolute alcohol. The alcoholic solution
should not be heated as a dangerous explosion may result. This
reaction is unaffected by the presence of ammonium salts.
HCl04 + KCI = KCI04 + HCI
4. Chloroplatinic Acid Solution (H 2[PtCls]): yellow
crystalline precipitate of potassium chloroplatinate K~[PtCls]
from concentrated solutions; in dilute solutions, precipitation
takes place slowly on standing, but may be hastened by coolin~
* Or preferably saturated sodium hydrogen tartrate solution.
t Twenty per cent strength. An equivalent result is obtained by the URe
of sodium perchlorate solution.
316 Qualitative Inorganic Analysis [III.
and by rubbing the sides of the vessel with a glass rod. Tk
precipitate is slightly soluble in water, but is almost insolubi,'
in 75 per cent alcohol. Ammonium salts give a similar precipl
tate and must be absent.
2KCl + H2(PtC~1 = K2(PtC~1 + 2HCl
The reag,ent is 1?re1?ared by dissolving 2'7 grams of t\ \'
hydrated chloroplatinic acid H 2 [PtCI6 ],6H 2 0 in 10 ml. ofwat( r.
Owing to its expensive character, only small quantities shou', 1
be employed and all precipitates placed in the platinum
residues bottle.
t5. Sodium Cobaltinitrite-Silver Nitrate Test.-This is Ii
modification of reaction 1 and is applicable to halogen-free solutions.
Precipitation of potassium salts with sodium cobaltinitrite and silver
nitrate solution gives the compound K,Ag[Co(NOs)u], which is k~9
soluble than the corresponding sodium compound K 2Na[Co(NOs)e] and
hence the test is more sensitive. Lithium, thallium and ammonil'"1
salts must be absent for they give precipitates with sodium cobal- I-
nitrite solution.
Place a drop of the neutral or acetic acid test solution on a bla'·).;:
spot plate, and add a drop of 0'05 per cent silver nitrate solution and 'I
small amount of finely-powdered sodium cobaltinitrite. A yellow P' ,'-
cipitate or turbidity appears.
Sensitivity: 1 p,g. K. Concentration limit: 1 in 50,000.
If silver nitrate solution is not added, the sensitivity is 4 p,g. K.
t6. Dipicrylamine (or Hexanitro-diphenylamine) Rea~ent

NOs NO. )

(
OJ'ONH3=>-NO' ,
'NOs NO.
the hydrogen atom of the NH group is replaceable by metals; ti,,,
sodium salt is soluble in water to yield a yellow solution. With sol ..
tions of potassium salts, the latter gives a crystalline orange-red precil
tate of the potassium derivative. The test is applicable in the presen·
of 80 times as much sodium and 130 times as much lithium. Amm
nium salts should be removed before applying the test. Magnesiul"
does not interfere.
Place a drop of the neutral test solution upon drop-reaction pap ,.
and immediately add a drop of the slightly alkaline reagent. l\ \
orange-red spot is obtained, which is unaffected by treatment with I :!
drops of 2N hydrochloric acid.
Sensitivity: 3 p,g. K. Concentration limit: 1 in 10,000.
The reagent is prepared by dissolving 0'2 gram of dipicrylamine in
20 ml. of boiling O'lN -sodium carbonate and filtering the cooled liqui':'
35] Reactions of the Metal Ions or Cations 317
Dry Test
Flame coloration.-Potassium compounds, preferably the
chloride, colour the non-luminous Bunsen flame violet (lilac).
The yellow flame produced by small quantities of sodium
obscures the violet colour, but by viewing the flame through
two thicknesses of cobalt blue glass, the yellow sodium rays
are absorbed and tbe reddisb-violet potassium flame becomes
visible. A solution of chrome alum (310 grams per litrp), 3 cm.
thick, also makes a good filter.

SODIUM, Na
Sodium is a silver-white, soft metal. It oxidises rapidly in moist
air and is therefore kept under solvent naphtha or xylene. The
metal reacts violently with water forming sodium hydroxide and
evolving hydrogen. The salts are derived from the monoxide Na20.

III, 35. REACTIONS OF THE SODIUM ION, Na +

Use a solution of sodium chloride, NaCl.
1. Uranyl Magnesium Acetate Solution: yellow, crystal-
line precipitate of sodium magnesium uranyl acetate
NaMg(U02h(C2H302)9,9H20 from concentrated solutions. The
addition of about one-third volume of alcohol helps the pre-
cipitation.
NaCI + 3U02(C2H 30 2)Z + Mg(C2H 30 2)z + H.C2H30z
= NaMg(UOz)a(CzH30Z)9 + HCI
The reagent is prepared as follows. Dissolve 10 grams of uranyl
acetate U02(CzH30Z)2,2H20 in 6 grams of glacial acetio aoid and
100 ml. of water (solution a). Dissolve 33 grams of magnesium
acetate Mg(C 2H 30 2)2,4H 20 in 10 grams of acetio acid and 100 ml.
of water (solution b). Mix the two solutions a and b, a,llow to
stand for 24 hours, and filter. Alternatively, a reagent of equivalent
concentration may be prepared by dissolving uranyl magnesium
acetate in the appropriate volume of water or of N aoetio acid.
2. Chloroplatinic Acid, Tartaric Acid or Sodium
Cobaltinitrite Solution: no preoipitate with solutions of
sodium salts.
3. Uranyl Zinc Acetate Reagent.-As a delicate test for
sodium, the uranyl zinc acetate reagent is sometimes pre1erred to
that employing uranyl magnesium acetate. The yellow crystal-
line sodium zinc uranyl acetate NaZn(U02)s(C2Ha02)9,9H20
is obtained. The reaction is fairly seleotive for sodium.
318 Qualitative Inorganic Analysis [III,
The sensitivity of the reaction is affected by cop}?er, mercury,
cadmium, aluminium, cobalt, nickel, manganese, %inc, calcium
strontium, barium and ammonium when present in concentra
tions exceeding 5 grams per litre; potassium an~ lithium salt '
are precipitated if their concentration in solutIon exceeds
grams and 1 gram per litre respectively.
t Place a drop of the neutral test solution on a black spot plate Of
upon a black watch glass, add 8 drops of the reagent, and stir with .1
glass rod. A yellow cloudiness or precipitate forms.
Sensitivity: 12·5 fLg. Na. Concentration limit: 1 in 4,000.
The reagent is prepared as follows. Dissolve 10 grams of uram I
acetate in 6 grams of 30 per cent acetic acid, warmil}g if necessar:\ ,
and dilute with water to 50 m!. (solution a). In a separate vessel
stir 30 grams of zinc acetate with 3 grams of 30 per t;)ent acetic acid
and dilute with water to 50 m!. (solution b). Mix th~ two solutiolls .
a and b, and add a small quantity of sodium chlOl'ide. Allow to
stand for 24 hours, and filter from the precipitat(ld sodium zinc
uranyl acetate.
Alternatively, a reagent of equivalent cOIIcentratrl)n may be pr<;-
pared by dissolving uranyl zinc acetate in the appropriate volume
of water or of N acetic acid.

Dry Test
Flame coloration.-The non-luminous BUllf~en flame is
coloured an intense yellow by vapours of sodium salts. Tll'l
colour is not visible when viewed through two thicknesses ( r
cobalt blue glass. Minute quantities of sodium salts give thi"
test, and it is only when the colour is intense ftnd persisteli1
that appreciable quantities of sodium are presen1i.

III, 36. REACTIONS OF THE AMMONIUM ION, NH; ,

Use a solution of ammonium chloride, NH4Cl.
1. Sodium Hydroxide Solution: ammonia ~as is evolved
on warming. This may be identified (a) by its odour (cautious!'
smell the vapour after removing the test-tube 01' small beak, :'
from the flame); (b) by the formation of white fumes ofamm,,-
nium chloride when a glass rod moistened with concentrak,l
hydrochloric acid is held in the vapour; (c) by its turniI':2:
moistened red litmus paper blue or turmeric }?aper broWl ..
(d) by its ability to turn filter paper moistened with mercurOlI,
nitrate solution black (this is a very trustworthy test *); and
* Arsine, however, blackens mercurous nitrate paper, an'j must therefonj
be absent.
36] Reactions of the Metal Ions or Oationa 319
(e) filter paper moistened with a solution of manganous ,mlphate
and hydrogen peroxide gives a brown colour, due to the
oxidation of the manganese by the alkaline solution thus
formed.
NH,CI + +
NaOH = NH3 'H 2 0 +NaCI
Hg 2 (NO a)2 + 2NHs = Hg(NH 2)NO a + Hg +
NH,NO a
black
2MnSO, + H 20 2 + 4NHs + 4H 0 2 = 2Mn(OH)s + 2(NH')2S04
2. Nessler's Reagent: brown precipitate, or brown or
yellow coloration, is produced according to the amount of
ammonia or of ammonium ions. The test is an extremely
delicate one and will detect the traces of ammonia present in
drinking water. All metals, except those of the alkalis, must
be absent.
The formula of the brown precipitate has been given as
3HgO.Hg(NHa)212 (Britton and Wilson, 1933) and as
NH 2 .Hg 2I a (Nichols and Willits, 1934).
The reagent is prepared by dissolving 10 grams of potassium
iodide in 10 ml. of ammonia-free water, adding saturated mercuric
chloride solution (60 grams per litre) in small quantities at a time,
with shaking, until a slight permanent precipitate is formed, then
adding 80 ml. of 9M potassium hydroxide solution and diluting to
200 ml. Allow to stand overnight and decant the clear liquid.
The reagent thus consists of an alkaline solution of potassium
mercuri-iodide K2[HgI4J.
Nessler's reagent has been described as a solution which is
ca. 0'09M in potassium mercuri-iodide and 2·5N in potassium
hydroxide.
An alternative method for the preparation of the reagent is as
follows. Dissolve 23 grams of mercuric iodide and 16 grams of
potassium iodide in ammonia-free water and make up tho volume
to 100 ml.; add 100 rul. of 6N sodium hydroxide. Allow to stand
for 24 hours, and decant the solution from any precipitate 1hat may
have formed. The solution should be kept in the dark.
t The spot-test technique is as follows. Mix a drop of the test solu-
tion with a drop of concentrated sodiwn hydroxide solution OIl a watoh
glass. Transfer a micro-drop of the resulting solution or suspension to
drop reaction paper and add a drop of Nessler's reagent. A yellow or
orange-red stain or ring is produced.
Sensitivity: 0·3p.g. NH. (in 0·002 ml.).
A better procedure is to employ the technique described lwder the
manganous nitrate-silver nitrate reagent in reaction 9 below. A drop
320 Qualitative Inorganic Analysis [III,
of Nessler's solution is placed on the glass knob of the apparatus. After
the reaction is complete, the drop of the reagent is touched with a piece
of drop reaction or quantitative filter paper when a yellow coloration
will be apparent.
Sensitivity: 0·25 ,."g. NH a•
3. Sodium Cobaltinitrite Solution (Na3[Co(N02)6]): yel-
low precipitate of ammonium cobaltinitrite (NH4 MCo(N0 2)a],
similar to that produced by potassium ions.
3NH4Cl + Nas[Co(N02)6] = (NH4 )s[Co(N02 )6] + 3NaCI
4. Chloroplatinic Acid Solution (H 2[PtCla]): yellow, crys-
talline precipitate of ammonium chloroplatinate (NH4 MPtCla],
similar to that of the corresponding potassium salt, but
differing from it in being decomposed by warming with sodium
hydroxide solution with the evolution of ammonia gas.
2NH4Cl + H 2[PtC4] = (NH,h[PtC4] + 2HCl;
(NH4 MPtC4] + 2NaOH = Na2[PtCle] + 2NHs + 2H20
5. Saturated Sodium Hydrogen Tartrate Solution
(NaH.C4H 40 a)*: white precipitate of ammonium acid tartrate
NH4 • H.C4H 4 0 a, similar to but slightly more soluble than the
corresponding potassium salt, from which it is distinguished
by the evolution of ammonia gas on being heated with sodium
hydroxide solution.
NaH.C4H,06 + NH4Cl = NH,.H.C,H,06 + NaCl
6. Perchloric Acid or Sodium Perchlorate Solution: no
precipitate (distinction from potassium).

7. Tannic Acid-Silver Nitrate Test.-The basis of this

test is the reducing action of tannic acid (a glucoside of digallic
acid) upon the silver ammine complex [Ag(NH s)2] + to yield
black silver: it therefore precipitates silver in the presence of
ammonia but not from a slightly acid silver nitrate solution.
Mix 2 drops of 5 per cent tannic acid (tannin) solution with
2 drops of 20 per cent silver nitrate solution, and place the
mixture upon drop-reaction paper or upon a little cotton wool.
Hold the paper in the vapour produced by heating an ammo-
lium salt with sodium hydroxide solution. A black stain is
:armed on the paper or upon the cotton wool. The test is a
lensitive one.
• Or, less effectively, tartaric acid solution.
36] Reactions of the Metal Ions or Oations 321
t8. para-Nitrobenzene-diazonium Chloride Reagent.-The re-
agent (I) yields a red coloration (due to IT) with an ammonium salt in
the presence of sodium hydroxide solution.

OzN-Q-NaCl+2NHs+H zO

(I)
OaN-Q-N = NONH.+NH.Cl

(II)

Place a drop of the neutral or i'lightly acid test solution on a spot plate,
followed by a drop of the reagent and a fine granule of calcium oxide
between the two drops. A red zone forms round the calcium oxide.
A blank test should be carried out on a drop of water.
Sensitivity: 0·7 ttg. Concentration limit: 1 in 75,000.
The reagent (sometimes known as Riegler's solution) is prepared as
follows. Dissolve 1 gram of p·nitraniline in 2 m!. of concentrated hydro-
chloric acid and 20 ml. of distilled water (warming may be necessary)
and dilute with 160 ml. of water. Cool, add 20 ml. of 2-5 per <lent
sodium nitrite solution with vigorous shaking. Continue the shaking
until all dissolves. The reagent becomes turbid on keeping, but can
be employed again after filtering.
t9. Ammonia-Formation Test.-This is a modification of reaction
1 as adapted to delicate analysis. The apparatus is shown in Fig. II,
6, 12 and consists of a small glass tube of 1 ml. capacity, which can be
closed with a small ground-glass stopper carrying a small glass hook at
the lower end.
Place a drop of the test solution or a little of the solid in the micro
test-tube, and add a drop of 2N sodium hydroxide solution. Fix a
small piece of red litmus paper on the glass hook and insert the stopper
into position. Warm to 40°0 for 5 minutes. The paper assumes a
blue colour.
Sensitivity: 0'01 ttg.NHa. Concentration limit: 1 in 5,000,000.
Cyanides should be absent, for they give ammonia. with alkalis:
KCN +
2H.O = HCOOK NH. +
If, however, a little mercuric oxide or a mercuric salt is added, the
alkali-stable mercuric cyanide Hg(CN)a is formed and the interforing
effect of cyanides is largely eliminated.
An alternative method for carrying out the test is to employ the
manganous nitrate-silver nitrate reagent. Upon treating a. neutra.l
solution of manganous and silver salts with alkalis (e.g. that produced
from ammonia), a black precipitate is formed:
Mo++ + 2Ag+ + 40H- = MoOs + 2Ag +
2HaO
The sensitivity can be increased by treating the resultant precipitate
with an acetic acid solution of benzidine whereupon the manganese
dioxide oxidises the benzidine to a. blue oxidation product.
Use the apparatus shown in Fig. II, 6, 10 or in Fig. II, 6, 11. Place
a drop of the test solution and a drop of 2N sodium hydroxide in the
11+
3!J Qualitative Inorganic Analysis [JII,
micro test-tube; also place a drop of the reagent on the glass knol )f
the ~pper and close the apparatus_ Heat at 40°0 for 5 minU' "s,
Wash'tihe drop of the reagent on to a piece of quantitative filter pa 'lr
when a'black or grey fleck will become apparent; this turns blue UJ 'n
treatment with a solution of benzidine (the latter is prepared by I j' ,-

solving 0'05 gram of benzidine or its hydrochloride in 10 ml. of glal ,1

acetic acid, diluting to 100 ml. with water, and filtering).
Sensitivity: 0,005 p.g. NH s• Concentration limit: 1 in 10,000,00(1.
The manganous nitrate-silver nitrate reagent is prepared tI, '"
Dissolve 2,87 grams of manganous nitrate in 40 ml. of water, and filt, ":
add a solution of 3,55 grams of silver nitrate in 40 ml. of water, t",d
dilute the mixture to 100 ml. Neutralise the acid formed by hydrol: s
by adding dilute alkali dropwise until a black precipitate is formed h' ,.d
filter. Keep the reagent in a dark bottle.

Dry Test
All ammonium salts are either volatilised or decompm·d
when heated to just below red heat. In some cases, wh. ! e
the acid is volatile, the vapours recombine on cooling to fOl '11
a sublimate of the salt, e.g. ammonium chloride.

DETECTION AND SEPARATION OF THE METALS OF THE ALKALI GRO' P

(GROUP v)
The metals of this group are not precipitated by the earlier gro d)
reagents. It is assumed that the elements of Groups I to IV ha ' e
been removed as already described, or that only metals of Group V
are present. The student should, as in previous groups, prepare 1 'r
himself or obtain from the teacher, a solution containing some or :1
of the simple salts of the metals of the group. The filtrate ff( .11
Group IV, if employed, should be evaporated to dryness and ,'I
ammonium salts eliminated. This is m'ost conveniently carried () ,t
by concentrating the solution in an evaporating dish (FU~! E
CUPBOARD!) until salts begin to crystallise out, allowing to co' ,
then adding a little concentrated nitric acid by means of a droP} "
pipette in such a manner as to wash down the solid from the sid .i
to the centre of the dish, then heating cautiously until dry a, ,I
finally more strongly until fuming ceases. The cold residue m \'
then be divided into two portions: one is used in testing for Mg wi 'l
the "oxine" reagent, and the other in testing for Na and K and al ,
for the confirmatory test for Mg,
The sodium phosphate test for Mg (see Section 111,33, reaction ,;)
is not altogether satisfactory, particularly in dilute solutions wh, 1
precipitation is comparatively slow, and also the magnesium amm '
nium phosphate has a tendency to form supersaturated solution
traces of alkaline earth metals tend to interfere with the test.
37J Reactions of the Metal Ions or Oations 323

111,37. Table VII. Analysis of the Alkali Group (Group V)

Treat the dry residue from Group IV with 3-4 mI. of water, stir and
warm for 1 minute. Filter. *

Residue. Dissolve in a few drops Filtrate. Divide the filtrate into

of dilute HCl and add 2-3 ml. of two parts (a) and (b).
water. Divide the solution into (a) Add a little uranyl magneHium
two unequal parts. acetate reagent, shake and allow to
(i) Larger portion (I). Treat 1 ml. stand for a few minutes.
of 2% oxine solution in 2N acetic Yellow crystalline ppt.
acid with 4 ml. of 2·5N ammonia Na present.
solution and, if necessary, warm to Confirm by flame test: perSl'stent
dissolve any precipitated oxine. yellow flame.
Add a little NH,CI solution to the (b) Add a little sodium col,alti-
test· solution, followed by the ammo- nitrite solution and a few drops of
niacal oxine reagent, and heat to the dilute acetic acid, preferably 'on a
boiling point for 1-2 minutes (the watch glass.
odour ofNH. should be discernible). Yellow ppt. of K.[Co(NOz).J.
Pale yellow ppt. ofMg" oxinate." K present.
Mg present. Confirm by flame test and view
(ii) Smaller portion. To 3-4 drops through two thicknesses of cobalt
add 2 drops of" magneson " reagent, glass (2): red coloration (usClally
followed by several drops of NaOH transient).
solution until alkaline.
A blue ppt. confirms Mg.

Test jor ammonium by boiling the original substance with sodium

hydroxide solution: odour of ammonia, and vapour turns red litmus paper
blue and also mercurous nitrate paper black. Ammonium present.

Notes. (I) If it is desired to carry out the Na,HPO, test for comparison
with the "oxine" test for Mg, treat the ncid solution with a little NH,Cl,
followed by dilute NHa solution until basic, and Nn 2 HPO, solution. Shake
or stir vigorously. A white crystalline ppt. of Mg{NH.)PO.,6H.O indicates
Mg. Confirm by dissolving the ppt. in a little dilute HCI and then applying
the "magneson" test. A blue ppt. confirms Mg. '
(2) It is advisable to test the cobalt glass with a potassium salt, to be
certain that the glass is satisfactory: somo samples of cobalt glass completely
absorb the red lines due to potassium.
* If the residue dissolves completely (or almost completely) in water, dilute
the resulting solution (after filtration, if necessary) to about 6 ml. and divide it
into three approximately equal parts:- (i) Use the major portion to tes~ for Mg
with the prepared" oxine" solution: confirni Mg by applying the" magneson "
test to 3-4 drops of the solution; (ii) and (iii) Test for Na and K respectively,
as described in the TabJe.
 \
324 Qualitative Inorganic Analysis [III,
111,37. Table SMVII. Analysis of the Alkali Group
(Group V)

Treat the dry residue (contained in a small crucible) from Group IV

with I ml. of water, stir for I minute, and transfer with the aid of a furtL"r
0·5 ml. of water to a semimicro centrifuge tube. Centrifuge. *

Residue. Dissolve in a few drops Centrifugate. Divide into ,,0

of dilute HCI, and add I ml. of parts (a) and (b).
water. Divide into two unequal (a) Add 5-10 drops of ural d
parts; retain the smaller portion in magnesium acetate reagent, sh, i e
the centrifuge tube. or stir, and allow to stand fOl 5
(i) Larger portion (I). Treat 0·25 minutes.
ml. of 2% oxine solution in 2N Yellow crystalline ppt.
acetic acid with 1 ml. of 2·5N Na present.
ammonia solution. Add a little Confirm by flame test: persist
NH.Cl to the test solution followed yellow flame.
by the ammoniacal oxine reagent, (b) Add 3 drops of sodhl!ll
and heat in a water bath for 1-2 cobaltinitrite reagent (or 5 mg. ,f
minutes (the odour of NH, should the A.R. solid) and 2 drops of dill,' "
be apparent). acetic acid, warm gently on wal
Pale yellow ppt. ofMg "oxinate." bath, and allow to stand for :;
Mg present. minutes.
(ii) Smaller portion. To 3-4 drops Yellow ppt. of K 3 [Co(N0 2 ).J.
add 2 drops of "magneson "reagent, K present.
followed by several drops of NaOH Confirm by flame test and vie'"
solution until alkaline. through two thicknesses of coba '
A blue ppt. confirms Mg. glass (2): red (crimson) f1an"
(usually transient).

Test Jor ammonium by placing 10 mg. of the original substance wit!.

about 0·5 ml. of sodium hydroxide solution in a semimicro test· tub<
(without rim) and attach a "filter tube" (Fig. 11,3,19). Place a piec'
of red litmus paper or mercurous nitrate paper in the funnel. Warm 01
a water bath. Odour of ammonia: red litmus paper turns blue; mer
curous nitrate paper turns black. Ammollium present.

Notes. (1) If it is desired to carry out the Na.HPO. test for comparil' I
with the "oxine" test for Mg, treat the acid solution with a little NH"
followed by dilute Nfl. solution until alkaline, and 5-6 drops of Na 2Hl' ,
solution. Shake or stir the mixture and allow to stand for 3-5 minut,
A white crystalline ppt. of Mg(NH.)PO.,6H.O indicates Mg. Centrifuge at
wash the ppt. with 0·3 ml. of water: discard the washings. Dissolve t i
ppt. in 5 drops of dilute HCI, warming if necessary. Add 1 drop of t
"magneson" reagent, and then NaOH solution until alkaline. A blue PI'
confirms Mg.
(2) See Note 2 in macro Table VII.
* If the residue dissolves completely (or almost completely) in water, dilu'"
the resulting solution (after centrifugation, if necessary) to about 1·5 ml. all '
divide it into three approximately equal parts:- (i) Use the major portion 1
test for Mg with the prepared "oxine" solution; confirm Mg by applying tl,
"magneson" test to 3-4 drops of the solution; (ii) and (iii) Test for Na an"
K respectively, as described in the Table.
 CHAPTER IV

REACTIONS OF THE ACID RADICALS OR ANIONS

IV, 1. Scheme of Classification.-The methods nvailable

for the detection of ncid radicals or anions are not as systematic
as those which have been described in the previous chapter for
cations. No really satisfactory scheme has yet been proposed
which permits of the separation of the common acid radicals
into major groups, and the subsequent unequivocal separation
of each group into its independent constituents. [t must,
however, be mentioned that it is possible to separate the
anions into major groups dependent upon the solubilities of
the silver salts, of the calcium or barium salts, and of the zinc
salts; these, however, can only be regarded as useful in giving
an indication of the . limitations of the method and for the
confirmation of the results obtained by the simpler procedures
to be described below. For this reason their discussion is
deferred until Section VII, 16 in connexion with the complete
systematic detection of acid radicals.
The following 8cheme of Clas8ification has been found to work
well in practice; it is not a rigid one since some of the acid
radicals belong to more than one of the subdivisions, and,
furthermore, it has no theoretical basis. Essentially the pro-
cesses employed mp.y be divided into (A) those involving the
identification by volatile products obtained on treatment with
acids, and (B) those dependent upon reactions in solution.
Class (A) is subdivided into (i) gases evolved with dilute hydro-
chloric acid or dilute sulphuric acid, and (ii) gases or vapours
evolved with concentrated sulphuric acid. Class (B) is sub-
divided into (i) precipitation reactions, and (ii) oxidntion and
reduction in solution.
This leads to the following classification.
GLASS A
(i) Ga8es evolved with dilute hydrochloric acid or dilute .sul-
phuric acid.
Carbonate, bicarbonate, sulphite, thio8ulphate, sulphide,
nitrite, hypochlorite, cyanide and cyanate.
(ii) Gases or acid vapours evolved with concentrated sulphuric
acid.
326
326 Qualitative Inorganic AnalY8i8 [IV,
These include those of (i) with the addition of the following:
fluoride, silicofluoride, * chloride, bromide, iodide, nit I a,te,
chlorate (DANGER), perchlorate, permanganate (DANG ie'R) ,
bromate, borate,* ferro cyanide, ferricyanide, thiocyali:tte,
formate, acetate, oxalate, tartrate and citrate.

CLASS B
(i) Precipitation reactions.
Sulphate, persulphate, t phosphate, phosphite, hypophosp: ,te,
arsenate, arsenite, chromate, dichromate, silicate, silicofluo! Ide,
salicylate, benzoate and succinate.
(ii) Oxidation and reduction in 8olution.
Manganate, permanganate, chromate and dichromate,
The reactions of all these acid radicals or anions will be
systematically studied in the following pages. For ",n-
venience the reactions of certain organic acids are grou 1,ed
together; these include acetates, formates, oxalat.es, tartra; I)S,
citrates, salicylates, benzoates and succinates, It may be
pointed out that acetates, formates, salicylates, benzoates : nd
succinates all belong to another group; all give a characteri : ic
coloration or precipitate upon the addition of ferric ch101l,1e
solution to a practically neutral solution.

IV, 2. REACTIONS OF CARBONATES, C0 3 - -

Solubility.-All normal carbonates, with the exception of those of the aL ,Ii
mat"Is and of ammonium, are insoluble in water. The acid carbonate, 'lr
bicarbonates of calcium, strontium, barium, magnesium and possibly of j n
exist in aqueous solution; they are formed by the action of excess of carb"" 'c
acid upon the normal carbonates either in aqueous solution or suspension" I ,d
are decomposed on boiling the solutions.
CaCO, +H 20 + CO a ~ Ca(HCO.).
The bicarbonates of the alkali metals are soluble in water, but are lesB solu! I')
than the corresponding normal carbonates.
Use sodium carbonate, Na2C03,lOH20.
1. Dilute Hydrochloric Acidt: decomposition with effe'
vescence, due to the evolution of carbon dioxide, which mil \
be detected by its property of rendering lime water (!
baryta water) turbid. Some natural carbonates, such as mat:
nesite MgC0 3, siderite FeCO s and dolomite (Ca,Mg)CO a, do nt"~
* This is often included in Class B (i),
t Strictly speaking persulphates should be groupod with Class B (ii), bUl
are best studied together with sulphates.
t Or any other dilute mineral acid.
2] Reactions of the Acid Radicals or Anions 327
react appreciably in the cold; they must be finely powdered
and the reaction mixture warmed.
The lime water or baryta water test is best carried out in the
apparatus shown in Fig. IV, 2, 1. The solid substance is placed in
the test-tube or small distilling flask (10-25 m!. capacity), dilute
hydrochloric acid added and the cork immediately replaced. The
gas which is evolved (warming may be necessary) is passed into
lime water or baryta water contained in the test-tube; the produc-
tion of a turbidity indicates the presence of a carbonate. It must
be remembered that with prolonged passage of carbon dioxide, the
turbidity slowly disappears as a result of the formation of;t soluble
bicarbonate. Any acid which if' "stronger," i.e. has a higher

Fig. IV, 2, 1.

ionisation constant, than carbonic acid (K 1 ) will dispIacn it from

its salts, especially on warming. The weak hydrocyanic acid, boric
acid and hydrogen sulphide do not decompose carbonates.
NaaCO~ + 2HCI = 2NaCl + HIO + COa;
Ca(OH)2 + COl = CaCO a + HIO
CaCO a + CO 2 + H 20 = Ca(HCO a).
2. Barium Chloride or Calcium Chloride Solution:
white precipitate of barium carbonate BaCO a or calcium car-
bonate CaC0 3 with solutions of normal carbonates. The pre-
cipitate is soluble in mineral acids and in carbonic acid.
BaCl 2 + Na2COS = BaCOs + 2NaCI
3. Silver Nitrate Solution: white precipitate of silver
carbonate Ag 2CO S with solutions of normal carbonate::!, soluble
328 Qualitative Inorganic Analysia (IV,
in ammonia solution and in nitric acid. The precipita 1 " be-
comes yellow upon addition of excess of the reagent, I ltd is
partly decomposed on boiling with water into brown "ilver
oxide Ag 2 0 and carbon dioxide.
t4. Sodium Carbonate-Phenolphthalein Test.-This test d,·;,ends
upon the fact that phenolphthalein is turned pink by soluble carl nates
and colourless by soluble bicarbonates. Hence if the carbon (: udde
liberated by dilute acids from carbonates is allowed to come into (. atact
with phenolphthalein solution coloured pink by sodium car' Inate
solution, it may be identified by the decolourisation which takes . lace:
COa+ NaaCO a+ HaO ~ 2NaHCO a
The concentration of the sodium carbonate solution must be s,.··h as
not to be decolourised under the conditions of the experiment,.y the
carbon dioxide in the atmosphere.
Place 1-2 drops of the test solution (or a small quantity of tI,,, test
solid) in the apparatus shown in Fig. II, 6, 10, and place a drop f the
sodium carbonate-phenolphthalein reagent on the knob of the st :Jper.
Add 3-4 drops of 2N sulphuric acid and insert the stopper into po ., tion.
The drop is decolourised either immediately or after a shorl time
according to the quantity of carbon dioxide formed. Perform a ; ,lank
test in a similar apparatus.
Sensitivity: 4/Lg. CO a (in 2 drops of solution). Concentration limit:
1 in 12,500.
The reagent is prepared by mixing 1 mI. of O'IN sodium carll, ,nate
with 2 mi. of a 0'5 per cent solution of phenolphthalein and 10 . ,I. of
water.
Sulphides, sulphites, thiosulphates, cyanides, cyanates, fluI' ides,
nitrites and acetates interfere. The sulphur-containing anions l'iln be
quantitatively oxidised to sulphates by hydrogen peroxide:
NaaS + 4HaOa = NaaSO, + 4HaO
NaaSO s + HaOa = NaaSO, + HaO
NaaSaO a + 4HaOa = NaaSO, + HaSO, + 3H aO
The modified procedure in the presence of these anions is theref, 'te to
stir a drop of the test solution with 2 drops of" 20-40 volume" hyd mgen
peroxide, then to add 2 drops of 2N sulphuric acid, and to contiL'.e as
above. Cyanides are rendered innocuous by treating the test SOl ,tion
with 4 drops of a saturated solution of mercuric chloride, followeu by 2
drops of sulphuric acid, etc.; the slightly dissociated mercuric cyanide
is formed. Nitrites can be removed by treatment with aniline }J':dro-
chloride.
IV, 3. Tests for bicarbonates.-The following tests dis-
tinguish carbonates from bicarbonates.
(i) To a cold solution of a bicarbonate, e.g. sodium bi-
carbonate NaHCO a, add a solution of magnesium sulpl"Lte.
No precipitate is formed in the cold since magnesiuDi bi-
carbonate Mg(HCO a)2 is soluble in water. Boil the solUl ion:
a white precipitate of magnesium carbonate MgCO a, "ilich
4] Reactions oj the Acid Radicals or Anions 329
may be contaminated with some of the basic carbonate, is
produced. Solutions of carbonates give a white precipitate of
magnesium carbonate with magnesium sulphate solution in
the cold.
2NaHCO a + MgS04 = Mg(HC0 3)2 + Na2S04
Mg(HC0 3)2 ~ MgC0 3 + CO 2 + H 20
MgS04 + K 2C03 = l\IgC0 3 + K 2S04
(ii) Boil a solution of a bicarbonate. Carbon ruoxide IS
evolved which may be identified by the lime water test.
(iii) Add mercuric chloride solution to a solution of a bi-
carbonate. No precipitate is formed. Normal caebonates
yield a reddish-brown precipitate of basic carbonate
Hg40 S • COs in the cold. ""
4Na2C03 + 4HgCl2 = Hg4 0 3 .C0 3 + SNaCI + 3C0 2
(iv) Heat some solid sodium bicarbonate in a dry test-tube;
carbon dioxide is evolved. The residue evolves carboll dioxide
upon treatment with dilute mineral acid.
2NaHCOs = Na2C03 + H 20 + CO 2
(v) To test for bicarbonate in the presence of a carbonate,
use is made of the fact that calcium bicarbonate Ca(HC0 3)2 is soluble
in water and is converted into calcium carbonate CaC0 3 by the
addition of ammonia solution. Add excess of calcium chloride
solution; this will precipitate all the carbonate and part of the bi-
carbonate as CaC03. After a few minutes, filter rapidly '1nd treat
the clear filtrate with a little ammonia solution. A white precipitate
or cloudiness is obtained if a bicarbonate is present.

IV, 4. REACTIONS OF SULPHITES, S03-

Solubility.-Only the sulphites of tho alkali metals and of amnlonium are
soluble in water; the sulphites of the other metals are either difficultly soluble
or insoluble in water. The bisulphites of the alkali metals are soluble in water;
the bisulphites of the alkaline earth metals are known only in solution.
Use sodium sulphite, Na2S0s,7H20.*
1. Dilute Hydrochloric or Dilute Sulphuric Acid: the
solid salt is decomposed, more rapidly on warming, with the
evolution of sulphur dioxide, which may be identified (i) by
its suffocating odour of burning sulphur, (ii) by the green
coloration produced when filter paper moistened with acidified
potassium dichromate solution is held over the momh of the
test-tube, and (iii) by the blue colour produced when filter
• Unless otherwise indicated, in this and all subsequent Sectioru; concerned
with anions, the aqueous solutions should be employed.
11*
 Qualitative Inorganic Analysis [IV,
paper moistened with potassium iodate solution and stl'I'ch
~ solution is held in the vapour.
N a2S0S + 2HCI = 2NaCI + S02 + H 2 0
K2Cr207+ 3H 2SO S + H 2S04 = K 2S04 + Cr2(S04h + 4H 2()
2KIO s + 580 2 + 4H20 = 12 + 2KHS04 + 3H 2S04
2. Barium Chloride or Strontium Chloride Soluti ,n:
white precipitate of the sulphite BaS03 or SrS03, rea,!,ly
soluble in dilute hydrochloric acid. On standing, the pre(' ,li-
tate is slowly oxidised to the sulphate and is then insolubL in
dilute mineral acids; this change is rapidly effected by warm: ng
with bromine water or a little concentrated nitric acid or "lth
hydrogen peroxide. The solubilities at 18° of the sulphite~ of
calcium, strontium and barium are respectively 1·25 gra:, IS,
0·033 gram and 0·022 gram per litre.
Na280a + BaCl 2 = BaSOs + 2NaCI
3. Silver Nitrate Solution: white crystalline precipit:, te
of silver sulphite Ag 2S0 3 , soluble in excess of the sulpVte
solution forming the complex salt, sodium argenti-sulpJ! ce
Na[AgS03J. The precipitate is also soluble in ammonia S( 1-
tion and in dilute nitric acid. On boiling a solution of : 'Ie
complex salt or an aqueous suspension of the precipitate, g:' y
metallic silver is precipitated.
Na2S0S + 2AgNO a = 2NaNO g + Ag 2SO a;
Ag2 SOg + Na2S0S = 2Na[AgSOsJ;
2Na[AgSOg J = Na2S04 + S02 + 2Ag
4. Potassium Permanganate Solution*: decolouri:-, d
owing to the formation of solutions of potassium and m, :l-
ganous sulphates.
2KMn04 + 5H 2SO S = K 2S04 + 2MnS04 + 2H 2S04 + 3H 20
5. Potassium Dichromate Solution*: a green soluti Q
containing a chromic salt is produced. (Equation under ' '-
action 1.)
6. Lead Acetate Solution: white precipitate of Ie" I
sulphite PbSO a, readily soluble in cold dilute nitric acid, and
precipitating white lead SUlphate on boiling (distinction fr(Jm
thiosulphate ).
Pb(C 2H g0 2 )2 + Na2S0a = PbS0 3 + 2Na.C2H s0 2
PbSO a + 0 = PbS04
* Aoidified with dilute sulphurio aoid.
4J fteaction8 of the Acid ftadzcals or Anions 331
7. Iodine Solution: decolouri:sed.
H 2SO a + 12 + H 2 0 ~ 2H1 + H 2S04
8. Nascent Hydro~en.-Add the solution of the sulphite
to a test-tube containing zinc and dilute sulphmic acid;
hydrogen sulphide is evolved which may be detected by
holding some lead acetate paper at the mouth of the 1,est-tube
(see Section IV, 6, reaction 1).
H 2SOa + 6H = H 2S + 3H2 0
9. Lime Water.-This test is carried out by adding dilute
hydrochloric acid to the solid sulphite, and bubhling the
evolved sulphur dioxide through lime water (Fig. IV, 2, 1); a
white precipitate of calcium sulphite CaS0 3 is formed. The
precipitate dissolves on prolonged passage of the gas, due to
the formation of the soluble calcium bisulphite Ca(HSOab.
A turbidity is also produced by carbonates; the sulphur di-
oxide must therefore be first removed when testing for the
latter. This may be effected by adding potassium diuhromate
solution to the test-tube before acidifying. The dichromate
oxidises and destroys the sulphur dioxide without affecting the
carbon dioxide (compare Section IV, 2).
Ca(OH)2 + S02 = CaSOg + H 2 0
CaS0 3 +S02 + H 2 0 ~ Ca(HSOg)2
t 1 O. Fuchsin Test.~Dilute solutions of triphenylmetham, dyestuffs,
such as fuchsin (for formula, see Scction IV, 15, reaction 9) and mala-
chite green, are immediately decolourised by neutral sulphite:-. Sulphur
dioxide also decolourises fuchsin solution, but the reaction i,.; not quite
complete: nevertheless it is a very useful test for sulphurous acid and
acid sulphites; carbon dioxide does not interfere, but nitrogen dioxide
does. If the test solution is acid, it should preferably be just '18utralised
with sodium bicarbonate. Thiosulphates do not interfere bUl sulphides,
polysulphides and free alkali do. Zinc, lead and cadmium s tIts reduce
the sensitivity of the test, hence the interference of sulphidef cannot be
obviated by the addition of these salts.
Place I drop of the fuchsin reagent on a spot plate and add 1 drop of
the neutral test solution. The reagent is decolourised.
Sensitivity: I l,g. S02' Concentration limit: I in 50.000.
The fuchsin reagent is prepared by dissolving 0·015 gram of fuchsin
in 100 m!. of water.
t 11. Nickelous Hydroxide Test.-The auto-oxidation of sulphur
dioxide (or sulphurous acid) indu0es the oxidation of green nickelous
hydroxide to the black nickelic hydroxide. The colour change is quite
distinct, but for very small amounts of sulphur dioxide use m<1y be made
of the conversion of benzidine acetate to "benzidine blue" by the higher
nickel oxide. Thiosulphates give a similar reaction and mu ,t therefore
be absent: sulphides also interfere.
332 Qualitative Inorganic Analysis [IV,
Place a drop of the test solution (or a little of the test solid) in the
tube of the apparatus shown in Fig. II, 6, 10, and place a little washed
nickelous hydroxide on the glass knob under the stopper. Add 1-2
drops of 5-6N hydrochloric acid, close the apparatus and warm gently.
The green hydroxide turns grey to black according to the amount of
sulphite present. For small amounts of sulphites, transfer the nickel
hydroxide to a quantitative filter paper and treat with a drop of the
benzidine reagent: a blue colour is formed.
An alternative technique is to warm (water bath) the test solution in
a semimicro test-tube with a little dilute hydrochloric acid, and expose
the evolved gas to filter paper upon which a stain of nickelous hydroxide
has been made. The stain acquires a black colour.
Sensitivity: 0·4 fLg. S02' Concentration limit: 1 in 125,000.
The nickelous hydroxide is prepared by precipitating nickelOll~
chloride solution with sodium hydroxide solution and washin"
thoroughly Lmtil free from alkali. It should be freshly prepared.
The benzidine reagent is prepared by dissolving 0·05 gram (.f
benzidine or of its hydrochloride in 10 ml. of glacial acetic acid, dilutirl ~
to 100 ml. with water and filtering.

t 12. Sodium Nitroprusside-Zinc Sulphate Test.--Sodium nitro-

prusside solution reacts with a solution of a zinc salt to yield a salmOl'-
coloured precipitate of zinc nitroprusside Zn(Fe(CN)oNO]. The latt< •
reacts with moist sulphur dioxide to give a red compoLllid of unkno>\
composition; the test is rendered more sensitive when the reacti('i.
product is held over ammonia vapour which decolourises the unus(', I
zinc nitroprusside.
Place a drop of the test solution (or a grain of the solid test samph-l
in the tube of Fig. II, 6, 10 and coat the knob of the glass stopper wit It
a thin layer of the zinc nitrovrusside paste. Add a dr()~ ()t '1.N b..'J&
",,-.,,-<>~-,c <>< bU\.p'n\ll·lC amu anu close the apparatus. After the sulphur
dlOxlde has been evolved, hold the stopper for a short time in ammonia
vapour. The paste is coloured more or less deep red.
Sensitivity: 3·5f-l-g. S02' Concentration limit: 1 in 14,000.
. The zi~c nitrop~ssi~e paste is prepared by precipitating sodium
m~r?prusslde solutl<;m WIth an excess of zinc sulphate solution and
bOllmg for a few mmutes: the precipitate is filtered and washed, an.'
kept in a dark glass bottle or tube.
The test is not applicable in the presence of sulphides and/or thio-
sul.phates. These can be removed by the addition of mercuric chlorid(·.
whwh reacts forming the acid-stable mercuric sulphide:
Hg++ + S-- = HgS;
Hg++ + S203-- + H 0 = 2 Hg8 + 80,-- + 2H+
PI~e a drop Of. the test solution and 2 drops of saturated mercuri,'
c~lorIde so~u~lOn J? the same apparatus (Fig. II, 6, 10) and, after :'
mmute, aCIdIfy WIth 2N hydrochloric or sulphuric acid, and proceed
as above.
20 f-l-g. of Na 2SO a can be detected in the presence of 900 f-l-g. of Na 2S 20:
. and 1,500/Lg. of Na,S.
5] Reactions of the Ac~:d Rwiieals or Anions 333

IV, 5. REACTIONS OF THIOSULPHA TES, 8 2 0 a--

Solubility.-Most of the thiosulphates that have been prepared are soluble
in water; those of lead, silver and barium are very sparingly soluble. Many
of them dissolve in an excess of sodium thiosulphate solution forming complex
salts.
Use sodium thiosulphate, Na2S20a,5H20.
1. Dilute Hydrochloric Acid: no immediate change in the
cold with a solution of a thiosulphate; the acidified liquid soon
becomes turbid owing to the separation of sulphur, and sul-
phurous acid is present in solution. On warming th(, solution,
sulphur dioxide is evolved which is recognised by its odour
and its action upon filter paper moistened with acidified potas-
sium dichromate solution. The unstable thiosulphuric acid is
first formed; this soon decomposes largely into sulphlITOUS acid
and sulphur. The sulphur first forms a colloidal solution,
which is gradually coagulated by the free acid present. Side
reactions also occur giving rise to thionic acids.
Na2S20a + 2HCl = +
H zS 2 0 a 2NaCI;
H 2S zOa = HzSO a S +
Na2S20a +
2HCl = S02 +
H 20 S + + 2NaCI
2. Iodine Solution: decolourised; a colourless solution of
sodium tetrathionate Na2S406 is formed.
2Na2S20a + 12 = Na2S406 + 2NaI
3. Barium Chloride Solution: white precipitate of barium
thiosulphate BaS20a from moderately concentrated solutions.
Precipitation is accelerated by agitation and by rubbing the
sides of the vessel with a glass rod. The solubility i-; 0·5 gram
per litre at ISO. No precipitate is obtained with calcium
chloride solution since calcium thiosulphate is fairly soluble
in water.
Na2Sz0a + BaC1 2 = BaS20a + 2NaCl
4. Silver Nitrate Solution: white precipitat~' of silver
thiosulphate Ag 2S 20 a, readily soluble in excess of the thio-
sulphate solution forming the complex salt Naa[.\'g(S20a)2]'
The precipitate is unstable, decomposing on standing and
rapidly on warming; the colour changes through yellow and
brown to black silver sulphide Ag 2S.
Na2Sz0a +2AgN0 3 = Ag 2S zOa +
2NaNOa ;
AgZS 20 S +
H 2 0 = Ag 2S +
H 2S04 ;
AgzSzOs + 3NszS20 3 = 2Nas[Ag(S20 S)2]
334 Qualitative Inorganic Analysi8 [IV,
5. Lead Acetate Solution: white precipitate of lead thio-
sulphate PbSzO a, soluble in excess of the precipitant; III
boiling the suspension, a black precipitate containing lciLd
sulphide PbS is obtained (distinction from sulphite).
PbS 20 s + H 20 = PbS + H 2S04
6. Potassium Cyanide Solution.-A thiocyanate is pro-
duced when a solution of a thiosulphate is boiled with solutions
of potassium cyanide and sodium hydroxide. On acidifying
with dilute hydrochloric acid and adding ferric chloride solu-
tion, the characteristic blood-red colour of the complex ferri-
thiocyanate ion [Fe(SCN)]++ is obtained (distinction from
sulphite).
Na2Sz0a + KCN = KSCN + Na2S0S
7. "Blue Ring" Test.-When a solution of a thiosulphate
mixed with ammonium molybdate solution is poured slowly
down the side of a test-tube containing concentrated sulphuric
acid, a blue ring is formed at the contact zone.
8. Ferric Chloride Solution: dark violet coloration
(perhaps due to sodium ferri-thiosulphate, Na[Fe(SzOs)z]J
which disappears after a short time leaving an almost colour-
less solution.
2NazSzOa + 2FeCla = NaZS406 + 2FeClz + 2NaCI
9. Nickel Ethylenediamine Nitrate Reagent
[Ni(NHz.CHz.CHz.NH2h](NOab abbreviated to [Ni ens](NOa)z.--
When a neutral or slightly alkaline solution of a thiosulphat('
is treated with the reagent, a crystalline violet precipitate ot
the complex thiosulphate is obtained;-
[Ni enaJ(N03)2 + Na2S20a = [Ni ena]S203 + 2NaNOa
Sulphites, sulphates, tetrathionates and thiocyanates do not
interfere, but hydrogen sulphide and ammonium sulphide de-
compose the reagent with the precipitation of nickel sulphide.
The nickel ethylenediamine nitrate reagent is conveniently
prepared when required by treating a little nickel nitrate solution
with ethylenediamine until a violet colour (due to the formation of
the complex [Ni ena]++ ion) appears.
The conoentration limit is 1 in 25,000.
By obvious modification the reaction may be used for the detection of nickel;
it is applicable in the presence of copper, cobalt, iron and chromium.
t] O. Catalysis of Iodine-Azide Reaction Test.-Solutions of
sodium azide NaN 8 and of iodine (as KIa) do not react, but on the
6J Reactions of the Acid Radicals or Anions 335
addition of a trace of thiosulphatn, which acts as a cataly ,t, there is
an immediate vigorous evolution of nitrogen:
2NaN 3 + Is = 2NaI + 3N I
Sulphides and thiocyanates act similarly and must therefore be absent.
Mix a drop of the test solution and a drop of the iodine-azide reagent
on a watch glass. A vigorous evolution of bubbles (nitrogen) ensues.
Sensitivity: 0·15,ug. Na aS a0 3 • Concentration limit: 1 in 330,000.
The sodium azide-iodine reagent consists of a solution of 3 grams
of sodium azide in 100 ml. of O'lN iodine.

IV, 6. REACTIONS OF SULPHIDES, S--

Solubility.-The acid, normal and poly-sulphides of the alkali metals are
soluble in water; their aqueous solutions react alkaline because of hydrolysis.
The normal sulphides of most other metals are insoluble; those oj the alkaline
earths are difficultly soluble, hut are gradually changed by contact with water
into soluble hydrosulphides. The sulphides of aluminium, ch"omium and
magnesium are completely hydrolysed by water, and can be prep<1red only by
dry methods. The characteristic colours and solubilities of m'tIly metallio
sulphides have already been discussed in connexion with the reactions of the
cations in Chapter III. The sulphidos of iron, manganese, zinc and the alkali
metals are decomposed by dilute hydrochloric acid with the evolution of
hydrogen sulphide; those of lead, cadmium, nickel, cobalt, alltimony and
stannic tin require concentrated hydrochloric acid for decomposltion; others,
such as mercuric sulphide, are insoluble in concentrated hydrt,chloric acid,
but dissolve in aqua regia with the separation of sulphur. The) presence of
sulphide in insoluble "ulphides may bo detected by reduction with nascent
hydrogen (qerived from zinc or tin and hydrochloric acid) to t'lO metal and
hydrogen sulphide, the latter being identified with lead aceta' e paper (see
reaction 1 below). An alternative method is to fuse the sulpl ide with an-
hydrous sodium carbonate, extract the mass with water and to tre, tt the filtered
solution with freshly prepared sodillm nitroprusside solution, "hen a purple
colour will be obtained: the sodium carbonate solution may al'lo be treated
with lead nitrate solution when black lead sulphide is precipitated.
Na.S + H 20 ~ NaHS + NaOH;
NaHS + H 0 ~ R,S + NaOH;
2

2CaS + 2H.O ~ Ca(SH), + Ca(OH)>>

AI,Ss + 6H.O = 2Al(OH)3 + 3H t S

Use sodium sulphide, Na2S,9H20.

1. Dilute Hydrochloric Acid*: hydrogen sulphide gas is
evolved, which may be identified by its characteristic odour
and by the blackening of filter paper moistened with lead
acetate solution; alternatively, filter paper moistened with
cadmium acetate solution is turned yellow (CdS). A more
sensitive test is attained by the use of sodium pluillbite solu-
tion, prepared by adding sodium hydroxide solution to lead
• Or dilute sulphuric acid.
336 Qualitative Inorganic AnalY8i8 [IV,
acetate solution until the initial precipitate of lead hydrox[cte
has just dissolved.
Na2S + 2HCl = H 2S + 2NaCl;
Pb(C 2H 30 2h + H 2S = PbS + 2H. C2H a0 2
Pb(ONah + H 2S = PbS + 2NaOH
Hydrogen sulphide, like sulphur dioxide, is a good reducing
agent; it reduces (1) acidified potassium permanganate solu-
tion, (ii) acidified potassium dichromate solution and (iii) iodine
solution.
2KMn04 + 5H2S + 6HCI = 2KCI + 2MnC12 + SH20 + 5S;
K2Cr207 + 3H2S + SHCI = 2KCl + 2CrCI s + 7H20 + 3S;
H 2S + 12 ~ 2H1 +S
Small quantities of chlorine may be produced in (i) and (ii)
if the hydrochloric acid is other than very dilute; this is
avoided by using dilute sulphuric acid.
2. Silver Nitrate Solution: black precipitate of silver
sulphide Ag 2S, insoluble in cold, but soluble in hot dilute
nitric acid.
Na2S + 2AgN03 = Ag 2S + 2NaNOs
3. Lead Acetate Solution: black precipitate of lead
sulphide PbS (see under Lead, Section III, 2, reaction 5).
4. Barium Chloride Solution: no precipitate.
5. Silver.-When a solution of a sulphide is brought into
contact with a bright silver coin, a brown to black stain of
silver sulphide is produced. The result is obtained more
expeditiously by the addition of a few drops of dilute hydro-
chloric acid. The stain may be removed by rubbing the coin
with moist lime.
6. Sodium Nitroprusside Solution (Na2[Fe(CN)5NO]):
transient purple colour in the presence of solutions of alkalis.
No reaction occurs with solutions of hydrogen sulphide or with
the free gas: if, however, filter paper is moistened with a solu-
tion of the reagent made alkaline with sodium hydroxide or
ammonia solution, a purple coloration is produced with free
hydrogen sulphide.
Na2S + Na2[Fe(CN)5NO] = Na4 [Fe(CN)5NOS]
The reagent must be freshly prepared by dissolving a crystal
(about the size of a pea) of pure sodium nitroprusside in a little
distilled water.
 6] Reactions of the Acid Radica18 or Anion8 337
t The spot-test technique is as follows_ Mix on a spot plate a drop
of the alkaline test solution with a drop of a 1 per cent solution of
sodium nitroprusside_ A violet colour appears_ Alternativtlly, filter
paper impregnated with an ammoniacal (5 per cent) solution of sodium
nitroprusside may be employed.
Sensitivity: 1 /Lg. Na 2S. Concentration limit: 1 in 50,000.
t7.
Methylene Blue Test.-para-Aminodimethylaniline is con·
verted by ferric chloride and hydrogen sulphide in strongly aci,l solution
into the water-soluble dyestuff. methylene blue:

This is a sensitive test for soluble sulphides and hydrogen sulphide.

Place a drop of the test solution on a spot plate, add a drop of con·
centrated hydrochloric acid, mix, then dissolve a few grains of p-amino.
dimethylaniline in the mixture (or add 1 drop of a 1 per cent solution of
the chloride or sulphate) and add a drop of O'IN ferric chloride solution.
A clear blue coloration appears after a short time (2-3 minutos).
Sensitivity: I/Lg. H 2S. Concentration limit: 1 in 50,000.
tS. Catalysis of Iodine-Azide Reaction Test.-Soilltions of
sodium azide NaN s and of iodine (as KIa) do not react, but on the
addition of a trace of a sulphide, which acts as a catalyst, there is an
immediate evolution of nitrogen:
2NaN3 + 12 = 2NaI + 3N z
Thiosulphates and thiocyanates act similarly and must therefore be
absent. The sulphide can, however, be separated by precipita tion with
zinc or cadmium carbonate. The precipitated sulphide may then be
introduced, say, at the end of a platinum wire into a semimicro test·
tube or centrifuge tube containing the iodine-azide reagent, when the
evolution of nitrogen will be seen.
Mix a drop of the test solution and a drop of the reagent OIl a watch
glass. An immediate evolution of gas in the form of fine bubbles occurs.
Sensitivity: 0·3/Lg. Na 2 S. Concentration limit: 1 in 166,000.
The sodium azide-iodine reagent is prepared by dissolvin;: 3 grams
of sodium azide in 100 m!. of O'IN iodine. The solution is stable.
{The test is rendered more sensitive (to 0·02 /Lg. Na 2 S) by employing a
more concentrated reagent composed of I gram of sodium azide and a
few crystals of iodine in 3 m!. of water.}
338 Qualitative Inorganic AnalY8i8 [IV,

IV, 7. REACTIONS OF NITRITES, N02~

Solubility.-Silver nitrite is sparingly soluble in watQr. AU other 1, i: rites
are soluble in water. '
Use sodium nitrite, NaN0 2.
1. Dilute Hydrochloric Acid.-Cautiom; addition of the
acid to a solid nitrite in the cold yields a trltnsient, pale "Iue
liquid (due to the presence of free nitrous lLcid HN0 2 (J its
anhydride N 2 0 3 ) and the evolution of brown fumes of nitr ',~en
dioxide, the latter being largely produced by combinatic" 1 of
nitric oxide with the oxygen of the air. Similar result::: are
obtained with the aqueous solution.
NaNO z HCl+ = +
RNO z NaCl;
3RN02 = HzO + RNO s + 2NO;
2NO O2+ = 2N0 2
2. Ferrous Sulphate Solution.-When the nitrite solw ;,01\
is added carefully to a concentrated solution of ferrous sulp: •• ~te
acidified with dilute acetic acid or with dilute sulphuric ac: I, a
brown ring, due to the compound [Fe,NO]S04' is forme.! at
the junction of the two liquids. If the addition has not 1" 'cn
made cautiously, a brown coloration results. This reactic" 1 is
similar to the brown ring test for nitrates (see Section IV, 18,
reaction 3), for which a stronger acid (concentrated suIph 'I'ic 1

acid) must be employed.

2NaNO z 2Na.C2 H a0 2 + 2HN0 2 ;
+ 2H.C2 H s0 2 =
3HN02 = H 2 0 +
HNO a NO; +
FeS04 + NO = [Fe,NO]S04
Iodides, bromides, coloured ions and anions that give coloured
compounds with ferrous salts must be absent.
3. Barium Chloride Solution: no precipitate.
4. Silver Nitrate Solution: white crystalline precipitate
of silver nitrite from concentrated solutions.
AgNO s + NaN02 = AgN0 2 + NttNO a
5. Potassium Iodide Solution.-The addition of a nitrite
solution to a solution of potassium iodide, followed by acidi li-
cation with acetic acid or with dilute sulphuric acid, results
in the liberation of iodine, which may be identified by the blue
colour produced with starch paste. A similar result is obtained
7] Reactions of the Acid Radical,s or Anions 339
by dipping potassium iodide-starch paper moistened with a
little dilute acid into the solution. An alternative method is
to extract the liberated iodine with chloroform or carbon tetra-
chloride (see Section IV, 16, reaction 4).
2KI + 2HN02 + 2H. C2H s0 2
= 2K. CzHaO z + I2 + 2NO + 2H2 0
6. Acidified Potassium Permanganate Solution: de-
colourised by a solution of a nitrite, but no gas is evolved.
2KMn04 + 3H2S04 + 5HN02
= K 2S04 + 2MnS04 + 5HNOa + 3H20
7. Ammonium Chloride.-By boiling a solution of a
nitrite with excess of the solid reagent, nitrogen is evolved
and the nitrite is completely destroyed.
NaN0 2 + NH4Cl = NaCl + N2 + 2H 20
8. Urea {CO(NH2h}.-When a solution of a nitrite is
treated with urea and the mixture acidified with dilute hydro-
chloric acid, the nitrite is decomposed, and nitrogen and
carbon dioxide are evolved.
CO(NH 2)2 + 2HN02 = 2N2 + CO2 + 3H20
9. Thiourea {CS(NHzh}.-When a dilute acetic acid
solution of a nitrite is treated with a little thiourea, nitrogen
is evolved and thiocyanic acid is produced. The latter may
be identified by the red colour produced with dilute HCI and
FeCla solution.
1 CS(NH 2)2 + HN0 2 = N2 + HSCN + 2H 20.
Thiocyanates and iodides interfere and, if present, must be
removed either with excess of solid Ag 2S04 or with dilute
AgNO a solution before adding the acetic acid and thicurea.
10. Sulphamic Acid (HO.S0 2 .NH 2 ).-When a solution
of a nitrite is treated with sulphamic acid, it is completely
decomposed:
HO.S0 2 ·NII 2 + HN0 2 = Nz + H 2S04 + H 20
No nitrate is formed in this reaction, and it is then~fore an
excellent method for the complete removal of nitrite. Traces
of nitrates are formed with ammonium chloride, urea and thio-
urea (reactions 7, 8 and 9).
340 Qualitative Inorganic Analysis rIV,
t 11. SulphaniUc Acid-Cl-Naphthylamine Reagent.-Thi~ test
depends upon the diazotisation of sulphanilic acid by nitrous acid,
followed by coupling with Cl-naphthylamine to form a red azo dy(';

o'H'C'H,O~ RNO. O,K.o. + 'H,O,

~O.H ~H
I··C,HaO. QN=NQ:)
cp
~,:? ~

O
,:?
+
~
I # ~
I ~
I #
+ H.C. lI aO••
~OaH NH. SOsH NH.
Ferric salts must be masked by tartaric acid.
Place a drop of the neutral or acetic acid test solution on a spot i iate
and mix it with a drop of the sulphanilic acid reagent, followed "y a
drop of the oc-naphthylamine reagent. A red colour is formed.
Sensitivity: 0·01 J.Lg. HN0 2 • Concentration limit: 1 in 5,000,0(1 1).
The sulpbanilic acid rea~ent is prepared by dissolving 1 gralll of
sulphanilic acid in 100 ml. of warm 30 per cent acetic acid. ehe
Cl-naphthylamine reagent is prepared by boiling 0·3 gram cd oc-
naphthylamine with 70 ml. of water, filtering or decanting from the
small residue, and mixing with 30 ml. of glacial acetic acid.
t 12. Indole Reagent

a red-coloured nitroso-indole is formed.

Place a drop of the test solution in a semimicro test-tube, add 10
drops of the reagent and 5 drops of 15N sulphuric acid. A purplish-red
coloration appears.
Concentration limit: 1 in 1,000,000.
The reagent consists of a 0·015 per cent solution of indole in 96 per
cent alcohol.
IV, 8. REACTIONS OF CYANIDES, CN-
Solubility.-Only the cyanides of the alkali and alkaline earth metals ,"re
soluble in water; the solutions react alkaline owing to hydrolysis. Merc ., ric
cyanide Hg(CN), is also soluble in water, but is practically a non-electro,>te
and therefore does not exhibit the ionic reactions of cyanides. Many of I he
metallic cyanides dissolve in solutions of potassium cyanide to yield complex
salts (compare Section I, 20).
KCN + HIO -= KOH + HON
Use potassium cyanide, KeN.
8] Reactions of the Acid Radicals or Anions 341
Note. All cyanides are highly poisonous. The free acid
HON is volatile and is particularly dangerous so that all experi-
ments in which the gas is likely to be evolved, or those in
which cyanides are heated, should be carried out in the fume
cupboard.
1. Dilute Hydrochloric acid: hydrocyanic acid HON,
with an odour reminiscent of bitter almonds, is evolved in the
cold. It should be smelled with great caution. A more satis-
factory method for identifying hydrocyanic acid consists in
converting it into ammonium thiocyanate by allowing the
vapour to come into contact with a little yellow ammonium
sulphide on filter paper. The paper may be conveniently
placed over the test-tube or dish in which the substance is
being treated with the dilute acid. Upon adding a drop of
ferric chloride solution and a drop of dilute hydrochloric acid
to the filter paper, the characteristic red coloration, due to the
ferri-thiocyanate ion (Fe(SON)] + +, is obtained (see reaction 6
below). Mercuric cyanide is not decomposed by dilute acids.
KCN + HCI = KOI + HON
2. Silver Nitrate Solution: white precipitate of silver
cyanide AgON, readily soluble in excess of the cyanide solu-
tion forming the complex salt, potassium argentocyanide
K[Ag(ONh] (compare Section I, 20). Silver cyanide is soluble
in ammonia solution and in sodium thiosulphate solution, but
is insoluble in dilute nitric acid.
AgNO a + KON = AgON + KNO a ;
AgON + KON = K[Ag(ON)2]
3. Concentrated Sulphuric Acid.-Heat a little of the
solid salt with concentrated sulphuric acid; carbon monoxide
is evolved which may be ignited and burns with a blue flame.
All cyanides, complex and simple, are decomposed by this
treatment.
2KON + 2H 2S04 + 2H20 = 200 + K 2S04 + (NH4)~S04
4. Prussian Blue Test.-This is a delicate test and is
carried out in the following manner. The solution of the
cyanide is rendered strongly alkaline with sodium hydroxide
solution, a few ml. of a freshly prepared solution of ferrous
sulphate added (if only traces of cyanide are present, it is best
to use a saturated solution of ferrous sulphate) and the mixture
boiled. Potassium ferro cyanide is thus formed. Upon acidi-
fying with hydrochloric acid (in order to neutralise any free
alkali which may be present), a clear solution is obtained,
342 Qualitative Inorganic Analysi8 flV,
which gives a precipitate of Prussian blue upon the addi'lon
of a little ferric chloride solution. If only a little cyal,'lde
was used, or is present, in the solution to be tested, a g:'l,en
solution is obtained at first; this deposits Prussian blue on
standing.
FeS04 + 2NaOH = Fe(OHh + Na2S04;
Fe(OH)2 + 2KCN = Fe(CN)2 + 2KOH;
Fe(CN)2 + 4KCN = K 4[Fe(CN)6];
K 4[Fe(CN)6] + FeCla = KFe[Fe(CN)6Ja + 3KCl
5. Mercurous Nitrate Solution: grey precipitate of
metallic mercury (difference from chloride, bromide aad
iodide).
Hg2(NO ah + 2KCN = Hg(CN)2 + Hg + 2KNO s
Mercuric cyanide is very little ionised in solution. It is best analysed i 'y
adding excess of potassium iodide solution when the cyanogen is obtained In
an ionisable form:
Hg(CN)2 + 4KI = K 2[HgI.] + 2KCN
Mercuric cyanide is decomposed in solution by hydrogen sulphide, mercurio
sulphide (solubility product 4 X 10- 63 ) being precipitated (compare Solubility
Product, Section I, 15) and hydrocyanic acid being formed in solution. H the
precipitate is filtered off, the thiocyanate test may be applied to the solution.
Hg(CN). + H.S = EgS + 2ECN
6. "Ferri -thiocyanate" Test.-This is another excelle. di
test for cyanides and depends upon the direct combination ,f
alkali cyanides with sulphur (best derived from an alkali pol,l .
sulphide). A little ammonium polysulphide solution is addt d
to the potassium cyanide solution contained in a porcelain dis!',
and the whole evaporated to dryness on the water bath in tk
fume cupboard. The residue contains alkali and ammoniu]lI
thiocyanates together with any residual polysulphide. Th,.'
latter is destroyed by the addition of a few drops of hydro
chloric acid. One or two drops of ferric chloride solution a)'I'
then added. A blood-red coloration, due to the complex ferri
thiocyanate cation, is produced immediately:
CN- + S2-- = SCN- + S--;
SCN- + Fe+++ ~ [Fe(SCN)]++ (compare Section IV, 10,
reaction 6)
t The spot-test technique is as follows. Stir a drop of the test
solution with a drop of yellow ammonium sulphide on a watch glas~
and warm until a rim of sulphur is formed round the liquid (evaporation
to dryness, other than on a water bath, should be avoided). Add l-~
drops of dilute hydrochloric acid, allow to cool, and add 1-2 drops of
3 per cent ferric chloride solution. A red coloration is obtained.
Sensitivity: 1 /Lg. CN-. Concentration limit; 1 in 50,000.
8] Reactions of the AcU'"Raa"icals or Anions 343
The test is applicable in the presence of sulphide or sulphite; if thio-
cyanate is originally present, the cyanide must be isolated tirst by
precipitation, e.g. as zinc cyanide.
t7. Copper Sulphide Test.-Solutions of cyanides readily dissolve
oupric sulphide forming the oolourless potassium cuprocyanide:
2CuS + 10KCN = 2K a[Cu(CN),] + 2K zS + (CN)I
The test is best carried out on filter paper or drop-reaction paper and
is applicable in the presence of chlorides, bromides, iodides, fe1'ro- and
ferri-cyanides.
Place a drop of a freshly prepared copper sulphide suspension on a
filter paper (or on a spot plate) and add a drop of the test solution. The
brown colour of copper sulphide disappears at once.
Sensitivity: 2·5 p,g. CN-. Concentration limit: 1 in 20,000.
The copper sulphide suspension is prepared by dissolving 0·12
gram of crystallised copper sulphate in 100 m!. of water, adding a few
drops of ammonia solution and rendering the solution cloudy with a
little hydrogen sulphide.
An alternative procedure is to employ quantitative filter paper or drop-
reaction paper which has been impregnated with an ammoniacal solution
containing 0·1 gram of copper sulphate per 100 m!. and dried. Imme-
diately before the test a little hydrogen sulphide is blown on to the
paper so that it acquire" a uniform brown colour. Place a drop of the
test solution upon this paper when a white ring will be obtained.
Sensitivity: 2·5 p,g. CN-. Concentration limit: 1 in 20,000.
t8. Copper Acetate-Benzidine Acetate Test.-This reaction takes
place because the oxidation potential of cupric copper is increa,.,ed when
cuprous copper is removed by cyanide ions.
Mix a few drops of the test solution with a little dilute sulphuric acid
in a micro test-tube and tie (or otherwise fix) a piece of drop reaction
paper which has been moistened with II> mixture of equal parts of the
copper acetate and benzidine reagents on to the top of the tube. A blue
coloration is produced.
Sensitivity: 0·25 pg. CN-. Concentration limit: 1 in 200,000.
Oxidising and reducing gases interfere: it has been recommended that
the hydrocyanic acid be liberated by heating with sodium bicarbonate.
Alternatively, place a drop of the test solution (or a few milligrams
of the test solid) in the reaction bulb of Fig. II, 6, 13, add 2 thin pieces
of zinc foil and 2-3 drops of dilute sulphuric acid. Place a small circle of
quantitative filter paper (or drop reaction paper) moistened with cupric
acetate-benzidine acetate reagent across the funnel. The paper is
coloured blue by the hydrocyanic acid carried over with the hydrogen.
Sensitivity: lp,g. CN-. Concentration limit: 1 in 50,000.
The copper acetate reagent (solution I) is a 3 per cent solution of
copper acetate in water.
The benzidine reagent (solution II) is a 1 per oent solution of
benzidine in 10 per cent acetic acid.
These solutions are best "kept apart in black well-stopperEd bottles.
Equal volumes of solutions I and II are mixed immediately before
required.
344 Qualitative Inorganic Analy8is [IV,
IV, 9. REACTIONS OF CYANATES, CNO-
Solubility.-The cyanates of the alkalis and of the alkaline earths are so) ,ble
in water. Those of silver, mercurous mercury, lead and copper are insolilble
in water. The free acid is a colourless liquid with an unpleasant odour; it is
very unstable.
Use potassium cyanate, KCNO.
1. Dilute Sulphuric Acid: vigorous effervescence, due
largely to the evolution of carbon dioxide. The free cyanic
acid HCNO, which is liberated initially, is decomposed into
carbon dioxide and ammonia, the latter combining with the
sulphuric acid present to form ammonium sulphate. A little
cyanic acid, however, escapes decomposition and may be
recognised in the evolved gas by its penetrating odour. Upon
warming the resulting solution with sodium hydroxide soluti, Jil,
ammonia is evolved (test with mercurous nitrate paper).
KCNO + H 2S04 = HCNO + KHS04 ;
HCNO + H 2 0 + H 2S04 = CO 2 + NH4HS04
2. Concentrated Sulphuric Acid.-The reaction is simihr
to that with the dilute acid, but is somewhat more vigoroll".
3. Silver Nitrate Solution: white, curdy precipitate ,)f
silver cyanate AgCNO, soluble in ammonia solution and 111
dilute nitric acid (difference from silver cyanide).
KCNO + AgNO a = AgCNO + KNO s
4. Barium Chloride Solution: no precipitate.
D. Cobalt Acetate Solution.-When the reagent is addp·l
to a concentrated solution of potassium cyanate, a blue color;,
tion, due to potassium cobaltocyanate K 2[Co(CNO)4], is pr{)-
duced. The colour is stabilised and_ intensified somewhat Lv'
the addition of ethyl alcohol. .
Co(C 2H s0 2)z + 4KCNO = K 2[Co(CNO),] + 2K. C2H s0 2
6. Copper Sulphate-Pyridine Test.-When a cyanate
added to a dilute solution of a copper salt to which a few drop.;
of pyridine have been previously added, a lilac blue precipitate
is formed of the compound [CU(C5H5Nb (CNOb]; this is soluble
in chloroform with the production of a sapphire blue solution.
Thiocyanates interfere; excess of copper solution should be
avoided.
t Add a few drops of pyridine to 2-3 drops of a 1 per cent solution of
copper sulphate in about 10 mI. of water, then introduce about 2 ml
of chloroform followed by a few drops of the neutral cyanate solution.
Shake the mixture briskly: the chloroform will acquire a blue colour.
Concentration limit: 1 part cyanate in 20,000.
10] Reactions of the Acid Radica1-8 or Anions 345
The blue complex is stable in the presence of a moderate exces,~ of
acetic acid; the reaction can therefore be applied to the detection of
cyanates in alkaline solution. The solution to be tested is added to the
copper-pyridine-chloroform mixture, acetic acid added slowly and the
solution shaken vigorously after each addition. As soon 8S the solution
is neutral, the chloroform will assume a blue colour.

IV, 10. REACTIONS OF THIOCYANATES, SCN-·

Solubility.-Silver and cuprous thiocyanates are practically insoluhle in
water, mercuric and lead thioeyanates are sparingly soluble; the solubilities,
in grams per litre at 20°, are 0'0003, 0'0005, 0·7 and 0·45 respectively. The
thiocyanates of most other metals are soluble.
Use potassium thiocyanate (or sulphocyanide), KSCN.
1. Sulphuric Acid.-With the concentrated acid a yellow
coloration is produced in the cold: upon warming a violent
reaction occurs, carbonyl sulphide (burns with a blue flame)
and sulphur dioxide (fuchsin solution decolourised) may be
detected in the gaseous decomposition products, and a yellow
residue of sulphur remains.
KSCN + 2H2S04 + H 20 = COS + NH,HS04 + KHS04,
With the 5N acid no reaction occurs in the cold, but on
boiling a yellow solution is formed, sulphur dioxide and a. little
carbonyl sulphide are evolved. A similar but slower reaction
takes place with 2N sulphuric acid.
2. Silver Nitrate Solution: white, curdy precipitate of
silver thiocyanate AgSCN, soluble in ammonia solution but
insoluble in dilute nitric acid.
KSCN + AgNO s = AgSCN + KNOs
Upon boiling with N sodium chloride solution, silver thio-
cyanate is converted into silver chloride (AgSCN NaCI ~ +
AgCI + NaSCN-distinction and method of separation from
the silver halides); the aqueous solution may be acidified with
dilute hydrochloric acid and ferric chloride solutioll added
when the characteristic red coloration of the ferri-thiocyanate
ion will be obtained.
Silver thiocyanate also decomposes upon ignition or upon
fusion with sodium carbonate.
3. Copper Sulphate Solution: solution is coloured green;
with excess of the reagent, black cupric thiocyanate Cu(SCN)2
'" Raman spectra of thiocyanates appear to indicate that the ion is
S - C:=: N rather than S = C = N, since a line assignable to the triple
link and none for the double link was observed. Salts will be written as,
e.g., KSCN and the ion [SCNr or SCW.
 346 Qualitative Inorganic Analysis [IV,
is precipitated. If a mixture of solutions of cupric sull,hate
and sulphurous acid is added to the thiocyanate solution, \\ hite
cuprous thiocyanate (''uSCN is precipitated; it is insolub i " in
dilute hydrochloric and sulphuric acids.
2KSON + 2CuS04 + H 2SOS + H 2 0 = 2CuSON + K 2S04 + 211 S04
4. Mercuric Nitrate Solution: white precipitate of !er-
curie thiocyanate Hg(SCNh, readily soluble in excess 01 the
thiocyanate solution. If the precipitate is heated, it swell.; up
enormously forming "Pharaoh's serpents," a polymeI i ',ed
cyanogen product.
Hg(NOs)2 + 2KSCN = Hg(SON)2 + 2KN03 ;
Hg(SCN)2 + 2KSON = K 2[Hg(SON)4]
5. Zinc and Dilute Hydrochloric Acid: hydrogen sulpl1 ide
and hydrogen cyanide (poisonous) are evolved.
KSON + Zn + 3HOl = H 2 S + HON + ZnCl 2 + KCl
6. Ferric Chloride Solution: blood red coloration, dm' to
the complex ferri-thiocyanate cation [Fe(SCN)] + +. * The
colour can be extracted by shaking with ether. The red
colour is discharged by fluorides ([FeF6r-- formed), mercuric
chloride ([Hg(SCN)4r- formed) and oxalatea ([Fe(C 20 4hr---
formed). Tartrates, other hydroxy acids, ferrocyanides, phos-
phates, sulphides, thiosulphates and iodides interfere (the last-
named because free iodine is produced by the ferric ions).
Fe+++ + SON- ~ [Fe(SON)]H
7. Dilute Nitric Acid: decomposition occurs upon warming,
a red coloration is produced, and nitric oxide and hydrogen
cyanide (poisonous) are evolved.
KSCN + 2HNO s = KHS04 + 2NO HON +
A vigorous reaction occurs with concentrated nitric acid, nitric
oxide and carbon dioxide being evolved.
t8. Thiocyanic Acid (HSCN) Distillation Test.-This test is a
modification of 6, and avoids interferences such as those due to iodid"s
and ferrocyanides.
Place a few drops of the test solution in a semimicro test-tube,
acidify with dilute hydrochloric acid, add a small fragment of broken
porcelain and attach a gas absorption pipette (Fig.1l. 3, 19,0) charged
with a drop or two of ammonia solution. Boil the solution in the test-
tube gently so as to distil any HSCN present into the ammonia solution,
Rinse the ammonia solution into a clean semimicro test-tube, acidify
* At high concentrations of thiocyanate there is t!orne evidence that
(Fe(SCN)2]+ also exists in solution: the complexes have been formulated as
[Fe(SCN)n](~-n). The evidence for the presence of [Fe(SCN)]++ seeInS
indisputable and this formula will be adopted throughout this book.
10] Reactions of the Acid Radicals or Anions 347
slightly with dilute hydrochloric acid and add a drop of ferric chloride
solution. A red coloration is obtained.
9. Cobalt Nitrate Solution: blue coloration, due to
K 2[Co(CNS)4] (see under Cobalt, Section III, 24, reaction 6),
but no precipitate (distinction from cyanide, ferrocyanide and
ferricyanide) .
t The spot-test teclmique is as follows. Mix a drop of the test
solution in a micro-crucible with a very small drop (0·02 mI.) of a 1 per
cent solution of cobalt sulphate or nitrate and evaporate to dryness.
The residue, whether thiocyanate is present or not, is colourod violet
and the colour slowly fades. Add a jew drops of acetone. A blue-
green or green coloration is obtained.
Sensitivity: 1 p.g. SCN-. Concentration limit: 1 in 50,000.
Nitrites yield a red colour due to nitrosyl thiocyanate and therefore
interfere with the test.
t 1 O. Catalysis of Iodine-Azide Reaction Test.-Traces of thio-
cyanates act as powerful catalysts in tho otherwise extremely slow
reaction between iodine and sodium azide:
12 + 2NaN3 = 2Nal + 3N,
Sulphides (see Section IV, 6, reaction 8) and thiosulphates (seo Section
IV, 5, reaction 9) have a similar catalytic effect; these may be removed
by precipitation with mercuric chloride solution:
Hg++ + S-- = HgS;
Hg++ +S203-- +H 2 0 =HgS +SO,-- +2H+
Considerable amounts of iodine retard the reaction; iodine is therefore
best largely removed by the addition of cold saturated mercuril' chloride
solution whereupon the complex [HgJ,r-- ion, which does lIot affect
the catalysis, is formed.
Mix a drop of the test solution with 1 drop of the iodine-azide reagent
on a spot plate. Bubbles of gas (nitrogen) are evolved.
Sensitivity: 1·5p.g. KSCN. Concentration limit: 1 in 30,000.
The reagent is prepared by dissolving 3 grams of sodium azide in
100 ml. of O·}N iodine.
11. Cupric Sulphate-Pyridine Reagent.-Wben a neutral
solution of a thiocyanate is added to a dilute solution of a
copper salt containing a few drops of pyridine, a ydlowish-
green precipitate of the composition [Cu(C5H5Nh(SCN)21 is
formed; the compound is soluble in chloroforlf. to which it
imparts an emerald green coloration. Cyanates'interfere with
this reaction; excess of pyridine should be avoided.
t Add a few drops of pyridine to 3-4 drops of a 1 per cent solution of
copper sulphate in about 5 ml. of water, then introduce about 2 ml.
of chloroform, followed by a fow drops of the neutral thiocyanate
solution. Shake the mixture vigorolL'lly. The chloroform will acquire
a green colour.
Concentration limit: 1 part thiocyanate in 50,000.
348 Qualitative Inorganio Analysia [IV,

IV, 11. REACTIONS OF FERROCYANIDES,

[Fe(CN)6r---
Solubility.-The ferrocyanides of the alkali and alkaline earth met. ; are
soluble in water; those of the other metals are insoluble in water and , cold
dilute acids, but are decomposed by alkalis.
Use potassium ferrocyanide, K 4[Fe(CN)6],3H 20.
1. Concentrated Sulphuric Acid: complete decompo~ition
occurs on prolonged boiling with the evolution of c ['bon
monoxide, which burns with a blue flame. A little SD phur
dioxide may also be produced, due to the reduction oi the
sulphuric' acid by some of the ferrous sulphate.
K,[Fe(ON)6] + 6H2SO, + 6H20
= 2K 2SO, + 3(NH,hSO, + FeS04 + ! ;00;
2FeSO, + 2H2SO, ~ Fe2(804)a +
802 2H20 +
With dilute sulphuric acid, little reaction occurs in the I :old,
but on boiling a partial decomposition of the ferrocY;'lude
occurs with the evolution of hydrogen cyanide and the fo; ma-
tion of some ferrous sulphate. The latter reacts with sOJlle of
the undecomposed ferrocyanide yielding initially a precip,l,ate
of K 2Fe[Fe(CN)6], which is gradually oxidised to Prussian i Ilue
(see under Iron, Section III, 19, reaction 6).
K 4[Fe(CN)6] + 3H2SO, ~ 6HON + FeS04 +
2K2SO.
K 4[Fe(ON)6) + FeSO, ~ K2Fe[Fe(ON)6J + K 2 804

2. Silver Nitrate Solution: white precipitate of «,' ver

ferrocyanide Ag,[Fe(CN)6]' insoluble in ammonia solution tis-
tinction from ferricyanide) and in <Ulute nitric acid, but sol ble
in potassium cyanide solution and in sodium thiosulpi"Lte
solution. Upon warming with concentrated nitric acid, :he
precipitate is converted into the orange-red silver ferricyaliJde
and is then soluble in ammonia solution.
K 4[Fe(ON)6] + 4AgNO a = Ag4[Fe(ON}6] + 4KN(j~
3. Ferric Chloride Solution: precipitate of Prussian hlue
KFe[Fe(CN)6J in neutral and acid solutions (see under IJ' ,n,
Section III, 20, reaction 5); the precipitate is decomposed by
solutions of caustic alkalis, brown ferric hydroxide bcmg
formed.
t The spot-test technique is as follows. Mix a drop of the '"st
solution on a spot plate with a drop of ferrio chloride solution. A
blue precipitate or stain is formed.
Sensitivity: 1·3 p.g. K4[Fe(CN)e]. Concentration limit: 1 in 400,000.
II] iteactiona of the Acid itad~cal8 or Amona 349
4. Ferrous Sulphate Solution: white precipitate of potas-
sium ferrous ferro cyanide K 2Fe[Fe(CN)6], rapidly turning blue
owing to oxidation (see under Iron, Section II, 19, reaction 6).
5. Copper Sulphate Solution: brown precipitate of copper
ferro cyanide CU2[Fe(CN)6], insoluble in dilute acetic acid, but
decomposed by solutions of caustic alkalis.
K 4[Fe(CN)6] + 2CUS04 = CU2[Fe(CN)6] + 2K S04
2

6. Thorium Nitrate Solution: white precipitate of thorium

ferrocyanide Th[Fe(CN)6]' which is difficult to filter (distinction
and separation from ferricyanide and thiocyanate).
Th(N0 3 )4 + K 4[Fe(CN)6] = 4KN0 3 + Th[Fe(CN)61
7. Hydrochloric Acid.-Treatment of a concentrated solu-
tion of potassium ferro cyanide with hydrochloric acid results in
the formation of hydro ferro cyanic acid H 4 [Fe(CN)6J, which may
be isolated by extraction with ether, and obtained as a white
solid.
K 4[Fe(CN)6] + 4HCl = 4KCl + H 4[Fe(CN)6]
8. Ammonium Molybdate in Dilute Hydrochloric Acid
Solution: brown precipitate of molybdenyl ferrocyanide (dif-
ference and separation from ferricyanide and thiocyanate),
insoluble in dilute acids but soluble in solutions of alkali
hydroxides.
9. Titanium Chloride Reagent Test.-Ferrocyanides give
with the pale yellow solution of titanium tetrachloride in dilute
hydrochloric acid a reddish-brown, flocculent precipitate of
titanium ferrocyanide Ti[Fe(CN)6]' which is insoluble in 6N
hydrochloric acid. Ferricyanides give no precipitate: anions
(e.g. chromate, arsenate and nitrite) which oxidise ferro-
cyanides interfere.
t Place a drop of the test solution on a spot plate, just acidify with
dilute hydrochloric acid, and introduce 1 drop of the reagent. A
reddish-brown precipitate is produced by ferrocyanides.
The reagent is prepared (FUME CUPBOARD) by adding 10 ml.
of liquid TiCI, to 90 ml. of dilute hydrochloric acid (1 : 1).

10. Cobalt Nitrate Solution: greyish-green precipitate of

cobalt ferro cyanide CO 2[Fe(CN)6J with excess of the reagent,
insoluble in dilute hydrochloric and dilute acetic acids.
t 11. U rany! Acetate Solution: brown precipitate of uranyl ferro-
cyanide (U02)2[Fe(C~)6] in the presence of dilute acetic acid. Ferri-
cyanides react only in concentrated solutions, and after long standing
or heating to give the dirty yellow uranyl ferricyanide. Ferricyanides
350 Qualitative Inorganic Analysis [IV,
are reduced by filter paper to ferrocyanides. hence the test should not
be carried out on filter paper.
Place a drop of the test solution on a spot plate and add a dro:, of
N uranyl acetate solution. A brown precipitate or spot is obtained
within 2 minutes.
Sensitivity: 1 fLg. K 4[Fe(CN)61. Concentration limit: 1 in 50,00 11 ,
12. Action of Heat.-All ferro cyanides are decomposed on
heating, nitrogen and cyanogen being evolved.
3K4[Fe(ON)6] = N2 + 2(ON)2 + 12KON + FesO + 0

IV, 12. REACTIONS OF FERRICYANIDES,

[Fe(CN)6r--
Solubility.-The ferricyanides of the alkali and alkaline earth metals ',ud
of ferric iron are soluble in water; those of most of the other metals ,Ire
iILSoluble or sparingly soluble.
Use potassium ferricyanide, K3[Fe(CN)6J.
1. Concentrated Sulphuric Acid.-On warming a s,.lid
ferricyanide with this acid, it is decomposed completely, carl,)n
monoxide being evolved.
2K 3[Fe(ON}6] + 12H2S04 + 12H2 0
= 1200 + Fe2(S04h + 3K2S04 + 6(NH4h:- 0 4
With dilute sulphuric acid, no reaction occurs in the cold but
on boiling hydrocyanic acid is evolved.
2. Silver Nitrate Solution: orange-red precipitate of sil . er
ferricyanide Ag 3[Fe(ON)6J, soluble in dilute ammonia solut, Jll
(distinction from ferrocyanide), but insoluble in dilute ni': ric
acid.
Ks[Fe(ON)6] + 3AgNO s = Ag s[Fe(ON)6] + 3KNO a
3. Ferrous Sulphate Solution: dark blue precipitnte,
formerly termed Turnbull's blue, but now known to be identi 'al
with Prussian blue KFe[Fe(ON)6], in neutral or acid solut'l)n
(see under Iron, Section III, 19, reaction 7).
4. Ferric Chloride Solution: brown coloration, due to
ferric ferricyanide Fe[Fe(ON)6J (see under Iron, Section III, 20,
reaction 6).
5. Copper Sulphate Solution: green precipitate of cupric
ferricyanide OU3[Fe(ON)6h, insoluble in hydrochloric acid.
2Ks[Fe(ON)6) + 30US04 = OU3[Fe(ON)6)2 + 3K2S04
6. Concentrated Hydrochloric Acid.-The addition of
concentrated hydrochloric acid to a cold saturated solution of
potassium ferricyanide results in the separation of brown ferri-
cyanic acid H3[Fe(ON)6]'
l;iJ lteactwns OJ the Acut .lCaawal8 or Anwns 351
7. Potassium Iodide Solution: iodine is liberated. which
may be identified by the blue colour produced with starch
solution.
2K 3 [Fe(ON)6] + 2KI = 2~[Fe(ON}6] + 12
8. Cobalt Nitrate Solution: red precipitate of cobalt ferri-
cyanide Co 3 [Fe(CN)6]2, insoluble in hydrochloric add but
soluble in ammonia solution.
t9. Benzidine Reagent: blue precipitate of oxidation product.
Other oxidising agents (molybdates, c1Jromates, etc.) must be absent.
The test is applicable in the presence of ferrocyanide for benzidine
ferrocyanide is white: the sensitivity is, however, reduced end it is
best to precipitate the ferrocyanide first as the white insoluble lead
ferro cyanide by the addition of lead acetate, the ferricyanide remaining
in solution.
Mix a drop of the test solution on a spot plate with a dre p of the
benzidine reagent. If ferro cyanides are present, a drop of 1 per cent
lead nitrate solution should be added before the reagent. A blue
precipitate or coloration appears.
Sensitivity: 1 fLg. Ka[Fe(CN)s]. Con~entration limit: I in 50,000.
The reagent consists of 2N acetic acid saturated with benzidir:le in the
cold.
10. Action of Heat.-The decomposition is similar to that
of ferrocyanides (Section IV, 11, reaction 12).
6K 3[Fe(ON)6] = 6N2 + 3(ON)z + 18KON + 2FesO + 100
IV, 13. REACTION OF HYPOCHLORITES, CIO-
Solubility.-All hypochlorites are soluble in water. The solutions are
alkaline because of hydrolysis, and are decomposed by boiling.
NaOCl + H 2 0 ~ HOCI + NaOH
Use a solution of sodium hypochlorite, NaOCl. *
1. Dilute Hydrochloric Acid: the solution at first assumes
a yellow colour, effervescence occurs and chlorine is evolved.
The gas may be identified (a) by its greenish-yellow colour and
irritating odour, (b) by its bleaching of litmus paper and (c) by
its action upon potassium iodide-starch paper which it turns
blue-black.
NaOOI + HCI = HOOl + NaCl;
HOOl + HOI = Cl2 + H 20
2. Potassium Iodide-Starch Paper: assumes a bluish-
black colour in weakly alkaline solution as a resu] t of the
separation of iodine.
2KI + NaOOI + H 2 0 = 12 + 2KOH + NaOl
• Chloride is invariably present, and this will vitiate many ionic reactiOWI.
 352 CJualitatwe lnorganw AnatysM II Y t

3. Lead Acetate or Lead Nitrate Solution: brown I, ad

- dioxide Pb0 2 is produced on boiling.
Pb(C 2H a0 2 h + NaOCl + H 20= 2H.CzH a0 2 + Pb0 2 + NaCI
4. Cobalt Nitrate Solution.-Add a few drops of the re-
agent to a solution of the hypochlorite; a black precipitat ' of
cobalt oxide is obtained. On warming, oxygen is evo ,;ed
(identified by the rekindling of a glowing splint), the cobalt
oxide acting as a catalyst.
5. Mercury.-On shaking a slightly acidified (sulpli ;ric
acid) solution of a hypochlorite with mercury, a brown pre, ,pi-
tate of basic mercuric chloride (HgClhO is formed, whit I is
insoluble in water, but soluble in dilute hydrochloric l' 'id.
The precipitate is filtered off and dissolved in dilute hy: ro .
chloric acid; a black precipitate of mercuric sulphide is 0 bta; iled
on passing hydrogen sulphide into the solution.
Chlorine water, under similar conditions, gives a ""lite
precipitate of mercurous chloride Hg 2C1 2, insoluble in hy •ro-
chloric acid.
2Hg + 2HOOI = (HgCl)20 + H 20;
(HgCl)20 + 2HCl = 2HgC12 + H 2 0

IV, 14. REACTIONS OF CHLORIDES, cr

Solubility.-Most chlorides are soluble in water. Mercurous chI, ,! ide
Hg.CI., silver chloride AgCI, lead chloride PbCI, (this is sparingly solub> in
cold but readily soluble in boiling water), cuprous chloride CuCI, bisl] Ith
oxychloride BiOCI, antimony oxychloride SbOCI and mercuric oxychl,'ride
Hg.OCl. are insoluble in water.
Use sodium chloride, NaCl.
1. Concentrated Sulphuric Ac_id: considerable decomp"si-
tion of the chloride occurs in the cold, completely on warm Ilg,
with the evolution of hydrogen chloride, which is recogn' oed
(a) by its pungent odour and the production of white fun,es,
consisting of fine drops of hydrochloric acid, on blowing across
the mouth of the tube, (b) by the formation of white cloud of
ammonium chloride when a glass rod moistened with amm('; lia
solution is held near the mouth of the vessel and (c) by its
turning blue litmus paper red.
NaCl + H 2S04 = NaHS04 + HOI
2. Manganese Dioxide and Concentrated Sulphuric
Acid.-If the solid chloride is mixed with an equal quantity of
precipitated manganese dioxide, * concentrated sulphurio 11, ,id
• The commercial substanoe (pyrolusite) usually contains considel i ble
quantities of chlorides.
14] Reactions of the Acid Radicals or Anions 353
added and the mixture gently warmed, chlorine is evolved
which is identified by its suffocating odour, yellowish-green
colour, its bleaching of moistened litmus paper, and turning of
potassium iodide-starch paper blue. The hydrogen chloride
first formed is oxidised to chlorine.
Mn0 2 + 4HOI = Mn012 + 01 2 + 2H20
3. Silver Nitrate Solution: white, curdy precipitate of
silver chloride AgCl, insoluble in water and in dilute nitric acid,
but soluble in dilute ammonia solution and in potassium
cyanide and sodium thiosulphate solutions (see under Silver,
Section III, 4, reaction 1; also Complex Ions, Section I, 20).
The silver chloride is re-precipitated from the ammoniacal
solution by the addition of dilute nitric acid.
NaO} + AgNOs = AgOI + NaNOs;
AgOI + 2NHs = [Ag(NHs)2]01;
[Ag(NHal2]OI + 2HNOa = AgOI + 2NH4NO s
If the silver chloride precipitate is filtered off, washed with distilled
water and then shaken with sodium arsenite solution it is converted
into yellow silver arsenite and sodium chloride is formed (dhtinction
from silver bromide and silver iodide, which are unaffected by this
treatment). This may be used as a confirmatory test for a chloride.
NaaAsOa +3AgCl = 3NaCl +
AgaAsOa
4. Lead Acetate Solution: white precipitate of lead
chloride PbCl2 from concentrated solutions (see under Lead,
Section III, 2, reaction 1).
6. Potassium Dichromate and Sulphuric Acid (Chromyl
Chloride Test).-The solid chloride is intimately mixed with
three times its weight of powdered potassium dichromate in a
small distilling flask (Fig. IV, 2, 1), an equal bulk of concen-
trated sulphuric acid added and the mixture gently warmed. *
The deep-red vapours of chromyl chloride Cr02Cl2 which are
evolved are passed into sodium hydroxide solution contained
in a test-tube. The resulting yellow solution in the test-tube
contains sodium chromate; this is confirmed by acidifying with
dilute sulphuric acid, adding 1-2 m!. of amyl alcoholt followed
by a little hydrogen peroxide solution. The organic layer is
coloured blue. Alternatively, the diphenylcarbazide reagent
* This test must not be carried out in the presence of chlorates because of
the danger of fOrInmg explosive chlorme dioxide (Section IV, 19, reaction 1).
t Diethyl ether may alae be used, but owing to its highly inflammable
character and the possible presence of peroxides (unless previously removed
by special treatment), it is preferable to employ amyl aloohol or, less efficiently,
amyl acetate.
12+
354 Qualitative Inorganic AnalY8i8 [IV,
test (Section IV, 33, reaction 10) may be applied. The forllla-
tion of a chromate in the distillate indicates that a chloride xas
present in the solid substance, since chromyl chloride I'" a
readily volatile liquid (b.p. 116·5°0).
K2Cr207 + 4NaCI + 6H2S0 4
= 2Cr0 2Cl 2 + 2KHS04 + 4NaHS04 + 3H 0;
Cr02Cl2 + 4NaOH = Na2Cr04 + 2NaCI + 2H20
Some chlorine may be liberated by the reaction:
K2Cr207 + 6NaCI + 7H2S04
= 3C12 + K 2S04 + 3Na2S04 + Cr2(S04h + 7H cO
and this decreases the sensitivity of the test.
Bromides and iodides give rise to the free halogens, wh i, h
yield colourless solutions with sodium hydroxide: if the ral io
of iodide to chloride exceeds 1 : 15, the chromyl chloride
formation is largely prevented and chlorine is evolved *
Fluorides give rise to the volatile chromyl fluoride Cr021 c"
which is decomposed by water, and hence should be absent"r
removed. Nitrites and nitrates interfere as nitrosyl chlori, \)~
may be formed. Chlorates must, of course, be absent.
The chlorides of mercury, owing to their slight ionisation, do not respowi
to this test. Only partial conversion to CrO.Cl. occurs with the chlorides, ,f
lead, silver, antimony and tin.
t The spot-test technique is as follows. Into the tube of Fig. 11,6, 11
place a few milligrams of the solid sample (or evaporate a drop or tv.·'
of the test solution in it), add a small quantity of powdered potassiUl"
dichromate and a drop of ooncentrated sulphuric acid. Place a coIum' I
about 1 rom. long of a 1 per cent solution of diphenylcarbazide i
alcohol into the capillary of the stopper and heat the apparatus fl.'
a few minutes. The chromyl chloride evolved causes the reagent t,
assume a violet colour.
Sensitivity: 1·5 ILg. cr. Concentration limit: 1 in 30,000.
Alternatively, employ the same quantities of materials in the appara
tus of Fig. II, 6, 10, and replace the diphenylcarbazide solution by }\
drop of dilute alkali on the glass knob. Warm for a few minutes and.
after cooling, dip the glass knob into a few drops of the alcoholio di
phenylcarbazide solution which has been treated with a little dilut<-
sulphuric acid and is contained on a spot plate. A violet coloration i;,;
obtained.
Sensitivity: 0'3 ILg. Cl-. Concentration limit: 1 in 150,000.
* The iodine reacts with the chromic acid yielding iodic acid: the latter,
in the presence of concentrated sulphuric acid and especially on warming,
liberates chlorine from chlorides, regenerating iodide. This explains the
failure to form chromyl chloride.
15] Reaction8 of the Acid Radical8 or Anion8 355
Small amounts of bromides « 5 per cent) do not interfere, but large
amounts of bromides give rise to sufficient bromine to oxidise the
reagent. It is therefore best to add a little phenol to the reagent
solution, whereupon the bromine is removed as tribromophenol.
Nitrates interfere since nitrosyl chloride is formed, but they may be
reduced to ammonium salts. The interference of iodides is discussed
above.

IV, 15. REACTIONS OF BROMIDES, Br-

Solubility.-Silver, mercurous and cuprous bromides are insoluble in water.
Lead bromide is sparingly soluble in cold, but more soluble in boiling water.
All other bromides are soluble.
Use potassium bromide, KBr.
1. Concentrated Sulphuric Acid.-With the solid bromide,
a reddish-brown solution is first formed and reddish-brown
vapours of bromine accompany the hydrogen bromide (fuming
in moist air) which is evolved; the reaction is accelerated by
warming. The bromine is produced by the oxidation of the
hydrogen bromide by the sulphuric acid. If syrupy phos-
phoric acid H 3P04 is substituted for the sulphuric acid and
the mixture warmed, only hydrogen bromide, the properties
of which are similar to hydrogen chloride, is evolved.
KBr + H 2S0 = KHS0 + HBr;
4 4

2HBr + H 2S04 ~ Br2 + S02 + 2H20

KBr + H aP04 = KH 2 P04 + HBr
2. Manganese Dioxide and Concentrated Sulphuric
Acid.-When a mixture of a solid bromide, precipitated man-
ganese dioxide and concentrated sulphuric acid is warmed,
reddish-brown vapours of bromine are evolved, which is
recognised (a) by its powerful irritating odour, (b) by its
bleaching of litmus paper, (c) by its staining of starch paper
orange-red and (d) by the red coloration produced upon filter
paper impregnated with fluorescein (see Test 8 below).
2KBr + Mn0 2 + 3H2S04 = Br2 + 2KHS04 + MnS04 + 2H 20
3. Silver Nitrate Solution: curdy, pale yellow' precipitate
of silver bromide AgEr, sparingly soluble in dilute, but readily
soluble in concentrated ammonia solution. The precipitate is
also soluble in potassium cyanide and sodium thiosulphate
solutions, but insoluble in dilute nitric acid.
AgBr + 2NHa = [Ag(NHa)2JBr;
AgBl' + 2KCN = K[ Ag(CN)2J + KEr
 356 Qualitative Inorganic AnalY8i8 [IV,
4. Lead Acetate Solution: white crystalline precipitate of
- lead bromide PbBr2, sparingly soluble in cold, but soluble in
boiling water.
2KBr + Pb(C zH a0 2)2 = PbBr2 + 2K. C2H s0 2
5. Chlorine Water.*-The addition of this reagent drop-
wise to a solution of a bromide liberates free bromine, which
colours the solution orange-red; if carbon disulphide, chloro-
form or carbon tetrachloride (2 mI.) is added and the liquid
shaken, the bromine dissolves in the solvent (see The Distri-
bution Law, Section I, 43) and, after allowing to stand, forms
a reddish-brown solution below the colourless aqueous layer.
With excess of chlorine water, the bromine is converted into
yellow bromine monochloride or into colourless hypobromous
or bromic acid, and a pale-yellow or colourless solution result8
(difference from iodide).
2KBr + C12 = 2KC1 + Br2;
+
C12 Br2 + 2H 20 = 2HOBr 2HOl;+
5012+ Br2 + 6HzO = 2HBrOa + IORC1
2KBr + ROOl + HCI = 2KCI Br2+ H 20; +
Br2 + 5HOCI + H 20 = 2HBrOa 5HOI+
6. Potassium Dichromate and Concentrated Sulphuri c
Acid.-On gently warming a mixture of a solid bromide, COl \
centrated sulphuric acid and potassium dichromate (St'"
Chlorides, Section IV, 14, reaction 5) and passing the evolv(' I
vapours into water, a yellowish-brown solution, containiII'
free bromine but no chromium, is produced. A colourless (t·
sometimes a pale yellow) solution is o~tained on treatment wit:,
sodium hydroxide solution; this does not give the chroma1,'
reaction with dilute sulphuric acid, hydrogen peroxide an :
amyl alcohol, or with the diphenylcarbazide reagent (distinctio!,
from chloride). "-
-----------..........._
KZCr207 + 6KBr + 7H2S0 4
'.

= 3Br2 + Cr2(S04)a + 4K2S0 + 7H2l ) 4

7. Nitric Acid.-Hot and fairly concentrated nitric aci, I
oxidises bromides to bromine:
2KBr + 4HNOs = 2KNO a + 2N02 + Br2 + 2H20
t8. Fl_uores.celn Test.-Free bromine converts the yellow dyestuff
fiuorescem (I) mto the red tetrabromo-fiuorescein or eosin (II). Filtel
• In practice, it is more convenient to use dilute sodium hypochlorit,
solution, acidified with dilute hydrochloric acid. This may also react a
hypochlorous acid, HOCI.
 15] Reactions of the Acid Radicals or Anions 357
paper impregnated with fluorescein solution is therefore a valuable
reagent for bromine vapour since the paper acquires a red colour.
Br Br

H°Yy°II~O HOVY 0( 0

V~~~~
~COaH
B)~'~lli
U (I) (II)

Chlorine tends to bleach the reagent.. Iodine forms the red-violet

coloured iodo-eosin and hence must be absent. If the bromide is
oxidised to free bromine by heating with lead dioxide and acotic acid,
practically no chlorine is simultaneously evolved from chlorides, and
hence the test may be conducted in the presence of chlorides.
2NaBr + PbO. + <iR.CaRaOI
= Pb(C aH aO a)2+ 2Na.C zH aO z +
Bra +2HaO
Place a drop of the test solution together with a few milligrams of
lead dioxide and acetic acid into the apparatus of Fig. II, 6, 13, and
close the tube with the funnel stopper carrying a piece of filter paper
which has been impregnated with the reagent and dried. vVarm the
apparatus gently. A circular red spot is formed on the yellow test paper.
Altematively, the apparatus of Fig. II, 6, 14 may be used; a column,
about 1 mm. long of the reagent, is employed.
Sensitivity: 2 jLg. Bra. Concentration limit: 1 in 25,000.
The fluorescein reagent consists of a saturated solution of fluo-
rescein in 50 per cent alcohol.
t 9. Fuchsin (or Ma~enta) Test.-The dyestuff fuchsin (1) forms a

-HaN-c\ _ +
-
C=O=NHa CJ
HaND -
I
CH, (I)

colourless addition compound with a bisulphite. Free bromine con-

verts the thus decolourised fuchsin into a blue or violet brominated
dyestuff. Neither free chlorine nor free iodine affect the colourless
fuchsin bisulphite compound, hence the reaction may be employed for
the detection of bromides in the presence of chlorides and iodides.
Place a drop of the test solution (or a few milligrams of the test solid)
in the tube of the apparatus shown in Fig. II, 6, 14, add 2-,1 drops of
25 per cent chromic acid solution and close the apparatus with the
"head" which contains 1-2 drops of the reagent solution in the capillary.
358 Qualitative Inorganic Analysis [IV,
Warm the apparatus gently (do not allow it to boil). In a shor1 time
the liquid in the capillary assumes a violet colour.
Sensitivity: 3p.g. Br-. Concentration limit: I in 15,000.
The fuchsin-bisulphite rea~ent consists of a 0'1 per cent fu· hsin
solution just decolourised by sodium bisulphite.

IV, 16. REACTION OF IODIDES, r

Solubility.-The solubilities of the iodides are similar to those of the chI, ,ides
and bromides. Silver, mercurous, mercuric, cuprous and lead iodides afp the
least soluble salts.
Use potassium iodide, KI.
1. Concentrated Sulphuric Acid.-With a solid ioel de,
iodine is liberated; on warming, violet vapours are evol'., ·d,
which turn starch paper blue. Some hydrogen iodide is
formed-this can be seen by blowing across the mouth of (!1o
vessel, when white fumes are produced-but most of it redli' es
the sulphuric acid to sulphur dioxide, hydrogen sulphide i' Id
Bulphur, the relative proportions of which depend upon . ile
concentrations of the reagents. Pure hydrogen iodide is
formed on warming with syrupy phosphoric acid.
KI + H 2S04 = KHS04 + HI;
H 2S04 + 2HI ~ 12 + S02 + 2H2 0;
H 2S04 + 6HI = 312 + S + 4H 2 0;
H zS04 + SHI = 412 + HzS + 4H20
KI + H SP04 = KH 2P04 + HI
If manganese dioxide is added to the mixture, only iodine ;..
evolved.
2K1 + Mn0 2 + 3H2S04 = I2 + 2KHS04 + MnS04 + 3HzO
2. Silver Nitrate Solution: yellow, curdy precipitate (01
silver iodide AgI, readily soluble in potassium cyanide and il.
sodium thiosulphate solutions, very slightly soluble in con
centrated ammonia solution, and insoluble in dilute nitric acid.
KI + AgNO a = AgI + KNO a
3. Lead Acetate Solution: yellow precipitate of lead iodide
PbI 2 , soluble in much hot water forming a colourless solution,
and yielding golden-yellow plates (" spangles") on cooling.
Ph(CzHsOz)z + 2KI = PhIz + 2K. CzHsO z
4. Chlorine Water.*-When this reagent is added drop-
wise to a solution of an iodide, iodine is liberated, which colours
* In practice it is more convenient to use dilute sodium hypochlorite
solution acidified with dilute hydrochloric acid. This may react as hypo-
ohlorous acid, HOCI.
16] Reaction8 of the Acid Radicals or Anion" 359
the solution brown; on shaking with 1-2 ml. of carbon di-
sulphide, chloroform or carbon tetrachloride (see Section I, 43),
it dissolves forming a violet solution, which settles out below
the aqueous layer. The free iodine may also be identified by
the characteristic blue colour it forms with starch solution.
If excess of chlorine water is added, the iodine is oxidised to
colourless iodic acid.
2KI +
01 2 = 2KOI +
12;
+
5012 12 + 6H20 = 2HIOa + lOHOI
2KI +HOOI +
HOI = 2KOl + +
12 H 20;
12 + 5HOOI + H 20 = 2HIO a + 5HOI
5. Potassium Dichromate and Concentrated Sulphuric
Acid: only iodine is liberated, and no chromate is present in the
distillate (see Chlorides, Section IV, 14, reaction 5) (difference
from chloride).
K20r207 + 6KI + 7H S04 = 312 + Cr2(S04)a + 4K2S04 + 7H20
2

6. Sodium Nitrite Solution.-Iodine is liberated when this

reagent is added to an iodide solution acidified with dilute acetic
or sulphuric acid (difference from bromide and chloride). The
iodine may be identified by colouring starch paste blue, or
carbon tetrachloride violet.
+
NaN0 2 + H.02Ha02 = HN0 2 Na.02H S0 2;
2HN02 + 2HI = 12 +
2NO + 2H 20
7. Copper Sulphate Solution: brown precipitate consist-
ing of a mixture of cuprous iodide CuI and iodine. The iodine
may be removed by the addition of sodium thiosulphate solu-
tion or sulphurous acid, and a nearly white precipitate of
cuprous iodide obtained.
20US04 +4KI = 2CuI 12 + +
2K2S04
12 + 2Na2S20S = Na2S406 +
2NaI
8. Mercuric Chloride Solution: scarlet precipitate of
mercuric iodide HgI2' soluble in excess of .potassium iodide
solution.
HgCl z + 2KI = +
HgI z 2KOI;
HgI2 + 2KI = K 2[HgI41
t9. Starch Test.-Iodides are readily oxidised in acid solution to
free iodine by a number of oxidising agents; the free iodine may then be
identified by the deep blue coloration produced with starch solution.
The best oxidising agent to employ in the spot test reaction is aoidified
potassium nitrite solution:
2HI + 2HNO. = II +2NO +2H IO
360 Qualitative Inorganic Analy'" [IV,
Cyanides interfere because of the formation of cyg.no~en i~dide, they
are therefore removed before the test either by heatwg wIth s. i ium
bicarbonate solution or by acidifying and hea.ting:
I, + HCN .= lCN + HI
Mix a drop of the acid test solution on a spot plate with a. drop of the
reagent and a.dd a. drop of 10 per cent potassium nitrite solutiOl} A
blue coloration is obtained.
Sensitivity: 2·5 p.g. Ia. Concentration limit: 1 in 20,000.
The starch reagent is prepared by mixing 1 gram of soluble s: 'fch
and 0·005 gram of mercuric iodide (which acts as a preservative) VI . h a
little water into a padte and then pouring 500 ml. of boiling water ver
the paste.
t 10. Catalytic Reduction of Ceric Salts Test.-The reducti,," of
ceric salts in acid solution by arsenites takes place very slowly:
2Ce++++ + AsO a--- + H 20 = 2Ce+++ + AsO,--- + 2H+
Iodides accelerate this change, possibly owing to iodine liberated ll· ! he
instantaneous reaction (i):
2Ce H H + 2r = 2Ce+ H + I, \i)
reacting according to (ii):
AsO a--- + 12 + HIO = AsO,--- + 2r + 2H+ (ii)
the iodide ion reacting again as in (i). The completion of the reduc1 J' ,n
is indicated by the disappearance of the yellow colour of the c,' tC
solution. Osmium and ruthenium salts have a similar catalytic eff, . t.
Moderate amounts of chlorides, bromides, BulphawB and nitratBB hH \e
no llifluence, but cyanides and also mercuric, silver and mangan. "e
BaIts interfere.
Place a drop of the test solution together with a drop each of neutral
or slightly acid O'lN sodium arsenite solution and 0'05N ceric amn,
nium sulphate solution (in 2N sulphuric acid) on a spot plate. T 'l
yellow colour soon disappears.
Sensitivity: 0·03 p.g. l-. Concentration limit: 1 in 1,000,000.
tIl. Palladous Chloride Test.-Solutions of iodides react wi,',
paUadous chloride solution to yield a brownish.red precipitate of pHI-
ladous iodide PdIs, insoluble in mineral acids.
Mix a drop of the test solution on drop-reaction paper with a drop, ,f
a 1 per cent aqueous solution of palladous chloride. A brownish-blae
precipitate forms.
Sensitivity: 1 p.g. r. Concentration limit: 1 in 50,000.

IV, 17. REACTIONS OF FLUORIDES, F-

Solubility.-The fluorides of the common alkali metals ltnd of silver, mercury
aluminium and nickel are readily soluble in water, those of lead, copper, ferri,
iron, barium and lithium are slightly soluble, and those of the alkalme sarti
metals are insoluble in water.
Use sodium fluoride, NaF.
17] Reactions of the Acid Radicals or Anions 361
1. Concentrated Sulphuric Acid.-With the solid fluoride,
a colourless, corrosive gas, hydrogen fluoride HF, is evolved
on warming; the gas fumes in moist air, and the test-tube
acquires a greasy appearance as a result of the corrosive action
of the vapour on the silica in the glass, which liberates the gas,
silicon tetrafluoride SiF4 , By holding a moistened glass rod
in the vapour, gelatinous silicic acid H 4Si04 is deposited on the
rod; this is a product of the decomposition of the silicon tetra-
fluoride (compare Section VII, 17, test 8).
NaF + H 2S04 = NaHS04 + HF;
SiOz + 4HF = SiF4 + 2HzO;
3SiF4 + 4H zO = 2H 2 [SiF6] + H 4Si04
The same result is more readily attained by mixing the solid
fluoride with an equal bulk of silica, making into a pa:,te with
concentrated sulphuric acid and warming gently; silicon tetra-
fluoride is readily evolved.
t The spot-test teclmique of the reaction utilises the conversion of
the silicic and fluosilicic acids by mealls of ammonium molybdate into
silico-molybdic acid H 4 [SilVlo n O,o]' The latter, unlike free molybdic
acid, oxidises benzidine in acetic acid solution to a blue dyestuff and
"molybdenum blue" is simultaneously produced.
Mix the solid test sample with a little pure silica powder in the tube
of the apparatus shown in Fig. II, 6, 10 and moisten the silica with 1-2
drops of concentrated sulphuric acid. Place a drop of wator on the
glass knob of the stopper, insert it in position and heat the LLpparatus
gently for about 1 minute. Remove the source of heat and allow to
stand for 5 minutes. Wash the drop of water into a micro crucible,
add 1-2 drops of the ammonium molybdate reagent and warm the
mixture until bubbling just commences. Allow to cool, introduce a
drop of a 1 per cent solution of benzidine in 10 per cent aeetic acid
and a few drops of saturated sodium acetate solution. A blue colour
is obtained.
Sensitivity: 1 p.g. F.
The ammonium molybdate reagent is prepared by dissolving 1·5
grams of ammonium molybdate in 30 ml. of water (the addition of a
little ammonia solution may be nec'~ssary) and pouring into 10 m!. of
nitric acid (sp. gr. 1·2).
2. The Etchin~ Test.-A clean watch-glass is coated on
the convex side with paraffin wax, and part of the glass is
exposed by scratching a design on the wax with a nail or wire.
A mixture of about 0·3 gram of the fluoride and I ml. of con-
centrated sulphuric acid is placed in a small lead or platinum
crucible, and the latter immediately covered with the watch-
glass, convex side down. A little water should be poured in
the upper (concave) side of the watch-glass to prevent the wax
*12
362 Qualitative I nor'gan'ic A nalY8is IIV,
from melting. The crucible is very gently warmed (best (,n a
boiling water bath). After 5-10 minutes, the hydru' en
fluoride will have etched the glass. This is readily seen a i' er
removing the paraffin wax by holding above a flame or ", i th
hot water, and then breathing upon the surface of the glat.
The test may also be conducted in a small lead capsule, provj, led
with a close-fitting lid made from lead foil. A small hole of a1- at
3 mm. diameter is pierced in the lid. About 0·1 gram of the, 18-
pected fluoride and a few drops of concentrated sulphuric acid 're
placed in the clean capsule, and a small piece of glass (e.g. a micro-
scope slide) is placed over the hole in the lid. Upon warming vcry
gently (best on a water bath) it will be found that an etched spot
appears on the glass where it covers the hole.
Chlorates, silicates and borates interfere and should therefore be
absent.
3. Silver Nitrate Solution: no precipitate, since silyer
fluoride is soluble in water.
4. Calcium Chloride Solution: white, slimy precipita te
of calcium fluoride CaF2 , sparingly soluble in acetic acid, hit
slightly more soluble in dilute hydrochloric acid.
2NaF + CaCl z = CaFz + 2NaF
5. Ferric Chloride Solution: white crystalline precipita I e
of the complex salt Na3[FeF6] from concentrated solutions ,f
fluorides, sparingly soluble in water. The precipitate does TI, ,t
give the reactions of iron (e.g. with ammonium thiocyanate),
except upon acidification.
FeCl s + 6NaF = Nas[FeF6J + 3NaCI
t6. Zirconium-Alizarin Lake Test.~Hydrochloric acid solutionfl
of zirconium salts are coloured reddish-violet by alizarin-S or by alizarin
(see under Aluminium, Section III, 21, reactions 8 and 9, and under
Zirconium, Section IX, 14, reaction 12); upon adding a solution of It
fluoride the colour of such solutions changes immediately to a pale
yellow (that of the liberated alizarin sulphonic acid or alizarin) because
of the formation of the colourless zirconi-fluoride ion [ZrF.r-. Tho
test may be performed on a spot plate.
Mix together on a spot plate 2 drops each (equal volumes) of a 0' I
per cent aqueous solution of alizarin-S (sodium alizarin sulphonate) and
zirconyl nitrate solution (0'1 gram of the solid zirconyl nitrate dis-
solved in 20 ml. of concentrated hydrochloric acid and diluted to 100
mI. with water): upon the addition of a drop or two of the fluoride
solution the zirconium lake is decolourised to a clear yellow solution.
Alternatively, mix 2 drops each of the alizarill-S and zil'conyl nitrate
solutions in a semimicro test-tube, add a drop of dilute hydrochloric
acid or of 50 per cent acetic acid, followed by 2 drops of the test solution.
The pink colour will change to yellow.
18J Reactions of the Acid Radicals or Anions 363
The most sensitive method of carrying out the spot test is as follows.
Impregnate some quantitative filter paper or drop reaction pllper with
the zirconium-alizarin-S reagent, dry it and moisten with a drop of 50
per cent acetic acid. Place a drop of the neutral test solution upon the
moist red spot,; the spot will turn yellow.
Sensitivity: 1 /Lg. F-. Concentration limit: 1 in 50,OO!}.
Large amounts of sulphates, thiosul phates, nitrites, arsenates, phos-
phates and oxalates interfere with the test.
The zirconium-alizarin-S paper is prepared as follows. Immerse
quantitative filter paper (or drop-reaction paper) in a 5 per cent solution
of zirconium nitrate in 5 per cent hydrochloric acid, drain and place in
a 2 per cent aqueous solution of alizarin-So Wash the paper, which is
coloured red-violet by the zirconium lake, until the washings are nearly
colourless and then dry in air.

IV, 18. REACTIONS OF NITRATES, N0 3 -

Solubility.-All nitrates are soluble in water. The nitrates of mercury and
bismuth yield basic salts on treatment with water; these are solublo in dilute
nitric acid.
Use sodium nitrate, NaNO a•
1. Concentrated Sulphuric Acid: reddish-brown vapours
of nitrogen dioxide, accompanied by pungent acid vapours of
nitric acid which fume in the air, are formed on heating the
solid nitrate with the reagent. The nitric acid initially formed
is decomposed by heating. Dilute sulphuric acid has no action
(difference from nitrite).
NaNO a + H 2S04 = NaHS04 + HNO a ;
4HNO a = 4N0 2 + O2 + 2H2 0
Z. Concentrated Sulphuric Acid and Bright Copper
Turnings.-On heating these with the solid nitrate, reddish-
brown fumes of nitrogen dioxide are evolved, and the solution
acquires a blue colour owing to the production of cupric nitrate.
A solution of the nitrate may also be used; the sulphuric acid
is then added very cautiously.
Cu + 4HNOa = CU(NO a)2 + 2N02 + 2H 2 0;
3Cu + SHNO a = 3Cu(NO ah + 2NO + 4H 20
2NO + O2 = 2N02
3. Ferrous Sulphate Solution and Concentrated Sul-
phuric Acid (Brown Ring Test).-This test is carried out
in either of two ways: (a) Add 3 ml. of a freshly prepared
saturated solution of ferrous sulphate to 2 ml. of the nitrate
solution, and pour 3-5 ml. of concentrated sulphuric acid slowly
down the side of the test-tube so that the acid forms a layer
 ,
364 Qualitative Inorganic AnalY8i8 [IV,
beneath the mixture. A brown ring will form where the lie I' dds
meet. (b) Add 4 m!. of concentrated sulphuric acid slowl." to
2 m!. of the nitrate solution, mix the liquids thoroughly md
cool the mixture under a stream of cold water from the ; ap.
Pour a saturated solution of ferrous sulphate slowly down "he
side of the tube so that it forms a layer on top of the lie Ilid.
A brown ring will form at the zone of contact of the two liql;ids.
The brown ring is due to the formation of the comp<"!lld
[Fe(NO)]S04. On shaking and warming the mixture the bI ,wn
colour disappears, nitric oxide is evolved and a yellow solutio, of
ferric sulphate remains. The test is unreliable in the present of
bromide, iodide, nitrite, chlorate and chromate (see Section IV, 45,
3 and 4).
NaNOs + H 2SO, = NaHSO, + HNO s ;
6FeSO, + 2HNO a + 3H 2SO, = 3Fe s(SO,)s + 2NO + 4H sO;
FeSO, + NO = [Fe(NO)]SO,
Bromides and iodides interfere because of the liberated halog"n;
the test is not trustworthy in the presence of chromates, sulphi' 's,
thiosulphates, iodates, cyanides, thiocyanates, ferro- and ft, :'i-
cyanides. All of these anions may be removed by adding ex(' -;s
of nitrate-free Ag 2S04 to an aqueous solution (or sodium carbon, "e
extract), shaking vigorously for 3-4 minutes, and filtering the .1\-
soluble silver salts, etc.
Nitrites react similarly to nitrates. They are best removed by
adding a little sulphamic acid (compare Section IV, 7, reaction 10).
The following reaction takes place in the cold:
HO.SOa.NHa + NaNOs = N2 + NaHSO, + H 20
t The spot-test technique is as follows. Place a crystal of ferr(,,,,,
sulphate about as large as a pin head on _a spot plate. Add a drop, ,f
the test solution and allow a drop of concentrated sulphuric acid to 1""1
in at the side of the drop. A brown ring forms round the crystal, ,f
ferrous sulphate.
Sensitivity: 2·5 p.g. NOs -. Concentration limit: I in 25,000.
4. Aluminium or Zinc and Sodium Hydroxide Solution
(Ammonia Test).-Ammonia is evolved (detected by it,
odour; by its action upon red litmus paper and upon mercurou"
nitrate paper; or by the tannic acid-silver nitrate test, Section
III, 36, reaction 7) when a solution of a nitrate is boiled wit, I
zinc dust or gently warmed with aluminium powder an']
sodium hydroxide solution. Excellent results are obtained bl
the use of Devarda's alloy (45 per cent Al, 5 per cent Zn an,!
50 per cent eu). The reduction is due to the nascent hydrogel!
produced in the reaction. Ammonium ions must, of course,
18) Reactions oj the Acid Radicals or Anions 365
be removed by boiling the solution with sodium hydroxide
solution (and, preferably, evaporating almost to drynesH) before
the addition of the metal.
NaN0 3 + 4Zn + 7Na0H = NH3 + 4Na2[Zn02] + 2H20
3NaNO a + SAl + 5NaOH + 2H20 = 3NH3 +- SNa[AI0 2]
Nitrites give a similar reaction and may be removed mmt simply
with the aid of sulphamic acid (see test 3). Another, but more expen-
sive, procedure involves the addition of sodium azide to the acid solution;
the solution is allowed to stand for a short time and then boiled in order
to complete the reaction and to expel the readily volatile hydrogen
azide:
RNO! + HNII = Na + NaO + HaO
Other nitrogen compounds which evolve ammonia under the auove
conditions are cyanides, thiocyanates, ferrocyanides and ferricyanides.
These may be removed by treating the aqueous solution (or a sodium
carbonate extract) with excess of nitrute-free AgzSO, (Compare Section
IV, 45, 3), warming the mixture to about 60°, shaking vigorously for
3-4 minutes and filtering from the silver salts of the interfering anions
and excess of precipitant. The excess of silver ions is removed from
the filtrate by adding an excess of NaOH solution, and filtering from
the precipitated silver oxide. The filtrate is concentrated and tested
with zinc, aluminium or Devarda's alloy.
Attention is directed to the fact that arsanites are reduced in alkaline
solution by aluminium, Devarda's alloy, etc., to arsine, which blackens
mercurous nitrate paper and also gives a positive tannic ucid-silver
nitrate test. Hence neither the mercurous nitrate test nor the tannic
acid-silver nitrate test for ammonia is applicable if arsenites are present.
t The spot-test technique is carried out as follows. Place a drop of
the test solution in the tube of Fig. II, G, 13, add 1-2 drop" of 10 per
cent sodium hydroxide solution and a few milligrams of Devarda's
alloy. Place a watch-glass with a drop of p-nit,robenzene-djazonium
chloride reagent (for preparation, see under Ammonium, Section III, 36,
reaction 7) on its under side upon the funnel stopper. Heat the
apparatus gently for a short time. Add a tiny fragment (If calcium
oxide to the drop of the reagent.: a red ring forms within 10-15 seconds.
Sensitivity: 10 p,g. NOs -. Concentration limit: 1 in 5,000.
5. Diphenylamine Reagent (C6Ho' NH. C6Ho).-Pour the
nitrate solution carefully down the side of the test-tube so
that it forms a layer above the solution of the reagent; a blue
ring is formed at the zone of contact of the two liqujds. The
test is a very sensitive one, but unfortunately is also given by
a number of oxidising agents, such as nitrites, d ..lorates,
bromates, iodates, permangaml,tes, chromates, vanadates,
molybdates and ferric salts.
The rea~ent is prepared by dissolving 0·5 gram of diphenylamine
in 100 ml. of concentrated sulphuric acid diluted with 20 m1. of water.
 366 Qualitative Inorganic Analysis [IV,
6. Nitron Reagent (diphenyl-endo-anilo-dihydrotr!:Lzole
C2oH 16N 4),
C.H6N N

II NC6H,ll
HdOc
NC.H6
white crystalline precipitate of nitron nitrate C2oH16N4,}i ~03
with solutions of nitrates. Bromides, iodides, nitrites, ':lro·
mates, chlorates, perchlorates, thiocyanates, oxalates :1nd
picrates also yield insoluble compounds, and hence the rea, ,t ion
is not very characteristic.
The reagent is prepared by dissolving 5 grams of nitron in 10" ml.
of 5 per cent acetic acid.

7. Action of Beat.-The result varies with the metal. The

nitrates of sodium and potassium evolve oxygen (test ,\ ith
glowing splint) and leave solid nitrites (brown fumes with di ILte
acid); ammonium nitrate yields nitrous oxide and steam; I he
nitrates of the noble metals leave a residue of the metal, ,nd
a mixture of nitrogen dioxide and oxygen is evolved; '!le
nitrates of the other metals, such as those of lead and COPVT,
evolve oxygen and nitrogen dioxide, and leave a residue of ,lie
oxide.
2NaNO s = 2NaNO z O2 ; +
NH4NO s = N 20 + 2H zO;
2AgNO s = 2Ag +2NO z O2 ;+
2Pb(NO s)2 = 2PbO +4N0 2 O2 +
tB. Reduction to Nitrite Test.-Nitrates are reduced to mtntes /,_v
metallic zinc in acetic acid solution; the nitrite can be readily detect, d
by means of the sulphanilic acid-OG.naphthylamine reagent (see unli. r
Nitrites, Section IV, 7, reaction 11). Nitrites, of course, interfere al ,I
are best removed with sulphamic acid (see reaction 3 above).
Mix on a spot plate a drop of the neutral or acetic acid test soluti, "
with a drop of the sulphanilic acid reagent and a drop of the OG.naphth~
amine reagent, and add a few milligrams of zinc dust. A red colorati(",
develops.
Sensitivity: 0·05p.g. NO a-. Concentration limit: 1 in 1,000,000.

IV, 19. REACTIONS OF CHLORATES, CIO s-

Solubility.-All chlorates are soluble in water; potassium chlorate is one of
the least soluble (66 grams per litre at 18°) and lithium chlorate one of th,
most soluble (3150 grams per litre at 18°).
Use potassium chlorate, KCl0 3 •
19] Reactions oj the Acid Radicals or Anion" 367
1. Concentrated Sulphuric Acid (DANGER).-All
chlorates are decomposed with the formation of the greenish-
yellow gas, chlorine dioxide CI0 2 , which dissolves in the sul-
phuric acid to give an orange-yellow solution. On warming
gently (DANGER) an explosive crackling occurs, which may
develop into a violent explosion. In carrying out this test one
or two small crystals of potassium chlorate (weighing not more
than 0'1 gram) are treated with 1 mi. of concentrated sulphuric
acid in the cold; the yellow explosive chlorine dioxidn can be
seen on shaking the solution. The test-tube should not be
warmed, and its mouth should be directed away fl'om the
student.
3KCI0 s + 3H2S04 = 2CI0 2 + HCI04 + 3KHSO, + H 2 0
2. Concentrated Hydrochloric Acid.-All chlorates are
decomposed by this acid, and chlorine, together with varying
quantities of the explosive chlorine dioxide, are evol \Ted; the
latter imparts a yellow colour to the acid. The mixture of
gases is sometimes known as "euchlorine." The experiment
should be conducted on a very small scale, not more than
0·1 gram of potassium chlorate being used. The following
two chemical reactions probably occur simultaneously:
2KCI0s + 4HCl = 2CI0 2 + C1 2 + 2H zO + 2KCI;
KCIO s + 6HCl = 3Cl2 + 3H2 0 + KOI
3. Sodium Nitrite Solution.-On warming this reagent
with a solution of the chlorate, the latter is redueed to a
chloride, which may be identified by adding silver nitrate
solution after acidification with dilute nitric acid. The nitrite
must, of course, be free from chloride. A solution of sul-
phurous acid or offormaldehyde (10 per cent; 1 part of formalin
to 3 parts of water) acts similarly. Excellent results are
obtained with zinc, aluminium or Devarda's alloy and sodium
hydroxide solution (see under Nitrates, Section IV, 18, re-
action 4); the solution is acidified with dilute nitric acid after
several minutes boiling, * and silver nitrate solution added.
KCIOs + 3NaN02 = KCl + 3NaNOs
KOlOs + 3HzSOs = KOI + 3HzS04
KOlOs + 3H.OHO = KOI + 3H.COOH
KClO a + 3Zn + 6NaOH = KCI + 3Na2[Zn02] + 3HzO
KOlOs + 2Al + 2NaOH = KCI + 2Na[Al0 2] + H:!O
... It is best to filter off the excess of metal before adding the silver nitrate
solution.
368 Qualitative Inorganic A nalysilf rIV,
4. Silver Nitrate Solution: no precipitate in neutral' ,lu-
tion or in the presence of dilute nitric acid. Upon the add,' ion
of a little pure (chloride-free) sodium nitrite to the dilute IJ, ~ ·ric
acid solution, a white precipitate of silver chloride is obta"led
because of the reduction of the chlorate to chloride, (sec re-
action 3 above).
No precipitate is obtained with barium chloride solution.
5. Potassium Iodide Solution: iodine is liberated ira
mineral acid is present. If acetic acid is used, no io(' i ne
separates even on long standing (difference from iodate).
6. Ferrous Sulphate Solution: reduction to chloride U' 'dn
boiling in the presence of dilute mineral acid (difference fi ,m
perchlorate) .
KOl0 3 + 6FeS04 + 3H2S04 = KCl + 3Fc2(S04)s + 3H20
7. Indigo Test.-A dilute solution of indigo in concentra: "d
sulphuric acid is added to the chlorate solution until the lat; ,~r
has a pale-blue colour. Dilute sulphurous acid or sodh m
sulphite solution is then added drop by drop; the blue col(·, lr
is discharged. The chlorate is reduced by the sulphurous a, .:1
to chlorine or to hypochlorite, and the latter bleaches 1 i ,e
indigo.
S. Aniline Sulphate Test {(C6H5 .NH2)2H2S04 }.-A sm,!!l
quantity of the solid chlorate (say, :j>O'05 gram) (DANGE I:)
is mixed with 1 m!. of concentrated sulphuric acid, and 2-3 1 .!.
of aqueous aniline sulphate solution added; a deep-blue colo r
is obtained (distinction from nitrate).
t9. Manganous Sulphate. Phosphoric Acid Test.-Mangano 1
sulphate in syrupy phosphoric acid solution reacts with chlorates
form the violet-coloured mangani-phosphate ion:
6Mn++ + 12PO,--- + 6H+ + ClO s-
= 6[Mn(PO')2r-- + Cl- + 3H~ )
Persulphates, nitrites, bromates, iodates and also periodates rea"
similarly. The first-named may be decomposed by evaporating tJ
sulphuric acid solution with a little silver nitrate as catalyst:
2H 2S 20 S + 2H 20 = 4H 2SO, + O 2
Place a drop of the test solution in a micro crucible and add a dro:,
of the reagent. 'Warm rapidly over a micro burner and allow to coo
A violet coloration appears. Very pale colorations may be intensifie·!
by adding a drop of 1 per cent alcoholic diphenylcarbazide solutio"
when a deep violet colour, due to an oxidation product of the dipheny:
carbazide, is obtained.
Sensitivity: 0·05/Lg. CIO a-. Concentration limit: 1 in 1,000,000.
The reagent is prepared by mixing equal volumes of saturated man-
ganous sulphate solution and syrupy phosphoric acid.
20] ReactioM of the Acid Radicala or AnioM 369
10. Action of Heat.-All chlorates are decomposed by heat
into chlorides and oxygen. Some perchlorate is usually formed
as an intermediate product. The chloride is identified in the
residue by extracting with water and adding dilute nitl'ic acid
and silver nitrate solution. An insoluble chlorate should be
mixed with sodium carbonate before ignition.
2KCIO s = 2KCI + 30 2 ;
2KCIOs = KCI04 + KCI + O2

IV,20. REACTIONS OF BROMATES, BrOa-

Solubility.-Silver, barium and lead bromates are slightly soluble in water,
the solubilities being respectively 2·0 grams, 7·0 grams and 13·5 grams per
litre at 20°; mercurous bromate is also sparingly soluble. Most of the other
metallic bromatea are readily soluble in water.
Use potassium bromate, KBrOa.
1. Concentrated Sulphuric Acid.-Add 2 ml. of the acid
to 0·5 gram of the solid bromate; bromine and oxygen are
evolved in the cold in consequence of the decomposition of the
liberated bromic acid.
4HBrOs = 2Brz + 50 2 + 2H20
2. Silver Nitrate Solution.-A white crystalline preCIpI-
tate of silver bromate AgBrOa is produced with a concentrated
solution of a bromate. The precipitate is soluble in hot water,
readily soluble in dilute ammonia solution forming a complex
salt, and difficultly soluble in dilute nitric acid.
AgBr03 + 2NH3 = [Ag(NH 3 h]BrOs
Precipitates of the corresponding bromates are also produced
by the addition of solutions of barium chloride, lead acetate
or mercurous nitrate to a concentrated solution of a bromate.
If the solution of silver bromate in dilute ammonia solution
is treated dropwise with sulphurous acid solution, silver
bromide separates: the latter dissolves in concentrated ammonia
solution (difference from iodate).
3. Sulphur Dioxide.-If the gas is bubbled through a solu-
tion of a bromate, the latter is reduced to a bromide (see
Bromides, Section IV, 15). A similar result is obtained with
hydrogen sulphide and with sodium nitrite solution (see under
Chlorates, Section IV, 19, reaction 3).
KBr03 + 3H 2SO S = KBr + 3H2S04
KBrOs + 3H2S = KBr + 3H2 0 + 3S
KBrOs + 3NaN0 2 = KBr + 3NaNO s
370 Qualitative Inorganic Analy8is [IV,
4. Hydrobromic Acid.-Mix together solutions of P' ,tas-
sium bromate and bromide, and acidify with dilute sulpLuric
acid; bromine is liberated as a result of interaction bet II een
the bromic and hydrobromic acids set free. The bromine may
be extracted by adding a little chloroform or carbon t\·tra-
chloride.
HBrOs + 5HBr = 3Br2 + 3H20
5. Action of Heat.-Potassium bromate on heating ev, ,ives
oxygen and a bromide remains. No perbromate is forilled.
Sodium and calcium bromates behave similarly, but co halt,
zinc and other similar metallic bromates evolve oxygen and
bromine, and leave an oxide.
6. Manganous Sulphate Test.-If a bromate soluti. :1 is
treated with a little of a 1 : 1 mixture of saturated manga"ous
sulphate solution and 2N sulphuric acid, a transient red
coloration (due to manganic sulphate) is observed. Vpon
concentrating the solution rapidly, brown hydrated manganese
dioxide separates. The latter is insoluble in dilute sulp] ! lric
acid, but dissolves in a mixture of dilute sulphuric and 0'. Llic
acids (difference from chlorates and iodates, which neither ~ive
the coloration nor yield the brown precipitate).
HBr03 + 6MnS0 + 3H2S0 = HBr + 3Mn (S04h + 3H~O;
4 4 Z
HBrOs + 5HBr = 3Br2 + 3HzO
MnzOs + Br2 + H 20 = 2Mn0 2 + 2HBr
t In the spot test technique, the reaction is combined with a sem l! ive
test for manganese (oxidation of benzidine by manganese dioxic, to
"benzidine blue"). Place a drop of the test solution in a semiI" ,ero
centrifuge tube, add a drop or two of 2 per cent manganous suII",,1te
solution acidified with dilute sulphuric acid and warm for 2-3 mil, Ites
in a boiling water bath. Cool, add a few drops ofthe benzidine reo_"mt
und a few small crystals of sodium acetate. A blue coloration re~'Jlts.
Sensitivity: 30 p,g. ErOa -. Concentration limit: I in 2500.
The benzidine reagent is prepared by dissolving 0·05 grall, of
benzidine in 10 m!. of acetic acid, diluting to 100 ml. with water Ind
filtering, if necessary.

IV, 21. REACTIONS OF IODATES, 10-a

Solubility.-The iodates of the alkali metals are soluble in water; tho",' of
the other metals are sparingly soluble and, in general, less soluble than 'he
corresponding chlorates and bromates. Some solubilities in grams per ., tre
at 20° are: lead iodate 0·03 (25°). silver iodate 0'06, barium iodate I' :l2,
calcium iodate 3'7, potassium iodate 81'3 and sodium iodate 90·0. rodie "dd
is a crystalline solid, and has a solubility of 2330 grams per litre at 20°.
Use potassium iodate, KIO a•
 21] Reactions or the Acid Radicals or Anions 371
1. Concentrated Sulphuric Acid: no action in the absence
of reducing agents; readily converted into hydriodic ,wid in
the presence of ferrous sulphate.
HIO s + 6FeS04 + 3H2S04 = HI + 3Fe2(S04)a + 3H2 0*
2. Silver Nitrate Solution: white, curdy precipitate of
silver iodate AgIO a, readily soluble in dilute ammonia solution,
but difficulty soluble in dilute nitric acid.
KIO a + AgNO s = AgIOa + KNO a ;
AgIO s + 2NHs = [Ag(NHs)z]IOs
If the ammoniacal solution of the precipitate is treated dropwise
with sulphurous acid solution, silver iodide is precipitated; the
latter is not dissolved by concentrated ammonia solution (dif-
ference from bromate).
3. Barium Chloride Solution: white precipitate of barium
iodate Ba(IO a)2 (difference from chlorate), difficultly soluble in
hot water and in dilute nitric acid, but insoluble in alcohol
(difference from iodide). If the precipitate of barium iodate is
well washed, treated with a little sulphurous acid solution and
1-2 ml. of carbon tetrachloride, the latter is coloured violet by
the liberated iodine.
2KIO a + BaC12 = Ba(IO s)2 + 2KCI
4. Mercuric Nitrate Solution: white precipitate of mer-
curic iodate Hg(IOal2 (difference from chlorate and bromate).
Lead acetate solution similarly gives a precipitate of lead
iodate Pb(IO a)2'
2KIO a + H g(NOsh = Hg(IOah + 2KNO g
Mercuric chloride solution, which is practically unionised (as
mercuric chloride is covalent), gives no precipitate.
5. Sulphur Dioxide or Hydrogen Sulphide.-Pa lsage of
sulphur dioxide or of hydrogen sulphide into a solution of an
iodate, acidified with dilute hydrochloric acid, liberate:-; iodine,
which may be recognised by the addition of starch solution or
chloroform or carbon tetrachloride. With an excess of either
reagent, the iodine is further reduced to hydriodic acid.
KIO a + HCI = HIO a + KCI;
2HIOa + 5H 2SOg = 12 + 5H2S04 + H:,:O;
12 + H 2SO a + H 20 ~ 2HI + H 2S04
2HIO a + 5H2S = 12 + 5S + 6H 2 0;
12 + H 2S ~ 2H1 + S
• Iodine will eventually separate owing to the interaction between the
hydriodic and iodic acid (see reaction 6 below).
372 Qualitative Inorganic Analysis [IV,
6. Potassium Iodide Solution.-Mix together solu. ions
of potassium iodide and potassium iodate, and acidify with
acetic acid or with tartaric acid solution; iodine is immedi tely
liberated (use the chloroform or carbon tetrachloride test)
H10 a + 5H1 = 312 + 3H20
7. Action of Heat.-The alkali iodates decompose ,nto
oxygen and an iodide. Most iodates of the divalent m,'tals
yield iodine and oxygen and leave a residue of oxide; barium
iodate, exceptionally, gives the periodate.
2KIO a = 2KI + 302;
2Pb(IOa)2 = 212 + 502 + 2PbO;
5Ba(10a)2 = Ba5(IOe)2 + 412 + 902
t8. Hypophosphorous Acid-Starch Solution Test.-Iodate. lre
reduced by hypophosphorous acid eventually to iodides. The real, Ion
takes place in three stages:
10 8 - + 3H aPO a = r + 3H aPO a (i)
5r + 10 3 - + 6H+ = 31 2 + 3I-I aO (ii)
II + HaPOa + H 20 = 2HI + HaPO, (iii)
The first two stages are rapid and the third stage is a slow reacL 'll.
The iodine can be readily identified by the starch reaction. Chlor,,' 0S
and bromates do not react under these conditions.
Place a drop of the neutral test solution on a spot plate and mb it
with a drop of starch solution (for preparation, see under Iodilks,
Section IV, 16, reaction 9) and a drop of a dilute solution of hy!!o-
phosphorous acid. A transitory blue coloration is produced.
Sensitivity: 1 p.g. 10 3 - , Concentration limit: 1 in 50,000.
t9. Potassium Thiocyanate Test.-Iodates react with thioc~ il-
nates in acid solution with the liberation -of iodine:
610 3 - + 5SCN- +
6H+ +
2HaO = 31a +
5HCN 5HSO,- +
Treat a piece of starch paper successively with it drop of 5 per cent
potassium thiocyanate solution and a drop of thQ acid test solution.
A blue spot is obtained.
Sensitivity: 3 p.g. lOa -. Concentration limit: 1 in 12,000.

IV, 22. REACTIONS OF PERCHLORATES, CI04 -

Solubility.-The perchlorates arc generally soluble in water. Potassium
perchlorate is one of the least soluble (7'5 grams and 218 grams per litre at ()O
and 100° respectively), and sodium perchlorate is one of the most solubio
(2096 grams per litre at 25°).
Use sodium perchlorate, NaCl04 •
1. Concentrated Sulphuric Acid: no visible action wit],
the solid salt although the free perchloric acid HOIO. it<
23] Reactions of the Acid Radicals or Anions 373
liberated; on strong heating, white fumes of the hydrate,
HCI0 4 ,H 20, are evolved.
NaCI04 + H 2S04 = HCI04 + NaHS04
2. Potassium Chloride Solution: white precipitate of
potassium perchlorate KCI04 , insoluble in alcohol (see under
Potassium, Section III, 34, reaction 3). Ammonium chloride
solution gives a similar white precipitate of ammonium per-
chlorate NH4C104 •
3. Barium Chloride Solution: no precipitate. A similar
result is obtained with silver nitrate solution.
4. Indigo Test: no decolourisation even in the presence of
acid (difference from hypochlorite and chlorate).
5. Sulphur Dioxide or Hydrogen Sulphide or Ferrous
Salts: no reduction (difference from chlorate).
6. Titanous Sulphate Solution: reduced to chloride.
7. Cadmium Ammonium Perchlorate Test.-When a
solution of a perchlorate is treated with a saturated solution of
cadmium nitrate in concentrated ammonia solution, a white
crystalline precipitate of cadmium ammonium perchlorate is
obtained.
2NaCI04 + [Cd(NHs)4](NOs)2 ~ [Cd(NHs)4](CI04)2 + 2NaNOs
Sulphides interfere and should therefore be absent.
8. Action of Heat: oxygen is evolved, and a chloride (for
tests see under Chlorides, Section IV, 14) is produced.
NaCI04 = NaC} + 202
IV, 23. REACTIONS OF BORATES,
BO s---' B 4 0 7 --, BO z-
The borates are derived from the three boric acids: ortho-boric acid H.BO ••
pyro-boric acid H2B(07 and meta-boric acid HBO I • Ortho-boric acid is a
white crystalline solid, sparingly soluble in cold but more soluble in hot water;
very few salts of this acid are definitely known. On heating ortho-boric acid
at 100 0 , it is converted into meta-boric acid; at 140 0 pyro-boric add is pro-
duced. Most of the salts are derived from the meta- and pyro-acids. Owing
to the weakness of boric acid, the soluble salts are hydrolysed in solution and
therefore react alkaline.
+
Na 2B.0 7 3H 20 ~ 2NaB0 2 + 2H.BO.;
NaB0 2+ 2H.O ~ NaOH + HaBO.
Solubility.-The borates of the alkali metals are readily soluble in water.
The borates of the other metals are, in general, difficultly soluble in water, but
fairly soluble in acids and in ammonium chloride solution.
Use sodium pyro-borate ("borax"), Na2B407,lOH20.
374 Qualitative Inorganic Analysis [IV
1. Concentrated Sulphuric Acid: no visible action i i i thE
cold, although ortho-boric acid HaBOa is set free. On hel!' ing,
however, white fumes of boric acid are evolved. If COIl(,en-
trated hydrochloric acid is added to a concentrated soluti(}ll of
borax, boric acid is precipitated.
Na2B407 + H 2S04 + 5HzO = 4H g BO a + Na2S04
Na2B407 + 2HCl + 5H2 0 = 4HaBOa + 2NaCI
2. Concentrated Sulphuric Acid and Alcohol (FIn me
Test).-If a little borax is mixed 'with 1 ml. of concentr led I

sulphuric acid and 5 ml. of methyl or ethyl alcohol (the fQInter

is to be preferred owing to its greater volatility) in a sll,all
porcelain basin, and the alcohol ignited, the latter will burn \\ Ith
a green-edged flame, due to the formation of methyl bOl Ita
B(OCH3h or of ethyl borate B(OC2H5h. Both these esl,'ra
are poisonous. Copper and barium salts may give a similar
green flame. The following modification of the test, whi\\h
depends upon the greater volatility of boron trifluoride B J '3'
can be used in the presence of copper and barium compounds;
these do not form volatile compounds under the experimental
conditions given below. Thoroughly mix the borate with
powdered calcium fluoride and a little concentrated sulphuric
acid, and bring a little of the paste thus formed on the loop of
a platinum wire, or upon the end of a glass rod, very close to
the edge of the base of a Bunsen flame without actually touch-
ing it; volatile boron trifluoride is formed and colours tllt.l
flame green.
HaB03 + 3CH sOH ~ B(OCHsh + 3H20
CaF 2 + H 2S04 = CaS04 + 2HF;
Na2 B497 + H 2S04 ~ 2B 2 0 a + Na ZS04 + H 2 0;
B 20 S + 6HF ~ 2BF S + 3H2 0
t The reaction may be adapted as a spot test in the following manner.
The methyl borate is distilled off and passed into an aqueous solution
containing potassium fluoride, manganous nitrate and silver nitrat~'.
The ester is hydrolysed by the water to boric acid:
B(OCHa)a + 3Hp = HaBOa + 3CH sOH;
the boric acid reacts with the alkali fluoride forming a borofluoride and
liberating free caustic alkali:
HaBOa + 4KF = K[BF,J + 3KOH;
the free caustic alkali is identified by the formation of a black precipitate
with manganous nitrate-silver nitrate solution (see under Ammonium,
Section III, 36, reaction 9):
Mn++ + 2Ag+ + 40H- = MuO. + 2Ag + 2H,D
23] Reactions of the Acid Radicals or Anion8 375
Place a drop of the alkaline test solution in the distillation apparatus
of Fig. 11, 6, 16 and evaporate to dryness. Add 5 drops of concentrated
sulphuric acid and 5 drops of pure methyl alcohol, stopper the apparatuB
and heat to 80 0 0 in a water bath. Collect the methyl borat') which
distils over in a micro porcelain crucible, waxed on the inside, and
containing about 1 ml. of the reagent. A black precipitak forms.
For very small amounts of borate it is best to add a few drops of ben-
zidine acetate solution and thus to detoct the traces of manganese di-
oxide by the resulting blue colour.
Sensitivity: 0·01 f£g. B. Concentration limit: J in 5,000,000.
The reagent (a manganous nitrate-silver nitrate solution containing
potassium fluoride) is prepared as follows. Dissolve 2'87 grams of
manganous nitrate and 1·69 grams of silver nitrate in 100 ml. of water,
add a drop of dilute alkali and filter the solution from the bJack precipi-
tate. Treat the filtrate with a solution of 3'5 grams of potassium
fluoride in 50 ml. of water; a white precipitate will form waich on
heating becomes grey and black. Boil, filter and use the clear "olution
as the reagent.

3. Turmeric Paper Test.-If a piece of turmeric paper is

dipped into a solution of a borate acidified with dilute hydro-
chloric acid and then dried at 100°, it becomes reddish-brown.
The drying of the paper is most simply carried out by winding
it on the outside near the rim of a test-tube containing water,
and boiling the water for 2-3 minutes. On moistening the
paper with dilute sodium hydroxide solution, it becomes bluish-
black or greenish-black. Chromates, chlorates, nitrites, iodides
and other oxidising agents interfere because of their bleaching
action on the turmeric.
4. Silver Nitrate Solution: white precipitate of silver
meta borate AgB0 2 from fairly concentrated borax solution,
soluble in both dilute ammonia solution and in acetic acid.
On boiling the precipitate with water, it is completely hydro-
lysed and a brown precipitate of silver oxide is obtained. A
brown precipitate of silver oxide is produced directly in very
dilute solutions.
Na zB4 0 7 + 3HzO + 2AgNOs = 2AgB0 2 + 2HsBOs + 2NaN0 3 ;
2AgB0 2 + 3H2 0 = Ag 2 0 + 2HsBOs
5. Barium Chloride Solution: white precipitate of barium
meta-borate Ba(B0 2 )z from fairly concentrated solutions; the
precipitate is soluble in excess of the reagent, in dilute acids
and in solutions of ammonium salts. Solutions of calcium and
strontium chloride behave similarly.
Na2B,07 + 3H20 + BaOIl! = Ba(BO z)2 + 2HllBOa + 2Na.Cl
~7t> tiuatUatwe lnorgamc .Anaty8~s L' V \
"
6. Action of Heat.-Powdered borax when heated an
ignition tube, or upon a platinum wire, swells up consider:, bly,
and then subsides, leaving a colourless glass of the anhy(l tOUS
salt. The glass possesses the property of dissolving wany
oxides on heating, forming meta-borates, which often llilve
characteristic colours. This is the basis of the borax ! ,cad
test for various metals (see Section II, 1, reaction 5).
t7. para-Nitrobenzene-azo-chromotropic Acid* Reagent

,
OR OR )

O,N-OM~
(
ROIS~OIR
Borates cause the blue-violet reagent to assume a greenish-blue CUi'>lIr.
Evaporate a drop of the slightly alkaline solution to dryness ,\ a
semimicro crucible. Stir the warm residue with 2-3 drops of the
reagent. A greenish-blue coloration is obtained on cooling. A j,;,mk
test should be performed simultaneously.
Sensitivity: 0·1 p,g. B. Concentration limit: I in 500,000.
Oxidising agents and fluorides interfere, the latter because of the
formation of borofluorides. Oxidising agents, including nitrates and
chlorates, are rendered innocuous by evaporating with solid hydra: lIle
sulphate, whilst fluorides may be removed as silicon tetrafluoride, by
evaporation with silicic acid and sulphuric acid.
The experimental details are as follows. Treat 2 drops of the tost
solution in a small porcelain crucible either with a little solid hydrazi.ne
sulphate or with a few specks of precipitated silica and 1-2 drop' of
concentrated sulphuric acid, and heat cautiously until fumes of sulph, 1ric
acid appear. Add 3-4 drops of the reagent whilst the residue is ~~ill
warm and observe the colour on cooling.
Sensitivity: 0·25 p,g. B in the presence of 12,000 times the am01ll1t
of KCIO a or KNO a ; 0·5 p,g. B in the presence of 2,500 times the amo illt
of NaF.
The rea~ent consists of a 0·005 per cent solution of Chromotrope :2B
in concentrated sulphuric acid.
t8. Mannitol-Bromothymol Blue Test.-Boric acid acts a a
very weak monobasic aid (KG = 5·8 X 10- 1 °), but upon the additi, (IS
of certain organic poly-hydroxy compounds, such as mannitol (mannit" i,
glycerol, dextrose or invert sugar, it is transformed into a relativ"lY
strong acid, probably of the type:

-l-OR RO,
+ 'B-OR
-LOR RO/
I
• Alternative names are: p-nitrobenzene-azo.l : 8-dihydroxyn.e.phthalen., ..
3: 6-disulphonic acid and "Chromotrope 2B" (the latter is the sodium se.l~).
24J Reactions of the Acid Radicals or Anions 377
The pH of the solution therefore decreases. Hence if the solution is
initially almost neutral to, say, bromothymol blue (green), then upon
the addition of mannitol the colour beeomes yellow. It is advisable
when testing for minute quantities of borates to recrystallise the man·
nitol from a solution neutralised to bromothymol blue, wash with pure
acetone and dry at 100°. The reagent (a. 10 per cent aqueous Holution
of mannitol) may also be neutralised with O·OIN potassium hydroxide
solution, using bromothymol blue (a 0·04 per cent solution in 96 per
cent ethyl alcohol) as indicator. Only periodate interferes with the
test: it can be decomposed by heating on charcoal.
Render the test solution almost neutral to bromothymol blue by
treating it with dilute acid or alkali (as necessary) wltil the indicator
turns green. Place a few drops of the test solution in a micro test-tube,
and add a few drops of the reagent solution. A yellow coloration is
obtained in the presence of a borate. It is advisable to carry out a
blank test with distilled water simultaneously.
Sensitivity: 0·001 fLg. B. Concentration limit: I in 30,000,000.

IV, 24. REACTIONS OF SULPHATES, S04--

Solubility.-The sulphates of barium, strontium and lead are practically
insoluble in water, * those of calcium and mercuric mercury are Blightl;' soluble,
and most of the remaining metallic sulphates are soluble. Some hasic sul-
phates, such as those of mercury, bismuth and chromium, are also illiloluble
in water, but these dissolve in dilute hydrochloric or nitric acid.
Sulphuric acid is a colourless, oily and hygroscopic liquid, of specific gravity
1'838. The pure, commercial, concentrated acid is a constant boiling point
mixture, boiling point 338 0 and containing ca. 98 per cent of aCid. It is
miscible with water in all proportiollil with the evolution of considerHble heat;
on mixing the two, the acid should always be poured in a thin stream into the
water (if the water is poured into the heavier acid, steam may be suddenly
generated which will carry with it Borne of the acid and may therefore cause
cOlliliderable damage).
Use sodium sulphate, Na2S04,lOH20.
1. Barium Chloride Solution: white precipitate of barium
sulphate BaS04 (see under Barium, Section III, 29), insoluble
in warm dilute hydrochloric acid and in dilute nitrio aoid, but
moderately soluble in boiling, concentrated hydrochloric acid.
The test is usually carried out by adding the reagent to the
solution acidified with dilute hydrochloric acid; carbonates,
sulphites and phosphates are not precipitated under these
conditions. Concentrated hydrochloric acid or concentrated
nitrio acid should not be used, as a precipitate of barium
chloride or of barium nitrate may form; these dissolve, how-
ever, upon dilution with water. The barium sulphate precipi-
tate may be filtered from the hot solution and fused on charcoal
with sodium carbonate, when sodium sulphide will be formed.
The latter may be extracted with water, and the extract filtered
into a freshly prepared solution of sodium nitroprusside, when
* Of these three sulphates, that of strontium is the most soluble.
378 Qualitative Inorganic Analysis [IV,
a transient, purple coloration is obtained (see under Sul}'!lides,
Section IV, 6, reaction 5). An alternative method is to Idd a
few drops of very dilute hydrochloric acid to the fused :'lass,
and to cover the latter with lead acetate paper; a black ,tain
of lead sulphide is produced on the paper. The so-' ,Ued
Hepar reaction, which is less sensitive than the abov, two
tests, consists in placing the fusion product on a silver coin
and moistening with a little water; a brownish-black stH:11 of
silver sulphide results.
Na2S0, + BaCl2 = BaSO, + 2NaOl;
BaSO, + Na200S + 40 = Na2S + BaOOs + 400;
+
2Na2S + 4Ag + O2 2H20 = 2Ag2S + 4NaOH
A m01:e effi.~ien.t 'ffi~tb.~d. ~m: d.~~~mpoBing most sulphur comp" Imds
consists in heating them with sodium or potassium, and then t, ' ting
the solution of the product for sulphide. The test is rendered "usi-
tive by heating the substance with potassium in an ignition: Ilbe,
dissolving the melt in water, and testing for sulphide by the 1 : bro-
prusside or methylene blue reactions (see under Sulphides, Set I ion
IV, 6, reactions 6 and 7).
The reader is warned that the above tests (depending \I! Ion
the formation of a sulphide) are not exclusive to sulphates Imt
are given by most sulphur compounds. If, however, the
barium sulphate precipitated in the presence of hydrochloric
acid is employed, then the reaction may be employed ft ~ a
confirmatory test for sulphates.
2. Lead Acetate Solution: white precipitate of lead flul-
phate PbSO" soluble in hot concentrated sulphuric acid, in
solutions of ammonium acetate and of ammonium tartrate ( f)e
under Lead, Section 111,2, reaction 3), and in sodium hydroxi' le
solution. In the last case sodium plum bite is formed, and'·n
acidification with hydrochloric acid, the lead crystallises out ,IS
the chloride. If any of the aqueous solutions of the precipitil , e
are acidified with acetic acid and potassium chromate solutit n
added, yellow lead chromate is precipitated (see under Lea I,
loco cit.).
Pb(02Ha02)2 + Na2S04 = PbS04 + 2Na.02H a0 2
3. Silver Nitrate Solution: white, crystalline precipital,'
of silver sulphate Ag 2SO, (solubility 5·8 grams per litre at 18 )
from concentrated solutions.
Na2S0, + 2AgNO a = Ag 2SO, + 2NaNO a
t 4. Sodium Rhodizonate Test.-Barium salts yield a reddish-brown
precipitate with sodium rhodizonate (see under Barium, Section III, 29,
25J Reactiona of the Acid Radica18 or Aniona 379
reaction 7). Sulphates and sulphuric acid cause immediate decolorisa-
tion because of the formation of insoluble barium sulphate. This test
is specific for sulphates.
Place a drop of barium chloride solution upon filter or drop reaction
paper, followed by a drop of a freshly prepared 0'1 per cent aqueous
solution of sodium rhodizonate. Treat the reddish-brown spot with a
drop of the acid or alkaline test solution. The coloured spot disi1ppears.
Sensitivity: 4 fLg. SO,--. Concentration limit: 1 in 10,000.
t5. Potassium Permanganate-Barium Sulphate Test.-If
barium SUlphate is precipitated in a solution containing potassium per-
manganate, it is coloured pink (violet) by adsorption of som!} of the
permanganate. The permanganate which has been adsorbed on the
precipitate cannot be reduced by the common reducing agents (including
hydrogen peroxide); the excess of potassium permanganate in the
mother liquor reacts readily with reducing agents, thus rendering the
pink barium sulphate clearly visible in the colourless solution.
Place 3 drops of the test solution in a semimicro centrifuge tube, add
2 drops of 1 per cent potassium permanganate solution and 1 drop of
1 per cent barium chloride solution. A pink precipitate is obtained.
Add a few drops of 3 per cent hydrogen peroxide solution or .V oxalic
acid solution (in the latter case it will be necessary to warm on a water
bath until decolourisation is complete). Centrifuge: the coloured pre-
cipitate is clearly visible.
Sensitivity: 2·5fLg. SO,--. Concentration limit: 1 in 20,000.
6. Mercuric Nitrate Solution: yellow precipitate of the
basic sulphate, 3HgO. S03' This is a sensitive test, and is
given by barium and lead sulphates.

IV, 25. REACTIONS OF PERSULPHA TES, S208--

Solubility.-The best·known persulphates, those of sodium, potassium.
ammonium and barium, are soluble in water, the potassium salt being the
least soluble (17'7 grams per litre at 0°).
Use ammonium persulphate, (NH,bS20S.
1. Water.-All persulphates are decomposed on boiling with
water into the sulphate, free sulphuric acid and oxygen. The
oxygen contains appreciable quantities of ozone, which may be
detected by its odour or by its property of turning starch-
iodide paper blue. A similar result is obtained with dilute
sulphuric or nitric acid. With dilute hydrochloric acid,
chlorine is evolved (see reaction 4 below). By dissolving the
solid persulphate in concentrated sulphuric acid at 0°, permono-
sulphuric acid (Caro's acid) H 2SOS is formed in solution; this
possesses strong oxidising properties.
2(NH4)zS20S+ 2H zO = 2(NH4)zS04 + 2HzSO~ + Oz
Os + 2KI + HliO = Is + O2 + 2KOH
380 Qualitative Inorganic Analysis [IVI
2. Silver Nitrate Solution: black precipitate oj silver
peroxide Ag 20 2 from concentrated solutions. If only little
silver nitrate solution be added and then dilute an •aonia
solution, the silver peroxide, or the silver ion, acts catal) : rcally
leading to the evolution of nitrogen and the liberat i un of
considerable heat.
(NH4)zS20S + 2AgNO a + 2H20 = Ag 20 2 + 2NH4HS04 + 2f[NOa
SNHs + 3(NH4)zS20S( +Ag) = N2 + 6(NH')2S0,( +Ag)
3. Barium Chloride Solution: no immediate preci"itate
in the cold with a solution of a pure persulphate; on sta iding
for some time or on boiling, a precipitate of barium sul;· hate
is obtained, due to the decomposition of the persulphate.
4. Potassium Iodide Solution: iodine is slowly liberated
in the cold and rapidly on warming (test with starch solution)
(distinction from perborate and percarbonate, which liberate
iodine immediately). Ferrous sulphate solution is oxidised to
ferric sulphate.
(NH')ZS20S + 2KI = I2 + (NH,hS04 + K ZS04
5. Manganous Sulphate Solution: brown precipitate,
Mn02,H20 or H 2l\fuO s, in neutral or preferably alkaline
(sodium hydroxide) solution. In nitric acid solution and in
the presence of a little silver nitrate (which acts catalytically,
see reaction 2 above), permanganic acid is formed on warming.
MnS04 + (NH4)2S20S + 3H20
= HzMnOa + (NH,)zS04 + 2Hzt- 114 ;
2MnS04 + 5H 2S2 0 a + 8H20 = 2HMn04 + 12HzSO,
6. Potassium Permanganate Solution: unaffected ((1;,,-
tinction from hydrogen peroxide). Persulphates are unaffected
by a solution of titanous sulphate. ________ ,
t7. Benzidine Acetate Test.-A neutral or a weakly acetic a, ld
solution of a persulphate converts benzidine into a blue oxidation pc ,.
duct. Alkali perborates, percarbonates and also hydrogen peroxide i ')
not give the test. Chromates, ferricyanides, permanganates and hY1" ,.
halides react similarly to persulphates.
Mix 1 drop of the test solution (neutral or faintly acid with aCell!]
acid) with 1 drop of the benzidine acetate reagent. A blue colorati, 'll
is produced.
Sensitivity: 1 p.g. S,O.--. Concentration limit: 1 in 100,000.
The reagent consists of a 2 per cent solution of benzidine in dilUl'"
acetic acid.
26] Reaction8 of the Acid Radical., or Anion.! 381

IV, 26. REACTIONS OF SILICATES, S103--

The silicic acids may be represented by the general formula xSiO., yR.O.
Salts corresponding to ortho-silicic acid H.SiO, (SiO.,2H.O) roeta-sili"ic acid
R.SiO. (SiO.,H.O) and di-silicic acid H 2Si.O.(2SiO.,H.O) are d0finitely
known. The meta-silicates are sometimes designated simply as silicates.
Solubility.-Only the silicates of the alkali metals are soluble in water;
they are hydrolysed in aqueous solution and therefore react alkaline.
Na.SiO. + 2R.O ~ 2NaOH +
H.BiO.
Use a solution of water glass; tills contains, largely, sodium
meta-silicate Na2SiOa.
1. Dilute Hydrochloric Acid.-Add dilute hydronhloric
acid to the solution of the silicate; a gelatinous precipit ate of
meta-silicic acid is obtained, particularly on boiling. The
precipitate is insoluble in concentrated acids. The freshly
precipitated substance is appreciably soluble in water and in
dilute acids. It is converted by repeated evaporation with
concentrated hydrochloric acid on the water bath into a white
insoluble powder (silica Si0 2 ).
If a dilute solution (say, 1-10 per cent) of water glass is
quickly added to moderately concentrated hydrochloric acid,
no precipitation of silicic acid takes place; it remains in col-
loidal solution (sol).
Na2SiOa + 2HCI = H 2SiO a + 2NaCI
2. Ammonium Chloride or Ammonium Carbonate
Solution: gelatinous precipitate of silicic acid. This reaction
is important in routine qualitative analysis since sHicates,
unless previously removed, will be precipitated by ammonium
chloride solution in Group IlIA.
NazSiO a + 2NH4CI = HzSiOs + 2NaCI + 2NHs
Na2SiOa +
(NH4)2COa = H 2SiOs + NazCOs + 2NH3
The reaction is essentially:
SiO.-- + 2NH, + ~ H 2 SiO a + 2NHa
Basel Acid. Acid l Base,
The NH4 + ion functions as an acid.
3. Silver Nitrate Solution: yellow precipitate of silver
silicate Ag 2Si0 3 , soluble in dilute acids and in dilute ammonia
solution.
NazSiO s + 2AgNO s = AgzSiO a + 2NaNO a
4. Barium Chloride Solution: white precipitate of barium
silicate BaSiO a, soluble in dilute nitric acid. Calcium chloride
solution gives a similar precipitate of calcium silicate.
NazSiO s + BaClz = BaSiOs + 2NaCl
382 Qualitative Inorganic Analysis [IV,
5. Microcosmic Salt Bead Test.-Most silicatet'. and
also silica, when fused in a bead of microcosmic salt,
Na(NH,!)HP04,,4H 20, in a loop of platinum wire gh this
test. The microcosmic salt first fuses to a transparent bead
consisting largely of sodium meta-phosphate (see Section 1I, 1,
reaction 6); when a minute quantity of the solid silic;' i e or
even of the solution is introduced into the bead (best b:. dip-
ping the hot bead into the substance) and the whole .gain
heated, the silica produced will not dissolve in the bead, but
will swim about in the fused mass, and is visible as '\ hite
opaque masses or "skeletons" in both the fused and tht 'Jold
bead.
CaSiOs + NaPO s = CaNaP04 + Si0 2
Insoluble silicates are best brought into solution by fusing the pow,lered
solid, mixed with 6 times its weight of fusion mixture. in a platinum crv ;ble'"
or upon platinum foil; the alkali carbonates react with the silicate yi ! ling
an alkali silicate. The cold mass is then evaporated to dryness on the \\ ater
bath with excess of dilute hydrochloric acid; the alkali silicate is tl, reby
first decomposed yielding gelatinous silicic acid and ultimately into \.Itite,
amorphous silica. whilst the metallic oxides derived from the insoluble si Ilcate
are converted into chlorides. The residue is extracted with boiling dilute
hydrochloric acid; this removes the metals as chlorides and insoluble "ilica
remains behind. A simpler. but not quantitative, method is to extract the
fusion mixture melt with boiling water: sufficient sodium or potassium sili"ate
passes into solution to give any of the reactions referred to above.

6. Silicon Tetrafluoride Test.-This test depends \I! ,on

the fact that when silica (isolated from a silicate by treatn" nt
with ammonium chloride solution or with hydrochloric a. id,
etc.) is heated with defect of calcium fluoride and some con-
centrated sulphuric acid, silicon tetrafluoride is evolved. The
latter is identified by its action upon a drop of water held i II a
loop of platinum wire, when a turbidity (due to silicic acid! is
produced.
Si0 2 + 2CaF2 + 2H2S04 = 2CaS04 + SiF4 t + 2H20;
3SiF4 + 4H 2 0 = H 4Si04 + 2H 2[SiF61
Excess of calcium fluoride should be avoided since a mixtme
of HF and SiF4 will be formed and interfere with the test.
Mix the solid substance (or, preferably, silicic acid isola1 ('d
by treatment of the silicate with ammonium chloride soluti(llt)
with one-third of its weight of calcium fluoride in a smallleild
(or platinum) capsule, and add sufficient concentrated sulphuric
acid to form a thin paste: mix the contents of the capsule wi t h
a stout platinum wire. Warm gently [FUME GUPBOAR!»
* A nickel or iron crucible should be used if metals of Group I or II are
likely to be present.
26] Reactions of the Acid Radical8 or Anions 383
and hold close above the mixture a loop of platinum wire
supporting a drop of water. The drop of water will become
turbid, due to the hydrolysis of the silicon tetrafluoride
absorbed.
p. Ammonium Molybdate-Benzidine Test.-Silicates react
with molybdates in acid solution to form the complex silico-molybdic
acid H 4 [SiMo 120 4o ], of which the ammonium salt, unlike the analogous
phosphoric acid and arsonic acid compounds, is soluble in water and
acids to give a yellow solution. The test depends upon the reaction
between silico-molybdic acid and benzidine in acetic acid solution
whereby "molybdenum blue" and a blue quinonoid oxidation com-
pound of benzidine are produced.
Place a drop of the test solution and of the molybdate reagent upon
drop reaction paper, and warm gently over a wire gauze. Add a drop
of the benzidine reagent and hold the paper over ammonia vapour. A
blue coloration results.
Sensitivity: I p,g. SiO.. Concentration limit: I in 50,000.
A better method for conducting the test is the following. Place a
drop of the slightly acid test solution (the acidity should not exceed
0'5N) in a small porcelain crucible of good quality, and add a drop of
the molybdate reagent. Warm cautiously over a wire gauze (or upon a
sheet of asbestos resting upon a hot plate) until bubbles escape. Cool,
add a drop of the benzidine reagent followed by a drop of saturated
sodium acetate solution. A blue colour is obtained. It is eSRential to
carry out a blank test with a drop of water and a drop of the molybdate
reagent in another crucible of similar quality.
Sensitivity: O·I/Lg. SiO:. Concentration limit: I in 500,000.
Phosphoric and arsenic acids form compounds analogous to silico-
molybdic acid which also react with benzidine with colour formation
hence these acids should be removed before applying the test. In the
presence of phosphoric acid, the test is carried out as follows. Mix
a drop of the test solution with 2 drops of the molybdate reagent in a
micro centrifuge tube and centrifuge the mixture. Transfer the super-
natant liquid to a micro-crucible by means of a capillary tube, warm
gently, cool and add 2 drops of 1 per cent oxalic acid solution (the
latter decomposes the small quantity of residual phosphomolybdate
(NH 4 la[PMo 120 40 ] but has little action on the silico-molybdic acid
complex), then introduce a drop of the benzidine reagent and 2-3 drops
of saturated sodium acetate solution. A blue colour forms.
Sensitivity: 6/Lg. Si0 2 in the presence of 250 times the amountofP.0 5 •
Concentration limit: 1 in 8,000.
The ammonium molybdate reagent is prepared by dissolving 5
grams of ammonium molybdate in 100 ml. of cold water and pouring
into 35 ml. of nitric acid (sp. gr. 1·2).
The benzidine reagent is made by dissolving 0·05 gram of benzidine
or its hydrochloride in 10 m!. of glacial acetic acid and diluting with
water to 100 ml.
t8. Ammonium Molybdate-Stannous Chloride Test.-The
silicate is separated by volatilisation as silicon tet,rafiuoride and the
384 Qualitative Jnorganic AnalY8i8 [1 V,
latter collected in a little sodium hydroxide solution. The res"lting
silicate is treated with ammonium molybdate solution and the a' I uno-
nium salt of silicomolybdic acid H,[SiMo 120,o] is reduced by ste "lOUS
chloride solution to "molybdenum blue." Stannous chloride do., not
reduce ammonium molybdate solution.
Phosphates and arsenates give the same reaction, but do not int. ,fere
under the conditions of the test: large amounts of borates ShOl,,·i be
absent, but may be removed by warming with methyl alcohu: and
sulphuric acid.
Place a little of the solid silicate in a small lead or platinum crll 'hIe.
add a little sodium fluoride and a few drops of concentrated sulI" Llric
acid. Cover the crucible with a small sheet of cellophane from wI. h is
suspended a drop of 2N sodium hydroxide solution (freshly pre! red
from the A.R. solid). Warm gently for 3-5 minutes over a micro b::"ner
with the crucible about Scm. from the flame. Transfer the dr, ') of
sodium hydroxide solution to a micro porcelain crucible, add 2 ," ops
of a freshly prepared lO per cent aqueous solution of ammonium ill i yb-
date and then 4N acetic acid until feebly acidic. Then add a few, ops
of a 5 per cent solution of stannous chloride in 3N hydrochloric lid,
followed by sufficient sodium hydroxide solution to dissolve the stall, ous
hydroxide. A blue coloration is obtained.
Concentration limit: 1 in 10,000.
The reaction may be applied to aqueous solutions of silicates, but
phosphates and arsenates must be absent.

IV, 27. REACTIONS OF SILICOFLUORIDES

(FLUOSILICATES), [SiF6 r-
Solubility.-Most metallic silicofluorides, with the exception of the ba! un
and potassium salts which are sparingly soluble. are soluble in water A
solution of the acid (hydrofluosilicic acid H.[SiF,) is one of the produCl of
the action of water upon silicon tetrafluoride, and is also formed by dissol \ JUg
silica in hydrofluoric acid.
SiO. + 6HF = Hs[SiF.l + 2H.O
Use sodium silicofluoride or ammonium silicofluoride.
1. Concentrated Sulphuric Acid: silicon fluoride !I ,d
hydrogen fluoride are evolved on warming the reagent ,,: t h
the solid salt. If the reaction is carried out in a platinum Ir
lead capsule or crucible, the escaping gas will etch glass a: d
will cause a drop of water to become turbid (see under SiIicat, '1,
Section IV, 26, reaction 6).
Na2[SiF6] + H 2S04 = SiF4 + 2HF + Na2S0.
2. Barium Chloride Solution: white, crystalline preci! >i-
tate of barium silicofluoride Ba[SiF6], sparingly soluble in wal .r
(0·25 gram per litre at 25°) and insoluble in dilute hydrochloi ,)
acid. The precipitate is distinguished from barium sulpha' d
by the evolution of hydrogen fluoride and silicon fiuoride,
28] Reactions of the Acid Radicals or Anions 385
which etoh glass, on heating with oonoentrated sulphuric aoid
in a lead orucible.
N az[SiF6] + BaClz = Bu,[SiF6] + 2NaCI
3. Potassium Chloride Solution: white, gelatinous pre-
cipitate of potassium silicofluoride K 2[SiF6] from concentrated
solutions. The precipitate is slightly soluble in water (1'77
grams per litre at 25°), less soluble in excess of the reagent and
in 50 per cent alcohol.
4. Ammonia Solution: decomposition occurs with the
separation of gelatinous silicic acid.
Naz[SiF6] + 4NHs + 3HzO = HzSiO a + 2NaF + 4NH,F
. o. Action of Heat: decomposition occurs into Si1iCOll tetra-
fluoride, which renders a drop of water turbid, and the metallic
fluoride, which can be tested for in the usual manner (see
under Fluorides, Section IV, 17).
Naz[SiF6] = SiF4 + 2NaF
IV, 28. REACTIONS OF ORTHOPHOSPHATES,
PO,---
Three phosphoric acids are known: ortho-RaPO" pyro-R,P.O, and meta-
phosphoric acid HPO.. Salts of the three acids exist; the orthophosphates
are the most stable and incidentally the most important"'; solutions of pyro-
and meta-phosphates pass into orthophosphates slowly at the ordinary tem-
perature, and more rapidly on boiling. Metaphosphates, unless prepared by
special methods, are usually polymeric, i.e. are derived from (HPO.Jn'
Orthophosphorio acid is a tribasic acid giving rise to three series of salts:
primary orthophosphates, e.g. NaH,PO,; secondary orthophosphates, e.g.
Na,HPO,; and tertiary orthophosphates, e.g. Na.PO,. If a solution of
orthophosphorio acid is neutralised with sodium hydroxide solution using
methyl orange as indicator, the neutral point is reached when the acid is
converted into the primary phosphate (1 equivalent of alkali); with phenol
phthalein as indicator, the solution will react neutral when the becondary
phosphate is formed (2 equivalents of all<ali); with 3 equivalents of alkali.
the tertiary or normal phosphate is formed. NaH.PO. is neutral to methyl
orange and acid to phenol phthalein, Na.HPO. is neutral to phenol phthalein
and alkaline to methyl orange, Na.PO, is alkaline to most indicators because of
its extended hydrolysis. Ordinary "sodium phosphate" is disodium hydrogen
phosphate, Na.HPO,,12H.O.
Solubility.-The phosphates of the alkali metals, with the exception of
lithium, and of ammonium are soluble in water; the primary phosphates
of the alkaline earth metals are also soluble. All the phosphates of the other
metals, and also the secondary and tertiary phosphates of the alkaline earth
qletals, are sparingly soluble or insoluble in water.
Use disodium hydrogen phosphate, Na2HPO,,12H:aO.
1. Silver Nitrate Solution: yellow precipitate of normal
silver orthophosphate Ag 3PO" (distinction from meta- and
• These are often referred to simply 88 phosphates.
13+
386 Qualitative Inorganic Analysis [IV,
pyro-phosphate), soluble in dilute ammonia solution and III
dilute nitric acid.
Na2HP04 + 3AgNOs = Ag SP04 + 2NaN03 + HNO s
Na2HP04 + HN0 3 = NaH 2P04 + NaNOs;
2Na2HP04 + 3AgNOs = Ag SP04 + 3NaNO s + NaH 2] '()4
2. Barium Chloride Solution: white, amorphous pi cipi-
tate of secondary barium phosphate BaHP04 from n',ltral
solutions, soluble in dilute mineral acids and in acetic ,"cid.
In the presence of dilute ammonia solution, the less S(' I uble
tertiary phosphate Ba3(P04)2 is precipitated.
BaC1 2 + Na2HP04 = BaHP04 + 2NaCI
2Na2HP04 + 3BaC12 + 2NHs = Bas(P04h + 4NaCl + 21\ t (4Cl
3. Magnesium Nitrate Reagent or Magnesia Mix' ure.
-The former is a solution containing Mg(N0 3b NH4NO and
a little aqueous NH 3, and the latter is a solution conta:: ling
MgC1 2, NH4Cl and a little aqueous NH3 : the magnesium nj \ rate
reagent is generally preferred since it may be employed in ,tny
subsequent test with silver nitrate solution. With eithe, re-
agent a white crystalline precipitate of magnesium ammo' i um i

phosphate Mg(NH4)P04,6H 2 0 is produced: this precipita \,J is

soluble in acetic acid and in mineral acids, but practi oIly
insoluble in 2·5 per cent ammonia solution (see under Mag-
nesium, Section III, 33, reaction 5; also under Arsenic, Sec1 ion
III, 12, reaction 3).
Na2HP04 + Mg(NO s)2 + NHs = Mg(NH4)P04 + 2NaNO;l
Arsenates give a similar precipitate {Mg(NH4)As04,6H20} ',I ith
either reagent. They are most simply distinguished from 'me
another by treating the washed precipitate with silver ni Lte
solution containing a few drops of dilute acetic acid: the phosl" Lte
turns yellow (AgSP04), whilst the arsenate assumes a brownisJl ,'ed
colour (AgSAs04)'
4. Ammonium Molybdate Reagent.-The addition (,I' a
large excess (2-3 ml.) of this reagent to a small volume (0'5 ' :l)
of a phosphate solution produces a yellow crystalline pre( f)i- I

tate of ammonium phosphomolybdate, to which the fOrD ;la

(NH4)sP04,12Mo0 3 was formerly assigned. The COl" "ct
formula is (NH4h[PMo12040] or (NH4MP04(Mo12036)]' ; he
resulting solution should be strongly acid with nitric acid; lw
latter is usually present in the reagent and addition is thereJ \,re
unnecessary. Precipitation is accelerated by warming t . , a
 J(,eactions of the Acid J(,adicals or Anions 387
temperature not exceeding 40°, and by the addition of ammo-
nium nitrate solution.
The precipitate is soluble in ammonia solution and in solut ions of
caustic alkalis. Large quantities of hydrochloric acid interfere with
the test and should preferably be removed by evaporation to i1 small
volume with excess of concentrated nitric acid. Reducing agents, such
as sulphides, sulphites, ferrocyanides and tartrates, seriously aflect the
reaction, and should be destroyed before carrying out the test.
Arsenates give a similar reaction on boiling (see under
Arsenic, Section III, 12, reaction 4). Both ammonium phos-
phomolybdate and ammonium arsenomolybdate dissolve on
boiling with ammonium acetate solution, but only the latter
yields a white precipitate on cooling.
Na zHP04+12(NH4h:\fo04 + 23HN03
= (NH4)s[PMolZ040] + 2NaNO g + 21NH4N0 3 + 12HzO
Note. Commercial aID1)lonium molybdate has the formula (NH.),'.I0 7 0",-
4H.O (a paramolybdate) and not (NR.),MoO.; the latter formula is employed
in the equations for purposes of simplicity, and may exist under the- experi-
mental conditions of the reaction.
5. Ferric Chloride Solution: yellowish-white preC'lpitate
of ferric phosphate FeP04 , soluble in dilute mineral acids, but
insoluble in dilute acetic acid.
Na2HP04 + FeCl 3 ~ FeP04 + 2NaCI + HOI
Precipitation is incomplete owing to the free mineral acid produced. If the
hydrogen ions, arising from the complete ionisation of the mineral ltcid, are
removed by the addition of the salt of a weak acid, such as ammonium or
sodium acetate which give rise to the feebly dissociated acetic acid, then
precipitation is almost complete. The presence of a large excess of sodium or
ammonium acetate reduces the ionisation of the acetic acid still furt her as a
result of the common ion effect (Section I, 14). This is the basis of olle of the
methods for the removal of phosphates, which interfere with the precipitation
of Group ilIA metals, in qualitative analysis.

6. Zirconyl Nitrate Reagent.-When the reagent is added

to a solution of a phosphate containing hydrochloric acid not
exceeding N in concentration, a white gelatinous precipitate of
zirconyl phosphate ZrO(H 2P04 )2 or ZrO(HP04 ) is obtained.
This reaction forms the basis of a simple method for the
removal of phosphate prior to the precipitation of Grou pIllA
(compare Section VII, 7, Table II).
ZrO(N0 3)z + 2Na zHP04 + 2HOI
= ZrO(H ZP04)z + 2NaOl + ::NaNO s
or ZrO(N0 3)2 + Na zHP04 = ZrO(HP04 ) + 2NaNO a
7. Cobalt Nitrate Test.-Phosphates when heated on
charcoal and then moistened with a few drops of cobalt nitrate
 solution, give a blue mass of the phosphate N aCoP04 • This
must not be confused with the blue mass produced with
aluminium compounds (see Section III, 21).
Na(NH4 )HP04 = NaPOa + NHa + H 2 0;
NaPOa + CoO = NaCoP04
8. Magnesium.-The only simple method for reducil'.!~ the
stable phosphates consists in heating with magnesium p( \vder,
whereby a phosphide is produced. The latter is 1; ILdily
identified by the odour and the inflammability of the phos-
phine formed on the addition of water. Intimately Il>ix a
small quantity of sodium phosphate with magnesium p' wder
and heat in an ignition tube. Moisten the cold maSi- with
water and observe the unpleasant odour of phosphine.
Na aP04 + 4Mg = 4MgO + NaaP;
NasP + 3H2 0 = PHa + 3NaOH
t9. Ammonium Molybdate-Benzidine Test.-In this test use is
made of the fact that benzidine, which is unaffected by normall"olyb-
dates and by free molybdic acid, is oxidised in acetic acid solut ,n by
phosphomolybdic acid or by its insoluble ammonium salt (see rea, ' ,on 4
above). This reaction is extremely sensitive; two coloured produ, s are
formed, viz. the blue reduction product of molybdenum com]" unds
("molybdenum blue") and the blue oxidation product of ber, Idine
("benzidine blue"). Moreover, solutions of phosphates which Sl., too
dilute to show a visible precipitate with the ammonium molJ i date
reagent will react with the molybdate reagent and benzidine to give a
blue coloration.
Arsenates and silicates with ammonium molybdate yield the s",mo-
nium salts of arseno-molybdic {H 3[AsMo 120 4o ]} and silico-mol, bdic
{H,[SiMo u 0 4o ] } acids respectively; these complex acids and thei! "alta
react similarly with benzidine. However, phosphates may be de!' 'Jted
in the presence of arsenates and silicates hy preventing the forn];ltion
of the corresponding molybdo-acids by the use of a tartaric Hcid-
ammonium molybdate reagent which does not react with arseni' and
silicic acids but does react with phosphoric acid when the react n is
carried out on filter paper.
Hydrogen peroxide, oxalates and fluorides interfere with the pr,'eipi-
tation of the phosphomolybdate and should therefore be absent.
Place a drop of the acid solution under test upon quantitative :lter
paper, add a drop of the molybdate reagent, followed by a drop ( : the
benzidine reagent. Hold the paper over ammonia vapour. A hlue
stain is formed when most of the mineral acid has been neutralise, I.
Sensitivity: 1·25 fLg. P 205' Concentration limit: 1 in 40,000.
The ammonium molybdate and the benzidine reagent are preJ 'red
as described under Silicates, Section IV, 26, reaction 7.
In the presence of silicates and/or arsenates, proceed as foJi ,ws.
Place a drop of the test solution upon quantit,ative filter paper, foIl, ,wed
by a drop of the tartaric acid-ammonium molybdate reagent. 1I old
29] Reactions of the Acid Radicals or Anion8 389
the paper over a hot wire gauze (or over a sheet of asbestos heated on
a hot plate) to accelerate the reaction. Then add a drop of the benzidine
reagent and develop over ammonia vapour. A blue coloration results.
Sensitivity: 1·5/-tg. P a06 in the presence of 500 times the amount of
SiO a. Concentration limit: 1 in 50,000.
The tartaric acid-ammonium molybdate reagent is prepared by
dissolving 15 grams of crystallised tartaric acid in 100 ml. of the
ammonium molybdate reagent referred to above.
t 10. Ammonium MolYbdate-Quinine Sulphate Reagent.-
Phosphates give a yellow precipitate with this reagent: tho exact
composition appears to be unknown.
Reducing agents (sulphides, thiosulphates, etc.) interfere since they
yield "molybdenum blue"; ferrocyauides give a red col<Jration.
Arsenates (warming is usually required), arsenites, chromates, oxalates,
tartrates and silicates give a similar reaction with some variation in the
colour of the precipitate. All should be removed before applying the
test.
Place 1 mI. of the test solution in a semimicro test-tube and add 1 ml.
of the reagent. A yellow precipitate is produced within a few minutes:
gentle warming (water bath) is sometimes necessary.
Concentration limit: 1 in 20,000.
The reagent is prepared by dissolving 4·0 grams of finely powdered
ammonium molybdate {(NH4)6Mo70w4HaO} in 20 ml. of water and
adding, with stirring, a solution of 0,] gram of quinine sulphate in
80 mI. of concentrated nitric acid.

IV, 29. REACTIONS OF PYROPHOSPHATES, P 2 0 7 - - - -

AND OF METAPHOSPHATES, PO a-
Sodium pyrophosphate is prepared by heating disodium hydrogen
phosphate:
2Na 2HPO, = Na,P 207 + HaO
This is the normal salt. Acid salts, e.g. Na 2H aP Z0 7, are known.
Sodium metaphosphate (polymeric) may be prepared by heating
microcosmic salt or sodium dihydrogen phosphate:
Na(NH,)HPO, = NaPO, + NHa + HIO
Na.HaPO, = NaPO. + HaO
A number of metaphosphates are known and these may be regarded
as derived from the polymeric acid (HPOul n , i.e. poly-metaphosphoric
acid. Calgon, used for wa.ter softening, is probably (Nal'Oa). or
Na 2 [Na,(PO a).]·
Pyro- and meta-phosphates give the ammonium molybdate
test on warming for some time; this is doubtless due to their
initial conversion in solution into orthophosphates. The
chief differences between ortho-, pyro- and meta-phosphates
are incorporated in the following table. The student should
carry out all the tests.
390 Qualitative Inorganic AnalY8is [IV,
Reactions of Ortho-, Pyro- and Meta-phosphate~
~-

R6a(/ent Ortlwphosphate Pyrophosphate

1. Silver Yellow ppt., sol· White ppt., sol. White ppt. (E pa·
nitrate uble in dilute uble in dilute rates Blo" y),
solution. ENO a and in HNO a and in soluble in d, lte
dilute NH~ dilute NH~ HNO".ind,j'lte
solution. solution: NHa solut .,m
sparingly sol. and in di:te
uble in dilute acetic acid.
acetic acid.
2. Albumin No coagulation. No coagulation. Coagulation.
and dilute
acetic acid.
3. Copper Pale blue ppt. Very pale blue No ppt.
sulphate ppt.
solution.
4. Magnesia White ppt., in. White ppt., sol· No ppt., even "n
mixture or soluble in ex· uble in excess boiling.
Mg(NO.)2 cellS of the reo of reagent, but
reagent. agent. reprecipitated
on boiling.

-
5. Cadmium No ppt. White ppt. No ppt.
chloride
solution
and dilute
acetic acid.
6. Zinc White ppt., sol· White ppt., in· White ppt. II
sulphate uble in dilute soluble in dilute warming; ~ ,I.
solution. acetic acid. acetic acid; sol. uble in dill i' ,}
uble in dilute acetic acid.
NH. solution,
yielding a white
ppt. on boiling.

IV, 30. REACTIONS OF PHOSPHITES, HP0 3- -

Solubility.-The phoephites of the alkali metals are soluble in water; ;ell
other metallic phosphites are insoluble in water.
Use sodium phosphite, Na2HPOa,5H20.
1. Silver Nitrate Solution: white precipitate of sih ,·r
phosphite Ag 2HP0 3 , which soon passes in the cold into bla, k
metallic silver. Warming is necessary with dilute solutiOl '.
Upon adding the reagent to a warm solution of a phosphite, :t
black precipitate of metallic silver IS obtained immediately.
Na2HPOa + 2AgNOa = Ag 2HPO a + 2NaNO a ;
Ag2 HPO a +
H 20 = 2Ag H aP04 +
2Na2HPOg +
AgNO g = Ag ~Na2HP04 + NO +
2. Barium Chloride Solution: white precipitate of barim II
phosphite BaHPO a, soluble in dilute acids.
31] Reactions of the Acid Radicals or Anions 391
3. Mercuric Chloride Solution: white precipitate of
calomel in the cold; on warming with excess of the phosphite
solution, grey metallic mercury is produced.
Na2HPOs + 2HgCl 2 + H 20 = H SP04 + Hg2Cl 2 + 2N:1CI;
Hg 2Cl2 + Na2HPOs + H 20 = H SP04 + 2Hg + 2NaC!
4. Potassium Perman~anate Solution: no action in the
cold with a solution acidified with acetic acid, but decolourised
on warming.
6. Concentrated Sulphuric Acid: no reaction in the cold
with the solid salt, but on warming sulphur dioxide is evolved.
HsPOs + H 2S04 = S02 + H aP04 + H 20

6. Zinc and Dilute Sulphuric Acid.-Phosphiies are

reduced by the nascent hydrogen to phosphine PH 3 , which
may be identified as described in the Gutzeit test lllder
Arsenic (Section IV, 13); the silver nitrate paper is "tained
first yellow and then black.
HaPOa + 3Zn + 3HzS04 = PH3 + 3ZnS04 + 3H20;
PH 3 + 6AgNO s = Ag sP,3AgNO a(yelIow) + 3H~03;
Ag aP,3AgN0 + 3H 0 = 6Ag(black) + 3HNO a + HaJ>Os
3 2

7. Copper Sulphate Solution: light blue precipir;ato of

copper phosphite CuHPO a; the precipitate merely d;ssolves
when it is boiled with acetic acid (compare Hypophof;phites,
Section IV, 31).
CUS04 + NazHPOs = CuHPO a + Na2S04
8. Lead Acetate Solution: white precipitate, insoluble in
acetic acid.
Na2HPOa + Pb(CzHsOzb = PbHPOa + 2NaC 2H sO l
9. Action of Heat: inflammable phosphine is evolved, and
a mixture of phosphates is produced.
8Na2HPOs = 2PHs + 4Na SP04 + Na4PZ07 + H 20
IV, 31. REACTIONS OF HYPOPHOSPHITES,
H 2P0 2-
Solubility.-All hypophosphites are soluble in water.
Use sodium hypophosphite, NaH 2P0 2 ,H 20.
1. Silver Nitrate Solution: white precipitate of silver
hypophosphite AgH 2PO z, which is slowly reduced to silver at
392 Qualitative Inorganic Analyail [IV,
the ordinary temperature, but more rapidly on wal'ning,
hydrogen being simultaneously evolved.
NaH2PO S + AgNO s = AgH2P02 + NaNOs;'
2AgH2POZ + 4H zO = 2Ag + 2HaPO, + 3H2
2. Barium Chloride Solution: no precipitate.
3. Mercuric Chloride Solution: white precipitat, of
calomel in the cold, converted by warming into grey, mel tllic
mercury.
NaH2PO Z + 4HgCl2 + 2H20
= 2Hg zC1 + HaPO, + 3HCI + ~ tCI:
2
NaH 2PO Z + 2HgC12 + 2H 0 = 2Hg + H aP0 + 3HCl + N ,01
2 4

4. Copper Sulphate Solution: no precipitate in the "<lId,

but on warming red cuprous hydride CuR is precipitll' ed.
The latter evolves hydrogen on treatment with concentr Ged I

hydrochloric acid.
3HaP0 2 + 4CuSO, + 6H 20 = 4CuH + 3HaP04 + 4H zSO,;
CuH + HOI = euOl + Hz
5. Potassium Permanganate Solution: reduced imme-
diately in the cold.
6. Concentrated Sulphuric Acid: reduced to sulpLur
dioxide (and to sulphur) by the solid salt, only on warmi;;g.
7. Concentrated Sodium Hydroxide Solution: hydro~ 'n
is evolved, and a phosphate is produced on warming.
NaH zP0 2 + 2NaOH = 2Hz + NaaP04
8. Zinc and Dilute Sulphuric· Acid: inflammable phi '.'1-
phine is evolved (see under Phosphites, Section IV, 30, re-
action 6).
9. Ammonium Molybdate Solution: reduced to "moly!,.
denum blue" in solution acidified with dilute sulphuric aCid
(difference from phosphite).
10. Action of Heat: phosphine is evolved, and a pyro-
phosphate is produced.
4NaH2PO Z = Na,P 2 0 7 + 2PHa + HzO
IV, 32. REACTIONS OF ARSENITES, As0 3 - - - AND
OF ARSENATES, As 0 4- - -
See under Arsenic, Sections III, 11 and III, 12.
33] Reactions of the Acid Radicals or Anions 393
IV, 33. REACTIONS OF CHROMATES, Cr04 -- (AND
DICHROMATES, Cr207 --)
The metallic chromates are usually coloured solids, yielding yellow solutions
when soluble in water. In the presence of dilute mineral acids, i.e. of hydrogen
ions, chromates are converted into dichromates; the latter yield orange·red
aqueous solutions. The change is reversed by alkalis, i.e. by hydroxyl ions.
2K 2CrO,+ 2HCl = K.Cr 20 7 + H 20 + 2KCI;
or 2CrO,- + 2H+-+ Cr 20,- + H 20
+
K 2 Cr 2 0 7 2KOH = 2K 2CrO. + H 2 0;
or Cr.0 7- + 2011 -+ 2CrO,- + H.O
The reactions may also be expressed:
2CrO,-- + 2H+ -= 2HCrO.- -= Cr 2 0 7-+ H 20
Solubility.-The chromates of the alkali metals and of calcium and mag.
nesium are soluble in water; strontium chromate is sparingly soluble. Most
other metallic chrornates are insoluble in water. Sodium, pota.'lsium and
ammonium dichromatos are soluble in water.
Use potassium chromate, K2Cr04, or potassium dichromate,
K 2Cr 207'
1. Barium Chloride Solution: pale yellow precipitate of
barium chromate BaCr04, insoluble in water and in acetio
acid, but soluble iu dilute mineral acids (for explanation, see
Section I, 17).
K 2CrO, + BaCl2 = BaCr04 + 2KCI
2. Silver Nitrate Solution: brownish-red precipitate of
silver chromate Ag2Cr04 with a solution of a chromate. The
precipitate is soluble in dilute nitric acid and in ammonia
solution, but is insoluble in acetio acid. Hydrochloric acid
converts the precipitate into silver chloride (white).
A reddish-brown precipitate of silver dichromate Ag2Cr207
is formed with a concentrated solution of a. dichromate; this
passes, on boiling with water, into the less soluble silver
chromate.
K 2Cr04 + 2AgNO s = Ag2Cr04 + 2KNO s ;
K 2Cr20 7 + 2AgNOs = Ag ZCr20 7 + 2KNO s ;
2Ag2Cr207 + H 20 = 2Ag 2Cr04 + H zCr20 7
3. Lead Acetate Solution: yellow precipitate of lead
chromate PbCr04, insoluble in acetic acid, but soluble in dilute
nitric acid.
K2Cr04 + Pb(CzH s0 2 )2 = PhCrO, + 2K.C2H s0 2
The precipitate is soluble in sodium hydroxide solution; acetio
acid reprecipitates the chromate from the latter solution.
The solubility in sodium hydroxide solution is due to the forma-
tion of the soluble complex salt, sodium plumbite Na2[Pb02], which
reduces the Pb++ ion concentration to such an extent that the
13*
394 Qualitative Inorganic AnalY8i8 [IV,
solubility product of lead chromate is no longer exceeded, i nd
consequently the latter dissolves (compare Section I, 17).
PbCr04, + 4NaOH = Na2[PbOz] + Na2CrO, + 2H zO
4. Hydrogen Peroxide.-If an aeid solution of a ehroD' 'te
is treated with hydrogen peroxide, a deep-blue solution of ! h.e
so-called perchromic acid is obtained (compare Chromiun,
Section III, 22, reaction 6). The blue solution is very unstahle
and soon decomposes, yielding oxygen and a green solution of
a chromic salt. The blue compound is soluble in amyl alcohol
and also in amyl acetate and in diethyl ether, and can be
extracted from aqueous solutions by these solvents to yidd
somewhat more stable solutions.
Amyl alcohol is recommended. Diethyl ether is not recommend"d
for general student use owing to its highly inflammable character h:,d
also because it frequently contains peroxides after storage for C,';lI-
paratively short periods: a blank test is therefore necessary. Peroxi, i'-8
may be removed from diethyl ether by shaking with a concentrat,'d
solution of a ferrous salt or with sodium sulphite.
The blue coloration is attributed to the presence of chron, 1 C
diperoxide Cr05:
H2Cr207 + 4H20 2 ~ 2Cr05 + 5H zO
The enhanced stability in solutions of amyl alcohol, ether, etc.,
is due to the formation of complexes with these oxygen,
containing compounds.
Just acidify a cold solution of a chromate with dilute Sll:
phuric acid or dilute nitric acid, add 1-2 m!. of amyl alcoh(,;
then 1 m!. of lO-volume (3 per cent) hydrogen peroxide soluti(",
dropwise and with shaking after each addition: the organl:'
layer is coloured blue. The chromic peroxide is more stabl,'
below OOG than at the laboratory teniperature.
5. Hydrogen Sulphide.-An acid solution of a chromat"
is reduced by this reagent to a green solution of a chromic sa11 ,
accompanied by the separation of sulphur.*
2K 2Cr0 + H 2S0 = K2Cr207 + K S04 + H 0;
4 4 Z 2
K2Cr207 + 3H 2S + 4H2S04 = Crz(S04h + 3S + K 2S04 + 7H20
* In qualitat.ive analysis, the production of sulphur in the reduction ",
dichromates by hydrogen sulphide is sometimes troublesome. This can h
avoided (a) by heating the solid substance with concentrated hydrochlorj,
acid, evaporating off most of the acid and then diluting with wat.er, or (b) b\
warming with hydrochloric acid and alcohol or 10 per cent formaldehyd,
solution. The use of sulphur dioxide is not recommended as sulphuric aci,.
is formed, and this will precipitate lead, strontium and barium, if these metab
are present.
K,Cr.0 7 + SHCl + aH.CHO = 2CrCl. + 2KCI + 3H.CO,H + 4 H.O
K.Cr.0 7 + SHCI + aCIHI.OH = 2CrC1. + 2KCI + aCR •. CHO +7R,O
34] Reaction8 of the Acid Radical8 or Anion8 395
6. Sulphur Dioxide: in the presence of dilute mineral acid,
a green chromic salt is produced.
K2Cr207 + 3H2SOS -+ H 2S04 = Cr 2 (S04)s + K 2 S04 + 4H 20
K2Cr207 + 3H2SO S + 8HCl = -+ +
2CrCIs 2KCl 3H2S04 + 4H 2 0
Chromates in acid solution, or dichl'omates, are similarly
reduced to green chromic salts by potassium iodide, ferrous
sulphate and ethyl alcohol.
-+
K 2 Cr 20 7 + 6K1 + 7H 2S04 = Cr2(S04)s + 31 2 4K 2S04 +- 7H20
K2Cr207 + 6FeS04 -+ 7H 2S04
+
= Cr2(S04)s K 2S04 + 3Fe2(S04)s 7H20 +
K 2 Cr 20 7 + 3C 2H 5 • OH -+4H 2S04
= Cr2 (S04)s + K 2S04 + 7H2 0 +
3CHs .CHO (acetaldehyde)
7. Concentrated Hydrochloric Acid.-On heating a solid
chromate or dichromate with concentrated hydrochloric acid,
chlorine is evolved, and a solution of chromic chloride is
produced.
K2Cr207 -+ 14HCl = 2KCl + 2CrCIs -+ 3C12 + 7H2 0
8. Concentrated Sulphuric Acid and a Chloride.--See
chromyl chloride test under Chlorides, Section IV, 14, re-
action 5; also Section IV, 45, 5.
9. Diphenylcarbazide Reagent.-The solution is acidified
with dilute sulphuric acid or with dilute acetic acid, and 1-2 ml.
of the reagent added. A deep red coloration is produced.
With small quantities of chromates, the solution is coloured
violet.
Full details of the use of the reagent as a spot test are given
under Chromium, Section III, 22, reaction 7.
10. Chromotropic Acid Test.-A red coloration, best seen
by transmitted light, is given by chromates. For details, see
under Chromium, Section III, 22, reaction 8.

IV, 34. REACTIONS OF PERMANGANATES MnO",-

Solubility.-All permanganates are soluble in water forming purple (reddish.
violet) solutions.
Use potassium permanganate, KMnO",.
1. Hydrogen Peroxide.-The addition of this reagent to
a solution of potassium permanganate, acidified wit h dilute
sulphuric acid, results in decolourisation and the evolution of
pure but moist oxygen.
2KMn04 + 3H zS04 -+ 5H 20 Z = 2MnS04 -+ K 2S04 + 50 2 -+ 8H zO
396 Qualitative Inorganic Analysis [IV,
2. Hydro~en Sulphide: in the presence of dilute sulphurio
acid, the purple colour of the solution is discharged and sulpf1ur
is precipitated. *
2KMn04 + 3H2804 + 5H2S = K 2S04 + 2Mn804 + 58 + S] I ~O
Similar results are obtained with other reducing agents in
the presence of dilute sulphuric acid. These include sulplur
dioxide, ferrous sulphate, potassium iodide, sodium nitrite H nd
oxalic acid; in the last case, the reaction proceeds best :It
about 60°.
2KMn04 + 5802 + 2H 2 0 = 2Mn804 + K 2S04 + 2H 2S04t
2KMn04 + lOFeS04 + SH 2 S04
= 2MnS04 + K 2S04 + 5Fe2(S04)s + SIl 20
2KMn04 + lOKI + 8H 2S04
= 2Mn804 + 6K 2S04 + 512 + Sl! ,0
2KMn04 + 5HN02 + 3H2S04
= 2l\fuS04 + K 2S0 + 5HNOs + 3H :0
4
2KMn04 + 5H C20 4 + 3H S04
2 2
= 2MnS04 + K 2S04 + lOC0 2 + SH. 0
In alkaline solution, the permanganate is decolourised, }, It
manganese dioxide is precipitated. In the presence of sodil ::1
hydroxide solution, potassium iodide is converted into pot:l"-
sium iodate, and sodium sulphite solution into sodium sulpht, e
on boiling.
2KMn04 + KI + H 20 = KIO a + 2Mn0 2 + 2KOH
2KMn04 + 3Na2S0a + H 20 = 3Na2S04 + 2Mn0 2 + 2KOH
3. Concentrated Hydrochloric Acid.-All permangana1 ,
on boiling with concentrated hydrochloric acid evolve chloriI],-.
2KMn04 + 16HCl = 2MnC12 + 2K01 + 5012 + SH 20
4. Concentrated Sulphuric Acid (GREAT DANGER).
Permanganates dissolve in this reagent to yield a green solutio!;,
which contains manganese heptoxide (permanganic anhydrid,')
Mn207; the solution is liable to explode spontaneously at tl,,'
• To avoid the production of sulphur by the reduction of potassium pH
manganate by hydrogen sulphide in systematic qualitative analysis, the sol, i
tion may be reduced with formaldehyde solution, or the solid substance ma',
be boiled with concentrated hydrochloric acid. The use of sulphur dioxide '
not recommended (see footnote in connexion with Chromates, Section IV, 3,
reaction 5).
2KMn04 + 6HCI + 5H.CHO = 2l\'InCI. + 2KCl + 5H.CO.H + 3H.0
t Some dithionic acid H.S.O. may be formed in this reaction, the quantity
being dependent upon the experimental conditions.
2KMnO. + +
680 , 2H.0 = 2MnSO. +
2KHSO, + HIS.O.
35J Reactions of the Acid Radical.s or AniOM 397
ordinary temperature, and a very vigorous explosion may result
on warming. The student is therefore warned not to carry out
this experiment except with minute quantities of materials
(not more than 0·05 gram) and in the latter case under the
direct supervision of the teacher. The experiment is best
omitted.
Upon warming potassium permanganate with dilute sulphuric
acid, oxygen is evolved.
2KMn04 + H 2S04 (conc.) = ]\fn 2 0 7 + K 2S04 + H 2 0
4KMn04 + 4H 2S04 = 4Mn0 2 + 4KHS04 + 30 2 + 2H 2 0
5. Potassium Hydroxide Solution.-Upon warming a
concentrated solution of potassium permanganate with con-
centrated potassium hydroxide solution, a green solution of
potassium manganate is produced and oxygen is evolved.
When the manganate solution is poured into a large volume
of water or is acidified with dilute sulphuric acid, the purple
colour of the potassium permanganate is restored.
4KMn04 + ·:lXOH = 4K 21'1fn04 + 2H2 0 + O2
3K zMn04 + 2H2 0 = 2KMn04 + l\fn0 2 + 4KOH
A manganatc is produced when a manganese compound is
fused with potassium nitrate and sodium carbonate (see Section
III, 26).
6. Action of Heat.-When potassium permanganate is
heated in a test-tube, pure oxygen is evolved, and a black
residue of potassium manganate K2Mn04 and manganese di-
oxide remains behind. Upon extracting with a little water
and filtering, a green solution of potassium manganate is
obtained.
2KMn04 = K ZMn04 + MnO z + Oz

IV,35. REACTIONS OF ACETATES, C zH 3 0 z-

Solubility.-All normal acetates, with the exception of silver and mercurous
acetates which are sparingly soluble, are readily soluble in water. Nome basic
acetates, e.g. those of iron, ahmlinium and chromium, are insolubl" in water.
The free acid, CH •. CO,H or H.C,H.O" is a colourless liquid with a pungent
odour, boiling point 117°, melting point) 7° and is miscible with water in all
proportions; it has a corrosive action on the skin.
Use sodium acetate, Na.C 2H 3 0 2 ,3H zO (or CH 3 .CO zNa,3H zO).
1. Dilute Sulphuric Acid: acetic acid, easily recognised by
its vinegar-like odour, is evolved on warming.
Na.C2 H sOz + H 2S04 = NaHS04 + H.C zH a0 2
398 Qualitative bwrganic Analysis [IV,
2. Concentrated Sulphuric Acid: acetic acid is evolvl'd
on heating, together with sulphur dioxide, the latter tendi:rl~
to mask the penetrating odour of the concentrated acetic aC11 i
vapour. The test with dilute sulphuric acid, in which the
acetic acid vapour is diluted with steam, is therefore to 1"J
preferred as a test for an acetate.
3. Ethyl Alcohol and Concentrated Sulphuric Acid.-
One gram of the solid acetate is treated with 1 ml. of concell
trated sulphuric acid and 2-3 ml. of rectified spirit in a teB t
tube, and the whole gently warmed for several minutes; eth_'. \
acetate C2H5.C2Ha02 is formed, which is recognised by 11,;
pleasant, fruity odour. On cooling and dilution with wat!'!'
on a clock glass, the fragrant odour will be more readii~'
detected.
CZH 5 ·OH + H. CzHsOz ~ CZH 6 • CZH S0 2 + H 20
(the sulphuric acid acts as a dehydrating agent).
It is preferable to use iso-amyl alcohol because the odour (d
the resulting iso-amyl acetate is more readily distinguishell
from the alcohol itself than is the case with ethyl alcohol. J t
is well to run a parallel test with a known acetate and t,l
compare the odours of the two products.
4. Silver Nitrate Solution: a white, crystalline precipitate
of silver acetate Ag. C2H 3 0 2 is produced in concentrated solu
tions in the cold. The precipitate is more soluble in boilin~,
water (10'4 grams per litre at 20° and 25·2 grams per litre at
80°) and readily soluble in dilute ammonia solution.
Na.C 2H s0 2 + AgNOs = Ag.C2H s0 2 + NaNOs
o. Barium, Calcium or Mercuric Chloride Solution:
no precipitate.
6. Ferric Chloride Solution: deep-red coloration, due to
ferric acetate Fe(C2Ha02h, is produced with practically neutraJ
solutions of acetates. On diluting and boiling the red solution,
the iron is precipitated as basic ferric acetate Fe(OH)z. C2H a0 2 .
The coloration is destroyed by dilute hydrochloric acid.
FeCl s + 3Na.C2H s0 2 = Fe(C2H s0 2 )s + 3NaCI;
Fe(CzHsOz)s + 2H zO = Fe(OH)2' CzHsOz + 2H. CzHsOz
7. Cacodyl Oxide Reaction.-If a dry acetate, preferably
that of sodium or potassium, is heated in an ignition tube or
test-tube with a small quantity of arsenious oxide, an extremely
nauseating odour of cacodyl oxide is produced. All cacodyl
compounds are extremely poisonous; the experiment must
 35] Reactions of the Acid Radicals or Anions 399
therefore be performed on a very small scale, and preferably
in the fume chamber. Mix not more than 0·2 gram of sodium
acetate with 0·2 gram of arsenious oxide in an ignition tube
and warm; observe the extremely unpleasant odour that is
produced.
4Na.02H302 + As 20 S
= (OHa)2As . O. As(OHs)2 + 2Na200a + 200 2
8. Lanthanum Nitrate Test.--Treat 0·5 mI. of the acetate
solution with 0·5 ml. of a 5 per cent lanthanum nitrate sl)lution,
add 0·5 ml. of iodine solution and a few drops of dilute ammonia
solution, and heat slowly to the boiling point. A blue colour
is produced; this is probably due to the adsorption of the
iodine by the basic lanthanum acetate. This reaction provides
an extremely sensitive test for an acetate.
SUlphates and phosphates interfere, but can be removed by
precipitation with barium nitrate solution before applying the test.
Propionates give a similar reaction.
t The spot-test technique is as follows. Mix a drop of the test
solution on a spot plate with a drop of 5 per cent lanthanum nitrate
solution and a drop of O'OIN iodine. Add a drop of N ammonia solu-
tion. Within a few minutes a blue to blue-brown ring will develop
round the drop of ammonia solution.
Sensitivity: 50 JLg. ILC zH 3 0 2 • Concentration limit: 1 in ~,OOO.
t9. Formation of Indigo Test.-The test depends upon the con-
version of acetone, formed by the dry distillation of acetates (see
reaction 10), into indigo. No other fatty acids give this test, but the
sensitivity is reduced in their presence.
Mix the solid test sample with calcium carbonate 01', alternatively,
evaporate a drop of the test solution to dryness with calcium cs rbonate;
both operations may be carried out in the hard glass tube of Fig. II,
6, 15. Cover the open end of the tube with a strip of quantitat ive filter
paper moistened with a freshly prepared solution of o-nitrobenzalde-
hyde in 2N sodium hydroxide, and hold the paper in position with a
small glass cap or a small watch glass. Insert the tube into a hole in
an asbestos or "uralite" sheet and heat the tube gently. Anetone is
evolved which colours the paper blue 01' bluish-green. For minute
amounts of acetates, it is best to remove the filter paper after the
reaction and treat it with a drop of dilute hydrochloric acid; the original
yellow colour of the paper is thus bleached and the blue colour of the
indigo is more readily apparent.
Sensitivity: 60JLg. H.C 2H 30.
10. Action of Heat.-All acetates decompose upon strong
ignition, yielding the highly inflammable acetone OH a . CO .0Ha
and a residue, which consists of the carbonates for the alkali
acetates, of the oxides for the acetates of the alkaline earth
and heavy metals, and of the metal for the acetates of silver
 400 Qualitative Inorganic Analy.m [IV,
~ the noble metals. CatTY out the experiment in an ignit'Jn
- tUoJe with sodium acetate and lead acetate.
2Na.C2H a0 2 = CHs.CO.CHs + NajlCO s

IV,36. REACTIONS OF FORMATES, H.C0 2-

Solubility.-With the exception of the lead, silver and mercurous ,,;,lts
which are sparingly soluble, most formates are soluble in water. The se
acid H.CO.H is a pungent smelling liquid, boiling point 100'5°, melting p,.:llt
8°, miscible with water in all proportions, and producing blisters when allo\\'od
to come into contact with the skin.
Use sodium formate, H. C0 2Na.
1. Dilute Sulphuric Acid: formic acid is liberated, t];e
pungent odour of which can be detected on warming tLe
mixture.
H.00 2Na + H 2S04 = NaHS04 + H.OOzH
2. Concentrated Sulphuric Acid: carbon monoxide (highly
poisonous) is evolved on warming; the gas should be ignited
and the characteristic blue flame obtained.
H.C0 2Na + H 2S04 = CO + NaHS04 + H 20
3. Ethyl Alcohol and Concentrated Sulphuric Acid: :~
pleasant odour, due to ethyl formate H.C0 2C2H 5 , is appareL\)
on warming (for details, see under Acetates, Section IV, 35,
reaction 3).
H.00 2H + 02H50H ;F H. 00Z02H5 + H 2 0
4. Silver Nitrate Solution: white precipitate of silver
formate H. C0 2Ag in neutral solutions, slowly reduced at tl,
ordinary temperature and more rapidly on warming, a bla(':,
precipitate of silver being formed (distinction from acetate'
With very dilute solutions, the silver may be deposited in t}w
form of a mirror on the walls of the tube.
H.OOzNa + AgNOs = H.COzAg + NaNOs;
2H.C02Ag = 2Ag + H.COzH + 002 ~
5. Barium or Calcium Chloride Solution: no precipitate,
6. Ferric Chloride Solution: a red coloration, due to ferric
formate Fe(H. CO 2 )s, is produced in practically neutral solu
tions; the colour is discharged by hydrochloric acid. If the
red solution is diluted and boiled, a brown basic ferric
formate (H. CO 2 )Fe(OH)2 is precipitated.
3H.002Na + FeOls = Fe(H.002)s + 3NaO);
Fe(H. CO2 )s + 2H 2 0 = (H. 00z)Fe(OH)2 + 2H. 002H
37] Reactiom of the Acid Radicau Of' .Anions 401
7. Mercuric Chloride Solution: white precipitate of mer-
curous chloride Hg 2C1 2 is produced on warming; this passes
into grey, metallic mercury in presence of excess of the formate
solution (distinction from acetate).
2H.C0 2Na + 2HgC12 = Hg2Cl2 + 2NaCI + CO + CO2 + H 20;
2H.C02Na + Hg2Cl2 = 2Hg + 2NaCI + CO + CO2 + H 20
8. Mercuric Formate Test.-Free formic acid is necessary
for this test. The solution of the formate is acidified with
dilute sulphuric acid and shaken vigorously with a little mer-
curic oxide; it is then filtered from the undissolved oxide. The
filtrate, which contains mercuric formate (H.C0 2)2Hg, on boil-
ing gives momentarily a white precipitate of mercurous formate
(H. CO2)2Hg2, which rapidly changes to a grey precipitate of
metallic mercury.
2H. C0 2H +
HgO = (H. CO2)2Hg + H 20;
2(H.C02)2Hg = (H.C02)2Hg2 H.C0 2H + + CO 2 ;
(H. CO2)2Hg2 = 2Hg H. C0 2H + CO 2 +
t9. Formaldehyde-Chromotropic Acid Test.-Formic acid
H.COOH is reduced to formaldehyde R.CHO by magnesium and
hydrochloric acid. The formaldehyde is identified by its reaction with
chromotropic acid (see Section III, 22, reaction 8) in strong sulphuric
acid when a violet-pink coloration appears. Other aliphatic aldehydes
do not give the violet coloration.
Place a drop or two of the test solution in a semimicro test-tube, add
a drop or two of dilute hydrochloric acid, followed by magnesium
powder until the evolution of gas ceases. Introduce 3 ml. of f->ulphuric
acid (3 acid: 2 water) and a little solid chromotropic acid, and warm
to 60°0. A violet-pink coloration appears within a few minutes.
Sensitivity: 1·5p,g. H.OOOH. Concentration limit: I in 20,000.
10. Action of Reat.-Cautious ignition of the formates of
the alkali metals yields the corresponding oxalates (for tests,
see Section IV, 37) and hydrogen.
2H.C02Na = Naz'C20" + H2
IV, 37. REACTIONS OF OXALATES, C 2 0,,--
Solubility.-The oxalates of the alkali metals and of ferrous iron are soluble
in water; all other oxalate" are either insoluble or sparingly solublE' in water.
They are all soluble in dilute acids:
Ca.C.O, + 2HCl = H •. C.O, + 2HCl
Some of the oxalates dissolve in a. concentrated solution of Oll:alic acid
by virtue of the formation of soluble acid or complex oxalat('s. Oxalic
acid (a dibasic acid) is a colourless, crystalline solid H.C.O,.2H.O (or
HO.C.CO.H,2H.O), and becomes anhydrous on heating to 110°; it is readily
soluble in wa.ter (111 graIIlll per litre at 20°).
402 Qualitative Inorganic Analyaia
Use sodium oxalate, Na2' 0 20" or ammonium OXll l q,te,
(NH4)2· 0 20 4,H 20.
1. Concentrated Sulphuric Acid: decomposition 01 all
solid oxalates occurs with the evolution of carbon mono 'jde
and carbon dioxide; the latter can be detected by passing "he
escaping gases through lime water (distinction from fornllte)
and the former by burning it at the mouth of the tube. \\ ith
dilute sulphuric acid, there is no visible action; in the pres! :lce
of manganese dioxide, however, carbon dioxide is evolved.
. H 2 .02 0, + H 2SO, = 00 + 00 2 + H 2 0 + H 2S04
(the sulphuric acid acts as a dehydrating agent).
2. Silver Nitrate Solution: white, curdy precipitate of
silver oxalate Ag 2 • C2 0 4 , sparingly soluble in water, solubk in
ammonia solution and in dilute nitric acid.
(NH4h.0204 + 2AgNO a = Ag2 • 0 2 0 4 + 2NH 4NO a
3. Calcium Chloride Solution: white, crystalline precic)i-
tate of calcium oxalate Ca. C2 0 4 from neutral solutions, i i 1-
soluble in dilute acetic acid, oxalic acid and in ammonili ill
oxalate solution, but soluble in dilute hydrochloric acid awl
in dilute nitric acid. It is the most insoluble of all oxalat ,."
(0·0067 gram per litre at 13°) and is even precipitated L\'
calcium sulphate solution and acetic acid. Barium chloride,
solution similarly gives a white precipitate of barium oxalal.,
Ba.C 2 0 4 , sparingly soluble in water (0'016 gram per litre at ge i
but soluble in solutions of acetic and of oxalic acids.
(NH4h.0204 + OaOl2 = Oa.0204 + 2NH401
4. Potassium Permanganate Solution: decolourised when
warmed in acid solution to 60°-700.. The bleaching of pel'
manganate solution is also effected by many other organi,'
compounds, but if the evolved carbon dioxide is tested for
by the lime water reaction (Section IV, 2, reaction 1), the test
becomes specific for oxalates. ____
2KMn04 + 3H2S04 + 5H2 • 0 20 4
= 2MnS04 + K 2S04 + 10002 + 8H20
5. Resorcinol Test.-Place a few drops of the test solution
in a test-tube: "fad several drops of dilute sulphuric acid and
a speck or two of magnesium powder. When the metal has
dissolved, add about 0·1 gram of resorcinol, and shake until
dissolved. Cool. Carefully pour down the side of the tube
3-4 ml. of concentrated sulphuric acid. A blue ring will form
at the junction of the two liquids. Upon warming the sul-
phuric acid layer at the bottom of the tube very gently
 37] Reactions of the Acid Radicals or Anions 403
(CAUTION), the blue colour spreads downwards from the
interface and eventually colours the whole of the sulphuric
acid layer.
Citrates do not interfere. In the presence of tartrates, a
blue ring is obtained in the cold or upon very gentle warming
(compare similar test under Tartrates in the following SeclJion).
6. Manganous Sulphate Test.-A solution of manganous
sulphate is treated "\"\'ith sodium hydroxide solution, and the
resulting mixture warmed gently to convert it into mangano-
manganic hydroxide. After cooling, the solution of the oxalate,
made acid with dilute sulphuric acid, is added. The precipi-
tate dissolves and a red colour is produced. The latter is pro-
bably due to the formation of the complex ion [Mn(C 20 4 hr--.
7. Action of Heat.-All oxalates decompose upon ign~tion.
Those of the alkali metals and of the alkaline earths yield
chiefly the carbonates and carbon monoxide; a little carhon is
also formed. The oxides of the metals whose carbonates are
easily decomposed into stable oxides, are converted into cnrbon
monoxide, carbon dioxide and the oxide, e.g. magnesium and
zinc oxalates. Silver oxalate yields silver and carbon dioxide;
silver oxide decomposes on heating. Oxalic acid decom poses
into carbon dioxide and formic acid, the latter being further
partially decomposed into carbon monoxide and water.
7Naz.OZ04 = 7Naz003 + 300 + 200z + 20;
Ba. 0 2 0 4 = BaOO a + 00;
Mg.0 2 0 4 = MgO + 00 + CO?,;
Ag2 .02 0 4 = 2Ag + 200 2 ;
H 2 .02 04, = H.00 2 H + CO 2 ;
H.00 2 H = 00 + H 20
t8. Formation of Aniline Blue Test.--Upon heating insoluble
oxalates with syrupy phosphoric acid and diphenylamine or upon
heating together oxalic acid and diphenylamine, the dyestuff aniline
blue (or diphenylamine blue) is formed. Formates, acetates, tartrates,
citrates, succinates, benz oates and salts of other organic acids do not
react under these experimental conditions. In the presence of other
anions which are precipitated by calcium chloride solution, e.g. tartrate,
sulphate, sulphite, phosphate and fluoride, it is best to heat the precipi-
tate formed by calcium chloride with phosphoric acid as detailed below.
Place a few milligrams of the test sample (or, alternatively, lise the
residue obtained by evaporating 2 drops of tho test solution to d,'yness)
in a micro test-tube, add a little pure diphenylamine and melt over a
free flame. When cold, take up the molt in a drop or two of alcohol
when the latter will be coloured blue.
Sensitivity: 5 p.g. HaCaO,. Concentration limit: 1 in 10,000.
404 Qualitative Inorganic Analysis [IV,
In the presence of anions which are precipitated by calcium chIc" ,de
solution, proceed as follows. Precipitate the acetic acid test solu' ,)n
with calcium chloride solution, and collect the precipitate on a lilte or
in a centrifuge tube. Remove the water from the precipitate eil her
by drying or by washing with alcohol and ether. Mix a small amour" of
the precipitate with diphenylamine in a dry micro test-tube, add a Ii' rle
syrupy phosphoric acid, and heat gently over a free fiame. Calc I ' ; m
phosphate and free oxalic acid are formed, and the latter conde], 'JS
with the diphenylamine to aniline blue and colours the hot phosph, . ic
acid blue. The colour disappears on cooling. Dissolve the melt III
alcohol, when a blue coloration appears. Pour the alcoholic solut ' n
into water thus precipitating the excess of diphenylamine, whicL is
coloured light blue by the adsorption of the dyestuff. The dye may i ,e
extracted from aqueous solution by ether.

IV, 38.
Solubility.-Tartaric acid, HO.C.CH(OH).CH(OH).CO.H or H •. C.H.o"
is a crystalline solid, which is extremely soluble in water; it is a dibasic a(",1.
The potassium and ammonium acid salts are sparingly soluble in wat, ,';
those of the other alkali metals are readily soluble. The norm~l tartrates "f
the alkali metals are easily soluble, those of the other metals being sparini' i ".
soluble in water, but dissolve in solutions of alkali tartrates forming comp).,·~
salts, which often do not give the typical reactions of the metals present.
The most important commercial salts are" tartar emetic" K(SbO). C.H.O. '
0·5 H 2 0, "Rochelle salt" KNa.C.H,O.,4H 2 0 and "cream of tartal
KH.C,H.O •.
Use Rochelle salt, KNa.C4H 4 0 6 ,4H 20.
1. Concentrated Sulphuric Acid.-When a solid tartrate
is heated with concentrated sulphuric acid, it is decomposed
in a complex manner. Charring occurs almost immediately
(owing to the separation of carbon), carbon dioxide and
carbon monoxide are evolved, together with some sulphu r
dioxide; the last-named probably arises from the reduction ot
the sulphuric acid by the carbon. An empyreumatic odour.
reminiscent of burnt sugar, can be detected in the evolved
gases. Dilute sulphuric acid has no visible action.
H Z .04H 40 6 = 00 + 002 + 20 + 3HzO;
o + 2H2S04 = 2S0 2 + 002 + 2H 20
2. Silver Nitrate Solution: white, curdy precipitate of
silver tartrate Ag 2 • C4 H 4 0 6 from neutral solutions of tartrates,
soluble in excess of the tartrate solution, in dilute ammonia
solution and in dilute nitric acid. On warming the ammoniacal
solution, metallic silver is precipitated; this can be deposited
in the form of a mirror under suitable conditions.
The silver mirror test is best performed as follows. The
solution of the tartrate is acidified with dilute nitric acid,
excess of silver nitrate solution added and any prccipitate
present filtered off. Very dilute ammonia solution (approxi-
38] Reaction,s of the Acid RadicalB or Aniona 405
mately M /50) is then added to the solution until the precipitate
at first formed is nearly redissolved, the solution is filtered,
and the filtrate collected in a clean test-tube; the latter is then
placed in a beaker of boiling water. A brilliant mirror is
formed on the sides of the tube after a few minutes. The test-
tube may be cleaned either by boiling with chromic acid
mixture or by boiling it with a little sodium hydroxide solution,
and then rinsing it well with distilled water.
An alternative method for carrying out the silver mirror test
is the following. Prepare ammoniacal silver nitrate solution
by placing 5 ml. of silver nitrate solution in a thoroughly clean
test-tube and add 2-3 drops of dilute sodium hydroxide solu-
tion; add dilute ammonia solution dropwise until the precipi-
tated silver oxide is almost redissolved (this procedure reduces
the danger of the formation of the explosive silver azide AgN 3
to a minimum). Introduce about 0·5 ml. of the neutral tar-
trate solution. Place the tube in warm water. A silver mirror
is formed in a few minutes.
The reaction is interfered with by other acids. It is best
to isolate the potassium hydrogen tartrate, as in reaction 4
below, before carrying out the test.
KNa.C4H 40 6 + 2AgN0 3 = Ag 2 .C4H 40 6 + KN0 3 + NaN0 3
3. Calcium Chloride Solution: white, crystalline precipi-
tate of calcium tartrate Ca. C4H 4 0 6 with a concentrated neutral
solution. The precipitate is soluble in dilute acetic acid (dif-
ference from oxalate), in dilute mineral acids and in cold alkali
solutions. An excess of the reagent must be added because
calcium tartrate dissolves in an excess of an alkali tartrate
solution forming a complex tartrate ion, [Ca(C4H 40 6)2r-.
Precipitation is slow in dilute solutions, but may be accelerated
by vigorous shaking or by rubbing the walls of the te~t-tube
with a glass rod.
CaCI2 + NaK.C4H 4 0 6 = Ca.C4H 4 0 6 + NaCI + KCI
4. Potassium Chloride Solution.-When a concentrated,
neutral solution of a tartrate is treated with a solution of a
potassium salt (e.g. potassium chloride or potassium acetate)
and then acidified with acetic acid, a colourless cry~talline
precipitate of potassium hydrogen tartrate KH. C4H,06 is
obtained. The precipitate forms slowly in dilute solutions;
crystallisation is induced by vigorous shaking or by rubbing
the walls of the vessel with a glass rod.
KNa.C4H,06 + KCI + H.C2 H s0 2
= KH.C,H.'oe + NaCl + K.CzHaO z
406 Qualitative Inorganic Analysis [IV,
6. Fenton's Test.-Add 1 drop of a saturated solution "f
ferrous sulphate to about 5 m!. of the neutral or acid solutit n
of the tartrate, and then 2-3 drops of hydrogen peroxide sol,.1 -
tion (10 volume). A deep violet or blue coloration is developd
on adding excess of sodium hydroxide solution. The colo;,,'
becomes more intense upon the addition of a drop of fen ,(j

chloride solution.
The violet colour is due to the formation of a salt of dihydroxy-maleic acid
C0 2H.C(OH) = C(OH).C0 2H.
The test is not given by citrates, malates or succinates.
6. Resorcinol Test.-Place a few drops of the test solutioll
in a test-tube; add several drops of dilute sulphuric acid al, i
a speck or two of magnesium powder. When the metal h;,:;
dissolved, add about 0·1 gram of resorcinol, and shake um II
dissolved. Cool. Carefully pour down the side of the tuLe
3-4 m!. of concentrated sulphuric acid. Upon warming tllc
sulphuric acid layer at the bottom of the tube very gent] ,\'
(CAUTION), a red layer (or ring) forms at the junction of tb,
two liquids. With continued gentle heating, the red colml f
spreads downwards from the interface and eventually colour,;
the whole of the sulphuric acid layer.
Citrates do not interfere. In the presence of oxalate, a bhu'
ring is formed in the cold and on gentle warming of the su 1-
phuric acid layer at the bottom of the tube the blue coloratioll
spreads downwards into the concentrated acid layer and a red
ring fonns at the interface.
The colour is due to the formation of a condensation product of resorcin !
C.H.(OH). and glycollic aldehyde CH,OH.CHO, the latter arising from th'
action of the sulphuric acid upon the tartaric acid. The formula of tl."
condensation product is CH.OH.CH[C.H.(OH).Jz.
7. Copper Hydroxide Test.-Tartrates dissolve coppu
hydroxide in the presence of excess of alkali hydroxide solution
to form the dark blue cupri-tartrate ion, which is best detecte,!
by filtering the solution. If only small quantities of tartrai{'
are present, the filtrate should be acidified with acetic aci,i
and tested for copper by the potassium ferro cyanide test
Arsenites, ammonium salts and organic compounds convertibl,'
into tartaric acid also give a blue coloration, and should there-
fore be absent or be removed.
The experimental details are as follows. Treat the teE'
solution with an equal volume of 2N sodium or potassiun I
hydroxide (or treat the test solid directly with a few ml. of th,
alkali hydroxide solution, warm for a few minutes with stirrin f:
and then cool), add a few drops of M copper sulphate solutio];
39] Reactions of the Acid Radica18 or Anions 407
(i.e. just sufficient to yield a visible precipitate of cupric
hydroxide), shake the mixture vigorously for 5 minutes, and
filter. If the filtrate is not clear, warm to coagulate the col-
loidal copper hydroxide and filter again. A distinct blue
coloration indicates the presence of a tartrate. If a paJe
coloration is obtained, it is advisable to add concentrated
ammonia solution dropwise when the blue colour intensifies;
it is perhaps better to acidify with 2N acetic acid and add
potassium ferro cyanide solution to the clear solution where-
upon a reddish-brown precipitate or (with a trace of a tarkate)
a red coloration is obtained.
t8. fjfj-Dinaphthol Test

When a solution of fiW-dinaphthol in concentrated sulphuric acid is

heated with tartaric acid, a green coloration is obtained. Oxalic, citric,
succinic and cinnamic acids do not interfere.
Heat a few milligrams of the solid test sample or a drop of tLe test
solution with 1-2 mI. of the dinaphthol reagent in a water bath at 85°0
for 30 minutes. A luminous green fluorescence appears durlllg the
heating, which intensifies on cooling, and at the same time the violet
fluorescence of the reagent disappears.
Sensitivity: 10 fLg. tartaric acid. Concentration limit: 1 in 5,\JOO.
The reagent consists of a solution of 0·05 gram of fjfj' -dinaphi hoI in
100 mI. of concentrated sulphuric acid.
9. Action of Heat.-The tartrates and also tartaric acid
decompose in a complex manner on heating; charring takes
place, a smell of burnt sugar is apparent and inflammable
vapours are evolved.

IV, 39. REACTIONS OF CITRA TES, C6H 5 0 7 - - -

Solubility.-Citric acid, HO.C.CH •. C(OH)CO.H.CH•. CO.H,H.O or
Hs.C.H,;O"H.O, is a crystalline solid which is very soluble in w.cter; it
becomes anhydrous at 55° and melts at 160°. It is a tribasic acid, and th'3re-
fore gives rise to three series of saJ.ts. The normal citrates of th" alkali
metals dissolve readily in water; other metallic citrates are sparingly ~oluble.
The acid citrates are more soluble than the [wid tartrates.
Use sodium citrate, NaS.C6H507,2H20.
1. Concentrated Sulphuric Add.-·-When a solid ,:itrate
is heated with concentrated sulphuric acid, carbon mO;lOxide
and carbon dioxide are evolved; the solution slowly d,trkens
owing to the separation of carbon, and sulphur dioxide is
 408 Qualitative Inorganic AnalY8is [IV,
evolved (compare Tartrates, Section IV, 30, which char alm. ,St
~ immediately).
The first products of the reaction are carbon mon~ndde and ac.e~one, ,ii·
carboxylic acid (1); the latter undergoes further partlal decompositlOn nto
acetone (II) and carbon dioxide.
HO.C.CH •. C(OH)CO.H.CH •. CO.H
= CO+ +
H 20 HO.C.CH•. CO.CH•. CO.R i 1) ;
RO.C.CR •. CO.CH •. CO.H = CRa.CO.CHa (II) + 2CO.
Use may be made of the intermediate formation of acetone dicarbox dic
acid and of the interaction of the latter with sodium nitroprusside solutio,; to
yield a red coloration as a test for citrates. When about 0·5 grams of a cit, ,te
or of citric acid is treated with 1 m!. of concentrated sulphuric acid f I
minute, the mixture cooled, cautiously diluted with water, rendered alku,· ne
with sodium hydroxide solution and then a few c.c. of a freshly prep" .. ,d
solution of sodium nitroprusside added, an intense red coloration results.
2. Silver Nitrate Solution: white, curdy precipitate ,)f
silver citrate Aga . CaHC;07 from neutral solutions. The preci i li-
tate is soluble in dilute ammonia solution, and this solut!, ,n
undergoes only very slight reduction to silver on boiling ((!,.-;-
tinction from tartrate).
Nas.CoH607 + 3AgNO s = Aga .CIIH 60 7 + 3NaNOs
3. Calcium Chloride Solution: no precipitate with neut ial
solutions in the cold (difference from tartrate), but on boilj'ig
for several minutes a crystalline precipitate of calcium citru t e
Ca3(C6H507 b,4H 20 is produced. If sodium hydroxide soluti, .n
is added to the cold solution containing excess of calciu i i1
chloride, there results an immediate precipitation of amorpho.: 3
calcium citrate, insoluble in solutions of caustic alkalis, b, i t
soluble in ammonium chloride solution; on boiling the amm ,-
nium chloride solution, crystalline calcium citrate is precil'!'
tated, which is now insoluble in ammonium chloride solutio>!.
2Naa.CoH607 + 3CaCl2 = CaS(COH607)2 + 6NaCI
4. Cadmium Chloride Solution: white, gelatinous prec:·
pitate of cadmium citrate Cd 3(C6H li 0 7b. practically insolub '\
in boiling water, but readily soluble in warm acetic acid (tal'
trate gives no precipitate).
2Nas,CIIH607 + 3CdC12 = Cda(CoH 60 7)2 + 6NaCl
5. Deniges' Test.-Add 0·5 ml. of acid merouric sulphatl'
solution to 3 ml. of the citrate solution, heat to boiling anJ
then add a few drops of a 2 per cent solution of potassium
permanganate. Decolourisation of the permanganate will take
place rapidly and then, somewhat suddenly, a heavy white
precipitate, consisting of the double salt of basic mercuric
sulphate with merouric acetone dioarboxylate
HgSO,,2HgO,2[CO(CH 2 • CO 2)2Hg],
40] ReactWnB of the Acid RadicalB or Anion8 409
is formed. Salts of the halogen acids interfere and must there-
fore be removed before carrying out the test.
The reagent (an acid solution of mercuric sulphate) is prepared
by adding 10 m!. of concentrated sulphuric acid slowly to 50 mL of
water, and dissolving 2·5 grams of mercuric oxide in the hot solution.
6. Action of Heat.-Citrates and citric acid char on heating;
carbon monoxide, carbon dioxide and acrid-smelling vapours
are evolved.

IV, 40. REACTIONS OF SALICYLATES,

C6H 4 (OH)C0 2- OR C 7H 50 a-
Solubility.-Salicylic acid C.H.(OH)CO.H (o-hydroxybenzoic acid) forms
colourless needles, which melt at 155°. The acid is sparingly soluble in cold
water, but more soluble in hot water, from which it can be recrystalliHed. It
is readily soluble in alcohol and ether. ·With the exception of tlJe load,
mercury, silver and barium salts, the monobasic salts C.H.(OH)CO.M-these
are the most commonly occurring salts-are readily soluble in cold wl~ter.
Use sodium salicylate, C6 H 4 (OH)C0 2Na or Na.C7HfjOa'
1. Concentrated Sulphuric Acid: dissolves on warming;
charring occurs slowly, accompanied by the evolution of carhon
monoxide and sulphur dioxide.
2. Concentrated Sulphuric Acid and Methyl Alcohol
(" Oil of Winter-green" Test).-When 0·5 gram of a sali-
cylate or of salicylic acid is treated with a mixture of 1·5 m1.
of concentrated sulphuric acid and 3 m!. of methyl alcohol nnd
the whole gently warmed, the characteristic, fragrant odour of
the ester, methyl salicylate (I) (" oil of winter-green "). is
obtained. The odour is readily detected by POUrlltg the
mixture into dilute sodium carbonate solution contaim,d in a
porcelain dish.
C6H 4 (OH)C0 2H + CHsOH ~ C6H 4 (OH)C0 2CHa (I) + H 2 0
(The sulphuric acid acts as a dehydrating agent.)
3. Dilute Hydrochloric Acid*: crystalline precipitate of
salicylic acid from solutions of the salts. The precipitate is
moderately soluble in hot water, from which it crystalEses on
cooling.
4. Silver Nitrate Solution: heavy, crystalline precipitate
of silver salicylate Ag. ~H503 from neutral solutions; it is
soluble in boiling water and crystallises from the solution on
cooling.
C6H 4(OH)C0 2Na + AgN0 3 = C6H 4 (OH)C0 2Ag + NaNO a
• Or any other mineral acid.
410 Qualitative Inorganic Analysi8 [IV,
5. Ferric Chloride Solution: intense violet-red coloratioll
with neutral solutions of salicylates or with free salicylic acid
the colour disappears upon the addition of dilute mineral acidf'
but not of a little acetic acid. The presence of a large exces,
of many organic acids (acetic, tartaric and citric) prevents tht
development of the colour, but the addition of a few drops 0;
dilute ammonia solution will cause it to appear.
6. Dilute Nitric Acid.-When a salicylate or the free acid
is boiled with dilute nitric acid (1 : 5) and the mixture poured
into 4 times its volume of cold water, a crystalline precipitate
of 5-nitro-salicylic acid (I) is obtained. The precipitate if:'
filtered off and recrystallised from boiling water; the acid.
after drying, has a melting point of 226°.
C6H 4 (OH)C0 2H + HNO s = C6H s(NO z)(OH)C0 2H (I) H 20 +
Poly-nitro salicylic acids are formed when the concentration oj
nitric acid exceeds 2-3N. It must be emphasised that nitro-
salicylic acids rrw,y explode on strong heating, and this must be borne
in mind when removing salicylates by oxidation with nitric acid
and evaporating to dryness prior to the precipitation of Group IlIA.
If salicylate is suspected, it is probably best to remove it by acidify-
ing the concentrated solution with dilute hydrochloric acid: most
of the salicylic acid will separate out upon cooling.
7. Soda Lime.-When salicylic acid or one of its salts is
heated with excess of soda lime in an ignition tube, phenol
C6H 5 (OH) is evolved, which may be recognised by its charac-
teristic odour.
C6H 4 (OH)CO zNa + NaOH = C6H 5 0H + NazCO s
8. Action of Heat.-Salicylic acid, when gradually heated
above its melting point, sublimes. If it is rapidly heated, it is
decomposed into carbon dioxide and phenol (I). Salicylates
char on heating and phenol is evolved.
CaH 4 (OH)CO zH = C6H 5 0H (I) + CO 2
IV,41. REACTIONS OF BENZOATES, C6H 5 .CO Z- OR
C7H 5 0 Z-
Solubility.-Benzoic acid, C.H•. CO.H or H.C 7 H.02' is a white, crystalline
solid; it has a melting point of 121 0 and sublimes at a somewhat higher
temperatw·e. The acid is sparingly soluble in cold water, but more soluble
in hot water, from which it crystallises out on cooling; it is soluble in alcohol
and in ether. All the benzoates, with the exception of the silver and basic
ferric salts, are readily soluble in cold water.
Use potassium benzoate, C6H Il • COzK or K. C7H/iOz.
 41] Reactions of the Acid Radicals or Anions 411
1. Concentrated Sulphuric Acid: no charring occurs on
heating; the acid forms a sublimate on the sides of the test-
tube and irritating fumes are evolved.
2. Dilute Sulphuric Acid*: white, crystalline precipitate
of benzoic acid from cold solutions of benzoates. The acid
may be filtered off, dried between filter paper or upon a porous
tile and identified by means of its melting point (121°). If the
latter is somewhat low, it may be recrystallised from hot water.
C6Hs. C0 2K + HCI = C6Hs. C0 2 H + KCI
3. Concentrated Sulphuric Acid and Ethyl Alcohol.-
Heat 0·5 gram of a benzoate or of benzoic acid with a mixture
of 1·5 m!. of concentrated sulphuric acid and 3 mI. of ethyl
alcohol for a few minutes. Allow the mixture to cool, and
note tbe pleasant and cbaracteristic aromatic odour of the e~ter,
ethyl benzoate (I). The odour is more apparent if the mixt,ure
is poured into dilute sodium carbonate solution contained ill
an evaporating basin; oily drops of ethyl benzoate will sepaeate
out.
C6Hs. C0 2H + C2H 5 0H .=: C6Ho' C02C2 H 5 (I) +H 20
4. Silver Nitrate Solution: white precipitate of silver
benzoate Ag. C7H 5 0 2 from neutral solutions. The precipi tate
is soluble in hot water and crystallises from the solution on
cooling; it is also soluble in dilute ammonia solution.
C6H 5 • C0 2K + AgN0 3 = C6H!). C0 2 Ag + KN03
5. Ferric Chloride Solution: buff-coloured precipitate of
basic ferric benzoate (II) from neutral solutions. The preoipi-
tate is soluble in hydrochlol"ic acid, with the simultaneous
separation of benzoic acid (see reaction 2).
3C6H!). C0 2K + 2FeCl 3 + 3H20
= (C6H5.C02)aFe.Fe(OH)a(II) + 3KCI + ;3HCI
6. Soda Lime.-Benzoic acid and benzoates are decomposed
when heated in an ignition tube with excess of soda lime into
benzene C6R 6 , which burns with a smoky flame, and carbon
dioxide, the latter combining with the alkali present.
C6H 5 .C02H + 2NaOH = C6H6 + Na2COa + H 20
7. Action of Heat.-When benzoic acid is heated in an
ignition tube, it melts, sublimes and condenses in the cool
parts of the tube. An irritating vapour is simultane<msly
evolved, but no charring occurs. If a little of the acid or of
one of its salts is heated upon platinum foil or broken porcdain,
it burns with a blue, smoky flame (distinction from succinate) .
... Or any other minel'a} acid.
412 Qualitative Inorganic AnalY8i8 [IV.
IV, 42. REACTIONS OF SUCCINATES, C 4H 40 4--
Solubility.-Succinic acid, HO~C.C~2.CH2.C~2H 0: H 2.C.H._?.(a di_basj,
acid), is a white. crystalline solId wIth a meltmg pomt of 182 ; It bOlls B'
235° with the formation of succinic anhydride C.H.O. by the loss of on,'
molecule of water. The acid is fairly soluble in water (68·4 grams per litr'
at 20°). but more soluble in hot water; it is .moderately s_oluble in alcohol an"
in acetone, slightly soluble in e~her and sparmgly so~uble m c~orofor~. Mm,
normal succinates are soluble In cold water; the SlIver, calcmm, barIUm an,:
basic ferric salts are sparingly soluble.
Use sodium succinate, C2H 4(C0 2Na)2 or Na2,C4H404'
1. Concentrated Sulphuric Acid.-The acid or its salts
dissolve in warm, concentrated sulphuric acid without charring;
if the solution is strongly heated, slight charring takes place
and sulphur dioxide is evolved.
Dilute sulphuric acid has no visible action.
2. Silver Nitrate Solution: white precipitate of silver
succinate Ag 2 .C4H 4 0 4 from neutral solutions, readily soluble
in dilute ammonia solution.
C2H 4(C0 2Na}2 + 2AgNO a = C2H 4(C0 2Ag}2 + 2NaNO a
3. Ferric Chloride Solution: light-brown precipitate of
basic ferric succinate (I) with a neutral solution; some free
succinio aoid is simultaneously produoed, and the solution
acquires an acid reaction.
3C2H 4(C0 2Na}2 + 2FeCl a + 2H20
= 2C2H4(C02)2Fe(OH) (I) + 6NaCI + C2H 4(C02H)2
4. Barium Chloride Solution: white precipitate of barium
succinate Ba.C4H 40 4 from neutral or slightly ammoniacal
solutions (distinotion from benzoate). Precipitation is slow
from dilute solutions, but may be accelerated by vigorous
shaking or by rubbing the inner wall of the test-tube with a
glass rod.
C2H 4 (C0 2Na)2 + BaCl2 = C2H4(C02}2Ba + 2NaCl
5. Calcium Chloride Solution: a precipitate of oalcium
suooinate is very slowly produoed from ooncentrated neutral
solutions.
6. Fluorescein Test.-About 0·5 gram of the acid or one
of its salts is mixed with I gram of resorcinol, a few drops of
concentrated sulphuric acid added, and the mixture gently
heated; a deep-red solution is formed. On pouring the latter
into a large volume of water, an orange-yellow solution is
obtained, whioh exhibits an intense green fluorescence. The
addition of exoess of sodium hydroxide solution intensifies the
 43] Reaction8 of the Acid Radicals or Anions 413
fluorescence, and the colour of the solution changes to hright
red.
Under the influence of concentrated sulphuric acid, succinic anhydride (II)
is first formed, and this condenses with the resorcinol (III) to yield succinyl.
fluorescein (IV). .
CH •. CO", CHa.CO",
/0+2C.H,(OH)2= I
I
(JR •. CO
(II) (III)
...-/0.------ C.H 3 (OH)",
CH •. C ~
~-------- CqH.(OH)/
° (IV)+ 2H °
•

For the quinonoid structure, which is probably to be preferr8d, see

the analogous formula for fluorescein in Section IV, 15, reaction 8.
7. Action of Heat.-When succinic acid or its salts are
strongly heated in an ignition tube, a white sublimate of
succinic anhydride C4H 4 0 3 is formed and irritating vapours are
evolved. If the ignition is carried out on platinum foil or upon
broken porcelain, the vapour burns with a non-luminous, blue
flame, leaving a residue of carbon (distinction from benzoate).

IV, 43. REACTIONS OF HYDROGEN PEROXIDE, H 2 0 2

This substance is marketed in the form of "la, 20, 40 and 100.volume"
solutions. It is formed upon adding sodium peroxide in small portions to
ice water:
Na.O. + 2H.O = H.O, + 2NaOH
Owing to the heat liberated in the reaction, part of the hydrogen poroxide
is decomposed:
2H.O. = 2H.O + 0.
It is usually more convenient to employ a solution of hydrogen peroxide made
alkaline with sodium hydroxide solution. A convenient source is 1 he in.
expensive sodium perborato NaBO a,4H.0; this yields hydrogen pi roxide
when its aqueous solution is heated:
NaBOa + H.O = NaBO. + H.O.
Use a dilute solution (say, 3 per cent) of hydrogen peroxide.
1. "Perchromic Acid" Test.-If an acidified solution of
hydrogen peroxide is mixed with a little diethyl ether (highly
inflammable), amyl alcohol or amyl ace~ate and a few drops
of potassium dichromate solution added and the mixture gently
shaken, the upper organic layer is coloured a beautiful blue.
For further details, see Section IV, 33, reaction 4. Tho test
will detect 0·1 mg. of hydrogen peroxide.
If ether is employed, a blank test must always bo carried out with the ether
alone because after standing it may contain organic peroxides which give the
test. The peroxides may be removed by shaking I litre of ether with a
solution containing 60 grams of FeSO,,7H.O, 6 m!. of concentrated H.SO,
and llD ml. of water, then with chromic acid solution (to oxidise any acetal.
dehyde produced), washing with alkali and redistilling. The peroxid.,s may
also be removed by treatment with aqueous sodium sulphite. The use of
amyl alcohol is, however, to be preferred.
414 Qualitative Inorganic Analysis [IV.
2. Potassium Iodide-Starch Test.-If hydrogen peroxidt
is added to a solution containing potassium iodide and stare},
and acidified, a blue coloration of "starch iodide" appears.
2KI + H 20 2 + H 2S04 = 12 + K 2S04 + 2H 2 0
3. Potassium Permanganate Solution: decolourised hi
acid solution and oxygen is evolved.
2KMn04 + 3H2S04 + 5H 2 0 2
= K 2S04 + 2MnS04 + 50 2 + 8H2 0
4. Titanic Sulphate Solution: orange-red coloration (set
under Titanium, Section IX, 12, reaction 6). This is a very
delicate test.
The titanic sulphate solution may be prepared by heatinv
titania with three times its volume of concentrated sulphuric acid
cooling, diluting cautiously with ice water and filtering, if necessary_
5. Potassium Ferricyanide-Ferric Chloride Test.-If ,:
nearly neutral solution of pure ferric chloride is treated with "
little pure potassium ferricyanide and the resulting yello"\\
solution mixed with a nearly neutral solution of hydrogel!
peroxide, the mixture will assume a green coloration and then,
on standing, Prussian blue will separate.
2[Fe(CN)6r-- + H 2 0 2 = 2[Fe(CN)6r--- + 2H + + O2
Other substances, e.g. stannous chloride, sodium sulphite and
sodium thiosulphate, will reduce potassium ferricyanide to
potassium ferro cyanide so that this reaction alone is not alway"
a reliable test.
t The spot-test technique is as follows. In adjacent depressions of
a spot plate place a drop of distilled water and a drop of the test solu-
tion. Add a drop of the reagent (equal volumes of 0'5 per cent ferric
chloride solution and 0-8 per cent potassium ferricyanide solution) tl,
each. A blue coloration or precipitate is formed.
Sensitivity: 0'1 JLg. H 20 2• Concentration limit: I in 600,000.
6. Gold Chloride Solution: reduced to finely divided
metallic gold, which appears greenish-blue by transmitted light
and brown by reflected light.
2AuC13 + 3H2 0 2 = 2Au + 6HCl + 30 2
t The spot-test technique is as follows. Mix a drop of the neutral
test solution with a drop of 0·01 per cent gold chloride solution in a
micro crucible and warm. After a short time, the solution is coloured
red or blue with colloidal gold.
Sensitivity: 0·07 JLg. H,O I · Concentration limit: I in 700,000.
44] Reactions of the Acid Radicals or AnionB 415
p. Lead Sulphate Test.-Hydrogen peroxide converts black lead
sulphide into white lead sulphate:
PbS + 4HaOa = PbSO. + 4HaO
Place a drop of the neutral or slightly acid test solution upon drop
reaction paper impregnated with lead sulphide. A white spot is
formed on the brown paper.
Sensitivity: 0·04 fLg. H 20 2• Concentration limit: 1 in 1,250,000.
The lead sulphide paper is prepared by soaking drop-reactioll paper
in a 0·05 per cent solution of lead acetate, exposing it to a little hydrogen
sulphide gas and then drying in a vacuum desiccator. The paper will
keep in a stoppered bottle.

IV, 44. REACTIONS OF HYDROSULPHITES

(HYPOSULPHITES OR DITHIONITES). S,204--
Hydrosulphites are obtained by the action of reducing agents, such as zinc,
upon acid sulphites:
2NaHSO. + Zn + SO. = Na.SaO, + ZnSO. + H.O
Sulphur dioxide may also be passed into a cooled suspension of zinc dust in
water:

The sodium salt may be obtained by double decomposition with sodium

carbonate:
ZnS.O, + Na.CO. = ZnCO. +
Na.S.O.
Sodium hydrosulphite is a powerful and important reducing agent. A
solution of the salt containing excess of sodium hydroxide is used as an
absorbent for oxygen in gas analysis.
Use sodium hydrosulphite, Na2S20,.
1. Dilute Sulphuric Acid: orange coloration, which soon
disappears, accompanied by the evolution of sulphur dioxide
and the precipitation of sulphur.
2H28 2 0 4 = 380 2 + S + 2H2 0
2. Concentrated Sulphuric Acid: immediate evolution of
sulphur dioxide and the precipitation of pale yellow sulphur.
3. Silver Nitrate Solution: black precipitate of metallic
silver.
4. Copper Sulphate Solution: red precipitate of metallic
copper.
5. Mercuric Chloride Solution: grey precipitate of met~llic
mercury.
6. Methylene Blue Solution: immediate decolourisl"tion in
the cold. The methylene blue is reduced to the colourless
leuco compound.
416 Qualitative Inorganic AnalY8i8 [IV,
7. Indigo Solution: reduced to the colourless leuco com-
pound, known as indigo white.
Na2S204 + 2H zO = 2NaHSO a + 2H (nascent)
C16HlO02N2 + 2H = C16H1202N2
Indigo Indigo white
The indi~o solution is prepared by digesting 2 grams of in<! igo
with 10 grams of fuming sulphuric acid (OAUTION), and tllen
pouring very slowly into 1 litre of 4 per cent sulphuric acid.
8. Potassium Ferrous Ferrocyanide Test.-Upon adding
potassium ferro cyanide solution to a solution of a ferrous ',Llt
containing a little sodium hydrosulphite, a white precipi' Lte
of potassium ferrous ferro cyanide K2Fe[Fe(CN)6J is prodll' 'cd
(compare Section III, 19, reaction 6).
9. Action of Heat.-Upon heating sodium hydrosulpl ite,
it suddenly evolves sulphur dioxide at about 190 0 (exotheI' ,lie
reaction). The residue has lost its reducing power to indigo
and methylene blue solution, being a mixture of sodium ,ul-
phite and sodium thiosulphate.
2Na2S204 = Na2S0S + Na2S20a + 80 2

IV,45. SPECIAL TESTS FOR MIXTURES OF

ACID RADICALS'"
1. Carbonate in the presence of Sulphite.-Sulphitef' on
treatment with dilute sulphuric acid, liberate sulphur dio lde
which, like carbon dioxide, produces a turbidity with lim or
baryta water. The dichromate test for sulphites is, howe er,
not influenced by the presence of carbonates. To detect ar-
bonates in the presence of sulphites, treat the solid mix llte
with dilute sulphuric acid and pass the evolved gases thn .:gh
a small wash-bottle or boiling tube containing potassium di-
chromate solution and dilute sulphuric acid. The solution will
be turned green and the sulphur dioxide will, at the same tune,
be completely removed; the residual gas is then tested \Iith
lime or baryta water in the usual manner.
An alternative procedure is to add a little solid potas:· am
dichromate or a small volume of 10-volume hydrogen pero~jde
solution to the mixture and then to warm with dilute sulp!' ,ll'ic
... Full experimental details of the various tests referred to in this sution
will be fOlmd under the reactions of the anions. Reference will be ma,ie to
the "NapCO a prepared solution" and to the "Na 2CO a practically D. ,(trw
solution' (see 20) as these are normally used in systematio a.nalysi', A
solution of the sodium salts of the variollB anions may. of OOU1'll8. be uH·.d in
checking the procedures.
45] Reaction8 of the Acid Radical8 (Y1' Anions 417
acid; the evolved gas is then passed through lime or IJaryta
water.
2. Nitrate in the presence of Nitrite.-The nitrite is
readily identified in the presence of a nitrate by treatment with
dilute mineral acid, potassium iodide and starch paste (or
potassium iodide-starch paper). The nitrate cannot, however,
be detected in the presence of a nitrite since the latter gh-es the
brown ring test with ferrous sulphate solution and dilute sul-
phuric acid. The nitrite is therefore completely decomposed
first by one of the following methods:
(i) Boil with ammonium chloride solution until effervescence
ceases.*
(ii) Warm with urea and dilute sulphuric acid until evolution
of gas ceases. *
(iii) Add the solution to solid hydrazine sulphate; reaction
takes place in the cold, and the danger of slight oxidation of
nitrite to nitrate is thereby avoided.
N2H4 + 2HN02 = Na + N 2 0 + 3H20;
N2H4 +HN02 =NHa +N2 0 + H 2 0
(iv) Add a little sulphamic acid to the solution:
HO.S0 2 ·NH2 + HN0 2 = Na + H 2S04 + H 2 0
The sulphamic acid procedure is probably the simplest and
most efficient method for the removal of nitrite in aqueous
solution.
The nitrate can then be tested for by the brown ring test.
3. Nitrate in the presence of Bromide and Iodide.-
The brown ring test for nitrates cannot be applied in the
presence of bromides and iodides since the liberation of -che free
halogen with concentrated sulphuric acid will obscure the brown
ring due to the nitrate. The solution is therefore boiled with
sodium hydroxide solution until ammonium salts, if present, are
completely decomposed; powdered Devarda's alloy or alu-
minium powder (or wire) is then added and the solutior~ gently
warmed. The evolution of ammoni~1, detected by its smell
and its action upon mercurous nitrate paper (see Section III,
36, reaction 1) and upon red litmus paper, indicates the
presence of a nitrate.
An alternative method is to remove the halides by adding saturated
silver sulphate solution. Since silver sulphate is only slightly soluble
in water, it is better to use ammoniacal silver sulphate solution.
• Tracea of nitrate are always formed in this reaction.
14+
'lUG LJ:. T ,

This reagent contains [Ag(NH s )2hSO, and provides a high conc('n·

tration of silver ions: it is prepared by dissolving 7·8 grams of {'lire
silver sulphate in 25 ml. of 4N ammonia solution and diluting GO
100 ml. with water. The test solution is treated with sufficient 'Jf
the reagent to precipitate all the halides; the silver halides ee
filtered off, a portion of the filtrate is carefully mixed with a fj, e·
fold excess of concentrated sulphuric acid, and the ferrous sulpL Ge
solution cautiously introduced down the side of the tube.
4. Nitrate in the presence of Chlorate.-The chlor Ite
obscures the brown ring test. The nitrate is reduced 10
ammonia as described under 3; the chlorate is at the saille
time reduced to chloride, which may be tested for with sihnr
nitrate solution and dilute nitric acid.
If a chloride is originally present, it may be removed fj, ;t
by the addition of silver sulphate solution or ammoniacal sil" ()r
sulphate solution.
5. Chloride in the presence of Bromide and/or Iodi.,le.
-Method A. This procedure involves the removal of 1 ;:e
bromide and iodide (but not chloride) by oxidation with pot., ;-
sium or ammonium persulphate in the presence of dilute s :t-
phuric acid. The free halogens are thus liberated, and ill ,y
be removed either by simple evaporation (addition of wal, T
may be necessary to maintain the original volume) or by eval"J-
ration at about 80° in a stream of air.
K 2S2 0 S + 2KI = 12 + 2K 2S04 ;
K 2S 20 S + 2KBr +
2H 2S04 = Br2 +
4KHSO,
Add solid potassium persulphate all,l
dilute sulphuric acid to the "Na2C()3
practically neutral solution" of the mix, d
halides contained in a conical flask; he, t
the flask to about 80°, and aspirate a
current of air through the solution witlt
the aid of a filter pump until the soluti(:n
is colourless (Fig. IV, 45, I; T is a drawll-
out capillary tube). Add more potassium
persulphate or water as may be found
necessary. Test the residual colourle~"
liquid for chloride with silver nitra j {~
Fig. IV, 45, 1 solution and dilute nitric acid. *
* Do not mistake precipitated silver sulphate for silver chloride. III d
modification of this method, lead dioxide is substituted for potassium p"'"
sulphate. Acidify the solution with acetic acid, add lead dioxide, and h"l
the mixture until bromine and iodine are no longer evolved. Filter, alld
test the filtrate, which should be colourless, with silver nitra.te solution a.1l'!
dilute nitric acid.
45] Reactions of the Acid Radicals or Ani01U! 419
Method B. Acidify the "Na2COa practically neutral solu-
tion" (see 20 below) of the halides with dilute nitric acid, add
excess of silver nitrate solution, filter and wash until the
washings no longer give the reactions of silver ions. Shake
the precipitate with ammonium carbonate solution, filter and
add a few drops of potassium bromide solution to the filtrate;
a yellowish-white precipitate of silver bromide is obtained if a
chloride is present.
The hydrolysis of the ammonium carbonate in aqueous
solution gives rise to free dilute ammonia solution in which
silver chloride, but not silver bromide or silver iodide, is
appreciably soluble. The addition of bromide ions to the
solution of silver chloride in ammonia results in the solubility
product of silver bromide being exceeded, and precipitation
occurs.
Alternatively, wash the precipitated halides until free from
excess of silver nitrate solution, and then treat the precipitate
with a cold, freshly prepared solution containing 4 per cent
formaldehyde in O·IN sodium carbonate solution: pour a little
of the latter reagent through the filter several times. Test the
filtrate for chloride with silver nitrate solution and dilute nitric
acid. Silver bromide reacts slightly with the reagent yielding
a faint opalescence; silver iodide is unaffected.
6. Chloride in the presence of Bromide.-Warm the
solid mixture* with a little potassium dichromate and con-
centrated sulphuric acid in a small distilling flask (Fig. IV, 2, 1),
and pass the vapours, which contain chromyl chloride, into
sodium hydroxide solution. Test for chromate, which proves
the presence of a chloride, with hydrogen peroxide and amyl
alcohol or with the diphenylcarbazide reagent.
7. Chloride in the presence of Iodide.-Add excess of
silver nitrate solution to the "Na2COa practically neutral
solution" (see 20) and filter; reject the filtrate. Wash the
precipitate with dilute ammonia solution and filter again. Add
dilute nitric acid to the washings; a white precipitate of silver
chloride indicates the presence of chloride.
The separation is based upon the solubility of silver chloride
in dilute ammonia solution and the practical insolUbility of
silver iodide in this reagent.
8. Bromide and Iodide in the presence of each other
and of Chloride.-The presence of a chloride does not inter-
• If a solution is being analysed, it should be evaporated to dryness before
applying the test. Chlorates must, of course, be absent.
420 Qualitative Inorganic Analysis [IV,
fere with the reactions described below. To the "Nal'Oa
prepared solution" strongly acidified with dilute hydrochl, ;ric
acid add 1-2 drops of chlorine water (the solution obtained i)y
carefully acidifying a dilute solution of sodium hypochlo, i te
with dilute hydrochloric acid may also be used) and 2-3 m!. of
chloroform or carbon tetrachloride; shake; a violet colour in-
dicates iodide. Continue the addition of chlorine water at of
acidified sodium hypochlorite solution drop by drop to oxi,! ise
the iodine to iodate and shake after each addition. The vi, ·Iet
colour will disappear, and a reddish-brown coloration of ! he
chloroform or carbon tetrachloride, due to dissolved bron ! ne
(and/or bromine mono chloride BrCl) , will be obtained " a
bromide is present. If iodide alone is present, the solli! ton
will be colourless after the violet colour has disappeared.
9. Chloride, Chlorate and Perchlorate in the pres('"ce
of each other.-Each acid radical (anion) must be tested c'or
separately. Divide the "Na2COa prepared solution" int ' 3
parts.
(i) Chloride. Acidify with dilute nitric acid and boil to expel
carbon dioxide. Add silver nitrate solution; a white precipii lte
of silver chloride indicates the presence of chloride. Silver"
chlorate and perchlorate are soluble in water.
(ii) Chlorate. Any of the following methods may be uc;,·d.
(a) Acidify with dilute nitric acid and add excess of sih'er
nitrate solution; filter off the precipitated silver chlor;' Ie.
Now introduce a little chloride-free sodium nitrite (wI] ,)h
reduces the chlorate to chloride) and more silver nitl ite
solution into the filtrate: a white, curdy precipitatE' of
silver chloride indicates the presence of chlorate.
Alternatively, the reduction may be effected by heat-
ing the filtrate with a few m!. of 5-10 per cent forn1:Ll-
dehyde solution: a white precipitate of silver chlonde
forms if a chlorate is present.
KCl0 3 + 3H,CHO = KCl + 3H.COOH
(b) Acidify with dilute sulphuric acid, add a little ind:,~o
solution followed by sulphurous acid solution: the ind,;o
is bleached if a chlorate is present.
(iii) Perchlorate. Pass excess of sulphur dioxide into t I te
solution to reduce chlorate to chloride, boil off the excess ,)f
sulphur dioxide, and precipitate the chloride with silver 1':11-
phate solution, afterwards removing the excess of silver w:; h
a solution of sodium carbonate. Evaporate the resulting so;,,-
45] Reactions of lite Acid Radicals or Anions 421
tion to dryness and heat to dull redness (better in the pre~
sence of a little halide-free lime) to convert the perchlorate
into chloride. Extract the residue with water, and te:~t for
chloride with silver nitrate solution and dilute nitric acid.
10. Iodate and Iodide in the presence of each other.-
The addition of dilute acid to a mixture of iodate and iodide
results in the separation of free iodine, due to the interaction
between the liberated iodic and hydriodic acids.
HIO a + 5H1 = 312 + 3H2 0
Neither iodates nor iodides alone do this when acidified with
dilute hydrochloric, sulphuric or acetic acids in the cold.
Test for iodide in the "Na2C03 practically neutral solu tion"
or in a solution of the sodium salts by the addition of a few
drops of chlorine water (or acidified sodium hypochlorite solu~
tion) and 2-3 mI. of chloroform or carbon tetrachlorid£,; the
latter is coloured violet. Add excess of silver sulphate solution
to another portion of the neutral solution and filter off the
silver iodide; remove the excess of silver sulphate with sodium
carbonate solution. Pass sulphur dioxide into the filtrate to
reduce iodate to iodide, boil off the excess of sulphur dioxide,
and add silver nitrate solution and dilute nitric acid. A yellow
precipitate of silver iodide confirms the presence of iodate in
the original substance.
11. Phosphate in the presence of Arsenate.--Both
arsenate and phosphate give a yellow precipitate on warming
with ammonium molybdate solution and nitric acid, the latter
on gentle warming and the former on boiling.
Acidify the "Na2C03 prepared solution" with dilute hydro-
chloric acid, pass in sulphur dioxide to reduce the arsenate to
arsenite, boil off the excess of sulphur dioxide (test with potas-
sium dichromate paper), and pass hydrogen sulphide into the
solution to precipitate the arsenic as arsenious sulphide; con~
tinue the passage of hydrogen sulphide until no more precipi~
tate forms. Filter, boil off the hydrogen sulphide, and ttst the
filtrate for phosphate by the ammonium molybdate test or with
the magnesium nitrate reagent.
An alternative method for the elimination of arsenate is the
following. Acidify the" N a2COa prepared solution" with dilute
hydrochloric acid and then add about one~quarter of the
volume of concentrated hydrochloric acid (the total volume
should be about 10 mI.). Add 0·5 m!. of 5 per cent ammonium
iodide solution, heat to boiling, and pass hydrogen sulphide
into the boiling solution until precipita·bion is complete (5-10
 422 Qualitative Inorganic Analysis rIV,
_ minutes). Filter off the arsenious sulphide, and boil off \;he
hydrogen sulphide from the filtrate. Add ammonia solll I :on
until alkaline and excess of the magnesium nitrate reaf nt.
A white precipitate indicates the presence of a phosphate.
AS 20 5 + 4H1 = As 2 0 S + 2H 2 0 + 21 2 ;
AS 2 0 3 + 3H28 = As 28 a + 3H20;
212 + 2H 8 ~ 4H1 + 28
2

12. Phosphate, Arsenate and Arsenite in the prese;lce

of each other.-Treat the "Na2COS prepared solution" "\ :th
dilute sulphuric acid until acidic, warm to expel carbon ,li-
oxide, render just alkaline with dilute ammonia solution ,nd
filter, if necessary. Add a few ml. of the magnesium nit, ite
reagent and allow to stand for 5-10 minutes: shake or t,ir
from time to time. Filter off the white, crystalline precipil ,ite
of magnesium ammonium phosphate and/or magnesium am, iO-
nium arsenate (A), and keep the filtrate (B). Test for arse, te
in the filtrate (B) by acidifying with dilute hydrochloric [i' id
and passing hydrogen sulphide, when a yellow precipitatl of
arsenious sulphide is immediately produced if arsenite is
present.
Wash the precipitate (A) with O'5N ammonia solution, tiled
remove half of it to a small beaker with the aid of a ck; m
spatula. Treat the residue on the filter with a little sil \ ,)r
nitrate solution containing a few drops of dilute acetic a(:' 1:
a brownish-red residue (due to Ag aAs0 4 ) indicates arsen,,',e
present. If the residue is yellow (largely Ag aP0 4 ), pour ,Y
hydrochloric acid through the filter a number of times, L' ,d
add a little potassium iodide solution and 1-2 ml. of chlorofo! ,n
or carbon tetrachloride to the extract and shake; if the orga ; to
layer acquires a purple colour, an arsenate is present.
Dissolve the white precipitate in the beaker in dilute hyd I (j-
chloric acid, reduce the arsenate (if present) with sulphur li-
oxide or, better, with ammonium iodide solution (as descril" d
under 11), precipitate the arsenic as arsenious sulphide w,: h
hydrogen sulphide and boil off the hydrogen sulphide in the
filtrate. Render the filtrate (0) slightly ammoniacal and add
a little magnesium nitrate reagent: white, crystalline mu);-
nesium ammonium phosphate will be precipitated if a phosphll t e
is present. Filter off the precipitate, wash with a little wat. r,
and pour a little silver nitrate solution (containing a few dro I' 3
of dilute acetic acid) over it: yellow silver phosphate will }' l
formed. Alternatively, the ammonium molybdate test may; 'I
applied to the filtrate (0) after evaporating to a small volun'I".
 45] Reactions of the Acid Radicals or Anions 423
13. Sulphide, Sulphite, Thiosulphate and Sulphate in
the presence of each other.-Upon the addition of dilute
acid to the mixture, the hydrogen sulphide, liberated from the
sulphide, and the sulphur dioxide, liberated from the sulphite
and thiosulphate, react and sulphur is precipitated; this com-
plication necessitates the use of a special procedure for their
separation.
A mixture of the sodium salts or "Na2C03 prepared solution"
is employed for this separation.

Shake the solution with excess of freshly precipitated CdCO., and filter.

Residue. CdS and Filtrate. Add Sr(NO.), solution· in siight

excess of CdOO •. excess, shake. allow to stand overnigh t and
Wash and reject filter.
washings. Digest
residue with dilute
acetic acid to remove Residue. 8r80. and Filtrate. Con-
excess of carbonate. SrSO•. Wash, treat with tains SrS.O •.
A yellow residue indi- dilute HCI and filter. Acidify with
cates sulphide. Con- dilute HCl and
firm by warming with b 0 i I; 80, is
dilute HCI and test Residue. Filtrate. evolved and 8 is
the evolved H.8 with 8rSO,. Contains slowly precipi-
lead acetate paper. White. sulphurous tated.
Sulphate acid. Add a Thiosulphate
present. few drops present.
Confirm by of a dilute
fusion with solution of
Na.CO. and iodine; the
apply sodium latter is de-
nitroprusside colourised. t
test. Sulphite
present.

An alternative procedure for the removal of the sulphide

is the following. Treat the solution of the sodium salts with
. a solution of zinc hexammine hydroxide [Zn(NH 3 )6](OH)2
{prepared by adding ammonia solution to zinc nitrate 8olution
until the initial precipitate of zinc hydroxide has redissolved,
and then adding a further excess:
Zn(OH)2 + 6NHs = [Zn(NH s)6](OH)2}
when zinc sulphide will be precipitated and is filtered off. The
precipitate may be treated with dilute hydrochloric acid and a
few drops of copper sulphate solution, when a black precipitate
... Solubility in grams per litre: SrS.O •• 250 at 13°; 8rSO •• 0'033 at 17°.
t Alternatively, add a few drops of fuchsin reagent; if it is decolourised.
sulphite is present.
 424 Qualitative Inorganic Analy8il [IV,
of cupric sulphide will indicate sulphide, or it may be test.·d
- for sulphide in the usual manner.
A simple method for separating sulphite and 8ulph:l 'e
consists in acidifying the neutral solution of the alkali S8" s
with dilute hydrochloric acid and adding excess of barh ':1
chloride solution; the sulphate is precipitated as barium s' -
phate and is removed by filtration. The production of 1
further preeipitate of barium sulphate upon the addition
the filtrate of a little concentrated nitric acid or of bromi
water and warming, proves the presence of sulphite.
14. Sulphide, Sulphite and Thiosulphate in the presence
of each other.-It is assumed that the solution is slightly
alkaline and contains the sodium sal t"
of the anions, e.g. the "Na2C03 prr"
pared solution. "
(i) Test a portion of the solution
for sulphide with sodium nitroprusside
solution. The formation of a purp:"
coloration indicates the presence of
sulphide.
(ii) If sulphide is present, remove:
by shaking with freshly precipitat€'/
cadmium carbonate and filter. Test:,
portion of the filtrate with sodiutl,
nitroprusside solution to see that al!
the sulphide has been removed. Wher:
no sulphide is present, treat the re
mainder of the filtrate with a drop 0
phenol-phthalein solution and pass iI
carbon dioxide until the solution i>
decolourised by it. Test 2-3 ml. oi
the colourless solution with 0·5-1 mL
Fig. IV, 45, 2 of the fuchsin reagent. If the re·
agent is decolourised, the presence
of sulphite is indicated.
(iii) Treat the remainder of the colourless solution with
dilute hydrochloric acid and boil for a few minutes. If sul-
phur separates, a thiosulphate is indicated. Alternatively, the
nickel ethylenediamine nitrate test (Section IV, 5, reaction 9)
may be applied.
15. Borate in the presence of Copper and Barium Salts.
-When carrying out the ethyl borate test for borates (Section
IV, 23, reaction 2), it must be remembered that copper and
45] Reactions of the Acid Radicals or Aniona 425
barium salts may also impart a green colour to the alcohol
flame. The test may be carried out in the following way when
salts of either or both of these metals are presellli. The
mixture of the borate, concentrated sulphuric acid and ethyl
alcohol is placed in a small round-bottomed flask, fitted with a
glass jet and surmounted by a wide glass tube, which acts as
a "chimney" (Fig. IV, 45, 2). The mixture is gently warmed,
and the vapours ignited at the top of the wide glass tube. A
green flame confirms the presence of a borate.
An alternative procedure is given in Section VII, 3, tost (ix).
16. Fluoride, Silicofluoride and Sulphate in the pre-
sence of each other.-The following differences in solubilities
ofthe lead salts are utilised in this separation: lead silicofluoride
is soluble in water; lead fluoride is insoluble in water but
soluble in dilute acetic acid; lead sulphate is insoluble in water
and in boiling dilute acetic acid, but soluble in concentrated
ammonium acetate solution.

Add excess of lead acetate solution to the solution of the alkali metal
salts, and filter cold.

Residue. 'Vaah well with cold water. Filtrate. Add

Divide into two parts. Ea(NO.). sol u-
(i) Smaller portion. Add excess of dilute acetic tion and warm
acid and boil (this will diBBolve any lead fluoride). gently. White
White residue indicates sulphate. The residue is crystalline pre-
soluble in ammonium acetate solution. cipitate indi-
(ii) Larger portion. Treat cautiously with concen- cates Silico-
trated sulphuric acid and teet with a moist glass rod. fluoride.
Milkiness of the water and etching of the tube in-
dicates fluoride.
"
17. Oxalate in the presence of Fluoride.-Both calcium
fluoride and calcium oxalate are precipitated by ammonium
oxalate solution in the presence of dilute acetic acid. The
fluoride may be identified in the usual manner with concentrated
sulphuric acid or as described below. The oxalate is most
simply detected by dissolving a portion of the precipitate in
hot dilute sulphuric acid and then adding a few drops of a very
dilute solution of potassium permanganate. The latter will be
decolourised if an oxalate is present.
Use may be made of the fact that even solid calcium fluoride
reacts with the zirconium-alizarin-S reagent (compare Section IV,
17, reaction 6) and, in consequence, the fluoride test may be carried
out in the presence of oxalate and phosphate, which interfere in
14*
426 Qualitative Inorganic Analysis [IV.
aqueous solution. The calcium salts are precipitated in neutral or
faintly basic solution. The precipitate is ignited and digested wi h I

dilute acid. The residue is then tested for fluoride by adding ,0

little of the zirconium-alizarin-S reagent: the red hue of the reage;: t
disappears and a yellow coloration results.
The reagent is prepared by dissolving 0·05 gram of zircon
nitrate in 10 ml. of concentrated hydrochloric acid and 50 ml. '
water, and this solution is mixed with a solution of 0·05 gram
sodium alizarin sulphonate in 50 ml. of water.

18. Chloride and Cyanide in the presence of each otheL

-Both silver chloride and silver cyanide are insoluble in watt'
but soluble in dilute ammonia solution. Three methods a "
available for the detection of cyanide in the presence of chlorio
(i) The concentrated solution, or preferably the solid mixtu
of sodium salts, is treated with about 5 times its weight
"100 volume" hydrogen peroxide and the mixture gent
warmed; ammonia is evolved, which is recognised by its acti(,!
upon mercurous nitrate paper. The solution is then boiled ~"
decompose all the hydrogen peroxide, and then tested f,;,'
chloride with silver nitrate solution and dilute nitric acid.
NaCN +H Z 0 2 = NaCNO +H 2 0;
NaCNO + 2H2 0 = NaHCO a + NH3
(ii) The cyanide is precipitated as the pale green nick,,!
cyanide by the addition of excess of a solution of nickel su
phate to the neutral solution; the whole is filtered and t}:.
excess of nickel sulphate removed by boiling with sodiUl
hydroxide solution and filtering off the precipitate of nick, !
hydroxide. The filtrate is acidified with dilute nitric acid an I
excess of silver nitrate solution added. A white, curdy prj
cipitate of silver chloride confirms the presence of chloride.
(iii) The solution of the- mixed sodium salts is treated wit,
excess of solid sodium bicarbonate (see Fig. IV, 2, 1), th
mixture warmed, and the evolved hydrogen cyanide passe:
into silver nitrate solution acidified with dilute nitric acid; . I

white precipitate of silver cyanide is obtained. This methol i

can be employed in the presence of ferro cyanides, ferricyanide
and thiocyanates.
For the detection of cyanide, chloride, bromide and iodid .
in the presence of one another the cyanide is first complete]
removed, and the separation of chloride, bromide and iodid·
carried out as detailed under 8.
The cyanide can also be detected by the usual Prussian blu._,
45] Reactions of the Acid Radica18 or Anions 427
test or "ferri4hiocyanate" test (Section IV, 8, reaction!:! 4
and 6).

19. Ferrocyanide, Ferricyanide and Thiocyanate in the

presence of each other.

Acidify the" Na 2CO. practically neutral solution" of the sodium salts

with acetic acid, add excess of It solution of thorium nitrate and a little
Gooch asbestos and shake well; filter.

Residue. Th[Fe(CNJ6J and Filtrate. Add CdSO. solution and

asbestos (the latter is added to a little Oooch asbestos, shake, filter.
facilitate filtration of the gela-
tinous precipitate J. * Wash - - - -
with a little cold wator. Treat Residue. Orange. Filtrate.
the ppt. on the filter paper with Cd 3 [Fe(CNJ6J. and Add FeCI.
dilute NaOH solution; acidify asbestos. Extract solu'Jion and
the alkaline extract" ith dilute with NaOH solution, ether. Red
HCI and add a few drops of acidify extract with coloration of
FeCI. solution. dilute HCl, add freshly ether proves
A precipitate of Prussian blue prepared FeSO, solu- pree ence of
indicates ferrocyanide. tion. Ppt. of Prussian thio'~yanate.
blue indicates ferri-
cyanide.
I

20. Separation of Organic Acids (Oxalate, Tartrate,

Citrate, Benzoate, Succinate, Acetate, Formate and Sali-
cylate in the presence of each other).-Intimately mix the
mixture of acids and/or their salts with 3-4 times the bulk of
anhydrous sodium carbonate, add just sufficient water to dis-
solve the sodium carbonate, heat under reflux for 15 minutes,
and filter. Wash and neglect the residue. The filtrate will be
termed the "Na2C03 prepared solution." Treat the com-
bined filtrate and washings with dilute nitric acid a little at a
time with stirring until acid (use litn1Us paper test), b~il gently
to expel carbon dioxide and allow to cool. Add dilute ammonia
solution portionwisc and with stirring until just alkaline.
Filter, if not clear. It is advisable to boil gently for a minute
or two to remove any appreciable excess of ammonia. The
resulting solution will be free from heavy metals and almost
neutral. It will be referred to as the "Na2C03 practically
neutral solution. "t
* Filter paper pulp (e.g. in the form of a Whatman filtration accelerator)
cannot be used as the organic matter may cause appreciable reduction of the
ferricyanide.
t See Section VII, 17, tests " and ,5 for a slightly modified procedure.
428 Qualitative Inorganic Analysi8 [IV,
~-----------------------------------------
Add CaCI, solution to the cold "Na 2CO. practically neutral solution, '"
rub sides of vessel with a glass rod, allow to stand for 10 minutes wit],
occasional shaking; filter.

Residue. May be Co. Filtrate. Add more CaCl 2 solution, boi'

oxalate (formed imme- under reflux for at least 5 minutes. A ppt.
diately) or Co. tartrate may form gradually; filter.
(formed on standing).'"
Wash. Boil with dilute
acetic acid and filter. Residue. Filtrate. If citrate present,
Co. citrate. evaporate to dryness on water
White. bath, add a little cold water, and
Residue. I Filtrate. Citrate
present.
filter from any residue of Co.
citrate.
CaC.O,. May con-
Dissolve in tain Co. Divide If citrate absent, proceed
a little tartrate. into 2 with solution.
dilute HCI, Test parts. Add FeCl a solution; filter
add NHs neutral (i) Con- (if necessary).
solution solution firm by
in slight with Deniges'
excess. Fenton's test. Residue. Filtrate. Coloured.
White ppt. reagent, (ii) Dis- Ferric Dilute, boil and
insoluble violet solve in benzoate filter.
in dilute coloration dilute and/or
acetic acid. (see Note), HCI, con- ferric
Oxalate or by silver vert into suc~
Residue. Filtrate.
present. mirror test neutral cinate. Basic Coloured.
Confirm by for tartrate. solution Separate ferric (a) Vio-
resorcinol Confirm with by formate let-sali-
test, or by by copper NH. solu- procedure and basic cylate.
decolouri s- hydroxide tion, etc., A. ferric Confirm
ation of test. and add acetate. by "oil
a dilute CdCI. Separate of winter-
solution of solution. by pro- green"
acidified White cedure B. test.
KMnO. at gelatinous (b) Deep
60-70°. precipi- blue or
tate. greenish
black-
gallate
or tan-
I
nate·t

Note.-With Fenton's reagent and a neutral solution of a citrate,

a yellow or brown colour is obtained, but there is no precipitation
of iron; with an oxalate, the iron is precipitated as the hydroxide.

Procedure A
Separation of benzoate and succinate.-Boil the precipi-
tated ferric salts with a little dilute ammonia solution, filter off
* It must be remembered that phosphates, fluorides. sulphatas. etc., are
precipitated by calcium chloride solution.
t Ga.llates and tannates are of rare occurrence in general qualitative anaIyllis.
45] Reactions of the Acid Radicals or AnioM 429
the precipitated ferric hydroxide and discard the precipitate;
boil off the excess of ammonia from the filtrate. Divide the
filtrate into two parts.
Treat one portion with barium chloride solution and filter off
precipitate formed. The residue consists of barium succirw,te.
Confirm the succinate by the fluorescein test. Acidify the
second portion of the filtrate with dilute hydrochloeic acid,
when benzoic acid will separate out on cooling. It can be
identified by its melting point.

Procedure B
Formates and Acetates in the presence of each other.-
Formate. (i) In the absence oj tartrates, citrates and reducing
agents. Add silver nitrate solution to the "Na2COa practically
neutral solution"; a white precipitate, which is conve;·ted into
a black deposit of silver on boiling, indicates formate. A little
of the solid substance may be treated with concentrated sul-
phuric acid, when carbon monoxide (burns with blue flame)
will be evolved in the cold.
(ii) In the presence oj tartrates, citrates and reducin,l agents.
Acidify the mixture with dilute sulphuric acid and distil. A
solution of formic and acetic acids will pass over. Neutralise
distillate with dilute ammonia solution, boil off excess of
ammonia (if necessary) and test as in (i).
Acetate. If other organic acids are present, obtain the
solution of mixed acids as in (ii); otherwise, use the "Na2COa
practically neutral solution. " Boil under reflux with an equal
volume of potassium dichromate solution and dilute mlphuric
acid; this will decompose the formic acid. Distil off the acetic
acid, neutralise and test with ferric chloride solution.
If the solid is available, the cacodyl test may be employed.
For other methods of separation and detection of selected
anions, see Section VII, 17, Tables A and O.
 CHAPTER V

SYSTEMATIC MACRO QUALITATIVE INORGANfC

ANALYSIS FOR ELEMENTARY STUDENTS*

IT is assumed that the student is already familiar with "( '3

operations (ignition tests, blowpipe tests, flame tests, bm '(
bead tests, precipitation, filtration, etc.) described in Chapter ., [
(Sections II, 1 and II, 2). For the cations, a limited num! r
of preliminary reactions should first be studied, followed 1 ,'I
the analysis of a mixture or solution containing a member l
members of each group. This will provide practice at the ve "
outset ~.t~e use o~the Group Separation Tables. T~e ~l,,:~
of the InItIal solutIOn should be kept as small as pOSSIbl€~: "'1- n '.
is a convenient volume) as should also the weight of solia us, r
(say, :;j:>O·5 gram). The student should pay particular atte
tion to (i) the exact experimental conditions for the reactio
(ii) the colour and physical characteristics (e.g. whether crystl"
line, amorphous or gelatinous) of each precipitate and (iii) tl "
solubility of each precipitate in excess of the precipitant, or '
solutions of other reagents. He should, as far as possibl'
represent the chemical reactions by ionic equations and the':
check his own equations against the molecular equations givf l
in the text. This will give the student excellent practice i I
writing and balancing equations, and also help to impress tIt .
reactions upon his (or her) memory. -
Droppers.-The so-called" medicine droppers" and also tL
similar dropper pipettes (the latter have a longer tip) may t
purchased and are inexpensive. They are very useful fe.·
adding small volumes of reagents (particularly dropwise) an':
also for washing precipitates. If calibrated, say at 0·5 m:
intervals, droppers may be employed for measuring smal i
volumes. The rubber teat (bulb) should be removed and th,
* This chapter has been retained in the present edition as it appears V
meet the wishes of numerous correspondents. It covers the requirements 01
those who desire a brief introductory course and have only a limited time a;
their disposal. Additional anions (e.g. fluoride, borate and phosphate) call
be readily introduced if required. The abbreviated course will be found suit.
able for the General Certificate of Education (Advanced Level), for the Inter-
mediate Science Examinations of the various Universities, for the Ordinary
National Certificate in Chemistry, and for examinations of similar scope.
430
1] SY8tematic Macro Qualitative Inorganic AnalY8is 431
glass tube thoroughly rinsed with distilled water immediately
after use.
Droppers can be readily made by the student as follows.
Draw out a length of glass tubing (about 20 cm. long and of
about 7 mm. diameter) in the centre by suitably heating in a
flame: the narrow part of the tube should be about 3 mm.
external diameter. Cut the tube in the middle of the drawn-
out portion, and thus obtain two jets. Heat the wjder end
and enlarge it with the aid of a file so that it will securely hold
a rubber teat (bulb). The teat should be of such size that
liquid cannot be drawn into it. The dropper may be calibrated
by holding it vertically after filling with distilled W[l,ter and
allowing the water to flow dropwise into a small measuring
cylinder: 0·5 ml. intervals should be marked by means of a
file or "glass" pencil. The number of drops (preferably about
20 per m!.) should also be determined.
V, 1. Abbreviated Course of Instruction.-The following
preliminary reactions should be carried out by the student.
REACTIONS OF THE CATIONS
Pb++. Section III, 2, reactions 1, 2, 3, 4; blowpipe test.
Hg 2 ++. Section III, 3, reactions 1, 6, 7.
Ag+. Section III, 4, reactions 1, 2, 3; blowpipe test.
Identification of a metal in the solution supplied by the teacher
by means of Table I (Section III, 5).
Hg++. Section 111,6, reactions 1,2,3; dry test.
Bi+++. Section III, 7, reactions 1, 3, 5, 6, 10.
Cu++. Section III, 8, reactions 1, 2, 3, 4, 5, 8; dry test.
Cd ++. Section III, 9, reactions 1, 3, 4; dry test.
Identification of a metal or metals in the solution supplied by
means of Table II or IIA (Section III, 10).
As (ous). Section III, 11, reactions 1, 2, 3.
As (ic). Section III, 12, reactions 1, 2, S, 4.
Sb (ous). Section III, 14, reactions 1, 2, 8.
Sn++. Section III, 16, reactions, 1, 2, 3.
Sn++++. Section 111,17, reactions 1, 3, 4.
Identification of a metal or metals in the solution supplied by
means of Table III or IlIA (Section III, 18).
Fe++. Section III, 19, reactions 1, 2, 3, 4, 6, 7, 8.
Fe+++. Section III, 20, reactions 1, 2, 3, 4, 5, 6, 10.
Al+++. Section III, 21, reactions 1, 2, 3, 7; dry test.
Cr+++. Section III, 22, reactions 1, 2, 3, 6; dry test (iii).
Identification of a metal or metals in the solution su pplied by
means of Table IV (Section III, 23).
 432 Qualitative Inorganic Analysis
Co++. Seotion III, 24, reaotions 1, 2, 3, 5, 6, 7; dry test (ti).
Ni++. Seotion III, 25, reaotions 1, 2, 3, 6, 7, 8; dry test (ti).
Mn++. Seotion III, 26, reaotions 1, 2, 3, 5, 7; dry t~st (ii).
Zn++. Section III, 27, reactions 1, 2, 3, 6, 8, 9; dry test.
Identification of a metal or metals in the solution supplied In
means of Table V (Section III, 28).
Ba++. Section III, 29, reactions 1, 2, 3, 4, 6; dry test.
Sr++. Section III, 30, reactions 1, 2, 3, 5, 6; dry teElt.
Ca++. Section III, 31, reactions 1, 2, 3, 5, 6; dry telilt.
Identification of a metal or metals in the solution supplied L'
means of Table VI (Section III, 32).
Mg++. Section III, 33, reactions, 1, 2, 3, 5, 7, 8; dry test.
K +. Section III, 34, reaction 1; dry test.
Na+. Section III, 35, reaction 1; dry test.
NH4+. Section III, 36, reactions 1, 3,7; dry test.
Identification of a metal or metals in the solution supplied b:'
means of Table VII (Section III, 37).

REACTIONS OF THE ANIONS

CO s--. Section IV, 2, reactions 1, 2.
HCO s-. Section IV, 3, reactions (i), (ii), (iii).
SOs--. Section IV, 4, reactions 1, 2, 4, 5, 9, 10.
S20S--. Section IV, 5, reactions 1, 2, 3, 6, 8.
S--. Section IV, 6, reactions 1, 2, 3, 5, 6.
N0 2-. Section IV, 7, reactions 1, 2, 7, 10.
*SCN-. Section IV, 10, reactions 1, 2, 3, 6.
ce. Section IV, 14, reactions 1, 2, 3.
Br-. Section IV, 15, reaotions 1, 2, 3, 5, 8.
r. Section IV, 16, reactions 1, 2, 4, 7.
F-. Section IV, 17, reactions 1, 2, 6.
NO s-. Section IV, 18, reactions 1, 2, 3,-4.
*ClO s-. Section IV, 19, reactions 1, 2, 3, 7, 10.
S04 --. Section IV, 24, reactions 1, 2, 5, 6.
P04---. Section IV, 28, reactions 1, 3, 4, 5, 6.
Cr04--. Section IV, 33, reactions 1, 2, 4, 5, 6.
*C 2H s 0 2 - (acetate). Section IV, 35, reactions 1, 2, 3, 4, 6. _
*C 20 4 - - (oxalate). Section IV, 37, reactions 1, 2, 3, 4.
V, 2. Systematic Analysis. General Considerations.--
The student must realise that the object of qualitative analysi,
is not simply to detect the constituents of a given mixture; ali
equally important aim is to ascertain the approximate relativ(
amounts of each component. For this purpose about 0·5 gp,ll,
of material is usually employed for the analysis ~ the re! ":" 7'
magnitudes of the various precipitates will provide a rougL
guide as to the proportions of the constituents pr{~sent.
• To be studied at the discretion of the teacheJ:.
3] System{ltic Macro Qualitative Inorganic Analysis 4:33
Every analysis is divided into three parts:
(I) The preliminary examination. This includes preliminary
examination by dry tests, examination of the volatile products
with sodium hydroxide solution (for ammonium), and with
dilute and concentrated sulphuric acid (for acid radicals or
anions). A special preliminary test for nitrate and/or nitrite
is also made here.
(2) The examination ICYI' acid radicals (CYI' anions) in solution.
(3) The examination JCYl' metal ions (or cations) in 801ut'ion.

V, 3. PRELIMINARY TESTS
Test (i). Heating in a closed tube.-Place about 0·1 gram
of the substance in a dry ignition tube so that none of it remains
adhering to the sides and heat cautiously; the tube should be
held in an almost horizontal position. Raise the temperature
gradually and carefully note any changes which take place.
[Table on p. 434]
Test (ii). Charcoal block reductions.
(a) Heat a little of the substance (ca. 0·1 gram) in a small
cavity in a charcoal block in a blowpipe flame.
ObseTVatwTI Inference
1. The substance decrepitates. Crystalline salts, e.g. NaCl, KCl.
2. The substance deflagrates. Oxidising agents, e.g. nitrates,
nitrites and chIorates.
3. The substance is infusible or incan· Apply test (b) below.
descent, or forms an incrustation upon
the charcoal.

(b) Mix the substance (ca. 0·1 gram) with twice its bulk of
anhydrous sodium carbonate, place it in a cavity in a charcoal
block and heat in the reducing flame of the blowpipe.
Ob8ervation Inference
1. Incrustation without metal:
White, yellow when hot. ZnO.
White, garlic odour. As.O •.
Brown. CdO.
2. Incrustation with metal:
'White incrustation; brittle metal. Sh.
Yellow incrustation; brittle metal. Bi.
Yellow incrustation; grey and soft Ph.
metal, marks paper.
3. Metal without incrustation:
Grey metallic particles, attracted by Fe, Ni, Co.
magnet.
Malleable beads. Ag and Sn (white); eu (red
flakes).
 I' ,

Observation Inference

(a) A gas or vapour is evolved.

1. Water is evolved; test with Htmus Compounds with water
paper. crystallisation (often accon
panied by change of oolour
ammonium salts, acid sal;
and hydroxides.
The water is alkaline. Ammonium salts.
The water is acid. Readily decomposable salts (,:
strong acids.
2. Oxygen is evolved (rekindles a glow- Nitrates, chlorates and certai"
ing splint). oxides.
3. Nitrous oxide (rekindles glowing Ammonium nitrate or nitrat,>
splint) and steam are evolved. mixed with an ammoniUl"
salt.
4. Dark brown Or reddish fumes (oxides Nitrates or nitrites of heBv\,
of nitrogen); acidic in reaction. metals. .
5. Carbon dioxide is evolved (lime water Carbonates or bicarbonates.
is rendered turbid).
6. Ammonia is evolved (turns red litmus Ammonium salts.
paper blue).
7. Sulphur dioxide is evolved (odour of Normal and acid sulphites
burning sulphur; turns potassium di- thiosulphates; certain su]
chromate paper green; decolourises phates.
fuchsin solution).
8. Hydrogen sulphide is evolved (odour Hydrated sulphides or suI
of rotten eggs; turns lead acetat,e phides in the presence 0 i
paper black or cadmium acetate paper water.
yellow).
9. Chlorine is evolved (yellowish-green Unstable chlorides, .e.g. of
gas; bleaches litmus paper; turns copper; chlorides In the
potassium iodide-starch paper blue); presence of oxidising agents.
very poisonou8.
10. Bromine is evolved (reddish-brown Sources similar to chlorine.
vapour; choking odour; turns fluo-
rescein paper red).
II. Iodine is evolved (violet vapours Free iodine and certain
condensing to black crystals). iodides.

(b) A sublimate is formed.

1. White sublimate. * Ammonium and mercuric
salts; As.O s ; Sb 20 •.
2. Grey sublimate, easily rubbed to Hg.
globules.
3. Steel-grey sublimate; garlic odour. As.
4. Yellow sublimate. S (melts on heating), As,S3'
HgI. (red when rubbed with
a glass rod).

* If a white sublimate forms, heat with four times the blllk of anhydrous
Na.C0 3 and a little KeN in an ignition tube. A grey mirror, convertible
into globules on rubbing with a glass rod, indicates Hg (Note: Hg vapour
is very poisonous); a brownish-black mirror, yielding a white sublimate
and an odour of garlic when heated in a wide tube, indicates As; ammonia
evolved (test with mercurous nitrate paper) indicates ammonium salts.
 .. ,~.. --,.,_"" .
3] Systematic Macro Qualitative Inorganic Analysis 435
Test (iii). Flame colorations.-Place a small quantit,y of
the substance (ca. 0·05 gram) on a watch glass, moisten with a
little concentrated hydrochloric acid and introduce a little of
the substance on a clean platinum wire into the base of the
non-luminous Bunsen flame. An alternative method is til dip
the platinum wire into concentrated hydrochloric acid con-
tained in a watch glass or test-tube and then into the substnnce;
sufficient will adhere to the platinuDl wire for the test to be
carried out.

Observation Inference

Persistent golden-yellow Hilme. Na.

Violet (lilac) Hame (crimson through I K.
cobalt·blue glass).
Brick-red (yellowish-red) flame. Ca.
Crimson flame. Sr.
Yellowish-green flame. Ba.
Livid·blue flame (wire slowly corroded). Pb, As, Sb, Bi, Cu.

The sodium flame masks that of other elements, e.g. that of

potassium. lVIixtures can be readily dE·tected with a cirect-
vision spectroscope. A less delicate method is to view the
flame through two thicknesses of cobalt-blue glass, wbereby
the yellow colour due to sodium is masked or absorbed; potas-
sium then appears crimson.
Test (iv). Borax bead reactions.-Make a borax boad in
a loop of platinum wire by dipping the hot wire into borax and
heating until colourless and tranHparent. Bring a minute
quantity of the substance into contact with the hot bea d and
heat in the outer or oxidising flame. Observe the colour when
the bead is hot and also when it is cold. Heat the bead in the
inner or reducing flame and observe tho colour in the h,)t and
cold states. Coloured beads are obtained with compounds of
copper, iron, chromium, mangane8e, nickel and cobaJ t; the
most characteristic result is for cobalt.

Oxidising flame Reducing flame 1Y1 ~tal

1. Green when hot; blue Colourless when hot Cu.

when cold. or opaque.red when cold.
Yellow, hot and cold. Green, hot and cold. Fe.
3. Dark yellow when hot, Green, hot and cold. Cr.
green when cold.
4. Violet (amethyst), hot and Colourles8, hot and cold. Mn.

5.
cold.
Blue, hot and cold.
I Blue, hot and cold. Co.
6. Reddish·brown when cold. Grey when cold. Ni.
436 Qua,litative Inorganic Analysis lV,
Test (v). Test for the ammonium radical.-Boil ah ,ut
0·2 gram of the substance with 2-3 m!. sodium hydro).. :de
solution. The evolution of ammonia, detected by its odc"lr,
its action upon litmus paper and upon mercurous nitrate pal '(~r,
indicates the presence of an ammonium salt.
In order to avoid the necessity of holding the test-po! 'er
(litmus, etc.) in the vapour, the following simple device ll':ty
be used. A test-tube is fitted with a cork carrying a wide t; be
(at least half the diameter of the test-tube) about 5 cm. IOlg;
the bottom of the wide tube should protrude just below • he
cork (Fig. VII, 2, 1). A test-paper can then be supporteu in
the wide tube by simply folding it slightly over the upper e i ge
of the glass tube. This device is recommended for all reacti ,as
on the macro scale in which evolved gases are identified by
means of test-papers.
Note.-Sodium hydroxide is a dangerous substance because of
its destructive action upon the eyes. Great care should be tal ,m
that the test-tube containing the hot sodium hydroxide solutiOi' is
directed away from the eyes of the observer and of near neighboli rs.
Test (vi). Test for nitrate (or nitrite).-If ammonium is
found, continue boiling until ammonia can no longer be detec1 , ·d
by its action upon red litmus paper or upon mercurous nitr I te
paper; it may be necessary to add a further 2-3 m!. of SOdililll
hydroxide solution. Then add a little zinc dust or aluminil (m
powder or finely powdered Devarda's alloy (Cu, 50 per cel:i.;
AI, 45 per cent; Zn, 5 per cent) and warm the mixture gent'y.
Remove the flame as soon as evolution of hydrogen commen' ':s
and allow the reduction to proceed (the reaction may becol!'e
vigorous with aluminium powder and cooling with tap wa:' r
may be necessary to moderate the vigour of the reactir, I I ;
alternatively, thin aluminium foil may be used). If amn',)-
nium is absent, add zinc dust or aluminium powder or Devard;, s
alloy to the reaction mixture from test (v). If ammonia is
evolved, as detected by its action upon red litmus paper '.'r
upon filter paper moistened with mercurous nitrate solutioll,
then the presence of nitrate or nitrite is indicated. The pre-
sence of nitrite will generally also be detected in the reaction
with dilute sulphuric acid {see test (vii)}; if nitrite is absent,
then the presence of nitrate alone is established.
It must be emphasised that the mercurous nitrate paper test for.
ammonia is not applicable in the presence of arsenites. Arsenites
are reduced under the above conditions to arsine, which also
blackens mercurous nitrate paper. Similar remarks apply to the
tannic acid-silver nitrate test (Section III, 36, reaction 7).
,jJ t:;ystemattc Macro (JuaHtatwe lnorganf,C AnatYIJM 43'(

Test (vii). Action of dilute sulphuric acid.-Treat ahout

0·2 gram of the substance in a test-tube with 2-3 ml. dilute
(2N) sulphuric acid and note whether any reaction takes place
in the cold (indicated by C). Warm gently and observe the
effect produced.

1------------------____________________
Ob8ervation I Inference
1_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _;

1. Colourless gas is evolved with effervescence; I CO. from carbonate or

gas is odourless and produces a turbidity when bicarbonate.
passed into lime water (see Fig. IV, 2, 1). (0)
2. Nitrous fumes evolved; recognised by reddish· NO a from nitrite.
brown colour and odour. (0)
3. Yellowish-green gas evolved; suffocating CIa from hypochlorite.
odour, reddens then bleaches litmus paper,
also turns starch-KI paper blue; very
poisonou8. (0)
4. Colourless gas evolved with suffocating odour; SO a from sulphite.
turns filter paper moistened with K,Cr.O,
solution green; decolourises fuchsin solution.
5. Colourless gas evolved: gives above tests for SO. and S from thio·
SO,; sulphur is deposited in the solution. Bulphate.
6. Colourless gas evolved; odour of rotten eggs; HoS from aulphide.*
blackens filter paper moistened with lead
acetate solution; tunlS cadmium acetate
paper yellow.
7. Odour of vinegar. H. C,HaO. from acetate.
8. Colourless gas is evolved; rekindles glowing O 2 from peroxides or
splint. per-8alts of alkali and
alkaline earth metals.
9. Upon boiling, yellow solution formed and S02 SO., etc., from thio·
(fuchsin solution test, etc.) evolved. cyanate.

Test (viii). Action of concentrated sulphuric acid.-

Treat about 0·2 gram of the substance with 2-3 ml. of con-
centrated sulphuric acid and warm the mixture gently, and
incline the mouth of the test-tube away from you. (H chlorate
is suspected from the preliminary charcoal reduction test to be
present, use a very small quantity (less than 0·05 gram) for
this test, as a dangerous explosion may result on warming.)
If the substance reacted with dilute sulphuric acid, the
addition of concentrated sulphuric acid may result in vigorous
reaction and rapid evolution of gas, which may be accompanied
by a very fine spray of acid. In such a case, it is best to add
dilute sulphuric acid drop wise (best with a clean dropper) to
another portion of the substance until action ceases, and then
to add 3-4 ml. of concentrated sulphuric acid.
* Many sulphides, espeoially native ones, are not affected by dilute HISO,;
some HIS is evolved upon warming with ooncentrated HCI alone or with a
little tin.
438 Qualitative Inorganic Analysis
The following results may be obtained.

Observation Inference

1. Colourless gas evolved with pungent odour HCl from chloride.

and which fumes in the air; white fumes of
NH.Cl in contact with glass rod moistened
with concentrated NHs solution; CI. evolved
on addition of MnO. (reddens, then bleaches
litmus paper).
2. Gas evolved with pungent odour, reddish HBr and Br, fr·,
colour and fumes in moist air; on addition bro-rnide.
of MnO. increased amount of red fumes with
odour of Br. (fumes colour filter paper
moistened with fluorescein solution red).
3. Violet vapours evolved, accompanied by HI and I, from iodi
pungent acid fumes, and often SO. and even
H.S.
4. Pungent acid fumes evolved, often coloured HNO. and NO. fr(·"
brown by NO.; colour deepens upon addition nitrate.
of copper turnings (if nitrite absent).
5. Yellow gas evolved in the cold with charac- CIO. from chlorate.
teristic odour; explosion or crackling noise
<m. wann.ill.g g~n.tly (DA.NGERt~.
6. "Oily" appearance of tube in cold; on HF from fluoride.
warming, pungent gas evolved, which corrodes
the glass; if moistened glass rod introduced
into the vapour, a gelatinous precipitate of
hydrated silica is deposited upon it.
7. Colourless gas evolved; burns with a blue CO (:rom formate.
flame; no charring (very poisonous).
8. Colourless gas evolved; renders lime water CO and CO. fro'"
turbid and also burns with a blue flame; no oxalate.
blackening.
9. Yellow coloration in cold: upon warming, COS, SO 2 and S frol
vigorous reaction, COS (burns with blue thiocyanate.
flame), SO. (decolourises fuchsin solution)
and free S produced.

V, 4. EXAMINATION FOR ACID RADIC.t\.LS (ANIONS

IN SOLUTION
The preliminary tests (vii) and (viii) with dilute sulphur (
acid and with concentrated sulphuric acid will have provid··,
useful information as to many acid radicalS present. F I
more detailed information, it is necessary to have a soluti( 11
containing all (or most) anions free from heavy metals. Tl··,
is best prepared by boiling the substance with concentrate
sodium carbonate solution; double decomposition occurs (eith !
partially or completely) with the production of the insolub "
carbonates* of the metals (other than alkali 1lletals) and tL
soluble sodium salts of the anions, which paeS into solution.
• Certain carbonates, initially formed. are converted into insoluble basi,'
carbonates or into hydroxides.
4] Systematic Macro Qualitative,lnorgan~c Analysis 439
Thus, if the unknown substance is the salt of a bivalent metal
M and an acid RA, the following reaction will occur:
MA2 + Na2COa ~ MC0 3 + 2NaA
The carbonate MCO a is insoluble and the sodium salt .'iaA
will pass into solution whether MA2 is soluble in water or not.
Preparation of solution for testing for anions.-B,}il 1
gram of the finely divided substance or mixture with 25 ml. of
a saturated solution of pure sodium carbonate* (prepared from
4 grams of anhydrous sodium carbonate and 25 ml. of distllled
water) for 10 minutes in a small conical flask with a funnl)} in
the mouth to reduce the loss by evaporation. Filter,t wash
the residue with hot distilled water and collect the wasbings
together with the main filtrate; the total volume shoulli be
30-35 ml. Reject the residue. The sodium carbonate extract
will be termed the "Na2 CO a prepared solution." Use this
solution to carry out the following tests.
1. Sulphate test.-'_ro 2 mI. of the "Na2C03 prepared
solution" add dilute hydrochloric acid until acid (test with
litmus paper) and then add 2 mI. in excess. Boil for 1-2
minutes to expel carbon dioxide completely, and then add about
1 ml. of barium chloride solution. A white precipitate (BaS04)
shows the presence of sulphate. Confirm by test 1 in Se,}tion
IV, 24 (charcoal reduction of precipitate).
2. Test for reducing agents.-Acidify 2 ml. of the
"Na2COa prepared solution" with dilute sulphuric acid and
add 1 ml. of dilute sulphuric acid in excess. Add 3-4 drops
of 0'02N potassium permanganate solution (prepared by
diluting 1 ml. of O·1N KMn04 to 5 ml.) from a dropper.
Bleaching of the permanganate indicates the presence of one
or more of the following reducing anions: sulphite, thiosulphate,
sulphide, nitrite, bromide, iodide and arsenite. If the perman-
ganate is not decolourised, heat and observe the result. If the
reagent is bleached only on heating, the presence of oxalate is
indicated. A negative test shows the absence of the I~bove
anions.
3. Test for oxidising agents.-Treat, 2 rol. of the "NU'2COa
prepared solution" cautiously with 1 rol. of concentra.ted
hydrochloric acid, followed by 2 rol. of the manganous chloride
* It is essential to use pure sodium carbonate; the A.R. solid is satisf':lctory.
Some "pure" samples may contain traces of sulphate or chloride: the hbsenoe
of these impurities should be confirmed by a blank experiment.
t If no precipitate is obtained, the Bubstance is free from heavy metals,
and the sodium carbonate treatment may be omitted if more of the solution
i.I required.
440 Qualitative.] norganic Analysis [V,
reagent. A brown (or black) coloration indicates the presl'nce
of nitrate, nitrite, chlorate or chromate. A negative tesl in-
dicates the absence of the above oxidising anions except S ilall
amounts of nitrates and nitrites. If reducing anions j, we
been found, this test is inconclusive.
Note.-The rea~ent consists of a saturated solution of manga ,ous
chloride, MnCI 2 ,4H2 0, in concentrated hydrochloric acid. Its a, ,ion
depends upon its conversion by even mild oxidising agents ',) a
dark-brown coloured manganic salt, probably containing the
complex [MnC~r- or [MnCI4 r ions.
4. Tests with silver nitrate solution.-Sulphide and >ul-
phite interfere in the tests with silver nitrate solution, hen '\ if
either of these anions was detected in the preliminary test \\ lth
dilute sulphuric acid, it must be removed first as foll., \VS.
Acidify 10 ml. of the "Na2C03 prepared solution" with di'llte
acetic acid (use litmus paper): boil gently in a conical flas! or
porcelain dish in the fume cupboard to expel hydrogen sulpl :de
or sulphur dioxide (3-5 minutes). It is important that 'he
solution be acid throughout. Filter, if necessary, and aUo\\ to
cool. If the volume has been reduced appreciably. add wu,ter
to restore the original volume (solution S).
.,

Acidify 10 ml. of the "Na.CO. prepared solution" cautiously with dilv' \

acetic acid (use litmus paper). Determine the volume of the acidifi· 1
solution (or of solution S) with the aid of a small measuring cylinder, a( i
one-tenth of the volume of concentrated HNO. and stir for 30 secon"
Then add AgNO s solution with stirring until precipitation is complel'
Heat to the boiling point, allow the precipitate to settle, cool and tilt, ,
Wash the precipitate with 2-3 ml. of N nitric acid.
Residue. Filtrate. Add 1 mI. of AgNO. solution, then 20"
AgCI-white. NaNO. solution (prepared from the A.E. solid) dr01
AgBr-pa.le wise and with stirring until precipitation is complet'
yellow. [If no precipitate forms, do not add more than 0·5 m
AgI-yeUow. of NaNO. solution.] Filter, if necessary, and wasJ
with 2-3 ml. of N nitric acid.
Residue. Filtrate. Add N aOH solution drol
AgCI wise (use a dropper) and with vigorolJ
derived stirring until neutral to litmus (1). the'
from add 0·5 ml. of dilute acetic acid, followe I
AgCIO •. by 1 ml. of AgNO. solution, and heat t
about 80°C (2). If a permanent precip;
tate forms, add more AgNO. solutiol
until precipitation is complete. Filt('·
and wash with hot water.
Residue (3). Filtrate.
Ag.PO.-yellow.
Ag.AsO.-brownish-red.
Ag.AsO,-yellow. Discard.
Ag,C,O,-white.
4] SY8tematic Macro Q'lUllitative Inorganic Analysis 441
Notes. (1) It is esscntial that the solution be just neutral to
litmus or, at most, barely alkaline: the latter will be indicl~ted by
a very slight brown opalescence (due to Ag 20) obtained upon stirring
or shaking. If much silver oxide separates, it will re-dissol ve only
with difficulty.
(2) Silver acetate is soluble in hot water and is held in s,)lution.
(3) If chromate is present (yellow or orange solution), it will be
reduced by the NaN0 2 treatment and will precipitate here as
green chromic hydroxide. Ohromate is readily detected in the
"Na2COa prepared solution" as follows: acidify (say, 2 mt.) with
dilute HNO a, cool, add 1 mI. of amyl alcohol and 0·5 mI. (If 3 per
cent H 2 0 2 solution and stir. A blue coloration ("perehromic
acid") in the organic layer confirms chromate.
The separations described in the above table are based upon
the following facts:
(i) AgNO a solution precipitates only AgCI, AgBr and AgI
from a dilute nitric acid solution, the other silver salts being
soluble.
(ii) NaN0 2 solution reduces chlorate to chloride, which is
precipitated as AgCI in the presence of AgNO a solution:
NaCIO s + 3NaN02 = NaCI + 3NaNOa
(iii) In solutions faintly acid with acetic acid, pho3phate,
arsenate, arsenite and oxalate are precipitated by AgNO a
solution.
If a mixture of the halides, or of phosphate, arsenate or
arsenite, is suspected, use Table A or Table 0 given in Section
VII, 17. The confirmatory tests for individual anions are
collected in Section V, 5. The reactions with silver nitrate
solution are intended to act as a guide to the presence of groups
of anions, and the table must be interpreted in conjuncti,m with
the observations made in the preliminary tests. Arsenite,
arsenate and chromate will also be found in the analysis for
cations (Section V, 7).
5. Test with calcium chloride solution.* For tests 5 and 6
a "NaaCO a practically neutral solution" is required. This is
obtained as follows. Transfer 4-5 m!. of the "Naj!COa Fepared
solution" to a porcelain dish and render it faintly acid with dilute
nitric acid (use litmus paper). Boil for 3-4 minutes to expei carbon
dioxide, allow to cool, then add dilute ammonia solution until just
alkalinet; boil gently for 1 minute to remove any appreciable excess
'" Tests 5 and 6 may be omitted by those requiring only a beginney's course
in qualitative analysis.
t If a ppt. forms on neutralising the solution, the presence of arsenic,
antimony and tin sulphides and possibly salts of amphoteric bases (lead, tin.
aluminium and zinc) is indica.ted. The ppt. should be filtered off and rejected.
 Qualitative Inorganic AnalY8i8 iV,
of ammonia. Divide the solution into two equal parts; reserve i~,tlf
for test 6.
Add CaCl 2 solution (equal in volume to that of the ~olution). a,d a
little dilute acetic acid and allow to stand. A white preClpr . te
indicates the presence of oxalate and/or fluoride . . Filter off t~e ",,~­
cipitate and dissolve it by pouring a little hot dIlute sulphurIC ;,. old
into the filter. Treat the hot filtrate with a few drops of potasE "m
permanganate solution. If the permanganate is reduced, oxala, is
present.
6. Test with ferric chloride solution.· Treat the Oi Iler
portion of the "neutral" solution from test 5 with aqueous F. ! jla
solution.
Reddish-purple coloration indicates thiosulphate.
Reddish-brown coloration, yielding a brown precipitate on dilul ;on
and boiling, indicates acetate.
, Yellowish-white precipitate indicates phosphate.
Blood-red coloration, discharged by HgCl 2 solution, indicat.es
thiocyanate.

V, 5. CONFIRMATORY TESTS FOR ACID RADICA LS

(ANIONS)
The tests in the preceding section will indicate the 11' id
radicals or anions present. In general, these should be l ·n-
firmed by at least one distinctive confirmatory test. '; i1e
following are recommended. Full experimental details ill
usually be found in Chapter IV under the reactions of the p id
radicals (anions); the reference to these will be abbrevia. ',ld
as follows: thus (IV, 2, 7) is to be interpreted as Section 1V,
2, reaction 7. It is assumed, of course, that interfering at' .ls
are absent or have been removed .as described below un ; elr
Special Tests for Mixtures of Acid Radicals.
Chloride. Heat solid with concentrated H 2S04 and Mn0 2 ; ('1 2
evolved (reddens then bleaches litmus paper and also turns h [.
starch paper blue) (IV, 14, 2).
Bromide. Heat solid with concentrated H 2S04 and Mn0 2 ; Lr2
evolved (IV, 15, 2) OR chlorine water (or the equivalent NaOCI
solution and dilute HCI) and CC14 test; reddish-brown coloration 'If
CC14 layer (IV, 15, 5).
Iodide. Chlorine water (or NaOCI solution and dilute HCI) a ld
CCl4 test; violet coloration of CCl4 layer (IV, 16, 4).
• The bench reagent usually contains excess of free acid added during 1LS
preparation in order to produce a clear solution: this may prevent the precii,i-
tation of the basic acetate on boiling. It is therefore recommended tLat
dilute NB. solution be added dropwise to the side-shelf FeCI. solution until a
slight permanent precipitate forms; the precipitate is filtered off. The filtrate
may be termed "neutral FeCI. solution."
 5] Systematic Macro Qualitative Inorganic Analysis 443
Fluoride. Silicon tetrafluoride test (heat with concentrated
H 2S04 in a test-tube) (IV, 17, 1); test 8 in VII, 16; zirconium-
alizarin-S test (IV, 17, 6).
Nitrite. Brown ring test with dilute acetic acid or with dilute
H 2S04 (IV, 7, 2) OR thiourea test (IV, 7, 9).
Nitrate. Brown ring test with concentrated H 2S04 (IV, 18, 3),
if bromide, iodide and nitrite absent.
Sulphide. Dilute H 2S04 on solid, and action of H 2S on lead or
cadmium acetate paper (IV, 6, 1).
Sulphite. Dilute H 2S04 on solid, odour of S02 and antion of
S02 on K20r207 paper (IV, 4, 1), or upon fuchsin solution (IV, 4,
10); BaOI2-Br2 water test (IV, 4,2).
Thiosulphate. Dilute H 2S04 on solid and liberation of S02
(K20r207 paper test or fuchsin solution test) and sulphur (IV, 5, 1).
Sulphate. The BaCl2 solutIOn and dilute HOI test is fairly con-
clusive. Further confirmation is obtained by reduction of [he ppt.
(BaS04) on charcoal to sulphide (test for latter with lead acetate
solution) (IV, 24, 1).
Carbonate. Action of dilute H zS04 on solid, and lime water test
(IV, 2, 1).
Hypochlorite. Action of dilute HOI and test for 01 2 evolved
(IV, 13, 4).
Chlorate. The AgNOs-NaNO z test (IV, 19. 3).
Chromate. Hydrogen peroxide test with amyl alcohol as organic
solvent (IV, 33, 4).
Arsenite. Immediate ppt. of As 2S a in dilute HOI solution (III,
11, 1) and absence of ppt. with Mg(NO a)2 reagent (III, 11, 3).
Arsenate. Action of HzS on acid solution (III, 12, 1), AgNO s
solution test in faintly acetic acid solution (III, 12, 2) and Mg(NO a)2
reagent test (III, 12, 3).
Phosphate. Ammonium molybdate test (temperature not above
40°) (IV, 28, 4).
Cyanide. Prussian blue test (IV, 8, 4) or ammonium sulphide
test (IV, 8, 16).
Thiocyanate. Ferric chloride solution test: colour discharged by
HgCl 2 solution or by NaF solution, but not by HOI (IV, 10, 6).
Acetate. Action of ethyl or of n- butyl alcohol and concentrated
H 2S04 (IV, 35, 3) OR indigo test (IV, 35, 9) using ordin,try test-
tube or ignition tube.
Oxalate. The Oa012 test and decolourisation of acidified KMn0 4
solution at about 70° is sufficiently conclusive.
444 Qualitative Inorganic Analysis [V,

V, 6. SPECIAL TESTS FOR MIXTURES OF ACID

RADICALS*
1. Carbonate in the presence of Sulphite.-Sulphites, on
treatment with dilute sulphuric acid, liberate sulphur dioxide
which, like carbon dioxide, produces a turbidity with lime (lr
baryta water. The dichromate test for sulphites is, howev,·t',
not influenced by the presence of carbonates. To detect c:;1'-
bonates in the presence of sulphites, treat the solid mixture
with dilute sulphuric acid and pass the evolved gases throll O'h
a small wash-bottle or boiling tube containing potassium li-
chromate solution and dilute sulphuric acid. The solution \' ill
be turned green and the sulphur dioxide will, at the same til I),
be completely removed; the residual gas is then tested w, ~ h
lime water in the usual manner.
An alternative procedure is to add a little powdered potn.,-
sium dichromate to the mixture and then to warm with dill' e
sulphuric acid: the evolved gas is then passed through lillie
water.
The above method can, of course, be applied in the preSel] e
of thiosulphates.
2. Nitrate in the presence of Nitrite.-The nitrite is
readily identified in the presence of a nitrate by treatment with
dilute mineral acid, potassium iodide and starch paste (or
potassium iodide-starch paper) or by means of the thiourea,
test. The nitrate cannot, however, be detected in the presen, ,)
of nitrite since the latter gives the brown ring test with ferro .;
sulphate solution and dilute sulphuric acid. The nitrite i'i
therefore completely decomposed firf!t by one of the followillg
methods:
(i) boil with ammonium chloride solution until effervescence
ceases;t
(ii) warm with urea and dilute sulphuric acid until evolution
of gas ceases; t
(iii) add a little sulphamic acid to the solution:
+
HO.S0 2·NH2 HN0 2 = N2 H 2SO, H 20 + +
The last-named is probably the simplest and most efficieJ'!'
method for the removal of nitrite in aqueous solution.
The brown ring test for nitrate can then be applied.
3. Nitrate in the presence of Bromide and Iodide.-
The brown ring test for nitrates cannot be applied in tIl"
... Full experimental details of the various tests will be found in Chapter IV.
t T,.ocu of nitrate are always formed in this reaction.
6] . Systematic Macro Qual,itative Inorganic Analysi8 445
presence of bromides and iodides since the liberation of free
halogen with concentrated sulphuric acid will obscure the
brown ring due to the nitrate. The solution is therefore boiled
with sodium hydroxide solution until ammonium salts, if
present, are completely decomposed, and the solution is then
cooled under the tap. Powdered Devarda's alloy or aluminium
powder or zinc dust is then added and the mixture gently
warmed. The evolution of ammonia, detected by its smell,
its action upon red litmus paper and upon mercurous nitrate
paper (see Section III, 36, reaction 1) indicates the preFence of
a nitrate.
An alternative method is to remove the halides by precipi-
tation with an almost saturated solution of silver sulphate
(nitrate-free) and any excess of the latter with sodium car-
bonate solution; the nitrate is then tested for in the filtrate in
the usual way (see also Section IV, 45, 4).
4. Nitrate in the presence of Chlorate.-The chlorate
interferes with the brown ring test (compare Section IV, 19,
reaction 1). The nitrate is reduced to ammonia as described
under 3; the chlorate is at the same time reduced to chloride
which may be tested for with silver nitrate solution and dilute
nitric acid.
If a chloride is originally present, it may be removed first
by the addition of saturated silver sulphate solution.
5. Chloride in the presence of Bromide and Iodide.-
This procedure involves the removal of the bromide and iodide
with potassium or ammonium persulphate in the presence of
dilute sulphuric acid. The free halogens are thus liberated,
and may be eliminated either by simple evaporation (addition
of water may be necessary to maintain the original volume) or
by evaporation at about 80 0 in a stream of air.
K 2S20 S + 2K1 = 12 + 2K2S04 ;
K 2S20 S + 2KBr + 2H2S04 = Brz + 4KHS04
Add solid potassium or ammonium persulphate to the
"Na2COa prepared solution" of the mixed halides contained in
a conical flask; strongly acidify with dilute sulphuric acid; heat
0
the flask to about 80 and aspirate a current of air through
,

the solution with the aid of a filter pump (see Fig. IV, d5, 1 in
Section IV, 45, 5) until the solution is colourless. Add more
solid persulphate or water as may be found necessary. Test
the residual colourless liquid for chloride with silver nitrate
solution and dilute nitric acid.
4,46 Qualitative Inorganic Analysis (V.
6. Chloride in the presence of Iodide (Bromide bel!\g
absent).-Acidify the "Na2C03 prepared solution" with dil!!te
nitric acid, add excess of silver nitrate solution, and filter; reJ ct
the filtrate. Wash the precipitate with dilute ammonia sl,lu-
tion and collect the washings. Add dilute nitric acid to : ile
washings; a white precipitate of silver chloride indicates . he
presence of chloride.
The separation is based upon the solubility of silver chlOJ ide
in dilute ammonia solution and the practical insolubility of
silver iodide in this reagent.
7. Chloride in the presence of Bromide (Iodide bei ng
absent).-Acidify the "Na2C03 prepared solution" with dil'.!te
nitric acid and add an equal volume of concentrated nitric aCid.
Boil for 5 minutes or until all the bromine is expelled; then" ld
silver nitrate solution. A white precipitate indicates chlOllde
present.
8. Bromide and Iodide in the presence of one anotht'r.
-The presencl'l of a chloride does not interfere with the re-
actions described below. Acidify the "Na2COa prepared solu-
tion" with dilute sulphuric acid and add 1-2 m!. of carl\(m
tetrachloride; add 1-2 drops of dilute sodium hypochlO1 te
solution* (best with a dropper), and shake; a violet colorak In
in the carbon tetrachloride layer indicates iodide. Contil.; le
the addition of the hypochlorite solution drop by drop to oxic!. le
the iodine to iodate (colourless) and shake after each additi, a.
The violet colour will disappear, and a reddish-brown colorati ,n
of the carbon tetrachloride layer, due to dissolved bromine :or
to bromine chloride BrCI), will be. obtained if a bromide is
present. If iodide alone is present, the solution will be colo:! c-
less after the violet colour has disappeared.
9. Phosphate in the presence of Arsenate.-B(11 h
arsenate and phosphate give a yellow precipitate on warmj: Ig
with ammonium molybdate solution and nitric acid, the lat 1 "r
on gentle warming (not above 40°) and the former on boili~'~.
Also both anions give a white precipitate with the magnesit. -n
nitrate reagent (or with magnesia mixture). It must also ! Ie
remembered in connexion with the precipitation of Group ! I
• The use of dilute sodium hypochlorite solution and dilute acid is t "r
more satisfactory than chlorine water. Alternatively, a solution of chl, ,r·
amine·T (15 grams per litre) may be employed; this is a source of hYI'''·
chlorous acid (and therefore of chlorine) :
CH •. C,H,.SO.NClNa + HIO ~ CH•. C.H,.SO.NH, + NaOCl
6] Systematic Jiacro Qualitative Inorganic Analysi8 447
that arsenates are only slowly precipitated by hydrogen sul-
phide in dilute acid solution.
Acidify the "Na2C03 prepared solution" with dilute hydro-
chloric acid, pass in sulphur dioxide to reduce the arsenate to
arsenite, boil off the excess of sulphur dioxide (test with potas-
sium dichromate paper), and pass hydrogen sulphide into the
solution to precipitate the arsenic as arsenious sulphide: con-
tinue the passage of hydrogen sulphide until no more precipitate
forms. Filter, boil off the hydrogen sulphide and test the
filtrate for phosphate by the ammonium molybdate test (Jr with
the magnesium nitrate reagent.
An alternative method for the elimination of arsenate is the
following. Acidify the "Na2C03 prepared solution" with dilute
hydrochloric acid and then add one-quarter of the volume of
concentrated hydrochloric acid (the total volume should be
about 10 mI.). Add 0·5 mI. of 5 per cent ammonium iodide
solution, heat to boiling and pass hydrogen sulphide into the
boiling solution until precipitation is complete (5-10 minutes).
Filter off the arsenious sulphide, and boil off the hydrogen
sulphide from the filtrate. Add dilute ammonia solution until
alkaline and excess of the magnesium nitrate reagent (or of
magnesia mixture). A white precipitate indicates the presence
of phosphate.
As 20 S + 4H1 ~ As20 S + 2H20 + 21 2;
As 2 0 S + 3H2S = As 28 s + 3H20;
212 + 2H~ ~ ill1 + 28
If the white precipitate of magnesium ammonium phosphate
be washed with a little water, and then treated on the filter
with a little silver nitrate solution containing a few ill'ops of
dilute acetic acid, a yellow coloration, due to silver phosphate,
is obtained. However, a similar reaction with the white pre-
cipitate produced by the magnesium nitrate reagent with a
mixture of phosphate and arsenate (i.e. Mg(NH4 )P04 ,6H 20 +
Mg(NH4 )As04 ,6H 20) yields a brownish-red coloration on the
white precipitate; this is due to silver arsenate.
It may be pointed out that if arsenite is also present, it may
be readily detected in the filtrate obtained by treating the
original mixture of arsenate, phosphate and arsenite with thE:)
magnesium nitrate reagent: upon acidifying with N hydro-
chloric acid and passing hydrogen sulphide, an immediate
yellow precipitate of arsenious sulphide is produced.
448 Qua,lif.4tive Inorganio Analyai8 [V,

V,7. EXAMINATION FOR METAL IONS (CATIO.'IS)

IN SOLUTION
Preparation of a solution of the solid.-Since the w! ole
scheme for the analysis of cations depends upon the reaCl :.ms
of ions, it is clear that it is first necessary to get the subst dIce
into solution. Water is first tried in the cold and thm on
warming. If insoluble in water, the following reagents art in-
vestigated as solvents in the order indicated; dilute hydrocb;, Jric
acid, concentrated hydrochloric acid, dilute nitric acid, . on-
centrated nitric acid, and aqua regia (3 volumes of concentr .ted
HOI to 1 volume of concentrated HNO a). Most substa nces
encountered in an elementary course will dissolve in e! \ her
water or dilute hydrochloric acid. If concentrated h:' lro-
chloric acid has to be used, the solution must be considel ,bly
diluted (to 0·3N) before proceeding with the analysis, other ,vise
certain cations, such as cadmium and lead, will not be pr( ipi-
tated by hydrogen sulphide. When concentrated nitric Lcid
or aqua regia is employed as the solvent, the solution mu if) be
evaporated almost to dryness, a little hydrochloric acid added,
the solution evaporated again to small bulk, and then dil uted
with water to dissolve the soluble nitrates (or chlorides). This
evaporation is necessary because the nitric acid may react ,vith
the hydrogen sulphide subsequently employed in the (,: oup
analysis.
To discover the most suitable solvent, treat portions (.1 0·2
gram* of the finely powdered substance successively wit]; 3-4
ml. of (1) water, (2) dilute hydrochloric acid, (3) concent, tted
hydrochloric acid, (4) dilute nitric acid, (5) concentrated, ,itric
acid and (6) aqua regia in the order given. Try the solu: ,ility
first in the cold and then on warming; if in doubt wheth( , the
substance or a portion of the substance has dissolved, evap, Irate
a little of the clear solution on a watch glass. If the subs! itnce
dissolves in water, proceed immediately to the test for the
metal ions. If the use of dilute hydrochloric acid results in
the formation of a precipitate, this may consist of the n ,tals
of Group I; the precipitate may either be filtered ofi and
examined for this Group, or else the original substance m" y be
dissolved in dilute nitric acid. If concentrated acid:, are
employed for dissolution, the remarks in the previous I iara-
graph must be bome in mind.
When a suitable solvent has been found, the soluti(J)I for
• This is most simply estimated by weighing out 1 gram BIld dividing it
into 5 approximately equal parts.
7] Systematic Macro Qualitative Inorganic Analysis 449
analysis is prepared with about 0·5 gram of the solid: the
volume of the final solution should not exceed 15 m!.
Before describing the general scheme for the separation of
the cations into groups, the student should take note of the
following facts:
(1) The analysis should not be conducted with large quan-
tities of the substance because much time will be spent in
filtering the precipitates and difficulty may be experienced in
washing and dissolving them. It is therefore recommended
that about 0·5 gram be employed for the analysis. After a
little experience the student will be able to judge from the
relative sizes of the precipitates the relative quantities of the
various components present in the mixture.
(2) The tests must, in the first place, be carried out in the
order given. A group reagent will separate its particular group
from those which follow it and not from those which precede it.
Thus hydrogen sulphide in the presence of 0·3N hydrochloric
acid will separate Group II from Groups IlIA, IIIB, IV and V,
but does not separate Group II from Group 1. It is most
important, therefore, that one group should be completely pre-
cipitated before precipitation of the next group is attempted,
otherwise the group precipitate will be contaminated by metals
from the preceding groups and misleading results will be
obtained.
Oxides, Hydroxides, Free Metals and Simple Alloys.-
If a solid substance is found to contain no anions, it may be an
oxide, or hydroxide, or a metal or a mixture of meta~, or an
alloy. Metals and alloys have certain characteristic physical
properties; many metals evolve hydrogen on treatment with
dilute acids. As a rule, nitric acid must be employed as solvent,
and it will then be necessary to remove the excess of nitric acid
(as already described above) before proceeding to the group
analysis.
Table S below contains full details for the separation of the
cations into the individual groups: the Notes following the
Table contain much useful information and should be read
before the separation into groups is attempted. The references
to individual Group Separation Tables are to those already
given in Chapter III.
NOTES ON TABLE S (SIMPLIFIED GENERAL TABLE FOR
SEPARATION OF CATIONS INTO GROUPS)
This Table and the Notes which follow are intended for beginners
and in consequence the various operations are given in somewhat
greater detail than in Table I (Seotion VII, 6).
US+
460 Qualitative Inorganic Analysis [V,
8] Systematic Macro Qualitative Inorganic Analysis 451
(1) If the substance was completely soluble in dilute HCI, it is
evident that no silver or mercurous salt is present. When lead is
present, the solution may be clear while hot, but PbCl 2 is deposited
upon cooling the solution, due to the slight solubility of the salt in
cold water. Lead may be found in Group II, even if it is not pre-
cipitated in Group 1.
(2) It is usually advisable in group separations to wash u. precipi-
tate with a small volume of a suitable wa,sh solution and to add the
washings to the filtrate. In the present instance cold wator or cold
very dilute HOI (say, O·5N) may be used. The precipitating re-
agent, diluted lO-lOO-fold, is generally a suit8,ble wash liquid_
Specific directions for washing precipitates will usually bf' omitted
from the present Table in order to economise space.
(3) The H 20 2 solution is added to oxidise Sn ++ to Sn ++++, thus
leading ultimately to the precipitation of SnS2 instead of the some-
what gelatinous SnS. The excess of H 20 2 should be decomposed by
boiling before passing H 2S, otherwise some S may be precipitated.
The subsequent separation of Groups IIA and lIB by means of
aqueous KOH is thus rendered more complete, since SnS2 dissolves
entirely and SnS dissolves only partially in aqueous KOH.
If it is intended to use ammonium polysulphide in the separation
of Groups lIA and lIB, the addition of H 2 0 2 is not essential since
the (NH4)2Sz will oxidise the SnS to SnS2 and the latter dissolves
as the thiostannate (NH4)2SnSS'
(4) It is important that the concentration of the HCI be approxi-
mately correct, i.e. 0·3M, before passing H 2S: with higher concentra-
tions of acid, lead, cadmium and stannous tin will be incompletely
precipitated. If the acidity is too low, sulphides of Group lIIB
(NiS, CoS and ZnS) may be precipitated.
Either of two methods may be employed to adjust the acid
concentration.
(a) Concentrate the solution (if necessary) to a volume of 10-15
ml., cool. Add concentrated NHs solution dropwise from a drop-
per (the commercial "medicine dropper" is satisfactory), with
constant stirring, until the mixture is just alkaline. Cntroduce
dilute HOI dropwise (use a dropper) until the mixture is just acid
(use litmus paper). Then add 2·0 ml. of 3N HCI (measured from
a graduated pipette or calibrated dropper) and dilute the solution
to a volume of 20 ml. with distilled water.
(b) An alternative procedure is to make use of the indicator
methyl violet (0'1 per cent aqueous solution or, better, the pur-
chased or prepared indicator paper). The following table gives the
colour of the indicator at various concentrations of acid:
Acid concentration pH Methyl violet indicntor
Neutral or alkaline 7+ Violet.
O'IN Hel 1·0 Blue.
O'25N Hel 0·6 Blue-green.
0'33N Hel 0'5 Yellow-green.
O'SON Hel 0·3 Yellow.
 L' •

Add 1 drop of methyl violet indicator solution and introducf'

dilute HOI or dilute NHs solution (as necessary) dropwise and wit},
constant stirring until the colour of the solution is yellow-green: a
blue-green colour is almost but not quite acid enough, yet it i,
acceptable for most analyses. [If the indicator paper is available,
the thoroughly stirred solution should be spotted on fresh portion~
of the paper.] It is recommended that a comparison solution con
taining, say, 10 m!. of 0·3N HOI and 1 drop of indicator be freshly
prepared: this will facilitate the correct adjustment of the acidity
A more satisfactory standard is a buffer solution prepared by
mixing 5 m!. of N sodium acetate and 10 m!. of N HOI: this has a
pH of 0·5.
(5) For the passage of H 2S into the solution, the latter is
placed in a small conical flask (one of 50 m!. capacity is suitable)
or in a boiling tube and the "pressure" method used as detailed
in Section II, 2, 7. Heat the solution almost to boiling and pass
in H 2S, whilst slowly shaking the flask with a swirling motion, until
precipitation is complete: the latter will be apparent when bubbling
either stops altogether or is reduced to a very slow rate of 1-2
bubbles per minute. Saturation is normally reached in 2-5
minutes. The best method of determining whether precipitation
is complete is to filter off a portion of the solution and test the
filtrate with H 2S. If only a white precipitate or suspension of
sulphur is obtained, the presence of an oxidising agent is indicated.
If an oxidising agent is present (e.g. a permanganate, di-
chromate or a ferric salt), as is shown by the gradual separation of
a fine white precipitate of sulphur and/or a change in colour of the
solution, it is usual to pass S02 into the hot solution until reduction
is complete, then to boil off the excess of S02 (test with K20r207
paper), and finally to pass H 2S. Arsenates, in particular, are slowly
precipitated by H 2S: they are therefore usually reduced by S02 to
arsenites and then precipitated as As 2Ss with H 2S, after prior
removal of the excess of S02 in order to avoid interaction of the
latter with H 2S and the consequent separation of S. Stannic
compounds may be very slightly reduced to the stannous state by
this treatment; the amount of reduction is, however, so small that
it may be neglected. The original solution or substance must be
tested for the valence state of the arsenic.
The objection to the use of S02 is that some sulphuric acid may
be formed, especially upon boiling, and this may partially precipitate
Pb, Sr and Ba as sulphates. Any precipitate formed in this process
should accordingly be examined for these cations: PbS04 is soluble
in ammonium acetate solution.
An alternative procedure to be borne in mind when arsenate, etc.,
is present, which does not possess the disadvantages associated with
S02 and is perhaps more expeditious, is to add 2-3 m!. of con-
centrated HOI and 0·5 m!. of 10 per cent NH4I solution. The
arsenate is thereby reduced to arsenite and upon saturation of the
8] . Systematic Macro Qualitative Inorganic Analysis 453
hot solution with H 2S under "pressure," the arsenic is completely
precipitated as As 2Sa. This reduction can be carried out after the
sulphides of the other elements have been precipitated in the
presence of 0·3N HCI.
(6) The wash liquid is prepared by dissolving 0·5 gram ofNH4NO a
in 10 ml. of water and treating this solution with H 2S; about 5 m!.
will suffice for the washing. The H 2S must be present in the wash
liquid to prevent oxidation of some of the moist sulphides to
sulphates.
(7) If the iron was originally present in the ferric state, it will be
reduced to the ferrous condition by H 2S. It must be oxidised to the
ferric state (1-2 mI. of saturated Br2 water may also be used) in
order to ensure complete precipitation with NH4CI and dilute NHs
solution. The original solution must be tested to determine whether
the iron is present as Fe++ or as Fe+++.
(8) The washing may be made with a little hot water or, better,
with 2 per cent NH4NO a solution.
(9) If the filtrate is brown or dark.coloured, Ni may be suspected.
The dark·coloured solution contains colloidal NiS, whic·h runs
through the filter paper. It may be acidified with acetic acid and
boiled until the NiS is coagulated: this may either be added to the
Group HIB precipitate or tested separately for Ni. As a general
rule the addition of macerated filter paper (e.g. in the form of a
portion of a Whatman filtration accelerator or ashless tablet) to
the suspension before filtration will lead to a clear or colourless
filtrate.
(10) The wash liquid may consist of 1 per cent NH4CI solution
containing 1 per cent by volume of ammonium sulphide solution.
Oxidation of the moist sulphides to soluble sulphates is thus con·
siderably minimised.
(11) The filtrate must be immediately acidified and concentrated
to remove H 2S. Ammonium sulphide solution on exposure to air
slowly oxidises to ammonium sulphate and would then precipitate
any barium or strontium present as BaSO.. and SrS04. Another
reason for acidifying the filtrate from Group HIB is to prevent the
absorption of CO 2 from the air with the formation of carbonate ions;
the latter would also precipitate the ions of Group IV.
(12) The initial filtrate from Group HIB will be almost saturated
with ammonium salts. This concentration of ammonium ions is
higher than is necessary to prevent the precipitation of lUg(OH)2
and it may also lead to incomplete precipitation of the carbonates
of Group IV metals. The latter effect is due to the acidic properties
of ammonium ion:
NH,+ + CO a-- ... NHa + HCO a-;
the concentration of COs-- ions upon the addition of (NH.. )2COS
would thus be considerably decreased, and incomplete precipitation
~54 Qualitative Inorganic Analysia [V,
)f Group IV may occur. For these reasons most of the ammonium
alts must be eliminated first.
Concentrated HNO s decomposes NH4Cl at a lower temperature
,han is required for its volatilisation: \
NH 4 Cl + HNO a ~ NH4 N0 8 + HCI = N sO + 2HaO + HCI
.oss by decrepitation and spirting during this operation must be
voided.
(13) Ammonium carbonate decomposes appreciably above 60°0:
(NH,)aCO a ~ 2NHa + COli + H 2 0
'he digestion also improves the filtering properties of the precipitate.
(14) Owing to the slight solubility of CaCO a, SrCO a and BaC0 3 in
)lutions of ammonium salts, the filtrate from Group IV will, when
rrese metals are present, contain minute amounts of the ions of the
lkaline earth metals. Since the Group IV metals may interfere to
limited extent with the flame tests for Na and K and also the
fa zHP04 test for Mg (if employed), it has been recommended that
1e filtrate from Group IV be heated with a little (say, 1 ml.) of
~H4hS04 solution and (NH4)zC Z0 4 solution and filtered from any
recipitate which forms. Owing to the comparatively small con-
mtration of ammonium salts, this is generally unnecessary if the
wcedure described in Table VII (Section III, 37) is adopted.

,9. Modification of the analysis in the presence of phos-

hate.-Certain anions, which include phosphate, fluoride,
)rate, silicate and also those derived from organic acids such
; acetate and oxalate, interfere with the cation analysis after
roup II. Thus the presence of phosphate, fluoride, borate
. oxalate ions will cause the metals of Groups IIIB and IV
ld also Mg to precipitate when the solution is made ammo-
acal in Group IlIA. The various interfering anions and their
moval or elimination are discussed in detail in Chapters VII
ld VIII. It is unlikely that the student will encounter any
, the interfering anions in elementary analysis with the pos-
)le exception of phosphate. The manner of removal of
lOsphate is therefore given in the following table (Table P)
an illustration of the procedure to be adopted in dealing
th an important interfering anion. The student will appre-
Lte that the phosphate separation need not be made even if
)4 --- has been shown to be present (e.g. by the ammonium
)lybdate test) if no precipitate is obtained in Group IIIA.
ith NH4 CI and aqueous NH 3 ) and also when it is known that
'oup IV and Mg are absent.
 10] Systematic Macro Qualitative Inorganic Analysi8 455
V,9. Table P.-Phosphate Separation Table

Boil the filtrate from Group II until free from H,S, add a few drops of
concentrated RNO. (or 1-2 mi. of bromine water) and boil gently for
I minute. Test a small portion for phosphate with ammonium molyb.
date and nitric acid, and a further portion for the presence of Groups
lIlA, IIIB, IV or Mg by the addition of NE.CI Hnd Nfl. solution. If
both tests are positive, proceed as follows.
Adjust the volume of the solution to 10 ml. (1). Add 0,5-1 gram of
solid NE.Cl, stir until dissolved, then add the zirconium nitrate reagent
slowly and with stirring until precipitation is complete (2): a large eXCfSB
of the reagent must be avoided. Heat the contents of the test· tube or
small conical flask to boiling and stir with a glass rod to prevent bumping.
Filter through a Whatman No. 32 fIlter paper (3): wash the ppt. with a
little hot water and combine the washings with the filtrate.

Residue. Filtrate. Test if all the phosphate has been precipi.

Zirconium tated by the addition of a drop of the zirconium nitrate
phosphate. reagent: if no ppt. forms, all the phosphate has been
Reject. removed. Add about 0·5 gram of solid NH.Cl, heat to
boiling. add a slight excess of dilute NE. solution (i.e.
until the odour of ammonia is permanent in the boiling
solution), boil for 2--3 minutes and filter.
I-----------------------------~-----------
Residue. Examine for Group IlIA. Filtrate.
The excess of Zr will be found in the Examine for
residue after treatment with R.O. and Groups IIIB,
NaOR solution (or with sodium per. IV and V.
borate NaBO.,4R.O and boiling), and
will accompany any Fe, if present.

Notes. (1) It is essential that the acidity with respect to hydro-

chloric acid should not exceed N, otherwise a turbid supernatant
liquid is obtained and the removal of phosphate is not quite complete.
Test with methyl violet or any other suitable indicator (brilliant
cresyl blue, cresol red, etc.).
(2) It is important that the excess of the zirconium nitrate re-
agent should not exceed 25 per cent, otherwise a turbid supernatant
liquid will be obtained; this turbidity cannot be removed by filtra-
tion or centrifugation. It is best, therefore, to add the zirconium
nitrate solution slowly and with stirring until precipitation appears
complete, heat just to boiling, filter, and test the filtrate with the
reagent, etc.
(3) The addition of half a Whatman filtration accelerator (or a
little filter paper pulp) assists filtration; the precipitate must be
washed thoroughly with hot water.

V, 10. ANALYSIS OF A LIQUID (SOLUTION)

If a liquid is supplied for analysis, proceed as follows:
(1) Observe the colour, odour and any special physical
properties.
(56 Qualitative Inorganic Analysis [V,
(2) Test its reaction towards litmus paper.
(a) The solution is neutral: free acids, free bases, acid salts,
and salts which give an acid or alkaline reaction owing
to hydrolysis, are absent.
(b) The solution reacts alkaline: this may be due to ! he
hydroxides of the alkali and alkaline earth metals, to
the carbonates, sulphides, hypochlorites and peroDi les
of the alkali metals, etc.
(c) The 8olution reacts acid: this may be due to free acids,
acid salts, salts which yield an acid reaction because of
hydrolysis, or to a solution of salts in acids.
(3) Evaporate a portion of the liquid to dryness on 1 he
water bath (use a porcelain dish and stand it on a beaker half
filled with water, the latter being heated by a Bunsen burner);
carefully smell vapours evolved from time to time. If a solid
residue remains, examine as detailed above for a solid au b-
stance. If a liquid remains, evaporate cautiously on a wire
gauze in the fume cupboard; a solid residue should then be
examined in the usual way. If no residue remains, then i he
liquid consists of some volatile substance which may be wai "r
or water containing certain gases or volatile substances, su, h
as CO 2, NH a, S02, H 2S, HCI, HBr, HI, H 2 0 2 or (NH4)2C() j,
all of which can be readily detected by special tests. It IS
best to neutralise with sodium carbonate and test for aCid
radicals (anions).
 CHAPTER VI

INTRODUCTION TO SYSTEMATIC SEMIMICRO

QUALITATIVE INORGANIC ANALYSIS

VI, 1. Preliminary Discussion.-It is assumed that the

student is already familiar with the operations (ignition tests,
blowpipe tests, flame tests, borax bead tests, precipitation,
filtration, evaporation, etc.) described in Sections II, 1 and 11,2.
A detailed description of semimicro apparatus and of semimicro
analytical operations is given in Section II, 3. The student
should read this carefully and thus acquire a general knowledge
of semimicro technique. To secure the introductory practical
experience the following course of instruction may be followed.
Reactions are normally carried out in 4 mI. test-tubes or in
3 ml. centrifuge tubes, unless otherwise stated. The solutions
employed in testing for cations or anions contain 10 mg. of
cation or anion per ml. For purposes of calculation a drop of
solution may be assumed to have a volume of 0'05 wI.: this
will help in rough computations as to volumes required in
adding excess of reagents, etc.
For the cations, a limited number of preliminary reactions
should be studied first, followed by an analysis of a mixture or
solution containing a member or members of each group. This
will give practical experience in the routine operations of semi-
micro analysis and also provide practice from the very outset
in the use of Group Separation Tables. Particular attention
should be paid to:
(i) the exact experimental conditions of the reaction;
(ii) the colour and physical characteristics (e.g. whether
crystalline, amorphous or gelatinous) of each precipitate; and
(iii) the solubility of each precipitate in excess of precipitant,
or in solutions of other reagents.
The student should, as far as possible, represent the chemical
reactions by ionic equations and then check the equations
against the molecular equations given in Chapters III and IV.
In this way excellent practice will be obtained in writing and
balancing equations, and also help to impress the reactions
upon the memory.
15* ~7
458 Qualitative Inorganic Analysis [VI,
To illustrate the manner in which the simple reactions should
be carried out, a few selected examples will be given. \
LEAD ION, Pb++
1. Dilute Hydrochloric Acid. Place 2 drops of the est
solution in a 3 ml. centrifuge tube, and add 2-3 drops of d .:Ite
HCl. Note the colour and characteristics of the precipi 1 ete.
Centrifuge the mixture, balancing the tube with am·' ller
similar tube containmg an approximately equal volume of
water. Remove the supernatant liquid, termed the c(·tri-
jugate, by means of a capillary dropper to another tube, "nd
test with a further drop of dilute HCI to ensure that pre· :pi-
tation is complete: if this is so, discard the solution. 'J; oat
the precipitate, usually termed the residue, with 2 drop of
water, stir and centrifuge. Reject the solution, called j he
washings. Add 5-6 drops of water to the washed residue, ;,tir
and place the tube containing it in the rack in the boi! I ng
water bath. Stir frequently whilst heating. Observe that . he
precipitate dissolves completely. Cool the clear solution I : a
stream of water from the cold water tap: observe that col(Jur-
less crystals of PbCl2 separate.
3. Dilute Sulphuric Acid. To 2 drops of the test solut "m
in a 3 ml. centrifuge tube or 4 ml. test-tube, add 2-3 drop, of
dilute H 2S04 , Centrifuge: remove the centrifugate and i, 'st
for complete precipitation with 1 drop of dilute H 2S04 , W:l:;h
the precipitate with 2-3 drops of water, centrifuge and discIll'd
the washings . Now introduce 2-3 drops of ammonium acet,· te
solution and stir: the precipitate will dissolve.
4 Potassium Chromate Solution. Treat 2 drops of tile
test solution with 1-2 drops of K 2Cr04 solution. Note the
formation of a yellow precipitate. Centrifuge and wash. Add
2 drops of dilute acetic acid to the precipitate and stir: n(': e
that the precipitate does not dissolve.
The above examples should suffice to give a general con-
ception as to how the various reactions should be performc 1.
In the reactions involving the passage of hydrogen sulphi, II)
into a solution, the apparatus depicted in Fig. II, 3, 17 should
be used.
VI, 2. Abbreviated Course of Instruction.-The followill~
preliminary reactions, etc., should be carried out by the studen,
In the case of anions, those marked with an asterisk may 1,,·
omitted when an elementary course is required: the fin; I!
decision should be made by the teacher.
2] Systematic Semimicro Qualitative Inorganic Analysis 459

REACTIONS OF THE CATIONS

Pb++, Section III, 2, reactions 1, 2, 3, 4; blowpipe test,
Hg 2 ++, Section 111,3, reactions 1, 6, 7.
Ag +, Section III, 4, reactions 1, 2, 3; blowpipe test.
Identification of a metal in the solution supplied by the teacher
by means of Table SMI (Section III, 5).
Hg++, Section III, 6, reactions 1, 2, 3; dry test.
Bi+++, Section III, 7, reactions 1, 3, 5, 6, 10.
Cu++, Section III, 8, reactions 1, 2, 3, 4, 5, 8; dry test.
Cd++, Section 111,9, reactions 1, 3, 4; dry test.
Identification of a metal or metals in the solution supplied by
means of Table SMIIA (Section III, 10).
As (ous), Section III, 11, reactions 1, 2, 3.
As (ic). Section III, 12, reactions 1, 2, 3, 4,
Sb (ous), Section III, 14, reactions 1, 2, 8.
Sn ++, Section III, 16, reactions 1, 2, 3.
Sn++++, Section III, 17, reactions 1, 3, 4,
Identification of a metal or metals in the solution supplied by
means of Table SMIIIA (Section III, 18).
Fe++, Section III, 19, reactions 1, 2, 3, 4, 6, 7, 8.
Fe+++, Section III, 20, reactions 1, 2, 3, 4, 5, 6, 10.
Al+++, Section III, 21, reactions 1, 2, 3, 7; dry test.
Cr+++, Section III, 22, reactions 1, 2, 3, 6; dry test (iii),
Identification of a metal or metals in the solution supplied by
means of Table SMIV (Section III, 23).
Co++, Section III, 24, reactions 1, 2, 3, 5, 6, 7; dry test (ti),
Ni++, Section III, 25, reactions 1, 2, 3, 6, 7, 8; dry test (ii),
Mn ++. Section III, 26, reactions 1, 2, 3, 5, 7; dry test (ii).
Zn++, Section III, 27, reactions 1, 2, 3, 6, 8, 9; dry test.
Identification of a metal or metals in the solution supplied by
means of Table SMV (Section III, 28).
Ba++, Section III, 29, reactions 1, 2, 3, 4, 6; dry test.
Sr++, Section III, 30, reactions 1, 2, 3, 5, 6; dry test.
Ca ++, Section III, 31, reactions 1, 2, 3, 5, 6; dry test.
Identification of a metal or metals in the solution supplied by
means of Table SMYI (Section III, 32).
Mg++, Section III, 33, reactions 1, 2, 3, 5, 7, 8; dry test,
K+, Section III, 34, reactions 1, 2; dry test.
Na +, Section III, 35, reaction 1; dry test.
NH4 +, Section 111,36, reactions 1, 3, 7; dry test.
Identification of a metal or metals in the solution supplied by
means of Table SMVn (Section III, 37),
460 Qualitative Inorganic Analysis [VI,
REACTIONS OF THE ANIONS
COs--. Section IV, 2, reactions 1, 2.
HCO s-. Section IV, 3, reactions (i), (ti), (iii).
S03--' Section IV, 4, reactions 1, 2, 4, 5, 9, 10.
S203--' Section IV, 5, reactions 1, 2, 4, 6, 8.
S--, Section IV, 6, reactions 1, 2, 3, 5, 6.
N0 2 - , Section IV, 7, reactions 1, 2, 7, 10.
*CN-. Section IV, 8, reactions 1, 2, 3, 4, 6.
*SCN-, Section IV, 10, reactions 1, 2, 3, 6, 8.
CI-, Section IV, 14, reactions 1, 2, 3.
Br-, Section IV, 15, reactions 1, 2, 5, 8.
r. Section IV, 16, reactions 1, 2, 4, 7, 9.
F-, Section IV, 17, reactions 1, 2, 6.
NO s-' Section IV, 18, reactions 1, 2, 3, 4. ,---
*CIOs-, Section IV, 19, reactions 1, 2, 3, 6, 7, 10.
*B40 7 - - (borate), Section IV, 23, reactions 1, 2, 3, 8.
S04--' Section IV, 24, reactions 1, 2, 5, 6.
P04 - - - . Section IV, 28, reactions 1, 3,4,5,6.
Cr04- - . Section IV, 33, reactions 1, 2,3,5,6.
*C~H30~- (acetate). Section IV, 35, reactions 1, 2, 3, 4, 6.
*C2 0 4-- (oxalate). Section IV, 37, reactions 1, 2, 3, 4, 5.

VI, 3. Systematic Analysis. General Considerations.-

The student must realise that the object of qualitative analysis
is not simply to detect the constituents of a given mixturf';
an equally important aim is to ascertain the approximatu
relative amounts of each component. For this purpose abom
0·2 gram of material is usually employed for the analysis: tl",
relative magnitudes of the various precipitates will provide 'I
rough guide as to the proportions of the constituents present.
Every analysis is divided into three parts:
(1) The preliminary examination. This includes preliminary
examination by dry tests, examination of the volatile products
with sodium hydroxide solution (for ammonium), and with
dilute and concentrated sulphuric acid (for i1cid radicals or
anions). A special preliminary test for nitrate and/or nitrite
is also made here.
(2) The examination for acid radicals (or anions) in solution
(3) The examination for metal ions (or cations) in solution.

VI, 4. PRELIMINARY TESTS

Test (i). Heatin~ in a closed tube.-Place about 5 mg.
of the substance in a dry ignition tube (70 X 4:-5 mm.) so that
none of it remains adhering to the sides and heat cautiously
with a semimicro burner; the tube should be held in an almost
4] Systematic Semimicro Qualitative Inorganic Analysis 461

Observ<Uwn InjMen«.
(a) A gas or vapour is evolved.
1. Water is evolved; test with litmus Compounds with water of
paper. crystallisation (often accom-
panied by change of colour),
ammonium salts, acid salts
and hydroxides.
The water is alkaline. Ammonium salts.
The water is acid. Readily decomposable salts of
strong acids.
2. Oxygen is evolved (rekindles a glow. Nitrates, chlorates and certain
ing splint). oxides.
3. Nitrous oxide (rekindles a glowing Ammonium nitrate or nitrate
splint) and steam are evolved. mixed with an ammonium
salt.
4. Dark brown or reddish fumes (oxides Nitrates or nitrites of heavy
of nitrogen); acidic in reaction. metals.
5. Carbon dioxide is evolved (lime water Carbonates or bicarbonates.
is rendered turbid).
5. Ammonia is evolved (turns red litmus Ammonium salts.
paper blue).
7. Sulphur dioxide is evolved (odour of Normal and acid sulphites;
burning sulphur; turns potassium di- thiosulphates; oerta,in sul-
chromate paper green; decolourises phates.
fuchsin solution.)
8. Hydrogen sulphide is evolved (odour Hydrated sulphides or sul·
of rotten eggs; turns lead acetate phides in the presence of
paper black or cadmium acetate water.
paper yellow).
9. Chlorine is evolved (yellowish-green Unstable chlorides, e.g. of
gas; bleaches litmus paper; turns copper; chlorides in the
potassium iodidlrStarch paper blue); presence of oxidising agents.
very p0i8onoU8.
10. Bromine is evolved (reddish-brown Sources similar to chlorine.
vapour; choking odour; turns fluo-
rescein paper red).
11. Iodine is evolved (violet vapours Free iodine and certain
condensing to black crystals). iodides.

(b) A sublimate is formed.

1. White sublimate.* Ammonium and mercuric
salts; AssO I ; Sb,Oa'
2. Grey sublimate, easily rubbed to Hg.
globules.
3. Steel-grey sublimate; garlic odour. As.
4. Yellow sublimate. S (melts on heating), As,S"
HgI. (red when rubbed with
a glass rod).

* If a white sublimate forms, heat with four times the bulk of anhydrous
Na 2CO. and a little KeN in an ignition tube. A grey mirror, convertible
into globules on rubbing with a glass rod, indicates Hy (Note: Hg vapour
is very poi8onou8); a brownish·black mirror, yielding a white Hublimate
and an odour of garlic when heated in a wide tube, indicates As; ammonia
evolved (test with mercurous nitrate paper) indicates ammonium salt8.
462 Qualitative Inorganic AnalY8i8 [VI.
horizontal position. Raise the temperature gradually anI l
carefully note a.ny changes which take place.

Test (ii). Charcoal block reductions.

(a) Heat a little of the substance (say, 2-3 mg.) in a smai:
cavity in a charcoal block in a blowpipe flame.

Observation Inference
1. The substance decrepitates. Crystalline salts, e.g. NaCI, KC!. '
2. The substance deflagrates. Oxidising agents, e.g. nitrates,
nitrites and ohlorates.
3. The substance is infusible or incan- Apply test (b) below.
descent, or fol'lIlll an incrustation upon
the charcoal.

(b) Mix the substance (3-5 mg.) with twice its bulk of an-
hydrous sodium carbonate, place it in a cavity in a charcoal
block, and heat in the reducing flame of the blowpipe.

Observation Inference
1. Incrustation without metal:
White, yellow when hot. ZnO.
White, garlic odour. As.O •.
Brown. CdO.
2. Incrustation with metal:
White incrustation; brittle metal. Sb.
Yellow incrustation; brittle metal. Bi.
Yellow incrustation; grey and soft Pb.
metal, marks paper.
3. Metal without incrustation:
Grey metallic particles, attracted by Fe, Ni, Co.
magnet.
Malleable beads. Ag and Sn (white); Cu (rod
flakes).

Test (iii). Flame colorations.-Place 2-3 milligrams of

the substance in a depression of a spot-plate, moisten with a
few drops of concentrated hydrochloric acid, and introduce a
little of the substance on a clean platinum wire into the base
of It non-luminous flame of a semimicro burner. Alternatively,
dip the platinum wire into concentrated hydrochloric acid con-
tained in a depression of a spot plate and then into the sub-
stance; sufficient will adhere to the platinum wire for the test
1:.0 be carried out.
 4) Systematic Semi micro Qualitative Inorganic AnalY8is 463

Observation Inference
Persistent golden-yellow flame. Na.
Violet (lilac) flame (crimson through K.
cobalt-blue glass).
Brick.red (yellowish-red) flame. Ca.
Crimson flame. Sr.
Yellowish-green flame. Ba.
Livid-blue flame (wire slowly corroded). Pb, As, Sb, Bi, Cu.

The sodium flame masks that of other elements, e.g. that of

potassium. Mixtures can be readily detected with a direct-
vision spectroscope (see Section II, 1, 4). A less delicate
method is to view the flame through two thicknesses of cobalt-
blue glass, whereby the yellow colour due to sodium is masked
or absorbed; potassium then appears crimson.
Test (iv). Borax bead reactions.-Make a borax bead in
a loop of platinum wire by dipping the hot wire into borax and
heating until colourless and transparent. Bring a minute
quantity of the substance into contact with the hot bead and
heat in the outer or oxidising flame. Observe the colour when
the bead is hot and also when it is cold. Heat the bead in the
inner or reducing flame and observe the colour in the hot and
cold states. Coloured beads are obtained with compounds of
copper, iron, chromium, manganese, nickel and cobalt; the
most characteristic result is for cobalt.

Oxidising flame Reducing flame .'lfetal

1. Green when hot; blue Colourless when hot, Cu.
when cold. opaque-red when cold.
2. Yellow, hot and cold. Green, hot and cold. Fe.
3. Dark yellow when hot, Green, hot and cold. Cr.
green when cold.
4. Violet (amethyst), hot and Colourless, hot and cold. Mn.
cold.
5. Blue, hot and cold. Blue, hot and cold. Co.
6. Reddish-brown when cold. Grey when cold. Ni.

Test (v). Test for ammonium radica1.-Mix 4-5 mg. of

the substance with about 0·2 ml. (say, 4-5 drops) of sodium
hydroxide solution in a semimicro test-tube, introduce a Pyrex
filter tube carrying a strip of red litmus paper and place the
assembly (Fig. II, 3, 19, a) in the hot water rack (Fig. II, 3, 13).
The evolution of ammonia, detected by its action upon the
reagent paper, indicates the presence of an ammonium salt.
.464 Qualitative Inorganic Analysis [VI,
Filter paper moistened with mercurous nitrate solution may alse be
used: this is blackened by ammonia. The mercurous nitrate reag"nt
contains an exces"l of free nitric acid; it is advisable, therefore, to ,. ld
sodium carbonate solution dropwise and with stirring to about 1 •• tI.
of mercurous nitrate solution until a slight permanent precipitat,· is
produced: the solution is centrifuged and the centrifugate is emplo; ··d
for the preparation of mercurous nitrate paper.
Alternatively, drop.reaction paper treated with 2-3 drops of 5 l"Jr
cent tannic acid solution and 2-3 drops of 20 per cent silver nitrate
solution may be used: it is blackened by ammonia.

Note. Sodium hydroxide is a dangerous substance because of j t s

destructive action upon the eyes. Great care should be taken that
the test. tube containing the hot sodium hydroxide solution, pH r·
ticularly in test (vi), is directed away from the eyes of the obserVt'r
and his near neighbours. The solution, when heated directly, ha~ :t
tendency to "bump."
Test (vi). Test for nitrate (or nitrite).-H ammonium i~
found, transfer the solution from test (v) with the aid of 0·:)
m!. of water to a semimicro boiling tube (or crucible), add 0.:,
m!. of sodium hydroxide solution and evaporate down to :t
volume of about 0·2 mI.-this treatment completely decomposes
the ammonium salt. Transfer the residue to a semimicro test-
tube, rinse the vessel with 0·5 m!. of sodium hydroxide solution
and add this to the contents of the test-tube. Then add 10
mg. of Devarda's alloy (or of aluminium powder or thin foil),
introduce a Pyrex filter tube provided with a loose plug of
cotton wool at the lower end and containing a strip of red
litmus paper or mercurous nitrate paper (Fig. II, 3, 19, a),
and place the assembly in the hot water rack. If frothing
occurs, remove the apparatus from the water bath until the
vigorous reaction has subsided.
If ammonium is absent, add about 10 mg. of Devarda's
alloy (or of aluminium as powder or thin foil) and 0·2-0·3 ml.
of sodium hydroxide solution to the reaction mixture from
test (v), introduce the filter tube carrying the reagent paper
and proceed as above.
If ammonia is evolved, as detected by its action upon red
litmus paper or upon mercurous nitrate paper, the presence of
a nitrate or nitrite is indicated. Nitrite will also be detected
in the reaction with dilute sulphuric acid {see test (vii)}: if
nitrite is absent, the presence of nitrate is established.
It must be emphasised that both the mercurous nitrate paper test
and the tannic acid-silver nitrate paper test is not applicable in the
presence of arsenites. Arsenites are reduced under the above conditions
to arsine, which also blackens the test papers.
4] Systematic Semimicro Qualitative Inorganic Analysis 465
Test (vii). Action of dilute sulphuric acid.-Treat 5-10
mg. of the substance in a semimicro test-tube with about
0'3-0,5 ml. of 2N sulphuric acid and note whether any reaction
takes place in the cold (indicated by 0). Heat the nlixture
on a water bath and observe the effect produced.

Observation Inference

1. Colourless gas is evolved with effervescence; CO. from carbonate or

gas is odourless and produces a turbidity bicarbonate.
when passed into lime water (see Fig. 11,3,
19). (0)
2. Nitrous fumes evolved; reCOgnised by red- NOs from nitrite.
dish-brown colour and odour. (0)
3. Yellowish-green gas evolved; suffocating Cl 2 from hypochlorite.
odour, reddens then bleaches litmus paper,
also turns starch-KI paper blue; very
poisonou8. (0)
4. Colourless gas evolved with suffocating SO 2 from sulphite.
odour; turns filter paper moistened with
K SCr.0 7 solution green; decolourises fuchsin
solution.
5. Colourless gas evolved; gives above tests for S02 and S from thio-
SOl; sulphur is deposited in the solution. sulphate.
6. Colourless gas evolved; odour of rotten eggs; H.S from 8ulph7·de.*
blackens filter paper moistened with lead
acetate solution; turns cadmium acetate
paper yellow.
7. Odour of vinegar. H.C.H.O. fr l) m
acetate.
8. Colourless gas is evolved; rekindles glowing O. from peroxid68 or
splint. per-salts of alkali and
alkaline earth metals.
9. Colourless gas evolved; odour of bitter HCN from cyan,ide or
almonds, t highly poisonous. from solublefe,-ri- and
ferro-cyanidBB.
10. Upon boiling, yellow solution formed and SO" etc., from thio-
SO. (fuchsin solution decolourised, etc.) cyanate.
evolved.

Test (viii). Action of concentrated sulphuric acid.-

Treat 5-10 mg. of the substance in a semimicro test-tube with
0·3-0·5 ml. of concentrated sulphuric acid. If no reaction
occurs in the cold, place the tube in the hot water rack. (If
* Many sulphides, especially native ones, are not affected by dilme H 2SO«;
some H 2 S is evolved by warming with concentrated HCI alone or with a
little tin.
t If cyanide is suspected, gently warm (water bath) 5 mg. of tha mixture
with 5 drops of 2N H 2SO, in a semimicro test-tube carrying over the mouth
a piece of filter paper moistened at the centre with 1 drop of dilute NaOH
solution. After 2 minutes, treat the drop on the paper with 1 drop of FeSO,
solution, warm and add a drop or two of 6N HCI. A blue colour indioates
the presence of a cyanide. For another test, ;100 Section IV, 8, r~8Ction 1.
Merourio oyanide is attacked slowly.
 466 Qualitative Inorganic Analysis [VI,
chlorate is suspected from the preliminary charcoal reductj, >11
test to be present, use not more than 5 mg. for this test, as an
explosion may result on warming.)
If the substance reacted with dilute sulphuric acid, ti,e
addition of the concentrated acid may result in a vigoro','!
reaction and rapid evolution of gas, which may be accompani' >,1
by a very fine spray of acid. In such a case it is best to ad'l
dilute (2N) sulphuric acid from a capillary dropper to anoth 'r
portion of the substance until action ceases, and then to a(:d
1 ml. of concentrated sulphuric acid.

Observation Inference
1. Colourless ga.s evolved with pungent odour HCl from chloride.
and which fumes in the air; white fumes of
NH,Cl in contact with glass rod moistened
with concentrated NH. solution; Cl. evolved
on addition of MnO. (reddens then bleaches
litmus paper).
2. Ga.s evolved with pungent odour, reddish HBr and Br 2 from
colour and fumes in moist air; on addition bromide.
of MnO. increa.sed amount of red fumes with
odour of Br. (fumes colour filter paper
moistened with fluorescein solution red).
3. Violet vapours evolved, accompanied by HI and I. from iodide,
pungent acid fumes, and often SO 2 and even
H.S.
4. Yellow gas evolved in the cold with charac· CIO. from chlorate.
teristic odour; explosion or crackling noise
on warming gently (DANGERI).
5. "Oily" appearance of tube in cold; on warm· HF from fluoride.
ing, pungent ga.s evolved, which corrodes the
glass; if moistened glass rod introduced into
the vapour, a gelatinous precipitate of hy-
drated silica is deposited upon it. -
6. Pungent acid fumes evolved, often coloured HNO s and NO. from
brown by NO.; colour deepens upon addition nitrate.
of copper turnings (if nitrite absent).
7. Yellow coloration in cold; upon warming, COS, SO. and S from
vigorous reaction, COS (burns with blue thiocyanate.
flame), SO~ (decolourises fuchsin solution) and
free S produced.
8. Colourless gas evolved; burns with a blue CO from formate.
flame;* no charring (very poisonous).
9. Colourless gas evolved; renders lime water co and CO 2 from
turbid and may also burn with a blue flame; oxalate.
no blackening.

* The burning splint should be introduced into the tube; the application
of a flame to the mouth of the tube frequently fails to ignite the ga.s owing
to its dilution with air in the tube.
5J SY8tematic Semimicro Qualitative Inorganic AnalY8i8 467

VI, 5. EXAMINATION FOR ACID RADICALS

(ANIONS) IN SOLUTION
The preliminary tests (vii) and (viii) with dilute sulphuric
acid and with concentrated sulphuric acid win have provided
useful information as to many acid radicals present. For more
detailed information, it is necessary to have a solution contain-
ing all (or most) anions free from heavy metal ions. 'J 'his is
best prepared by boiling the substance with concentrated
sodium carbonate solution; double decomposition occurs (either
partially or completely) with the production of the insoluble
carbonates* of the metals (other than alkali metals) and the
soluble sodium salts of the anions, which pass into solution.
Thus, if the unknown substance is the salt of a bivalent metal
M and an acid RA, the following reaction will occur:
MA2 + Na2COa ~ MCOa + 2NaA
The carbonate MCO s is insoluble and the sodium salt NaA will
pass into solution whether MA2 is soluble in water or not.
Preparation of solution for testing for anions.-Boil 200
mg. of the finely divided substance or mixture with 2·5 m!. of
a saturated solution of pure sodium carbonatet (prepared from
0·4 gram of anhydrous sodium carbonate and 2·5 mL of distilled
water) for 5-10 minutes in a 10 mL conical flask with a funnel
in the mouth to reduce the loss by evaporation.t Transfer,
with the aid of about 0·5 m!. of water, to a 4 m!. semimicro
test-tube and centrifuge. Remove the centrifugate to another
test-tube: add 1 mL of hot distilled water to the residue, stir
and add the clear washings to the original centrifugate; the
total volume should be 3-4 mL The sodium carbonate extract
will be termed the "N a 2 CO a prepared solution." r se the
solution to carry out the following tests.
1. Sulphate test.-To 5 drops of the "Na2C03 prepared
solution" in a 4 m!. test-tube add dilute hydrochloric acid until
acid (test with litmus paper) and then add 3 drops in excess.
Place in the hot water rack for 5 minutes to expel carbon di-
... Certain carbonates, initially formed, are converted into insoluble basic
carbonates or into hydroxides.
t It is essential to use pure sodium carbonate; the A.R. solid is satisfactory.
Some "pure" samples may contain traces of sulphate or chloride: th<3 absence
of these impurities should be confirmed by a bhtnk experiment.
t If no precipitate is ohtained, the substanco is virtually free from heavy
metals, and the sodium carbonat~ t.reatrrwnt may be omitwd if more of the
solution is required.
 468 Qualitative Inorganic Analysis [VI,
- oxide completely, and then add 2-3 drops of barium chlonde
solution. A white precipitate (BaS04) shows the presenc!' of
sulphate. "
2. Test for reducing agents.-Acidify 5 drops of i he
"Na 2C0 3 prepared solution" with dilute sulphuric acid and
add 3 drops of dilute sulphuric acid in excess. Add 2-3 drops
of O'02N potassium permanganate solution (prepared by dilu-
tion of 1 drop of O·lN KMn04 with 4 drops of water and mix! ng
well). Bleaching of the permanganate solution indicates he
presence of one or more of the following reducing aniolls:
8ulphite, thiosulphate, 8ulphide, nitrite, bromide, iodide (I nd
arsenite. If the permanganate is not decolourised, place i he
tube in the hot water rack for several minutes and observe 1 he
result. If the reagent is bleached only on heating, the presell <)e
of oxalate is indicated. A negative test shows the absence of
the above anions.

3. Test for oxidising agents.-Acidify 5 drops of 1 ile

"Na2C03 prepared solution" cautiously with concentrated
hydrochloric acid and add 2 drops in excess, followed by ;) 5
drops of the manganous chloride reagent. Place in the b ()t
water rack for 1 minute. A brown (or black) coloration In-
dicates the presence of nitrate, nitrite, chlorate or chromate. A,
negative test indicates the absence of the above oxidising
anions except for small amounts of nitrates or nitrites. If
reducing anions have been found, the test is inconclusive.
Note. The reagent consists of a saturated solution of manganO!IS
chloride, MnCI 2 ,4H 2 0, in concentrated hydrochloric acid. Its acti, '11
depends upon its conversion by even mild oxidising agents to a dark-
brown coloured manganic salt, probably containing the complpx
[MnClar- or [MnCI4 r ions.

4. Tests with silver nitrate solution.-Sulphide, cyanide

and sulphite interfere in tests with silver nitrate solution, hence
if any of these anions was detected in the preliminary test with
dilute sulphuric acid, it must be removed first as follows.
Acidify 1 ml. of the "Na2COa prepared solution" with dilute
acetic acid (use litmus paper) and boil gently in a small conical
flask or crucible in the fume cupboard to expel H 2S, HCN or
S02 (1-2 minutes). It is important that the solution be acid
throughout. Centrifuge, if necessary, and allow to cool. If
the volume has been reduced appreciably, add water to restore
the original volume (solution S).
5] Systematic Semimicro Qualitative Inorganic Analysis 469

Acidify 1·0 ml. of the "Na.CO. prepared solution" cautiously with dilute
RNO, (use litmus paper). Determine the total volume of the acidified
solution (or of solution S) with the aid of a small measuring cylinder or
calibrated 2 ml. pipette, add one·tenth of the volume of concenl;rated
RNO. and stir for 10-15 seconds. Then add a few drops of AgN0 3
solution with stirring. If a precipitate forms, place the test·t].;be or
centrifuge tube in the hot water rack and add AgNO. solution slowJy and
with stirring until precipitation is complete. Centrifuge and wash with
a few drops of N HNO •.

Residue. Centrifugate. Add 3-4 drops of AgNO. solution, then

AgCI-white. 1-2 drops of 20% NaNO. solution (prepared from the A.R.
AgBr-pale solid) and stir. If a white ppt. (AgCI) forms, chlorate is
yellow. present: continue the addition of NaNO. solution drop.
AgI-yellow. wise until precipitation is complete. [If no ppt. forms,
[AgSCN- do not add more NaNO. solution.} Centrifuge, if neces-
White.] sary, and wash with 2 drops of N RNO •.

Residue. Centrifugate. Add NaOH solution drop-

AgCI wise and with vigorous stirring until the
derived solution is just neutral to litmus or, better,
from barely alkaline to nitrazine yellow indicator
AgCIO •. (1); then add 2-3 drops of dilute acetic acid
and 5 drops of AgNO. solution. Roat to
about 80°0 in the water bath (2). If a per-
manent ppt. forms, add more AgNO. solution
until precipitation is complete. Centrifuge,
and wash with a few drops of hot water.

Residue (3). Centrifu~ate.

Ag.PO.-yellow. Reject.
Ag.AsO.-brownish.red.
Ag.AsO.-yellow.
Ag.C.O.-white.

Notes. (1) It is essential that the solution be just neutral to

litmus or, at most, barely alkaline; the latter will be indicated by
a very slight brown opalescence (due to Ag 2 0) obtained after
shaking. If much brown silver oxide separates, it will re-dissolve
only with difficulty.
The introduction of 1 drop of nitrazine yellow indicator into the
solution is to be preferred. (This indicator covers the pH range
5·5-7·2 and the colour change is from yellow to blue.) The addition
of NaOH solution is continued until the solution just assumes a pale
blue colour.
(2) Silver acetate is soluble in hot water and is thus held in
solution.
{3} If chromate is present (yellow or orange solution), it will be
reduced by the NaN0 2 treatment and will be precipitated here
as green chromic hydroxide. Chromate is readily detected in the
 470 Qualitative Inorganic Analysis [VI,
_ _" Na 2C0 3 prepared solution" as follows. Acidify 5 drops of ilia
solution with dilute HN0 3 and cool. Add 0·3 ml. of amyl alcoJ,ol
and 2 drops of 3 per cent H 2 0 2 solution. A blue coloration ("p"f'-
chromic acid") in the organic layer confirms chromate.

The separations described in the above table are based up()n

the following facts:
(i) AgN03 solution precipitates only AgCl, AgBr and AgI
from a dilute nitric acid solution, the other silver salts beillg
soluble.
(ii) NaN0 2 solution reduces chlorate to chloride, which is
precipitated as AgCl in the presence of AgN0 3 solution:
NaClOa + 3NaN02 = NaCl + 3NaN03
(iii) In solutions faintly acid with acetic acid, phosphate,
arsenate, arsenite and oxalate are precipitated by AgNO s
solution.
If a mixture of halides, or of phosphate, arsenate alld
arsenite, is suspected, use the methods of separation given in
Section VII, 16. The confirmatory tests for the individu:d
anions are collected in Section VI, 6.
The reactions with silver nitrate solution are intended to act
as a guide to the presence of groups of anions, and the taLle
must be interpreted in conjunction with the observations ma' Ie
in the preliminary tests. Arsenite, arsenate and chromate", \U
be found in the analysis for cations (Section VI, 8).

5. Tests with calcium chloride solution. *-For te~ 1 s

5 and 6 a "NazCO a practically neutral solution" is requir(',!.
This is obtained as follows. Take 0·5 m!. of the "Na 2C( '3
prepared solution" in a semimicro boiling tube (or sm;·II
crucible) and render it faintly acid with dilute nitric acid (U~I)
litmus paper). Heat to boiling for about 30 seconds to ex}"l
carbon dioxide, etc., allow to cool, then add dilute ammOlli;l.
solution until just alkaline, t and boil for 30 seconds to expd
the slight excess of ammonia. Transfer the "Na2C03 pra,-
tically neutral solution" to a semimicro test-tube and divide
into two equal parts; reserve half for test 6.
* Tests 5 and 6 may be omitted by those requiring only a beginner's COUTo"
in qualitative analysis.
t If a ppt. forms on neutralising the solution, the presence of arsen,,',
antimony and tin sulphides and possibly salts of amphoteric bases (lead, tl",
aluminium and zinc) is indicated. The ppt. should be filtered off and reject", i.
6] Systematic Semimicro Qualitative Inorganic Analysis 471

Add an equal volume of CaCI, solution and place in the hot water rack
for 5 minutes. Centrifuge and wash with a few drops of hot water.

Residue. May be calcium fluoride, oxalate, Phos-j Centrifugate.

phate and arsenate. Reject.
Add 1 mI. of dilute acetic acid, heat in the hot water
rack for 2-3 minutes and centrifuge. ~

------
Residue. May be calcium Centrifugate. Add NaUH
oxalate and calcium fluoride. solution dropwise until neutral (, Ise
Extract with 1 mI. of hot dilute litmus ornitrazine yellow indicator).
H.SO, and centrifuge, if necessary. White ppt. (sometimes separa-
Treat the hot centrifugate or solu· ting slowly).
tion with 2 drops of O'02N KMnO, Arsenate and/or phosphate
solution. If the permanganate is present.
decolourised, oxalate is present. Treat the suspension or neutral
If the ppt. is not completely solution with a few drops of AgKO B
soluble in dilute H 2S0 4 , test the solution. A yellow ppt. indicates
original substance for fluoride by phosphate: a brownish-red ppt.
the water.film test (Section VI, 6). indicates arsenate or arsenate +
phosphate.

6. Test with ferric chloride solution.-Treat the other

portion of the "Na2C03 practically neutral solution ,. from
test 5 with a few drops of aqueous FeCl 3 solution. *
Reddish-purple coloration indicates thiosulphate.
Reddish-brown coloration, yielding a brown precipitate on
dilution and boiling in a semimicro boiling tube, indicates
acetate.
Yellowish-white precipitate indicates phosphate.
Blood-red coloration, discharged by HgCl 2 solution, indicates
thiocyanate.

VI,6. CONFIRMATORY TESTS FOR ACID

RADICALS OR ANIONS
The tests in the preceding section will indicate the acid
radicals or anions present. In general, these should he con-
firmed by at least one distinctive confirmatory test. The
following are recommended. Full experimental details will be
* The bench reagent usually contains excess of free acid added during its
preparation in order to produce a clear solutiun; this may prevent tho precipi.
tation of the basic acetate on boiling. It is therefore recommended tLat dilute
NH. solution be added dropwise to 1 mI. of sidfl·shelf FeCl a solution until u
slight precipitate forms and the mixture centrifuged. The clear centrifugate
(t!ometimes termed "neutrai FeCI, solution") is employed in the tdllt.
6] SY8tematic Semimicro Qualitative Inorganic Analysi8 473
Nitrite. Treat 10-20 mg. of the substance with 0'5 rol. of
dilute acetic acid, 10 mg. of thiourea and 3 drops of FeCl 3
solution. Red coloration (IV, 7, 9).
Nitrate. Brown ring test with FeS04 solution and con-
centrated H 2S04 (IV, 18, 3) if bromide, iodide, chlorate and
nitrite absent. (i) Dissolve 10-20 mg. of the substance in 0·5
ml. of water. Cautiously add 1 m!. of concentrated H 2S04,
mix and cool under running water. Incline the tube and with
great care allow about 0·5 m!. of FeS04 solution to run slowly
down the side of the tube so that it forms a layer above the
heavy sulphuric acid (Fig. VI, 6, 1). Observe the brown ring

Fig. VI, 6, I

at the junction of the two liquids after 1-2 minutes. (ii) Dis
solve 10-20 mg. of the substance in 0·5 m!. of water and add
about 1 m!. of FeS04 solution. Incline the tube and allow
0·5-1 ml. of concentrated H 2S04 to run slowly down the side
of the tube to form a layer under the solution (Fig. VI, (/, 1),
and after 1-2 minutes observe the brown ring at the inter-
face.
~"\).~.~'\\\.~~. "\_"t.~~\' \._\\-~\\ -m._~. ~\ ~~ ~'U..\)~\'~"'I..\.~ ~~ \\.~ -m._\..
()\ m\'U..~ l\_~~~. ~"\'G.~ \'n.~ \o'\')._"\)e \._n_ \_~~ ~~" VI-a.'\R.1: 1:"3.<2K. -a.n.<\.
test with lead or cadmium acetate 'Pa'Per ,IV, 6, 1).
Su\\)hite. 'Treat l()-'2() mg. of the substance with ()'5 mL
of dilute H 2S04 , place the tube in the hot water racK. and. test
472 Qualitative Inorganic Analysis [VI,
found in Chapter IV under the reactioDB of the acid radical"
(anions); the reference to these will be abbreviated as follows
thus (IV, 2, 7) is to be interpreted as Section IV, 2, reaction 7.
It will of course be realised that the tests in Chapter IV refer
to reactions on the macro scale; the student should have n(;
difficulty in reducing these to the semimicro scale when onc('
the technique described in Section II, 3 has been acquired
Particular attention is directed to the apparatus shown iH
Fig. II, 3, 19, which is employed in testing for evolved gase:
with reagent papers and liquid reagents. It is assumed that
interfering anions are absent or have been removed as des
cribed in Section VI, 7 under Special Tests Jor Mixtures oj Acid
Radicals (Anions).
Chloride. Mix 20 mg. * of the substance with an equal
weight of Mn0 2 and 0·5 m!. of concentrated H 2S04 , and plac(
in the hot water rack; C1 2 evolved (reddens then bleache~
litmus paper and also turns KI-starch paper blue) (IV, 14, 2)
Bromide. Mn0 2 and concentrated H 2S04 test (as under
Chloride); Br2 evolved (IV, 15, 2) OR dissolve 20 mg. of th('
substance in 0'5 m!. of water, add 5 drops of dilute HCI, r.
drops of CCl4 and 2-3 drops of NaOCI solution and shake;
reddish-brown coloration of CCl4 layer (IV, 15, 5).
Iodide. NaOCl solution, dilute HCI and CCl4 test (as under
Bromide); violet coloration of CC14 layer (IV, 16, 4).
Fluoride. Fit a 4 m!. (75 X 10 mm.) test-tube with a corli.
carrying a tube about 8 cm. long and of about 3 mm. bore: cut
a V-shaped groove in the cork. Adjust the tube in the cork
so that the lower end is about 2·5 cm. from the bottom of the
test-tube (compare Fig. VII, 2, 1). Place 15-20 mg. of the
substance and 0·5 m!. of concentrated H 2S04 in the test-tube,
dip the glass tube into water so that a film. of water almost
seals the lower end to a depth of about 5 mm., insert into the
test-tube, and place in the hot water rack. The formation of
a white film in the water confirms fluoride (IV, 17, 1).
The zirconium-alizarin-S test (IV, 17, 6) may be used if
oxalate is known to be absent and also in the absence of sul-
phates, thiosulphates, nitrites, phosphates and arsenates in
quantities greater than that of the fluoride.
'" The weights and volumes given in the suggested confirmatory tests are
very approximate and serve to indicate II. rell.Bonable scale for the various
operations. They are given solely for the guidance of the stUdent; ,atiBJa.ctory
,.esult,
can, however, be obtained on an appreciably nnaller Boak.
6] SY8tematic Semimicro Qualitative Inorganic AnalY8i8 473
Nitrite. Treat 10-20 mg. of the substance with 0·5 rol. of
dilute acetic acid, 10 mg. of thiourea and 3 drops of FeCl 3
solution. Red coloration (IV, 7, 9).
Nitrate. Brown ring test with FeS04 lSolution and con-
centrated H 2S04 (IV, 18, 3) if bromide, iodide, chlorate and
nitrite absent. (i) Dissolve 10-20 mg. of the substance in 0·5
ml. of water. Cautiously add 1 ml. of concentrated H 2S04,
mix and cool under running water. Incline the tube and with
great care allow about 0·5 ml. of FeS04 solution to run slowly
down the side of the tube so that it forms a layer above the
heavy sulphuric acid (Fig. VI, 6, 1). Observe the brown ring

Fig. VI, 6, 1

at the junction of the two liquids after 1-2 minutes. (ii) Dis
solve 10-20 mg. of the substance in 0·5 ml. of water and add
about 1 ml. of FeS04 solution. Incline the tube and allow
0·5-1 ml. of concentrated H 2S04 to run slowly down the side
of the tube to form a layer under the solution (Fig. VI, G, 1),
and after 1-2 minutes observe the brown l'ing at the inter-
face.
Sulphide. Treat 10-20 mg. of the substance with 0·5 ml.
of dilute H 2S04. Place the tube in the hot water rack and
test with lead or cadmium acetate paper (IV) 6, 1).
Sulphite. Treat 10-20 mg. of the substance with 0·5 ml.
of dilute H 2S04 , place the tube in the hot wa.ter rack, and test
 474 Qualitative Inorganic Analysi8 [VI,
for S02 with K2Cr207 paper* (Fig. II, 3, 19, a) or with 0·2 m}.
of fuchsin solution (Fig. II, 3, 19, b) (IV, 4, 10).
Thiosulphate. Dilute H 2S04 on solid and liberation of SO:'
(K2Cr207 test-details under Sulphite) and sulphur (IV, 5, 1).
Sulphate. The BaCl 2 solution and dilute HCI test is fairly
conclusive.
Further confirmation is obtained as follows. Centrifuge the sus-
pension and remove the supematant liquid. Add 1 mI. of water, stir.
centrifuge and discard the centrifugate. Add 3-4 drops of water, stir
thoroughly to produce a fairly uniform suspension, transfer the sus
pension to a small plug of cotton wool in a small ignition tube, introduct,
2-3 drops of Na 2 CO S solution and heat cautiously to redness. MaintaiI
the lower part of the tube at a red heat for 2-3 minutes and allow t,
cool. Break the tube, transfer the residue as completely as possible t(,
a semimicro test-tube, add 0'5 mI. of dilute HCI and introduce a Pyre},
filter tube carrying a strip of filter paper moistened with lead acetak
solution. Place the assembly in the hot water rack. A brown staiI,
on the paper confirms sulphate.
The lead acetate test on the solution and the dissolution of
the resulting precipitate of lead sulphate in ammonium acetate
solution are also characteristic (IV, 24, 2).
Carbonate. Treat 10-20 mg. of the substance with 0·5 m!.
of dilute H 2S04 , place the tube in the hot water rack, and test
with 0·2-0·5 ml. of lime water (Fig. II, 3, 19, b or c) (IV, 2,1)
Hypochlorite. Treat 10-20 mg. of the substance with 0';-'
ml. of dilute HCI, place the tube in the hot water rack and test
for C1 2 with KI-starch paper and with litmus paper (IV, 13, 4)
Chlorate. The AgN0 3-NaN0 2 test is conclusive (see tabl(
in Section VI, 5, test 5; also IV, 19).
Chromate. Mix 10-20 mg. of the substance with 0·5 ml
of dilute H 2S04 , add 0·5 ml. of amyl alcohol and 0'3 ml. ot'
10-volume H 2 0 2 ; blue colour of alcohol layer (IV, 33, 4).
Arsenite. Immediate ppt. of As 2Sa in dilute HCI solutio}'
(III, 11, 1) and absence of ppt. with magnesium nitrate re
agent (III, 11, 3).
Arsenate. Action of H 2S on acid solution (III, 12, 1),
AgN03 solution test in faintly acetic acid solution (III, 12, 2),
and magnesium nitrate reagent test (III, 12, 3).
Phosphate. Mix 10-20 mg. of the substance with 0·5 m!.
of dilute HNO a, add 1 m!. of ammonium molybdate reagent.
• For the preparation of K 2Cr,07 paper, the dichromate solution should be
a.lmost satura.ted.
7] Systematic Semimicro Qualitative Inorganic Analysis 475
and place the tube in the hot-water rack for a minute or two.
Yellow ppt. (IV, 28, 4).
Cyanide. Prussian blue test (IV, 8, 4) or ammonium sul-
phide test (IV, 8, 1, 6).
Thiocyanate. Ferric chloride solution test; colour dis-
charged by HgC1 2 solution or by NaF solution, but not by HCI
(IV, 10, 6).
Borate. Flame test (IV, 23, 2); or turmeric paper test
(IV, 23, 3); or mannitol-bromothymol blue test (IV, 23, 8).
Acetate. Mix 20 mg. of the substance with 1 m!. of ethyl
or n-butyl alcohol and 5 drops of concentrated H 2S04 • Heat
in the hot water rack for 10 minutes, and pour into 2 m!. of
Na2C03 solution-characteristic odour of ester (IV, 35, 3)
OR, better, indigo test (IV, 35,9). Mix 15 mg. of the subsiance
with 15 mg. of CaC0 3 in a semimicro test-tube, introduce a
pressure-filter tube carrying a strip of filter paper mois1,ened
with a solution of 5 mg. of o-nitrobenzaldehyde in 1 m!. of
NaOH solution. Heat the test-tube strongly. Blue or green
stain on paper confirms acetate.
Oxalate. Precipitate with CaCl2 solution in the presence
of dilute acetic acid, the precipitate decolourises a dilute acid
solution of KMn0 4 (IV, 37, 3, 4 and VI, 5, 5); resorcinol test
(IV, 37, 5).

VI, 7. SPECIAL TESTS FOR MIXTURES OF ACID

RADICALS (ANIONS)
The subject is treated fully in Section IV, 45, and again (for
elementary students) in Section V, 6, but on a macro scale.
The student should be able to adapt these to semimicro work.
Some typical semimicro separations of mixtures of anions are
given below. The quantities are for guidance only and can
be reduced, if desired. If the mixture is insoluble in water,
it is often convenient to employ the "Na2C03 propared
solution" (Section VI, 5) or the "Na2 C03 practically neutral
solution" (Section VI, 5, test 5). The special gas 1esting
apparatus of Fig. 11, 3, 19 will, of necessity, find application
here.
1. Carbonate in the presence of Sulphite.-Treat 20 mg.
of the mixture with 20 mg. of finely I,owdered K2Cr207 and
0·5 m!. of dilute H 2S04 ; place the apparatus (Fig. 11, 3, 19,
476 Qualitative Inorganic Analysis [VI,
b or c) in the hot water rack, and test for CO 2 with lime or
baryta water. [The addition of a few mg. of finely divid(,d
zinc will generate H2 and assist in driving the CO 2 out of tho
tube.]
2. Nitrate in the presence of Nitrite.-Dissolve 10 mg.
of the solid in 1 m!. of water. Remove 1 drop with a gla;-;"
stirring rod and "spot" on KI-starch paper moistened with
very dilute H 2S04 : a blue colour is obtained, due to the iodilln
liberated by the nitrous acid. Add 20-30 mg. of sulphann t}
acid and stir until effervescence ceases:
HN0 2 + HO.S0 2 .NH 2 = N2 + H 2S04 + H 2 0
Test for absence of nitrite by "spotting" on KI-starch paper.
Then apply the brown ring test (Section VI, 6).
3. Nitrate in the presence of Bromide and Iodide. -
Treat 10-15 mg. of the substance with 1 m!. of sodium hydrc\-
ide solution and 10-15 mg. of Devarda's alloy (or of aluminill m
as powder or as thin foil), place in the hot water rack, and tl-;t
for ammonia with red litmus paper or mercurous nitrate paJ"'r
(Fig. II, 3, 19, a).
Another procedure is to just acidify 5 drops of the "Na2C('a
prepared solution" with dilute acetic acid, and then add tlte
ammoniacal silver sulphate reagent (see Section IV, 45, .J)
dropwise until precipitation is complete. Centrifuge. Add
excess of concentrated H 2S04 cautiously to the centrifugate
and apply the brown ring test.
4. Nitrate in the presence of Chlorate.-Test for nitrate
as under 3: then acidify with dilute HNO a and test for chloride
with a few drops of AgNO a solution.
If chloride is originally present, it may be removed by the
addition of saturated sUver sulphate solution or of the ammo-
niacal silver sulphate reagent.
o. Chloride in the presence of Bromide and Iodide.-
Dissolve 10-20 mg. of the solid in 0,5-1 m!. of water in a
semimicro boiling tube (or use 5-10 drops of the "Na2COa
prepared solution" acidified with dilute HNO a), add 1-1,5 ml.
of concentrated HNO a, and boil gently until the bromine and
iodine are volatiIised. Dilute with 1 m!. of water, and test
for chloride by the addition of a few drops of AgNO a solution.
Alternatively, repeat the experiment but add 20 mg. of
precipitated PbO instead of the concentrated HNO a. After
7] Systematic Semimicro Qualitative Inorganic Analysis 477
the bromine and iodine have been eliminated, add 1 mI. of
water, transfer to a centrifuge tube, centrifuge and add a few
drops of AgN0 3 solution to the clear centrifugate: a white
precipitate, soluble in dilute NH3 solution and reprecipitated
by dilute HN0 3, indicates chloride.
6. Chloride in the presence of Iodide (Bromide being
absent).-Add excess of AgN0 3 solution to 0'5 mI. of the
"Na2C03 prepared solution" acidified with dilute H~03:
centrifuge and reject the centrifugate. Wash the precipitate
with about 0·2 mI. of dilute NH3 solution and centrifuge again.
Acidify the clear washings with dilute HN0 3: a white precipi-
tate (AgCI) indicates the presence of chloride.
7. Chloride in the presence of Bromide (Iodide being
absent).-Acidify 0'5 ml. of the "Na2COa prepared solution"
contained in a semimicro boiling tube with dilute HN0 3, and
add an equal volume of concentrated HN0 3. Boil gently until
all the bromine is expelled, and then add AgN03 solution. A
white precipitate (AgCI) indicates chloride present.
8. Bromide and Iodide in the presence of each other.-
Dissolve 10-20 mg. of the mixture in 0·5-1 ml. of water, add
5 drops of dilute H 2S04 and 0,3-0,5 ml. of CCI4 : or use 0·;3 ml.
of the "Na2C03 prepared solution" acidified with dilute H:)SO",
add 5 drops of dilute H 2S04 and 0·5 ml. of CCI4 • Then in-
troduce dilute NaOCI solution dropwise, shaking after the
addition of each drop. A violet coloration of the CCI" layer,
which appears first, indicates iodide: this subsequently dis-
appears and is replaced by a reddish-brown (or brown) colora-
tion if a bromide is present.
9. Thiocyanate, Chloride, Bromide and Iodide in the
presence of each other.-This problem may arise in the tests
with AgN0 3 solution (see Section VI, 5, test 4) since AgSCN,
AgCI, AgBr and Agl are precipitated in ca. N HN0 3 solution:
interfering anions (e.g. 10 3- which reacts with SCN-) are
assumed to be absent. The precipitate may be formed, for
example, from 0·5 ml. of the "Na2COa prepared solution"
and is collected, after centrifuging, in a semimicro centrifuge or
test-tube. Add 5-10 drops of water, stir the suspension and
transfer three-quarters of it by means of a capillary pipette to
a small crucible; this portion will be used in the tests for Cl-,
Br- and r, and the remainder for SCN-.
Thiocyanate test.-Treat one-quarter of the precipitate
with 5-10 drops of 5 per cent NaCI solution, heat and stir in
478 Qualitative Inorganic Analysis [VI,
the hot water rack for 3-5 minutes (this converts part of the
AgSCN into NaSCN). Centrifuge and add to the clear centrl'
fugate one drop of dilute HCI and one drop of FeCl a solutiOlI
A red coloration indicates thiocyanate present.
If thiocyanate is present, it must be destroyed since it inte!
feres with the tests for the halides. Dry the main precipital"
in the crucible by heating gently in an air bath (Fig. II, 3, Hi),
remove the air bath and heat directly to dull redness for Olle
minute or until all the thiocyanate is decomposed, i.e. until
blackening of the precipitate and/or burning of sulphur jU:!j
ceases. Prolonged heating should be avoided. Allow 1 d
cool.
Mixtures of halides may now be identified as indicated III
5-8 above: a systematic procedure, which covers the thr, '13
halides, is given below.
To the residue in the crucible (if thiocyanate is present) or to t: Ie
remainder of the precipitate transferred to a 5 or 10 ml. beaker ,if
thiocyanate is absent), add 100-150 mg. of zinc powder (20 mesh) fl· .1
10-15 drops of dilute H 2 SO,. Allow the reduction to proceed for 5- i 0
minutes with intermittent stirring: gentle warming for a few secOl. is
may be necessary to start the reaction. Transfer the liquid, with 1 :.e
aid of a few drops of dilute H 2S0 4 , to a centrifuge tube, centrifuge a,:d
divide the clear centrifugate into three equal parts.
Iodide test. Add 4-5 drops of CCI, and 5 drops of 3 per cent H,' II
or 5 drops of 25 per cent Fe2(SO,)a solution. Agitate vigorously uild
allow to settle. Purple to violet colour of the CCI, layer. Iod ,le
present.
Bromide test. (a) If iodide is present, it must be removed Ily
treating one-third of the solution with 5 drops of dilute H 2SO, nl,d
2 drops of 30 per cent NaN0 2 solution (chloride-free). Boil do:'. n
gently to 3-4 drops and allow to cool; Transfer the solution t, a
centrifuge tube and test for bromide as under (b).
(b) If iodide is absent, use one-third of the solution directly. A, ld
an equal volume of concentrated HN0 3 , heat in the boiling water b,,:h
for 30 seconds, and cool to room temperature with cold water. Add
3-4 drops of CCI, and stir vigorously with a glass rod. A brown col"'lr
in the CCI, layer indicates bromide present.
Chloride test. (a) If iodide and/or bromide present, dilute ; lIe
remaining third of the solution to 0·5 mI., add 1 m!. of concentra: "d
HNO a and boil gently until evolution of bromine ceases. Cool, dil ite
and test for chloride as in (b) below with AgNOa solution only.
(b) If bromide and iodide are absent, add 2 drops each of dilute
HNO a and AgNO a solution. A white precipitate (AgCI) indicH'es
chloride present.

10. Phosphate, Arsenate and Arsenite in the preselu~e

of each other.-This problem may arise in the test w !,h
AgNO s in neutral solution (see Section VI, 5, test 4).
8] Systematic Semimicro Qualitative Inorganic Analysi.9 479

Dilute 5 drops of the" Na.CO. prepared solution" with an equal volume

of water, acidify with dilute HCI and render alkaline with dilute NH.
solution. Centrifuge, if necessary, and discard the ppt. Treat thE' clear
solution with 1<f-12 drops of Mg(NO.). reagent (or of magnesia mi<:ture)
added dropwise and with stirring. Allow to stand for 10 minutes, stirring
frequently: centrifuge. Wash the ppt. with 2-3 drops of dilute NH.
solution.

Residue. May contain Mg(NH.)PO,,- Centrifugate. May con-

6H.O and Mg(NH.)AsO.,6H.O (A). tain arsenite.
Dissolve the ppt. in 5-10 drops of dilute Add 6-8 drops of 3% H.O.
HCl, add 1 drop of 10% NH,I solution, solution (to oxidise arsenite
heat to boiling <1nd saturate with H.S to arsenate), heat on water
(Fig. II, J, 17). Centrifuge, and saturate bath for 1 minute, cool, add
again with H.S to ensure complete pre- 5-10 drops of Mg(NO,). re-
cipitation. Wash with a few drops of agent (or of magnesia mix-
0'5N HCI. ture), and allow to stalld for
5-10 minutes, stirring fre-
quently.
Residue. Centrifugate. Transfer White ppt. of Mg(NH,)-
As.S.- to a small crucible, boil until AsO,,6H.O.
yellow. H.S is expelled and volume Arsenite present.
Arsenate is reduced to 2-3 drops. Alternatively, acidify with
present. Transfer, with the aid of a dilute HCI and pass H.S.
few drops of water, to a Immediate yellow ppt. of
centrifuge tube, make alka· As.S •.
line with dilute NH. solu- Arsenite present.
tion and add 5 drops in
excess. Add 10 drops of
Mg(NO.). reagent (or of
magnesia mixture), and
allow to stand, with fre-
quent stirring, for 10
minutes.
White ppt. of Mg(NH,)-
PO,,6H t O.
Phosphate present.

Nate. The presence of arsenate is readily detected as follows. Treat a

portion of the ppt. A wit.h 5 drops of AgNO a solution to which 1 drop of
3N acetic acid has been added. If the ppt. acquires a reddish colom (due
to Ag.AsO,), arsenate is present. The yellow colour of Ag.I·O. is
obscured by the red colour of Ag,AsO,.

VI, 8. EXAMINATION FOR METAL IONS (CATIONS)

IN SOLUTION
Preparation of a solution of the solid.-Since the whole
scheme for the analysis of cations depends upon the reactions
of ions, it is clear that it is first necessary to get the substance
into solution. Water is first tried in the cold and then on
480 Qualitative Inorganic Analysis [VI,
warming. If insoluble in water, the following reagents are inve:,,-
tigated as solvents in the order indicated: dilute hydrochlof ll )
acid, concentrated hydrochloric acid, dilute nitric acid, CO! J -
centrated nitric acid and aqua regia (3 volumes of concentrakd
HOI to 1 volume of concentrated HN0 3 ). Most substances cu-
countered in an elementary course will dissolve in either wai"f
or dilute hydrochloric acid. If concentrated hydrochloric aCid
has to be used, the solution must be considerably diluted befc" e
proceeding with the analysis, otherwise certain cations, such ;IS
cadmium and lead, will not be precipitated by hydrog' U
sulphide. When concentrated nitric acid or aqua regia IS
employed as the solvent, the solution must be evaporat, d
almost to dryness, a little hydrochloric acid added, the soluti 'u
evaporated again to small bulk and then diluted with water i 0
dissolve the soluble nitrates (or chlorides). This evaporatj, ,n
is necessary because the nitric acid may react with the hydrof' ,'n
sulphide subsequently employed in the Group analysis.
To discover the most suitable solvent, treat portions of abc" It
15 mg.* of the finely powdered substance successively Wi' h
0,3-0,5 ml. of (1) water, (2) dilute hydrochloric acid, (3) C.'It-
centrated hydrochloric acid, (4) dilute nitric acid, (5) conc('n-
trated nitric acid and (6) aqua regia (3 volumes of concentral ,'d
HOI: 1 volume of concentrated liNDa) in the order giV"ll.
Try the solubility first in the cold and then at the temperatll re
of a boiling water bath for water and dilute hydrochloric a, (d
using a semimicro test-tube. For the other solvents, it will i)e
necessary to investigate the solubility in a semimicro boiL Ilg
tube; if solution does not take place in the cold, warm gently _j
with a semimicro burner. When all the substance has dis-
solved, transfer to a semimicro test-tube, rinse the boiling tu be
with a few drops of water, and add the "rinsings" to j he
solution. If you are in doubt as to whether the substance or
a portion of the substance has dissolved, evaporate a little of
the clear solution on a watch glass.
If the substance dissolves in water, proceed immediately to
the test for the metal ions. If the use of dilute hydrochlc,ric
acid results in the formation of a precipitate, this may conl,ist
of the metals of Group I; the precipitate may either be filte red
off and examined for this Group, or else the original Bubstance
may be dissolved in dilute nitric acid. If concentrated 80< ids
are employed for dissolution, the remarks in the first paragraph
must be borne in mind.
• This is most simply estimated by weighing out 75 mg. and dividir>t,i ii
into 5 approximately equal parta.
8J SY8tematic Semimicro Qualitative Inorganic Analysis 481
Oxides, Hydroxides, Free Metals and Simple Alloys.-
If a solid substance is found to contain no anions, it may be an
oxide, or hydroxide, or a metal or a mixture of metals, or an
alloy. Metals and alloys have certain characteristic physical
properties; many metals evolve hydrogen on treatment with
dilute acids. As a rule, nitric acid must be employed as solvent,
and it will then be necessary to remove the excess of nitric acid
(as already described above) before proceeding to the Group
analysis.
·When a suitable solvent has been found, prepare the solution
for analysis using about 50 mg. of the solid: the volume of the
final solution should be 1-1'5 ml. Use this solution for the
Separation of Cations into Groups according to Table SM.S
(Section VI, 9). The various precipitates are investigated by
means of the appropriate Group Separation Tables SM1-
SMVII, given in Chapter Ill.

NOTES ON TABLE SM.S (SrMPLIFIED GENERAL TABLE FOR

SEPARATION OF CATIONS INTO GROUPS)

(1) For the sake of uniformity throughout the text, a drop is

intended to mean 0·05 mI.-the volume of the drop delivered by
the commercial "medicine dropper." If the instructions require
the addition of 0·5 mI., this quantity can be measured out with the
aid of a small measuring cylinder or graduated pipette, or 10 drops
can be added directly from a reagent dropper provided, of course,
that a drop from the latter does not differ appreciably from 0·05 mI.
It is recommended that all droppers be calibrated (see TaUe SMI,
Note 1; Section III, 5) and a small label, stating the number of
drops per ml., attached to the upper part.
(2) The student must remember that in all operations with the
centrifuge, the tube must be counterbalanced with another similar
tube containing the same volume of water.
If the substance was completely soluble in dilute HOI, it is evident
that no silver or mercurous salt is present. When lead is present,
the solution may be clear while hot, but PbOl 2 is deposited on cooling
the solution, due to the slight solubility of this salt. in cold water.
Lead may be found in Group II, even if it is not precipitated in
Group I.
(3) It is usually advisable in Group Separations to wash a preci.
pitate with a small volume of a suitable wash solution and to add
the washings to the centrifugate. In the present instance culd water
or cold, very dilute HOI (say, ca. O·5N) may be used. The precipi.
tating reagent, diluted lO-lOO.fold, is generally a suitable wash
liquid. Specific directions for washing precipitates will uBually be
omitted from the present Table in order to economise space.
16+
482 Qualitative Irwrganic AnalY8i8 [VI;
'lJ i:::iy8temat~c i:::iem~m~Cro (Juat~tatwe lnorgantc AnatYSM 4~3

(4) The H 2 0 2 solution is added to oxidise Sn ++ to Sn +++ +, thus

leading ultimately to the precipitation of SnS2 instead of th(} some-
what gelatinous SnS. The excess of H Z0 2 should preferably be de-
composed by boiling before passing H 2S, otherwise some S may be
precipitated; the latter may mislead the unwary student if Group II
elements are absent. The subsequent separation of Groups IIA
and lIB by means of aqueous KOH is thus rendered more complete
since SnS2 dissolves completely and SnS dissolves only part,ially in
aqueous KOH.
If it is intended to use ammonium polysulphide in the separation
of Groups IIA and lIB (by an adaptation of Table III, Section
III, 18), the addition of H 2 0 2 is not essential since (NH4')2S. will
oxidise the SnS to SnSz and the latter dissolves as the thiostannate
(NH4)2 SnS a·
(5) It is important that the concentration of HOI be approxi-
mately correct, i.e. O·3M, before passing H 2S: with higher concen-
trations of acid, lead, cadmium and stannous tin will be incompletely
precipitated: if the acidity is too low, sulphides of Group lIm (NiS,
OoS and ZnS), may be precipitated. Either of two methods may
be employed to adjust the acid concentration.
(a) Run in exactly 5·0 ml. of distilled water from a burette, etc.,
into a clean, dry conical flask of 10 ml. capacity: attach a label to
the latter so that the upper edge of the label is in line with the level
of the water. Pour out the water.
Transfer the centrifugate from Group I to the calibrated 10 ml.
conical flask with the aid of a few drops of water. Add concentrated
NHs solution dropwise (use a capillary dropper) with constant
stirring, until the mixture is alkaline. [Ignore any precipitate
which may form: this will dissolve when HOI is added or will be
converted by the H 2S treatment into the sulphide.] Then add dilute
HOI by means of a capillary dropper, with constant stirring, until
the mixture is just acid (test with litmus paper by removing a drop
with a micro stirring rod). Now add exactly 0·50 ml. of 3N HOI
(measured from a calibrated dropper or from a 1 ml. graduated
pipette), and dilute the solution with distilled water to 1he 5 ml.
mark.
(b) A simple procedure is to use the indicator methyl violet (0·1
per cent aqueous solution or, better, the purchased or prepared
indicator paper). The following table gives the colour of the in-
dicator at various concentrations of acid.
Acid concentration pH Methyl violet indicator
Neutral or alkaline 7+ Violet.
O'lN Hel 1·0 Blue.
0'25N Hel 0'6 Blue-green.
0'33N Hel 0'5 Yellow-green.
0'50N Hel 0'3 Yellow.
Add 1 micro drop of methyl violet indicator solution and introduce
dilute NHs solution with constant stirring until the colour of the
solution is yellow-green. A blue-green colour is almost but not
quite acid enough, yet is acceptable for most analyses: stucients who
484 Qualitative Inorganic Analysis [VI,
find detection of slight colour changes difficult may, indeed, preh'
the blue-green colour change. If the indicator paper is availabl
the thoroughly stirred solution should be spotted with a micr '
stirring rod on fresh portions of the paper. It is recommend( i
that a comparison solution containing, say, 2 ml. of 0·3N HCI aI':
1 micro drop of indicator be freshly prepared: this will facilita: "
the correct adjustment of the acidity. A more satisfactory standar ]
is a buffer solution prepared by mixing 1 ml. of N sodium acetatd
and 2 ml. of N HCI: this has a pH of 0·5.
(6) For the passage of H 2 S into the solution, the "pressun"
method detailed in Section II, 2, 7 (see also Section II, 3, 1')
should be employed. The solution, contained in a 10 ill!. conical Bah
or in a 4 ml. test-tube, is heated (the former directly on a wire gauz
the latter in a hot water bath), a capillary delivery tube is insert! !
and H 2 S passed in, whilst slowly shaking the vessel with a swirlil
motion until precipitation is complete: the latter will be apparel '
when bubbling either stops altogether or is reduced to a very slo '
rate of 1-2 bubbles per minute. Saturation is normally comple r.
in 1-2 minutes. The best method of determining whether preciy;
tation is complete is to centrifuge a portion of the solution and ! }
test the centrifugate with H 2S. If only a white precipitate or
suspension of sulphur is obtained, the presence of an oxidising agel i
is indicated.
If an oxidising agent is present (e.g. a permanganate, d,
chromate or a ferric salt) as is shown by the gradual separation Ui'
a fine white precipitate of sulphur and/or a change in colour of t}"
solution, it is usual to pass S02 into the hot solution until reductic,.,
is complete, then to boil off the excess of S02 (conical flask or sma i
beaker or crucible; test with K2Cr207 paper), and finally to pa·
H 2S. Arsenates, in particular, are slowly precipitated by H2~
they are therefore usually reduced by S02 to arsenites and th(';l
precipitated as AS 2S3 with H 2S, after removal of the excess of SCI:
in order to avoid interaction of the latter with H 2S and consequC1!:
separation of S. Stannic compounds may be very slightly reduc(', I
to the stannous state by this treatment; the amount of reduction i
however, so small that it may be neglected. The original solutinli
or substance must be tested for the valence state of the arsenic.
The objection to the use of S02 is that some sulphuric acid mal'
be formed, especially on boiling, and this may partially precipitat"
Pb, Sr and Ba as sulphates. Any precipitate formed in this proce.·,,;
should therefore be examined for these cations: PbS04 is soluble ill
ammonium acetate solution.
An alternative procedure to be used when arsenate is present,
which does not possess the disadvantages associated with S02 all, i
is perhaps more expeditious, is to add 0·2 mI. of concentrated H< I
and 2 drops of 10 per cent NH4I solution: the arsenate is thereby
reduced to arsenite and upon saturation of the warm solution wit h
H 2S under "pressure," the arsenic is completely precipitated as
9J Systematic Semimicro Qualitative Inorganic Analys1:s 485
As 2Sa. This reduction may be carried out after the sulphides of
the other elements have been precipitated in the presence of
0'3N HCI.
(7) The wash liquid is prepared by dissolving 0·1 gram of NH4NO a
in 2 m!. of water and treating this solution with H 2S: about 0·2 ml.
will suffice for the washing. The H 2S must be present in the wash
liquid to prevent oxidation of the moist sulphides to sulphates.
(8) If iron was originally present in the ferric state, it will be
reduced to the ferrous condition by H 2S. It must be oxidised to
the ferric condition with concentrated nitric acid (or with a few
drops of saturated bromine water) to ensure complete precipitation
with NH4CI and dilute NHa solution. The original solution must
be tested to determine whether the iron is present as Fe++ or as
Fe+++.
The nitric acid will simultaneously oxidise any HI, if NH41 has
been used to reduce arsenates, etc.
(9) The washing may be made with a little hot water or, better,
2 per cent NH4NO s solution.
(10) If the centrifugate is brown or dark-coloured, Ni may be
suspected. The dark-coloured solution contains colloidal NiS,
which centrifuges with difficulty. It may be acidified wil;h dilute
acetic acid and boiled (crucible or semimicro boiling tube) until the
NiS has coagulated: this may be added to the Group lIIB precipi-
tate or tested separately for Ni.
(11) The wash liquid may consist of 1 per cent NH4 Cl solution to
which 1 per cent by volume of ammonium sulphide solution has
been added. Oxidation of the moist sulphides to sulphates is thus
reduced considerably.
(12) The filtrate must be acidified immediately and conoentrated
to remove H 2S. Ammonium sulphide solution upon exposure to air
slowly oxidises to ammonium SUlphate and would then precipitate
any Ba or Sr present as BaS04 or SrS04' Another roason for
acidifying the filtrate from Group lIIB is to prevent absorption of
CO 2 from the air with the formation of carbonate ions: 1,he latter
would also precipitate the ions of Group IV.
(13) The initial centrifugate from Group lIIB will be almost
saturated with ammonium salts and this concentration of ammonium
ions is higher than is necessary to prevent the precipitation of
Mg(OH)2 and it may also lead to incomplete precipitation of the
carbonates of Group IV_ The latter effect is due to the acidic
properties of the ammonium ion:
NH,+ + 00 3 - - ~NH3 + HOO a-;
the concentration of C0 3 - - ions upon the addition of (~4)2C03
would thus be considerably reduced. For these reasons most of the
ammonium salts must be eliminated first.
Concentrated HNO a decomposes NH4CI at a lower temperature
than is required for its volatilisation:
NH,OI + HNO. ? NH,NO. + HOI = N ,0 + 2H.O + HOI
486 Qualitative Inorganic AnalY8i8 [VI,
Loss by decrepitation and spitting during these operations must t·e
avoided.
(14) Ammonium carbonate decomposes appreciably above 60° 1 '
(NH')2COs --+ 2NHs + COl + HzO
The digestion also improves the filtering properties ofthe precipita ".
(15) Owing to the slight solubility of CaCO s , SrOOs and BaCI '3
in solutions of ammonium salts, the centrifugate from Group ; V
will, when these metals are present, contain minute amounts of t. Ie
ions of the alkaline earth metals. Since the Group IV metals m '.7
interfere to a limited extent with the flame tests for Na and K a, ,l
also the Na2HP04 test for Mg (if employed), it has been reCOl -
mended that the filtrate from Group IV be heated on a water ba:!l
for 2-3 minutes with half a drop each of (NH4)2S04 solution a; 1
(NH4)2C204 solution; any precipita,te which forms is removed :, V
centrifugation and discarded. Owing to the comparatively sm I
concentration of ammonium salts, this is generally unnecessary ,f
the procedure described in Table SMVII (Section III, 37) is adopt! i.

VI, 10. Modification of the analysis in the presence; {

Phosphate, etc.-With the experience gained in the foregoi'
comparatively elementary analysis, the student should have; )
serious difficulty in adapting the macro procedures of the m(; ,~
advanced analysis described in Chapters VII, VIII and IX ;;)
the semimicro scale. As an example, we may take the Ph(, -
phate Separation Table (compare Table II in Section VII, 7
and Table P in Section V, 10). This is given in Table SMVJ [
below.
A brief mention may be made here concerning the removal
of certain other interfering ions. This should be effected
before the phosphate separation.
If borate is found to be present, transfer the centrifugal e
from Group II to a small crucible, heat to e:s:pel hydrog ' 1\
sulphide (do not evaporate to dryness), and allow to COl '.
Add 2-3 drops of concentrated hydrochloric acid and 5-6 drol d
of methyl alcohol, and heat on a water bath until the soluti( 1\
is almost evaporated to dryness. Repeat the addition ofhydr 1-

chloric acid and methyl alcohol, and evaporate to dryness Oll

the water bath. If borate is the only interfering ion, dissoho
the residue in 2 ml. of 0·3N hydrochloric acid, and contimll~
the analysis for cations. The borate is volatilised as meth y I
borate (poi8onou8).
If oxalate or acetate is found to be present, add to tJ I' ~
residue from which borate has been removed (or, if borate I:;
absent, the centrifugate from Group II which hl1s been evap' ,-
rated almost to dryness) I ml. of concentrated hydrochlorir:
10] Systematic Semirnicro Qualitat'ive Inorganic Analy8'i,~ 487

VI,10. Table SMVIII.-Phosphate Separation Table

r--------------------------------------------------------
PlaM the centrifugate from Group II in a semimicro boiling tuoe (or
small crucible), boil to expel H 2S, add 1-2 drops of concentrated EINO.
(or 5-10 drops of bromino water) and boil gently for 1 minute. Transfer
to a 4 ml. test· tube with the aid of 0'5 fill. of water. Add 1 d,'op of
NH.Cl solution and 2-3 drops of the zirconium nitrate reagent, Warm on
water bath for 2 minutes and centrifuge. Test for completeness of pre-
cipitation by adding a further drop of the zirconium nitrate reagent to
the centrifugate: if a ppt. forms, centrifuge again and repeat the process
until the addition of 1 drop of the reagent to the clear centrifugate has
no visible effect. Heat on a boiling water bath, with stirring, for 1
minute; centrifuge. Wash with a few drops of hot water.

Residue. Centrifu~ate. Add 50 mg. of solid NH.OI (or 0·25

Zirconium ml. of 20% NH.OI solution), heat on a water bath, add
phosphate. concentrated NR. solution until alkaline and then 2
Reject. drops in excess. Place tho tube in the boiling water
bath for 3-5 minutes. Centrifuge. Wash with a few
drops of hot water or 2% NH,NO. solution.

Residue. Examine for Group IlIA. Centrifu~ate.

The excess of Zr will be found in the Examine for
residue after treatment with RaOa and GroupK IIIB,
NaOH Rolution (or with sodium per- IV and V.
borate NaBO.,4H 20 and boiling), and
will accompany any Fe(OR)., if Fe is
present.

acid and 0·5 m!. of concentrated nitric acid. Evaporate slowly

almost to dryness: use a crucible. Allow to cool, then add
1 ml. of concentrated hydrochloric acid and 1 m!. of concen-
trated nitric acid, and evaporate just to dryness. Dissolve the
residue in 2 ml. of 0'3N hydrochloric acid and continue the
analysis for cations. The evaporation with RCI-HN0 3 mixture
will destroy the organic acids and simultaneously remove any
fluoride which may be present.

VI, 11. ANALYSIS OF A LIQUID (SOLUTION)

If a liquid is supplied for analysis, proceed as follows:
(1) Observe the colour, odour and any special phyfical pro-
perties.
(2) Test its reaction to litmus (or equivalent test) p,1per.
(a) The solution is ne7Ltral: free acids, free bases, acid salts,
and salts which give an acid or alkaline reaction owing
to hydrolysis, are absent.
488 Qualitative Inorganic Analysis [VI,
(b) The solution reacts alkaline: this may be due to tlle
hydroxides of the alkali and alkaline earth metals, j 0
the carbonates, sulphides, hypochlorites and peron( I. '8
of the alkali metals, etc.
(c) The solution reacts acid: this may be due to free aei, "
acid salts, salts which yield an acid reaction because ,.f
hydrolysis, or to a solution of salts in acids.
(3) Evaporate a portion of the liquid to dryness on the wai r
bath (use a 5 or 8 ml. crucible and stand it over one of t 'e
openings in the hot water rack); carefully smell the vapons
evolved from time to time. If a solid residue remains, exami' Ie
it as detailed above for a solid substance. If a liquid remail i,
evaporate cautiously on a wire gauze in the fume chamb,';
a solid residue should then be examined in the usual WI' \'.
If no residue is obtained, the original liquid consists of SOl'le
volatile substances which may be water or water containi 'g
certain gases or volatile substances, such as CO 2, NH 3 , S('!,
H 2S, HOI, HBr, HI, H 2 0 2 or (NH4}2003, aII of which can i e
readily detected by special tests. It is best to neutralise Wi' h
sodium carbonate and test for acid radicals (anions).
 CHAPTER VII

SYSTEMATIC QUALITATIVE INORGANIC

ANALYSIS

IN the scheme of analysis to be described in the following

pages, it is assumed that the student is already familiar with
the tests and operations described in the preceding chapters.
It will be shown how these isolated facts are incorporated in
the systematic methods of qualitative analysis, applicable not
only to simple solid substances, but also to mixtures of solid
substances, to liquids, to alloys, and to "insoluble" sub-
stances, i.e. substances which are insoluble in aqua rebria and
acid solvents.
It must be emphasised that the object of qualitative analysis
is not simply to detect the constituents of a given mixture; an
equally important aim is to ascertain the approximate relative
amounts of each component. For this purpose 0·5-1 gram of
the substance is usually employed for the analysis; the relative
magnitudes of the various precipitates will provide a rough
guide as to the proportions of the constituents present.
Every analysis is divided into three parts:
(1) The preliminary examination. This includes preliminary
examination by dry tests, examination of the volatile products
with sodium hydroxide solution (for ammonium), and with
dilute and concentrated sulphuric acid (for acid radicals or
anions).
(2) The examination for metal ions (cations) in solution.
(3) The examination for acid radicals (or anions) in Eolution.
The substance to be analysed may be: (A) solid and non-
metallic, (B) a liquid (solution), (C) a metal or an alloy, and
(D) an "insoluble" substance. Each of these will be discussed
separately.

VII,1. ANALYSIS OF SOLID AND NON-METALLIC

SUBSTANCES
The appearance of the substance should be carefully noted;
a lens or microscope should be used, if necessary. Observe
whether it is crystalline or amorphous, whether it is magnetic
and whether it possesses any characteristic odour or colour.
16* 489
 490 Qualitative Inorganic A naly8i,~ [VII,
- - Some of the commonly occurring coloured compounds alO
listed below:
Red: Pb 3 0 4 , AS 2S 2 , HgO, HgI 2 , HgS, Sb 2Sa, CrOa, CU2' J,
K 3[Fe(CN)6]; dichromates are orange-red; permanganates awl
chrome alum are reddish-purple.
Pink: hydrated salts of manganese and of cobalt.
YeUow: CdS, AS 2S 3, SnS2, PbI 2, HgO (precipitatec! ,',
K 4[Fe(CN)6],3H 20; normal chromates; ferric chloride alofl
nitrate.
Green: Cr203, Hg 2I 2, Cr(OH)s; ferrous salts, e.g. FeS04,7H 2 \),
FeS04,(NH4l2S04,6H 20, FeCI 2,4H 20; nickel salts; CrCl a,6H 2 ,),
CuCl z,2H zO, CuCO a, K ZMn04 •
Blue: anhydrous cobalt salts; hydrated cupric salts; Prl ,-
sian blue.
Brown: Pb0 2, CdO,Fe 3 0 4, Ag aAs04, SnS, Fe20a and Fe(OIJ 3
(reddish-brown).
Black: PbS, CuS, CuO, HgS, FeS, Mn02, C0 3 0 4, CoS, Ni'~,
Ni 2 0 3 , Ag 2S, C.
The colour of the solution obtained when the substance ,'>
dissolved in water or in dilute acids should be noted, as tJ '3
may often give valuable information. The following COlO1' g
are shown by the ions (the cations are usually hydrate:)
present in the dilute solution:
Blue: cupric copper; green: nickel, ferrous iron, chroD' C
chromium, manganates; yellow: chromates, ferrocyanid,',
ferric iron; orange-red: dichromates; purple: permanganat( ;
pink: cobalt, manganese.
The substance should be reduced to a fine powder in a suital,;:)
mortar before proceeding with the following tests. These tee. s
usually give a great deal of useful information; they are quick i:v
performed (10-15 minutes) and should never be omitted.

VII,2. PRELIMINARY DRY TESTS

The following tests are made:
(i) action of heat; (ii) flame colorations; (iii) charcoal blwk
reductions; (iv) borax and phosphate bead reactions; (v) amnil'-
nium radical test. *
Test (i). Heating in a closed tube.-Place a small quantil,,'y
(4-5 mg.) of the substance in a dry ignition tube
80 that nOlle
of it remains adhering to the sides, and heat cautiously; the
tube should be held in an almost horizontal position. Th(}
• This is really a wet test, but is inoluded here (or the sake of oonvenien'''J.
2] Systematic Qualitative Inorganic Analysis 491
temperature is gradually raised, and any ohanges whioh take
place carefully noted.

Observation Inference
(a) The substance changes colour.
1. Blackening from separation of carbon, Organic substances, '~.g. tar-
often accompanied by burning. trates and citrates.
2. Blackening, not accompanied by Cu, Mn and Ni salts at a very
burning or odour. high temperature.
3. Yellow when hot, white when cold. ZnO and many Zn salta.
4. Yellowish-brown when hot, yellow SnO. or Bi.O •.
when cold.
5. Yellow when hot, yellow when cold. PbO and some Pb salta.
6. Brown when hot, brown when cold. CdO and many Cd'salta.
7. Red to black when hot, brown when FezO •.
cold.

(b) A sublim.ate is formed.

1. White sublimate. * IIgCl.,lIgBr.,lIg.CI" aznzno-
nium halides, AsIO" SbaO.,
certain volatile orga rno com-
pounds (oxalic acid benzoic
acid).
2. Grey Bublimate, easily rubbed to Hg.
globules.
3. Steel-grey sublimate; garlic odour. As.
4. Yellow sublimate. S (melts on heating), As.S.,
HgI. (red when rubbed with
a glass rod).
5. Blue-black sublimate; violet vapour. I.
6. Black; red on trituration. HgS.

* If a white sublimate forms, heat with 4 times the bulk of anhydrous

sodium carbonate and a little potassium cyanide in an ignition tube. A
grey mirror, convertible into globules on rubbing with a glass rod, indicates
Hg; a brownish-black mirror, yielding a white sublimate and an odour of
garlic when heated in a wide tube, indicates As; ammonia evo ved (test
with mercurous nitrate paper) indicates ammonium salts.

(c) A ~as or vapour is evolved.

1. Water is evolved; test with litmus Compounds with water of
paper. crystallisation (ofttn accom-
panied by change <f colour),
ammonium salts, I,cid salts,
oxy-acids, hydroxi,les.
The water is alkaline. A=onium salts.
The water is acid. Readily decompose' I salts of
strong acids, also "dds.
2. Oxygen is evolved (rekindles glowing Nitrates, chloral es, per·
splint). chlorates, bromate 1, iodates,
peroxides, per.saltH and per.
manganates.
3. Nitrous oxide (rekindles glowing Ammonium nitrate or nitrate
splint) and steam are evolved. mixed with an ammonium
salt.
492 Qualitative Inorganic An.alysis [VII,

Ob8ervation Inference
4. Dark·brown or reddish fumes (oxides Nitrates or nitrites of heavy
of nitrogen); acidic in reaction. metals.
5. Carbon dioxide is evolved (lime water Carbonates, bicarbonates,
rendered turbid). oxalates and organic com·
pounds.
6. Carbon monoxide is evolved (burns Oxalates.
with a blue flame forming carbon
dioxide); poisonous gaB.
7. Cyanogen is evolved (burns with Cyanides of heavy metals,
violet flame and characteristic odour); e.g. of Hg and Ag;
very poisonous gaB. K3[Fe(CN).].
8. Acetone is evolved (burns with Acetates.
luminous flame).
9. Ammonia is evolved (odour; turns red Ammonium salts; certain
litmus paper blue; turns mercurous complex ammines.
nitrate paper black).
10. Phosphine is evolved (odour of rotten Phosphites and hypophos.
fish; inflammable); very poisonous. phites.
11. Sulphur dioxide is evolved (odour of Normal and acid sulphites;
burning sulphur; turns potassium di- thiosulphates; certain sul-
chromate paper green; decolourises phates.
fuchsin solution).
12. Hydrogen sulphide is evolved (odour Acid sulphides; hydrated
of rotten eggs; turns lead acetate sulphides.
paper black or cadmium acetate paper
yellow).
13. Chlorine is evolved (yellowish.green Unstable chlorides, e.g. of Cu,
gas; bleaches litmus paper; turns Au and Pt; chlorides in pre·
potassium iodide-starch paper blue); sence of oxidising agents.
very poisonous.
14. Bromine is evolved (reddish.brown Sources similar to chlorine.
vapour; choking odour; turns fluo-
rescein paper red).
15. Iodine is evolved (violet vapours Free iodine and certain
condensing to black crystals). iodides.

Test (ii). Flame colorations.-Place a small quantity (3-4

mg.) of the substance on a watch glass, moisten with a little
concentrated hydrochloric acid, and introduce a little of the

Observation
I Inference
Persistent golden-yellow flame. Sodium.
Violet (lilac) flame. Potassium.
Carmine-red flame. Lithium.
Brick·red (yellowish. red) flame. Calcium.
Crimson :I:lame. Strontium.
Yellowish· green flame. Barium [molybdenum).
Green flame. Borates, copper [thallium].
Livid blue flame (wire slowly corroded). Lead, arsenic, antimony. bis-
muth, copper.
2] Systematic Qualitative Inorganic Analysis 493
substance on a clean platinum wire into the base of the non-
luminous Bunsen flame. An alternative method is to dip the
platinum wire into concentrated hydrochloric acid contained
in a watch glass and then into the substance; sufficient will
adhere to the platinum wire for the test to be carried oui.
The sodium flame masks that of other elements, e.g. that of
potassium. Mixtures can be readily detected with the direct
vision spectroscope (see Fig. 11, 1, 4). A less delicate method
is to view the flame through two thicknesses of cobalt blue
glass, whereby the yellow colour due to sodium is masked or
absorbed, and the other colours are modified as follows.

Flame coloration
Flame coloration tkrough cobalt glass Inference

Golden-yellow. Nil. Sodium.

Violet. Crimson. Potassium.
Brick-red. Light green. Calcium.
Crimson. Purple. Strontium.
Yellowish-green. Bluish-green. Barium.

Test (iii). Charcoal block reductions.

(a) Heat a little of the substance (3-4 mg.) in a small cavity
scooped in a charcoal block in a blowpipe flame.

Ob8ervation Inference
1. The substance decrepitates. Crystalline salts, e.g. NaCI,
KCl.
2. The substance deflagrates. Nitrates, nitrites, clJorates,
perchlorates, iodates, per-
manganates.
3. The 8ubstance fuses and is absorbed Salts of the alkalis aJ ld some
by the charcoal, or forms a liquid salts of the alkaline earths.
bead.
4. The substance is infusible and incan- Apply test (b) below.
descent, or forms an incrustation upon
the charcoal.

(b) Mix the substance (3-4 mg.) with twice its bulk of an-
hydrous sodium carbonate, place the mixture in a cavity of a
piece of charcoal and heat in the reducing flame of the blow-
pipe.
The sodium carbonate converts a metallic salt into a carbonate or oxide on
heating, and thus reduction occurs more rapidly than with the charcoal
alone, as in (al. Further, the sodium carbonate acts as a flux nnd, in the
fused state, protects any metallic globules, whioh Illay have formed benea.th
it, from oxidation.
494 Qualitative Inorganic Analysis [VII

Ob8ervation Inference

1. White, infusible and incandescent BaO, SrO, CaO, MgO (residue

when hot. alkaline to litmus paper).
Al.O s• ZnO, SiO, (residue not
alkaline to litmus paper).
2. Incrustation without metal:
White, yellow when hot. ZnO.
White, garlic odour. As.O •.
Brown. CdO.
3. Incrustation with metal:
White incrustation; brittle metal. Sb.
Yellow incrustation; brittle metal. Bi.
Yellow incrustation; malleable Pb.
metal, marks paper.
4. Metal without incrustation:
Grey metallic particles, attracted by Fe, Ni, Co.
magnet.
Malleable beads. Ag and Sn (white), Cu (red
flakes) [Au].

Sulphur compounds are reduced to sulphide by this treatment; the resid;.·

may be moistened with water and placed in contact with a silver coin wh,
a brown to black stain of silver sulphide is obtained (Hepar reaction), or
may be extracted with a little water and filtered into a freshly prepare
sodium nitroprusside solution, when an unstable purple coloration We;
indicate the presence of sulphur (see Section IV, 6, reaction 5).

(c) Moisten the substance or the infusible residue of test (b;

with one to two drops of cobalt nitrate solution and ignite
strongly.

Ob8ervation Inference

1. Blue residue. Al,O., phosphates, arsenates,

silicates, borates.
2. Green residue.
3. Pink residue.
ZnO.
MgO. I
I

Test (iv). Borax bead reactions.-Prepare a borax bead

in a loop of platinum wire by dipping the hot wire into bora)..
and heating until colourless and transparent. Bring a minutl
quantity of the substance into contact with the hot bead and
heat in the outer or oxidising flame. Observe the colour when
the bead is hot and also when it is cold. Heat the bead in the
inner or reducing flame and observe the colours in t,he hot and
cold states. Coloured beads are obtained with compounds of
copper, iron, chromium, manganese, cobalt and nickel (see,
however, Section IX, 19, Table VI).
2] Systematic Qualitative Inorganic Analysis 495

OxtdiMng flfWM Rf)(/,ucing flame Melrd

1. Green when hot; blue Colourless when hot, Copper.

when cold. opaque-red when cold.
2. Yellowish-brown or red Green, hot and cold. Iron.
when hot; yellow when
cold.
3. Dark yellow when hot, Green, hot and cold. Chromium.
green when cold.
4. Violet (amethyst), hot Colourless, hot and cold. MangRllese.
and cold.
5. Blue, hot and cold. Blue, hot and cold. Cobalt.
6. Reddish-brown when Grey or black and opa.que Nickel.
cold. when cold.

'.rhe presence of manganese and of chromium is cO:lfirmed

by fusing the substance with sodium carbonate and p01~assium
nitrate on platinum foil or broken porcelain. A green mass on
cooling indicates manganese; a yellow mass, ckromiullt. The
sodium carbonate bead test (Section II, 1, 7) may alse be em-
ployed.
A useful reaction which may be carried out at this stage is
the microcosmic bead test (Section II, 1, 6). This test is
carried out in a loop of platinum wire exactly as for tI,e borax
bead test. The presence of a white skeleton (of silien) in the
coloured glass indicates silicate. Stannic oxide Sn02 (lissolves
slowly in the bead and may be mistaken for silica.
Test (v). Test for the ammonium radical.-Boil a little
(ca. 0·1 gram) of the substance with sodium hydroxide ~olution.
The evolution of ammonia, detected by its odour and its action
upon red litmus paper and upon filter paper soaked in mer-
curous nitrate solution, * indicates the presence of an ammonium
salt.
Note. Great care must be exercised when heating mixtures rontaining
solutions of alkali hydroxides because of their destructive effects upon
the eyes. These mixtures tend to bump and should preferably be heated
in the fume cupboard. Under no circumstance8 8ho'uld one attempt to
smell the vapour whilst heating the mixture.
The following experimental details in testing for ammonia·
are of value for other gases (with suitable modificatlon of re-
agents). In order to avoid holding the test paper (litmus, etc.)
in the vapour, the apparatus shown in Fig. VII, 2, I may be
employed; the test paper is supported on the upper (:lid of the
* Drop-reaction pap~r, treated with tannic acid and silver nitrate solution
(see Section III, 36, reaction 7), may also be used.
496 Qualitative Inorganic Analysis [VH,
wide glass tube. H ammonia is present, the litmus paper
should show a gradual development of colour from the bottom
upwards and should eventually become uniformly
blue; scattered blue spots indicate that droplets
of the alkaline solution have come into contact
with the paper. The spray may be trapped, if
desired, by a loosely fitting plug of cotton wool
inserted in the upper part of the test- tube.
If the evolved gas is soluble in water and a
solution is required for further testing, the ,,1)-
paratus shown in Fig. IV, 2, 1 (with the deliv{ y
tube of fairly wide tubing and about twice i lie
length of the test-tube or distilling flfbsk in or(:,'r
to avoid the danger of "sucking bac!:") may; Ie
employed. In the present case the arrmonia m;l,'(
be absorbed in 3-4 ml. of distilled water. UP"i1
adding Nessler's reagent (Section III, 36, 2-t!!e
second method of preparation is recommende(i f,
an orange or brown precipitate confirm, ammoni I.
This test is an extremely sensitive c'ne and It I

Fig. VII, 2, 1 order to establish the presence of ammon f L

evolved in the reaction a precipitate and not fL
coloration must be obtained.

VII, 3. PRELIMINARY TESTS FOR ACID RADICALS

(ANIONS)
The action of dilute sulphuric acid (or of dilute hydrochlorie
acid) and of concentrated sulphuric acid upon the substance
combined with inferences drawn from the preliminary dry testf
supply much information which may be useful in the sub
sequent tests, notably for cations. Thus the pmsence 01
silicate, borate, fluoride, citrate, tartrate and possibly oxalat.
will have been indicated-phosphates are detected in the graUl'
separation after Group II; the course of systemati} ana]ysi,~
for the metal ions can then be appropriately modified {se,
Table I (Section VII, 6), and discussion in Chapier VIII}
The indications of the preliminary tests must, of (ourse, be
confirmed. The systematic examination for acid radical1:'
(anions) is usuaHy carried out after that of the cations.
Before describing these preliminary tests, a summ~;ry of the
solubilities of the salts of the more common acids in "ater may
be found useful in the subsequent deductions.
3] Systematic Qualitative Inorganic Analysis 497

Nitrates, chlorates, acetates, manganates and permanganates

are all soluble; exceptions are a few basic nitrates (e.g. Bi and
Sb) and basic acetates (e.g. Fe); silver and mercurous acetates
are sparingly soluble.
Nitrites are all soluble; silver nitrite is sparingly solu ble.
Ohlorides are generally soluble; exceptions are AgCl, Hg 2C1 2 ,
TlCl, CuCI, SbOCI, BiOCI, which are insoluble; PbCl 2 is
sparingly soluble.
Bromides have similar solubilities to the chlorides.
Iodides are generally soluble; exceptions are AgI, Hg 212 ,
HgI2' CuI, BiOI, SbOI, which are insoluble; PbI 2, Bila and
SnI 2 are slightly soluble.
Oarbonates are generally insoluble; those of Na, K and NH4
are soluble. The bicarbonates of the alkali metals and of Ca,
Sr, Ba, Mg, Fe and Mn are also soluble; those, other than the
alkali metals, exist only in solution.
Sulphides are generally insoluble; those of Ba, Sr and Ca are
slightly soluble; those of Na, K and NH4 are readily soluble.
SUlphites are generally insoluble; exceptions are those of the
alkali metals, and the bisulphites of the alkaline earth group.
SUlphates are generally soluble; those of Pb, Hg (ous), Sr
and Ba are insoluble; those of Ag, Hg (ic), Ca and a few basic
sulphates (e.g. Bi and Hg) are slightly soluble.
Phosphates, arsenates and arsenites are generally insoluble;
those of Na, K and NH4 are soluble.
Fluorides are generally insoluble; those of Na, K, NH4, Ag
and Hg (ous) are soluble.
Borates, with the exception of those of the alkali metals, are
insoluble.
Silicates possess solubilities similar to those of the borates.
Ohromates are generally insoluble or sparingly soluble;
exceptions are those of the alkali metals and Ca, Sr, IV[g, Mn,
Zn, Fe and Cu.
Thiocyanates of Hg (ic), Cu (ic), Fe, Ca, Sr, Ba, Mg, Na, K
and NH4 are soluble.
Thiosulphates are generally soluble; the Ag and Ba I"alts are
sparingly soluble.
Oxalates, !ormates, tartrates and citrates are generally in-
soluble; those of Na, K and NH4 are soluble.
Test (vi). Action of dilute sulphuric acid.-Treat 0·1
gram of the substance in a small test-tube with 2 ml. of 2N
sulphuric acid, and note whether any reaction takes place in
the cold (indicated by 0). Warm gently and observe the effect
produced.
 Qualitative Inorganic Analysis [VII,

Ob81l'1'vation

I. Colourless g88 is evolved with effervescenoe: CO. from carbonate ,. r

gas is odourless and produces turbidity when bicarbona teo
passed into lime water. * (0)
2. Nitrous fumes evolved: recognised by NO. from nitrite.
reddish-brown colour, and turning starch-
pot88sium iodide paper bluish-black. (0)
3. Yellowish-green gas evolved: suffocating Cl. from hypochlorite
odour, reddens and then bleaches litmus
paper: turns starch-KI paper blue: very
poiS01WUS. (0)
4. Odour of acetylene: burns with luminous, C.H. from carbide.
smoky flame. (0)
5. Colourless g88 is evolved with suffocating SO. from sulphite.
odour: turns filter paper moistened with
acidified potassium dichromate solution
green: decolourises fuchsin solution.
6. Colourless gas is evolved: gives above tests SO. and S from th, '
for SO.: sulphur is deposited in the solution. sulphate.
7. Colourless gas is evolved: odour of rotten H.S from sulphide. t
eggs: blackens filter paper moistened with
lead acetate solution: cadmium acetate paper
turned yellow.
8. Colourless g88 is evolved; gives above tests H 2S and S from pol,
for H.S; sulphur is deposited. 8ulphide.
9. Odour of vinegar. H. C2HaO 2 from aceta',
10. Colourless gas is evolved: odour of bitter HCN frow cyanide ,
almonds:j:: highly poisonous. from soh·bleferri- ai,
ferro-cya. ~ide8.
11. Colourless gas is evolved; rekindles glowing O 2 from 1leroxides an,!
splint. per-salts of alkali and
alkaline Jarth metak
12. Colourless gas is evolved; pungent odour, CO. and B little HCNO
reminiscent of SO 2; produces turbidity when from cya "late.
passed into lime water.
13. Upon boiling, yellow solution formed and SO., etc., from thi"
SO. (fuchsin solution decolourised, etc.) cya=te.
evolved. -

Test (vii). Action of concentrated sulphuric acid.-

Treat a small quantity (say, 0·1 gram) of the substance w;l,h
1-2 m!. of concentrated sulphuric acid, and warm the mixtlll'e
gently; incline the mouth of the test-tube away from the
* Magnesite, dolomite and a few other native carbonates give little 01' no
CO. in the cold; CO. is readily evolved upon warming.
t Many sulphides, especially native ones, are not affected by dilute H 2 SO.;
some H,S is evolved upon warming with concentrated HCI alone or witiJ a
little tin.
:j: If cyanide is suspected, gently warm (water bath) 5 mg. of the mix! lire
in a small test-tube (e.g. 75 X 10 mm.) with 5-10 drops of 2J1.- H 2SO.: place
a filter paper moistened at the centre with 1 drop of N aOH so lution over 1 he
mouth of the tube. After 2 minutes, treat the drop on the paper with 1 drop
of FeSO. solution, warm and add a drop or two of 6N HCI. A blue colUllr
indicates the presenCE! of a cyanide. For another test, see Section IV, 8,
_ .............. .: ......... ., 1\1f ..... '"" ... ,~_.:~ ... _, ... .,.~....:r . . . .: ................... 1.. 1"Io...J .... 1 .............1......
3] Systematic Qualitative Inorganic Analysis 499
observer. (If chlorates or permanganates are suspected from
the preliminary charcoal reduction tests to be present" very
small quantities must be used (about 0'02 gram) as a dangerous
explosion may occur on warming.)
If the substance reacted with dilute sulphuric aci(l, the
addition of the concentrated acid may result in vigorous re-
action and rapid evolution of gas, which may be accompanied
by a very fine spray of the acid. In such a case, it is best to
add dilute sulphuric fLcid dropwise to another portion of the
substance until action ceases, and then to add 2-3 ml. of
concentrated sulphuric acid.
The following results may be obtained.

Observation Inference
l. Colourless gas evolved with pungent odour HCI from chloride.
and which fumes in the air; white fumes of
NH 4 CI in contact with glass rod moistened
with concentrated NH. solution; CIa evolved
on addition of precipitated MnO. (bleaches
litmus paper; turns KI-starch paper blue).
2. Gas evolved with pungent odour, reddish HBr and Br 2 from
colour, and fumes in moist air; on addition bromide.
of precipitated MnO., increased amount of
red fumes with odour of bromine (fumes
colour moist starch paper orange-red or fluo-
rescein paper red).
3. Violet vapours evolved, accompanied by HI and Ia from iodide.
pungent acid fumes, and often SO. and even
H.S.
4. Reddish-brown fumes evolved (similar in CrO.CI. from "hloride
colour to bromine); on passing into water, in presence of
obtain chromic and hydrochloric acids, both chromate.
readily identified (yellow ppt. of PbCrO,
with excess of NH3 solution, lead acetate
solution and acetic acid; or by "perchromic
acid" test).
5. Pungent acid fumes evolved, often coloured HNO. and NO. from
brown by NO.; colour deepens upon addi- nitrate.
tion of copper turnings (if nitrites absent).
6. Yellow gas evolved in the cold with charac- CIO. from chlorate.
teristic odour; explosion or crackling noise
on warming (DANGER).
7. Yellowish-green gas evolved; irritating CIa from chloride in
odour; bleaches litmus paper; turns KI- presence of oxiduing
starch paper blue; very poisono'u8. agent8.
8. "Oily" appearance of tube in cold; on HF from fluoride or
warming, pungent gas evolved which cor- silicofluoride.
rodes the glass; if moistened glass rod intro-
duced into the vapour, gelatinous ppt. of
silicic acid is deposited upon it.

[Contin'ued (i1)erleaJ
500 Qualitative Inorganic Analysis [VII,

Observation Inference
9. Purple fumes evolved with explosion l\fn.O, f'om permu,,-
(GREAT DANGER). ganate.
10. Colourless gas evolved; burns with blue CO from formate, 0"
flame; no charring. late, cyanide, fer,
cyanid J or Jerr
cyanide."
II. Colourless gus evolved; renders lime water CO and CO. fro
turbid and also burns with a blue flame; no oxalate.
blackening.
12. COlourless gas evolved; burns with a blue CO, CO. and SO. fro'
flame and/or renders lime water turbid; as (a) tartmte,
heating is continued, SO. is evolved and (b) citrale.
residue in tube
(a) chars rapidly (odour of burnt sugar),
(b) chars slowly, accompanied by irritant
vapours.
13. Irritating fumes evolved. Benzoate.
14. Pungent odour of vinegar. H. C.H30~ from acetu
15. Dark-crimson coloration of acid. Gallate.
16. Brownish-purple coloration of acid. Tannate.
17. Colourless gas evolved; rekindles glowing 0. from peroxide
splint. some per-salts ( "
chromate,
18. Colourless gas evolved, burns with blue CO and anhydrol;',
flame, deep blue solution produced. CoSO, from cobalt,.
cyanide·t
19. Yellow coloration in cold: upon warming, COS, SO. and S frolll
vigorous reaction, COS (burns with blue thiocyanate.
flame), SO. (decolourises fuchsin solution,
etc.) and free S produced.
20. Red fumes of Br. (turn fluorescein paper Br. and 0. fro]
red) and also 01 evolved. bromate.

* If ferro- and/or ferri-cyanides are present, they mUSG be destroY"d

before proceeding with the analysis for cations because they would yj,ld
precipitates when the solution is acidified and boiled, and would also introd , 'e
other disturbing effects. This may be effected by heating abJut 1 gram "f
the mixture with 3-4 m!. of concentrated sulphuric acid in a porcelain cruci ,ie
placed in an inclined position over the flame and directing the flame agai "t
the upper part of the crucible. The heating is continued until fu mes of sulp] ,Lr
trioxide cease to be evolved. The residue is then treated with a little c, it·
centrated sulphuric acid, warmed gently and water added portionwise. '1! e
whole is then boiled for about 5 minutes, and filtered when cold, The filtr;, ' e
may be analysed for aU metals except lead, strontium and baJ'ium which, If
present, will be found in the residue.
Alternatively, the complex cyanides may be eliminated fron the mixtll f'e
by fusing with an equal weight of sodium or potassium carbonate in a porcel;, Cl
crucible. Soluble cyanates and cyanides are formed, which ma:, be extract, ,,f
with water; the residual metallic iron may be dissolved in dilutoJ hydrochloric
acid.
K.[Fe(ON).J + K.CO. = 5KCN + KONO + CO. + Fe
t Rarely encountered in routine qualitative analysis; it characteristic teHt
is the white precipitate, insoluble in nitric acid, produced with ferrous
Bulphate solution (see under Cobalt, Section III, 24, reaction 4),
3] Systematic Qualitative Inorganic Analysis 501
Test (viii). Test for nitrate (or nitrite).-If ammonium
has been found {test (v)}, boiling is continued until ammonia
can no longer be detected by its action upon mercurous nitrate
paper or upon red litmus paper. Add a little (say, 0·1 gram)
aluminium powder or zinc dust or finely powdered Devarda's
alloy to the cooled solution and warm the mixture gently.
Remove the flame as soon as evolution of hydrogen commences
(with aluminium powder the reaction may become vigorous;
cooling with tap water may be necessary to moderate the vigour
of the reaction).
If ammonia is evolved, as detected by its odour, its action
upon litmus paper and upon filter paper soaked in mercurous
nitrate solution, * then the presence of a nitrate or nitrite is
indicated (compare Section IV, 18, reaction 4). The presence
of a nitrite will generally also be detected in the reaction with
dilute sulphuric acid {see test (vi)}; if nitrite be absent, then
the presence of nitrate alone is indicated.
Cyanides, thiocyanates, ferro- and ferri-cyanides also yield ammonia
under these experimental conditions. The reaction is somewhat
slower for these anions; up to 5 minutes may elapse before ammonia
can be detected from ferro- and ferri-cyanides. If these are present,
or are suspected as a result of the preliminary tests, particularly
that with concentrated sulphuric acid, they must first be removed
as follows. Treat the "Na2COg prepared solution" with excess of
nitrate-free silver sulphate, warm the mixture to about 60°, shake
vigorously for 3-4 minutes, ar.d filter from the silver salts of the
interfering anions and excess of precipitant. Remove the excess
of silver ions from the filtrate by adding an excess of sodium hydrox-
ide solution and filter off the precipitated silver oxide. Evaporate
the filtrate to about half bulk and test with zinc, aluminillm or
Devarda's alloy. If cyanides alone are present, they may be
rendered innocuous by the addition of a little mercuric chloride
solution.

Test (ix). Borate test.-Make a paste of the original sub-

stance with calcium fluoride and concentrated sulphuric acid.
Hold some of this in a platinum loop just outside the base of
the Bunsen flame. A green flame, due to boron trifluoride,
indicates borates. Barium and copper do not interfere when
the test is carried out in the above manner.
* It must be emphasised that the mercurous nitrate paper test for ammonia
is not applicable in the presence of arsenite. Arsenite is reduced by alkaline
reducing agents to arsine, which blackens mercurous nitrate paper. The
tannic acid-silver nitrate test (Section III, 36, reaction 7) may also be used;
this test is likewise not applicable in the presence of arsenite.
 Qualitative Inorganic Analysis (VII,
Alternatively, the following test (which is strongly reci dn-
- mended) may be employed. Fit up the appara1us showy, in
Fig. VII, 3, 1, using rubber stoppers; the end )f the ri& itt-
angled bend should be drawn out into a capillary of not m"re
than 0·5 mm. bore and 3-4 cm. long. The empty test-tilbe
acts as a trap between the mOllth
and the test-tube cOLtaining : ~le
solution under test to prevent ; he
solution from reaching the mOilth
should the capillary become blod; d.
Place about 0·1 grarr of the S i! b-
stance in the test-tube, add 1-2 ;,11.
of concentrated sulphu::ic acid " 1th
the aid of a dropper or small pipe 1 0e,
followed by 5-6 ml. of methyl alc( :lol
in I ml. portions (caution!). In m-
duce the modified "wash-boM Ie"
'--" ~ tubes and connect by a short leI1:!th
Fig. VII, 3, 1 of rubber tubing to the trap. B'!I)W
gently through the liquid and din'ct
the vapours issuing from the capillary into a colourless Bun ,en
flame. If a borate is present, the flame will acquiro a charac ' or-
istic green colour due to the volatile methyl borate B(OCB :h.
Under these experimental conditions copper and barium, w); !ch
colour the flame green, do not interfere. *

EXAMINATION FOR METAL IONS (CATJONS) H,

SOLUTION
VII,4. PREPARATION OF A SOLUTION OF TdE
SOLID
Use small quantities (5-10 mg.) of the powdered solid ,Ind
examine the solubility in the following solvents in the or ler
given: (l) water, (2) dilute hydrochloric acid, (3) 'Joncentrfl' ed
hydrochloric acid, (4) dilute nitric acid, (5) concerctrated nj, !'ic
acid and (6) aqua regia. Try the solubility first in the c' ,ld
and then on warming; if in doubt whether the substance ( " a
portion of the substance has dissolved, evaporate a little of he
clear solution on a watch glass. If the substance dissolve, in
water, proceed immediately to test for the metal ions. If the
* This procedure is simpler than that of Section IV, 45, 15; the lalter.
however, is fool-proof and perfectly Wlambiguous.
5] Systematic Qualitative Inorganic Analysis ~03

use of dilute hydrocllioric aoid results in the formation of a

precipitate, this may consist of the metals of Group I; the
precipitate may either be filtered off and examined fur this
group, or else the original substance may be dissolved in dilute
nitric acid. If concentrated hydrochloric acid is employed for
solution, it will be necessary to evaporate off most of the a.cid
since certain metals of Group II (e.g. cadmium and lei1d) are
not completely precipitated in the presence of large coneentra-
tions of acid. Where nitric acid has been used for the process
of solution, all of the acid must be removed by evaporating
nearly to dryness, adding a little hydrochloric acid, evaporating
again to a small bulk and then diluting with water; these
remarks also apply to aqua regia. For this reason nitric acid
is often omitted from the solvents, and the tests confined to
solvents 1, 2, 3 and 6.
When a suitable solvent has been found, the solution for
analysis is prepared with 0·5-1 gram of the solid; the volume
of the final solution should be 15-20 m!.
If the substance is insolu ble in aqua regia (and in concentrated
acids), it is regarded as in80luble and is treated by the special
methods detailed in Section VII, 21 below.

VII,5. GENERAL SCHEME FOR THE SEPARATION

OF THE CATIONS INTO GROUPS
Before describing the general scheme (for a simplified general
scheme, see Section V, 8) for the separation of the met,al ions
into groups, the following facts are brought to the notice of the
student as it is believed that by their proper understanding and
appreciation, many of the usual pitfalls will be avoided.
(I) The analysis should not be conducted with large quan-
tities of the substance because much time will be spent in
filtering the precipitates and diffioulty will be experienoed in
washing and dissolving them. It is therefore recommended
that 0·5-1 gram should be employed for the analysis. After
a little experience the student will be able to judge from the
relative sizes of the precipitates, the relative quantities of the
various components present in the mixture.·
(2) The tests must, in the first place, be carried ouf, in the
order given. A group reagent will separate its partioular group
only from those whioh follow it and not from those which
precede it. Thus hydrogen sulphide in the presence of O'3N
hydrochloric acid will separate Group II from Groups IlIA,.
UIB, IV and V, but does not separate Group II from Group I.
504 Qualitative Inorganic Analysis [V: I,
It is most important therefore that one group should be COill-
pletely precipitated before precipitation of the noxt group is
attempted, otherwise the group precipitates will be con-
taminated by metals from the preceding groups, and misleading
results will be obtained.
(3) The conditions for precipitation and for solution mU:3t
be rigidly followed.
(4) All precipitates must be washed to remove adheriflg
solution in order to avoid contamination by the ml.:,tals rema: '1-
ing in the filtrate. The first washings should be added to i 11e
solution from which the precipitate has been filtered; later
washings may be discarded.
(5) If the volume of the solution at any stage of the analY:'is
becomes too large, it should be reduced by evaporation.
(6) All the apparatus employed in the analy-;is must be
scrupulously clean. The use of dirty appara1ius may be
sufficient to introduce impurities into the substance under
examination.

NOTES ON TABLE I (GENERAL TABLE FOR SEPARATION

OF CATIONS INTO GROUPS)
(1) If the original substance was completely soluble in dilute H. a,
it is evident that no silver or mercurous salt is present. When It ,d
is present, the solution may be clear whilst hot, but PbCl 2 is le-
posited on cooling the solution. Any lead missed in this group will
be precipitated with H 2S in Group II.
A precipitate may form upon the addition of HCI to cert;jjn
neutral or slightly acid solutions even when none of the Group I
metals are present. This may occur under the following conditio: ;~:
(a) Aqueous solutions of Sb, Bi and-Sn, not containing free Hi '1,
precipitate as the oxychlorides upon the addition of this acid. The
precipitate dissolves, however, upon the addition of excess of acid.
(b) Concentrated solutions of certain chlorides, e.g. NaCI and
BaCI2 , may form precipitates upon the addition of HCI; these dis-
solve on diluting with water.
(c) Borates may yield a white crystalline precipitate of boric acid,
particularly if the acid is concentrated; only partial precipitation
may occur here.
(d) Silicates may yield a gelatinous precipitate of silinic acid; only
partial precipitation may occur here.
(e) The thio-salts of arsenic, antimony and tin will give the cor-
responding sulphides.
(2) The H 2 0 2 solution is added to oxidise Sn ++ to Sn ++++, thus
leading ultimately to the precipitation of SnS2 in place of the SODle-
what gelatinous SnS. The excess of H 20 2 should preferably be de-
composed by boiling before passing H 2S, otherwise some S may be
precipitated. The subsequent separation of Groups lIA and IIB by
 6] Systematic Qualitative Inorganic Analysis 505

~
.........o
~
o
606 Qualitative Inorganic A nalysia [VII,
means of aqueous KOH is thus rendered more complet<3 since SJ'~2
dissolves entirely and SnS dissolves only partially in 211 KOH.
If it is intended to use ammonium polysulphide in the separatilln
of Groups IIA and IIB, the addition of H 2 0 2 is not es~ential sj, ,)e
(NH4)2S, will oxidise SnS to SnS2 and the latter disfDlves as ' he
thiostalmate (NH4hSnSs'
(3) It is important that the concentration of HCI be appr{;\ci.
mately correct, i.e. 0'3N, before passing H 2S: with higher com,'n·
trations of acid, lead, cadmium and stannous tin will be ;ncomple1' Iy
precipitated; if the acidity is too low, sulphides of Group nIB (~;S,
CoS and ZnS) may be precipitated.
Either of two methods may be employed to adj'lst the : ,id
concentration.
(a) Concentrate the solution until it has a volume of 10-15 111.
Cool. Add concentrated NHs solution dropwise from a drO] per
pipette, with constant stirring, until the mixture is alkaLne. (IgI,' lre
any precipitate which may form: this either dissolves when the '[CI
is added or else is converted into the sulphide by the H 2 S treatm'·:lt.)
Introduce dilute HCI dropwise until the mixture is just acid, Ise
litmus paper). Then add 2·0 ml. of 3N HCI (mea:mred fro 'l a
graduated pipette or a calibrated dropper) and dilut<, the soIl: ion
to a volume of 20 m!. with distilled water.
(b) An alternative procedure is to make use ofthe indicator m. ! hyl
violet (0·1 per cent aqueous solution or, better, the purchase·! or
prepared indicator paper). The following table gives the C010I'1 of
the indicator at various concentrations of acid.
Acid concentration pH Methyl violet i,tdicator
Neutral or alkaline 7+ Violet.
O'lN HOI 1'0 Blue.
0'25N HOI 0'6 Blue-green.
0'33N HOI 0'5 Yellow-~<"""
0'50N HOI 0'3 Yellow.

Add 1 drop of the methyl violet indicator solution aucf'intr( luce I'

dilute HCI or dilute aqueous NHa (as necessary) drol'wise and 'vith
constant stirring until the colour of the solution is yellow-grl' '1: a
blue. green colour is almost but not quite acid enough, yet is a( ept-
able for most analyses. (If the indicator paper is availablt the
thoroughly stirred solution should be spotted on frEsh portic"s of
the paper.) It is recommended that a comparison solution con·
taining, say, 10 mI. of O'3N HCI and I drop of indicltor be f],'shly
prepared: this will facilitate the correct adjustment of the ae"lity.
A more satisfactory standard is a buffer solution prep.tred by IJ" xing
5 mL of N sodium acetate and 10m!. of N HOI: this solution as a
pH of 0·5.
(4) For the passage of H 2 S into the solution, the la1 er is
placed in a small conical flask (one of 50 m1. capacity is suit;lble)
and the "pressure" method used as detailed in S<,ction II, l, 7.
6] Systematic Qualitative Inorganic Analysis 507
Heat the solution almost to boiling and pass in H 2S, whilst slowly
shaking the flask with a swirling motion, until precipit1~tion is
complete: the latter will be apparent when bubbling either stops
altogether or is reduced to a very slow rate of 1-2 bubbles per minute.
Saturation is normally reached in 2-5 minutes. The best method
of determining whether precipitation is complete is to filter off a
portion of the solution and to test the filtrate with H 2S. If only a
white precipitate or suspension of sulphur is obtained, the presence
of an oxidising agent is indicated.
If an oxidising agent is present (e.g. a permangan;tte, di-
chromate or ferric salt), as is shown by the gradual separat:on of a
fine white precipitate of sulphur and/or change in colour of the
solution, it is usual to pass 80 2 into the hot solution until reduction
is complete, then to boil off the excess of S02 (test with K2Cr207
paper) and finally to pass H 2S. Arsenates, in particular, are slowly
precipitated by H 2S: they are therefore generally reduced by S02
to arsenites and then precipitated as As 2Ss with H 2S, after prior
removal of the excess of S02 in order to avoid interaction of the
latter with H 28 and the consequent separation of S. Stannic
compounds may be very slightly reduced to the stannous Etate by
this treatment; the amount of reduction is, however, so small that
it may be neglected. The original solution or substance must be
tested for the valence state of the arsenic.
The objection to the use of S02 is that some sulphuric add may
be formed, especially upon boiling, and this may partially precipi-
tate Pb, Sr and Ba as sulphates. Any precipitate formed in this
process should accordingly be examined for these cations: PbS04
is soluble in ammonium acetate solution.
An alternative procedure to be borne in mind when arsem~te, etc.,
is present, which does not possess the disadvantages associa~ed with
S02 and is perhaps more expeditious, is to add 2-3 m!. of concen-
trated HCI and 0·5 m!. of 10 per cent ammonium iodide solution.
The arsenate is thereby reduced to arsenite, and upon saturation of
the hot solution with H 2S under "pressure," the arsenic is com-
pletely precipitated as AszS s. This reduction can be carried out
after the sulphides of the other elements have been precipitated in
the presence of 0'3N HCI.
The precipitated sulphides may be washed with a wash liquid
prepared by dissolving 0·25 gram of NH4NO a in 5 ml. of water and
treating this solution with HzS. The H 2S must be present in the
wash liquid to prevent oxidation of some of the moist sulphides to
sulphates.
(5) Nitric acid is added to oxidise ferrous iron to the ferric state;
if ferric iron was originally present, it will have been reduced by the
H 2S. Alternatively, bromine water may be used for the o;xidation:
the excess of bromine must be removed by boiling. Ferrous iron
is incompletely precipitated by NHs solution in the pr(':ience of
NH,Cl.
508 Qualitative Inorganic Analysis [VII,
Organic acids interfere with the normal course of ar alysis. , hus
in the presence of oxalic, tartaric or citric acids, the addition 0 the
group reagent NH4CI and NHs solution might fail to Jause the !lre-
cipitation of the hydroxides of Fe, Al and Cr. FlIIthermO! , if
oxalic acid is present, the oxalates of some of the me "als of Gr ups
IIIB, IV and of Mg, which are insoluble in ammon acal sole ,on,
might be precipitated at this stage. It is therefof3 essenti" 1 to
destroy the organic acids, the presence of which has 1>ee11 indie ted
!

in the preliminary tests, before precipitation of Grou;:> IlIA. ;'his

is best effected by evaporation with concentrated nLric acid :ntil
the black residue is completely oxidised. It is important DI to
heat the residue too strongly as it may convert any Fe, AI (: Cr
present into the form of the sesquioxide which is difLcultly so [ble
in concentrated HCI.
If benzoic and/or salicylic acid are present, the free acidl-! will
separate upon the addition of HCI and they shoulc therefOl be
looked for in the Group I precipitate. If any salicylic acid sl ,uld
pass through to Group III, great care must be taker when e\ !po-
rating to dryness with concentrated HNO s since the nitro-sali ylic
acids explode on strong heating.
(6) Borates and fluorides of the metals of Group IIIB, IV 1nd
of Mg are insoluble (or sparingly soluble) in ammoncacal solu ion,
and are therefore liable to be precipitated at this stag3. They nay
be removed by repeated evaporation with concentrated HCI the
boric acid will slowly volatilise in the steam and the hydl gen
fluoride with the excess of HCI.
(7) Boric acid alone is more rapidly eliminated as the vo ,tile
methyl borate B(OCHs)s (highly poisonous). If much boric a' i is
present, two treatments with CHsOH and HCI may te require I.

(8) Unless silicates are removed here, they are likflly to be 'on-
fused with AI(OH)s in the group separation. RepeatEd evapor lion
with concentrated HCI converts silicates into a gra:mlar for I of
hydrated silica, which is readily filtered, particularl~' after a -inal
digestion with dilute :e:CI. The precipitate should h3 subject! l to
the microcosmic salt bead test or to the silicon tekafluoride test
(Section IV, 26).
Solutions of silicates are decomposed by dilute B CI into f :icic
acid, which may partially separate in Group I in the gElatinous: rm.
That not precipitated in Group I will be precipitat ed by N 1[4CI
solution in Group IlIA (see under Silicates, Section 1'1, 26, real,tion
2).
(9) The phosphates of the metals of Group IlIA, IIIB, IV al:l} of
Mg are insoluble in water and in ammoniacal solutioll, and ma,\' be
precipitated at this stage. An excellent method for the remo';11 of
phosphate is given in Table II (Section VII, 7).
(10) It is recommended that a small portion of tho filtrate! ,'om
Group IlIA be tested first with a little aqueous NHa and H 28 If
a precipitate is obtained, the main solution should be ~reated iJ this
6] Systematic Qualitative Inorganic Analysis 509
manner. If there is no precipitate, metals of Group HIB are absent
and the main filtrate from Group IlIA may then be employed in
testing for Group IV, etc.
The student should remember that the conditions for the precipi-
tation of Group HIB differ from those in Group H. In the latter
Group, H 2 S is passed into an acid solution in which the gas is only
slightly soluble and hence much of it escapes unabsorbed unless the
"pressure" technique is employed. In the former Group, the
solution is alkaline and therefore the H 2 S is readily absorbed.
Moreover, if too much H 2 S is employed, NiS may partially form a
colloidal solution. This is largely avoided by passing H 2S for 30-60
seconds, and testing for completeness of precipitation. Some
authors recommend that H 2S be passed into a solution :1cidified
with acetic acid and thus avoid the complication due to colloidal NiS
(11) The wash liquid for the Group HIB precipitate may consist
of 1 per cent NH4CI to which 1 per cent by volume of ammonium
sulphide solution is added. Oxidation of the moist sulphides to the
soluble sulphates is thus considerably reduced.
(12) If the solution or the filtrate from Group HIB is brown or
dark in colour, Ni may be suspected. The dark-coloured Kolution
contains colloidal NiS, which runs through the filter paper. It may
be acidified with acetic acid, and then boiled until the NiS has
coagulated: this may either be added to the Group HIB precipitate
or tested separately for Ni. As a geneml rule, the addition of
macerated filter paper (e.g. in the form of a portion of a Whatman
filtration accelerator or ashless tablet) to the suspension before
filtration will lead to a clear or colourless solution.
(13) The filtrate must be acidified immediately and concentrated
to remove H 2S. Ammonium sulphide solution on exposure to air
slowly oxidises to ammonium sulphate and would then precipitate
any barium or strontium present as BaS04 or SrS04' Another
reason for the immediate acidification of the filtrate from Group
HIB is to prevent the absorption of CO 2 from the air \yith the
attendant formation of carbonate ions: the latter would also pre-
cipitate the ions of Group IV.
(14) The initial filtrate from Group HIB will contain a very high
concentration of ammonium salts. The concentration of ammonium
ions is much greater than is necessary to prevent the precipitation
of Mg(OHh and it may also lead to incomplete precipitation of the
carbonates of Group IV metals. The latter effect is due to the acidic
properties of the ammonium ion:
NH4+ + CO a-- ~NH3 + HC0 3 - ;
the concentration of C0 3-- ions upon the addition of (NH4)2C03
would thus be reduced considerably. For these reasons most of
the ammonium salts must be eliminated first.
Concentrated HN0 3 decomposes NH4Cl at a lower temperature
than is required for its volatilisation:
NH,CI + HNO. OF'1\TH,NO. + HCI = N.O + 2H.O + HCl
510 Qualitative Inorganic Analysis [VII,
Loss by decrepitation and spurting during this Opel ation must
be avoided.
(15) The" ammonium carbonate solution" contains neuch ammo.
nium bicarbonate NH4HCO a and will accordingly form soluble ! ,i.
carbonates with the alkaline earth metals unless excess ·)f ammo,· la
solution is present; in the latter case the amount of lormal C'1'·
bonate (NH4)2COg present will be increased. When Irecipitati Ilg
Group IV, the solution should be warm (ca. 50°0) to decomp' )~e
any bicarbonates formed. The solution must not, lowever, be
boiled because the reaction
MCO a + 2NH,Cl ~ MCl a + (NH,)aCOa
is reversible; boiling decomposes the (NH4)zC0 3 , the I eaction \I ill
proceed from left to right and the precipitate will dissolve (see a);,o
Section III, 29, reaction 2).
Ammonium carbonate decomposes appreciably above 60°0:
(NH,)2COa -+ 2NHa + CO 2 + Hp
The digestion also improves the filtering properties of thE precipitate.
(16) Owing to the slight solubility of CaCO s, SrCO s and BaCOa
in solutions of ammonium salts, the filtrate from Group IV 'W ill,
when these metals are present, contain minute amount3 of the j')IlS
of the alkaline earth metals. Since the Group IV metals llJcl.y
interfere to a limited extent with the flame tests for Na and K :lnd
also with the Na2HP04 test for Mg (if employed), it has been recoill-
mended that the filtrate from Group IV be heated with a Ii t tIe
(say, 1 ml.) of (NH4hS04 solution and (NH4)2C204 ilolution and
filtered from any precipitate which forms. Owing ,0 the com·
paratively small concentration of ammonium salts, thit. is genet:lUy
unnecessary if the procedure described in Table X (Sec ;ion VII, 15)
is adopted.

NOTES ON PHOSPHATE SEPARATION TABLE (TABGE II)

(1) The HCI concentration should not exceed N, otherwi,,· a
turbid supernatant liquid is obtained and the pre;ipitatioJ' of
phosphate is not quantitative.
(2) This is usually termed the zirconium nitrate :·~eagent. Its
preparation is described in the Appendix (Section A, 2).
(3) It is important that the excess of the zirconium nitrate rea 'lnt
should not exceed 25 per cent, otherwise a turbid supernatant Iir, 'lid
will be obtained: this turbidity cannot be removed by filtratio;, or
centrifugation. It is best, therefore, to add the zirccnium nil l),te
solution slowly and with stirring until precipitation appears ,. 'ID-
plete, heat just to boiling, filter and test the filtrate with th,· re-
agent, etc.
(4) The addition of half a Whatman filtration accolerator ( if a
little filter paper pulp) assists filtration; the precipLate IDm' be
washed thoroughly with hot water. The filtration acoelerator . On-
sists of compressed filter paper which disintegrates on boilinc; it
7] Systematic Qualitative bwrganic Analysis 511
VII,7. Table II.-Phosphate Separation Table (Zirconyl
Nitrate Method)·

Reduce the volume of the solution to about 10 mI. by evaporati,m, if

necessary. Adjust the Hel concentration so that it does not exceed N (1).
Add 0·5-1 gram of solid NR.C1, stir until dissolved and then add zirt)onyl
nitrate reagent (2) slowly and with stirring until precipitation is com·
plete (3): a large excess of the reagent must be avoided. Rea" the
contents of the test·tube or small conical flask just to boiling aml stir
with a glass rod to prevent bumping. Filter through a Whatman 1\ o. 32
filter paper (4). Wash the ppt. with a little hot water, and combine the
washings with the filtrate.
---------.-----------------------------------------
Residue. Filtrate. Test if all phosphate has been precipitated
Zirconium by the addition of a drop of the zirconyl nitrate reagent.
phosphate. Add about 0·5 gram of solid NH.el, heat to boiling. add
Reject. a slight excess of dilute NH3 solution (i.e. until the
odour of NH. is permanent in the boiling solution),
boil for 2-3 minutes and filter.

Residue. Examine for Group Filtrate. Exa.

lIlA by Group Separation Table mine for Groups
IX or IXA (Section VII, 14). The IIIB, IV and V as
excess of Zr will be found in the detailed in C.meral
residue after treatment with H.O. Table I (Sflction
and N aOH solution (or with sodium VII,6).
perborate NaBO.,4H.O and boil·
ing), and will accompany any
Fe(OR)., if Fe is present.

,
increases the speed of filtration by retaining part of the precipitate
and thus preventing the clogging of the pores of the filter paper.

Explanation (Table Ill)

The metal ions of lead, silver and mercurous mercury are
precipitated by dilute HCI as the insoluble chlorides PbCI 2,
AgCI and Hg 2Cl 2 respectively; the chlorides of all the other
common metals are soluble. The separation of these is based
upon the following facts:
(1) PbCl 2 is soluble in boiling water, whilst Hg 2 Cl 2 and AgCI
are insoluble. Extraction of the precipitate with hot water
therefore removes the PbCI 2 • Confirmatory tests for lead ions
are applied to the solution so obtained, e.g.
PbC1 2 + K 2CrO, = PbCrO, + 2KCl, etc.,
(for details, see under Lead, Seotion III, 2).
• For an alternative, but less satisfaotory, phosphate separatlon, see
Table I (Section VIII, 1).
512 Qualitative bwrganic Analysis [V't,
VII, 8. Table IlL-Analysis of Group I (SHver Groul:
The ppt. may contain PbOI" AgOI and Hg 2Cl.. Wash the ppt. on tit
filter first with 2 ml. of 1-2N HOI, then 2-3 times with 1 ml, portions of
cold water and reject the washings with water. Transfer the ppt. to '.'
small beaker or to a boiling tube, and boil with 5-10 ml. of water. Filte,·
hot.

Residue. May contain Hg 2Cl 2 and Filtrate. May cant", I

AgCl. Wash the ppt. several times with PbCI •.
hot water until the washings give no ppt. 0001 a portion of the so! ,
with K.OrO. solution: this ensures the tion: a white crj stalline p!
complete removal of the Pb. of PbCI. is obtained if Pb
Pour 3-4 ml. of warm dilute NH. solu. present in any ql.antity.
tion over the ppt. and collect the filtrate. Divide the fil ;rate into :3
parts:
(i) Add K.CrJ. eoluti l.
Residue. If Filtrate. t May con· Yellow ppt. of PhCrO"
black, consists of tain [Ag(NH 3 ).]Cl. soluble in dilute l.cetic aciL
Hg(NH.)CI + Divide into 3 parts: (ii) Add KI sc lution. 1 [-
low ppt. of Ph1., soluble n
Hg. (i) Acidify with
H~ (ous) dilute HN0 3 • White boiling water to a colour' ;8
present. * ppt. of AgOl. solution, which ieposits 1, 1-
(ii) Add a few drops liant yellow Q) 'Ystals u; n
of KI solution. Pale cooling.
yellow ppt. of AgI. (iii) Add dilute Hoi" •.
(iii) Add a few drops White ppt. of PbSO., soh Ie
of the rhodanine re- in ammonium acetate s, .1
agent. tion.
A~ present. Pb pre~ent.

(2) AgOI is solu ble in dilute NH3 solution, yielding the so (ble
complex salt [Ag(NH 3 )2]Ol. The solution of this comple:l. salt
is decomposed by both dilute HN0 3 and by KI Ilolution fith
the precipitation of the insoluble- salts AgOI and AgI re pec-
tively.
AgOl + 2NHa = [Ag(NHsh]Ol;
[Ag(NHs)z]CJ + 2HNOs = AgOl + 2NH,N')s;
[Ag(NHs)z]Ol + KI = AgI + KOl + 2NHs
* This is a conclusive test for mercurous mercury. It may be j ~ther
confirmed by dissolving the ppt. in 3-4 ml. of boiling aqUl, regia, di ting,
filtering if necessary, and then adding SnOl s solution. A white ppt. (I! ,01.),
turning grey (Hg), is obtained.
t IfHg is present in reasonably large quantity and Ag has nlt, been dE' cted,
carry out the above confirmatory test for Hg, and treat the thor 19h1y
washed residue, insoluble in aqua regia, with dilute NB. "olution. 'ilter,
if necessary, and add dilute RNO. to the clear solution. A white !'i)t. oj
AgCl will form if small amounts of Ag are present. This ,s an alten,ativE
procedure for separating Ug and Ag in Hg.Cl.-AgCI mixtur!,.
When the amount of Hg(NH.)Cl + Hg is large and that )f AgCI i" mall,
the latter may be reduced to metallic silver according to tho, reaction,
2Hg + 2AgCl = Hg.Cl. + 2Ag,
and thUIJ .cape detection.
9] Systematic Qualitative Inorganic Analysis 513
The rhodanine reagent (Section III, 4, reaction 7) gives a.
precipitate with a solution of [Ag(NH s}2]Cl: any interference
by mercury (or cuprous copper) is thus eliminated.
(3) The conversion of Hg 2C1 2 by dilute NH40H solution
into the insoluble black mixture of amino mercuric chloride
Hg(NR2}CI and finely divided mercury.
Hg2Cl 2 + 2NHs = Hg(NH2lCI + Hg + NH4CI
Aqua regia converts the black mixture into RgCl 2 (see under
Mercury (Section III, 3, reaction 1)}. The mercuric ion is then
detected with SnC1 2 solution.
2HgC12 + SnC12 = SnC~ + Hg2C12 ;
Hg 2Cl 2 + SnC12 = SnCI, + 2Hg
VII, 9. Table IV.-Analysis of Group II (Copper and
Arsenic Groups). Separation of Group IIA (Copper
Group) and Group lIB (Arsenic Group)
Metluxl A
The ppt. may consist of the sulphides of the Group IIA metals (HgS,
PbS, Bi.S., CUS, CdS) and those of Group IIB (As.S" SbIS" Sb.S" SnS,
SnS,). Wash the precipitated sulphides with a little 5% NH,CI solution
that has been saturated with H.S (the latter to prevent conversion of CuS
into CuSO, by atmospherio oxidation), transfer to a porcelain dish, add
about 5 mI. of yellow ammonium sulphide solution, heat to 50-60 cO,· and
maintain at this temperature for ~4 minutes with constant stirring.
Filter·t

Residue. May contain HgS, Filtrate. May contain solutions of

PbS, Bi,S., CuS and CdS. the thio-salts (NH,).AsS" (NH,)aSbS,
Wash once or twice with small and (NH,).SnS •. Just acidify by add-
volumes of dilute (1 : 100) am- ing concentrated Hel dropwise (test
monium sulphide solution, then with litmus paper), and warm gently.
with 1% NR,NO. solution and A yellow or orange ppt., which may
reject all washings. contain As.S" As,S" Sb,S" Sh,S, and
Group lIA present. snS"t indicates Group lIB present.

Explanation (Table IV)

The sulphides of mercuric mercury, lead, bismuth, copper
and cadmium a.nd of arsenic, antimony and tin are precipitated.
by H 2S in the presence of dilute (O·3N) HCI. The 6ulphides
• If the ammonium sulphide extract is boiled for BOme time in the air, a
red antimony oxysulphide Sb sOS 2 may be precipitated.
t If the precipitate is completely soluble in yellow amm0nium sulphide
solution, Group IIA is absent. '
t If much S and little sulphide is suspected, shake with a littl" benzene:
the sulphides oollect at the boundary .urface.
17+
14 Qualitative Inorganic Analysi8 [VII,
f arsenic (As 2S 3 ), antimony (Sb zS 3 and Sb zS5 ) and d tin
,nSz) (Group HB) are soluble in yellow ammonium sulphide
)lution forming thio-salts, whilst those of the other netals
:troup HA) are insoluble. Stannous sulphide SnS is insoluble
ld antimony trisulphide Sb 2S 3 is sparingly soluble in c.)lour-
ss ammonium sulphide solution, but both of these di:lsolve
,adily in the yellow ammonium sulphide solution; the E;nS is
mverted into the thio-stannate. Colourless ammoniulll sul-
lUde solution consists largely of ammonium hydrosulphide
H 4HS (the normal ammonium sulphide (NH 4)zS doe:; not
lem to exist in aqueous solution). The yellow ammcnium
Llphide solution contains an excess of sulphur and may be
Irmulated (NH4)2S",: the formula (NH.1)2S2 is often used for
te last-named in writing equations, but there is some evidence
tat the solution contains the pentasulphide (NH4)zS5. Yellow
nmonium sulphide and not colourless ammonium sulphide is
lerefore generally used in one method for the separati)n of
roups IIA and lIB. The separation of sulphur upon anidifi-
,tion is a disadvantage.
As 2S S + 3(NH4 l2S2
= S + 2(NH,lsAsS, (ammonium thio-arsenate)
Sb 2S a + 3(NH4 )2S2
= S + 2(NH4 )aSbS4 (ammonium thio-antime,nate)
SnSz + (NH')2SZ = S + (NH4l2SnSa (ammonium thio-staDIlate)
SnS + (NH')2S2 = (NH')2SnSa
Upon acidifying the solutions of the thio-salts with dilute
Cl, the sulphides are precipitated, and the excess of ammo-
um sulphide is decomposed.
2(NH,)aAsS4 + 6HCl = AS 2S6 + 6NH,CI + 3H2S
2(NH,)aSbS, + 6HCl = Sb 2S5 + 6NH,CI + 3H2S
(NH,hSnSs + 2HCI = SnS2 + 2NH,CI + H 2S
(NH')2S2 + 2HCI = S + 2NH,CI + H 2S

Explanation (Table IVA)

By digesting the Group II precipitate with 2N KOH solution,
e sulphides of As, Sb and Sn (ic) dissolve whilst those of Hg,
), Bi, Cu and Cd are largely wlattacked. The very slight
lubility of PbS is reduced by adding a little H 2S ,rater
~. S--): some HgS will dissolve in the presence of S-- and,
consequence, provision is made for the detection of fIg in
th Groups lIA and lIB.
9J Systematic Qualitative Inorganic Analysis 515
VII, 9. Table IVA.-Analysis of Group II (Copper and
Arsenic Groups). Separation of Group IIA (Copper
Group) and Group lIB (Arsenic Group)
Method B
The ppt. may consist of the sulphides of the Group IIA metals (HgS.
PbS. Bi,S •• CuS and CdS) and those of Group IIB (As.S •• Sb 2S •• Sb,8 5
and SnS 2*). Wash the precipitated sulphides with a small volume of 5%
NH.Cl solution that has been saturated with H 2S. Transfer the ppt. to
a roo ml. beaker or porcelain basin. add 10 m!. of 2N KOH solution and
boil with constant stirring (CAUTIONt) for 2-3 minutes. Add 3 ml. of
freshly prepared, saturated H,S water. stir and filter (preferably through
a double filter). Wash the residue with a little water and collect ),he
washings with the filtrate.

Residue. May con· Filtrate. May contain RAsO., KAsS,.

tain HgS, PbS. Bi,S" KSbO., KSbS 2 , K,[Sn(OH).], K 2SnS. and a
CuS and CdS. little K.[HgS.]. Transfer to a small conical flask
Group IIA present. or beaker, add concentrated HCl dropwise and
Reserve the ppt. for with stirring until the mixture is distinctly add
analysis by Table V. to litmus paper. Treat with H.S for 2 minutes
to ensure complete precipitation of the sulphidos.
The formation of a ppt. indicates the possible
presence of Hg, As, Sb or Sn. Filter and wash
the ppt. with a little water. Reserve the residlle
for analysis by Table VIA.
Group lIB present.

Potassium hydroxide is employed in preference to sodium

hydroxide since sodium antimonate is sparingly soluble.
+ 6KOH
As 2S a
= 3H 0 + KaAsOa + KsAsSa (potassium thio-arsenite)
2
2Sb 2S a + 4KOH = 2H 2 0 + KSb0 2 + 3KSbS z
Sb 2S5 + 6KOH = 3H 2 0 + K aSbS4 + KaSbSOa
3SnS2 + 6KOH
= 3H zO + KzSnOa + 2K2SnSa (potassium thio-stannate)
HgS + KzS = K 2[HgS z]
Upon acidification with Hel, the sulphides are precipitated:
KaAsOa + KaAsSa + 6HCI = 3H2 0 + ASzS a + 6KCI
KSb0 2 + 3KSbS 2 + 4HCI = 2H2 0 + 2Sb 2S a + 4KCl
K aSbS4 + KaSbSOa + 6HCI = 3H2 0 + Sb 2S6 + 6KCl
K2SnOa + 2K2SnSa + 6HCI = 3HzO + 3SnS2 + 6KCl
K 2 [HgS z] + 2HCI = HgS + 2KCl + H 2S
* Stannous sulphide is not completely soluble in 2N KOll. The oxidation
with H 2 0 2 solution will have converted Sn ++ into Sn ++++ (see Table I).
t Potassium hydroxide is an extremely dangflrous substance because of ita
destructive effect upon the eyes. Precipitates, when heated with KOll
solution, tend to bump. Suitable precautions should therefore be taken:
the process should be carried out in the fume cupboard.
 516 Qualitative Inorganic Analysis [VII,
The disadvantages attending the use of ammonium poly-
_ sulphide in the separation of Groups IIA and lIB Hre:
(i) Some CuS and HgS are dissolved.
(ii) In the presence of large quantities of the Copper Group,
small amounts of tin may escape detection.
(iii) Acidification of the ammonium polysulphide extJ"ct
leads to the precipitation of sulphur, which may obscure i he
presence of sulphides of Group lIB.
(iv) Ammonium polysulphide solution, unless freshly l't'e-
pared, may contain sulphate and this will lead to jihe preci pi-
tation of barium as BaS04, etc.

Explanation (Table V)
The residue insoluble in yellow ammonium sulphide solution
or in 2N KOH solution may contain HgS, PbS, Bi 2S 3, ells
and CdS. Their separation is based upon the following fact,,:
(1) HgS is insoluble in dilute HNO a ; the sulphidefc ofPb, 1:1,
Cu and Cd dissolve with the formation of nitrates.
3PbS + 8HNO a = 3Pb(NO a)2 + 2NO + 38 + 4 Ei2 0
Bi28 a + 8HNOs = 2Bi(NO a)a + 2NO + 3S + 4H 2 0
One confirmatory test for Hg involves the convemion of t;i0
HgS by aqua regia or by NaOCI-HCl into HgCI 2 , and tL'j
familiar reduction of the latter by SnCl 2 solution. *
3HgS +2HNO s +
6HCl = 3HgCl2 38 + +
2NO + 4H 2 0
(2) The filtrate from the nitric acid treatment contains t}l(~
nitrates of Pb, Bi, au and Cd. Dilute H 2S04 precipitates l'l}
as PbS04, leaving the other metals (which form se,luble sul-
phates) in solution.
Pb(NOs )2 + H 2S04 = PbS04 + 2HNOs
The object of the evaporation with H 2S04 until white fumt~~
appear is to eliminate the HCI and HN0 3 , which have a slight.
solvent action upon the PbS0 4. The PbS0 4 is converted by
ammonium acetate solution into lead acetate, which. is only
feebly ionised in the presence of excess of acetate iens. The
insoluble PbCr0 4 is precipitated upon the addition of K2CrO~
or K 2Cr20 7 solution.
PbS04 + 2NH4 • C2H a0 2 = Pb(C2 H a0 2 )2 + (NH4 )2S04
2Pb(C2H s 0 2 )2 + K 2 Cr2 0 7 + H 2 0
= 2PbCr04 + 2H. C2H a0 2 + 2K. C2H sOc
• Confirmatory tests will not, in general, be described in detail where they
have already been given under the reactions of the metal ions.
 10] Systematic Qualitative Inorganic Analysis 517
VII, 10. Table V.-Analysis of Group IIA (Copper Group)·
The ppt. may contain HgS, PbS, Bi.S., CuS and CdS. Transfer to B
beakert or porcelain basin, add 5-10 ml. of dilute HNO a, boil gently for
2-3 minutes, filter and wash with a little water.
Residue. Filtrate. May contain nitrates of Pb, Bi, Cu and Cd.
Black: HgS. Test a Rmall portion for Pb by adding dilute H.SO, and
Dissolve in alcohol. A white ppt. of PbSO. indicates Pb J,resent.
a mixture of If Ph present, add dilute H 2S0 4 to the remainder of the
2·5 mI. of solution, concentrate in the fume cupboard until white
10% NaOCI fumes (from the dissociation of the H.SO,) appear. Cool,
solution and add 10 ml. of water, stir, allow to stand 2--3 minutes, filter
0·5 ml. of and wash with a little wa.ter.
dilute HCI. Residue. Filtrate. May contain nitrates and sul-
Add 1 ml. of White: phates of Bi, Cu and Cd. Add concen.
dilute HCI, PbSO,. trated NH. solution until solution is
boil off excess Pour 2 ml. distinctly alkaline. Filter.
of CI. and of ammon- Residue. Filtrate. Mav contain
cool. Add ium acetate White: may be [Cu(NH')4]++ a;'d
SnCI. solu- through Bi(OH)a. Wash. [Cd(NH.).J++.
tion. the filter Dissolve in the If deep blue in colour,
'White ppt., several minimum Cu is present in quantity.
turning grey times, add volume of dilute Confirm Cu § by acidify-
or black. to the fil- HCI and pour ing a portion of the fil.
Hg (ie) trate a few into cold sodium trate with dilute acetio
present. drops of stannite solu- acidandaddK,[Fe(CN),]
dilute acetic tion.t I solution.
acid and Black ppt. Reddish·brown ppt.
then K.CrO. Bi present. Cu present.
solution. Alternatively, To the remainder of the
Yellow ppt. dissolve a little filtrate, add KUN Bolu·
of PbCrO,. of ppt. in 2-3 tion Ii drop wise until
Pb present. drops of dilute colour is discharged, and
HNO.. Place 1 add a further ml. in
drop of this excess. Pass H.S for 20-
solution upon 30 seconds.
filter paper Yellow ppt., s,)metimes
moistened with discoloured, of CdS.
cinchonine·KI Cd present.
reagent. Filter off ppt. and dis.
Orange-red spot. solve a portion of it in
Bi present. 1 ml. of dilute HCl: boil
to expel HIS and most of
the acid and apply the
"cadion-2B" test on 1
drop of the solution. A
pink spot confirms Cd. 'If

* For an alternative Table, which is stron.gly recommended, see Section

III, 10, Table IIA.
t This is most easily effected by making a small hole in the Glter with B
pointed glass rod, and washing the ppt. into the beaker or basin with dilute
HNO a•
:j: Sodium stannite is prepared by adding NaOH solution to 1 mI. of SnCI,
solution until the ppt. of Sn(OH). first formed redissolves.
§ Alternatively, just acidify a small portion with dilute H 2SO,. Add I
drop of this solution to a few drops of dilute znSo, solution, and then intro-
duce a little ammonium mercuri.thiocyanate reagent.. A violet ppt. confirms
Cu. The ppt. can be rendered clearly visible by adding B little nmyl alcohol
and shaking: it collects in and colours the organic layer.
" If the solution is colourless, the addition of KCN solution may be omitted.
~ Cd may also be confirmed in the ppt. by the ignition taRt with NB,C,O.,
ete. (Section III, 9).
 I I!
518 Qualitative Inorganic And,lysi8 - - rVII •
(3) The addition of excess of NHa solution results in the
precipitation of Bi(OHh and the formation of tlte soluble
complex salts, [Cu(NIIa)4]S04 and [Cd(NH a)4JS04.
Bi2 (804)s + 6NHs + 6H20 = 2Bi(OH)a + 3(NH4: 2804
CUS04 + 4NHs = [CU(NH )4]S04 S

CdS04 + 4NHa = [Cd(NH a)4]S04

The sodium stannite solution reduces the Bi(OH)a to Bi and
is itself oxidised to sodium stannate.
2Bi(OH)s + 3Na2[Sn02] = 2Bi + 3Na2[SnOa] + 3H20
(4) The addition of acetic acid to the blue solution decom-
poses the complex into CUS04 and NH4 .C 2H a0 2 ; K.[Fe(CN)GJ
solution yields reddish-brown CU2[Fe(CN)6].
[Cu(NH s)4]S04 + 4H.C2H sOz = CUS04 + 4NH4 .C2H a0 2
K 4[Fe(CN)e] + 2CUS04 = CU2[Fe(CN)e] + 2K zS04
If copper is absent, passage of H 2S into the solution of tl,,~
complex salt precipitates CdS, the final reaction being:
[Cd(NHa)4]S04 + H 2S = CdS + (NH4)2S04 + 2~-Hs
If copper is present, the addition of excess of KCN solutio::
converts the ammine complexes into the colourless complex
cyanides, potassium cuprocyanide K 3 [Cu(CN)4J and potassium
cadmicyanide K 2[Cd(CN)4J.
2[Cu(NH s )4]S04 + lOKCN
= 2K 3[Cu(CN)4] +
2K 2S04 (CNh+ 8N11 1 +
[Cd(NHs )4]804 + 4KCN = K 2[Cd(ON)4] + K 2S04 4NHs-+
the cyanogen produced reacts with the solution:
(CN)z + 2NHs + H 20 = NH4CNO + NH4CN
With potassium cuprocyanide, the concentration ofth~ cuprou~l
ions produced by the secondary ionisation of the complex ion
[Cu(CN)4r-- is insufficient to exceed the solubility product of
CU 2S upon the addition of H 2S; no precipitation therefore
occurs. Potassium cadmicyanide, on the other hand, lH
relatively unstable (compare Section I, 20) and the concentra-
tion of cadmium ions arising from the secondary diE sociation
of the [Cd(CN)4r- iE1 sufficient to exceed the solubilit~· product
of CdS when H 2S is passed into the solution.
Ks[Cu(CN),t] ? 3K + + [Cu(CN)4r-- ? 3K + + Cu + -+- 4CN-
KII[Cd(CN),] ~ 2K + + [Cd(CN),r- ~ 2K + + Cd ++ + 4CN-
11] Systematic Qualitative bwrganie Analysis 519
VII, 11. Table VI.-Analysis of Group liB (Arsenic Group)
Method A

Treat the yellow ammonium sulphide extract of the Group II ppt. (see
Table IV) with dilute HCI, with constant still'ing, until it is slightly acid
(test with litmus paper), warm and shake or stir for 1-2 minutes. A fine
white or yellow ppt. is sulphur only. A yellow or orange flocoulent ppt.
indicates As, Sb and/or Sn present. * Filter and wash the ppt., whioh may
contain As.S., As.S" Sb.S., SnS. and S, with a little HaS water'; rejeot
the washings.
Transfer the ppt. to a small conical flask, add 5-10 ml. of oonoentrated
Hel and boil gently for 5 minutes (with funnel in mouth of flask). Dilute
with 2-3 ml. of water, pass HaS for 1 minute to reprecipitate small amounts
of arsenic that may have dissolved, and filter.

Residue. May contain Filtrate. May contain H[SbCl,] and

As.S, (and/or As.S.) + S: H.[SnCI.]. Boil to expel HaS, and divide the
yellow. cold solution into three parts.
Dissolve the ppt. in :{-4 (i) Render just alkaline with dilate NBs
mL of warm dilute NBs solution, disregard any slight ppt., add 1-2
solution, filter (if neces· grams of solid oxalic acid, boil and pass H.S
sary), add 3-4 ml. of 3% for ca. I minute into the hot filtrate.
H.O. solution and warm Orange ppt. of Sb.S •.
for a few minutes to oxi· Sb present.
dise arsenite to arsenate. (ii) To 2 drops of the solution on a spot
Add a few ml. of the plate, add a minute crystal of NaN0 2 and then
Mg(NO.). reagent. Stir 2 drops of Rhodamine·B reagent.
and allow to stand. Violet solution or ppt.
White, crystalline ppt. of Sb present.
Mg(NH.)AsO.,6H.O. (iii) Partially neutralise the liquid, add 10
As present. t em. of clean iron wire to 1 ml. of the solution.
Confirm as follows. (If much Sb is present, it is better to reduce
Filter off ppt., and pour with Mg powder.) \Varm gently to reduce the
1 ml. of AgNO. solution tin to the stannous state, and filter into a
containing 6-7 drops of solution of HgCI •.
2N acetic acid on to White ppt. of Hg.Cl 2 or grey ppt. of Hg.
residue on filter. Brown. Sn present.t
ish.red residue of (iv) Treat 0·2-0·3 ml. of the solution with
Ag,AsO,. 5-10 mg. of Mg powder, add 2 drops of FeCl a
solution, 2-3 drops of 5% tartaric acid solu·
tion, 1-2 drops of dimethylglyoxime reagent
and then dilute NHs solution until basic.
Red coloration.
Sn present. t

Explanation (Table V J)
The precipitate obtained upon acidifying the ammonium
sulphide (NH4)2S", extract may contain As 2S5 (and/or AS 2S 3 ),
* If eu is present in the original Group II ppt., a small amount may be
dissolved by the armnonium sulphide solution and re.predpitate here
(brownish.red).
t If As or Sn is found, the original solution must bo tested to 811Certain
whether present in the .Q1U or .iI: state.
520 Qualitative Inorganic A nalY8i8 [VII,
Sb 2SIIo Sn8 z and S. Their separation depends upon the follo"\v "
ing facts: \
(1) As 28 5 is almost unaffected by coucehtrated Hel, whil~L
8b 285 and Sn8 2 dissolve forming chlorides:
Sb 2Sfj + 6ilCl = 2SbCI s+ 3H2S + 2S
SnS2 + 4HCI = SuCl, + 2H2S
(2) The AS z8l) and/or As 2Sa is converted by ammoniach!
H 20 2 solution into arsenate:
AS 2S5 + 16NHs + 20H20 2
= 2(NH4)sAsO" + 5(NH4)2S0" + 12H2()
As 2S S + 12NHs + 14H20 2
= 2(NH4)sAs04 + 3(NH4)2S04 + 8H20
The arsenate is readily identified with the Mg(NO a)2 reagen!
or with magnesia mixture as the crystalline Mg (NHdAs 0",
6H 20:
(NH4hAs04 + Mg(NO a)2 = Mg(NH4)As04 + 2NH4NO a
(3) The filtrate from the HCI treatment contains 81>C1 3 (OJ
H[8bCI4 ]) and 8nCl4 (or H 2[8nClt;]). Antimony is identified by
adding NH3 solution and a large excess of oxalic acid to the
mixture: a relatively stable tin-oxalate complex ion is formed.
The antimony-oxalate complex ion is less stable and an appre-
ciabJe concentration of 8b + + + ions is present in solution.
Hence whei~., 1I 28 is passed into the solution, Sb 28 3 alone is
precipitated. -'-'Co;~tinued treatment with H 28 (beyond 3-5
minutes) may, howe~1:' ~es~t in t~e ~ecomposition of the t.in-
oxalate complex ion: tillS will be mdlCated by the darkenmg
of the orange 8b 8 pre{,ipitate. Antimony is also identified
by the characteri:ti~ reacti9n with Rhodamine-B (8ection III,
14, reaction 7). . -~_
(4) The addition of met~Pic iron to the diluted solution
reduces the 8nCl4 to 8nCl 2 a)~d the 8bC13 to. black 8b; upon
Illtration, the solution contajns 8nC1 2 a~d IS. free from Sb.
~he 8nC1 2 is identified by the'l,usual. reactIOn WIth H~CI!~ solu-
,IOn; the FeC1 2 produced has Ill:0 actIOn upon the HgC1 2·
SnOl4 + Fe ==1= SuOl2 + FeC1 2
G
2SbOl a + 3Fe = 2Sb + 3FeCl 2
'he tin may also be identified "4 by the dimethylglyoxime test
3ection III, 16, reaction 6). ' ".. ,
11] Systematic Qualitative Irwrganic AnalY8i8 521
VII, 11. Table VIA.-Analysis of Group lIB (Arsenic
Group)
Method B

The filtrate from the Copper Group (KOH extract) may contain KAsO.,
KAsS., KSbO., KSbS., KzSnO. or K.[Sn(OH)a], K.SnS. and a little
K.[HgS.]. Add concentrated HCI cautiously (dropwise and with cantious
stirring) until the solution is distinctly acid to litmus paper. Treat; with
H.S for 2-3 minutes to ensure complete precipitation of the sulphides.
The formation of a ppt. indicates the possible presence of HgS, .\s.S.,
Sb.S. and SnS.. Filter; wash the ppt. with a little water and discard
the washings. Transfer the ppt. to a small conical flask, add 5- J 0 m!.
of concentrated HCl, heat to boiling [FUME CUPBOARD] and maintain
the mixture near the boiling point over a free flame for 3-5 minutes; stir
constantly. Dilute with a little water and filter.

Residue. May contain HgS and Filtrate. May contain

As,S.. If yellow, ouly As.S. present. H[SbCI.] and H,[SnCl.].
Wash with water. Pour 5 mI. of dilute Divide into three parts.
NH. solution through the filter 2 or 3 (i) Render just alkaline with
times. dilute NH. solution, disregard
any slight ppt., add 1-2 grams
of solid oxalic acid, boil and pass
Residue. Filtrate. Add dilute HaS for ca. 1 minute into the hot
If dark. HNO. until distinctly solution.
coloured acid. Orange ppt. of Sb,S,.
(HgS). Yellow ppt. of As.S •. Sb present.
Hg As present. t (ii) To 2 drops of the solution
present. Confirm by redissolving on a spot plate, add a minute
Confirm ppt. in 3-4 mI. of warm, crystal of NaNO~ and then 2
as in Table dilute NH. solution, add drops of Rhodamme·B r£,agent.
V, if Hg 3-4 mI. of 3% H.O. solu· Violet ppt. or solution.
not found tion and warm for a few Sb present. t
in Group minutes to oxidise arsenite (iii) Partially neutraliHe the
IIA. to arsenate. Add a few liquid, add 10 cm. of clean iron
mI. of Mg(NOala reagent, wire to 1 mI. of the solution.
stir and allow to stand. (If much Sb is present. it is
White ppt. of Mg(Nfl.). better to reduce with Mg
AsO.,6H.O. Pour on the powder.) Warm gently to reo
filter 1 m!. of AgNO. duce the tin to the stannous
solution containing 6-7 state, and filter into a sulution
drops of 2N acetic acid. ofHgel,.
Brownish.red residue of White ppt. of Hg.Cl. or grey
Ag.AsO,. ppt.ofHg.
Sn present. t
(iv) Treat 0·2-0·3 mI. of the
solution with 5-10 mg. of Mg
powder, add 2 drops of FeCI.
solution, 2-3 dropa of 5 % tar·
taric acid solution, 1-2 drops of
dimethylglyoxime reagent, and
then dilute Nfl, solution until
basic.
Red coloration.
Sn present.

t If AI or Sn is found, the original solution must be te.ted to ascertain

whether present in the ·OWI or .f(; state.
17·
 LVU,
Explanation (Table VIA)
The precipitate obtained upon acidifying the KOH extract
may contain As 2Sa, Sb 2S a, SnS2 and a little HgS (for equations,
see Explanation to Table IVA). The basis of the subsequent
steps is similar to that described for Table VI with the variation
that HgS may accompany the As 2Sa precipitate. These two
sulphides are readily separated by utilising the fact that As 2S S
alone is soluble in NHa solution; upon acidifying the ammo-
niacal extract, yellow As 2Sa is precipitated.
ASzS a +
6NHs +
3H2 0 = (NH4)aAsOa + (NH4)aAsS s
(NH4hAsOa +
(NH4hAsSs 6HNOa+
= As 2S a + 6NH4NO a + 3H20
Explanation (Table VII)
The precipitate may contain Fe(OH)a, Cr(OH)a, Al(OH)a and
a little Mn0 2 ,xH 2 0: Co, Ni, Zn and some Mn remain in solution
as the complex ammine ions. {The Mn0 2,xH 20 owes its
formation to oxidation of some Mn(OH)z (which is held in
solution by NH 4Cl and aqueous NHs) by air and also pn,rtially
to the HNO a or Br2 water treatment made primarily to oxidise
Fe + + to Fe + + +: some Mn + + is simultaneously oxidised to
Mn ++++ and the latter is precipitated as MnOz,xHzO by the
group reagent.} The separation is based upon the following
facts:
(1) When the precipitate is boiled with NaOH and H 20 Z
solution (or with NaB.0 a,4H 20 solution), the Al(OH)a is con-
verted into the soluble sodium aluminate NaAl0 2 and the
Cr(OH)a is oxidised to the yellow, soluble sodium chromate
Na2Cr04. The Fe(OH)s and Mn0 2 ,xH 20 remain undiswlved.
The excess of H 20 2 is decomposed upon boiling: any reduction
of chromate upon acidification is thus avoided.
AI(OH)a + NaOH = NaAl0 2 + 2H 2 0 '
2Cr(OHh + 3H20 2 + 4NaOH = 2Na2Cr04 + 8H20
NaBO a + H 20 = NaB0 2 + H 20 2
The tests for Or in the yellow solution of Na20r04 include
the precipitation of PbCr04 with acetic acid and lead acetate
solution (Section IV, 33, reaction 3) and the formation of
"perchromic acid," best in the presence of a little amyl
alcohol (Section IV, 33, reaction 4).
Aluminium is identified by reprecipitation as Al(OH)s by
 12] Systematic Qualitative Inorganic Analysis 523
VII, 12. Table VII.-Analysis of Group IlIA (Iron Group)*

The ppt. produced by adding NH,CI and NH. solution may oontain
Fe(OH)., Or(OH)., Al(OH). and a little MnO.,xH.O. Wash with a little
hot 1% NH,OI solution. Transfer the ppt. with the aid of 5-10 m!. of
water to a small evaporating basin or a small beaker, add 1-1·5 grants of
sodium perborate NaBO.,4H.0 (or add 5 mI. of NaOH solution, followed
by 5 ml. of 3% H.O. solution). Boil gently until the evolution of O.
ceases (2-3 minutes). Filter.

Residue. May contain Filtrate. May contain Na.CrO,

Fe(OH). and l\1nO.,xH.O. (yellow) and/or NaAlO, (colourless).
Wash with a little hot water. If colourless, Cr is absent and need not
Dissolve a small portion of be considered further.
the ppt. in 1 ml. of dilute If the solution is yellow, Or is indicated.
HNO a (1 : 1) with the aid (if Divide the liquid into three portions.
necessary) of 3-4 drops of 3% (i) Acidify with acetic acid and add
H.Oa solution or 1 drop of lead acetate solution.
saturated H.SO. solution. Yellow ppt. of PbCrO,.
Boil (to decompose H 20,), Cr present.
cool thoroughly, add 0·05-0·1 (ii) Acidify 2 mi. with dilute HNO"
gram of sodium bisIDuthate, cool thoroughly, add 1 mi. of amyl alcohol,
shake and allow the solid to and 4 drops of 3% H.O, solution. Shake
settle. well and allow the two layers to sephrate.
Violet solution of HMnO,. Blue upper layer (containing "per-
Mn present. chromic acid"; it does not keep well).
Dissolve another portion of Cr present.
the ppt. in dilute HOI (filter, (iii) Acidify with dilute HOI (test with
if necessary). litmus paper), then add dilute NH. solu-
Either-Add a few drops of tion until just alkaline. Heat to boiling.
KSCN solution. Filter.
Deep red coloration. White gelatinous ppt. of Al(OH),.
Fe present. Al present.
Or-Add K.[Fe(CN}.J solu- Dissolve II small portion of the ppt. in
tion. 1 m!. of hot dilute HOI. Cool, add 1 mI.
Blue ppt. of 10% ammonium acetate solution and
Fe present. 0·5 mI. of the "aluminon" reagent. Stir
The original solution or sub- the solution and render basic with ammo-
stance should be tested with nium carbonate solution. A red ppt.
K.[Fe(ON)e] and with KSCN confirms the presence of Al.
to determine whether Fe + + or
Fe+++.

boiling in the presence of NH4Cl and by the "aluminon" test

(Section III, 21, reaction 7).
NaAl0 2 + NH4Cl + H 2 0 = Al(OH)a + NaCl + NHa
(2) The precipitate (Fe(OHh +
Mn02,xH20), remammg
after boiling with NaOH + H 20 2 or with NaBO a,4H 20, is
tested portionwise for Fe and Mn. Extraction with dilute HCI
dissolves the Fe(OHh as FeCl a : the solution may be treated
* The removal of interfering acid radicals (organic acids, borates, fluorides,
silicates and phosphates) has been described in Tables I and II; ,jee alto
Chapter VIII.
524 Qualitative Inorganic Analysis [VII,
with K.[Fe(CN)6J or with KSCN solution (Section III, 20,
reactions 5 and 10) and the presence of Fe established.
Another portion of the precipitate is dissplved in dilute HN0 3
and a few drops of H 20 2 solution: )
Mn0 2 + H 20 Z + 2HNOa = Mn(NOa)2 + 2H2 0 + O2 ,
and the Mn ++ is oxidised to permanganic acid HMn04 wit,h
sodium bismuthate NaBi0 3 (Section III, 26, reaction 7) ,>r
with Pb0 2 and HNO a (Section III, 26, reaction 5).

VIl,13. Table VIlI.-Analysis of Group IlIB (Zinc GrOllp)

Method A
The ppt. may contain CoS, NiS, MnS and ZnS. Wash well with 1 ~ ..
NH,CI solution to which 1 % by volume of (NH4)2S has benn added
reject the washings. Transfer the ppt. to a small beaker. Add 10 ml
of N HCI (1 volume of concentrated acid: 11-12 volumes of \\ater), sti·
well, allow to stand for 2-3 minutes and filter.

Residue. If black, may Filtrate. May contain MnCl. Bnd ZnCl,

contain CoS and NiS. Test and, possibly, traces of Cocl. and NiCI 2 .
residue with borax bead. Boil until H.S removed (test with lead
If blue, Co is indicated. acetate paper), cool, add excess of NaOl i
Dissolve the ppt. in a solution, followed by 1 mI. of 3% H 20,
mixture of 1'5 m!. of 10% solution. Boil for 3 minutes. Filter.
NaOCI solution and 0·5 mI.
of dilute HCl. Add 1 mI. of
dilute HCl, and boil until Residue. Largely Filtrate. May
all Cl. is expelled. Cool MnO.,xH 20 and per- contain Na.[ZnO.].
and dilute to about 4 mI. haps traces of Ni(OH). Divide into two
Divide the solution into and Co(OHls (1). Dis- parts.
two equal parts. solve the ppt. in 5 mI. (1) AC!dify with
(i) Add J mI. of amyl of dilute HNO. (1 : 1) acetic acid and
alcohol, 2 grams of solid with the addition of a pass HaS. White
NH,SCN and shake well. a few drops of 3% H 20. ppt. of ZnS.
Amyl alcohol layer coloured solution, if necessary (2). Zn present.
blue. Boil to decompose ex- (ii) J Uf.t acidify
Co present. cess of H.O. and cool. with dilute H 2SO.,
(ii) Add 2 ml. of NH.CI Add 0·05 gram of add 0'5 mI. 01
solution, NH. solution until sodium bismuthate, stir o . 1 % 'J 0 b a 1 t
alkaline, and then excess and allow to settle. acetate 30lution
of dimethylglyoxime reo Purple solution of and 0·5 m!. of
agent. HMnO•. the ammonium
Red ppt. Mn present. mercuri-thio-
Ni present. cyanate reagent:
stir.
Pale blue ppt.
Zn pr("sent.

Notes. (1) The Mn may be separated, if desired, from any Co

or Ni by reprecipitating as Mn0 2 in ammoniacal solution. To
the nitric acid solution {Mn02 + 2HNOa + H 20 2 = Mn(NO a)2 +
13) Systematic Qualitative Inorganic Analysi,9 525
O2 + 2H zO}, add 5 m!. of NH401 solution and about 5 ml. excess
of dilute aqueous NHs. Then add 1 gram of solid K 2S2 0 S , boil for
30 seconds, filter and wash. The 00 and Ni remain in solution as
[00(NHs)6]+++ and [Ni(NH3)6]++' The Mn0 2 may be filtered off,
dissolved in HNO s + H 20 2 , etc. This separation is not essential.
(2) Any Ni(OH)2 and Oo(OH)s present will dissolve in the
HNO s + H 2 0 2 to form Ni(NOs)z and OO(NOSJ2 respectively. They
dissolve less readily than Mn0 2 , so that if any difficulty is ex-
perienced in effecting complete solution of the precipitate, the
undissolved solid may be discarded and the clear solution used to
test for Mn.

Explanation (Table VIII)

The separation of NiS, CoS, MnS and ZnS, which may be
contained in the pre~ipitate, is based upon the following facts:
(1) MnS and ZnS dissolve readily in cold, very dilute (ca. N)
HCl, whilst NiS and CoS dissolve only slightly during the short
period (2-3 minutes) that the sulphides are in contact with the
acid.
MnS + 2HOl = MnOl 2 + H 28
ZnS + 2HOI = ZnOl2 + H 28
The presence of small amounts of Ni + + and Co + + ions in the
filtrate (containing l\-fu ++ and Zn ++ ions) causes no serious
interference in the subsequent tests.
(2) The detection of Co and of Ni in a mixture of CoS and
NiS is carried out upon separate portions of the solution pre-
pared by dissolving the sulphides in aqua regia or in a mixture
of N aOCI solution and dilute HCI:
3008 + 2HNOs + 6HOI = 300012 + 2NO + 3S + 4H20;
8 + 6HNOs = H 2S04 + 6N0 2 + 2H 2 0
The tests employed are highly sensitive; moderate quantities
of other elements do not interfere and separation is therefore
unnecessary .
The NH4 SCN test for Co depends upon the formation of the
blue ammonium cobaltothiocyanate (NH4MCo(SCN)4] or of
the free acid H 2[Co(SCN)4] (in the presence of Hel), which
dissolve and are comparatively stable in amyl alcohol. The
disturbing effect of iron (due to the red [Fe (SCN)] +"-), may be
eliminated by the addition of a soluble fluoride when the
complex and highly stable ferrifiuoride ion [FeF6 r-- is
formed (Section III, 24, reaotion 6).
526 Qualitative Inorganic Analysis [VII,
The dimethylglyoxime test for Ni (Section III, 25, reaction
8) is applicable in the presence of Co provided exoess of the
reagent is added.
(3) The solution containing MnOl 2 and ZnOl2 and possibly
hraces of 0001 2 and NiOl 2 is boiled to remove HzS, and then
warmed with a little H Z0 2 solution to oxidise the 00 ++ to
Jo+++ and the Mn ++ to Mn ++++: 00(OH)2 is slightly soluble
but Oo(OHh is insoluble in excess of NaOH solution. Upon
:Ldding excess of NaOH solution, the Zn(OH)z precipitated
nitially will dissolve to form sodium zincate N aZ[Zn02]'
whilst MnOz,xHzO and traces of Ni(OH)2 and Oo(OHh will
be precipitated.
The Mn is readily identified in the precipitate by dissolving
:.t in dilute HN0 3 and a little H 20 Z and applying the sodium
bismuthate test (see Explanation to Table VII).
The Zn may be identified as white ZnS by passing H 2 S into
;he NaOH extract as such or acidified with acetic acid:
Na2Zn02 + H 2S = 2NaOH + znS
\. characteristic test for Zn is the mercuri-thiocyanate reaction
vith a small amount of 00(N0 3 )2 solution and the ammonium
nercuri-thiocyanate reagent. A pale blue precipitate is formed
which may be readily detected by shaking with a little amyl
~lcohol). This is due to coprecipitation of the cobalt complex
vith that of zinc (Section III, 27, reaction 9):
:n++ + Co++ + 2[Hg(SCN}4r- ~ Zn[Hg(SCN}4] + Co[Hg(SCN)4]
:inc ions, if present alone, give a white precipitate. With
races of copper salts, a blue-violet precipitate forms.
 13] SY8tematic Qualitative Inorganic AnalY8is 527
VII, 13. Table VIIIA.-Analysis of Group IIIB (Zinc
Group)
Method B
The ppt. may contain CoS, NiS, MnS and ZnS. Wash well with 1 %
NH.Cl solution to which 1 % by volume of yellow ammonium sulphide
solution has been added; reject the washings. Transfer the ppt. to a
porcelain basin, add 5 m!. of water and 5 mI. of concentrated HCl and
stir for 2-3 minutes. If a black residue is obtained, the presence of NiS
and OoS is indicated: if complete solution takes place, only small amounts
of Ni and Co are likely to be present. Evaporate the mixture to 2·-3 ml.
in the FUME OUPBOARD, add 4 ml. of concentrated RNO. (1) and
concentrate to 2-3 ml. If the solution is not clear, dilute with 8-10 ml.
of water, filter off the sulphur and return the filtrate to the porcelain basin
in the fume cupboard. Boil down to 1-2 mI., taking great care not to
evaporate to dryness. Add 5 ml. of concentra.ted RNO. and evaporate
again to 1-2 ml. (2).
Remove about 0·2 ml. of the solution with the aid of a dropper to a.
small test· tube, add 5 ml. of dilute RNO, and then O·} gram of sodium
bismuthate: stir and allow to stand. A purple coloration, due to R]\[nO.,
indicates Mn present. If Mn is present, treat the remainder of the
solution in the porcelain basin in accordance with the procedure com·
mencing at (A): if Mn is absent, continue the analysis from (B) onwards.
(A) Add 10-15 ml. of concentrated HNO" and heat just to boiling in
the fume cupboard. By means of a spatula (preferably of glass), add
finely-powdered KCIO. in 0·1 gram portions [GREAT OARE: DAAGER
OF EXPLOSION (3)]; after each addition boil gently until the greonish-
yellow vapours of chlorine dioxide are expelled. Continue the ad,lition
of 0·1 gram portions, boiling gently after each addition, until 1'5 grams
have been added. A brown or black ppt. of hydrated MnO. will form.
Dilute with 3 ml. of water. Filter the ppt. through a small sintered glass
funnel or crucible, and wash the ppt. with 2-3 ml. of water.

Residue. Filtrate. Evaporate in a porcelain basin [1" UME

MnO •• xH.O. OUPBOARD] to 2-3 ml. Allow to cool.
(B) Dilute with 5 ml. of water. Add excess of NaOH
solution and 1 ml. of 3Yo H 2 0! solution (4). Boil for
11 minutes and filter.
1-------------------------------,----------------
Residue. May contain Ni(OH). Filtrate. May
and OO(OR)3' contain Na~Zn02'
Dissolve the ppt. in dilute HOI, Test for Zn as
and test for Co and Ni as detailed detailed in Table
in Table VIII. VIII.

Notes. (1) The precipitate is first treated with dilute Hel alone,
partly to indicate the presence of Ni and Co in quantity but also
because much free sulphur and sulphate would be formE,d if an
oxidising agent were used with the HCI at this stage.
(2) The repeated evaporation with concentrated HN0 3 completely
removes chloride ion, which interferes with the subsequent precipi-
tation of Mn0 2 •
(3) The action of KCIO a in concentrated HN0 3 is rapid and
vigorous, and one of the decomposition products is the explosive,
528 Qualitative Inorganic Analyaia [VII,
greenish-yellow gas 010 2 , If the chlorate is added in small quan-
tities as instructed and the solution is boiled gently between each
addition to prevent the accumulation of 010 2 , the procedure is
reasonably safe and the only evidence of explosion will be a gentle
puff of gas. Under no circumstances may more than 0·1 gram of
KOlOa be added at one time.
(4) The H 2 0 2 solution is added to ensure the complete precipita-
tion of cobalt as cobaltic hydroxide Oo(OH)s, since cobaltous
hydroxide is slightly soluble in excess of NaOH solution.

Explanation (Table VIllA)

The salient facts in the separation of the elements in Group
IIIB a.re:
(1) The addition of dilute HCI to the group precipitate will
serve to indicate the presence of Co and Ni in quantity sinct'
CoS and NiS do not dissolve appreciably in the cold.
(2) Boiling of the undissolved sulphides with HCI in th(·
presence of concentrated HNO a or with concentrated HNO,
alone results in the solution of the sulphides and the separatiol;
of sulphur:
3008 + 2HNOa + 6HOl = 300012 + 2NO + 3S + 4H 20
or 300S + SHNOs = 30o(NOs)2 + 2NO + 38 +- 4H20
If the action of concentrated HNO a is continued, the 8 will
gradually pass into solution as H 2S04 ,
(3) The ]\!n is first precipitated from a concentrated HNO;s
solution by means of KCI0 3 :
Mn(NO a)2 + 2KOIO s = Mn0 2 + 2KNOa + 2010 2
(4) In the subsequent separation of Ni, Co and Zn, the
addition of excess of NaOH solution will yield a precipitate of
cobaltous and nickelous hydroxides and a solution (If sodium
zincate:
Zn(NO a)2 + 4NaOH ~ Na2Zn02 + 2NaN03 + 2H20
Cobaltous hydroxide is slightly soluble in alkali hydroxide
solution. The addition of a peroxide (or of bromine water)
oxidises it to cobaltic hydroxide, which is precipitated quanti-
tatively:
14] Systematic Qualitative Inorganic Analysis 529
VII, 14. Table IX.-Analysis of Group IV (Calcium Group)
Method A
The ppt. may oontain 13aCO" SrCO, and CaCO,. Wash with a little
hot water and rejeot the washings. Dissolve the ppt. in 5 ml. of hot
2N acetic acid by pouring the acid repeatedly through the filter paper.
Test 1 ml. for barium by adding K,CrO. solution dropwise to the nearly
boiling solution. A yellow ppt. indicates 13a.
Ba present. Heat the remainder of the solution almost to boiling
and add a slight excess of KICrO. solution (i.e. until the solution assumes
a yellow colour and precipitation is complete). Filter and wash tha ppt.
(0) with a little hot water. Render the hot filtrate and washings basic
with NflB solution and add an excess of (NH.).CO. solution or, better, a
little solid Na 2CO.. A white ppt. indicates the presence of SrCO, and/or
CaC0 8 • Wash the ppt. with hot water, and dissolve it in 4 ml. of warm
2N acetic acid: boil to remove excess of CO. (solution A).
Ba absent. Discard the portion used in testing for barium, and employ
the remainder of the solution (B), after boiling for 1 minute to expel CO.,
to test for strontium and calcium.

Residue (0). Solution A or Solution B. The volume Rhould

Yellow: BaCrO,. be about 4 m!.
Wash well with Either-To 2 ml. of the cold solution, add 2 ml. of
hot water. Dis- saturated (NH,).SO, solution, followed by 0·2 gram
solve the ppt. in of sodium thiosulphate, heat in a beaker of boiling
a little concentra- water for 5 minutes and allow to stand for 1-2
ted HCI, evaporate minutes. Filter.
almost to dryness Or-To 2 mI. of the solution add 2 mI. oftriethanol-
and apply the amine, 2 ml. of saturated (NH')2S0. solution, heat on
flame test. a boiling water bath with continuous stirring for 5
Green (or yel. minutes and allow to stand for 1-2 minutes. Dilute
lowish-green) with an equal volume of water and filter.
flame.
Ba present.
(Use spectro- Residue. Largely Filtrate. May con-
scope, ifavailable.) SrSO.. Wash with a tain Ca complex.
little water. Transfer (If Sr is absent, use 2
ppt. and filter paper to a m!. of solution A or B.)
small crucible, heat until Add a little {NH.).C.O,
ppt. has charred (or burn solution * and warm on a
filter paper and ppt., held water bath.
in a Pt wire, over a cru· White ppt. of CaC.O,.
cible), moisten ash with a Ca present. t
few drops of concentrated Confirm by flame test
HCI and apply the flame on ppt.-brick-red flame.
test. (Use spectroseope, if
Crimson flame. available. )
Sr present.
(Use spectroscope, if
available.)

• When triethanolamine has been used in the separation, acidification with

dilute acetic acid may assist the precipitation of the CaC.O,.
t The following is an alternative test for Ca. Place a drop or two of the
filtrate upon a glass slide, add a drop or two of dilute H 2 SO" and concentrate
by placing the slide on a small crucible and warming until crystalli»ation just
commences. Examine the crystals in a microscope (magnification: ca. 100 x).
Bundles of needles or elongated prisms. Ca present.
530 Qualitative I rwrganic Analysis [VII,

Explanation (Table IX)

The reasons for evaporating the filtrate from Group IJIB to dry-
ness eliminating ammonium salts and then dissolving the resi, i'le
in dilute HCI before precipitating with excess of (NH4hCOs. in 1.16
presence of a little NH4CI and aqueous NH s,. have been gl~~n. m
detail at the end of Section III, 31. Essentlally, the COa Ion
concentration is reduced by the high concentration of NH4 + j'ins
llresent in the solution so that, unless the latter are removed, 1'1'e-
cipitation of BaCOs• SrCOs and CaCOs is incomplete:
CO a-- + NH 1 + ~NHa + HCO a-
Magnesium is not precipitated either as Mg(OH)2 (S.P. 3·4 X 10 11)
or as MgCO s (S.P. 1·0 X 10-6 ) since both the concentratiOll of
OH- ions in the presence of NH4Cl and the concentratiOI of
COs-- ions are such that the solubility products of tho respec'ive
magnesium compounds are not exceeded. The solubility prod,,'Jts
of the carbonates constituting Group IV are: BaCO s, IH X Iii -9;
SrCO s• 1·6 X 10-9 ; and CaCO s• 4·8 X 10-9•
The precipitated carbonates are dissolved in dilute acetic
acid forming solutions of the acetates:
BaCO s + 2H. C2H a0 2 = Ba(C2H s02h + CO 2 + H 20
The procedure described for separating the three elemr'llts
utilises the following facts:
(1) BaCrO, (S.P. 1·6 X 10- 1 °) is almost insoluble in dililte
acetic acid, whilst SrCrO, (S.P. 3·6 X 10-5 ) and CaCrO, ('" P.
2·3 X 10-2) are soluble and are therefore not precipitated ill a
dilute acetic acid medium.
K 2Cr04 + Ba(C2H s0 2)2 = BaCr04 + 2K.C2H a0 2
The function of the acetic acid is to convert so me of l he
CrO, -- ions into Cr207 -- ions, thus lowering the erO, -- ion
concentration so that the solubility products of SrCrO, :1 nd
CaCrO, are not attained and in consequence they remairl in
solution:
2Cr04-- + 2H + ~ 2HCrO,- ~ Cr 2 0 7 - - + H 2 0
It will be realised that in the presence of a large H + ion con-
1centration (as distinct from the limited one due to the w!'ak
acetic acid), the [Cr04--] may be such that the S.P. of BaCI04
is not reached and under such conditions BaCr04 will not be
precipitated: this accounts for the solubility of tl:lis sal1 in
dilute mineral acids.
(2) Upon adding saturated (NH 4hS04 solution and warm I 'lg,
SrSO, is largely precipitated upon standing: the nddition of
14J Systematic Qualitative Inorganic AnalY8i8 531
some Na2S203 increases the solubility of CaS04 and this
reduces the amount of coprecipitation with SrS04' The forma-
tion of a soluble complex salt, such as (NH4MCa(S04h], has
been suggested to account for the failure of CaS04 to precipitate
in appreciable quantity with (NH4)2S04 solution.
In the alternative procedure, using triethanolamine
N(C 2H 40Hh and saturated (NH4)2S04 solution, it is probable
that a calcium triethanolamine complex ion is formed and, in
consequence, very little CaS04 is precipitated: however, the
concentration of Ca++ ions due to the dissociation of the
complex ion is such that the solubility product of CaC 20 4
(2·6 X 10-9 ) is exceeded upon adding (NH4hC 20 4 solution.
SrS04 does not give a flame coloration easily; it is therefore
partially reduced to SrS by the carbon of the filter paper.
Treatment of the residue containing SrS with HCI gives the
relatively volatile SrCI 2.
(3) Calcium is readily identified by precipitation as CaC 20"
followed by the flame test (best observed through a spectro-
scope). It may also be converted into CaS04,2H 20, and the
characteristic crystals examined in a microscope-magnifica-
tion of about 100 diameters.

Explanation (Table IXA)

The barium is separated as BaCr04 as in Table IX, and the
strontium and barium are precipitated as carbonates by
(NH4)2C03 solution in the presence of a little aqueous ammonia.
It is better to employ Na2COS to precipitate the carbonates;
the influence of ammonium salts in tending to reduce the car-
bonate ion concentration is thus eliminated:
NH4 + + C03 - - ~ NH3 + HC0 3-
The mixture of SrC0 3 and CaCO s is treated cautiously with
83 per cent HNO s ; the carbonates are thus converted into the
nitrates. Sr(NOsh is insoluble in the medium whilst the
Ca(NOsh dissolves. The Sr(NO a)2 is collected by filtration
through a sintered glass crucible or funnel: the presence of Sr
is confirmed by the flame test, preferably with the aid of a.
hand spectroscope.
Upon gentle evaporation of the filtrate to remove HN0 3,
the Ca(NOS)2 is obtained. The latter is dissolved in water,
rendered ammoniacal and then faintly acid with dilute acetic
acid, and (NH4)2C204 solution added whereupon CaC 20 4 is
precipitated; the flame test may be applied to the Ca.C2 0,
precipitate. Alternatively, the calcium may be converted into
532 Qualitative Inorganic A nalysis [VII,
VII, 14. Table IXA.-Analysis of Group IV (Calcium Group)
Method B
The ppt. may contain BaCO., SrCO. and CaCO.. Wash with a little
hot water and reject the washings. Dissolve the ppt. in 5 mI. of hot
2N acetic acid by pouring the acid repaateilly through the filter paper.
Test I ml. for barium by adding K.CrO. solution dropwise to the nearly
boiling solution. A yellow ppt. indicates the presence of Ba.
Ba present. Heat the remainder of the solution almost to boiling
and add a slight excess of K.CrO. solution (i.e. until precipitati.)U is
complete and the solution assumes a yellow colour). Filter and wash
the ppt. (0) with a little hot water. Combine the filtrate and was'lings
(solution A).
Ba absent. Discard the portion used in testing for barium, and
employ the remainder of the solution (B), after boiling for I minute to
expel CO. to test for strontium and barium.
Residue (0). Solution A or Solution B. Render alkaline with
Yellow: BaCrO •. NH. solution, and add a slight excess of (NH.).CO.
Wash well solution or, better, a little solid Na.CO.. PlaCE the
with hot water. test-tube in a boiling water bath for 5 minutes. A
Dissolve the white ppt. indicates the presence of SrCO. aIld/or
ppt. in a little CaC0 3 • Filter and wash the precipitated carbonates
concentrated with hot water until the washings are colourless: dis-
HCl, evaporate card the washings. Drain the liquid from the ppt. as
almost to dry· completely as possible. Transfer the ppt. to a ~mall
ness and apply beaker, add cautiously 15-20 ml. of 83% HNO.,* stir
the flame test. for 3-4 minutes with a glass rod and filter through a
Green (or sintered glass crucible.
yellowish.green)
flame. Residue. Filtrate. May contain Ca(NO.) •.
Ba present. White: Transfer most of the liquid to a por-
(Use spectro- Sr(NO.) •. celain basin and evaporate almost to
scope, if avail- Sr present. dryness [FUME OUPBOARD]. Dis·
able.) Confirm by solve the residue in 2 ml. of water
flame test: (solution D), render alkaline with NH.
crimson flame. solution, then acid with dilute Bcetic
(Use spec· acid, add excess of (NH.).C.O. solation
troscope, if and warm on a water bath.
available.) White ppt. of CaC.O,.
Ca present.
Filter off the ppt. and apply the
flame test: brick-red flame.
(Use spectroscope, if available.)
Alternatively-Place a drop or two
of solution D on a glass slide, and add
a drop or two of dilute H 2SO,. Con.
centrate by placing the slide on a emaIl
crucible and warm until crystallislltion
just commences. Examine the cry stals
in a microscope (magnification, ca.
100X).
Bundles of needles or elongated
prisms.
Ca present.

>I<The 83 per cent HNO. (in which Sr(NO.). is insoluble) is prepa,·ed by

~dding 100 grams (68·0 mI.) of concentrated HNO. (sp. gr. 1·42: ca. 70 per
:ant) to 100 grams (66·2 mI.) of fuming HNO. (sp. gr. 1·5: ca. 95 per cent).
15] Systematic Qualitative Inorganic Analysis 533
the sulphate CaS04,2H 20, and the latter identified under the
microscope.
The nitric acid procedure gives an excellent separation of
strontium from calcium.
VII, 15. Table X.-Analysis of Group V (Alkali Group)
Treat the dry residue from Group IV with 4 ml. of water, stir, warm
for 1 minute and filter.t
Residue. Dissolve in a few drops of Filtrate. Divide into two
dilute HCI and add 2-3 rni. of water. parts (a) and (b)_
Divide the solution into two unequal (a) Add a little uranyl mag·
parts. nesium acetate reagent, shake
(i) Larger portion*: Treat 1 ml. of and allow to stand for a few
2% oxine solution in 2N acetic acid minutes.
with 4 ml. of 2·5N ammonia solution Yellow crystalline ppt.
and, if necessary, warm to dissolve any Na present.
precipitated oxine. Add a little NH.Cl Confirm by flame test: per-
solution to the test solution, followed sistent yellow flame.
by the ammoniacal oxine reagent, and (6) Add a little sodium cobalti-
heat to the boiling point for 1-2 minutes nitrite solution (or ca. 4 mg. of
(the odour of NEa should be discern- the solid) and a few drops of
ible). dilute acetic acid. Stir and, if
Pale yellow ppt. of Mg " oxinate. " necessary, allow to stand for 1-2
Mg present. minutes.
(ii) Smaller portion: To 3-4 drops, Yellow ppt. of K 8 [Co(NO a).1.
add 2 drops of the "magneson" re- K present.
agent, followed by several drops of Confirm by flame test and
NaOH solution until alkaline. A blue view through two thicknosses of
ppt. confirms Mg. cobalt glasst: red coloration
(usually transient).
Examination for ammonium. This has already been carried out
with the original substance in the preliminary tests (Section VII, 2. tl'Ht (v)).

Explanation (Table X)
The filtrate from Group IV may contain Mg, Na, K and
ammonium salts. It is evaporated to dryness and heated until
all the ammonium salts have been volatilised: a residue is
indicative of the presence of one or more of these metals. The
* If it is desired to carry out the less satisfactory NaaHPO. test for com-
parison with the oxine test for Mg, treat the acid solution with a littln NH.CI,
followed by dilute NH3 solution until basic and Na.HPO. solution. Shake
and stir vigorously. A white crystalline ppt. of Mg(NH.)PO.,6H aO indicates
Mg. This ppt. sometimes separates slowly. Dissolve the ppt. in a little
dilute Hel and apply the "magneson" test. A blue ppt. confirms Mg.
t It is advisable to test the cobalt glass with a potassium salt to be certain
that the glass is satisfactory: some samples of cobalt glass completely absorb
the red lines due to potassium. It is recommended that a hand spectroscope
be used, if available.
t If the residue dissolves completely (or almost completely) in water, dilut~
the resulting solution (after filtration, if necessary) to about 6 m!. and divide
it into three approximately equal parts:- (i) Use the major portion to test for
Mg with the prepared "oxine" solution: confirm Mg by applying the "mag.
neson" test to 3-4 drops of the solution; (ii) and (iii) Test for Na and K reo
spectively, as described in the Table.
 Qualitative Inorganic Analysis lVU,
dry residue is extracted with water to separate the soluble Na
and K salts and filtered: the residue (R) is tested for Mg and
the filtrate (8) is examined for Na and K.
Magnesium. The residue (R) is dissolved in dilute HOI
and the larger portion of the resulting solution is tested for
Mg with the oxine reagent (Section III, 33, reaction 7): the
smaller portion is subjected to the "magneson" test (Section
III, 33, reaction 8) when a blue precipitate should be obtained.
The precipitation of Mg as Mg(NH4)P04,6H 20 by the addi-
bion of a little NH401 and excess of Na2HP04 to the ammoniacal
1Olution (Section III, 33, reaction 5) is sometimes rather slow;
tlso traces of Group IV metals tend to interfere. For these
~easons the oxine and "magneson" tests are preferred.
Potassium. The precipitation of the yellow potaEsium
:obaltinitrite with Na3[Oo(N02)6] (Section III, 34, reaction 1)
md the flame test (best observed through a spectroscope) are
:haracteristic.
Sodium. The most satisfactory precipitation for sodium
ons is that with uranyl magnesium or zinc acetate (Section
II, 35, reactions 1 and 3). The flame test, in which an intense,
lersistent yellow coloration is produced, is characteristic.
~races of sodium may be introduced from the reagents during
he analysis, and hence it is important to look for a strong
'ersistent yellow coloration; a feeble yellow coloration may be
~ored.
Ammonium was tested for in preliminary test (v) (Section
'II, 2). By heating the original substance with NaOH ~olu­
on, NHa will be evolved from ammonium salts. The )fH a
'LS may be identified by its odour, by its action upon red litmus
a.per or upon filter paper moistened with mercurous nitrate
llution, or by the tannic acid-silver nitrate test (Section III,
), reaction 7). The insertion of a loose plug of cotton wool in
Le upper part of the tube will eliminate the danger of NaOH
Ilution spray affecting the reagent paper.
II, 16. EXAMINATION FOR ACID RADICALS
(ANIONS) IN SOLUTION
The preliminary dry tests with dilute sulphuric aclU ana
'lth concentrated sulphuric acid {Section VII, 3, tests (vi) and
ii)} will have provided useful information as to many £Lcid
dicals present. Furthermore, in the course of the examina-
m for metal ions (cations) in solution, the presence inter alia
the following acid radicals will have been indicated (the first
ree upon treatment with hydrogen sulphide in acid solution) :
 Systemat.ic Qualitative I norgan\e Ana~y8\8
Chromate (or dichromate)-reddish-yellow solution beooming
green and depositing white or yellowish-white sulphur;
Permanganate-purple solution becoming nearly colourless
and depositing sulphur;
Arsenate-yellow precipitate of arsenious sulphide slowly
formed in hot solution {see Note 4 to Table I (Section VII, 6)};
Silicate-insoluble residue of silica after evaporating filtrate
from Group II to dryness (during elimination of interfering
anions prior to precipitation of Group IlIA); and
Phosphate-tested for with nitric acid and ammoniulll molyb-
date solution before precipitating Group lIlA.
For the examination of acid radicals or anions, it is necessary
to obtain a solution containing all (or most) of the anions free,
as far as possible, from heavy metals. This is best prepared by
boiling the substance with concentrated sodium carbonate solu-
tion; double decomposition occurs (either partially or com-
pletely) with the production of the insoluble carbonates* of
the metals (other than alkali metals) and the soluble sodium
salts of the anions, which pass into solution. Thus, if the
unknown substance is the salt of a bivalent metal M and an
acid HA, the following reaction will occur:
MAg + Na2COS ~ MCOa + 2NaA
The carbonate MC0 3 is insoluble and the sodium salt NaA
will pass into solution whether MA2 is soluble in water or not.
Preparation of solution for testing for anions. Boil
1'0 gram of the finely divided substance or mixture (1) ",ith a
saturated solution of pure sodium carbonate (ca. 1'5M) (2)
(prepared from 4 grams of anhydrous sodium carbonate and
25 ml. of distilled water) for 10 minutes, or until no further
action appears to be taking place (3), in a small conical flask
with a small funnel in the mouth to reduce the loss by evapora-
tion; alternatively, a reflux condenser may be employed.
Filter (4), wash the residue with hot distilled water and collect
the washings together with the main filtrate; the total volume
should be 30-35 mI. Keep the residue (5). The sodium car-
bonate extract will be called the "Na2COS prepared solution."
NotC8. (1) If a solution is supplied for analysis, use sufficient to
contain 1·0 gram of solid material, render it strongly alkaline with
satura-ted sodi1llll carbonate solution and evaporate it down to 10-15 ml.
(2) It is essential to use pure sodi1llll carbonate; the A.R. product
is satisfactory. Some "pure" samples may contain traces of sulphate
* Certain carbonates, iniiially formed, are converted into insoluble basio
carbonates or into hydroxides.
536 Qualitative Inorganic Analysis [VII,
or chloride: the absence of these impurities should be confirmed by R
blank experiment.
(3) If ammonium is present, ammonia will be evolveq (indieated b:y
the smell above the solution), continue boiling until ammonia is com
pletely expelled, otherwise those basic elements which form ammonin
complexes may pass into the sodium carbonate extract.
(4) If no precipitate is obtained, the substance is largely free from
heavy metals, and the sodium carbonate treatment may be omitted il
more of the solution is required. Certain amphoteric elemercts may,
however, be present in the sodium carbonate solution, e,g. Cu, Sn, Sb,
As, AI, Cr and Mn, dissolve in appreciable quantities; mEtnganates, per·
manganates and chromates may also be present so that the ('olour of
the solution should be. noted. If cyanide. is present, C~in cations.
such as Ag, Hg, Fe, Nl and Co, may pass mto the alkaline extract by
virtue of the formation of complex cyanides (anions).
(5) The residue (R) from the Na 2CO a treatment mll,y contain, ill
addition to the carbonates, basic carbonates and hy<h-oxideH of thf'
heavy metals, certain phosphates (e.g. those of Pb, Ag, Cd, Cr, .lio, Mn.
Zn, Co. and Mg, which are less than 50 per cent transposed), alsenates.
sulphides, fluorides, silicates and complex cyanides, and the halides of
silver. This may be due in the case of products produced by high-
temperature processes or of certain natural products to the sIow ratE'
of reaction with the alkali carbonate or it may be due t<) the hct that
the solubilities are such that very little metathesis Clln tak-3 place.
Hence the residue should be kept until the tests for anions have been
completed, and then tested for the above anions if they are net found
in the alkaline extract or in the preliminary tests: the original su bstance
can, of course, be employed for these tests. After extraction of the
sodium ca~l)onate residue with dilute hydrochloric acid, the undissolved
portion (R) may be treated as an insoluble substance and inve:;tigated
according to Section VII, 20. It is generally more con.venient, how-
ever, to test the residue (R) for the various anions as follows.
Phosphate and arsenate. If the" N aaCO 3 prepared s<)lution." when
acidified with dilute nitric acid, boiled for 1 minute and rl)ndered
alkaline with ammonia solution, does not give a precipitate with tht'
magnesium nitrate reagent or with magnesia mixture. Ilhosphate and
arsenate are absent. Heat a small portion of the resi<iue with con-
centrated nitric acid; if brown fumes are evolved, indicating the pre-
sence of a reducing agent, add more concentrated nitric add and
continue the heating until all the reducing agent is oxidised. Dilute
the solution with water, heat to boiling and filter. Reneler the filtrate
alkaline with concentrated ammonia solution, and add the magnesium
nitrate reagent or magnesia mixture. A white precipitate iLdicates
ar8enate and/or pho8phate. Separate as described in SElction lV, 45,
11 and 12.
Sulphide. Reduce a portion of the residue with zinc and dilute
sulphuric acid. If hydrogen sulphide is evolved (lead acetate paper
test), 8ulphide is present. It is preferable to employ the sodium car-
bonate residue (R) rather than the original mixture In test ng for
"ulphide, for the latter may contain sulphite and thiollyana.1;tJ, both
of which give hydrogen sulphide with nascent hydrogen (compare
Section, IV, 4, reaction 8 and Section IV, 10, reaction 6),
16] SY8tematic Qualitative Inorganic Analysis 537
Cyanide. If this is suspected, hydrogen cyanide will be evolved in
the reduotion with zinc and sulphuric acid, particularly on warming.
Identify the hydrogen cyanide by the ammonium sulphide test
(Section IV, 8, reaotion 1). It will also be identified in the preliminary
test with dilute sulphuric acid {Section VII, 3, test (vi)}.
Halides of silver. Treat a portion of the residue (Il) with zinc and
dilute sulphurio acid (the solution remaining after testing for 8ulphide
may be used):
2AgCl + Zn = 2Ag + Zn++ + 2cr
Filter to remove the exceS3 of zino and the precipitated silver, boil the
solution to remove all the hydrogen sulphide (if sulphide is present),
and test the solution for Cl-, Br- and 1- as detailed in Section IV, 45.
Fluoride. A portion of the dried residue (or of the origirlal mixture)
may be decomposed with concentrated sulphuric acid. Heat in a. lead
capsule or crucible with concentrated sulphuric acid and apply the
etching test (Section IV, 17, reaction 2). Altematively, the "water"
test (Section VII, 16, reaction 8) may be used.
Use the "Na2COa prepared solution" to carry out the
following tests.
1. Sulphate test. To 2 ml. of the "Na2COa prepared
solution" add dilute hydrochloric acid until acid (test with
litmus paper) and then add 1-2 m!. in excess. Boil for 1-2
minutes to expel carbon dioxide completely, and then add
about 1 m!. of barium chloride solution. A white precipitate
indicates 8ulphate. Confirm by the charcoal test (Section IV,
24, reaction 1).
Silicofiuorides also give a white precipitate under the above
conditions, but are of comparatively rare occurrence. They
can be readily distinguished from sulphates by the action of
concentrated sulphuric acid (Section IV, 27, reaction 1) and, of
course, by the charcoal test.
2. Test for reducing agents. Pota88ium perman!lanate
test. Acidify 2 ml. of the "Na2COa prepared solution" with
dilute sulphuric acid and add 1 m}. of dilute sulphuric acid in
excess. Add 0·5 m!. of 0'02N potassium permanganate solu-
tion (prepared by diluting I m!. of O'lN KlVIn04 to 5 m!.) from
a dropper. Bleaching of the permanganate solution indicates
the presence of one or more of the following reducing anions;
8ulphite, thio8ulphate, sulphide, nitrite, cyanide, thiocyanate,
bromide, iodide, arsenite andferrocyanide. If the permanganate
is not decolourised, heat and observe the result. If the reagent
is bleached only on heating, the presence of oxalate, formate or
tartrate is indicated. A negative test points to the absence of
the above anions with the exception of cyanide, which, if
present in low concentration, may not act upon the perman-
ganate solution.
538 Qualitative Inorganic Analysis [VII.
3. Test for oxidising agents.-Manganous chloride reagenl
test. This t€st depends upon the fact that a saturated solution
of manganous chloride (MnCI 2 ,4H 20) in concentrated hydro-
chloric acid is converted by even mild oxidising agents to Dc
dark brown-coloured manganic salt, probably oontaining th(
complex [MnC16 r- r
or [MnCI4 ions.
To 2 m!. of the "Na2C03 prepared solution" add 1 ml. of
concentrated hydrochloric acid and 2 m!. of the manganom
chloride reagent. A brown (or black) coloration indicates the
presence of nitrate, nitrite, ferricyanide, chlorate, bromate, iodate.
chromate or permangana,te. A negative test indicates the
absence of the above oxidising agents except small amounts 01
nitrates and nitrites and of arsenate; if reducing anions have
been found, this test is inconclusive.

4. Tests with silver nitrate solution. The separation of

a comparatively large number of anions from the "Na 2CO:l
prepared solution" into several groups is possible with this
reagent.
The presence of thiosulphate, sulphide, cyanide, sulphite, ferro·
and ferri-cyanide, however, introduces difficulties in the subsequent
separations, hence these anions must be tested for first and, if
present, removed.
Thiosulphate will be detected in the preliminary test with dilute
sulphuric acid: if it is found, it should be eliminated by heating the
original mixture with dilute sUlphuric acid until no more sulphur di·
oxide is evolved, evaporating the residual mixture just to dryness and
then heating with 1'5M sodium carbonate solution, etc. The occurrence
of thiosulphates in mixtures is comparatively rare and hence this special
treatment prior to making the "Na 2C0 3 prepared solution" is rarely
necessary. The interference of the 8 2 0 3 - - ion with the silver nitrate
reaction may arise from (i) the formation of a precipitste of sulphur
upon acidification, (ii) the formation of white silver thiosulphate
Ag 2S 20 a which rapidly passes into the black silver sulphide Ag 2S.
thus giving a false test for S-- ion. and (iii) under certain circumstances
it will convert CN- into 8CN- and Fe+++ into Fe++.
SulphIde. This may have been detected in the preliminary test
with dilute sulphuric acid. Sulphide can be readily found by adding
a little lead nitrate solution to 0·5 m!. of the "Na200a prepared
solution," when a black precipitate of lead sulphide is produced.
Cyanide. This should have been detected and confirmed in the
preliminary test with dilute sulphuric acid (Prussian blue test or as
~ection IV, 8, reaction 1).
Sulphite. This anion will have been detected in the preliminary
test with dilute sulphuric acid (potassium dichromate paper or
fuchsin solution test).
16] Systematic Qualitative Inorganic Analysis 539
Ferrocyanide (and Thiocyanate). Acidify 1 ml. of the
"Na 2COS prepared solution" with dilute hydrochloric acid and add
a few drops of ferric chloride solution. A deep blue precipitate
indicates ferrocyanide present. Now add 0'5-1 m!. of ferric chloride
solution, 0·2 gram of sodium chloride and half a Whatman filtration
accelerator, shake the mixture vigorously and filter. A deep red
filtrate indicates thiocyanate present.
Ferricyanide. Acidify 1 m!. of the "Na2CO a prepared solution"
with dilute hydrochloric acid and add a few drops of freshly prepared
ferrous sulphate solution. A deep blue precipitate indicates Jerri-
cyanide present. This precipitate should not be confused with that
of light grey-blue colour produced by a ferro cyanide.
Use is made of the following facts in the preliminary and
partial separation of anions with silver nitrate solution:
(1) In dilute nitric acid solution (ca. l'5N), chloride, bromide,
iodide, iodate and thiocyanate are precipitated.
It will be appreciated that iodate is incompatible with both iodide
(compare Section IV, 21, reaction 6) and with thiocyanate (Scction
IV, 21, reaction 9) since iodine is liberated in acid solution. Also
sulphide is incompatible with both bromate and iodate (oxidation
to sulphate occurs), and an arsenite is oxidised by iodate in acid
solution. These facts should therefore be borne in mind when in-
terpreting Table XI. An independent test for iodate (test 11) is
provided below: this can be performed before the silver nitrate tests.
(2) Upon treatment of the filtrate from (1) with sodium
nitrite solution, chlorate and bromate are reduced to the simple
halides, the presence of which is revealed by the separation of
silver chloride and silver bromide respectively.
+
AgCIOa 3NaN02 = AgCI 3NaNOa +
Chromates (which, of course, yield a coloured solution) are
simultaneously reduced to chromic salts.
(3) If the acidity of the filtrate from (2) is reduced (to about
pH 5) by just neutralising with sodium hydroxide solution and
adding dilute acetic acid, silver nitrate solution will precipitate
phosphate, arsenate, arsenite, * oxalate and possibly other
organic acids.
It cannot be too strongly emphasised that Table XI is
intended to act merely as a guide and to indicate the presence
of groups of anions; it should therefore be considered carefully
in conjunction with the various observations which have been
made in the preliminary tests and particular note be taken of
• It must be remembered that arsenite may be partially oxidised by the
dilute nitric acid treatment and also by other oxidising anions which ma.y be
present. Arsenite is, however, readily detected in the analysis for ea.tions
(compare Section III, 11, reaction 1).
540 Qualitative Inorganic Analy.sis (VII.
possible interferences. The Table should therefore not be
interpreted as rigidly as a Group Separation Table for cations.
Table XI.-Separation of Anions with Silver Nitrate
Solution
It is essential to remove interfering anions first in the following order. r
These anions, if present, will have been detected in the preliminary tests.
1. Sulphide, cyanide and sulphite. Acidify 10 ml. of the "Na.CO.
prepared solution" with dilute acetic acid and boil gentl3' for 3-4 minutes:
make certain that the solution remains acid (e.g. to litmus) throughout.
If sulphite is present, it is advisable to heat the solution for 10-15 minutes
(maintaining the volume, if necessary) whilst a stream of air is drawn
through it (compare Fig. IV, 45, 1): test for complete removal of Bnlphur
dioxide with fuchsin solution.
2. Ferrocyanide and ferricyanide. Employ the original solution
from 1 or, if sulphide, cyanide and sulphite are absent, use 10 roi. of the
"Na.CO. prepared solution" made acid (to Congo red) with dilute acetic
acid. Add O·r;M zinc nitrate solution until precipitation ceases, introduce
a Whatman filtration accelerator, stir and filter the zinc ferro. and ferri'l
cyanides in the cold; wash with a little O'IM zinc nitrate solution.
Use the filtrate from 2 or, if ferro cyanide and/or ferricyanide and other
interfering anions are absent, acidify 10 ml. of the "NazCO. prepared I
solution" cautiously with dilute RNO. (to litmus or other indicator paper). ,I
Add one· tenth of the volume of concentrated RNO., stir for 30 seconds
and then add AgNO. solution with stirring until precipitation is complete. ,I.

Heat to the boiling point, allow the ppt. to settle, cool and filter. Wash.
the ppt. with 2-3 ml. of N nitric acid.

Residue (A). 1\ Filtrate. Add 1 ml. of AgNO. solution, then 20% i

Yellow or NaN0 2 solution (prepared from the A.R. solid) dropwiae j
white. May I and with stirring until precipitation is complete. (If no
contain: ppt. forma, do not add more than 0'5 ml. of NaNO.
AgOl, I solution.] Filter, and wash with 2-3 ml. of N nitric acid.
AgBr, !~-------;------------------
AgI (or Residue (B). Filtrate. Add NaOH solution (use B
AgIO,) May contain dropper) with vigorous stirring until
AgSON. Agel and neutral to litmus (1), then 0·5 ml. of dilute
Use Table A. AgBr derived acetic acid, followed by 1 ml. of AgNO.
from AgCIO. solution. Heat the mixture to about
and AgBrO •. 80°0 (2). If a permanent precipitate
Use Table B. forms, add more AgNO. solution until i
precipitation i!! complete. Filter and wash i
with hot water. I'

Residue (0) (3). Filtrate.

Ag.PO.-yellow. Discard.
Ag .AsO,-brownish.red.
AgaAsO.-yellow.
Ag.C.O.-white (4).
I Use Table C.
~------------------------~--------------------~-------------'
Notes. (I) The sodium hydroxide solution should be added unj j
the first permanent precipitate of C or of brown silver oxide appear: ,
The solution must not be allowed to become alkaline to litmus for
this will produce a large preoipitate of silver oxide which redissolves
only slowly.
 ,.
16] SY8tematic Qualitative Inorganic AnalY8i8 541
The pH required for the precipitation of C is about 5'5; this can
be more conveniently achieved by the use of either nitrazine (sodium
dinitrophenyl-azo-naphthol sulphonate) or bromocresol purple (di-
bromo-o-cresol-sulphone-phthalein) test-papers. All that is neces-
sary is to add the sodium hydroxide solution until the appropriate
colour change is produced; it is best to use a standard for com-
parison (nitrazine, pH range 5·5-7'2, yellow to blue; bromouesol
purple, pH range 5'2-6·8, yellow to purple).
(2) A crystalline precipitate of silver acetate may separate here;
this dissolves when the solution is heated.
(3) Chromate, if present, would normally be precipitated at a pH
of about 5'5, but the sodium nitrite treatment in B reduces it to the
chromic state. Chromic hydroxide is not precipitated in the acetic
acid-acetate solution unless present in very large amounts.
(4) Other organio acids may also separate here. If only a white
preoipitate is obtained, use the organio acids separation table of
Section IV, 45, 20. The presence of organic acids wW alHo be
indicated by some of the preliminary tests.
Table A (Examination of Residue A)
Thiocyanate test. Test one-quarter of the precipitate A
for thiocyanate by heating for 3-4 minutes with 5 ml. of 5 per
cent NaCI solution (this converts part of the AgSCN into
NaSCN), cool and allow the precipitate to settle. Treat the
supernatant liquid with 1 mI. of dHute HCI and a few drops of
FeCl a solution. Red coloration. Thiocyanate pre8ent.
If thiocyanate is present, it must be destroyed since it
interferes with the tests for the halides. Heat the remainder
of the residue A (previously dried in the steam oven or in an
air bath) in a porcelain crucible, gently at first and then
gradually to dull redness until all the thiocyanate is decom-
posed, i.e. until blackening of the precipitate and/or burning
of S ceases.
To the residue in the crucible (if thiocyanate is present) or
to the remainder of the residue A transferred to a small beaker
(if thiocyanate is absent), add 1-2 grams of granulated zinc
(but preferably of 20 mesh) and 5-10 ml. of dilute H 2S04 ,
Allow the reduction to proceed for 10 minutes with frequent
stirring; gentle warming may be necessary to start the reaction.
Filter and wash the precipitate with a little dilute H 2S04 ,
Divide the filtrate into three equal parts. *
* The preliminary test with concentrated H 2SO. will generally indicate
the presence of any of the three halides or mixtures of them. For individual
halides, the confirmatory tests of Section VII, 17, may be used. If mixtures
are present, the methods described in Section IV, 45, /i-8, may be adopted.
For those who prefer systematic testing for any or all of the halides, the
alternative procedures in Table A are recommended.
542 Qualitative Inorganic AnalY8i8 [VII,
Iodide test. Add 1-2 m!. of CC14 and 3 mI. of 10-volume
H 20 2 or 3 mI. of 25 per cent Fe2(S04)a solution to one-third of
the filtrate. Shake vigorously and allow to settle. Purple to
violet coloration of CC14 layer. Iodide pre8ent.
Bromide test. (a) If iodide is present, this must be
removed by treating one-third of the solution with 5 m!. of
dilute H 2S04 and 2 m!. of 30 per cent NaN0 2 solution (chloride-
free). Boil the solution with stirring, concentrate to 3 m!. and
allow to cool. Test for bromide as under (b).
(b) If iodide is absent, use one-third of the solution directly.
Add an equal volume of concentrated HN0 3 , immerse the test-
tube in a beaker of boiling water for 1 minute and cool to room
temperature with cold water. Add 1-2 m!. of CCl4 and stir
vigorously with a glass rod (if a glass-stoppered tube or conical
flask is available, this will facilitate shaking). Yellow or brown
colour of the CCl4 layer. Bromide present.
Chloride test. (a) If iodide and/or bromide present, dilute
the remaining third of the solution to 15 mI., add 8 mI. of
concentrated HN0 3 and boil (glass rod in beaker) for 5 minutes
or until no more Br2 is given off. Cool and test for chloride as
in (b) below with AgNO s solution only.
(b) If bromide and iodide are absent, add 3-4 mI. of dilute
HN0 3 and 3 m!. of AgNO a solution; stir and heat to boiling.
White precipitate. Chloride present.
Table B (Examination of Re8idue B)
Suspend the residue B in 5-10 mI. of dilute sulphuric acid
in a beaker, and add 1-2 grams of granulated zinc (but prefer-
ably of 20 mesh). Allow the reduction to proceed for 10
minutes with frequent stirring: gentle warming may be neces-
sary to start the reaction. Filter and wash the precipitate with
a little dilute sulphuric acid. Examine the solution for chloride
and bromide as in Table A.
Table C (Examination of Re8idue C)
If the precipitate is white, only organic acids may be present
and the other anions need not be tested for. Furthermore, the
preliminary tests of heating alone and heating with concen-
trated sulphuric acid will have indicated the presence of organic
acids. If organic acids are indicated or suspected, use the
separation Table given in Section IV, 45, 20. .
If the precipitate is yellow phosphate and/or arsenite may
be present and arsenate is absent. The following scheme pro~
vides for the separation of phosphate, arsenate and arsenite.
16] Systematic Qualitative Inorganic Analysis

Dissolve the residue C (1), which may contain AgaPO., AgaAsO. and
AgaAsO a, by pouring 10-15 ml. of 3N HCI repeatedly through it. Filter
and wash with 5 ml. of O'IN HCI.

Residue. Filtrate. Render alkaline with dilute aqueous NB. and

AgCl. add 5 ml. in eX(]eBS (2). Add 10 ml. of the Mg(NO.). reagent,
Reject. allow to stand for 10 minutes, stirring frequently, and filter.
Wash the ppt. with 5 ml. of O'IN NH. solution.

Residue. May contain Filtrate. Add 4 ml.

Mg(NH,)PO.,6H.O and of 3% H.O. solution,
Mg(NH.)AsO,,6H.O (3). Dissolve heat nearly to boiling
the ppt. by pouring 10 ml. of (to oxidise arsenite to
dilute HCl repeatedly through the arsenate), cool and allow
filter. Add to the cold solution 0·5 to stand for 10 minutes;
gram of solid NaHCO. and 0·5 shake frequently. Filter.
gram of solid KI. An immediate
yellow to brown iodine colour
indicates arsenate. Saturate the Residue. Filtrate.
solution with H.S (under "pres. Mg(NH,)AsO". Reject.
sure "). Filter and wash with 6H.O.
0'5N HCl. Arsenite
present.
Residue. Filtrate. Boil until
• Yellow: HoS is expelled and the
As,S •. volume i8 ca. 10 ml.
Arsenate Filter and discard any
present. ppt. of S. Render
alkaline with concen·
trated Nfl. solution
and add 3 ml. in
excess. Add 5 ml. of
the Mg(NO.). reagent
and allow to stand,
with frequent stirring,
for 10 minutes.
White ppt. of
Mg(NH.)PO,,6H.O.
Phosphate present.

Note8. (1) The "Na200S prepared solution" may also be used

for the detection of arsenate, phosphate and arsenite. Acidify 10
mi. of the "Na200S prepared solution" with dilute HOI and then
render alkaline with dilute aqueous NHs. Filter, if necessary, and
reject any precipitate. Treat the clear solution with the Mg(NO s )2
reagent, etc., and proceed as in Table.
(2) If chromate is present, it will have been reduced to chromic
ion by the NaN0 2 solution and may be partly precipitated as
Or(OH)s. This will be dissolved by HOI and reprecipitated by the
aqueous NHs. Hence any precipitate formed at this point should
be filtered off before the Mg(NO s)2 reagent is added.
544 Qualitative Inorganic Analysis [VII,
(3) If phosphate has been detected previously (e.g. in the cation
analysis), a qualitative test for arsenate may be made as followr.
Pour 1 ml. of AgNO s solution, to which 2 drops of dilute acetic acid
have been added, over the white precipitate. A brownish-re,l
coloration of the precipitate confirms the presence of arserwte. Th,
acetic acid is added to increase the solubility of the magnesium sal i
and thus facilitate the conversion of magnesium ammonium arsenal,
to the characteristic silver arsenate.

5. Test with calcium chloride solution. For tests 5-7 ,

"Na2COS practically neutral solution" is required. Till
is prepared as follows. Take 10 ml. of "Na2C03 prepare, I
solution" in a porcelain dish and render it faintly acid witL
dilute nitric acid (use litmus paper or other equivalent test
paper). Boil for 1-2 minutes to expel carbon dioxide, allo"
to cool, then add dilute ammonia solution until just alkaline'
and boil for 1 minute to expel the slight excess of ammonin
Divide the solution into three equal parts for tests 5, 6 and 7
Add CaC12 solution (equal in volume to that of the solution.
and allow to stand for several minutes. A white precipitat,
indicates fluoride, oxalate, phosphate, arsenate and tartratet; ;.
precipitate which separates on boiling for 1-2 minutes is citratr.
Of these only oxalate and fluoride are insoluble in dilute aceti
acid. Hence extract the white precipitate with dilute acetj,·
acid and filter. A residue (R) insoluble in dilute acetic acid.
indicates oxalate and/or fluoride. Exactly neutralise the aceti,
acid solution by adding sodium hydroxide solution from "
dropper and testing with an indicator paper or solutioJl
(bromothymol blue or nitrazine yellow is suitable); a whit;
precipitate indicates the presence of phosphate, arsenate and/oi
tartrate. The precipitate often separates slowly. Add a littlo
silver nitrate solution to the suspension or solution: a yellow
precipitate indicates the presence of phosphate; a brownish-rei l
precipitate indicates arsenate or arsenate plus phosphate.
It is convenient to test the residue R for oxalate hen'
Dissolve it by pouring hot dilute sulphuric acid into the filter
Treat the hot filtrate with a few drops of 0'02N potassiun'
permanganate solution. If the permanganate solution j.
reduced, oxalate is present. If no reduction occurs, the pre
sence of fluoride is indicated.
* If a precipitate forms on neutralising the solution, the presence of arseni,
antimony and tin sulphides and possibly salts of amphoteric elements (leao
tin, aluminium and zinc) is indicated. The precipitate should be filtered 0 j :
and rejected.
t CaBO. and Ca(BO.). may separate from sufficiently concentrated iiOlutiowL
16] Systematic Qualitative Inorganic Analysis 545
6. Test with ferric chloride solution. Treat the second
third of the "Na 2CO S practically neutral solution" drop by
drop with ferric chloride solution until no further ehange
occurs.
(The bench reagent contains free hydrochloric acid; add dilute
ammonia solution until a precipitate JURt forms, filter and use the
filtrate for the test. The filtrate is sometimes termed "neutral FeCl 3
solution". )

Yellow to brown precipi- Benzoate, auccinate (also chromate, pho8phate,

tate. arsenate and borate, all of which have been or
will be found by other tests).
Blue precipitate.
Reddish- brown colora -
I Ferrocyanide_
Acetate, formate.
tion, ppt. after dilution
and boiling. I
Blood-red coloration Thiocyanate (aulphocyanide).
discharged by HgCl.
solution.
Reddish-purple colora- Thioaulphate.·
tion; colour vanishes on
warming.
Brown coloration; blue Ferricyanide.
ppt. with FeSO, I!olu·
tion.
Violet coloration. Salicylate.
Greenish- black colora- GcUlate.
tion.
Bluish-black coloration. Tannate.

7. Test for silicate. To the remaining third of the "Ka2 CO S

practically neutral solution" add ammonium chloride and
ammonium carbonate solution. A gelatinous precipitate
indicates silicate.
A more satisfactory reagent for the precipitation of silicates
is hexammine zinc hydroxide, [Zn(NHa)6](OHh This preci-
pitates zinc silicate ZnSi0 3 , which is much more difiicultly
soluble in dilute alkaline solution than is the free silicic acid.
Na2SiOs + [Zn(NHs)6](OH)2 = ZnSiOs + 2NaOH + 6NHs
The reagent is added in slight excess and the solution boiled
until all the ammonia is expelled.
The reagent is prepared by treating pure zinc nitrate solution
with potassium hydroxide solution, filtering off the precipitated zinc
hydroxide, washing well, and dissolving the precipitate in dilute
ammonia solution.
• As a general rule, thiosulphate will not be found here 88 it should have
been more or less completely decomposed in the preparation of the" Na.CO.
practically neutral solution. "
18+
546 Qualitative Inorganic AnalY8i8 [VII,
8. Test for fluoride. The presence of fluoride will have
been indioated in the preliminary test with conoentrated sul-
phuric acid by the" oily" or "greasy" appearance of the tube
and also by the calcium chloride solution test.
It may be confirmed by the following test.
Fit a small test-tube with a cork canying a
piece of glass tubing open at both ends; cut a
V-shaped groove in the side of the cork to
allow for the expansion of the air in the tube
when heated. Mix a small quantity of the
original substance in a crucible with about
three times its bulk of ignited silica (quartz
powder is preferable, but results are obtained
with precipitated silica), transfer it carefully
to the tube, and add by means of a dropper or
small pipette about twice as much (by volume)
of concentrated sulphuric acid as there is solid.
Introduce the glass tube, wet on the inside
with water thus forming a ring of water at the
lower end (Fig. VII, 16, 1), into the test-tube
H2 S04 and adjust its height so that the bottom is at a
Fig. VII, 16, 1 distance of approximately one and a half times
the diameter of the tube from the paste in the
test-tube. Heat the mixture gently over a small flame for 2-3
minutes. A white film of silicic acid in the water confirms the
presence of fluoride. \
The reactions which occur are: -
MFa + HaSO, = MSO, + 2HF;
SiOs + 4HF = SiF, + 2H.O;
3SiF, + 4HaO = H,SiO, + 2H.[SiF.J
When the highly reactive precipitated silica. is employed, much of the
SiF, reacts with it to form a stable oxyfiuoride, probably
SiF, + SiO a = 2SiOF.
Hence the relatively unreactive-powdered quartz is to be preferred.
9. Test for cyanide. This is sometimes missed in the
preliminary test with dilute sulphuric acid and in the pota.ssium
permanganate test for reducing anions. The following test is
conclusive. Use the apparatus described in the test for car-
bonates (Fig. IV, 2, 1). Place 0·2 gram of the substance in
the test-tube together with three or four fragments of marble.
Introduce 5 ml. of 2-3 N hydrochloric acid, replace the cork
immediately and allow the evolved gas to bubble through
16J Systematic Qualitative Inorganic Analysis 547
5 ml. of 2-3 N sodium hydroxide solution. Mter 5-10 minutes
add 0'5 ml. of saturated ferrous sulphate solution to the alkaline
solution, heat to the boiling point, cool thoroughly, acidify with
concentrated hydrochloric acid and add a few drops of ferric
chloride solution. A blue precipitate (Prussian blue) is obtl1ined;
with small amounts of cyanide the solution acquires a hlue or
blue-green colour.
The test may also be conducted with the 2 ml. of the" Na.CO a pre-
pared solution." Carbonate, sulphite and thiosulphate have no in-
fluence upon the reaction. Nitrite interferes, presumably owing to the
oxidation of the hydrogen cyanide. In the presence of sulphide, the
test is complicated by the precipitation of black ferrous sulphide when
ferrous sulphate is added to the alkaline solution. It is best to boil the
solution containing the suspended ferrous sulphide, acidify with hydro-
chloric acid and boil again to expel most of the dissolved hydrogen
sulphide; upon adding a drop of ferric chloride solution, a. blue pre-
cipitate is produced if cyanide is present.
Complex cyanides, such as ferrocyanide and ferricyanide, do not
interfere when the test is conducted in the cold.

10. Test for chromate. If the "Na2C03 prepared solu-

tion" is colourless, chromate is absent. If yellow, chromate
may be present; ferro- and ferri-cyanides also impart a yellow
colour to the solution. The presence of chromate will have
been indicated by the precipitation of green chromic hydroxide
in the silver nitrate solution tests (Table 0) and also in the
analysis for cations.
To confirm chromate, acidify 2 ml. of the "Na2C03 prepared
solution" with dilute sulphuric acid, boil for one minute to
expel CO 2, etc., filter if necessary, add 1-2 ml. of amyl alcohol,
followed by 1-2 ml. 10-volume hydrogen peroxide and shake
gently (compare Section IV, 33, reaction 4). A blue coloration
of the amyl alcohol layer confirms chromate.
11. Test for iodate. This anion will give a positive test
for oxidising agents, but will not normally be detected in the
systematic analysis.
The presence of iodate in the "Na2C03 prepared solution"
can be readily detected as follows. Treat 2 m!. of the solution
with silver nitrate solution until precipitation ceases, heat to
boiling for 2-3 minutes and filter. Render the filtrate strongly
acid with hydrochloric acid, add 2 ml. of 10 per cent ferrous
sulphate solution (or 10 per cent sodium hisulphite solution)
and shake it with 2 ml. of carbon tetrachloride. A purple
coloration of the organic layer indicates iodate.
This test utilises the fact that silver iodide, but not silver
648 Qualitative 1rwrganic Analysis [VII,
iodate, is precipitated upon the addition of silver nitrate to the
"Na 2CO S prepared solution." \
An iodate does not react with concentrated s~lphuric acid in the
cold or upon gentle heating. A solution of an iodate gh es with
silver nitrate solution a white precipitate of silver iodate, insoluble
in N nitric acid but soluble in dilute ammonia soluticn, thus
simulating the behaviour of a chloride towards these reagents.
Iodates, however, give a white precipitate of barium iodate
Ba(IOs)z with barium chloride solution; the precipitate is sparingly
soluble in dilute nitric acid.
12. Test for periodate (1). This aniop will give a positive
test for oxidising agents, but will not be detected in the
systematic analysis. It will be necessary to remo're first
iodide or iodate by precipitation with silver nitrate in acid
solution, and the excess of silver ions with sodium I:hloride
solution: the resulting solution is strongly acidified with hydro-
chloric acid and a ferrous salt is added. If a perie.date if'
present, it will be reduced to iodine, which can be identified
with carbon tetrachloride.
Acidify 3 mI. of the "Na2C03 prepared solution" with 6(1
per cent perchloric acid and add I mI. in excess (2); add silver
nitrate solution, slowly and with stirring, until precipii ation i~
complete. Filter and collect the filtrate in a grou 1d-glass 1

stoppered conical flask or test-tube. Add 5 per cent sodium

chloride solution, 0·5 ml. at a time, to the filtrate until ::10 mor!'
precipitate forms. Stopper the flask or test-tube an:l shake
the mixture vigorously after each addition. Filter off thf'
silver chloride (3), transfer the filtrate to the stoppere<l vesseJ
add an equal volume of concentrated hydrochloric add (if ;,
precipitate of sodium chloride forms, filter), cool, then add 1-:'
grams of solid ferrous ammonium sUlphate and 2 m!. o~ carbol!
tetrachloride. Shake the mixture intermittently for 5 JUinute~
A purple colour in the carbon tetrachloride indicates periodatl'
present.
Notes. (1) This anion is rarely encountered and need not be teste' i
for in general qualitative analysis. It is given here for thol sake (,I

completeness as no reactions for periodates are included in Chapter n '

Four tests which distinguish periodates from iodates are:
(a) With mercuric nitrate solution an orange-red pree pitate ,,(
1 2 0 7 ,5HgO is obtained {oompare iodates which give whit,.,
Hg(IOa)a}·
(b) Upon boiling with ~lO per cent nitrio acid and a little mal
ganous sulphate solution, a purple solution of pennanganio am,j
is produced (compare iodates, which do not yield permangan,,;
acid).
 17J Systematic Qualitative inorganic AnalY8i8 549
(c) With silver nitrate solution a chocolate-brown pn1cipitate
(Ag&I0 6 ) is obtained; this darkens on boiling and is soluble in
dilute nitric acid (compare silver iodate AgIO •• which is white
and sparingly soluble in dilute nitric acid).
(d) With barium chloride solution a white precipitate is produced.
which is soluble in dilute nitric acid (compare barium iodate,
which is sparingly soluble in dilute nitric acid).
(2) Nitric acid tends to oxidise ferrous iron, hence it is advisable to
maintain the nitrate ion concentration as low as possible and to keep
the solution cold.
(3) The excess of silver ions is removed as silver chloride because
they are reduced by ferrous salts to silver.
The preliminary dry tests and the reactions in solution
described above will give a general (and, in some cases, a
particular) indication of the nature of the acid radicals or
anions present. For a number of anions (e.g. thiocyanate,
chloride, bromide, iodide, iodate, bromate, chlorate, phosphate,
silicate, fluoride, cyanide and chromate), the tests are more
or less conclusive. However, in the presence of mixtures of
anions, it will be necessary to distinguish between those which
give analogous reactions, for example, (i) sulphite, thiosulphate
and sulphate; (ii) chloride, chlorate and perchlorate; (iii)
arsenite, arsenate and phosphate; (iv) ferricyanide and ferro-
cyanide; (v) acetate and formate; (vi) succinate and benzoate;
and (vii) oxalate, tartrate and citrate. In some cases one anion
interferes with the reaction of the other, e.g. (viii) carbonate
and sulphite; (ix) nitrite and nitrate; (x) nitrate in the presence
of bromide, iodide, chlorate and perchlorate; (xi) iodate and
iodide; (xii) oxalate and fluoride; and (xiii) chloride and
cyanide. This subject is fully discussed in Section IV, 45.
Particular attention is directed to the table of separation of
organic acids (IV, 45, 20): this must be used with due con-
sideration as to the influence of interfering organic acids
(compare tests 5 and 6 above).

VII,17. CONFIRMATORY TESTS FOR ACID

RADICALS OR ANIONS
In every case where the presence of any acid radical has
been indicated, it must be confirmed by at least one distinctive
confirmatory test. Conclusive tests for anions (halides, sul-
phate, oxy-halides, thiocyanate, phosphate, silicate, fluoride,
cyanide and chromate) have already been given in Section VII,
16, it will, of course, be unnecessary to confirm these further.
The following list, which, for the sake of completeness includes
those anions already referred to, will assist the student. in the
 \ Ii
550 Qualitative Inorganic Analysis [VII,
choice of suitable tests. Full experimental details will bt, found
in Chapter IV under the reactions of the acid radicals (anions);
the reference to, these will be abbreviated as follow.: thus
(IV, 2, 7) is to be interpreted as Section IV, 2, reaction 7. It
is assumed, of course, that interfering acids are absent or have
been removed.
Chloride. (i) Heat solid with concentrated H 2 S04 and MnOz :
C1 2 evolved (bleaches litmus paper and also turns KI-starch paper
blue) (IV, 14, 2). (ii) Chromyl chloride test (IV, 14, 5). (iii) Silver
chloride-sodium arsenite test (IV, 14, 3).
Bromide. (i) Heat solid with concentrated H 2S04 and Mn0 2 ;
Br2 evolved (IV, 15, 2). (ii) NaOCI-HCl and CHCla or Qfjl4 test;
yellowish-brown to yellow coloration (IV, 15, 5).
Iodide. (i) NaOCI-HCl (or chlorine water) and CHCla or CCl4 test,
violet coloration (IV, 16, 4). (ii) NaOCl-HCI and starcb. past(
test; blue coloration (IV, 16, 4).
Fluoride. (i) Etching test (IV, 17, 2). (ii) Silicon tetmBuorid{'
test {heat with concentrated sulphuric acid in a test· tube} (n', 17, 1)
better, test 8 in VII, 16. (iii) Zirconium-alizarin test (IV, 17, 6).
Cyanide. (i) Prussian blue test (IV, 8, 4); better, tllst 9 iI'
VII, 16. (ii) Ammonium sulphide test (IV, 8, 1, 6).
Nitrite. (i) Brown ring test with dilute acetic acid or wLh diluk
sulphuric acid (IV, 7, 2). (ii) Thiourea test (IV, 7, 9). :iii) SuI
phanilic acid-IX-naphthylamine reagent test (IV, 7, 10).
Nitrate. (i) Brown ring test with concentrated H 2S04 (IV, 18, 3)
if bromide, iodide and nitrite absent. (ii) Ammonia t'lst wit],
Devarda's alloy (IV, 18, 4).
Sulphide. (i) Dilute H 2 S04 on solid, and action of H2E on lead
or cadmium acetate paper (IV, 6, 1). (ii) Sodium nitre prusside
test (IV, 6, 6).
Sulphite. (i) Dilute H 2S04 on solid, and action of SC>2 upon
potassium dichromate paper (IV, 4, 1). (ii) BaClz-Br2 water test
(IV, 4, 2). (iii) Fuchsin solution test (IV, 4, 10).
Thiosulphate. (i) Action of dilute H 2S04 upon solid, ar d libera-
tion of S02 (dichromate paper test or fuchsin solution 1est) and
sulphur (IV, 5, 1). (ii) Potassium cyanide test (IV, 5, 6). (iii)
Nickel ethylenediamine test (IV, 5, 9).
Sulphate. (i) BaCl 2 solution and dilute HCI test, and reduction
to sulphide {test for latter with sodium nitroprusside or lea i acetate
solution} (IV, 24,1). (ii) Lead acetate test and solubility 'Jf PbS0 4
in ammonium acetate solution (IV, 24, 2).
Carbonate. (i) Action of dilute H 2S04 upon solid, .1lld lime
water or baryta water test (IV, 2, 1).
 17] Systematic Qualitative Inorganic Analysis 5tH
Hypochlorite. (i) Action of dilute HOI, and test for 012 evolved
(IV, 13, 1). (ii) Cobalt nitrate solution test (IV, 13, 4).
Chlorate. (i) Sodium nitrite test (IV, 19, 4; also test 4 in VII,
16). (ti) Ferrous sulphate test (IV, 19, 6).
Bromate. (i) Action of conceutrated H 2S04 ; Br:) and O2 evolved
(IV, 20, 1). (ii) Hydrobromic acid test (IV, 20, 4).
Iodate. (i) Potassium iodide test (IV, 21, 6). (ii) Sulphur di-
oxide or hydrogen sulphide test (IV, 21, 5).
Perchlorate. (i) Action of heat and test for chloride (IV, 21, 7),
and non-reduction with NaN0 2 or FeS04 in acid solution (IV, 22, 5).
Borate. (il Flame test (IV, 23, 2; better, test (ix) in Section
VII, 3). (ii) Turmeric paper test (IV, 23, 3).
Silicate. (i) Microcosmic bead test (IV, 26, 5) and silicon tetra-
chloride test (IV, 26, 6). (ii) Ammonium molybdate solution and
SnCl 2 solution test (IV, 26, 8).
Silicofluoride. (i) Action of concentrated H 2S04 and BaCl 2
solution test (IV, 27, 1, 2).
Persulphate. (i) Action of boiling water (IV, 25, 1). (ii) Man-
ganous sulphate solution test (IV, 25, 5).
Chromate. (i) Hydrogen peroxide test (IV, 33, 4). (ii) Lead
acetate solution test (IV, 33, 3). (iii) Action of hydrogen sulphide
or sulphur dioxide (IV, 35, 5, 6). (iv) Solid when warmed with a
solid chloride and concentrated H 2S04 evolves chromyl ehloride
(IV, 14, 5). (v) Diphenylcarbazide reagent test (IV, 33, 10).
Permanganate. (i) Hydrogen peroxide test, and identification
ofMn ++ ion (IV, 34, 1). (ii) Action of oxalie acid, and identiiication
of Mn ++ ion (IV, 37, 4). (iii) Action of hydrogen sulphide or
sulphur dioxide (IV, 34, 2).
Arsenite. (il Action of H 2 S upon acid solution (III, 11, 1).
(ii) Silver nitrate solution test (III, 11, 2), and absence of precipi-
tate with magnesium nitrate reagent (III, 11,3) or on boiling with
ammonium molybdate solution and nitric acid. (iii) Bettendorff's
test (III, 11, 6).
Arsenate. (i) Action of H 2S on acid solution (III, 12, 1), and
silver nitrate solution test upon practically neutral solution (III,
12, 2). (ii) Magnesium nitrate reagent test (III, 12, 3). (iii) Am-
monium molybdate test (III, 12, 4).
Orthophosphate. (i) Ammonium molybdate test (temperature
not above 40°) (IV, 28, 4). (ii) Magnesium nitrate reagent test
(IV, 28, 3).
Phosphite. (i) Silver nitrate solution test (IV, 30, 1), and Zn +
dilute H 2S04 test (IV, 30, 6).
 [
552 Qualitative Inorganic A nalyai8 (VII,
Hypophosphite. (i) Silver nitrate solution test (IV, 31, 1), cop·
per sulphate solution test (IV, 31, 4), and ammonium molybdat.
test (IV, 31, 9).
Cyanate. (i) Dilute H 2S04 test (IV, 9, 1). (ii) Oobalt acetat"
solution test (IV, 9, 5). (iii) Copper sulphate-pyridine test (n
9, 6).
Ferrocyanide. (i) Ferric chloride solution test (IV, 11, 3). (il
Ferrous sulphate solution test (IV, 11, 4). (iii) Uranyl acetat·
solution test (IV, 11, 11). (iv) Titanium tetrachloride test (IY,
11,9).
Ferricyanide. (i) Ferrous sulphate solution test (IV, 12, 3,
(ii) Ferric chloride solution test (IV, 12, 4).
Thiocyanate. (i) Ferric chloride solution test; colour dischargE'd
by HgC1 2 solution or by NaF solution, but not by dilute HCI (IY,
10, 6). (li) Cobalt nitrate solution test (IV, 10, 7). (iii) COpP'!
sulphate-p)Tidine test (IV, 10, 9).
Acetate. (i) Action of ethyl or of iso-amyl alcohol and concell'
trated H 2S04 (IV, 35, 3), AgNO g solution test (IV, 35, 4) and FeCI:
solution test (IV, 35, 6). (ii) Cacodyl oxide test (IV, 35, 7). '(iii i
Indigo test (IV, 35, 9).
Formate. (i) Mercuric chloride solution test (IV, 36, 7) ('I'
AgNO g solution test (IV, 36, 4), and FeOls solution test (IV, 36, ( .
(ii) Mercuric formate test (IV, 36, 8).
Oxalate. (i) Immediate precipitation with CaCl 2 solution !!l
neutral solution; precipitate decolourises a dilute solution "f
KMn04 (IV, 37, 3, 4). (li) Resorcinol test (IV, 37, 5).
Tartrate. (i) Resorcinol test (IV, 38; 6). (ii) Copper hydroxide
test (IV, 38, 7).
Citrate. (i) Deniges' test (IV, 39, 5). (li) Cadmium chloride
solution test (IV, 39, 4), and negative results with resorcinol and
copper hydroxide tests (IV, 38, 6, 7).
Salicylate. (i) Violet coloration with FeCl3 solution, discharged
by mineral acids (IV, 40, 5), and soda lime test (IV, 40, 7). (ii)
"Oil of winter-green" test (IV, 40, 2).
lienzoate. (i) Buff-coloured precipitate with FeCl a solution,
soluble in dilute HCI with precipitation of benzoic acid (IV, 41, 1).
(li) Dilute H 2S04 test (IV, 41, 2), and no precipitate with Ba( '12
solution in neutral solution.
Succinate. (i) Light brown precipitate with FeCls solution,
soluble in dilute HCI, but no precipitation of acid occurs (IV, 42, 3).
(il) Ifluorescein test (IV, 42, 6).
18] Systematic Qualitative Inorganic Analysis 553

VII, 18. ANALYSIS OF A LIQUID (SOLUTION)

(1) Observe the colour, odour and any special physical
properties.
(2) Test its reaction towards litmus paper or a suitable
narrow range indicator paper.
(a) The solution is neutral: free acids, free bases, acid salts,
and salts which give an acid or alkaline reaction owing
to hydrolysis, are absent.
(b) The solution reacts alkaline: this may be due to the
hydroxides of the alkali and alkaline earth metals, to
the carbonates, borates, sulphides, cyanides, hypo-
chlorites, zincates, aluminates, silicates, per-salts and
peroxides of the alkali metals, etc.
(c) The solution reacts acid: this may be due to free acids,
acid salts, salts which yield an acid reaction because of
hydrolysis, or to solutions of salts in acids.
(3) Evaporate a known volume of the liquid to dryness on
the water bath; carefully smell vapours evolved from time to
time. If a solid residue remains, examine as described under
A for solid and non-metallic substances (Section VII, 1). If a
liquid remains, evaporate cautiously on a wire gauze in the
fume oupboard; a solid residue should be examined as already
stated. If oharring oocurs, organio matter is present, and
must be removed before testing for Group IlIA in the sub-
sequent systematio analysis. If no residue remains, then the
liquid consists of some volatile substance which may be water
or water containing certain gases or volatile substances, such
as CO 2 , NH3, S02, H 2S, HCI, HBr, HI, H 2 0 2 , (NH.hC03' etc.,
all of which can be readily detected by special tests. It is best
to neutralise the solution with sodium carbonate and test for
acid radicals (anions).
(4) If the solution reacts alkaline, the following tests should
be performed:
(a) Peroxides and per-salts (e.g. H 20 2 and NaB0 3 ).
(i) Heat a little of the solution with a few drops of
cobalt nitrate solution; a black precipitate of a higher
oxide of cobalt is obtained (sulphides and hypoohlorites
interfere and must be absent).
(li) Add a little titanous sulphate or chloride solution,
and carefully acidify with cold dilute sulphurio acid; a
yellow coloration is obtained in the presence of hydrogen
peroxide.
IS·
554 Qualitative Inorganic A nalY8i8 (VII,
(iii) Add a little ferric chloride and potassium ferri-
cyanide solutions; Prussian blue precipitate.
(b) Hydroxides and carbonates. Boil to decompose
hydrogen peroxide, if present. Add a slight excess of
barium chloride solution; if the solution now reacts
alkaline, hydroxyl ions are present. Filter off the pre-
cipitate, and examine for carbonate with dilute acid
(Section IV, 2, reaction 1).
(5) If the original solution is acidic, render a known volume
(say, 5 ml.) alkaline with aqueous ammonia before evaporating
it on a water bath. This will prevent the loss of volatile acids,
such as hydrochloric and boric acids. Examine the residue.

VII,19. ANALYSIS OF A METAL OR AN ALLOY

The analysis of a metal or of an alloy is simplified by ~he
fact that no acid radicals or anions need be looked for. Many
alloys contain small amounts of P, Si, C and S; phosphorus is
converted by the usual solution process into phosphate, and
may be identified as such (Section IV, 28).
The alloy or metal should be in the form of borings, turnings
or filings. About 0·5 gram is treated with 10 m!. of concen-
trated nitric acid in a porcelain basin in the fume chamber.
warmed gently until the evolution of red fumes ceases, and
evaporated almost to dryness. * About 10 m!. of water are
then added, the mixture heated for a few minutes and filtered,
if necessary.
Three cases may arise:
1. The metal or alloy dissolves completely. Examine
solution (A) by Table I (Section VII, 6), remembering that
phosphate may be present and should be tested for.
2. The metal or alloy does not dissolve completely.
The solution (A) is examined as in case 1. If the residue is
black, it may be either carbon or gold and/or platinum. Test
for carbon by igniting on a crucible lid; carbon glows and burns.
Gold and platinum dissolve in aqua regia (compare Sections
IX, 5 and IX, 6).
If the residue is white, it may contain inter alia hydrated
stannic oxide or antimony pent{)xide, bismuth oxide, together
with traces of copper, lead and iron, and is best analysed as
outlined in the following table.
• The nitric acid will oxidise the P to H,PO,. S to H.SO •• AB to H.ABO ••
Sb to Sb.O,.xH.O (converted by gentle heating into Sb.O.). Sn to SnO •• zH.O
and Si to gelatinous silicic acid.
19] Systematic Qualitative Inorganic Analysis 555

Table XII.-Analysis of Portion of Alloy Insoluble in

Concentrated Nitric Acid

Wash residue with water. and dry by heating in a crucible. Add 6

times its weight of an intimate mixture of equal parts of anhydrous
Na 2CO. and sulphur. mix well, cover the crucible and heat over" small
flame until the excess of sulphur has burned off. This operation llsually
occupies about 20 minutes. Allow to cool and extract content,.; of the
crucible with hot water and filter.

Residue. May contain Filtrate. May contain _K't 2 SnS ••

PbS. Bi 2S 3• CuS and FeS. Na.SbS.,* Na3AsS., Na.PO. and. possibly.
Dissolve in hot dilute Na,S. Acidify with dilute ROI (te'it with
RNO., filter off any S and litmus paper), and filter.
evaporate almost to dry.
ness. Dissolve in water
and add to original solu- Residue. May con- Filtrate. Test for
tion A. tain SnS,. Sb,S., phosphate. Boil off
As,S. and S. R 2S, add e'Ccess of
Examine by Tables NH. solution and
VI or VIA (Section then magrlesium
VII, 11) for As. Sb nitrate reagent. A
and Sn. white crystalline ppt.
indicates phosphate
present. Confirm.

3. The metal or alloy is unattacked. If the alloy is

not attacked by nitric acid (1 : 1), treat a separate 0·5 gram
sample with 20 ml. of aqua regia (15 ml. of concentrated hydro-
chloric acid and 5 ml. of concentrated nitric acid) in a porcelain
dish. Cover the latter with a clock glass and heat gently until
the alloy has disintegrated completely. Raise the clock glass,
boil down to about 5 ml. and finally evaporate to dryness on a
water bath. Add 5 ml. of concentrated hydrochloric acid,
heat gently, dilute with 15 ml. of water, stir and heat to boiling.
Cool to room temperature and filter. The residue may consist
of AgCI, PbCl2 and Si0 2 • The filtrate may contain the metals
of the remaining Groups together with arsenate, orthophosphate
and sulphate. Examine by Table I (Section VII, 6).
If the alloy resists the action of aqua regia, fuse it wil h sodium
hydroxide pellets in a silver dish or crucible (CAUTION f).
When decomposition is complete, allow to cool, transfer the
silver vessel to a beaker and extract the melt with water; re-
move the silver vessel from the beaker. Strongly acidify the
* These are formed in accordance with the following equations:
2SnO. + 2Na 00. + 9S = 2Na,SnS a + 3S0. + 2CO.
2
2Sb,O. + 6Na.CO a + 23S = 4Na.8bS, + 7S0. + 600.
Sb,O, + 3N~,CO. + 128 = 2Na.8bS, + 4S0. + 3CO.
556 Qualitative Inorganic Analysis [VII,
~ontent.s of the beaker with nitric acid, evaporate to dryness
on a water bath and proceed as above.
The alkali fusion is sometimes replaced by warming on a
water bath with concentrated hydrochloric acid and 10-::0 per
cent of its volume of liquid bromine.
The compositions of some of the common alloys are given in
Table XIII; the chief constituents are listed in the orller of
their predominance.
Table XIII. Composition of Alloys

Brasses CU,Zn,Sn,Pb
Bronzes CU,Sn,Zn,Pb
Phosphor bronzes CU,Sn,Pb,P
Solders Sn, Pb, Bi
Pewter Sn,Sb,Pb,Cu
Type metals Pb,Sb,Sn
German silver Cu, Ni, Zn
Monel metal Ni, Cu
Constantan Cu, Ni
Nichrome Ni, Fe, Cr
Manganin Cu, Mn, Ni
Wood's alloy Bi, Pb, Sn, Cd
Rose's alloy Bi, Pb, Sn

VII,20. ANALYSIS OF INSOLUBLE SUBSTANCES

A substance which cannot be dissolved by concentrated acids
(hydrochloric or nitric) or by aqua regia is described aE "in-
soluble." Special methods for solution must therefore be
employed, the actual process chosen depending largely upon
the nature of the insoluble substance.
The most common insoluble substances encountered in
qualitative analysis are: " _________________
AgCI, AgBr, AgI, AgCN; .
SrS04, BaS04, PbS0 4;
the strongly ignited oxides A1 20 3, Cr203, Fe203, 8n0 2,
Sb 20 4, [Ti0 2,Th0 2 ,W0 3·xH 20];
fused PbCr04, and certain minerals, e.g. CaF 2 (fluor 8par),
FeCr204 (chrome ironstone);
Cu 2[Fe(CN)6], Zn 2[Fe(CN)6]' Prussian blue;
Si0 2, and various silicates; SnS2 (mosaic gold); C and S;
metallic silicides; carborundum.
20] Systematic Qualitative Inorganic Analysis 557
The insoluble substance should be subjected to the tests
enumerated below in the order given until it is brought into
solution. (Some of these tests will have been carried out in
the preliminary examination.) The substance should be in the
form of a fine powder; use an agate mortar, if necessary.
(1) Note colour and appearance.
The following substances are coloured: Cr203 (green), Fe203
(dark red), SnS2 (bronze), PbCr04 (brown), Fe4[:Fe(CN)6Ja
(Prussian blue), CU2[Fe(CN)6] (dark brown), FeCr204 (dark
grey), AgBr* (very pale yellow), AgI* (light yellow), C and S.
The remaining substances listed above are white or nearly
so, but may be slightly coloured by traces of impurities; the
effect of the latter is less marked when the substance is in the
form of a fine powder.
(2) Examine the effect of heat.
Heat a small quantity in a small crucible or upon platinum
foil. Sulphur will melt to a yellow liquid, and burn with a
blue flame with the production of sulphur dioxide (test with
potassium dichromate paper or with fuchsin solution).
Carbon will glow and burn away almost completely; a light-
coloured ash may remain. If the black substance is dropped
in very small quantities into a little fused potassium nitrate
contained in a hard glass tube, the oxidation will be more
vigorous and some potassium carbonate will be formed. The
residue will evolve carbon dioxide on treatment with dilute
acids. Additional confirmation of carbon is obtained by heat-
ing an intimate mixture of the substance with dry cupric oxide
in a hard glass tube; carbon dioxide will be evolved (test with
lime water), and red metallic copper will remain.
2CuO +C = CO 2 + 2Cu
The silver salts, AgCI, AgBr and AgI, will melt without
further change; AgCN decomposes to give a residue of silver,
and cyanogen gas is evolved.
Antimony oxide Sb 20 4 melts to a yellow liquid.
(3) Heat with sodium carbonate upon charcoal.
The following observations may be made:
(a) No metallic button is produced. This indicates the
absence of Ag, Sn and Pb. Either moisten residue with a few
drops of dilute hydrochloric acid and place in contact with lead
• The silver halides become violet on exposure to light.
55S Q1WLitative Inorganic AnaLY8i8 (VII.
acetate paper or extract with a little water and filter into
freshly prepared sodium nitroprusside solution; a black stain
or a transient violet coloration respectively indicates the pre-
sence of sulphide and therefore of sulphate in the original sub-
stance.
The test should be repeated with another portion of the
original substance if a white residue is obtained. Add one or
two drops of cobalt nitrate solution and heat again. A blue
mass indicates aluminium.
(b) A metallic button or bead is obtained. The solubility
of the bead in nitric acid and in hydrochloric acid is tested.
(i) The bead dissolves in nitric acid forming a clear solu-
tion, and yielding a curdy, white precipitate of silver
chloride, soluble in dilute ammonia solution, upon the
addition of a little hydrochloric acid. The presence of
silver and the absence of tin is indicated.
(ii) The bead gives a clear solution with hydrochloric acid,
and the addition of mercuric chloride solution produces
a white precipitate of mercurous chloride. With nitric
acid, a white insoluble powder (" metastannic acid") is
produced. This test indicates the presence of tin and
the absence of silver.
(4) Heat with concentrated sulphuric acid.
(i) Escaping gas renders a drop of water upon a glass rod
turbid. Fluoride is indicated.
(ii) Carbon monoxide evolved, which burns with a blue
flame. Ferrocyanide is indicated.
(5) Heat upon a platinum wire in the reducing zone of
the Bunsen flame.
This process will reduce any sulphate present to sulphide (as
already indicated in test 3). Upon moistening with dilute
hydrochloric acid, the sulphide will be converted into the com-
paratively volatile chloride, and the usual flame test is applied.
The presence of barium or of a mixture of strontium and barium
will be indicated.
(6) Apply the microcosmic bead test.
If a skeleton bead is obtained, silica or a silicate is indicated.
A negative result does not definitely prove that silica or a
silicate is absent, as a skeleton is not always formed. The
silicon tetrafluoride test should then be employed (Section IV,
26, reaction 6).
20] Systematic Qualitative Inorganic Analysis 559
Heat the bead in the reducing flame in order to test for
titanium. If the bead is violet when cold (the colour is pro-
duced more readily by the addition of a minute speck of tin
or of stannous chloride), the presence of titanium is indicated.
If iron is also present, the bead will be coloured brownish-red
in the reducing flame.
When titanium is found, it is best to fuse with potassium
pyrosulphate in a silica or platinum crucible, and to extract
the residue with cold water whereby a solution of titanic sul-
phate is obtained.
(7) Heat with sodium carbonate and potassium nitrate.
This test may be carried out in a loop of platinum wire or
upon platinum foil or upon a piece of broken porcelain. If
chromium is present, a yellow melt is produced. This should
be dissolved in water, acidified with dilute acetic acid, and (a)
silver nitrate solution added, when brownish-red silver chromate
is precipitated, (b) lead acetate solution added, when yellow
lead chromate is precipitated, or (c) 1-2 mI. of diphenyl-
carbazide reagent added, when a deep red coloration is pro-
duced.
(8) Boil with sodium hydroxide solution.
(i) Lead chromate dissolves:
PbCr04 +4NaOH = Na2Cr04 +
Na2[Pb02] +
2H 20
(ii) Prussian blue yields ferric hydroxide and sodium ferro-
cyanide (see under Iron, Section III, 20, reaction 5).
(iii) Copper ferro cyanide yields copper oxide and sodium
ferrocyanide.
(iv) Zinc ferro cyanide yields sodium zincate and sodium
ferrocyanide, i.e. it dissolves completely. The zinc is readily
identified by passing hydrogen sulphide into the solution; the
ferro cyanide (see Section IV, 11) is detected in the filtrate after
acidifying and boiling off the hydrogen sulphide.
(v) Alumina and silica may dissolve, forming solutions of
sodium aluminate and sodium silicate respectively.
(9) Heat with concentrated hydriodic acid.
The powdered substance (0'5 gram) should be heated to just
below the boiling point with hydriodic acid, sp. gr. 1'7* (2'5 mI.).
* Where colour reactioIUI are to be observed. it is recommended that the
hydriodio acid be decolourised by the addition of 1-2 per cent by volume of
50 per cent hypophosphorous acid or by warming with a little potaaaium
hypophosphite.
660 Qualitative Inorganic AnalY8i8 [VII,
(i) Stannic oxide dissolves. A pink to red coloration is
produced when the solution cools; the coloration disappears
on warming to 90-100°0. A yellow to orange sublimate of
stannic iodide is frequently observed.
Sn02 + 4HI ? SnI" + 2H20
Upon filtration and dilution, the tin may be precipitated with
hydrogen sulphide.
(ii) The sulphates of lead, strontium and barium are
gradually decomposed and hydrogen sulphide is evolved, which
is identified by ammoniacal sodium nitroprusside paper (see
under Sulphides, Section IV, 6, reaction 6).
PbSO" + IIHI = H[PbI s] + 412 + Hl!S + 4H 20
BaSO" + IOHI = Balz + 412 + H 2S + 4H 2 0
Upon filtration through a sintered glass crucible and dilution,
golden yellow lead iodide is precipitated from lead sulphate.
Barium may be detected by the addition of dilute sulphuric
acid, and strontium by sulphuric acid and ethyl alcoho1.
(iii) The silver halides dissolve readily in the cold, owing to
complex formation:
3AgI + HI = H[Ag3~];
3AgX + 4HI = H[AgsI"J + 3HX (X = Cl or Br)
Upon warming the solution, the hydrogen halides are expelled
from solution with effervescence. When the solution is diluted,
the complex iodo-argentous acid is decomposed and silver
iodide is precipitated; it is best, however, to expel the excess
of hydriodic acid by evaporation before diluting with water.
If lead sulphate was originally present, lead iodide will be
precipitated on dilution; this can be separated from silver
iodide by extraction with ammonium acetate solution.
(iv) Calcium fluoride is attacked by the hot acid, hydrogen
fluoride being evolved, which will etch glass:
CaFl! + 2HI = Call! + 2HF
Upon dilution, neutralisation with ammonia solution and
addition of ammonium oxalate solution, the calcium is pre-
cipitated as calcium oxalate.
(10) Treat with ammonium sulphide solution.
If the insolubJe unknown or the washed residue from the
aqua regia extraction is white or light-coloured, treat it in a
porcelain dish or crucible with a few drops of ammonium
sulphide solution and stir. Lead and silver compounds are
20] Systematic Qualitative lrwrganic Analysis 561
probably absent if the oolour is unohanged. A blaokening of
the solid indicates that lead and silver compounds may be
present.

PREPARING A SOLUTION
The above preliminary tests may supply valuable informa-
tion as to the composition of the insoluble substance. In every
case, the following methods of bringing the substance into
solution for systematic analysis should be used.
(a) Removal of lead salts.
Treat about 1 gram of the insoluble unknown, or the residue
from the aqua regia extraction, with 3 m!. of concentrated
ammonium acetate solution slightly acidified with acetic acid.
(Excess of ammonia solution must be absent to avoid the
solvent action upon any silver chloride which may be present.)
Heat the mixture, with stirring, to about 70°0 and filter; wash
with about 5 ml. of water. Test separate portions of the
combined filtrate and washings for Pb++, S04 -- and CI-.
The silver nitrate test for chloride must be conducted in the
presence of about 10 per cent of the volume of concentrated
nitric acid and the mixture heated to boiling; silver acetate
will dissolve under these conditions. If lead salts are found,
repeat the extraction with ammonium acetate solution and
wash the residue with hot water until the washings give no
coloration with dilute ammonium sulphide solution.
Lead silicate is insoluble in ammonium acetate solution; it
will be detected in (c).
(b) Removal of silver salts.
Warm the insoluble unknown or the residue from (a) (if lead
salts are present) with a concentrated solution of potassium
cyanide. (If it dissolves completely, only AgCI, AgBr, AgI and
AgCN are present.) Filter and reserve the residue R for sub-
sequent treatment. Dilute the filtrate considerably and treat
with hydrogen sulphide. Filter off any black precipitate
(Ag 2S), wash, dissolve in hot dilute nitric acid and add dilute
hydrochloric acid. A white precipitate of silver chloride in-
dicates the presence of silver.
If silver is found, the halogen with which the metal was
originally combined is identified by melting another portion of
the insoluble substance, immersing it in dilute sulphuric acid,
placing a piece of zinc in contact with the acid and the fused
mass, warming and allowing to stand for a few minutes. The
;62 Qualitative Inorganic Analysis [VII,
lilver salt is reduced to metallic silver, whllst the acid radicals
anions) are present in solution in the presence of zinc ions, i.e.
LS zinc salts. Filter. The filtrate is tested for chloride,
)romide and iodide in the usual manner; the tests for mixtures
)f these anions are described in Section IV, 45, and in Section
VII, 16, Table A.
(c) Sodium carbonate fusion.

The residue R, free from lead and silver salts, or the original substance,
if lead and silver salts are absent, is mixed with 5---6 times its weight of
pure, sulphate-free, anhydrous Na.CO a or with a mixture of equal parts
of Na.CO a and K.CO. (fusion mixture). The mixture is heated upon
Pt foil or in a Ni crucible until a tranquil melt is obtained. (It may be
necessary to heat over the blowpipe flame.) Allow to cool, extract the
melt thoroughly by boiling it with water. Filter.

Residue. Wash well, first with 2% Filtrate. May contain

Na.CO. solution, and then with hot Na.CrO., Na[AIO.J, Na.[SnO.J,
water. May contain inter alia BaCO" Na.AsO., NaF, Na.SO. and the
SrCO., CaCO., other insoluble car- corresponding K salts, if fusion
bonates and unattacked CaF., SnO., mixture was employed. Acidify
I Sb.O" AI.O., Fe.O., etc. with concentrated HCI and
Extract with dilute HNO" and filter. evaporate to dryness in the
fume cupboard. Triturate the
dry mass with concentrated
Residue. If white, Filtrate. HCI, add water, warm and filter.
may contain CaF .' Evaporate
SnO., Sb.O., AI.O., almost to dry-
SiO., etc., which are in. ness to remove Residue. Filtrate. Test
completely attacked HNO" add May contain a portion for sul-
byNa.CO •. Fusewith dilute HCI and SiO.·t phate. Examine
N aOH in a Ni crucible. * examine for Confirm by for metals of
Allow to cool, extract metal ions by microcosmic Groups II and
with water and filter. Table I (Sec- bead test or III.
The filtrate may con- tion VII, 6). by the SiF.
tain sodium stannate, test in a lead
sodium antimonate, capsule.
sodium aluminate and
sodium silicate.
Test for Sn, Sb and
AI.

Metallic sUicides and carborundum are rarely encountered

n routine qualitative analysis. They are best brought into
* An alternative procedure is the Na.CO.-S fusion method already de-
cribed under the analysis of metals and alloys (Table XII, Section VII, 19).
The original insoluble substance may also be subjected to the Na.COa-S
usion, and the extract, after acidifying with 1 : I HCI, filtered. Any pre-
ipitate is washed, dissolved in concentrated HCI and H.S removed by
,oiling: Sb may be detected with Rhodamine-B and Sn with HgCI. solution.
t This precipitate may also contain WO.,xH.O from mineral tungstates
Ilso1uble in aqua regia. Confirm W by digesting with dilute NH. solution
o dissolve WO.,xH.O and then apply the SnCII-HCI test.
20] Systematic Qualitative Inorganic Analysis 563
solution by fusion with sodium or potassium hydroxide in a
silver crucible (OAUTION I):
CUzSi + 2KOH + H 20 = K 2SiOa + 2Cu + 2Hz ;
SiC + 4KOH + 2H 20 = K 2SiOs + K 2COS + 4H2
During the fusion the liberated hydrogen catches fire forming
water by combination with the oxygen of the air. Upon
treating the melt with water, the soluble potassium silicate,
etc., is extracted.
Carborundum when in the form of a fine powder is readily
decomposed by fusion with potassium carbonate in a platinum
crucible. Upon removing the cover of the crucible the blue
flame of burning carbon monoxide may be seen.
SiC + 3K2COS = K 2SiOs + 2K2 0 + 4CO
 CHAPTER VIII

MODIFICA TION OF THE SYSTEMATIC ANALYSIS

WHEN ORGANIC ACIDS, SILICATES, BORATES.
FLUORIDES AND PHOSPHATES ARE PRESENT

REFERENCE has already been made in Chapter VII, Tables I

and II, to the modification of the analysis after Group ] i
necessitated by the presence of various interfering acid radical..;
(anions). It is the express purpose of this Chapter to discu1-~
this subject in greater detail in order that the student may
understand the reason for each operation, and also to indicate
alternative procedures wherl3by some of the interfering radical,;
may be removed.
The interfering acid radicals may be divided into two main
groups:
(i) Those which, when present in solution, combine witl:
various metals to form stable complex ions (compare Sectio:!
I, 20); this may result in the failure of these metals to precipi
tate with the usual group reagent. To this class belong such
organic acids as oxalic, citric and tartaric acids, and als·,
hydroxy compounds, such as sugar and starch. In thei I
presence, iron, chromium and aluminium are either incOD;
pletely precipitated or not precipitated at all by ammoniUl!:
chloride and ammonia solution.
(ii) Those which, under certain conditions, form insoluble
compounds with some of the metals of the later groups. It is
conceivable, therefore, that under conditions which result in
the precipitation of the Group IlIA metals, metals of the sub
sequent groups will also be precipitated in consequence of thl'
formation of compounds which are insoluble or sparingly
soluble in the presence of ammonium chloride and ammonia
solution. The most important of these acid radicals are'
oxalates, tartrates, citrates, borates, fluorides and phosphates.
Silicates are included with these owing to the precipitation of
gelatinous silicic acid by ammonium chloride and ammonia
solution (see under Silicates, Section IV, 26, reaction 2).
Reference to a table of solubilities will show:
(a) That the oxalates, tartrates and citrates of most of the
metals of Groups lIlA, IIIB and IV and of magnesium art'
564
 M odiflcation of the Systematic Analysis 565
either insoluble or difficultly soluble in water. (It should be
noted that most oxalates and tartrates, with the exception of
those of calcium, strontium and barium, form soluble complex
salts with alkali oxalates and alkali tartrates respectively;
compare (i) above.)
(b) That the borates of the metals of Groups IlIA, IIlB and
IV are insoluble in water; magnesium borate is sparingly
soluble. (Some of these are, however, soluble in ammonium
chloride solution.)
(c) That the fluorides of calcium and magnesium are in-
soluble, and those of nickel, cobalt, strontium and barium are
sparingly soluble in water.
(d) That the phosphates of the metals of Groups IlIA, IIlB,
IV and of magnesium are insoluble in water.
Furthermore, the borates, fluorides, phosphates, oxalates,
tartrates and citrates of the Group IlIA, IIlB and IV metals
and of magnesium are insoluble in alkaline solution, but dis-
solve in acid solution.
It is evident that in the presence of these acids, Group IlIA
metals cannot be separated from those of the remaining groups
by the addition of the customary group reagent, NH 401 and
NHs solution. The usual scheme of systematic analysis is
therefore modified when any or all of these anions are present
before proceeding to the precipitation of Group IlIA.
The presence of some of these anions will have been indicated
in the preliminary tests. Organic acids are revealed in the dry
tests, and particularly by the action of concentrated sulphuric
acid. In view of the common occurrence of oxalates and the
somewhat indecisive indications of the preliminary tests, it is
recommended that this radical be tested for in a portion of the
filtrate from Group II, from which all the hydrogen sulphide
has been expelled by boiling. This is most simply carried out
by adding 1 m!. of CaOl2 solution and 1 ml. of Na.C 2H a0 2
solution to 1 m!. of the solution; if a crystalline precipitate
forms (the precipitate should not be confused with gelatinoU8
OaF 2), filter, wash, dissolve in a little hot dilute H 2S04 , filter
and add 2-3 drops of dilute KMn04 solution to the filtrate. If
the colour of the KMn04 solution is discharged, an oxalate is
present.
The presence of fluoride is indicated in the preliminary treat-
ment with concentrated sulphuric acid; a moistened glass rod
introduced into the tube becomes covered with a film of
gelatinous silicic acid.
The detection of borate is provided for in the preliminary
 l
566 Qualitative Inorganic Analysis [VIII,
test (ix) of Section VII, 3. Alternatively, it may be tested
for after the precipitation of Group II.
The presence of phosphate is always tested for in the Group 11
filtrate, from which all the H 2S has been expelled. To 1 m!.
of the solution, add 1 ml. of HNO a and 3 ml. of ammoniUlIi
molybdate solution, and warm to a temperature not exceediI,~
40°. The production of a bright yellow precipitate proves ti,l)
presence of a phosphate (Section IV, 28, reaction 4).

VIII, 1. PROCEDURE FOR THE REMOVAL OF INTER -

FERING ACIDS IN SYSTEMATIC QUALITATIVl
ANALYSIS
The acids are removed in the follOwing order:
1. Organic acids. The filtrate from Group II is evap, ,-
rated to dryness, when some carbon may be liberated and tI,e
organic acids decomposed. By repeated evaporation with con-
centrated HNO a, the black residue is completely oxidise, l.
The residue must not be heated too strongly as Fe20a, Cr2( 13
and Al 2 0 a may be rendered very difficultly soluble in HCI.
2. Borates and fluorides. The residue from 1 is It'-
peatedly evaporated almost to dryness with concentrated H( 1;
the HF volatilises with the HOI and the HaBOa volatilises 'll
the steam.
If borate is present and fluoride is absent, the former m;,.v
be removed by repeated evaporation to dryness on a wat!,r
bath with a mixture of 5 ml. of methyl alcohol (inflammable!)
and 10 ml. of concentrated HOI. The borate slowly volatilises
as methyl borate, (OHa)aBO a (poisonous).
3. Silicates. The evaporation with concentrated Hel
converts silicates into an insoluble form of Si0 2 • Hence hy
complete evaporation to dryness with a further quantity If I

concentrated HOI, extraction with water or dilute HCI, alld

filtration, the silicate is completely eliminated.
4. Phosphates. There are several methods for the removal
of phosphate ions: one of these, the zirconium nitrate method,
has already been outlined in Table II (Section VII, 7). The
zirconium nitrate procedure is by far the most convenient; if
correctly performed, all phosphate ions are quantitatively and
rapidly removed as the highly insoluble zirconium phosphate.
All the other "phosphate separations" are tedious and time-
consuming, and the quantitative removal of phosphate ions is
2] Modification of the Systematic Analysis 567
not always achieved: they are therefore not recommended for
general use. Only one of the alternative procedures will be
described in detail, since it incorporates a number of points of
theoretical interest and is accordingly of some pedagogic value.
Another procedure is described also since it finds application
in the presence of the "rarer" elements.

VIII, 2. ANALYTICAL PROCEDURES IN THE PRE-

SENCE OF PHOSPHATES. " PHOSPHATE
SEPARATIONS"
The various procedures which have been proposed for the
removal of the interfering phosphate ions in qualitative analysis
are all based upon precipitation processes. These include:
(a) the basic acetate method;
(b) the ferric chloride method;
(c) the tin method;
(d) the stannic chloride method;
(e) the formate buffer method; and
(j) the zirconium chloride method;
the last-named is similar, but inferior, to the zirconium nitrate
procedure. Only a modification of the basic acetate method
and also the stannic chloride method will be described here. *
The former is given in Table I: it is termed the acetate buffer-
ferric chloride method. The latter finds application in the
removal of phosphates when the so-called" rarer" elements are
present in Group IlIA (see Section IX, 18).
• For details of the other procedures, see the Third Edition of this Text
Book (1945).
568 Qualitative Inorganic Analysis [VIII,
VIII, 2. Table I.-Phosphate Separation by the
Acetate Buffer-FeCla Method
If a phosphate has been found in Table I (Separation of Cations into
Groups, Section VII, 6), proceed as follows. Dissolve the ppt. produced
by the action of NH.Cl and a slight excess of NH. solution in the minimum
volwne of dilute HOI. [The ppt. may contain Fe(OH)., Al(OH).,
Cr(OH)., MnOI,xH.O, traces of OaF. and the phosphates of Mg and of
the Group IlIA, IUB and IV metals.) Test about 0·5 mI. for Fe by the
addition of K.[Fe(ON).] or NH.SCN solution. To the main volwne of
the cold solution, add dilute NH. solution dropwise, with stirring, until
either a faint permanent precipitate is just obtained or until the solution
is just alkaline (test with litmus paper). Then add 2-3 mI. of dilute
acetic acid (I : 1) and 10 mI. of 3N ammoniwn acetate solution. Dis-
regard any ppt. which may form at this stage. If the solution is red or
brownish red, sufficient ferric iron is present (I) in the solution to combine
with all the phosphate ions. If the solution is not red in colour, add
"neutral" FeCI. solution (2), drop by drop and with stirring, until the
solution acquires a deep brownish·red colour (3). Dilute the solution to
about 150 mI. with hot water, boil gently for 1-2 minutes, filter hot (4)
and wash the residue with a little boiling water.

Residue. May contain the phosphates Filtrate. Boil down in an

(and, possibly, the basic acetates) of Fe, evaporating dish to 2{}-25 mI.
Al and Cr and also Fe(OH)a. Add 0·5 gram of NH.OI and
Group IlIA present. then dilute NH. solution in
Rinse the ppt. into a porcelain dish by slight el(cess. Filter, if neces·
means of 10 mI. of cold water, add 1-1'5 sary.
grams of sodiwn perborate NaBO.,4H.O
(or add 5 mI. of N aOH solution, followed
by 5 mI. of 3% H 20. solution), and boil ReSidue.
gently until the evolution of O 2 ceases Filtrate. !'i

Examine for Examine fOl

(2-3 minutes). Filter and wash with a Al and Cr, if Groups lIIB.
little hot water. not previously IV and for
tested for. Mg as detailed
[In general, in General
Residue. Filtrate. May contain no ppt. will Table I (Sec-
FePO, + NaMO. and Na.CrO,. be obtained tion VII, 6).
Fe(OH) •. Examine for AI and Cr as here.]
Reject. described in Group Separa-
tion Table VII (Section
VII,12).

Note8. (I) If the reddish-brown colour cannot be soon owing to

the formation of a precipitate or the presence of coloured ions, filter
a small portion of the mixture and render the filtrate alkaline 'Wit h
dilute ammonia solution. If a light coloured precipitate is obtained,
more ferric chloride solution should be added to the main mixture
with stirring until a similar test gives a reddish-brown precipitate,
indicating that Fe+++ is present in excess.
(2) "Neutral" FeCla solution is prepared by adding dilute
ammonia solution dropwise to the side-shelf Feels solution until a
slight permanent precipitate forms; this is filtered off. The side-
shelf reagent usually contains excess of free hydrochloric acid added
2] Modification of the Syste11lQ,tic Analysis 569
during its preparation to produce a clear solution; the free acid leads
to incomplete precipitation.
(3) If the colour cannot be seen because of the presence of a
precipitate or of coloured ions, filter a small portion of the mixture
and test the filtrate with dilute ammonia solution as in Note 1.
A large excess of FeCl s solution must be avoided since it exerts a
solvent action on ferric phosphate and the precipitation of the latter
will be incomplete.
(4) The addition of filter paper pulp or a Whatman filtration
accelerator will facilitate filtration.

Explanation (Table J)
The theoretical basis of the acetate buffer-FeCI a method may
be summarised as follows:
(a) FeP04 , AIP04 and, to a lesser extent, CrP04 are insoluble
in warm, dilute acetic acid buffered by a solution of ammonium
acetate: the phosphates of the metals of Group IIIB and IV
and of Mg are soluble.
(b) The precipitation of phosphate ions will be complete only
if the trivalent ions are present in excess. The procedure
depends upon having excess of femc ions present. Feme iron
is chosen because (i) it is easy to test for Fe + + + in the filtrate
from Group II, (ii) ferric phosphate is the least soluble in the
acetic acid medium and (iii) it can most easily be detected by
its colour in aqueous solution. Furthermore, the excess of
ferric ions can be readily removed since ferric acetate is con-
siderably hydrolysed upon dilution and boiling, and the excess
of iron is precipitated as basic ferric acetate (or as ferric
hydroxide occluding large amounts of acetate ions).
Fe(C2H a0 2 )s + 2H 20 ~ Fe(OH)2. C2H a0 2 + 2H. C2H s0 2
Fe(C 2H s0 2 )s + 3H2 0 ~ Fe(OH)s + 3H. C2H s02
The reaction tends to reverse upon cooling, hence filtration of
the hot solution is desirable.
(c) The addition of ammonium acetate solution to a solution
containing iron, aluminium and chromium ions yields the
acetates of these metals: upon boiling the highly diluted solu-
tions, the basic acetate of iron is almost completely and that
of aluminium is largely precipitated. Chromium acetate does
not appear to form a basic acetate under these conditions, but
in the presence of considerable quantities of iron and alu-
minium, chromium is coprecipitated to a considerable extent
with these two elements either as the basic acetate or as an
adsorption complex.
 ,
570 Qtutlitative Inorganic AnalY8is [VIII,
Phosphate separation by the stannic chloride method
-It has been found that a freshly prepared solution of stanni,
chloride readily removes phosphates from solution. It if
highly probable that the phosphate is removed largely as th,
insoluble stannic phosphate Sn3(P04)4; an alternative view i
that an adsorption complex of phosphoric acid and hydrated
stannic oxide is formed, but it may well be that both compound
formation and adsorption play a part. When small amount
of phosphates are present, the precipitate filters with difficult,
and the filtrate may be turbid; in such cases the addition ( ,
more phosphate, say as diammonium phosphate (NH4hHP0 4 .
to the solution before precipitation with the reagent is recall)
mended.
The experimental procedure is as follows. Boil the filtrai,'
from Group II to remove hydrogen sulphide, dilute to 50 ml .
add 3 m!. of 5 per cent diammonium phosphate solution (.!
necessary), followed by dilute ammonia solution until the prt
cipitate which forms initially does not redissolve on shakin.::.
(The pH should be 3'5-4; the use of congo red or bromophen, ,!
blue indicator paper is advantageous.) Add 1 m!. of dilu'
hydrochloric acid, heat to boiling and introduce 2 ml. of t}.;~
stannic chloride reagent (prepared by dissolving 5 grams of tl·"
crystalline salt in 5 ml. of water). Filter 1-2 m!. of the Sll
pension and test the filtrate for phosphate with ammoniu' It
molybdate and nitric acid. If the test is positive, add ,
further 0·5 m!. of the stannic chloride reagent to the boilik~
suspension; repeat the process until the phosphate test d
negative. Introduce a Whatman filtration accelerator aJld
filter the boiling suspension, preferably with the aid of sucti, 'n
(compare Section II, 2, 10); wash well with hot water. Tre ,t
the filtrate and washings with 1 m!. of dilute hydrochloric a( ,,1
and pass hydrogen sulphide until the precipitation of stamilC
sulphide is complete. Filter. Concentrate the filtrate a? ,d
examine it for Groups IlIA, IIIB, IV and V in accordance wit h
the General Table I (Section VII, 6).
If the stannic phosphate precipitate is green in colour,
chromium may be present. Boil a small portion of the precipi-
tate with sodium hydroxide solution, allow to cool and add a
little hydrogen peroxide solution and 1-2 m!. of amyl alcohol:
a blue coloration of the amyl alcohol layer confirms 'chromium.
 CH.APTER IX
REACTIONS OF SOME OF THE "RARER" ELEMENTS

No reference has been made in the earlier chapters to the charac-

teristic reactions of the so-called "rarer" elements. Many of these,
e.g. tungsten, molybdenum, titanium, uranium and beryllinm, have
important industrial applications, and it was felt that a brief account
of the analytical chemistry of a number of selected elements might
usefully be included in this volume.
The term "rarer" elements as originally employed in the sense
of their comparative rare occurrence and limited availability must
now, in a number of cases, be regarded as a misnomer. Large
quantities of some of these elements are utilised annually, and the
range of the application is slowly but surely widening. A few
examples may be mentioned: the use of molybdenum, ttmgsten,
titanium and beryllium in the steel industry, of tungsten in the
manufacture of incandescent lamps and of titanium and uranium
in the paint industry. The interpretation of the term "rarer"
elements, as applied to the elements described in this chapter, is
perhaps best accepted in the sense of their comparatively rare
occurrence in routine qualitative analysis.
No attempt has been made to give more than a short introduction
to the subject; to economise in space, most of the simple equations
have been omitted. The elements have been classified, in so far as
is possible, in the simple Groups with which the student is already
familiar, and methods of separation have been briefly indicated.
Thus thallium and tungsten are in Group I; molybdenum, gold,
platinum, selenium, tellurium and vanadium in Group II; and
beryllium, titanium, uranium, thorium and cerium in Group III.
The presence of vanadium will be revealed by the blue colour and
absence of precipitate produced by hydrogen sulphide in acid solu-
tion; its actual isolation as sulphide is effected by the addition of
acid to the ammonium sulphide solution in Group IIIll. It is
hoped that the subject-matter of this chapter will suffice to enable
the student to detect the presence of one or two of the compounds
of the "rarer" elements in a mixture.·
TlIALLIUlIt, TI
Thallium forms two oxides Tl 20 and TIIO. which corresponds to the tha.lloUB
thallic and salts respectively. The tha.lloUB salts are the more stable and hence
* Such knowledge is required of students preparing for the ABsociateship of
the Royal Institute of Chemistry, the Fellowship of the Royal Institute of
Chemistry in Inorganic a.nd in Analytical Chemistry and for certain University
examinations.
1S71
572 Qualitative Inorganic Analysis [IX,
of greater interest from the analytical viewpoint. Thallic salts are compar"
tively unstable and readily hydrolyse in solution: thus, when an aqueo,,"
solution of thallic sulphate or nitrate is boiled thallic hydroxide is precipitate,'
Thallous salts are oxidised to thallic by potassium permanganate, potassiu",
ferricyanide, lead dioxide, bromine, chlorine and aqua regia (but not by COl,
centrated nitric acid). The reduction of thallic to thallous compounds is eas; i,
effected by stannous chloride, sulphurous acid, ferrous salts, or hydroxylamin.'

IX,IA. REACTIONS OF THALLOUS COMPOUNDS

Use a solution of thallous nitrate, * TINO a or of thallous sulphak,
T1 2S04 • [All compounds of thallium are highly poisonous.]
1. Dilute Hydrochloric Acid: white precipitate of thallou,,,;
chloride TICI, sparingly soluble in cold, but more soluble in hot
water (compare lead).
2. Potassium Iodide Solution: yellow precipitate of thallous
iodide TII, almost insoluble in water; it is also insoluble in cold
sodium thiosulphate solution (difference and method of separation
from lead).
t The spot-test technique is as follows. Place a drop of the faintl:,
acid test solution on a black spot plate or upon a blackened watch glass
Add a drop of 10 per cent potassium iodide solution and, when a precipi
tate appears, a drop or two of 2 per cent sodium thiosulphate solution.
A yellow precipitate is produced.
Sensitivity: 0·6 /kg. Tl. Concentration limit: 1 in 80,000.
The potassium iodide removes mercury as potassium mercuri-iodid.·
K 2 [HgI 4 ], whilst the sodium thiosulphate dissolves lead and silver as
complex thiosulphates.
3. Potassium Chromate Solution: yellow precipitate of
thallous chromate TI2Cr04, insoluble in cold, dilute nitric or suI
phuric acid.
4. Hydrogen Sulphide: no precipitate in the presence of dilute
mineral acid. Incomplete precipitation of black thallous sulphide
TlzS occurs in neutral or acetic acid solution.
5. Ammonium Sulphide Solution: black precipitate of thalloul'
sulphide TlzS, soluble in mineral acids. The precipitate is oxidised
to thallous sulphate Tl zS04 upon exposure to air.
Owing to the slight solubility of thallous chloride, some of the
thallium is also precipitated in Group IIIB (compare lead). It is
often, however, precipitated with Group II ions.
6. Sodium Cobaltinitrite Solution: light-red precipitate of
thallous cobaltinitrite Tla[Co(N0 2)6]'
* Test solutions containing 10 milligrams per ml. of the reactive anion or
required the "rarer elements" should be prepared by the student when
cation of (compare Section A, 3); a volume of 5-10 ml. will usually suffice.
All the tests can be conveniently conducted on the semimicro Boale.
IB] Reactions of some of the" Rarer" Elements 573
7. Chloroplatinic Acid Solution: pale-yellow precipitate of
thallous chloroplatinate TI 2[PtClaJ, almost insoluble in water (solu-
bility, 0·06 gram per litre at 15°).
8. Potassium Ferricyanide Solution: brown precipitate of
thallic hydroxide, TI(OH)g or Tl 2 0 a,xH 20, in alkaline solution. A
similar result is obtained with sodium hypochlorite or hypobromite
solution or with hydrogen peroxide in alkaline solution.
TlzSO, + 4Ks(Fe(CNJ6J + 6KOH
= TlzOs + 4K,(Fe(CN)6] + KzSO, + 3HaO
9. Ammonium Thiocyanate Solution: white precipitate of
thallous thiocyanate, TISCN; the precipitate is soluble in hot water.

IX, lB. REACTIONS OF THALLIC COMPOUNDS

Use a solution of thallic chloride TICla, prepared by dissolving
thallic oxide or thallic hydroxide in moderately concentrated hydro-
chloric acid.
1. Sodium Hydroxide or Ammonia Solution: brown preci-
pitate of thallic hydroxide, insoluble in excess of the reagent
(difference from thallous salts, which give no precipitate), but
readily soluble in hydrochloric acid.
2. Hydrochloric Acid: no precipitate (difference from thallous
salts).
3. Potassium Chromate Solution: no precipitate (difference
from thallous salts).
4. Potassium Iodide Solution: brownish-black precipitate,
probably a mixture of thallous iodide and iodine.
5. Hydrogen Sulphide: reduced to the thallous state with the
precipitation of sulphur. If the acid is neutralised, thallous sul-
phide Tl 2S precipitates.

Dry Test.
All thallium salts impart an intense green coloration to the Bunsen
flame. This is best identified (and distinguished from barium) with
the aid of the spectroscope (see Fig. II, 1,5).
Separation.-The element may be precipitated as TICI in Group
I, separated from AgCI and Hg 2Cl 2 by solution in boiling water,
and from PbCl 2 by means of dilute H 2S04 ; the thallium can then
be precipitated as TIl by the addition of KI solution. It may also
be separated from lead by precipitation as the iodide and treatment
with Na2S20a solution, in which PbI 2 alone is soluble. Useful con-
firmatory tests are reaction 6 (Section IX, IA) and the flame test.
Any thallium not precipitated in Group I as TICI, will ultimately
be found in the precipitate of Group IIIB. It is best to dissolve
the Group IIIB precipitate in dilute nitric acid, boil to expel H 2 S,
add a few drops of sulphurous acid and boil to expel excess of S02.
574 Qualitative Inorganic Analysis [IX,
The resulting solution is then poured into excess of sodium carbonat,
solution when the carbonates of cobalt, nickel, manganese and zin
are precipitated. The thallium remains in solution as thallou
carbonate and can be precipitated as thallous sulphide T1 2S by tb"
addition of ammonium sulphide solution.
TUNGSTEN, W
Tungsten forms an unstable dioxide WO., and a stable, yellow acidic oxiC:
WO.. The latter oxide is almost insoluble in water and in dilute acids, bl,t
is soluble in solutions of (best in fused) caustic alkalis forming tungstate-
The latter are the most important compounds of tungsten.
Tungstates form complex acids with phosphoric, boric and silicic acid"
tungstic acid cannot therefore be precipitated from these compolUlds b,
hydrochloric acid. The complexes may usually be decomposed by heath,
with concentrated sulphuric acid, tungstic acid being liberated.

IX, 2. REACTIONS OF TUNGSTATES

Use a solution of sodium tungstate, Na2W04,2H20.
1. Dilute Hydrochloric Acid: white precipitate of hydrated
tungstic acid H 2W04.H2 0 in the cold; upon boiling the mixtur,.
this is converted into yellow tungstic acid H2 W0 4 , insoluble in
dilute acids. Similar results are obtained with dilute nitric aI,' I
sulphuric acids, but not with phosphoric acid. Tartrates, citrat, "
and oxalates inhibit the precipitation of tungstic acid. The ppt. ,
soluble in dilute ammonia solution (distinction from Si0 2 ,xH2 0).
2. Phosphoric Acid: white precipitate of phosphotungstic ac
H S[P04(W 120S6)],5H20, soluble in excess of the reagent.
3. Hydrogen Sulphide: no precipitate in acid solution.
4. Ammonium Sulphide Solution: no precipitate, but if the
solution is afterwards acidified with dilute hydrochloric acid, L
brown precipitate of tungsten trisulphide WS s is produced. T::e
precipitate dissolves in ammonium sulphide solution forming :L
thiotungstate (NH4 MWS4 ].
5. Zinc and Hydrochloric Acid.-If a solution of a tungstate
is treated with hydrochloric acid and then a little zinc added, a blue
coloration or precipitate is produced; this is probably due to W 2 ()s
or to wels.
6. Stannous Chloride Solution: yellow precipitate, which !.r.-
comes blue upon warming with concentrated hydrochloric acid.
t The spot-test technique is as follows. Mix 1-2 drops of the t"dt
solution with 3-5 drops of the stannous chloride reagent on a spot pIa 1 B.
A blue precipitate or coloration appears. This is probably due t(, a
lower tungsten oxide (W 206)'
Sensitivity': 5 p,g. W. Concentration limit: I in 10,000.
Molybdenum gives a similar reaction. If, however, a thiocyanate is
added, the red complex ion [Mo(SCN)s)]--- is formed, and upon the
addition of concentrated hydrochloric acid the red colour disappears
and the blue colour due to tungsten remains.
2J ReactiOn8 of some of the "Rarer" Elements 575
The spot test is conducted as follows in the presence of molybdenum
Place a drop of concentrated hydrochloric acid upon filter or drop.
reaction paper and a drop of the test solution in the centre of the spot.
A tungstate produces a yellow stain. Add a drop of 10 per cent potas.
sium thiocyanate solution and a drop of the stannous chloride reagent:
a red spot, due to [Mo(SCN)ar--, is produced, but this disappears
when a drop of concentrated hydrochloric acid is added and a blue
colour, due to WaO. (1), remains.
Sensitivity: 4 p.g. W. Concentration limit: 1 in 12,000.
The reagent consists of a 25 per cent solution of stannous chloride
in concentrated hydrochloric acid.
7. Ferrous Sulphate Solution: brown precipitate. This turns
white upon adding dilute hydrochloric acid, and then yellow upon
heating (difference from molybdates).
8. Silver Nitrate Solution: pale yellow precipitate of silver
tungstate, soluble in ammonia solution, decomposed by nitric acid
wit.h the formation of white hydrated tungstic acid.
9. KHSOc H 2 S04-Phenol Test (Defacqz Reaction).-A little
of the solid (or the residue obtained by evaporating a little of the
solution to dryness) is heated with 4-5 times the weight of potassium
hydrogen sulphate slowly to fusion, and the temperature is main-
tained until the fluid melt is clear. The cold melt is stirred with
concentrated sulphuric acid. Upon adding a few mg. of phenol to
a few drops of the sulphuric acid solution, an intense red coloration
is produced (difference from molybdate). A reddish-violet colora-
tion is obtained if hydro quinone replaces the phenol. The test is
a. highly sensitive one and will detect 2 p.g. of tungstate.
t Heat a few mg. of the solid unknown with 10-20 mg. of potassium
bisulphate and 2 drops of concentrated sulphuric acid in a small pore
celain crucible, allow to cool, and add a few mg. of solid phenol. A red
coloration is produced.

Dry Test
Microcosmic salt bead: oxidising flame-colourless or pale-yellow;
reducing flame-blue, changing to blood-red upon the addition of a
little ferrous sulphate.
Separation.-Tungsten is precipitated in Group I and is asso-
ciated with Ag in the ammoniacal filtrate of the group separation.
The filtrate is almost neutralised with dilute HOI (any precipitate
formed being kept in solution by the addition of ammonia solution),
and the silver precipitated as AgI by the addition of KI solution.
The filtrate is concentrated, acidified with dilute HOI and reactions
5, 6 or 9 applied.
The following table contains a scheme for the identification of
thallous thallium and tungsten (as tungstate) in the presence of lead,
mercurous mercury and silver.
576 Qualitative Inorganic Analysu [IX,
IX. 3. Table I.-Analysis of Group I (Silver Group) in the
presence of Tl and W*

The precipitate may contain PbCl., AgCl, Hg.Cl., TICI and tungstic acid
(WOa,nH.O). Wash the ppt. on the filter with 2 mI. portions of 2N
HCl, then 2-3 times with 1 mI. portions of cold water, and reject the
washings. Transfer the ppt. t to a boiling tube or to a small beaker,
and boil with 11}-15 ml. of water. Filter hot.

Residue. May contain Hg.CI s' AgCl Filtrate. May contain PbCl
and tungstic acid. Wash the ppt. several and TICl; these may crystallisf
times with hot water until the washings out on cooling.
give no ppt. with K.CrO, solution; this Evaporate to fuming wit]
ensures the complete removal of the Pb 2-3 mI. of concentrated H.SO.
and Tl. cool, dilute to 11}-20 mI., coo:
Pour 5 mI. of warm, dilute NR. solu- and filter.
tion repeatedly through the filter.

Residue. Filtrate. May contain Residue. Filtrate. May

If black, [Ag(NRa).]Cl and ammonium If white- contain Tl.SO,.
consists tungstate. Nearly neutralise consists of Just neutralise
of with dilute lICI, add just PbSO,. with dilute NEa
Hg(NR.)- enough dilute NR. solution This is solution, and
Cl + Hg. to redissolve any ppt. which soluble in add KI solution.
Hg (ous) forms. Add KI solution and ammonium Yellow ppt. of
present. filter. acetate TlI, insoluble in
solution; cold Na.S.O.
K.CrO, solution.
Residue. Filtrate. May solution TI present.
Pale contain a tung- then preci- Confirm by
yellow state. Evaporate pitates flame test;
(AgI). to a small volume, yellow intense green
Ag acidify with dilute PbCrO., flame. (Use
present. HCl, add 3 mI. of insoluble in spectroscope, if
SnCl. solution, 2N acetic available.) ,
boil, e.dd 3 ml. of acid.
concentrated HCl, Pb
and heat again to present.
boiling.
Blue ppt. or
coloration.
W present.
Confirm by the
Defacqz reaction.

MOLYBDENUM, Mo

Molybdenum forms three basic oxides MoO, Mo.O. and MoO., and onf'
acidic oxide :MoO.. The last-named is the most important; it is sparingly
soluble in water, but dissolves readily in solutions of alkalis forming molyb-
dates.

• Compare Table III, Section VII, 8.

t A gelatinous precipitate may also be hydrated silica, which is partially
precipitated here from silicate8 decomposable by acids.
4] Reactiona of aome of the " Rarer" Elementa 577

IX, 4. REACTIONS OF MOLYBDATES

Use a solution of ammonium molybdate (NH.)6M070z4,4HzO.
1. Dilute Hydrochloric Acid: white or yellow precipitate of
molybdic acid H 2Mo04 from concentrated solutions, soluble ill
excess of mineral acid.
2. Hydrogen Sulphide.-With a small quantity of the gas and
an acidified molybdate solution, a blue coloration is produced;
further passage of hydrogen sulphide yields a brown precipitate of
the trisulphide MoSs, soluble in ammonium sulphide solution to a
solution containing a thiomolybdate (NH 4 MMoS 4 ], from which
MoSs is reprecipitated by the addition of acids. The precipitation
in acid solution is incomplete in the cold; more extensive precipita-
tion is obtained by the prolonged passage of the gas into the boiling
solution and under pressure. Precipitation is quantitative with
excess of hydrogen sulphide at 0° in the presence of formic acid.
3. Reducing Agents, e.y. zinc, stannous chloride solution: colour
a molybdate solution acidified with dilute hydrochloric acid blue
(probably due to MoCI 3 ), then green and finally brown.
4. Ammonium Thiocyanate Solution: yellow coloration in
solution acidified with dilute hydrochloric acid, becoming blood-red
upon the addition of zinc or of stannous chloride on account of the
formation of ammonium molybdo-thiocyanate (NH4 )s[Mo(CNS)6];
the latter is soluble in ether. The red coloration is produced in the
presence of phosphoric acid (difference from iron).
t The spot-test technique is as follows. Place a drop of the test
solution and a drop of 10 per cent potassium or ammonium thiocyanate
solution upon quantitative filter paper or upon drop-reaction paper.
Add a drop of stannous chloride solution (5 per cent in 3N HCI). A
red spot is obtained.
Sensitivity: 0·1 f-tg. Mo. Concentration limit: 1 in 500,000.
If iron is present, a red spot will appear initially but this disappears
upon the addition of the stannous chloride solution (or of sodium
thiosulphate solution). Tungstates reduce the sensitivity of the test
(compare Section IX, 2, reaction 6).
5. Sodium Phosphate Solution: yellow, crystalline precipitate
of ammonium phosphomolybdate in the presence of excess of nitric
acid (compare Phosphates, Section IV, 28, reaction 4).
6. Potassium Ferrocyanide Solution: reddish-brown pre-
cipitate of molybdenum ferrocyanide, insoluble in dilute mineral
acids, but readily soluble in solutions of caustic alkalis and ammonia
(difference from uranyl and cupric ferrocyanides).
7. ~-Benzoin Oxime Reagent (or "Cupron" Reagent)
{ C.H•. CHOH.C ( =NOH)C8H D }.
The molybdate solution is strongly acidified with dilute aulphurio
19+
 Qualitative Inorganic Analysi8 ~lX,
578
a.cid. and. (J.'5 ml. ot the teagent a.d.d.ed.. A. white ptecipit: . e is
produced.
8. Potassium Xanthate (or Potassium Ethyl Xanthogenate)
Test {SC(SK)OCzH 5 }.-When a molybdate solution is treated with
a little solid potassium xanthate and then acidified with (\ilute
hydrochloric acid, a red-purple coloration is produced. With large
amounts of molybdenum, the compound separates as dark oily, J rops
which are readily soluble in organic solvents such as benzene, cl, ioro-
form and carbon disulphide. The reaction product has been even
the formula Mo0 2 [SC(SH)(OC 2H 5 )h. The test is said to be S1 cific
for molybdates, although copper, cobalt, nickel, iron, chrOli ium
and uranium under exceptional conditions interfere. Large ql: mti-
ties of oxalates, tartrates and citrates decrease the sensitivi \ v of
the test.
t The spot-test technique, for which the reaction is particularl~ well
adapted, is as follows. Place a drop of the nearly neutral or f, ·ltly
acid test solution on a spot plate, introduce a minute crystal of I 'tas-
sium xanthate, followed by 2 drops of 2N hydrochloric acid. An
intense red-violet coloration is obtained.
Sensitivity: 0·04/Lg. Mo. Concentration limit: I in 250,000.
t 9. Phenylhydrazine Reagent (C6Hs.NHNHs).-A red color jon
or precipitate is produced when molybdates and an acid soluti, . \ of
phenylhydrazine react. The latter is oxidised by the molybdate i 0 a
diazonium salt, which then couples with the excess of base lli the
presence of the molybdate to yield a coloured compound.
Mix a drop of the test solution and a drop of the reagent on a .pot
plate. A red coloration appears.
Sensitivity: 0·3 /Lg. Mo. Concentration limit: 1 in 150,000.
Alternatively, place a drop of the reagent on drop-reaction r 'per
and immediately add a drop of the test solution. A red ring f, 'ms
round the spot.
Se, Te, Sb (III), Sn (IV), tungstate, vanadate and oxalate intel 'reo
Sensitivity: O·I/Lg. Mo. Concentration limit: 1 in 300,000.
The reagent consists of a solution of 1 part of phenylhydrazine lis-
solved in 2 parts of glacial acetic acid.
10. Ferrous Sulphate Solution: reddish-brown colour. Uron
adding dilute mineral acid, the colour changes to blue; the co ur
becomes paler and more green upon warming but returns to ;, ue
on cooling (difference from tungstate).

Dry Tests
(i) Microcosmic salt bead: oxidising flame-yellow to green wi'ile
hot and colourless when cold; reducing flame-brown when IJOt,
green when cold.
(ii) Upon evaporation with concentrated sulphuric acid in a
porcelain dish or crucible, a blue mass (containing "molybdenum
 Reactions of some of tne " Rarer" Elements
blue") is obtained. The blue colour is destroyed by dilution wlth
water.
Separation.-Molybdenum appears along with As, Sb, Sn, Au
and Pt in the ordinary process of analysis. Upon acidification of
the yellow ammonium sulphide solution extract and boiling with
concentrated HOI, MoS 3 appears with the AS2S3 • The mixture of
MoS 3 and As 2S a is dissolved in HN0 3 , the As removed with the
magnesium nitrate reagent or with magnesia mixture and the Mo
detected in the filtrate by test 4 or 8 or the dry test (ii).
See also Table IV in Section IX, 10.
GOLD, Au
Gold is a very stable metal. It is unattacked by mineral acids, but dissolves
readily in aqua re~ia:
Au+ HNO. + 4HCI = H(AuCI,] + NO + 2H sO
The metal is also soluble inter alia in chlorine and bromine water forming
respectively AuCI. and AuBr.; these combine with potassium chloride and
potassium bromide to produce the crystalline aurichloride K[AuCI,] and
auribromide K(AuBr.] respectively. The commercial metal is usually alloyed
with copper and/or silver.
Two oxides Au 20 and Au 20. are known; these correspond to the aurous
and auric salts respectively. The latter are tho more stable and exhibit a
marked tendency to form complex salts of the type R[ AuX.].

IX, 5. REACTIONS OF AURIC COMPOUNDS

Use a solution of gold chloride (hydrogen aurichloride or auri
chloric acid), H[AuOI4],3H 2 0.
1. Hydrogen Sulphide: black precipitate of aurous sulphide
Au 2S (usually mixed with a little free gold) in the cold, insoluble in
dilute acids, but largely soluble in yellow ammonium sulphide solu-
tion, from which it is reprecipitated by dilute hydrochloric acid.
A brown precipitate of metallic gold, together with aurous sulphide
and sulphur, is obtained upon precipitation of a hot solution; this
is also largely dissolved by yellow ammonium sulphide solution.
2R[AuCI,] + 3R aS = AuaS + 2S + SRCI
2. Ammonia Solution: yellow precipitate of "fulminating
gold"; this has been formulated as AU20a.3NHa + NH(OlNH 2Au)2
but the exact composition is not fully established. The dry sub-
stance explodes upon heating or upon percussion.
3. Oxalic Acid Solution.-Gold is precipitated as a fine brown
powder (or sometimes as a mirror) from cold neutral solutions
(difference from platinum and other Group II metals). Under
suitable conditions, the gold is obtained in the colloidal state as a
red, violet or blue solution.
2R[AuCl,] + 3R a.C aO, = 2Au + 8RCl + 6CO B

Similar results are obtained with ferrous sulphate solution. Reduc-

tion also occurs with hydroxylamine and hydrazine salts.
580 Qualitative Inorganic Analysis fIX,
4. Stannous Chloride Solution: purple precipitate, "purpl,' of
Cassius," consisting of an adsorption compound of stannous hyei !'Ox-
ide Sn(OHh and colloidal gold, in neutral or weakly acid solu! Ion.
In extremely dilute solutions, only a purple coloration is prodl'" ed.
If the solution is strongly acid with hydrochloric acid, a dark-br' 'Wll
precipitate of pure gold is formed.
2H[AuCl,] + 3SnC1 2 = 2Au + 3SnCl, + 2HCl
5. Hydrogen Peroxide: the finely divided metal is precipit:: toed
in the presence of sodium hydroxide solution (distinction j ,om
platinum). The precipitated metal appears brownish-black by
reflected light and bluish-green by transmitted light.
2H[AuCl,J + 3H 0 t + 8NaOH =
2 2Au + 8NaCl + 30. + 8Hz' i

6. Sodium Hydroxide Solution: reddish-brown precipitat!' of

auric hydroxide Au(OH)3 from concentrated solutions. The pre, 'pi-
tate has amphoteric properties; it dissolves in excess of a:l.ali
forming aurates containing the [AU02r ion.
t7. para - Dimethylamino - benzylidene - rhodanine Reage, , t*:
red-violet precipitate in neutral or faintly acid solution. Silver, mer, 'U'Y
a.nd palladium salts give coloured compounds with the reagent and must
therefore be absent.
Moisten a piece of drop-reaction paper with the reagent and dr,' it.
Place a drop of the neutral or weakly acid test solution upon it. A
violet spot or ring is obtained.
Sensitivity: 0'1 jLg. Au. Concentration limit: I in 500,000.
The reagent consists of a 0'03 per cent solution of p-dimethylam; IlO-
benzylidene-rhodanine in acetone.
Dry Test
All gold compounds when heated upon charcoal with sodium
carbonate yield yellow, malleable, metallic particles, which :Ire
insoluble in nitric acid, but soluble in aqua regia. The aqua rt ;.:;ia
solution should be evaporated to dryness, dissolved in water <lnd
tests 1, 3 or 4 applied.
Separation.-Gold is usually detected and determined by dry
methods. In the wet way, it is precipitated by H 2S in Group fl,
dissolved by yellow ammonium sulphide solution and reprecipitat od
from the latter by concentrated HOI along with AS 2S 3 and MC'-':3'
Separation from AS 2 S3 and MoS 3 is effected by concentrated HKu 3 •
in which the gold precipitate is insoluble. The gold may then be
dissolved in aqua regia and identified by reactions 1, 3 or 4. Soe
also Table II in Section IX, 10.
PLATINUM, Pt
Platinum, like gold, is unattacked by mineral acids; it dissolves in aqua
regia to form a yellowish -orange solution of chloroplatinic acid H .[PtC 16 ] :
3Pt + 4HNO. + lSHCl = 3H,[PtCl.] +
4NO +
SHpO
This acid and its salts are the most commonly occurring platinum compound'3.
* For formula, soo under Silver, Section III, 4, reaction 7.
 6] Reactions of some of the" Rarer" Elements 581

IX, 6. REACTIONS OF CHLOROPLATINATES

Use a solution of chloroplatinic acid, H 2[PtCla],6H2 0.*
1. Hydrogen Sulphide: black (or dark brown) precipitate of the
disulphide PtS 2 (possibly containing a little elementary platinum),
slowly formed in the cold, but rapidly on warming. The precipitate
is insoluble in concentrated acids, but dissolves in aqua regia and also
in yellow ammonium sulphide solution; it is reprecipitated from the
last-named solution of thio salt by dilute acids.
Ha[PtClo] + 2HaS = PtS a + 6HCl
2. Potassium Chloride Solution: yellow precipitate of potas-
sium chloroplatinate K 2[PtCI6 ] from concentrated solutions (dif-
ference from gold). A similar result is obtained with ammonium
chloride solution.
3. Oxalic Acid Solution: no precipitate of platinum (difference
from gold). Hydrogen peroxide and sodium hydroxide solution
likewise do not precipitate metallic platinum.
4. Formic Acid: black powder of metallic platinum from neutral
boiling solutions.
Naa[PtCle] + 2HCOOH = Pt + 2NaCI + 4HCI + 2CO a
5. Zinc, Cadmium, Magnesium or Aluminium: all these
metals precipitate finely divided platinum.
Ha[PtCl o] + 3Zn = 2Pt + 3ZnCl a + HI
6. Hydrazine Hydrochloride: ready reduction in ammoniacal
solution to metallic platinum, some of which is deposited as a mirror
upon the sides of the tube.
(NH,)s[PtCloJ + N aH,,2HCl + 6NH. = 8NH,CI + N a + Pt
7. Silver Nitrate Solution: yellow precipitate of silver chloro-
platinate Ag 2[PtCla], sparingly soluble in ammonia solution but
soluble in solutions of alkali cyanides and of alkali thiosulphates.
8. Potassium Iodide Solution: intense brownish-red or red
coloration, due to [PtI6 r- ions. With excess of the reagent
K2[Pt~] may be precipitated as an unsta,ble brown solid. On
warming, black PtI4 may be precipitated.
9. Stannous Chloride Solution: red or yellow coloration, due
to colloidal platinum, soluble in ethyl acetate or in ether.
t To employ this reaction as a spot test in the presence of other noble
metals (gold, palladium, etc.), the platinum is fixed as thallous chloro·
platinate Tlz[PtCleJ, which is stable to ammonia solution; upon washing
the precipitate with ammonia solution, the thallium complexes with
gold, palladium, etc., pass into solution.
Place a drop of saturated thallous nitrate solution upon drop.reaction
paper, add a drop of the test solution and then another drop of the
• Commonly called "plat,inio chloride. "
582 Qualitative Inorganic Analysis [IX.
thallous nitrate solution. Wash the precipitate wit}} ammonia soliltion,
and add a drop of strongly acid stannous chloride solution. A ~ ,'llow
or orange spot remains.
Sensitivity: 0·5 p.g. Pt. Concentration limit: 1 in 80,000.
tlO. Rubeanic Acid (or Dithio~oxamide) 11
HaN--C--C-NH2 )
(
II II :
S S
a purplish-red precipitate of the complex

Pt( jC'NH,-C=S )
"'-s-6=NH 2

is formed. Palladium and a large proportion of gold interfere.

Place a drop of the test solution (acid with HCI) upon a spot ; late
and add a drop of the reagent. A purplish-red pre(lipitate is prod'.{'ed.
Concentration limit: 1 in 10,000.
The reagent consists of a 0·02 per cent solution of rubeanic ac ,i in
glacial acetic acid.

Dry Test
All platinum compounds when fused with sodium carbonate U lion
charcoal are reduced to the grey, spongy metal (distinction f' lm
gold). The residue is insoluble in concentrated mineral acids, ;!ut
dissolves in aqua regia. The solution is evaporated almost to <lry.
ness, dissolved in water and reactions 1, 2, 5, 9 or 10 applied.
Separation.-Platinum is precipitated in Group II as P: :-i 2 •
The Group lIB metals are extracted with yellow ammonium "d·
phide solution and reprecipitated with HCI. The sulphides of IS,
Sb, Sn, Au, Pt and Mo are dissolved in aqua regia, the excem :)f
acid evaporated and NH4Cl solution added. A yellow precipit, , te
of (NH4 MPtC1 6 ] indicates the presence of Pt. The filtrate is treai I'd
with FeS04 solution; Au is precipitated and is removed. Tile
filtrate is again treated with H 2S to reprecipitate As, Sb, Sn nlld
Mo as sulphides, which are filtered off. These sulphides are tl"'n
separated as described under Molybdates (Section IX, 4).
See also Table II in Section IX, 10.

PALLADIUM, Pd
Palladium, unlike platinum, is slowly dissolved by concentrat ,1
nitric acid {forming a brown solution of palladous nitrate, Pd(N0 3 ) •
and by hot concentrated sulphuric acid (forming palladous sulpha; •
PdS0 4 ; the latter is readily produced by fusing with potassium pyr
sulphate). The metal dissolves readily in aqua regia yielding a mixture
of palladous and palladic chlorides or, more probably, the complex
acids H 2[PdCl.] and H 2[PdCls]: upon evaporation to dryness, the latt"l"
loses chlorine so that on treating the residue with water a solution of
palladous chloride or of chloropalladous acid H.[PdCI,) is obtained.
 7] Reaction8 of 80rne of the "Rarer" Elernents 583
Palladium forms two oxides, PdQ and PdQ,: palladoUB compounds
may be regarded as derived from the former and palladic compounds
from the latter. The palladoUB compounds are by far the more stable
and their reactions will be studied.

IX, 7. REACTIONS OF PALLADOUS COMPOUNDS

Use a solution of palladous chloride, PdCl z.
1. Hydrogen Sulphide: black precipitate of palladous sulphide
PdS from acid or neutral solutions. The precipitate is insoluble in
ammonium sulphide solution.
2. Sodium Hydroxide Solution: reddish-brown, gelatinous
precipitate of the hydrated oxide PdO,nHzO (this may be con-
taminated with a basic salt), soluble in excess of the precipitant.
3. Ammonia Solution: red precipitate of [Pd(NHs )4][PdCI4],
soluble in excess of the reagent to give a colourless solution of
[Pd(NHs)4]CI2. Upon acidifying the latter solution with hydro-
chloric acid, a yellow crystalline precipitate of [Pd(NHa)zCI2J is
obtained.
4. Potassium Iodide Solution: black precipitate of palladous
iodide PdI 2 in neutral solution, soluble in excess of the reagent to
give a brown solution of K 2[PdI4]. In acid solution, black PdI 2 is
precipitated.
5. Mercuric Cyanide Solution: white precipitate of palladous
cyanide Pd(CN)2 (difference from platinum), difficultly soluble in
dilute hydrochloric acid, readily soluble in potassium cyanide solu-
tion and in ammonia solution.
6. <x-Nitroso-,8-naphthol Solution: brown, voluminous preci-
pitate of Pd(C 10H 60 2N)2 (difference from platinum).
The reagent consists of a cold, saturated solution of <x-nitroso-,8-
naphthol in 50 per cent acetio aoid.
7. Reducing Agents (Cd, Zn or Fe in acid solution, formio aoid,
sulphurous aoid, etc.): black, spongy preoipitate of metallio pal-
ladium, "palladium black." Stannous chloride yields a brown
suspension containing metallic palladium.
8. Dimethylglyoxime Reagent: yellow, crystalline precipitate
of palladium dimethylglyoxime Pd(C4H 70 2N 2)z. insoluble in N
hydrochloric acid (difference from nickel and from other platinum
metals) but soluble in dilute ammonia solution and in potassium
cyanide solution (compare Nickel, Section III, 25, reaction 8).
Salicylaldoxime reagent also precipitates palladium quantitatively
as Pd(C7H 6 0 2N)2 (compare Seotion III, 8, reaction 10) (difference
from platinum).
t Place a drop of the slightly acid solution on a microscope slide and
add a minute crystal of dimethylglyoxime. After some minutes, a
yellow precipitate is formed. This consists of long, very charaoteristic
needles when examined under a microscope (X 75).
584 Qualitative Inorganic Analys'i8 [~X'
ll\atm\lID. d.()\~s not \n\,enett, b\lt ~()\d. 801ld. n.\c\te\ ~ve a. ~\m\\.M te&.etlon,
Concentration limit: 1 in lO,()()().
A useful spot test utilises the fact that a suspension of red nick,
dimethylglyoxime in water when treated with a neutral or acetic 8.(' l
solution of a. palladium salt yields the yellow palladium dimeth:, i-
glyoxime, which is sparingly soluble in dilute acids. The test is bi t
performed with dimethylglyoxime paper: the latter is prepared ,g
follows. Immerse drop-reaction paper in a cold, saturated alcoho: ,J
solution of dimethylglyoxime, dry, then immerse again in a soluti'''1
of 2N nickel nitrate rendered barely ammoniacal: the nickel compl. '(
precipitates; wash thoroughly with water, immerse in alcohol and dJ .
Place a drop of the neutral or acetic acid test solution upon nicl ' I
dimethylglyoxime paper, and almost dry by waving over a flan·,'.
Immerse the paper in dilute hydrochloric acid until the surface Sl:r-
rounding the fleck becomes white, and then wash the paper with c( I
water. A pink to red spot remains, depending upon the quantity f
palladium present. The acid-stable palladium dimethylglyoxime . t
the site of the fleck protects the underlying red nickel dimethylglyoxiI ..,
from attack by the acid.
Sensitivity: 0·05 f'g. Pd. Concentration limit: 1 in 1,000,000.
9. Mercurous Chloride: reduced to metallic palladium.
PdCI s + HgsCl s "'" Pd + 2HgCl s
Shake the slightly acid test solution with solid mercurous chloride
in the cold. The solid acquires a grey colour.
Concentration limit: 1 in 100,000.
Separation. Palladium is precipitated in Group II as PdS; :t
is insoluble in yellow ammonium sulphide solution and therefo' '3
accompanies the elements of Group IIA. It is ultimately identifi(''[
in acid solution as the dimethylglyoxime complex.
SELENIUM, Be
Selenium resembles sulphur in many of its properties. It is converted hy
nitric acid or by aqua regia into selenium dioxide SeO. (or selenioUB a('iu
H.SeO.). In analytical work the element is most frequently encountered ill
the form of selenites R.SeO. and as the less stable selenates R.SeO,.

IX, SA. REACTIONS OF SELENITES

Use a solution of selenious acid, H2Se03'* or of sodium selenite,
N a2Se03,5H20.
1. Hydrogen Sulphide: yellow precipitate, consisting of a
mixture of selenium and sulphur, in the cold, becoming red on
heating. The precipitate is readily soluble in yellow ammoniulIl
sulphide solution.
H.SeO. + 2H.S = Se + 2S + 3H.O
2. Reducing Agents {sulphur dioxide, solution of stannons
chloride, ferrous sulphate, hydroxylamine hydrochloride, hydrazine
• Also produced by dissolving selenium dioxide SeO. in water.
8A.! .n,W\jHVIIiO vJ uV"·V -J ----

h drochloride or hydriodic acid (Kl + HC1), zinc or iron}: :e~

~~~\~\\~\~ G\ ~~\e\\\u.m in b.~drochloric acid s~lution. 1 The pre~lpl.
1ate Ue(\Uellt\~ turns ~t~~~'n~\a~ ~\\ \'l~\\\\\\\~, ~~~\\ ~~\~\\~\\~
in concentrated hydrochloric acid are bOlled or (.wa~orate(\, senous
losses of selenium as SeO~ occur.
3. Copper Sulphate Solution: bluish-green, crystalline precipi-
tate of copper selenite CuSe03 in neutral solution (difference from
selenate). The precipitate is soluble in dilute acetic acid.
4. Barium Chloride Solution: white precipitate of barium
selenite BaSeOg in neutral solution, soluble in dilute mineral acids.
to. Thiourea Test {CS(NH 2}2}.-Solid or dissolved thiourea precipi-
tates selenium as a red powder from cold dilute solutions of selenites.
Tellurium and bismuth give yellow precipitates, whilst large amounts
of nitrite and of copper interfere.
Place a little powdered thiourea on quantitative filter paper and
moisten it with a drop of the test solution. Orange-red selenium
separates out.
Sensitivity: 2 p.g. Se.
t6. Hydriodic Acid Test.-Selenites are reduced by hydriodic acid
(or by potassium iodide and hydrochloric acid):
H.SeO a + 4HI = Se + 212 + 3H aO
The iodine is removed by IUlding a thiosulphate, and the selenium
remains as a reddish-brown powder. Tellurites react under these con-
ditions forming the complex anion [Te1 e r-,
which also has a reddish
brown colour; it is, however. decomposed and decolourised by a thio-
sulphate, thus permitting the detection of selenium in the presence of
not too large an excess of tellurium.
Place a drop of concentrated hydriodic acid (or a drop each of con-
centrated potassium iodide solution and of concentrated hydrochloric
acid) upon drop-reaction paper and introduce a drop of the acid test
solution into the middle of the original drop. A brownish-black spot
appears. Add a drop of 5 per cent sodium thiosulphate solution to the
spot; a reddish-brown stain of elementary selenium remains.
Sensitivity: 1 p.g. Se (in 0·025 ml.). Concentration limit: 1 in 25,000.
t '1. Pyrrole Reagent
CR-CR)
II II
CR CR .
( "-/
NH
Selenious acid oxidises pyrrole to a blue dyestuff of unknown com-
position ("pyrrole blue"). Iron salts accelerate the reaction when it is
carried out in phosphoric acid solution. Selenic, tellurous and telluric
acids do not react under the conditions given below: the test therefore
provides a method of distinguishing selenites and selenates.
Place a. drop of 5 per cent ferric chloride solution and 7 drops of
syrupy phosphoric acid (sp. gr. 1'75) on a. spot plate containing 1 drop
19*
 Qualitative inorganic Analysis [IX,
of the test solution and stir well. Add a drop of the pyrrole reagen I
and stir again. A greenish.blue coloration is obtained.
Sensitivity: 0·5 p.g. Se. Concentration limit: 1 in 100,000.
The reagent consists of a 1 per cent solution of pyrrole in aldehydt'-
free ethyl alcohol.
8. Ammonium Thiocyanate and Hydrochloric Acid.-
Selenites are reduced in acid solution to elementary selenium:
2H2SeOa + HSCN = 2Se + COa + NH,HSO,
Mix 0·5 ml. of the test solution with 2 ml. of saturated ammoniUl ..
thiocyanate solution and 5 ml. of 6N hydrochloric acid, and boil f( ,
30 seconds. A red coloration, due to selenium, is produoed.
This sensitive test may be adapted to the semimicro scale: the COl:
centration limit is I part in 100,000. The following interfere: arseni,:
(III), antimony (III), iron (II) and molybdates.

IX, SB. REACTIONS OF SELENATES

Use a solution of potassium selenate, K2Se04 or of sodiml.
selenate, Na2Se04,lOH20.
1. Hydrogen Sulphide: no precipitation occurs. If the solution
is boiled with concentrated hydrochloric acid, the selenic acid i.
reduced to selenious acid; hydrogen sulphide then precipitates
mixture of selenium and sulphur.
H 2SeO, + 2HCI = H 2SeO a + CIa + HaO
2. Sulphur Dioxide: no reducing action.
3. Copper Sulphate Solution: no precipitate (difference frOJ'l
selenite).
4. Barium Chloride Solution: white precipitate of bariuIll
selenate BaSe04' insoluble in dilute mineral acids. The precipitat(·
dissolves when boiled with concentrated hydrochloric acid, and
chlorine is evolved (distinction and separation from sulphate).
BaSeO, + 4HCl = HaSeOs + BaCIa + CIa + HaO
Dry Tests
(i) All selenium compounds when mixed with sodium carbonatn
and heated upon charcoal emit the odour of rotten horseradislJ.
A foul odour, due to hydrogen selenide H 2Se, is obtained UpOIi
moistening the residue with a few drops of dilute hydrochloric acid.
A black stain (due to Ag 2 Se) is produced when the moistened residue
is placed in contact with a silver coin.
(ii) Elementary selenium dissolves in concentrated sulphuric acid
to yield a green solution, due to the presence of the compound SSeO:>
Upon dilution with water, red selenium is precipitated.
Separation.-See under tellurium (Section IX, 9).
8B] Reactions of some of the "Rarer" Elements 587
TELLURIUM, Te
Tellurium is less widely distributed in nature than selenium; both elements
belong to Group VI of the periodic system. VVhen fused with potassium
cyanide, it is converted into potassium telluride K,Te, which dissolves in
water to yield a red solution. If air is passed through the solution, the
tellurium is precipitated as a black powder (difference and method of separa-
tion from selenium). Selenium under similar conditions yields the stable
potassium selenocyanide KSeCN; the selenium may be precipitated by the
addition of dilute hydrochloric acid to its aqueous solution.
2KCN + Te = KaTe + (CN).;
2KaTe + 2H.0 + O 2 = 2Te + 4KOH
KCN + Se = KSeCN
KSeCN + HCI = Se + KCl + HON
Tellurium is converted into the dioxide TeO. by nitric acid. Like sulphur
and selenium, it forms two series of salts, the tellurites RaTeO. and the
tellurates R.TeO,.

IX,9A. REACTIONS OF TELLURITES

Use a solution of sodium or potassium tellurite, NazTeOa or
KzTeOa.
1. Hydrogen Sulphide: brown precipitate of the disulphide TeSs
from acid solutions. The sulphide decomposes easily into tellurium
and sulphur, and is readily soluble in ammonium sulphide solution
but insoluble in concentrated hydrochloric acid.
2. Sulphur Dioxide: complete precipitation of tellurium from
dilute (1-5N) hydrochloric acid solutions as a black powder. In
the presence of much concentrated hydrochloric acid, no precipitate
is formed (difference and method of separation from selenium).
3. Ferrous Sulphate Solution: no precipitation of tellurium
(difierence from selenium). A similar result is obtained with
hydriodic acid (KI + Hel).
4. Stannous Chloride or Hydrazine Hydrochloride Solution
or Zinc: black tellurium is precipitated.
5. Dilute Hydrochloric Acid: white precipitate of tellurous
acid H2Te03 (difference from selenite), soluble in excess of the
precipitant.
6. Barium Chloride Solution: white precipitate of barium
tellurite BaTeOa, soluble in dilute hydrochloric acid but insoluble
in 30 per cent acetic acid.
7. Potassium Iodide Solution: black precipitate of Tel, in
faintly acid solution, dissolving in excess of the reagent to form the
red potassium telluri-iodide K 2[TeI6 ] (difierence from selenite).
t8. Hypophosphorous Acid Test.-Both telluritea and telluratea
are reduced to tellurium upon evaporation with hypophosphorous acid
HaPO a- + TeOa-- = PO,--- Te+ + R,O;
3H.PO.- + 2TeO,-- = 3PO,--- + +
2Te 2H+ 2H.O+
 . I
588 Qualitative Inorganic Analysi8 [IX,
Selenites are likewise reduced to selenium. If, however, the solution
of the selenite in concentrated sulphuric acid is treated with sodium
sulphite, selenium separates but the tellurite is una.ffected; the lattpr
can be detected in the solution after eliminating the sulphur dioxid,·.
Salts of silver, copper, gold and platinum must be a.bsent for they ard
reduced to the metal by the reagent.
Mix a drop of the test solution in mineral acid and a. drop of 50 per
cent hypophosphorous acid in a porcelain microcrucible, and evaporate
almost to dryness. Black grains or a grey stain of tellurium art.l
obtained.
Sensitivity: 0·1 ,."g. tellurous acid; concentration limit: 1 in 500~OO();
0·5,."g. telluric acid; concentration limit: 1 in 100,000.

IX,9B. REACTIONS OF TELLURATES

Use a solution of potassium tellurate, K2Te04'
1. Hydro~en Sulphide: no precipitate in hydrochloric alid
solution in the cold. In hot acid solution, the tellurate is fir;-;t
reduced to tellurite, and precipitation of the tellurium then occms
(compare Section IX, 9A). Other reducing agents give similar
results.
KaTe0 4 + 2HCI = K 2TeO a + H 2 0 + Cl 2

Z. Hydrochloric Acid: no precipitate in the cold. Upon boiling

the solution, chlorine is evolved; tellurous acid H 2TeOa is thrown
down upon dilution (distinction from selenium).
K 2Te0 4 + 4HCl = HaTeOa + 2KCl + RsO + Cl.
3. Barium Chloride Solution: white precipitate of barium
tellurate BaTe04 from neutral solutions; the precipitate is readily
soluble in dilute hydrochloric acid and in dilute acetic acid (dis-
tinction from selenate).
4. Potassium or Sodium Iodide Solution: yellow to red
colour, due to [TeI6 r-,
from dilute acid solutions (difference from
tellurites) .
5. Reducin~ A~ents.-No precipitate is produced in cold solu-
tions with hydrogen sulphide or sulphur dioxide: with hot solutions,
or with solutions that have been boiled with hydrochloric acid,
precipitates of brown TeS (or Te +
S) and of black Te respectively
are formed. Stannous chloride, hydrazine or zinc in acid solution
give black tellurium upon warming.

Dry Tests
(i) Fusion of any tellurium compound with sodium carbonate
upon charcoal results in the formation of sodium telluride Naz'I'e,
which produces a black stain (due to Ag2Te) when placed in contact
with a moist silver coin.
10] lleactions of some oj the " Rarer l> Elements 589
(li) Elementary tellurium dissolves in concentrated sulphurio
acid to yield a red solution, due to the presence of STe03. Upon
dilution with water, grey tellurium is precipitated.
Separatir;n.-Selenium and tellurium are precipitated in Group
II as the yellow Se-S mixture and brown Te-S mixture reHpectively.
Both dissolve in ammonium sulphide solution and are precipitated
with As 2S 3 upon the addition of concentrated Hel. They may be
identified by the H 2S03 tests.
The following table contains a scheme for the separation of the
Group II elements in the presence of Mo, Au, Pt, Pd, Se and Te.

IX, 10. Table H.-Analysis of Group H (Copper and Arsenic

Groups) in the presence of Mo, Au, Pt, Pd, Se and Te*
Hydrogen sulphide in aoid solution precipitates Mo,t Au, Pt, Pd, Se
and Te in addition to the "common" elements of Group II. Extraction
of the group precipitate with yellow ammonium sulphide solution brings
the greater part of the "rarer" elements (excluding PdS) into Group IIB
(arsenio group} but not oompletely, for appreciable quantities of Mo,
Au and Pt, as well as all the Pd, remain in the Group IIA (copper
group) precipitate. The latter three elements and also Pd are therefore
also tested for in Group ITA.

Transfer the Group II precipitate, which haa been well washed with
5% NH.Clsolution that haa been saturated with H.S, to a porcelain dish,
add 5-10 ml. of yellow ammonium sulphide solution, heat to 50-60°0
and maintain at this temperature for 3-4 minutes with constant stirring.
Filter. Wash the precipitate with dilute (1 : 100) ammonium sulphide
solution.

Residue. May contain HgS, Filtrate. May contain solutions of

PbS, Bi.S a, GuS, CdS, PdS the thio·salts of As, Sb and Sn together
together with Au, Pt, Mo (trace), with Mo, Au, Pt, Se and Te. Just
Sn (trace) as sulphides. acidify by adding concentrated HCI
Group lIA present. drop by drop (test with litmus paper)
and warm gently.
A coloured precipitate indicates
Group lIB present.

• Compare corresponding tables in Section VII, 9 to VII, 11.

t For the almost complete precipitation of Mo in Group II, it has been
recommended that the solution be first saturated in the cold with hydrogen
sulphide, then transferred to a pressure bottle and heated on a water bath.
 Qualitative Inorganic Analyaia [IX,
590
Proceed to the analysis of Groups llA and lIB as cleta.ueo. oo\ow
IX, 10. Table lll.-Analysis of Group lIA (Copper Group)

The precipitate may contain HgS, PbS, Bi 3 S s, CuS, CdS and PdS,
together with Au and Pt and also Mo sulphide (trace). Transfer to a
beaker or porcelain dish, add 5-10 ml. of dilute ENO., boil for 2-5
minutes and filter.

Residue. May contain HgS, Pt and Au. Filtrate. May contain

Boil with concentrated HCI and a little nitrates of Pb, Bi, Ou, Cd
bromine water, and filter, if necessary, from and Pd.
trace!! of SnO. and PbSO, which may Examine for Pb, Bi, Cu
separate here. Add KCI solution and HCI, and Cd by Table V in
and concentrate the solution. Filter. Section VII, 10. After
separation of Cu and Cd,
acidify the solution with
Residue. Filtrate. May contain dilute HOI, introduce a. few
Yellow AuCl a and HgOI!. zinc granules and after
and Boil to remove excess of several minutes filter off
crystalline acid, render alkaline with any solid and wash with
K 2[PtCl.]. NaOH solution and boil with water. Di880lve the ppt.
Pt excess of oxalic acid. Filter. in 2 ml. of aqua regia,
present. evaporate just to dryness,
dissolve the residue in N
Residue. Filtrate. May HOI and add dimethyl-
Brownish. contain HgCI,. glyoxime reagent.
black or Add a few drops Yellow ppt.
purplish· of SnCI. solution. Pd present.
black. White or grey
Au present. ppt.*
Hg present.

* Alternatively, the ethylenediamine test, Section III, 5, reaction 7, mlly

be applied to the neutral or slightly ammoniacal solution.
10J Reactions of some of the ,I Rarer" Ele~enu

IX, 10. Table IV.-Analysis of Group \\\\ \~rS~l\\~ ~~~\\~\

Transfer the ppt. to a Hmall conical flask, add 5 ml. of concentrated ~Cl,
and boil gently for 5 minutes (with funnel in mouth of flask). Dilute
with 2-3 ml. of water, and filter.
Residue. May contain As, Au, Pt, Mo, Se and Te as Filtrate. May
sulphides. Dissolve in concentrated HOI + a little contain Sb and
solid KCIO a ; concentrate the solution to the crystallisa. Sn as chlorides
tion point (use a water bath to reduce loss of Se to a or complex
minimum). Filter. chloro-acids.
Residue. Filtrate. May contain As, Au, Mo, Se Examine by
Yellow and Te as chlorides or acids. Render alka- Table VI in
K.[PtCl.]. line with ammonia solution, add Mg(NO.la Section VII, 11.
Pt reagent or magnesia mixture, allow to stand
present. for 5 minutes with frequent stirring or ~
Confirm shaking. Filter. ~
by dis- Residue. Filtrate. May contain Au, Mo, Se and Te
solving in White as chlorides or acids. Concentrate to remove
a little crystal- ammonia, boil with several ml. of saturated
hot water line oxalic acid solution, dilute, boil and filter.
and add- Mg(NH.)- Extract ppt. with HCI to remove coprecipi-
ing KI AsO.,- tated tellurous acid.
solution. 6H.0. I-=OR;"e':"s:"'i':"d":'u-'e::'.::":":"':::'~I<';;i;:lt::'r::'a-t-e-. -~C~o-n-c-e-n-t-r-a""'t-e~w-l'""t"'h-
Red or As Brownish- strong HCI on a water bath and,
brownish- present. black or after removing the precipitated
red
coloration. purplish- Kel, treat with a slight excess 0 f
black. solid Na 2 SO.. Filter.
Alterna-
tively, Au Residue. Filtrate. Dilute with
apply the present. Red. an equal volume of
rubeanic Se water, and add Emcces-
acid test present. sively a little KI solu-
(Section tion and excess of solid
IX, 6, re- Na.SO a whereby the
action 10). K.[TeI.] is reduced to
Te. Filter.
Residue. Filtrate.
Black. Boil with HCl
Te to remove
present. dissolved SO.
and treat suc-
cessively with
10 per cent
NH.SCN solu-
tion and a
little SnOI I
solution.
Red colora-
tion, soluble
in ether.
Mo present.
Confirm by
potassium
xanthate test
or by the 0:-
benzoin oxime
test.
592 Qualitative Inorganic A nalys1,a [IX,
If Pt, Au, Se and Te are known to be absent, Table IV may
be simplified as follows.

Boil the Group ppt. with 5 mI. of concentrated HCI for 5 minutes, dilute
with 2-3 ml. of water, pass H,S for 1 minute (to reprecipitate small
amounts of As that may have dissolved) and filter.

Residue. May contain As,Ss (or As.S I ) and MoSs. Filtrate. May
Wash with dilute HCI, followed by water; reject the contain Sb and
washings. Warm the ppt. with 3-4 m!. of 4N NBs Sn as chlorides
solution for 3 minutes, and filter. or complex
chloro ·acids.
Examine by
Residue. May Filtrate. May contain As Table VI (Sec.
contain undissolved and some of the Mo. tion VII, 11).
MoSs· Dissolve in Identify As as in Table VI
concentrated HCI (Section VII, 11) or by the
and Br. water, and Gutzeit test (Section III, 13).
boil to expel Br 2. Identify Mo thus: acidify a
Test for Mo by the portion of the filtrate with dilute
NB.SCN.SnCl. HCl and add a little solid potas.
reaction. sium xanthate.
A red.purple coloration con·
firms Mo.
Note. If the alternative potassium hydroxide method is employed
for the separation of Groups IIA and IIB, the KOH extract may contain
As, Sb, Sn, Se, Te and part of the Mo; the residue may contain, in
addition to HgS, PbS, Bi.S s' CUS, CdS and PdS, the gold and platinum
partly as sulphides and possibly partly in the form of the free metals.
Mo is readily identified by the potassium xanthate or (X·benzoin oxime
t.est. The Au and Pt will accompany HgS after extraction with dilute
Ilitric acid: upon dissolution in aqua regia, Pt may be identified and
removed as K.[PtCl e] and the Au with oxalic acid. Pd is identified as
bhe dimethylglyoxime complex in the presence of N hydrochloric acid
'tfter the Pb, Bi, Cu and Cd have been removed.
VANADIUM, V
The most important compounds of vanadium are derived from the oxides
V 20. and V.O., both of which exhibit acidic properties, but the latter to the
~eater degree. Vanadium pentoxide, the anhydride of vanadic acid, is only
llightly soluble in water, but dissolves readily in concentrated solutions of
)austic alkalis, forming vanadates. Vanadic acid, like phosphoric acid,
lxists in the form of meta·, pyro· and ortho.compounds (HVO a, H.V.0 7 and
EIsVO. respectively). Unlike the salts of phosphoric acid, the meta·vanadates
Lre the most stable and the ortho-vanadates the least stable. A solution of
ill ortho·vanadate passes on boiling into the meta·vanadate, the pyro.salt
:>eing formed intermediately.

[X,H. REACTIONS OF VANADATES

Use a solution of ammonium (meta-) vanadate, NH\tVO s, or the
nore soluble sodium meta-vanadate, Na V0 3 •
1. Hydrogen Sulphide.-No precipitate is produced in acid
olution, but a blue solution (due to the production of a quadrivalent
11] Reactions of some of the" Rarer" Elements 593
vanadium compound) is formed and sulphur separates. Other
reducing agents, such as sulphur dioxide, oxalio acid, ferrous sul-
phate, hydrazine, formio acid and ethyl alcohol, also yield the blue
vanadium (IV) salts (compare Molybdates, Section IX, 4). The
reaction takes place slowly in the cold, but more rapidly on warming.
2. Zinc, Cadmium or Aluminium in Acid Solution.-These
carry the reduction still further. The solutions turn at first blue
(vanadyl salt-quadrivalent vanadium), then green (tervalent vana·
dium) and finally violet (bivalent vanadium).
3. Ammonium Sulphide Solution.-The solution is coloured
olaret-red, due to the formation of thiovanadates {probably
(NH4h VS4}. Upon acidification of the solution, brown vanadium
sulphide V285 is incompletely precipitated, and the filtrate usually
has a blue colour. The precipitate is soluble in solutions of alkalis,
alkali carbonates and sulphides.
4. Hydrogen Peroxide.-A red coloration is produced when a
few drop8 of hydrogen peroxide solution are added dropwise to an
acid (15-20 per cent sulphuric acid) solution of a vanadate; excess
of hydrogen peroxide should be avoided. The colour is not removed
by shaking the solution with ether nor is it affected by phosphates
or fluorides (distinction from titanium).
The red colour is probably due to the per-salt {V0 2)2(S04)s, which
is converted by excess of hydrogen peroxide into the yellow ortho
peroxy-vanadio acid H a[V(02)Oa], hence excess of hydrogen per-
oxide must be avoided.
H20 2
(VO.)z(SO')8 + 6II,O ~
H2S04
2H s[V(O,)08J + 3H , SO.

t The spot· test technique is as follows. Mix a drop of 15-20 per cent
sulphuric acid and a drop of the test solution either on a spot plate or
in a porcelain micro crucible. Mter a few minutes add 1 drop of 1 per
cent hydrogen peroxide solution and then another drop, if necessary.
A red to pink coloration appears.
Sensitivity: 2·5 pg. V. Concentration limit: 1 in 20,000.
Molybdates, chromates, iodides, bromides, eerie salts and also large
amounts of coloured metallic salts reduce the sensitivity of the reaction.
5. Ammonium Chloride.-The addition of solid ammonium
chloride to a solution of an alkali vanadate results in the separation
of colourless, crystalline ammonium vanadate NH4VO a, sparingly
soluble in a concentrated solution of ammonium chloride.
6. Lead Acetate Solution: yellow precipitate of lead vanadate,
turning white or pale yellow on standing; the precipitate is insoluble
in dilute acetic acid but soluble in dilute nitric acid.
7. Barium Chloride Solution: yellow precipitate of barium
vanadate (distinction from arsenate and phosphate), soluble in dilute
hydrochloric acid.
594 Qualitative Inorganic Analysis [IX,
8. Copper Sulphate Solution: green precipitate with mHta-
vanadates. Pyro-vanadates give a yellow precipitate.
9. Mercurous Nitrate Solution: white precipitate ofmercur(,us
vanadate from neutral solutions.
10. Ammonia Solution.-When this reagent is added to a
solution of a salt containing quadrivalent vanadium (e.g. that pro-
duced by reduction of a vanadate with hydrogen sulphide), dark
grey hypovanadic acid H2 VOs is formed; the precipitation is )lot
complete unless excess of ferric chloride be present.
11. Ammonium Molybdate SoIution.-No precipitate is pro-
duced in the presence of ammonium nitrate and nitric acid, a soluLle
molybdo-vanadate being formed (compare phosphate). If 1 he
vanadate is mixed with a phosphate, much of the vanadium is ,0,)-
precipitated with the ammonium phospho-molybdate.
12. Potassium Chlorate-p-Phenetidine Test_-Vanadildu
catalyses the reaction between p- phenetidine (H 2N. 06H4' 00 211 5,
1 : 4) and potassium chlorate: potassium hydrogen tartrate has an
activating effect upon the reaction.
Treat 0·5 mI. of the test solution in a semimicro test-tube with
0·05 gram of potassium hydrogen tartrate, 1 ml. of the p- phenetidine
reagent, I mI. of saturated potassium chlorate solution and dilute
to 5 mI. with distilled water. Immerse the test-tube in a water bat:1 :
a violet colour appears within a few minutes.
Lead interferes but is rendered harmless with 100 mg. of Na 2SO ,;
ferric iron also interferes and is rendered innocuous by adding 50 m ','.
of NaNOs. A similar result is obtained by replacing KClO s with ;,
saturated solution of KBrO a, but iodide as well as lead and ferric ir. 011
interfere.
Sensitivity: 0-001 JLg. V.
The p-phenetidine reagent consists of a 0·1 per cent solution
of p-phenetidine in N hydrochloric acid.
13. Tannin Test.-When a neutral or acetic acid solution of a
vanadate is treated with an excess of 10 per cent tannin solution,
a deep blue (or blue-black) coloration is obtained. If ammonium
acetate is present, a dark blue (or blue-black) precipitate separates.
The precipitate or coloration is destroyed by mineral acids.
t 14. Ferric Chloride-Dimethyl~lyoxime Test.-The reaction:
yrv + Fe+++ .= VV + Fe++
proceeds from left to right in alkaline solution and in the reversfl
direction in acid solution. The test for vanadates utilises the deep ret!
coloration with dimethylglyoxime given by ferrous salts (compare
Ferrous Iron, Section III, 19, reaction 10) and the fact that vanadates
are readily reduced to the quadrivalent state by heating with con-
centrated hydrochloric acid:
Va05 + 10RCI = 2VCI. + CIa + 5RaO
All oxidising agents interfere and must be removed.
12J Reactions of some of the "Rare?'" Element8 595
Evaporate 1 drop of the test solution and 2 drops of concentrated
hydrochloric acid in a micro crucible almo8t to dryness. When cold,
add a drop of 1 per cent ferrio chloride solution, followed by 3 drops of a
1 per cent alcoholic solution of dimethylglyoxime, and render the
mixture alkaline with ammonia solution. Dip a strip of quantitative
filter paper or of drop-reaction paper into the solution. The precipi-
tated ferric hydroxide remains behind and the red solution of ferrous
dimethylglyoxime diffuses up the capillaries of the paper.
Sensitivity: 1 JLg. V. Concentration limit: 1 in 50,000.

Dry Test
Borax bead: oxidising flame-colourless (yellow in the presence
of much vanadium); reducing flame--green.
Separation.-Vanadates are not precipitated by H::S in acid
solution; reduction to the quadrivalent state occurs. With ammo-
nium sulphide solution, the soluble thio-salt is formed, from which
brown V2S5 is precipitated by pouring into 6N H 2S04 , The pre-
cipitate may be dissolved in concentrated HOI, and reactions 4 and
12 applied.
In general, however, the vanadyl salt present in the filtrate from
Group II will be largely re-oxidised to vanadate by the nitric acid
treatment before the precipitation of Group InA. If the solution
contains the cations of Group IlIA and certain members of later
groups, the vanadates of these metals may be precipitated. How-
ever, if no other member of Group IlIA is present, vanadium may
be incompletely precipitated as ammonium vanadate. It is there-
fore recommended where vanadium is suspected (pale-blue solution
left after the passage of hydrogen sulphide in Group IJ) that the
Group II filtrate be tested for iron with potassium ferrocyanide
solution. If iron is absent, some ferric chloride solution should be
added before precipitation of Group IlIA.
See also Table V in Section IX, 18.

BEBYIllUM (OB GLUCINUlII:), Be

Beryllium is a divalent metal and closely resembles aluminium in chemical
properties; it also exhibits resemblances to the alkaline earth metals. The
salts react acid in aqueous solution, and possess a sweet taste (hence the name
glucinum formerly given to the element). Beryllium compound~are highly
poisonous.

IX, 12. REACTIONS OF BERYLLIUM COMPOUNDS

Use a solution of beryllium sulphate, BeS04,4H20.
1. Ammonia or Ammonium Sulphide Solution: white pre-
cipitate of beryllium hydroxide Be(OHh, similar in appearance to
aluminium hydroxide, insoluble in excess of the reagent, but readily
soluble in dilute hydrochloric acid, forming a colourless solution.
Precipitation is prevented by tartrates and citrates.
596 Qualitative Inorganic Analysis [IX,
2. Sodium Hydroxide Solution: white gelatinous precipitnle
-of beryllium hydroxide, readily soluble in excess of the precipitant,
forming sodium beryllate Na2[Be02]; on boiling the latter solution
(best when largely diluted), beryllium hydroxide is reprecipitatcd
(distinction from aluminium). The precipitate is also soluble in 10
per cent sodium bicarbonate solution (distinction from aluminiuIll).
Be(OHh + 2NaOH ~ Na 2[Be0 2] + 2H 20
On the other hand, the precipitate is insoluble in aqueous eth.' \-
amine solution whereas aluminium hydroxide dissolves in a modern i I)
excess of the reagent. Precipitation is prevented by tartrates aJ ,\ l
citrates.
3. Ammonium Carbonate Solution: white precipitate of ba>·I\)
beryllium carbonate, soluble in excess of the reagent (differen, 1\
from aluminium). On boiling the solution, the white basic carbons i <l
is re-precipitated_
4. Oxalic Acid or Ammonium Oxalate Solution: no precipi-
tate (difference from thorium, zirconium and cerium).
5. Sodium Thiosulphate Solution: no precipitate (differen, (.
from aluminium).
6. Basic Acetate-Chloroform Test.-Upon dissolvir,.:
beryllium hydroxide (reaction 1) in glacial acetic acid an I
evaporating to dryness with a little water, basic beryllium acetal,'
BeO,3Be(C2H a0 2 )2 is produced, which dissolves readily upo:,
extraction with chloroform. This forms the basis of a metho' 1
for separating beryllium from aluminium, since basic aluminiUl' 1
acetate is insoluble in chloroform. The mixed hydroxides aT,
treated as detailed above.
t7. Quinalizarin Reagent*: cornflower-blue coloration with faint]·
alkaline solutions of beryllhun salts. The reagent alone gives a charac
teristic violet colour with dilute alkali; but this is quite distinct fron'
the blue of the beryllium complex: a blank test will render the difierenc"
clearly apparent.
Antimony, zinc and aluminium salts do not interfere; aluminiun,
should, however, be kept in solution by the addition of sufficient sodiun
hydroxide; the influence of copper, nickel and cobalt salts can b,
eliminated by the addition of potassium cyanide solution; iron salt
are "masked" by the addition of a tartrate but if aluminium salts ar.
also present a red colour is produced. Magnesium salts give a similal
blue colour, but beryllium can be detected in the presence of thi,
element by utilising the fact that in ammoniacal solution the mag-
nesium colour alone is completely destroyed by bromine water.
In adjacent depressions of a spot plate place a drop of the test solution
and a drop of distilled water, and add a drop of the freshly prepared
quinalizarin reagent to each. A blue coloration or precipitate, quite
distinct from the violet colour of the reagent, is obtained.
Sensitivity: 0·15j£g. Be. Concentration limit: 1 in 350,000.
• See Iwder Alwninium, Seotion III, 21, reaction 10.
12] Reactions of some of the " Rarer" Element8 597
If magnesium is present, treat 8 drop of the solution on a spot
plate with 2 drops of the reagent and I ml. of saturated bromine water.
The original deep blue colour becomes paler when the bromine is added,
but remains more or less permanently blue.
The reagent is prepared by dissolving 0·05 grams of quinalizarin in
100 ml. of O' IN sodium hydroxide.
t8. para-Nitrobenzene-azo-orcinol Reagent

orange-red lake with beryllium salts in alkaline solution. Magnesium

salts yield 8 brownish-yellow precipitate; salts and hydroxides of the
rare earths, aluminium and alkaline earths are without influence; the
interfering effect of silver, copper, cadmium, nickel, cobalt and zinc is
eliminated by the addition of potassium cyanide solution.
Place a drop of the reagent on drop-reaction paper and into the middle
of the resulting yeHow area introduce the tip of a capillary containing
the test solution so that the latter runs slowly on to the paper. Treat
the stain with a further drop of the reagent. The stain is coloured deep
orange-red.
Sensitivity: 0-2 fGg. Be. Concentration limit: I in 200,000.
The reagent consists of a 0·025 per cent solution of p-nitrobenzene-
azo-orcinol in N sodium hydroxide.
t 9. Acetylacetone Test.-Acetylacetone reacts with beryllium salts
to yield the complex Be(C sH 70 Z)z, which possesses a highly characteristic
appearance under the microscope.
2CH s .CO.CH z .CO.CH a +
BeS0 4 = Be(C,H70 Z)z + H 2 S0 4
Place a drop of the test solution on a microscope slide and add a drop
of acetylacetone. Crystals separate immediately: these will be found
to possess rhombic and hexagonal forms when observed under the
microscope (magnification: ca. 75 diameters).
Concentration limit: I in 10,000.

Dry Test
Upon heating beryllium salts with a few drops of cobalt nitrate
solution upon charcoal, a grey mass is obtained (difference from
aluminium).
Separation.-Beryllium is precipitated in Group IlIA. It is
ultimately associated with aluminium in solution as sodium alu-
minate and sodium beryllate respectively. Upon diluting and
boiling, only the Be(OHh is precipitated. Alternatively, the
quinalizarin test 7 may be applied to the solution or the basic
acetate-chloroform test 6 to the mixed hydroxides. BeryUium may
598 Qualitative Inorganic A nalyaia [IX,
also be detected in the presence of aluminium by the acetylacetOJH'
test 9; this is specific for Be.
Aluminium and beryllium are separated most satisfactorily k-
means of 8-hydroxyquinoline ("oxine") reagent; aluminiu'"
"oxinate" is precipitated in the presence of an ammonium acetak
acetic acid buffer solution, whereas beryllium "oxinate" is soluhll1
in acetic acid. For this purpose, the alcoholic solution of the n·_
agent (compare Magnesium, Section III, 33, reaction 7) should not
be employed as the aluminium complex is slightly soluble in alcoho: -
The solution of sodium aluminate and beryllate is just acidified wit!!
dilute hydrochloric acid, a slight excess of the "osine" solutioll
added, followed by 5 ml. of saturated ammonium acetate solutiOIJ_
The precipitate of the aluminium complex Al(C9H60N)3 is filtere- j
off. The filtrate is heated nearly to boiling and a slight excess (if
ammonia solution added. The production of a precipitate (beryllia _i i

usually coloured brown or yellow by adsorbed "oxille," indicath

the presence of beryllium.
The precipitating reagent consists of a 2 per cent solution of
"oxine" in 2N acetic acid to which ammonia solution is added
until a permanent precipitate is produced, and the latter is re-
dissolved by warming.
Another method for separating beryllium and aluminium consist"
in adding excess of a solution of sodium fluoride to the solution_
The complex sodium alumino-fluoride Na3[AlF6] is formed in whic)!
the aluminium is present as a complex ion and from which the metaJ
is not precipitated as hydroxide by ammonia solution. Berylliulll
is, however, readily precipitated as the hydroxide under these
conditions.
See also Note 6 to Table V in Section IX, 18.
TITANIUM, Ti
The most important compounds of titanium are those corresponding to
the two oxides Ti.O. and TiO., and are termed titanous &nd titanic com-
pounds respectively. The former usually yield violet aqueous eolutions.
and are powerful reducing agents; they behave like iron and aluminium com-
pounds towards the common reagents. The latter are usually colourless, an<!
are more frequently encountered in analytical work.

IX, 13. REACTIONS OF TITANIC COMPOUNDS

Use a solution of titanic sulphate, Ti(S04h.*
1. Solutions of Sodium Hydroxide, Ammonia or Ammo-
nium Sulphide.-All these reagents give a white gelatinous
precipitate of ortho-titanic acid H 4Ti04 or Ti(OH)4 in the cold,
• This may be prepared by fusing the dioxide TiO. with 8 12-15 fold excess
of potassium pyrosulphate K.S.0 1 • The melt, after powdering, is extracted
with cold dilute H 2SO, (say, 5 per cent) and filtered, if necessltry.
TiO, + 2K.S,01 = Ti(SO,). + 2K.SO~
13] Reactions of 80me of the "Rarer" Elements 599
almost insoluble in excess of the reagent, but soluble in mineral
acids. If precipitation takes place from hot solution, meta-titanic
acid H 2TiO s or TiO. (OHh is said to be formed, which is difficultly
soluble in dilute acids. Tartrates and citrates inhibit precipitation.
2. Water.-A white precipitate of meta-titanic acid is obtained
on boiling a solution of a titanic salt with excess of water.
3. Sodium Phosphate Solution: white precipitate of titanium
phosphate Ti(HP04)2 in dilute sulphuric acid solution.
4. Zinc, Cadmium or Tin.-When any of these metals is added
to an acid (preferably hydrochloric acid) solution of a titanic salt,
a violet coloration is produced, due to reduction to the titanous
state. No reduction occurs with sulphur dioxide or with hydrogen
sulphide.
5. Cupferron Reagent *: flocculent yellow precipitate of the
titanium salt, Ti(C6H 50 2 N 2 )4' in acid solution (distinction from
aluminium and beryllium). If iron is present, it can be removed
by precipitation with ammonia and ammonium sulphide solutions
in the presence of a tartrate; the titanium may then be precipitated
from the acidified solution by cupferron.
6. Hydrogen Peroxide.-An orange-red coloration is produced
in slightly acid solution. The colour is yellow with very dilute
solutions. The coloration has been variously attributed to per.
titanic acid TiOs,nH 20 or to peroxo-disulphato-titanic acid
H 2[Ti0 2 (S04h]·
Chromates, vanadates and cerium salts give colour reactions with
the reagent and should therefore be absent. Iron salts give a
yellow colour with hydrogen peroxide, but this is eliminated by
the addition of syrupy phosphoric acid. Fluorides bleach the colour
(stable [TiF6r- ions are formed), and large amounts of nitrates,
chlorides, bromides and acetates as well as coloured ions reduce
the sensitivity of the test. A decrease in the intensity of the
yellow coloration upon the addition of ammonium fluoride indicates
the presence of titanium.
t The spot-test technique is as follows. Place a drop of the sulphuric
acid test solution on a spot plate and add a drop of "lO-volume"
hydrogen peroxide. A yellow coloration m<;ults.
Sensitivity: 2 fLg. Ti. Concentration limit: 1 in 25,000.
The test is conducted on the semimicro scale as follows. Place 0·5 ml.
of the test solution in a small test-tube, add 2 drops of dilute sulphurio
acid and 1 drop of 3 per cent hydrogen peroxide solution. An orange-
yellow or orange-red coloration is produced. Introduce a small crystal
of ammonium fluoride: the colour disappears.

'" For the preparation of the reagent, see under fron, Section III, 20,
reaction 9.
600 Qualitative Inorganic Analysis [IX,
t7. Chromo tropic Acid· Reagent \

(RO&O~)\
·eddish·brown coloration with titanium salts in the presence of hydro-
lhloric or sulphuric acid. Appreciable concentrations of nitric acid
nhibit the reaction.
Mix a drop of the test solution and a drop of the reagent on drop-
'eaction paper or upon a spot plate. A reddish-brown (or purplish-
)ink) spot or coloration results.
Sensitivity: 5 p,g. TiO a. Concentration limit: 1 in 10,000.
Uranyl and ferric salts interfere and yield brown and deep green
:olorations respectively; these colours are destroyed by the addition
,f stannous chloride, for uranous and ferrous salts do not react with
hromotropic acid. Mercury salts give a yellow and silver salts a black
tain on drop-reaction paper; the colour due to titanium is, however,
till perceptible.
In the presence of uranyl salts and/or ferric salts, proceed as
allows. Mix a large drop of the test solution on a watch glass with a
mall quantity of a solution of stannous chloride in hydrochloric acid
1. large excess is to be avoided) and warm gently (hot plate). Place
drop of the reagent on some drop-reaction paper and then a drop of
he clear solution from the watch glass. A reddish-brown (or purplish-
,ink) spot appears.
The reagent consists of a 5 per cent aqueous solution of chromotropic
cid. The reagent does not keep well, hence it is preferable to impreg-
ate drop-reaction paper with the reagent solution and allow the paper
) dry in the air. The impregnated papers are stable for several months.
[l use, a drop of the test solution and a drop of N HaSO, are placed

pon the impregnated paper: a purplish-pink colour results.

t8. Pyrocatechol Reagent

/":::---_______
~llow coloration with neutral or weakly acid (sulphuric acid) solutions
, titanium salts. Ferric, chromium, cobalt and nickel salts interfere
I do also large amounts of free mineral acids: alkali hydroxides and
Irbonates reduce the sensitivity of the test.
Place a drop of the sulphuric acid test solution on drop-reaction paper
Ipregnated with the reagent. A yellow or yellowish-red spot is
)tained.
Sensitivity: 3 p,g. Ti. Concentration linlit: 1 in 20,000.
The reagent consists of 8. freshly prepared 10 per cent aqueous solu-
)n of pyrocatechol.
• Or 1 : 8-dihydroxynaphthalene-3 : 6-diaulphonio acid.
14) Reactions of some of the " Rarer" Element8 601
Dry Test
Microcosmic salt bead: oxidising flame--colourless; reducing flame
-yellow whilst hot and violet when cold (this result is obtained
more rapidly if a little stannous chloride is added). If the bead is
heated in the reducing flame with a trace of ferrous sulphate, it
acquires a blood-red colour.
Separation.-If sufficient acid is present in the earlier groups to
prevent its separation by hydrolysis, titanium is found in Group
lIlA. It can be readily detected in the precipitate obtained after
treatment with Na202 by means of the hydrogen peroxide test 6;
NH4F solution will discharge the colour. It is usually best to fuse
the precipitate with 10 times its weight of powdered K 2S20 7 or
KHS04; the melt, containing the metals as sulphates, is extracted
with cold water, and the extract boiled for about 30 minutes.
Meta-titanic acid separates out. This is filtered off, dissolved in
concentrated HCI and the H 2 0 2 test applied.
See also Table V in Section IX, 18.
ZmaoNIUM, Zr
Zirconium'" forms only one important oxide, zirconia ZrO a, which is
amphoteric in character. The normal zirconium salts, like ZrCl., are readily
hydrolysed in solution giving rise chiefly to zirconyl salts, containing the
bivalent radical ZrOrr. The zirconates, e.g. Na 2ZrO., are best produced from
ZrOa by fusion methods. Zirconium also readily forms complex salts, e.g.
potassium fluozirconate K 2[ZrF6 ], produced by fusing zirconia with potassium
hydrogen fluoride.
Ignited zirconium dioxide, or the mineral, is insoluble in all acids except
hydrofluoric acid. It is soluble in fused caustic alkalis and in sodium car.
bonate; the resulting alkali zirconate is practically insoluble in water, being
converted into zirconium hydroxide by this solvent.. It is therefore best
dissolved in hydrochloric acid, and the zirconium hydroxides precipitated by
ammonia solution, etc.

IX, 14. REACTIONS OF ZIRCONIUM COMPOUNDS

Use a solution of zirconyl nitrate ZrO(NO a)2,2H 2 0 or of zirconyl
chloride ZrOCI 2,8H20.
1. Sodium Hydroxide Solution: white, gelatinous precipitate
of the hydroxide Zr(OH}4 (or Zr02,xH20) in the cold, practically
insoluble in excess of the reagent (difference from aluminium and
beryllium), but soluble in dilute mineral acids (avoid sulphuric acid).
With a hot solution of a zirconium salt, a white precipitate of
ZrO(OHh is obtained; it is sparingly soluble in dilute but soluble in
concentrated mineral acids. Tartrates and citrates inhibit the
precipitation of the hydroxide.
2. Ammonia or Ammonium Sulphide Solution: white,
gelatinous precipitate of the hydroxide Zr(OH)4 (or Zr02,xH20),
insoluble in excess of the reagent.
'" Small quantities of hafnium are always present; the two elements cannot,
at present, be differentiated by qualitative analysis (see, however, Section X, 4).
 602 Qualitative Inorganic Analysis [IX,
- - 3. Sodium Phosphate Solution: white precipitate of zirconiu·.,
phosphate, Zr(HP04h or ZrO(H 2 P04 )z, even in solutions containir '
10 per cent of sulphurio acid by weight and also tartrates aJ l
citrates. No other element forms an insoluble phosphate undo '
these conditions except titanium. The latter element can be ke] .
in solution as the so-called "per-titanic acid" by the addition , i'
sufficient hydrogen peroxide solution, preferably of "lOO-volume .
strength, before the sodium phosphate is introduced.
4. Hydrogen Peroxide: white precipitate of zirconium "per
oxide" from slightly acid solutions; this liberates chlorine wh( 11
warmed with concentrated hydrochloric acid. When both hydrog< ,
peroxide and sodium phosphate are added to a solution containill '
zirconium, the precipitate is ziroonium phosphate (see reaction ::;.,
5. Ammonium Carbonate Solution: white precipitate of baSI.'
zirconium carbonate, readily soluble in excess of the reagent, b1 i
reprecipitated on boiling.
6. Oxalic Acid Solution: white precipitate of zirconium oxalak,
readily soluble in excess of the reagent and also in ammoniUlI,
oxalate solution (difference from thorium).
7. Ammonium Oxalate Solution: white precipitate of zil
conium oxalate, soluble in excess of the reagent (distinction frOll)
aluminium and beryllium); the solution gives no precipitate with
hydrochlorio acid (difference from thorium).
Note. A solution of zirconium sulphate or a zirconium salt solution contain.
ing excess of sulphate ions does not give a precipitate with either ammonim'l
oxalate or oxalic acid. This is due to the fact that the zirconium is pres8I,
as the anion [ZrO(SO,).]-, hence sulphuric acid should be avoided in pr.·
paring solutions of zirconium salts.
8. Saturated Potassium Sulphate Solution: white precipitat"
of K 2[ZrO(S04)2], insoluble in excess of the reagent. When pre
cipitation takes place in boiling solution, the resulting basic zirconiUJ,'
sulphate is insoluble in dilute hydrochlorio acid (difference froll,
thorium and cerium). No precipitate is obtained with sodium sul
phate solution.
9. Phenylarsonic Acid Reagent {C6H 5 .AsO(OH)2}: whit,
precipitate of zirconium phenylarsonate in the presence of 0'5-L'
hydrochloric acid; it is best to boil the solution. Tin and thoriur'
salts must be absent.
The reagent consists of a 10 per oent aqueous solution of phenyl.
arsonio aoid.
10. normal-Propylarsonic Acid Reagent
{CH3 . CH 2. CH 2. AsO(OH)2}:
white preoipitate of zirconium n-propylarsonate in dilute sulphuri,:
acid solution (separation from most other metals including titanium
but not tin).
14] Reactions of some of the " Rarer" Element8 603
The reagent consists of a 5 per cent aqueous solution of n-propyl-
arsonic acid.
11. Potassium or Sodium Iodate SoIution.-In faintly acid
solution, a voluminous, white precipitate of basic zirconium iodate
is obtained. The precipitate is soluble in warm hydrochloric acid
(difference from aluminium).
t12. Alizarin-S· Reagent: red precipitate in a strongly acid
medium. Fluorides disoharge the oolour because of the formation of
the stable zirconi-fluoride anion [ZrFer-.
Place a drop of the test solution (which has been acidified with hydro-
,chloric acid) on a spot plate, add a drop of the reagent and a drop of
concentrated hydrochloric acid. A red precipitate results.
The reagent oonsists of a 1 per cent aqueous solution of alizarin-S
(sodium alizarin sulphonate).
t 13. para - Dimethylaminohenzene - azo - phenylarsonic Acid
Reagent

Acid solutions of zirconium salts give a brown precipitate with the

reagent. If the test be conducted on filter paper, the brown precipitate
remains in the pores of the paper and the excess of the coloured reagent
may be washed out with dilute acid.
Impregnate some drop-reaction paper with the reagent and dry the
paper. Place a drop of the acid test solution on the paper. Dip the
paper into 2N hydrochloric acid at 50-60°C. A brown spot or ring
remains.
Sensitivity: 0·1 J.tg. Zr (in N HCI). Concentration limit: I in 500,000.
Free sulphuric acid exceeding N in concentration reduces the sensitivity
of the test; phosphates, fluorides and organic acids, which form precipi-
tates or stable complex compounds, either inhibit or retard the reaction;
molybdates, tungstates and salts of titanium or cerium give precipitates,
but their interference can be eliminated by mixing the test solution
with about an equal volume of concentrated hydrochloric acid, adding
some "100-volume" hydrogen peroxide, spotting the mixture on to
impregnated drop-reaction paper and finally washing the latter with
warm 2N hydrochloric acid. Tin also gives a coloured precipitate, but
this may be prevented by the above treatment and omitting the
hydrogen peroxide; a brown ring, surrounding a central zone, is
obtained.
The reagent is prepared by dissolving 0'1 gram of p-dimethylamino-
benzene-azo-phenylarsonio acid in 5 ml. of conoentrated hydrochlorio
acid and 100 ml. of ethyl alcohol

Dry Tests
No characteristic results are obtained with the borax or micro-
cosmic beads nor does zirconium yield a distinguishing flame test.
• For formula, Bee under Aluminium, Section III, 21, reaction 9.
 (
604 Qualitative Inorganic Analysi8 [IX,
Separation.-Zirconium is precipitated in Group IlIA a~
Zr02,xH20, if phosphates are absent. It can be readily detected
in the residue obtained after treating the Group lIlA precipitatn
with 10 per cent sodium hydroxide solution and "20- or 40-volume"
hydrogen peroxide. The residue is dissolved in hydrochloric aci(,
and boiled to expel chlorine. The resulting solution is treated wit]
sodium phosphate solution and hydrogen peroxide, when a whit,·
preoipitate indicates the presence of zirconium and an orange-yellm,
coloration the presence of titanium (see reaction 3 above). Alter
natively, the alizarin-S test (reaction 12) may be applied to th·
solution in hydrochloric acid.
See also Table V, Section IX, 18. "
U)lANIUM, U
The most important uranium compounds are the uranyl salts, which contaj"
the bivalent radical uranyl UO.<, and the uranates MoU 00" analogous to
the pyrosulphates M.S.O, and the dichromates M.Cr.O,. Only the reactions
of the former will be described.

IX, 15. REACTIONS OF URANYL COMPOUNDS

Use a solution of uranyl nitrate, U02(NO ab6H20, or of uranyl
acetate, U02(C2H302)z,2H20.
1. Ammonia Solution: yellow precipitate of ammonium d·
uranate (NH4)2U207, insoluble in excess of the reagent, but readil \
soluble in ammonium carbonate solution.
2UO a(NO a)a + 6NH a + 3H aO = (NH,laU a0 7 + 4NH,NO.
(NH,)aU a07 + 6(NH,laCO a + 3R sO
= 2(NR,).[U0 2(CO S)8J + 6NH,011
The sparingly soluble ammonium di-=anate is probably forme-j
through the intermediate uranyl hydroxide UOa(OH)a: the latter pass' .,
by loss of water into di-uranic acid {2DO a(OR)a = RaDaO? +
HaO:,
and thence into (NH,)aU 201'
No precipitation occurs in the presence of certain organic acid"
such as oxalic, tartaric and citric acids.
2. Sodium Hydroxide Solution: yellow amorphous precipitate
of sodium di-uranate Na2U207, soluble in ammonium carbonate
solution.
3. Ammonium Sulphide Solution: brown precipitate ofurany'
sulphide U0 28, soluble in dilute acids and in ammonium carbonate
solution.
4. Hydrogen Peroxide: pale-yellow precipitate of U04"xH2 0,
soluble in ammonium carbonate solution with the formation of a
deep yellow solution. Chromium, titanium and vanadium inter-
fere with this otherwise sensitive test.
15] ReactioM of some of the " Raret'" Elements 605
5. Cupferron Reagent: no precipitate (distinction from
titanium).
6. Sodium Phosphate Solution: white precipitate of uranyl
phosphate U0 2HPO" soluble in mineral acids but insoluble in dilute
acetic acid. Hprecipitation is effected in the presence of ammonium
sulphate or of ammonium acetate, uranyl ammonium phosphate
U02 (NH4 )P04 is precipitated.
7. Ammonium (or Sodium) Carbonate Solution: white pre.
cipitate of uranyl carbonate U0 200 3 , soluble in excess of the reagent
forming a clear, yellow solution containing ammonium uranyl
carbonate (NH4 MU0 2 (003)a].
8. Potassium Ferrocyanide Solution: brown precipitate of
uranyl ferro cyanide (U0 2 MFe(ON)6] in neutral or acetic acid
solutions, soluble in dilute hydrochloric acid (difference from copper).
The precipitate becomes yellow upon the addition of sodium
hydroxide solution, due to its conversion into sodium di·uranate
(distinction from copper and from molybdenum ferrocyanide).
(U0 2 )2[Fe(CN)6] + 6NaOR = Na,2U .0 7 + Na,[Fe(CN)6] + 3R 0 2

t The spot-test technique is as follows. Place a drop of the test

solution on drop-reaction paper and add a drop of potassiwn ferro-
cyanide solution. A brown spot is obtained.
Sensitivity: 0·9 p,g. U. Concentration limit: 1 in 50,000.
Both iron and copper inberfere. If, however, potassimn iodide
solution is added, they are reduced to the non-reactive ferrous and
cuprous states; the liberated iodine may be decolourised with sodium
thiosulphate solution. Alternatively, the reduction may be carried out
with sodium thiosulphate solution alone on a spot plate, the copper
acting as a catalyst for the reduction of the iron:
2Fe+++ + 28 20 8- - = 2Fe++ + S,06--;
2Cu++ + 28 0 = 2Cu+ + 8 0 6--
2 3
--
4

Place a drop of concentrated potassium iodide solution on a piece

of drop-reaction paper and, after the iodide solution has soaked into the
paper, add a drop of the acidified test solution. Add a further drop of
the potassium iodide solution to complete the reduction, followed by a
drop of sodiwn thiosulphate solution. Then add a drop of potassium
ferrocyanide solution to the decolourised spot, whereupon a brown ring
is obtained.

Dry Test
Borax or microcosmic salt bead: oxidising flame-yellow; reducing
flame-green.
Separation.-Uranium is precipitated in Group IlIA as
(NH4 hU2 0,. It is most simply separated from Fe(OHb Cr(OH)a
and AI(OH)s by digestion in the cold with a large excess of
606 Qualitative Inorganic AnalY8is [IX,
ammonium carbonate solution. The ammonium di-uranate dissolve,
(see reaction 1 above); upon acidification with HCI and additioi'
of K4[Fe(CN)61 solution, a brown precipitate is formed.
See also Table V in Section IX, 18.

THORIUM, Th
The analytically important compounds of thorium are derived from tb,
dioxide ThO., i.e. contain quadrivalent thorium.

IX, 16. REACTIONS OF THORIUM COMPOUNDS

Use a solution of thorium nitrate, Th(N0 3 )4,4H 20.
1. Ammonia, Ammonium Sulphide or Sodium Hydroxide
Solution: white precipitate of thorium hydroxide Th(OH)4 0["
Th0 2 • nR 2 0, insoluble in excess of the reagent, but readily soluble
in dilute acids when freshly precipitated. Tartrates and al~()
citrates prevent the precipitation of the hydroxide.
2. Ammonium or Sodium Carbonate Solution: white PI""
cipitate of basic carbonate, readily soluble in excess of the COI:-
centrated reagent forming [Th(C0 3 )51 6 -.
3. Oxalic Acid Solution: white, crystalline precipitate "f
thorium oxalate Th(C2 0 4h,6H2 0 (distinction from aluminium am!
beryllium), insoluble in excess of the reagent and in 0·5N hydro-
chloric acid.
4. Ammonium Oxalate Solution: white precipitate of thorill III
oxalate, which dissolves on boiling with a large excess of the reag61) t
forming [Th(C 2 0 4h1 2 -, but is reprecipitated upon the addition (If
hydrochloric acid (difference from zirconium).
5. Saturated Potassium Sulphate -Solution: white precipita f e
of the complex salt K 4 [Th(S04)4]2H2 0, insoluble in excess of t, 'J
precipitant, but soluble in dilute hydrochloric acid.
6. Hydrogen Peroxide: white precipitate of hydrated thorium
peroxide (variously formulated as Th0 3 ,2H20, Th(OH)aO. OR and
Th 2 0 7 ,4H2 0) in neutral or faintly acid solution.
7. Sodium Thiosulphate Solution: precipitate of thorium
hydroxide and sulphur on boiling (distinction from cerium).
8. Potassium Iodate Solution: white, bulky precipitate of
thorium iodate Th(IO a)4' Precipitation occurs in the presence of
50 per cent by volume of concentrated nitric acid (difference from
cerous cerium).
9. Potassium Ferrocyanide Solution: white precipitate of
thorium ferro cyanide Th[Fe(CN)61 in neutral or slightly acid
solution.
17Al Reactions of 80me of tke "Rarer" Elements 607
10. Potassium Fluoride Solution: bulky, white precipitate of
thorium fluoride ThF4, insoluble in excess of the reagent (distinction
and method of separation from aluminium, beryllium, zirconium
and titanium).
11. Saturated Sebacic Acid Solution {C02 H. (CH2 )s. C0 2H}:
white voluminous precipitate of thorium scbacate Th(C lO R 16 0 4 )Z
(difference from cerium).
12. meta-Nitrobenzoic Acid Reagent (N0 2 . C6R 4 . C0 2H).-
Upon addition of excess of the reagent to a neutral solution
of a thorium salt at about 80°, a white precipitate of the salt
Th(N0 2 .C6H 4 .C02)4 is obtained (distinction from. cerium).
The reagent is prepared by dissolving 1 gram of the acid in 250 ml. of
water at 80 0 , allowing to cool overnight and filtering.
There are no characteristic dry tests for thoriuln.
Separation.-8ee under Cerium (Section IX, 17B).

CE1UVM, Ce
Cerium forms two well-defined series of salts, corous and eerie, in which
the element is tervalent and quadrivalent respectively. 'l'he cerium is more
basic in the former than in the latter state, hence the cerous salts are the more
stable.

IX, 17A. REACTIONS OF CEROUS COMPOUNDS

Use a solution of cerous nitrate, Ce(NOs)a,6H20.
1. Ammonia or Ammonium Sulphide Solution: white pre-
cipitate of cerous hydroxide Ce(OH)s (or Ce20s,nH20), insoluble in
excess of the precipitant, but readily soluble in acids. The pre-
cipitate slowly oxidises in the air, finally becoming converted into
yellow ceric hydroxide Ce(OR)4 (or Ce02,nH20). Sodium hydrox-
ide solution gives a similar result. The precipitation is prevented
by tartrates and citrates.
2. Oxalic Acid or Ammonium Oxalate Solution: white
precipitate of cerous oxalate Ce2(C204)s, insoluble in excess of the
reagent (compare thorium and zirconium), ~d in very dilute
mineral acids. ..
3. Sodium Thiosulphate Solution: no precipitate (distinction
from thorium and from ceric cerium).
4. Saturated Potassium Sulphate Solution: white, crystal-
line precipitate, having the composition Ce2(S04)s,3K2S04 in neutral
solution and Ce2(S04)s,2K2S04,2R20 from slightly acid solution
(difference from aluminium and beryllium).
5. Sodium Bismuthate.-This reagent, in the presence of dilute
nitric acid, converts cerous into ceric salts in the cold. A similar
608 Qualitative Inorganic AnalY8is [IX,
result is obtained by heating with ammonium persulphate or w 'h
lead dioxide and dilute nitrio acid (1 : 2). In all cases, the soluti( )lS
become yellow or orange in colour.
6. Ammonium Carbonate Solution: white precipitate <If
cerous carbonate Ce2(COS)s, nearly insoluble in excess of the pre-
cipitant (difference from beryllium, thorium and zirconium) D nd
insoluble in sodium carbonate solution.
7. Hydrogen Pero::dde.-When a cerous salt is treated "\\ ih
ammonia solution and excess of hydrogen peroxide is added a
yellowish-brown or reddish-brown precipitate or coloration, due to
cerium peroxide Ce(OH)aO. OH or Ce03,2HzO, is formed. Thi,; is
not very stable. Upon boiling the mixture, yellow eerie hydroxi(ie
Ce(OH)" is obtained. The test cannot be applied directly in the
presence of iron since the colour of ferric hydroxide is similar to that
of cerie per-hydroxide. The precipitation of ferric hydroxide lll;),y
be prevented by the addition of an alkali tartrate in consequellce
of the formation of complex ferri-tartrate ions; this, howei pr,
reduces the sensitivity of the test for cerium.
t The spot-test technique is as follows. Mix a drop of the hot tost
solution, of'" 10-volume" hydrogen peroxide and of dilute amm( ia
solution in a porcelain micro-crucible and warm gently. A yello" or
yellowish-brown precipitate or coloration appears.
Sensitivity: 0·35 p.g. Ce. Concentration limit: 1 in 140,000.
8. Ammonium Fluoride Solution: white, gelatinous precipi·
tate of cerous fluoride CeF3 in neutral or slightly acid solutioG.
The precipitate becomes powdery upon standing.
9. Potassium Iodate Solution: white precipitate of eel lUS
iodate Ce(I0 3)s in neutral solution, soluble in nitric acid (differ( lce
from ceric iodate; compare thorium) .
. tlO. Ammoniacal Silver Nitrate Reagent.-This reagent reicts
with neutral solutions of cerous salts to form ceric hydroxide ,ad
metallic silver (difI'erence from C()ric cerium); the former is colo\'!'ed
black by the finely divided silver:
Ce(OH). + [Ag(NHa)a)+ + OH- = Ce(OH), + Ag + 2NHa
Ferric, manganous and cobaltous salts also give the higher met!!lic
hydroxides and silver, and must therefore be absent.
Mix a drop of the neutral test solution and a drop of the reagent n a
watch glass or in a porcelain micro crucible, and warm gently. A L',lck
precipitate or brown coloration appears.
Sensitivity: 1 p.g. Ceo Concentration limit: 1 in 50,000.
The ammoniacal silver nitrate reagent is prepared by treatin~ eG.
0·4N silver nitrate with dilute ammonia 8olution until the precip Late
first formed is just redissolved.
17B] Reactions of some of the "Rarer" Elements 609

IX, 17B. REACTIONS OF CERIC COMPOUNDS

Use a solution of "eerie ammonium sulphate"
(NH,MCe(SO,,),,]2H 20 {or Oe(SO")2,2(NH,,)zS04,2H 20}
or of ceric sulphate Oe(S04)2 in dilute sulphuric acid.
1. Ammonia or Sodium Hydroxide Solution: yellow precipi-
tate of ceric hydroxide Oe(OH)4' If the precipitate is warmed with
hydrochloric acid, chlorine is evolved and cerous chloride is formed.
2. Oxalic Acid or Ammonium Oxalate Solution: reduction
occurs, more rapidly on warming, to the cerous condit.ion, and
ultimately white cerous oxalate is precipitat.ed.
3. Saturated Potassium Sulphate Solution: no precipitate
(distinction from cerous salts).
4. Reducing Agents (e.g. hydrogen sulphide, sulphur dioxide,
hydrogen peroxide and hydriodic acid).-These convert ceric salts
into cerous salts.
5. Sodium Thiosulphate Solution: yellow colour of solution
discharged and sulphur precipitated, owing to reduction.
6. Ammonium Fluoride Solution: yellow colour of solution
is discharged but no precipitate is produced.
7. Potassium Iodate Solution: white precipitate of ceric iodate
Ce(IOs )" from concentrated nitric acid solution (difference from
cerous cerium; thorium and zirconium give a similar reaction).
t8. AnthraniUc Acid Reagent (NHs.CeH,.COaH,l: 2).-Cerio
cerium oxidises anthranilic acid to a brown compound. CI roUB cerium
does not react and must be oxidised first with lead dioxide and concen-
trated nitric acid (SN) to the eerie state: other oxidising agents cannot
be used since they react with the anthranilic acid. Ferric iron inhibits
the test and must be masked by the addition of phosphoric acid. The
ions of gold and vanadium, as well as chromate ion, react similarly
and therefore interfere. Reducing agents must be absent.
Place a drop of the test solution (slightly acid with nitric acid) on
a spot plate and add a drop of a. 5 per cent solution of anthranilic acid
in alcohol. A blackish-blue precipitate appears, which rapidly passes
into a soluble product and colours the solution brown.
Concentra.tion limit: 1 in 10,000.

Dry Test
Bo,.ax Bead: oxidising Bame-dark brown whilst hot and light
yellow to colourless when cold I reducing Bame--colourless.
20+
610 Qualitative Inorganic Analysi8 [IX,
Separation.-Cerium and thorium salts are precipitated in Grrl ip
lIlA. They may be separated from the other metals of the group
by dissolving the precipitate in dilute HCI and adding oxalio acid
solution, when the oxalates of both metals are precipitated. The
thorium and cerium may be separated: (a) by dissolving the thorium
oxalate in a mixture of ammonium acetate solution and acetic acid,
cerium oxalate being insoluble under these conditions; (b) by treat·
ment with a large excess of hot concentrated ammonium oxal:tte
solution; only the thorium oxalate dissolves (a complex ion being
formed), and may be reprecipitated from the resultant solution as
oxalate by the addition of hydrochloric acid.
In routine qualitative analysis, it is probably best to boil the
mixed oxalates (after washing with 2 per cent oxalic acid solution)
with 5 per cent potassium hydroxide solution, thereby converting
them into the hydroxides. The precipitate is separated by filtration,
washed with hot water, dissolved in the minimum volume of dill! te
hydrochloric acid and the solution divided into two parts:
(i) Th.-Neutralise with ammonia solution, and add the meta·
nitro-benzoio acid reagent (Section IX, 16, test 12) or a warm
saturated solution of sebacio acid (ibid. test 11). AIternativdy,
add hydrochloric acid to the neutral solution until the concentrat ion
is about O·3N, and then sodium pyrophosphate solution. A wi,ite
precipitate, ThP207, indicates Th.
(ii) Ce.-Identify by the addition of hydrogen peroxide, follo" ed
by ammonia solution until the liquid is alkaline. A reddish-brown
preoipitate indioates Ce (see Section IX, 17A, reaction 7).
The following Table contains a scheme for the identification of ; he
more common "rarer" elements (Ti, Zr, Ce, Th, V and U) in . he
presence of Fe, AI and Cr. If phosphate is present, it should be
removed by the stannic chloride method (Section VIII, 2).
18] Reactions of 80rne of the "Rarer" ElementB 611
IX, 18. Table V.-Analysis of Group lIlA in the presence of
Ti, Zr. Ce, Th, U and V

Dissolve the precipitate in the minimum volume of dilute HCI. Pour

the weakly acid solution into an equal volume of a solution which contains
10 ml. of 6% H.O. and is 2·5N with respect to NaOH. (The latter
solution should be freshly prepared.) Boil for [) minutes, but no longer.
Filter and wash the ppt. with hot 2% NH,NO a solution.
Residue. May Filtrate. May contain Na.CrO" NaAlO.,
contain Fe(OHla; Na aVO, and sodium peruranate (probably
TiO.,nH.O; Na.UO.).
ZrO.,nH.O; Acidify with dilute HNO., add 3-4 ml. of 20%
ThO.,nH.O; Pb(NO.). solution, followed by 2 grams of solid
CeO.,nH.O (and ammonium acetate. Stir well, filter and wash with
some MuO.,nH.O). hot water.
Dissolve in dilute
HCl, boil to expel Residue. May Filtrate. May contain
Cl. and divide the contain PbCrO, Al(NO a )., UO.(NO.). and
solution into five and Pb.(VO.). (4). excess of Pb(NO.)2' Pass
parts. Dissolve in the H.S to remove all th" Pb as
(i} Add KSCN minimwn volume PbS. Filter, wash and boil
solution (1). of hot 3N HNO. the filtrate to expel H.S.
Red coloration. (ca. 5-6 ml.), Almost neutralise with NH.
Fe present. thoroughly cool solution, cool and pour into
(ii) If Fe present, the resulting solu- an excess of concentrated
add just sufficient tion, and transfer (NH.).CO. solution. Warm
H.P0 4 (2) to de- to a small separa- for 5 mi.p.utes. Allow to stand,
colourise the ferric tory funnel. Add filter and 'Wash.
salt, and then H.O •. an equal volume
Orange-red colora- of amyl alcohol, Residue. Filtrate. May
tion, discharged by and a little 6% White: contain U, pro-
the addition of solid H.O.. Shake Al(OH) •. bably as (NH,).-
NH.F. well and allow the Al present. [UO.(CO.).].
Ti present (see two layers to sepa- Confirm by Evaporute to a
Section IX, 13). rate. Thenard's small volume (7),
White ppt. A blue colora- blue test (6). acidify with HCl,
Zr present (3; tion in the upper and add K.[Fe-
see also Section layer indicates Cr (CN).] solution.
IX, 14). present, and a. red Brown ppt. of
(iii) Add excess to brownish-red (UO.).[Fe(CN).],
of saturated oxalic coloration (5) in b,ecoming yellow
acid solution (ca. the lower layer upon the addi-
10%). White ppt. indicates V pre- tion of NaOH
Th and/or Ce sent. solution.
present. Confirm V by the U present.
For separation of KClOs-p-pheneti-
Th and Ce, see Sec- dine test (Section
tion IX, 17B. IX, 11, reaction
(iv) Evaporate to 12).
fuming with H 2SO,
to expel HCI. Cool,
dilute, add HNO a
and a little NaBiO •.
Stir and allow to
stand.
Purple coloration.
Mn present.
612 Qualitative Inorganic Analysis [IX,
Notes. (I) The potassium ferrocyanide test is not recommend",j
here when U is present. The NaOH-H 20 t separation is not qUi 'l
quantitative and sufficient U may be present in the precipitate to
introduce complications.
(2) The addition of phosphoric acid or of sodium phosphate is essent-II
if Zr is to be tested for, even if Fe is absent (compare Section IX, J !,
reaction 3).
(3) If both Ti and Zr are present, the ppt. of zirconium phosphlli<3
may be filtered off (best in the presence of a little macerated filter pap"",
or a Whatman filtration accelerator), and the filtrate treated WI II
Na 2SO a or with Na 2S 20 S solution and warmed. The so·called " tita,,-
ium peroxide" is reduced and titanium phosphate precipitates. It mity
be necessary to reduce the acidity of the solution somewhat to COItl-
pletely precipitate the titanium. Zr may also be identified by the
alizarin-S reaction.
(4) If Group IV metals are present, they may be precipitated as
vanadates. This is prevented by adding excess of FeCl a solution wh"rl
ferric vanadate is precipitated here.
(5) If much Cr and a little V is present, a second extraction w: h
amyl alcohol may be necessary in order to ensure the complete remo' .1
of the Cr, and to render the coloration due to V completely visit, ".
The addition of two drops of concentrated nitric acid intensifies l' e
colour.
(6) The dry test is preferable to the "aluminon" reaction, for 1 iU3
latter is not applicable in the presence of Be. If Be is absent, t'le
"aluminon" test may be applied.
(7) A precipitate that separates here may be (basic) berylli'"a
carbonate. It should be filtered off and tested for Be by the ba ,,0
acetate-chloroform test or by the acetylacetone test (see Section IX, ll,
reactions 6 and 9).

IX, 19. Notes on the Precipitation and Separation of Group

IIIB in the presence of "Rarer" Elements
If thallium has been found in Group I, some of it may pass il, i 0
Group IIIB because of the solubility of thallous chloride in water
and be precipitated as TI 2S. It may be readily detected by the
green flame coloration, preferably viewed through a hand spectro-
scope. Thallium is best separated from the other elements of Gro 11 p
IIIB by dissolving the precipitate in dilute nitric acid, boiling to
expel hydrogen sulphide, adding a little sulphurous acid solution
and boiling again to remove excess of sulphur dioxide. Up In
pouring the solution into excess of aqueous sodium carbonate, the
carbonates of cobalt, nickel, manganese and zinc are precipital I,d
and the thallium remains in solution as the soluble thallous ca r-
bonate. The precipitated carbonates may be dissolved in dilute
hydrochloric acid and the usual separation carried out. '] lie
thallium in the filtrate can be precipitated by the addition of fresLly
prepared, colourless ammonium sulphide solution.
If vanadium and/or molybdenum have been detected in the
earlier groups (as indicated by the production of a blue colorat;. ,0
20] Reactions of some of the " Rarer" Elements 613
with hydrogen sulphide in acid solution), these elements may also
be found in the filtrate from Group HIB: a violet-red colour points
to vanadium and a reddish-brown coloration to molybdenum. As a
general rule, vanadium is generally removed in Group lIlA as iron
vanadate and its presence in the Group IIIB filtrate is therefore
unlikely. However, when the filtrate from Group IIIB is acidified
with acetic acid and boiled, the production of a brown precipitate
will indicate the removal of any residual molybdenum, vanadium
or nickel in the form of sulphides. If desired, the precipitate may
be dissolved in concentrated nitric acid, evaporated to dryness and
the residue dissolved in hydrochloric acid. Molybdenum is detected
by the ammonium thiocyanate or the potassium xanthate test
(Section IX, 4), and vanadium by the KCIOs-p-phenetidine or
hydrogen peroxide reactions (Section IX, 11).

LITHIUM, Li
Lithium is a silver-white metal; it is the lightest metal known
(density 0·534 at 0 and floats upon petroleum. It oxidises on expo-
0
)

sure to air, and reacts with water forming lithium hydrmdde and
liberating hydrogen, but the reaction is not so vigorous as with sodium
and potassium. The metal dissolves in acids with the formation of
salts. The salts may be regarded as derived from the monoxide Li 20.
Some of the salts, notably the chloride LiCI and the chlorate LiCIO a,
are very deliquescent. The solubilities of the hydroxide LiOH (113
grams per litre at 100), carbonate LiaCO a (13'1 grams per litre at 13 0),
0
the phosphate Li aP0 4 (0·30 grams per litre at 25 and the fluoride LiE
)

(2·7 grams per litre at 18 are less than the corresponding sodium and
0
)

potassium salts, and in this respect lithium resembles the alkaline

earth metals.

IX, 20. REACTIONS OF LITHIUM COMPOUNDS

Use lithium carbonate Li2 COa dissolved in the minimum volume
of 2N hydrochloric acid.
1. Sodium Phosphate Solution: partial precipitation of
lithium phosphate Li sP04 in neutral solutions; the precipitate is
more readily obtained from dilute solutions on boiling. Precipita-
tion is almost complete in the presence of sodium hydroxide solution.
The precipitate is more soluble in ammonium chloride solution than
in water (distinction from magnesium).
3LiCI + NazHPO, + NaOH = Li.PO, + 3NaCI + HIO
Upon boiling the precipitate with barium hydroxide solution, it
passes into solution as lithium hydroxide (difference from mag-
nesium).
2. Sodium or Ammonium Carbonate Solution: white pre-
cipitate of lithium carbonate Li 2COs from concentrated solutions
and in the presence of ammonia solution. No precipitation ocours
in the presence of high concentrations of ammonium chloride since
614 Qualitative Inorganic Arialysi8 [IX,
the carbonate ion concentration is reduced to such an extent that
the solubility product of Li 2COs is not exceeded:
NH,+ + C0 3 - - ;= NHs + HCO s-
3. Ammonium Fluoride Solution: a white, gelatinous preci-
pitate of lithium fluoride LiF is slowly formed in ammoniacal
solution (distinction from sodium and potassium).
LiCl + NH,F = LiF + NH,Cl
4. Tartaric Acid, Sodium Cobaltinitrite or Chloroplatinic
Acid Solution: no precipitate (distinction from potassium).. A
precipitate of lithium cobaltinitrite is, however, produced in very
concentrated (almost saturated) solutions of lithium RaJts; inter-
ference with the sodium cobaltinitrite test for K + is therefore un-
likely.
t5. "Ferric Periodate" Test.-Ferric salts react with periodaLes
to yield a precipitate of a complex ferric periodate: this precipitate is
soluble in excess of the periodate solution and also in excess of potassium
hydroxide solution. The resulting alkaline solution of the ferric
periodate complex is a selective reagent for lithium, since it give" s
white precipitate KLiFe[IOe], even from dilute solutions and in the c' dd.
Sodium and potassium give no precipitate: ammonium salts, all me'· LIs
of Groups I to IV and magnesium should be absent.
Place a drop of the neutral or alkaline test solution in a micro i it-
tube, add 1 drop of saturated sodium chloride solution and 2 drop of
the ferric periodate reagent. Carry out a blank test with a dro;· of
distilled water simultaneously. Immerse both tubes for 15-20 sec,· ids
in water at 40-50°0. A white (or yellowish-white) precipitate indic 'es
the presence of lithium; the blank remains clear.
Sensitivity: 0'1 /l-g. Li. Concentration limit: 1 in 100,000.
The "ferric periodate" reagent is prepared by dissolving 2 gram of
potassium periodate (KIO,) in 10 ml. of freshly prepared 2N potasf;' .m
hydroxide solution, diluting with water to 50 mI., adding 3 ml. oj 10
per cent ferric ohloride solution and diluting to 100 ml. with 2N pOi ·LS-
sium hydroxide solution. The reagent is stable.
t6. Ammonium Carbonate Solution (Microscope Test).-
Lithium carbonate, when freshly formed, has a characteristic appear-
ance under the microscope.
Place a drop of the concentrated test solution on a microscope Sl. Ie.
Introduce a few minute specks of sodium or ammonium carbon. 1 ;,e.
Some lithium carbonate crystals are formed immediately. Exan J' ne
under the microscope (magnification: ca. 200 diameters): the cry~ i "Is
are in the form of either hexagonal stars or plates (compare CaSO,,2H 20,
Section III, 31, reaction 10).
The cations of the alkaline earth metals and of magnesium mus! be
absent.
Concentration limit: 1 in 10,000.
Dry Test
Flame coloration.-Lithium compounds impart a carmine' ed
colour to the non-luminous Bunsen flame. The colour is masked
by the presence of considerable amounts of sodium salts, but he
comes visible when observed through two thicknesses of cobalt glass.
21] Reactions of some of the " Rarer" Elements 615
The most distinctive test utilises the spectroscope; the spectrum
consists of a beautiful red line at 6708A.
To separate lithium from the other allmli metals, they are all
converted into the chlorides (by evaporation with concentrated
hydrochloric acid, if necessary), evaporated to dryness, and the
residue extracted with absolute alcohol which dissolves tho lithium
chloride only. Better solvents are dry dioxan (diethylene dioxide,
/CH2.CH2~
O( , 0) and dry acetone. Upon evaporation of the
"CH2.CH 2/
extract, the residue of lithium chloride is (a.) subjected to the flame
test, and (b) precipitated as the phosphate after dissolution in water
and adding sodium hydroxide solution.
Note on the Detection of Lithium in Group V
This element is readily detected in the residue of Group V by
means of the hand spectroscope (see Section II, 1, 4). Details for
the separation of Li from K and Na are given in the previous
paragraph.
In Table VI are collected the colorations produced with the borax
beads for difference elements and will be useful for reference pur-
poses (compare Section VII, 2, test (iv)).
IX, 21 Table VI. Borax Bead Tests
Oxidising jlame Reducing jlama
Metal
Hot Cold Hot Cold

1. Green Blue Colourless Opaque red Copper

or brown*
2. Yellowish- Yellow Green Green Iron
brown
3. Yellow Green Green Green Chromium
4. Violet Amethyst Colourless Colourless Manganese
(amethyst)
5. Blue Blue Blue Blue Cobalt
6. Violet Reddish- Grey Grey Nickel
brown
7. Yellow Colourless Brown Brown Molybdenum
8. Rose-violet Rose-violet Red Violet Gold
9. Yellow ColourleBB Yellow Yellow- Tungstent
brown
10. Yellow Pale Green Bottle- Uranium
yellow green
11. Yellow Greenish- Brownish Emerald- Vanadium
yellow green
12. Yellow Colourless Grey I'ale-violet Titanium:
13. Orange-red Colourless Colourless Colourless Cerium

* Bright red in the presence of a trace of tin.

t Microcosmic salt bead test: reducing flame, cold-blue; blood-red when
fused with a trace of ferrous sulphate.
: Microcosmic salt bead test: reducing flame, hot-yellow, cold-violet:
blood-red with a trace of ferrous sulphate.
 CHAPTER X

PAPER CHROMATOGRAPHY

X, 1. Introduction. RF Values.-In filter-paper chromat,)·

graphy a small amount of material (say, an aqueous soluti, rt
containing a mixture of cations) is placed upon a limited ar, t
near the end of a strip of filter paper, and a solvent is allow, ,1
to diffuse from the end of the paper by capillary action: und r
suitable conditions and after some time (1-30 hours), the
mixture will be found to have migrated from its limited an'a.
of application and separated wholly or partially into its COl 1-
ponents as distinct zones. The zones in the form of spots ., r
bands may be located by the application of appropri:1: '3
chemical reagents to the paper or by ultra-violet fiuorescen< '1.
The diffusion of the solvent and the resulting separation it, i 0
spots or bands is sometimes termed the development of t I! e
chromatogram; this term is a little misleading and should 1, ,t
be confused when employed in the above sense with the Sli i>-
sequent identification process by means of which the zones I' 'e
rendered clearly visible by treatment of the paper with varic is
reagents. The author prefers to confine the phrase "devel< :1-
ment of the chromatogram" to signify the treatment of 1 e
chmroatogram after it has been formed, and it will have t: s
significance when employed in the present chapter.
To specify the position attained by a substance or ion iI, a
paper chromatogram, the term RF was introduced: this is 1 ie
ratio of the distance travelled by the substance or ion to tJ! It
of the solvent front, measured from the point of application i)f
the mixture. Fig. X, 1, 1 will help to make the definiti' ,n
of RF clear: in (a) the strip of filter paper is shown immen d
in the solvent and supported by a glass rod; in (b) AB indica's
where the spot of the solution was applied at the beginni i g
of the experiment; in (c) the position of two bands (rendered
visible, for example, by spraying with an appropriate chemj('al
reagent) C and D, and also of the solvent front E, are indicated.
The RF value for the substance or ion at C is xjz and the
substance or ion at D is y/z. It is found that under comparable
conditions many ions have characteristic RF values; separation
by paper chromatography is usually possible when the HF
values differ by about 0·1.
616
1] Paper Ohromatography _ . _ 617
. Hdj; .,
The position of AB (usually a pencilled line) is fixed by
applying a drop of the solution from a capillary pipette or
micro syringe along the line. The distance moved by the
substance or ion is generally taken as the distance between
the line AB and the "centre of gravity" of the band; the
resulting RF value does not take into account the width of
the band and also some uncertainty may be introduced if the
band has diffuse boundaries.
The values of RF are reasonably constant providing close
control of all variables is maintained. It is found, however,
that the relative rates of movement are constant with less

(a) (b) (c)

Fig. X, 1, 1

rigid control, thus enabling one band on a strip to be identified

by its position relative to known bands. Furthermore, with
the large number of "spot" tests available for the detection
of individual inorganic radicals, the necessity for an accurate
knowledge of RF values is diminished. If constancy of pure
solvents, of temperature and saturation of the atmosphere are
maintained, it is found that RF values are influenced inter alia
by the following factors:
(a) The presence of other ions, e.g. the presence of chloride
in separations carried out with nitrate solutions.
(b) The acidity of the original solution: this may be due to
the need for acid in the formation of a complex which is soluble
in the organic solvent, to prevent hydrolysis of the salt, etc.
20*
618 Qualitative Inorganic A nalys1,s [X,
(c) The time of running of a strip; sometimes the RF valu,'s
increase with the time of running at the outset and this m,ty
correspond with a decrease in the rate of movement of the
solvent front.
(d) The presence and concentration of other cations.
It is not proposed to deal with the theory of paper chroma 1()-
graphy here, but it may be pointed out that an importD Ilt
factor is the distribution of the inorganic compound betw{' n
an organic solvent and water. The distribution may be vari j
inter alia by forming complexes of the cations with diffew,t
organic solvents or mixtures of solvents.
The separation of metals constituting the usual groups ,n
qualitative analysis, and also the isolation of the constituenLs
of mixtures containing some of the less common metals, will
be described. A few separations of anions will also be given in
outline.
Some advantages of paper chromatography may be men-
tioned:
(i) The procedure is simple and reasonably rapid.
(ii) Costly special apparatus and reagents are not necessal , .
(iii) Only small quantities of materials are required.
(iv) The method has proved successful for the separati 11
and deteotion of groups of metals which are difficult to deal
with by routine qualitative analysis, e.g. the separation of the
platinum metals from one another, of beryllium from al'l-
minium, of soandium from the rare earths and thorium, aJ" 1
of hafnium from zirconium.
X, 2. Apparatus and General Technique.-For general use,
Whatman No.1 paper is satisfactory. No. 3MM is similar in
speed but thicker, and therefore has a higher water content,.
Whatman No.4 is a very much "faster" paper; it is not widely
employed in inorganic chromatography.
For routine work in qualitative analysis, the apparatns
depicted in Fig. X, 2, 1 is inexpensive and efficient. It consist,s
of a. glass gas jar or measuring cylinder (say, 22 inches by 3
inches), closed with a tight-fitting cork or rubber bung whieh
carries a glass rod to which a glass boat is fused. (The glass
boat, with approximate dimensions, is shown in Fig. X, 2, 2.)
The boat is suspended about an inch below the bottom of the
cork, and serves as a container for the solvent employed in
the separations. Two side arms are fused to the glass rod
above the glass boat and these act as supports for a pair of
paper strips; only one paper strip is shown in position in the
2] Paper Chromatography 619
diagram. In order to saturate the atmosphere in the cylinder
with respect to the solvent, a layer of the latter is kept at the
bottom of the glass cylinder; this will prevent evaporation
effects from disturbing the equilibrium of the solvents travel-
ling down the paper. In some separations it is also necessary
to control the amount of water vapour in the atmosphere; for
this purpose a beaker containing water, s}lturated salt solution
or aqueous acid saturated with the solvent is
placed on the bottom of the jar. It is ad-
vantageous to maintain fairly constant tem-
perature conditions and for some separations
the whole apparatus is kept in a thermostatic-
ally controlled (± 1 0) cabinet or bath. The
size of the airtight container should be com-
mensurate with the narrow strips of filter paper

Fig. X, 2, I Fig. X, 2, 2
' :' J

ordinarily employed, otherwise with volatile solvents"1t is

difficult to maintain the equilibrium of the solvent mixture
running in the paper and which is essential for the separation.
The procedure permits the separation of 1-200 fLg. of ions:
under favourable conditions as much as 1 mg. (1000 fLg.) of
certain ions may be separated by chromatography. Strips of
Whatman No. 1 filter paper, 12-18 inches long and I inch
wide, are cut from the rolls supplied by the manufacturers.
 620 Qualitative Inorganic Analysis [X,
A light pencil line is drawn across the width of the pa per
about 3 inches from the upper edge; this acts as the zero line.
A convenient volume (say, 0·05 ml.) of the test solution,
containing not more than 1 mg. of the mixed metals (say as
chlorides) is applied to the centre of the zero line with the lid
of a micro pipette * : the strip is held horizontally until 'he
liquid is absorbed. The spot usually forms a wet patch ab> ,at
one inch square; this is generally allowed to dry completely in
the air (ca. one hour), although in some cases the degree of
drying is dependent upon the chemical stability of the s;11ts
undergoing separation. The strip is then hung vertically in
the cylinder with the upper end immersed in the solvent
contained in the glass boat; the upper end of the strip may be
held down in the glass boat by means of a glass rod, but with
two strips touching in the trough, the capillary and other
forces suffice to hold the strips in position without the necessity
of weighting. Mter the solvent has diffused down the pap or
a sufficient distance to effect a separation (1-24 hours; tilis
may be when the solvent front has travelled within 1-2 incl'I)S
of the lower edge of the paper), the strip is removed from 1 ile
cylinder. The position of the solvent front should be marl,,'d
whilst the strip is still wet with solvent, since it is sometin"'s
difficult to locate it when dry. t The solvent is then allowed to
evaporate, i.e. the strips are dried by pinning or clipping th( lU
over a glass rod clamped or supported at a convenient heigl· I ;.
The presence and position of the salts on the strip are detect,'d
by spraying with a suitable reagent. The simple type ,)f
atomiser shown in Fig. II, 6, 5, inserted in a test-tube or small
flask, may be used. [If available, it is more satisfactory to
employ a commercial form of atomiser operated by a constant
pressure device (ca. 10 lb./sq. in.).] Mter spraying, the
coloured bands may not reach their maximum intensity until
several hours have elapsed.
A large number of organic and inorganic reagents have been
used. The criteria applied in selecting a reagent for paper
chromatography differ from those usually employed in choosing
a "spot" test reagent. It is not necessary for the reagent to

• It has been recommended that a series of micro drops (say, from a micro
syringe of the Burroughs WeUcome type) be placed at intervals along tlJe
pencil line: this procedure is not essential for routine work in qualitatin,
inorganic analysis.
t For some mixed solvents containing water, there may be two solvent
fronts, one of the dry solvent (lower area-the position of this is noted) and
another wet solvent front (upper area, in which the paper is saturated with
water.
2] Paper ChromaJoflraph,ll 621
be specific for a certain ion or radical, but it is desirable to have
one which will give a test for as many ions or radicals as
possible. The reagents employed include diphenylthiocarba-
zone (dithizone), rubeanic acid, diphenylcarbazide, alizarin,
salicylaldoxime, morin, potassium ferrocyanide, potassium
chromate, ammonium sulphide and hydrogen sulphide (as the
free gas). In many instances mixtures of two or more of these
reagents are advantageous.
In order to obtain repeatable results., the compositions of
the solvents employed must be constant. In some cases,
particularly with water-miscible solvents, small variations in
the water content may affect considerably the efficiency of
the separation. All the solvents used must be of high purity.
Some of the solvents employed are detailed below:
(i) n-Butyl alcohol saturated with aN hydrochloric acid.
Equal volumes of the alcohol and aN hydrochloric acid are
shaken together; the upper layer is used.
(ii) Acetylacetone is saturated with water: to 7·5 m!. of the
saturated solvent, 0·05 ml. of concentrated hydrochloric acid
and 2·5 ml. of dry acetone are added. This solvent is de-
scribed as acetylacetone saturated with water and containing
0·5 per cent (vjv) of hydrochloric acid (d 1'18) and 25 per cent
(vjv) of dry acetone.
(iii) Glacial acetic acid containing 25 per cent (vjv) of dry
methyl alcohol.
(iv) Acetone containing 5 per cent (v jv) of water and 8 per
cent (vjv) of hydrochloric acid (d 1'18).
(v) Pyridine containing 20 per cent (vjv) of water and 1 per
cent (wjv) of potassium thiocyanate.
(vi) Methyl alcohol.
(vii) Methyl ethyl ketone containing 30 per cent (vjv) of
hydrochloric acid (d 1·18).
(viii) Cellosolve (ethylene glycol monoethyl ether) contain-
ing 20 per cent (vjv) of hydrochloric acid (d 1·18).
(ix) Ethyl ether containing 2 per cent (wjv) of dry hydrogen
chloride and 7·5 per cent (vjv) of dry methyl alcohol.
(x) Methyl acetate containing 3 per cent (vjv) of methyl
alcohol and 10 per cent (vjv) of water.
(xi) Dry n-butyl alcohol containing 40 per cent (vjv) of dry
methyl alcohol.
(xii) Tetrahydrosylvan containing 5 per cent (vjv) of water
and 10 per cent (vjv) of nitric acid (d 1·42).
(xiii) Pyridine containing 10 per cent (vjv) of water.
622 Qualitative Inorganic Analysis [X,
The following details for the purification of solvents for
paper chromatography may be useful:
Acetone. Reflux with solid potassium hydroxide ~nd pota,,-
sium permanganate for one hour, and fractionate. Use t):e
fraction, b.p. 56° ± 0'5°.
Methyl ethyl ketone. As for acetone. Use fraction, b.p. 79·5-8(1".
I II III IV V VI Vl1 I

Fig. X, 2, 3

Methyl n-propyl ketone. As for acetone. Use fraction, b.p.

99-102°.
Methyl alcohol. Redistil the purest commercial (synthetic)
alcohol. B.p. 63°.
n-Butyl alcohol. Dry over anhydrous calcium sulphate, filter
and distil. Use fraction, b.p. 116'5-117'5°.
Pyridine. The AnalaR brand is satisfactory.
Ethyl acetate. Shake with saturated calcium chloride solu-
tion, dry with anhydrous calcium sulphate, filter and distil.
B.p. 76'5-77'5°.
3] Paper Chromatography 623
Methyl acetate. As for ethyl acetate. B.p. 56.5-57.5°,
Diethyl ether. Reflux with alkaline potassium permanganate,
dry with anhydrous calcium Bulphate, filter and distil. B.p.
35 0. The ether is free from peroxides.
Tetrahydrosylvan. As for diet-hyl ether. B.p. 79-80°.
The results of some typical separations are shown in Fig.
X, 2, 3; the Figure has been drawn from actual photographs
of the paper chromatograms. The following separations are
indicated:
I-Group lIA, Cu, Pb, Bi, Cd and Mg.
II-Group lIIB, Ni, Mn, Co and Zn.
III-Group IV, Ba, Sr and Ca.
rv-K, Na and Li.
V-Rh, Pd, Pt and Au.
VI-Au from the Pt metals.
VII-Te and Se.
VIII-CI, Br and I.
Full details of these separations are given in the following
Sections.
X, 3. SOME TYPICAL GROUP SEPARATIONS
Group I.-A~, Ph and H~ (ous). The metals are present
as nitrates in dilute nitrio aoid. The solution is spotted upon
paper and allowed to dry in air for one hour. The solvent
oonsists of n-butyl alcohol, mixed with 5 per cent (vjv) of
glacial acetic acid, followed by water to turbidity. The separa-
tion (elution) is allowed to proceed for 12-16 hours in an
atmoflphere saturated with the solvent. The strip is removed
from the extraction vessel, dried in air and then sprayed with
a 0·05 per cent solution of dithizone in chloroform.

RF values Colour of band

Ph 0·08 Rose pink.

Ag 0·16 Orange.
Hg (ous) 0·85 Pink.

The paper chromatogram may also be developed by exposure

to hydrogen sulphide gas, but the result::; are not as satisfactory
as with dithizone.
Group IIA.-H~, Ph, Bi, Cu and Cd. The metals are
present as chlorides in dilute hydrochloric acid. The solvent
 624 Qualitative Inorganic Analys'is [X,
- used is n-butyl aloohol saturated with 3N hydroohloric al·id.
To obtain a good separation of copper and lead, the S' 'ip
should be at least 18 inches long. The solvent is allowed to
flow for 15-18 hours in an atmosphere saturated with resI" 'ct
to both organic solvent and aqueous phases. After evaporat :' m
of the solvent, the strip is sprayed with a solution of dithiz, ,ne
in chloroform (0·05 per cent wjv). Lead gives only a w(';Lk
colour with dithizone and is best detected by spraying the 1 ('p
portion of the strip with an aqueous solution of rhodizonic alA.

RF values Reagent Oolour of band

On 0·20 Dithizone Purple-brown.

Pb 0·27 Rhodizonic Bright blue.
acid
Bi 0·59 Dithizone Purple.
Cd 0·77 Dithizone Purple.
Hg (ic) 0·81 Dithizone Pink.

Group IIB.-As, Sb and Sn. The separation of a mixture ""

of the three elements is a difficult operation. The metals are
present as their lower chlorides in dilute (2-4N) hydrochloric
acid. The solution is spotted on paper and allowed to dry in
air for 15 minutes. The solvent consists of 7·5 ml. of acet\ l-
acetone (b.p. 137-141°) saturated with water and treated wi; h
0·05 ml. of concentrated hydrochlorio aoid and 2·5 ml. (,f
acetone (sufficient of the last-named to give a olear solutioll).
The separation is allowed to proceed for 1 hour in an atmosphere
saturated with respeot to a saturated solution of acetylaceto!le
in water; the solvent movement is about 15 cm. The oomplexes
formed are very stable, particularly that with tin (RF = 1).
The strip is removed from the extraction vessel, the solvent is
allowed to evaporate for several minutes, and the strip is
sprayed (before it is completely dry) with a chloroform solution
of dithizone (0,05 per cent wjv), and then allowed to dry
thoroughly. The tin is found in the solvent front.

RF values Oolour of band

As 0·2 Yellow.
Sb 0'5 Red.
Sn 1·0 Purple.
3] Paper Ohromatography 625
Group IIIA.-Fe, Al and Cr. The main difficulty here is
the separation of the aluminium and ohromium. The metals
are present as chlorides in 5N hydrochloric acid. The solvent
employed is glacial acetic acid containing 25 per cent (vjv) of
dry methyl alcohol. The test solution is spotted upon filter
paper and allowed to evaporate to dryness in air. The elution
is allowed to proceed for 12 hours in an atmosphere saturated
with respect to the mixed solvents: the use of a saturated
solution of potassium carbonate to maintain a low humidity
improves the separation. After the solvent has evaporated,
the strip is cut lengthwise in two portions. One portion is
sprayed with a saturated alcoholio solution of alizarin, made
alkaline by exposure to ammonia vapour and then warmed; AI
appears as a red band well separated from a purple band due
to iron. The other portion of the strip is sprayed first with
5 per cent aqueous sodium peroxide and then with a 0·05 per
cent solution of benzidine in 10 per cent acetic acid: Cr is
indicated as a bright blue band just behind the AI.
Group IIIB.-Ni, Co, Mn and Zn. The metals are present
as chlorides in dilute hydrochlorio acid. The solvent used is
acetone containing 5 per cent (vjv) of water and 8 per cent (vjv)
of hydrochloric acid (d 1'18). The separation is conducted in
an atmosphere saturated with respect to the solvent. The
strip is dried (after a solvent movement of about 25 cm.),
exposed to ammonia vapour and then sprayed with a saturated
alcoholic solution of alizarin containing 0·1 per cent of rubeanic
acid and 1 per cent salicylaldoxime. The following results
are obtained.

RF values Colour of band

Ni 0·07 Blue.
Mil 0·3 Brown.
Co 0·6 Brown.
Zn 0·9 Purple.

Group IV.-Ca, Sr and Ba. This is a difficult separation.

The metals are present as chlorides. The solvent used is
pyridine containing 20 per cent (vjv) of water and 1 per cent
(wjv) of potassium thiocyanate. The elution is allowed to
proceed for 5-6 hours in an atmosphere saturated with respect
to pyridine and also with a relative humidity of between 65
and 80 per cent; the latter is attained by the use of a saturated
826 Qualitative Inorganic Analysis [X,
aqueous solution of ammonium nitrate or chloride. The solvent
front moves about 20 cm. The strip is dried, and then sprayed
with a saturated alcoholic solution of alizarin to identify Ca,
and with 0·1 per cent (wjv) aqueous sodium rhodizonate (freshly
prepared) to reveal Ba and Sr. The RF values are: Ca, 0·9;");
Sr, 0'75; Ba, 0·15.
Group V.-Na, K and Li. The metals are present itS
ohlorides in neutral solution. The solvent used is methyl
alcohol. The position of the alkali metal chloride bands 'is
detected by spraying with O'IN silver nitrate and 0·1 per cent
fluorescein in 50 per cent alcohol, and then drying the stri p.
The RF values are: Li, 0'8; Na, 0'5; K, 0·1.
Alkaline earth and alkali metals.-Be, Ca, Sr, Ba, Mg;
Na, K. and Li. The experimental details given below permit.
the separation of Be, Mg, Ca, Sr and Baj Mg, Na and Kj
Mg, Ca, Na and K; and of Li, Na and K. The metals are
present as acetates in dilute acetic acid solution. The solvent
is a mixture of 80 per cent ethyl alcohol and 20 per cent (v j"-)
of 2N acetic acid. The elution is allowed to proceed for abm. I,
24 hours. The paper chromatogram, after drying in an fl :.
oven at 60°0, is developed by spraying with 0·1 molar aqueOl.,
solution of violuric acid (5-isonitroso-barbituric acid) and thf 'I
dried at 60°0. The RF values and the colours of the bands
are collected below.

Metal RF values Colour of band

Be 0'86 Yellowish-green.
Mg 0'76 Yellowish-red.
ea 0'68 Orange.
Sr 0'55 Reddish· violet.
Ba 0'43 Pale red.

Li 0·76 Reddish-violet.
Na 0'56 Reddish-violet.
K 0'45 Violet.

The reagent (obtainable from Eastman Kodak, etc.) is ex-

pensive.
Separation of Halides.-F, CI, Br and I. The anions are
present as their sodium salts. The solvent used is either
4] Paper Chromatography 627
pyridine containing 10 per cent (v/v) of water, or acetone
containing 20 per cent (v/v) of water. The elution is con-
ducted during 1·5-2 hours in an atmosphere saturated with
solvent vapour. After yaporation of the solvent from the
strip, the latter is-eutloiigitudinally. One part is sprayed with
O'IN silver nitrate and 0·1 per cent fluorescein in 50 per cent
alcohol, and the other is sprayed with the zirconium-alizarin
reagent. Upon drying, the halides are clearly visible as
characteristic bands, which when viewed under ultra-violet
light appear as dark areas on a fluorescent background. The
Rp values are as follows.

Radical Pyridine-l0% H 2 0 Acetone-20% H 2 0

Fluoride 0·00 0·25
Chloride 0·24 0·51
Bromide 0·47 0·62
Iodide 0·71 0·77

Separations of Various Anions. Using a solvent mixture

composed of n-butyl alcohol, pyridine and 1·5N ammonia
solution in the proportions of 2 : 1 : 2, the following BF values
are obtained for the sodium or potassium salts: chloride, 0'24;
bromide, 0·36, iodide, 0·47; chlorate, 0·42, bromate, 0'25,
iodate, 0·09; nitrite, 0·25; nitrate, 0·40; arsenite, 0·19: arsenate,
0·05; phosphate, 0'04; and thiocyanate, 0·56. The positions
of the anions may be detected by spraying with ammoniacal
silver nitrate; potassium iodide and hydrochloric acid is par-
ticularly effective for chlorates, bromates and iodates. The
RF values provide the basis for the separation of a namber of
mixtures of anions, e.g. chloride and iodide, bromide or iodide
and nitrate.

X, 4. MISCELLANEOUS SEPARATIONS
A number of interesting and, in some cases, difficult separa-
tions have been achieved by paper chromatography and details
of some of these are given below. They serve to emphasise the
great value of the technique.
Aluminium and Beryllium. The metals are present as
chlorides in dilute hydrochloric acid. The solvent consists of
80 per cent n-butyl alcohol and 20 per cent hydrochloric acid.
Mter elution overnight, the solvent front moves about 20 cm.
628 Qualitative Inorganic Analysis [X,
The positions of the aluminium and beryllium bands are 'hown
by spraying with an alcoholic solution of 8-hydroxyqui; ,oline.
The bands fluoresce under ultra-violet light; the fluor' cence
intensifies upon drying the paper and exposing to ammO! ;a gas.
The RF values are: AI, 0'03; Be, about 0·3.
This procedure permits the detection of 2 p,g. of AI ill the
presence of 300 p,g. of Be, and vice versa; traces of Be c;, 'l thus
be detected in AI salts and traces of AI in Be salts.

Separation of Mercury from other Metals. Tl!o pro-

cedure enables 1 p,g. of Hg to be identified in the preseJ;' e of a
large excess of Pb, Cu, Bi, Qd, As, Sb, Fe, AI, Cr, Ni, 0, Mn
and Zn. The metals are p:resent as chlorides. The )lvent
used is methyl acetate containing 3 per cent (vjv) of lethyl
alcohol and 10 per cent (vjv) of water.
The test solution should not contain more than 5 1" r cent
(vjv) of concentrated hydrochloric acid and must J;tve a
pH < 2. It is spotted on a paper strip and allowed to vapo- i

rate for 10-15 minutes. Diffusion of the solvent take place

in an atmosphere saturated with respect to the vapo:'!' of a
saturated solution of methyl acetate in water, and tl: tem-
perature is maintained constant at 22°. The solvent moves
sufficiently far in 20-30 minutes to effect a complete sep;' ; ation.
After evaporation of the solvent, the strip is made alka' ne by
exposure to ammonia vapour and then sprayed with a 1 per
cent solution of diphenylcarbazide in alcohol. Mer, ITy is
indicated by a narrow blue band in the dry solvent front.

The Platinum Metals: Pt, Pd, Rh, Jr, Ru, Os aid Au.
The metals are present as their chlorides or sodium chlor i-salts.
The solvent used is methyl ethyl ketone containing 30 p r cent
(vjv) of hydrochloric acid (d 1'18); it is freshly prepared The
solution is spotted on the paper strip and allowed ,) dry
thoroughly in the air. The atmosphere in the separation
vessel is saturated with respect to the solvent. F, 'r the
detection of Pt, Pd, Au and Rh, 0'5N stannous chlo ide in
dilute hydrochloric acid is a suitable developing rear 'nt; a
mixture of stannous chloride and potassium iodide soh:, ion is
somewhat more sensitive. Iridium is reduced to the co] urless
iridium trichloride by the stannous chloride, but can 1)e re-
oxidised to the brown tetrachloride by chlorine water.
Ruthenium and osmium are detected by spraying with a s ,lution
of thiourea in 5N hydrochloric acid; warming is ne< ussary
to develop the colours fully.
4) Paper Ohromatography 629
The RJ! values are: Ru, 0-08; Rh +
Ir, 0·10; Pd, 0-60; Pt,
0-80; Au, 0-95_ The separation of the four elements Rh, Pd,
Pt and Au is comparatively easy_
Gold from the Platinum Metals. The metals are present
as chlorides in hydrochloric acid (concentration> 2N). The
solvent is diethyl ether containing 2 per cent (w/v) of dry
hydrogen chloride and 7·5 per cent (v/v) of dry methyl alcohol.
The solution is spotted upon filter paper and the strip dried
for one hour only. The separation is conducted in an atmo-
sphere of soke_nt vapour_ The solvent mixture extracts gold
in a narrow ba~ the solvent front, while the platinum •
metals remain in the original spot; the developing reagent is
0'5N stannous chloride in dilute hydrochloric acid. It is easy
to detect I fLg- of gold in the presence of more than 100 times
the quantity of platinum metals_ i
Selenium and Tellurium. The elements are present as
selenite and tellurite in dilute nitric acid solution. The mixture
is spotted upon paper and dried thoroughly in the air. The
solvent is dry n-butyl alcohol containing 4 per cent (v/v) of
dry methyl alcohol. The atmosphere in the separation vessel
is saturated with respect to the solvent vapour and the relative
humidity is also maintained at 50 per cent by means of a
saturated solution of calcium nitrate. The solvent is allowed
to diffuse 8-10 cm. down the strip (ca. 2 hours)_ Mter evapo-
ration of the solvent, the strip is sprayed with 0·5N stannous
chloride in dilute hydrochloric acid. The tellurium is indicated
by a black band (RJ! 0'1) and the selenium as an orange band
(RF 0·5). It is possible to detect 1-5 fLg. of Se in the presence
of I mg. of Te by this method.
Scandium, Thorium and the Rare Earths. The metals
are present as nitrates in dilute nitric acid solution. The
solvent is tetrahydrosylvan containing 5 per cent (v/v) of water
and 10 per cent (vjv) of nitric acid (d 1'42). The mixture is
spotted upon paper and dried thoroughly in the air. The
relative humidity inside the extraction vessel is maintained at
80 per cent by means of a saturated solution of ammonium
chloride. Mter the solvent has diffused about 15 cm. down
the solvent strip, it is allowed to evaporate, and the strip is
placed for about 10 minutes in an atmosphere of ammonia
vapour. The paper chromatogram is then sprayed with an
alcoholic solution of alizarin and finally with N acetio aoid.
The following results are obtained. -
630 Qualitative Inorganic Analysis [X,

RJ! Colour of band

Th 0·96 Violet-blue.
So 0·17 Violet.
Rare earths 0·00 Violet-blue.

Scandium can also be separated from the rare earths bv

using methyl acetate containing 10 per cent (v/v) of water an:l
5 per cent (v/v) of nitric acid (d 1'42) as solvent. The strip is
subjected to a solvent run of 25 cm. Scandium is then found
in a narrow strip (RF 0·17), but thorium forms 1\ more diffuse
band.
Uranium in Mineral Ores. An approximately 10 per
cent solution of the sample containing 25-50 per cent of free
nitric acid (by volume) is prepared by a suitable method (e.g. a
potassium hydroxide or sodium peroxide fusion, followed by
treatment with. nitric acid}. (}·(}5 mL of th.e sample is spotted
upon filter paper in the usual manner and allowed to dry in
the air. The solvent consists of tetrahydro-sylv-an (2-methyl
tetrahydro-furan) saturated with water and to which sufficient
concentrated nitric acid has been added to give a 2·5-10 per
cent concentration of nitric acid. The paper strip is removed
when the solvent front has moved 5-7 cms. beyond the test
patch, and dried in a current of warm air. 'rhe uranium
moves in a narrow band near the solvent front. The paper is
sprayed with 1 per cent potassium ferro cyanide solution. A
brown stain appears in the presence of uranium. The quantity
of uranium may be estimated by comparison with standard
stains prepared with known amounts (0·1-200 fLg.) of uranium.
Zirconium and Hafnium. This separation must rank as
one of the major achievements of inorganic pftper chroma-
tography. The metals are present as zirconyl and hafnyl
nitrates; basic nitrates must be absent since these l:tre immobile.
The mixture is best prepared by digesting the sample at 80°0
with concentrated nitric acid and evaporating the excess of
acid at the same temperature under reduced }Jressure: tho
product gives a clear solution when dissolved in water.
The solvent is prepared by adding slowly 30 mL of concen-
trated nitric acid (d 1·42) to 70 ml. of dichlorotriethylene glycol;
the mixture is stable for 2-3 days at room temperature. .A
total of 150 fLg. of mixed oxides can be handled with a Whatman
No. 1 paper strip, 3 em. wide. The solution (0'02 ml.) is
4] Paper Ohromatography 631
applied to the paper and, without drying, is immediately trans-
ferred to the extraction vessel. The chromatogram is allowed
to run for 18 hours; the solvent moves about 3 cm. per hour,
and drips from the end of the strip at the end of the period.
The wet strip is sprayed with a saturated solution of alizarin in
ethyl alcohol containing 5 per cent (v/v) of 2N hydrochloric
acid. The strip is then heated gently, care being taken that it
never becomes completely dry; it is resprayed with the reagent,
if necessary. The characteristic red lines of the zirconium and
hafnium lakes appear slowly against the yellow background of
the reagent. Narrow bands are obtained with RF values of
0·1 for Hf and 0·2 for Zr. It is possible to detect 2 I-'g. of each
metal, and also the presence of about 2 per cent of hafnium in
commercial zirconium nitrate.
 APPENDIX

A, 1. ATOMIC WEIGHTS OF ELEMENTS (1952)

Aluminium, Al 26·98 Molybdenum, Mo 95·95

Antimony, Sb 121·76 Nickel, Ni 58·69
Argon, A 39·944 Niobium, Nb 92·91
Arsenic, As 74·91 Nitrogen, N 14·008
Barium, Ba 137·36 Osmium, Os 190·2
Beryllium, Be 9·013 Oxygen, 0 16·000
Bismuth, Bi 209·00 Palladium, Pd 106·7
Boron, B 10·82 Phosphorus, P 30·975
Bromine, Br 79·916 Platinum, Pt 195·23
Cadmium, Cd 112·41 Potassium, K 39·100
Calcium, Ca 40·08 Radium,Ra 226·05
Carbon, C 12·010 Rhenium, Re 186·31
Cerium, Ce 1~0·13 Rhodium, Rh 102·91
Chlorine, Cl 35·457 Ruthenium, Ru 101·7
Chromium, Cr 52·01 Scandium, Sc 44·96
Cobalt, Co 58·94 Selenium, Se 78·96
Copper, Cu 63·54 Silicon, Si 28·09
Fluorine, F 19·00 Silver, Ag 107·880
Germanium, Ge 72·60 Sodium, Na 22·997
Gold, Au 197·2 Strontium, Sr 87·63
Hafnium, ill 178·6 Sulphur, S 32·066
Helium, He 4·003 Tantalum, Ta 180·88
Hydrogen, H 1·008 Tellurium, Te 127·61
Iodine, I 126·91 Thallium, Tl 204·39
Iridium, Ir 193·1 Thorium, Th 232·12
Iron, Fe 55·85 Tin, Sn 118·70
Lanthanum, La 138·92 Titanium, Ti 47·90
Lead, Pb 207·21 Tungsten, W 183·92 i
Lithium, Li 6·940 Uranium, U 238·07
Magnesium, Mg 24·32 Vanadium, V 50·95
Manganese, Mn 54·93 Zinc, Zn 65·38
Mercury, Hg 200·61 Zirconium, Zr 91·22

632
 2] Appendix 833
A, 1. REAGENTS

CONCENTRATED ACIDS

Specific Per cent by Approximate

gravity weight normality

Acetic acid, glacial 1·05 99·5 17N

Hydrobromic acid 1·49 48 9N
Hydrochloric acid H9 38 12N
Hydrofluoric acid 48 27N
Hydriodic acid 1·70 57 7N
Nitric acid 1·42 70 16N
Perchloric acid 1·54 60 9N
Phosphoric acid 1·69 85 45N
Sulphuric acid 1·84 96 36N

DILUTED ACIDS
Approximate
normality
Acetic acid.-Dilute 285 ml. of the concentrated
acid to 1 litre with water 5N
Hydrochloric acid.-Dilute 430 m!. of the con·
centrated acid to 1 litre with water 5N
Nitric acid.-Dilute 310 m!. of the concentrated
acid to 1 litre with water 5N·
Sulphuric acid.-Pour 140 m!. of the concen·
trated acid slowly and with constant stirring into
500 ml. of water, cool, and dilute to 1 litre 5N
Sulphurous acid.-Prepare a saturated solu.
tion in water (6-7 per cent by weight) 0'3N

BASES
Ammonia solution, concentrated.-The com-
mercial product, sp. gr. 0-88, contains about 28 per
cent NHs 15N
Ammonia solution, dilute.-Dilute 335 m!. of
the concentrated solution to 1 litre with water ... 5N
Barium hydroxide solution.-Shake 70 grams
of crystallised barium hydroxide Ba(OHh,8H20
with 1 litre of water; filter or siphon off the liquid
(saturated solution) and protect from CO 2 of the
air 0-4N
634 Qualitative Inorganic Analysis [A,
Approximate
normality
Calcium hydroxide solution.-Shake 2-3
grams of calcium hydroxide with 1 litre of water;
filter or siphon off the liquid (saturated solution)
and protect from CO 2 of the air 0'04N
Potassium hydroxide solution.-Dissolve 125
grams of the ordinary "pure" sticks (about 90 per
cent KOH) or, better, pellets in water and dilute
to 1 litre 2N
Sodium hydroxide solution.-Dissolve 220
grams of the ordinary "pure" sticks (about 90 per
cent NaOH) or, better, pellets in water and dilute
to 1 litre 5N
4
SALT SOLUTIONS*
Ammonium acetate, NH4.C 2 H 3 0 2 (M.W.
77).-Dissolve 231 grams of the salt in 1 litre of
water ... 3d'
Ammonium carbonate (the commercial salt
is a mixture of NH4 HC0 3 and NH4C0 2 NH 2).-
Dissolve 160 grams of the salt in a mixture of
140 ml. of concentrated ammonia solution and 860
ml. of water .. , 4N
Ammonium chloride, NH 4CI (M.W. 53'5).-
Dissolve 270 grams of the salt in I litre of water... 5N
Ammonium nitrate, NH4N0 3 (M.W. 80).-
Dissolve 80 grams of the salt in 1 litre of water ... N
Ammonium oxalate, (NH4)2C204,H20 (M.W.
142).-Dissolve 35 grams of the crystalline salt in
1 litre of water 0·5.N
Ammonium sulphate, (NH4)zS04 (M.W. 132).
-Dissolve 132 grams of the salt in 1 litre of water 2N
Ammonium thiocyanate, NH4SCN (M.W.
76).-Dissolve 38 grams of the salt in 1 litre of - -
water ... 0·5.N
Yellow ammonium sulphide solution,
(NH4hS",.-Use the solution available com-
mercially. It may be prepared, if desired, as
follows. Saturate 150 ml. of concentrated am-
monia solution with H 2 S, keeping the solution cold;
add 10 grams of flowers of sulphur and 250 ml. of
concentrated ammonia solution, shake until the
sulphur has dissolved and dilute to 1 litre 6N
• The common reagents chlorine water, bromine water, iodine soluti
hydrogen sulphide water are included here.
2J Appendix 635
Approximate
normality
Colourless ammonium sulphide solution,
NH4HS.-Saturate 200 m!. of concentrated
ammonia solution cooled in ice water with H 2S,
add an equal volume of concentrated ammonia
solution and dilutr with water to 1 litre. This
solution is preparbd as required 6N
Barium chloride, BaCI 2,2H 20 (M.W. 244).-
Dissolve 61 grams of the salt in 1 litre of water ... 0·5N
Bromine water, Br2 (M.W. 160).-A
saturated aqueous solution is prepared by shaking
35 grams or 11 ml. of liquid bromine with water.
Add more bromine, if necessary, to ensure a
slight excess.
Calcium chloride, CaCI2 ,6H 20 (M.W. 219).-
Dissolve 55 grams of the hydrated salt in 1 litre
of water 0·5N
Calcium sulphate, CaS04,2H zO (M.W. 172).
-Shake 3 grams of the salt with 1 litre of water;
filter or decant the saturated solution after several
hours ... O'03N
Chlorine water, Cl2 (M.W. 7l).-Saturate 250
ml. of water with chlorine. The chlorine may be
generated by dropping concentrated HOI upon
KMn04. Preserve in a dark-coloured bottle. The
solution contains 6·5 grams of 012 per litre.
Cobalt nitrate, Co(NOsb6H 20 (M.W. 291).-
Dissolve 44 grams of the salt in 1 litre of water ... 0·3N
Copper sulphate, CuS04,5H 20 (M.W. 249·5).
-Dissolve 125 grams of the salt in 1 litre of water O·5N
containing 3 ml. of concentrated sulphuric acid ... (as oxidant)
Ferric chloride, FeCI3 ,6H20 (M.W. 270).-
Dissolve 135 grams of the hydrated salt in 1 litre O·f)N
of water containing 20 m!. of concentrated HOI ... (as oxidant)
Ferrous sulphate, FeS04,7H2 0 (M.W. 277).-
Dissolve 140 grams of the salt in 1 litre of water O'5N
containing 7 ml. of concentrated H 2S04 .•• (as reductant)
Hydrogen sulphide solution, H 2 S (M.W. 34).
-Saturate 250 ml. of water with HzS gas derived
from a Kipp's apparatus. The solution contains
approximately 4·2 grams of HzS per litre 0'05N
636 . Qualitative inol'ganic Analysis [At
Approximate
normality
Iodine solution, I'l. (M.W. 254).-Dissolve 12·7
grams of iodine in a solution of 20 grams of pure
KI in 30 ml. of water, and dilute to 1 litre with
water ... O'IN
Lead acetate, Pb(C 2H 3 0 2 b3H 2 0 (M.W. 379).
-Dissolve 95 grams of the salt in 1 litre of water 0·5N
Magnesium sulphate, MgS04,7H2 0 (M.W.
246).-Dissolve 62 grams of the salt in 1 litre of
water ... 0'5N
Mercuric chloride, HgCl 2 (M.W. 272).-Dis-
solve 27 grams of the salt in 1 litre of water 0'2N
Potassium chromate, K2Cr04 (M.W. 194).-
Dissolve 49 grams of the salt in 1 litre of water ... 0·5N
(as precipitant)
futassium cywllide, KeN (AI. W. S5l.-lJis-
solve 32·5 grams of the salt in 1 litre of water
(POISONOUS) 0'5N
Potassium ferricyanide, K 3[Fe(CN)6] (M.W.
329}.-Dissolve 55 grams of the salt in 1 litre of O'5N
water ... (as precipitant)
Potassium ferrocyanide, K4[Fe(CN)6],3H 2 0
(M.W. 422).-Dissolve 53 grams of the salt in 1 0'5N
litre of water ... . .. (as precipitant)
Potassium iodide, KI (M.W. 166).-Dissolve
83 grams of the salt in 1 litre of water 0'5N
Potassium permanganate, KMn04 (M.W.
316).-Dissolve 3·2 grams of the salt in 1 litre of O'IN
water; filter through glass wool (as oxidant)
Potassium thiocyanate, KSCN (M.W. 97).-
Dissolve 49 grams of the salt in 1 litre of water ... 0'5N
Silver nitrate, AgN0 3 (M.W. 170).-Dissolve
17 grams of the salt in 1 litre of water O'IN
Silver sulphate, Ag 2 S04 (M.W. 312).-Dis-
solve 8 grams of the salt in 1 litre of water. This
is nearly a saturated solution 0'05N
Sodium acetate, Na.C 2H 3 0 2 ,3H2 0 (M.W.
136).-Dissolve 408 grams of the crystallised salt
in 1 litre of water 3N
2J Appendix 637
A. pproximate
normality
Sodium carbonate, Na2 COs,lOH2 0 (M.W.
286).-Dissolve 430 grams of the crystallised salt
in 1 litre of water 3N
Disodium hydrogen phosphate Na2HP04>-
12H2 0 (M.W. 358).-Dissolve 120 grams of the salt
in 1 litre of water N
Stannous chloride, SnCl2 ,2H 20 (M.W. 226).
-Dissolve 56 grams of the salt in 100 m!. of con-
centrated Hel and dilute to 1 litre. Keep a few
pieces of tin in the bottle to prevent oxidation ... O'5N
Zinc Nitrate, Zn{NOS)2,6H 2 0 (M.W. 297).-
Dissolve 150 grams of the salt in 1 litre of water O·5N

SPECIAL REAGENTS
Experimental details for the preparation of many of the
special, largely organic, reagents are given in the text; these
can be locater' by reference to the Index. Some reagents,
which are required for macro and semimicro analysis and which
are not described in detail in the text, are collected below.
Ammonium molybdate reagent.-Method A. Dissolve
45 grams of the commercial salt (NH4)6Mo7024,4H20 (a para-
molybdate) or 40 grams of pure molybdenum trioxide Mo0 3 in
a mixture of 70 ml. of concentrated ammonia solution and 140
ml. of water; when solution is complete, add it very slowly
and with vigorous stirring to a mixture of 250 ml. of concen
trated nitric acid and 500 ml. of water; dilute to 1 litre. Allow
to stand 1-2 days and decant the clear solution.
Method B. Dissolve 45 grams of pere commercial ammonium
molybdate in a mixture of 40 ml. of concentrated ammonia
solution and 60 m!. of water, add 120 grams of ammonium
nitrate and dilute to 1 litre with water.
The alkaline solution of ammonium molybdate keeps better
than does the nitric acid solution; there is little tendency for
the separation of solid. Before using the alkaline solution, it
is important to ensure that the test solution contains a slight
excess of nitric acid.
Dimethylglyoxime reagent.-Dissolve 1 gram of di-
methylglyoxime in 100 ml. of rectified spirit (95 per cent ethyl
alcohol).
 i
640 Qualitative Inorganic' Analysis [A,

SOLID REAGENTS
Aluminium (turnings or foil), Al Potassium nitrite, KNOt
Ammonium chloride, NH,Cl Potassium iodide, KI
Ammonium nitrate, NH 4 NO a Potassium permanganate, '(MnO,
Ammonium thiocyanate, NH,SCN Potassium persulphate, K )IOS
Asbestos fibre, for filters Silica (precipitated), SiO a
Borax, Na 2B,07,lOH 2 0 Sodium acetate (fused),
Calcium chloride, CaCI. Na.C 2H aO a
Calcium fluoride, CaF 2 Sodium bicarbonate, NaIl' ~03
Copper (foil or turnings), Cu Sodium bismuthate, NaB'()a
Devarda's alloy (powder) Sodium bitartrate, NaH.\ '4H,Os
Ferrous sulphate, FeSO,,7H 20 Sodium hydroxide, NaOH
Fusion mixture, NaaCO a + K 2CO a Sodium nitrite, NaNO.
Glass wool Sodium nitroprusside,
Iron (wire or powder), Fe Na 2[Fe(CN).NO),2H 2(;
Lead dioxide (Mn free), PbO. Sodium perborate, NaB(' ,,4H 20
Litmus paper (red and blue) Sodium sulphite, NaaSO iH 20
Manganese dioxide (precipitated), Sodium thiosulphate,
MnO. Na 2S I O a,5H 20
Methyl violet paper Stannic chloride, SnCl"E" (sO
Microcosmic salt, Stannous chloride, SnClc,JH,O
Na(NH,)HPO,,~"t:::20 Starch (soluble)
Potassium bisulphate, KHSO, Starch-iodide paper
Potassium carbonate, KICO, Sulphur (flowers), S
Potassium chlorate, KCIO a Tartaric acid, H •. C,H,Os
Potassium cyanide, KCN Tin (pure foil), Sn
Potassium dichromate, K 2Cr,O, Turmeric paper
Potassium nitrate, KNO a Zinc (20 mesh), Zn

pH Indicator papers (narrow range: 2'5-4'0,4·0-5·5,5'5-, '),7'0-8·5

8'5-10'0; wide range: 2'0-10·5).

A, 3. TEST SOLUTIONS
In order that the student may be able to judge tl ' relative
proportions of the constituents of mixtures from t e size of
precipitates, it is essential that he employs solutions )f known
strengths from the very outset. The test solutionE' ,lescribed '
below contain 10 milligrams of the cation or ani( i per ml.
If desired, stock solutions containing 100 milligral 1 per ml.
may be prepared (provided the solubility of the s: it is suffi-
ciently high) and these subsequently diluted. Purl '3hemicals
should be employed for the preparation of these sol, dons.
The cations are arranged in the order of the G' 0UpS; the
anions in the order in which they are described in ( 'Iapter IV.
3] Appendix
CATIONS
Grams oj
Formula oj salt per Special precautions in
Cation dry sall litre oj preparation of the
solution solution

14·0 I Use
I
100
HNO •.
ml. of dilute

Ag+ 15·8
Pb++ 16·0 Use5ml. ofdiluteHNO •.
18·3 Use 5 ml. of dilute
H.O.HaOa.
Hg++ (ic) 13·5
Bi+++ 23·2 Dissolve salt in 100 ml.

00++ OoSO,,5H,O 39·3

I of dilute H..,\O. and
dilute to I litre.
Use5ml.ofdiluteH 2SO,.
or CuCl.,2H.O 26·8 Use 5 ml. of dilute HCI.
Cd++ 3CdSO,,8H.O 22·8 Use 5ml. ofdiluteH.SO,.
or Cd(NOs) •.4H.O 27·8 U Be 5 ml. of dilute HNO s.
As (ous) As,O, 13·2 Dissolve in hot water con-
taining 20 mi. of dilute
HOI and dilute to llitre.
As (ic) 15·3 As for arsenious com-
53'7 pound.
Sb (ous) 18·8 Dissolve in fiOO mi. of
dilute HCI and dilute
to 1 litre.
ISb (ic) SbCI, 24'5 As for antimonious com-
pound.
8n++ (ous) SnCI •. 2H.O 19·0 Dissolve in 100 mI. of
concentrated HOI and
dilute to 1 litre.
8n++++ (ic) 29·5 Dissolve in 500 ml. of
dilute HOI and dilute
to I litre.
Fe++ (ou.'!) FeSO"(NH,).So,,. 70·3 Use 20 mI. of dilute
6H.O H 2SO,.
Fe+++ (ic) FeCl.,61l.0 48·4 Use 50 mI. of dilute HOI.
Cr+++ CrOI.,61l.0 51·2 Use 50 ml. of dilute HOI.
or K.SO,,- 96·0 Use 50 ml. of dilute
Cr.(SO,).,241l.0 H 2 SO,.
Al+++ Al.(SO.).,18H.O 123·5 Use 20 mI. of dilute
or K.SO"Al.(SO.>S,. H 2 SO,.
24HP 175·9 Use 20 ml. of dilute
H.SO,.
00++ Oo(NO.).,6H.O 49·4
Ni++ NiSO.,7H.O 47·8
or NiOl.,61l.0 40·5
Mn++ MnSO.,4H.O 40·7
or MnOI.,4H.O 36·0
Zn++ ZnSO.,7H.O 44'0
or Zn(NO.).,6H.O 45·5
Ba++ BaCI.,2H.O 17'8
or Ba(NO.). 19·0
Sr++ SrCI.,6H.O 30'4
or Sr(NO.).,4H,O 32·4
C8++ CaOI.,2H.O 36'7
or Oa(NO a),,4H.O 58·9

21+
642 ) Qualitative lrwrganic Analysis [A,
Cations (contd.) ..,- ~
~
Grams of
Formula of salt per Special precau' )rt8 in
CIBion dry 8alt litre oj preparation the
Bolution 80lutio?

Mg++ Mg80,,7H,O or 101·4

---
Mg(NO ala,6H,O 105·4
K+ KCl 19·1
or KNO, 25·9
Na+ NaCI 25·4
or NaNO, 37·0
NH,+ NH.Cl
or NH,NO a
29·7
44·4 ,'","" ~
r
Note. If a slightly turbid solution is obtained with the catioIll' ,f Groups
HIB, IV and Mg, about 5 ml. per litre of the dilute acid, corres: Jnding to
the anion of the salt, should be added.
ANIONS
Grams of <'LEt per
Anion Formula of Balt litre of 8, ,,;,lion
CO.- Na.OO.,10H.O 49· 3
SO.- Na,SO.,7H,O'" 31· 5
8,Oa- Na.S,O,,5H.O· 22· 2
S-- Na.S,9H,O 75· I
NO.- NaNOs· 15· o
ON'"' KCN 25· o
CNO- KCNO 19',3
SC~ KCNS 16·'o
[Fe(CN).]- K,[Fe(ON).],3H.O 19· 9
[Fe(CN).]- Ka[Fe(ON).J 15" 5
CC NaCI 16· 5
Br- KBr 14· 9
r KI 13· I
F- NaF 22· I
AsO.- or AsO.- (arsenite) NaAs° a 12· o
NO.-
ClO,-
BrO,-
10,-
CIO,-
BO.- (borate)
,
AsO,- (arsenate) Na.HAsO,,7H aO
NaNO,
KOIO.
KBrO,
KIO,
KOIO,
22· 5
13· 7
14· 7
13· I
12· 2
12· 3
22· 5
Na.B,07,10H.O
80,- Na,80"lOH,O 33· 6
SiO a- Na.8iO. 16· 1
[8iF.]- (silicofluoride) Na.[8iF.] 13· 2
PO,-- Na eHPO,,12H O 37· 7
HPO.- (phosphite) Na,HPO.,2H, b 27· o
H.PO.- (hypophosphite) NaH.PO"H,O 16·'3
Cro,- K,CrO, 16· 7
MnO,- _ KMnO, 13· 3
C,H,O, (aeetate) Na. C,H aO,,3R.0 23·1
H.CO. (formate) n.COaNa 13' 5
C,O,- (oxalate) Na,.C,O, 15·2
C,H,O.- (tartrate) NaK.C,H,0.,4H,O 19·1
C,H,07- (citrate) N aa' C.H.0 7 ,2H,O 15·6
C,H,O,- (salicylate) C.H,(OH)CO,Na. 1l·7
C,H,O.- (benzoate) C,H,COIK 13·:'
C,H,O,- (succinate) O,H,(CO.Na) • 14'
... Th_ IIOlutions do not keep well and should be freshly pre,.a.red.
4] Appendix 643

A.4. BUFFER SOLUTIONS

The following standards are suitable for the calibration of
pH meters and for other purposes which require an accurate
knowledge of pH.

pH at
Solution
12°0 25°0 38°0

0'1M KHC204,H2C204,2H20 - 1·48 1·50

0'1M HCI +
0·09M KCI - 2·07 2·08
Saturated solution of potas.
sium hydrogen tartrate,
KHC4H4 0 0 - 3·57 -
O'05M potassium hydrogen
phthalate, KHC BH 40 4 4·000 (15°0) 4·005 4·015
0'1M CHsCOOH + 0'1M
CHgCOONa 4·65 4·64 4·65
0'025M KH zP04 + 0'025M
Na zHP04 ,l2H 2 O - 6·85 6·84
O'05M Na zB4 0 7 ,12HzO - 9·18 9·07

Solutions of known pH for colorimetric determinations are

conveniently prepared by mixing appropriate volumes of certain
standard solutions. The compositions of a number of typical
buffer solutions are given below.

pH Range: 1·40-2·20 at 25°C (German and Vogel, 1937)

X mi. oj O'lM p.toluenesulphonic acid monohydrate (19·012 gram8

per litre) and Y ml. oj 0'1M 80dium p.toluene8ulphonate (19·406
grams per litre), diluted to 100·0 mi.

X (mi.) Y (mi.) pH X (ml.) Y (mi.) pH

48·9 1'1 1·40 13·2 36·8 1·90
37·2 12'8 1·50 10·0 40·0 2·00
27,4 22'6 1·60 7·6 42·4 2·10
19·0 31'0 1·70 4·4 45·6 2·20
16·6 33'4 1·80
644 Qualitative Inorganio AnalY8is '[A, -

pH Range: 2·2-8·0 (McIlvaine, 1921)

20·00 ml. mixtures of X ml. of 0·2M Na2lIP04 and Y rll!. of

O·lM citric acid.
-
X (ml.) Y (ml.) X (ml.) Y (ml.) j,II
pH
Na2HP04 Citric acid Na2HP04 Citric acid
-
0·40 19·60 2·2 10·72 9·28 f. 2
1·24 18·76 2·4 11·15 8·85 ;, !
2·18 17·82 2·6 11·60 8·40 it d
3·17 16·83 2·8 12·09 7·91 f)~
4·11 15·89 3·0 12·63 7·37 (d)
4·94 15·06 3·2 13·22 6·78 (\~
5·70 14·30 3·4 13·85 6·15 tl t
6·44 13·56 3·6 14·55 5·45 {) ! i

7·10 12·90 3·8 15·45 4·55 fH

7·71 12·29 4·0 16·47 3·53 7:1
8·28 .11·72 4·2 17·39 2·61 7~
8·82 J IH8 4·4 18·17 1·83 7 I
9·35 10·65 4·6 18·73 1·27 7 ,i
9·86 10·14 4·8 19·15 0·85 7'·~
10·30 9·70 5·0 19·45 0·55 8"
~-
4] Appendix 645

pH Ranges: 2·2-3·8, 4·0-6·2, 5·8--8·0, 7'8-10·0 at 20°C

(Clark and Lubs, 1916)

(A) pH 2·2-3·8. 50 MI. 0·21v] KHphthalate P mi. 0·2M -+

HCl, diluted to 200 ml.
(B) pH 4·0-6·2. 50 MI. 0·2111 KHphthalate Q mI. 0·2M -+
NaOH, diluted to 200 ml.
(C) pH 5·8-8·0. 50 j}ll. 0·2jl1 KH 2P04 R mi. 0·2M +
NaOH, diluted to 200 ml.
(D) pH-r·S-10·0. 50Ml. O·2M H3B03and a'2M lWl* +Sml.
0·2M NaOH, diluted to 200 mi.

A B C D
I

P (mt.) pH I Q (mi.)
NaOH
I pH R (mi.)
NaOH pli S (ml.)
NaOH pH
HeI I
46·60 2·2 0·40 4·0 3·66 5'8 2·65 7·8
39·60 2·4 3·65 4·2 5·64 6'0 4·00 8·0
33·00 2·6 7·35 4·4 8·55 6'2 5·90 8·2
26·50 2·8 12·00 4·6 12·60 6'4 8·55 8·4
20·40 3·0 17·50 4·8 17·74 6'6 12·00 8·6
14·80 3·2 23·65 5·0 23·60 6'8 16·40 8·8
9·95 3-4 29·75 5·2 29·54 7'0 21·40 9·0
6·00 3·6 35·25 5·4 34·90 7'2 26·70 9·2
2·65 3·8 39·70 5·6 39·34 7'4 32·00 9·4
- - 43·10 5·8 42·74 7'6 36·85 9·6
- - 45,.40 6·0 45·17 7'8 40·80 9·8
- - 47·00 6·2 46·85 8'0 43·90 10·0

* That is, a solution containing 12'369 h'l'ams of HaBO. and 14'911 grams
of KCI per litre.
646 CJuat~tatwe lnorgan~c .AnatY8M

pH Range: 2·6-12·0 at 18°C-Universal Buffer Mixture

(Johnson and Lindsey, 1939)
A mixture of 6·008 grams of A.R. citric acid, 3·893 grams of A.R.
potassium dihydrogen phosphate, 1·769 grams of A.R. boric :id
and 5·266 grams of pure diethylbarbituric acid is dissolved in w :"er
and made up to 1 litre. The pH values of mixtures of 100 m of
this solution with various volumes (X) of 0'2N sodium hydro; Ide
solution (free from carbonate) are tabulated below.

pH X (ml.) pH X (ml.) pH X (ml

2·6 2·0 5·8 36·5 9'0 72·7
2·8 4·3 .6·0 38·9 9'2 74·0
3·0 6·4 6·2 41·2 9'4 74·9
3·2 8·3 6·4 43·5 9'6 77·6
3-4 10·1 6·6 46·0 9'8 79·3
3·6 11·8 6·8 48·3 10'0 80·8
3·8 13·7 7·0 50·6 10'2 82·0
4·0 15·5 7·2 52·9 10'4 82·9
4·2 17·6 7·4 55·8 10'6 83·9
4·4 19·9 7·6 58·6 10'8 84·9
4·6 22·4 7·8 61·7 11'0 86·0
4·8 24·8 8·0 63·7 11'2 87·7
5·0 27·1 8·2 65·6 11'4 89·7
5·2 29·5 8·4 67·5 11'6 92·0
5·4 31·8 8·6 69·3 .11'8 95·0
5·6 34·2 8·8 71·0 12'0 99·6
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 LOGARITHMS

0 1 21~_ i 4- ~- ~1_7_ 8 I9 1 23 41 5 6 78 9
51 7076 7084 709S 7101 7110 711R 712617135 7143 7152 1 2 3 3 4 6 6 7 8
52 7160 7168 7177 7185 7193 7203 7210 7218 7226 7235 1 2 2 3 4 5 6 7 7
53 7243 7251 7259 7267 7275 7284 7292 7300 7308 7316 1 2 2 3 4 5 6 6 7
64 7324 7332 7340 7348 7356 736·! 7372 7380 7388 7396 1 2 2 3 4 5 6 6 7
55 7404 7412 7419 7427 7435 7443 7451 7459 7466 7474 1 2 2 3 4 5 6 6 7
56 7482 7490 7497 7505 7513 7520 7528 7536 7643 7<151 1 2 2 3 4 6 6 6 7
57 7559 7566 7674 7582 7689 7597 7604 7612 7619 7627 1 2 2 3 4 5 5 6 7
58 7634 7642 7649 7657 7664 7672 7679 7G86 7694 7701 1 1 2 3 4 4 5 6 7
69 7709 7716 7723 7731 7738 7745 7752 7760 7767 7774 1 1 2 3 4 4 6 6 7
-60 '--- --
7782 7789 7796 7803 7810 7818 7825 7832 7839 7846 1 1 2 3 4 4 6 6 6
-- - - -
61 785.1 7860 7868 7875 7882 7896
f--~
78)"\)
f------
7903 7910 7917 1 1 2 3 4 4 6 n 6
62 7~24 7931 7938 7945 7952 79,'ln 7966 7an 7980 7987 1 J 3 3 4 :; 6
63 7993 80(JO 8007 8014 8021 S(c., 8035
64 8062 8069 8075 8082 8089 80,,!l; 8102
8041
8109
8048
8115
8055
8122
1
1
1
1
2
2
2
3
S
3
S
4,
4
5
5
"
f, 6
5 6
65 8129 8136
- -I - f--. I--
8142 8149 8156 81(;2 8169 8176 8182 8189 1 1 2 3 S
-4 -:; -:; -6
--
I - 1--- I - -
66 8195 8202 8209 8215 8222 82::S 8235 8241 8248 8254 1 1 2 3 3
------
4 :; l\ 6
67 821il 82fH 8274 8280 8287 82'.13 8299 8306 8312 8319 1 1 2 3 S 4 :; :; 6
68 8325 8331 8338 8344 8351 8307
8363 8370 8376 8382 1 1 2 3 l 4 4 :; 6
69 8388 8395 8401 8407 8414 8·1::0 8426 8432 8439 844. 1 1 2 2 3 4 4 5 6

70 8451
--
8457 8463 8470 8476 8-182 8488 8494 8500 8506 1 1 2 2 3 4 4 5 6
1 - 1---- '----
71 8513 8519 8525 8531 8537 8,13 8549 8555 8561 8567 1 1
,
2 2 3 4 4 5 :;

,,
72 8573 8579 8585 8591 8597 8!j1 13 8609 8615 8621 8627 1 1 2 3 4 4 :; :;
73 8633 8639 8045 8G51 8657 8(;1;3
8669 8675 8681 8686 1 1 2 2 3 4 4 6
74 8692 8uns 8704 8710 8716 87:.12 8727 8733 8730 874. 1 2 a 4 6 6
75 8761 8766 8762 8768 8774 8779 8785 8791 8797 . 8802 1 __
1

1
2
, 2 3 a ,, 6
i- I- - - --
76 8808 8814 8820 8825 8831 8837 8842 8848 8854 8859 1 1 2 2 3 S 46 6
77 88·;5 8871 8876 8882 8887 8~n 8899 8904 891U 8915 1 1 2 2 3 S ... 4 6
78
79
8921
8976
8927
8982
8932
8987
8938
8993
81143 8[\<19 8954
8998 9004 9009
8960
9015
89G5
9020
---
8971
9025
1
1
1
1 ,
2 2
2
3
a
3 4 4- 6
3 4 ... 6
80 9031 9036 9042 9047 9053 9058 9063 9069 9074 9079 1 a s ... ... 6
81 9085 9090 9096 9101 9106 9112 9117 9122 9128 9133 1 1 2 2
82 9138 9143 9149 9154 9159 QJ(;6 9170 9175 9180 9186 1 1 2 2
1 2 2
3
3
3
S
... 6,
4 4 :;
83 9191 9196 9201 9206 9212 9217 0222 9227 9232 9238 1 1 2 2 a s 4 4 6
84 9243 9248 9253 9258 9263 9:!69 9274 9279 9284 9289 1 1 S 2 3 S 4 4 6
85 9294 9299 9304 9309 9315 9320 9325 9330 9335 9340 1 1 2 2 3 3 ... 4 6
-- -I- 1----
86 9346 9350 9356 9360 936S D:J70 9375 9380 9385 9390 1 1 2 2 3 S 4 4 6
87 9395 9·tOO 9405 9410 9415 t).12Q 9420 9430 9435 9440 0 1 1 2 Z S, 3 4 4
88 9445 9450 9455 9460 94li5 \).169 9474 9479 9484 9489 0 1 1 2 2 $ 3 4 4
89 9494 9499 9504 9509 9513 t1518 952a 9528 9533 9538 0 1 1 2 2 3 S 4 4
90 9042 9547 9552 9557 9562 U536 9571 9576 9S81 9586 0 1 1 S 2 S 3 ... 4
91 9590 9595 9600 9605 9609 uG14 9619 9624 9628 9633 0 1 1 ll. 2 S S ... 4

" "...
92 9638 9643 P647 9662 9u57 9661 9666 9671 9675 9680 0 1 1 2 2 S 3 4
93 9685 9689 9694 9699 9703 n08 9713 9717 9722 9727 0 1
94 9731 9736 9741 9746 9750 9754 9759 9763 9768 9773 0 1
1 2
1 , 2
2
S
S
3
3 4
4

, a
96 9771 9782 9786 9791 9795 0800 9805 9809 9814 9818 0 1
1-
96 9Bl13 9827 9832 9836 9841 9845 9850 9854 9859 9863 0 1
1
1 2
2

2 3
3
3
""
4 4

i
97 9868 9872 9877 9881 9886 \\890 9894 9899 9903 9908 0 1 1 II ~ 3 3
• 4.
98 9912 9917 9921 992~ 9930 9934 9939 9943 9948 9952 0
99 9956 9961 9965 9969 9974 0978 9983 9987 9991 9fJ96 0
1
1
1
1
2
2
2
2
3
•
3
S
4
S ""
 0 1 2 3 4 5 6 7 8 9 12 3 4 5 6 7 8
-00 1000 1002 1006 1007 1009 1012 1014 1016 1019 1021 0 0 1 1 1 1 , S

·01 1023 1026 1028 1030 1033 1035 1038 1040 1042 1045 0 0 1 1 1 1 2 2
·02 1047 1050 1052 1054 1057 1059 1062 1064 1067 1069 0 0 1 1 1 1 2 2
'03 1072 1074 1076 1079 1081 1084 1086 1089 1091 1094 0 0 1 1 1 1 2 2
·04 1096 1099 1102 1104 1107 1109 1112 1114 1117 1119 0 1 1 1 1 2 2 2

-os 1122 1125 1121 1130 1132 1135 1138 1140 1143 1146 0 1 1 1 1 2 2 2

006 1148 1151 1153 1156 1159 1161

--
1164 1167 1169 1172 0 1 1 1 1 2 2 2
'07 1175 1178 1180 1183 1186 1189 1191 1194 1197 1199 0 1 1 1 1 2 2 2
·08 1202 1205 1208 1211 1213 1216 1219 1222 1225 1227 0 1 1 1 1 2 2 2
'09 1230 1233 1236 1239 1242 1245 1247 1250 1253 1256 0 1 1 1 1 2 2 2

·10 1259 1262 1265 1268 1271 1274 1276

--
1279 1282 1285 0 1 1 1 1 2 2 ,
·11 1288 1291 1294 1297 1300 1303 1306
-- 1315
1309 1312 0 1 1 1 2 2 2 2
·12 1318 1321 1324 1327 1330 1334 1337 1340 1343 1346 0 1 1 1 2 2 2 2
·13 1349 1352 1355 1358 1361 1365 1368 1371 1374 1377 0 1 1 1 2 2 2 3
14 1380 1384 1381 1390 1393 1396 1400 1403 1406 1409 0 1 1 1 2 2 2 3
- -I - - - e-- - -
·15 1413 1416 1419 1422 1426 1429 1432 1435 1439 1442 0 1 1 1 2 2 2 3
._- - - f -
·16 1445 1449 1452 1455 1459 1462
----
1466 1469 1472 1476 0 1 1 1 2 2 2 3
·17 1479 1483 1486 1489 1493 1496 1500 1503 1507 1510 0 1 1 1 2 2 2 3
'18 1514 1511 1521 1524 1528 1531 1535 1538 1542 1[\45 0 I 1 1 2 2 2 3
·19 1549 1552 1556 1560 1563 1567 1570 1574 1578 1581 0 1 1 1 2 2 3 3
·20 1585 1589 1592 1596 1600 1603 1607 1611 1614 1618 0 1 1 1 2 2 3 S
1-
'21 1622 1626 1629 1633 1637 1641 1644 1648 1652 1656 0 1 1 2 2 2 3 3
·22 1660 1663 1667 1671 1675 1679 1683 1687 1690 1694 0 1 1 2 2 2 3 3
23 1698 1702 1706 1710 1714 1718 1722 1726 1730 1734 0 1 1 2 2 2 3 3
·24 1738 1742 1746 1750 1754 1758 1762 1766 1770 1774 0 1 1 2 2 2 3 3
'25 1778 1782 1786 1791 1795 1799 1803 1807 1811 1816 0 1 1 2 2 2 3 3
'26 1820 1824 1828 1832 1837 1841 1845 1849 1854 1858 0 1 1 2 2 3 3 3
1f1 1862 1866 1871 1875 1879 1884 1888 1892 1897 1901 0 1 1 2 2 3 S s
·28 1905 1910 1914 1919 1923 1928 1932 1936 1941 1945 0 1 1 2 2 3 3 4
'29 1950 1954 1959 1963 1968 1972 1917 1982 1986 1991 0 1 1 2 2 3 3 4
'30 1995 2000 2004 2009 2014 2018 2023 2028 2032 2037 0 1 1 2 2 3 3 4
'31 2042 2046 2051 2056 2061 2065 2070 2075 2080 2084 0 1 1 2 2 3 3 4
'32 2089 2094 2099 2104 2109 2113 2118 2123 2128 2133 0 1 1 2 2 3 3 4
'33 2138 2143 2148 2153 2158 2163 2168 2173 2178 2183 0 1 1 2 2 3 3 4
'34 2188 2193 2198 2203 2208 2213 2218 2223 2228 2234 1 1 2 2 3 3 4 4
----
·35 2239 2244 2249 2254 2259 2265 2270 2275 2280 2286 1 1 2 2 3 3 4 4
'36 2291 2296
--
I - - - I--
2301 2307 2312 2317 2323 2328 2333 2339 1 1 2 2
-
3 3 4 4
'37 2344 2350 2355 2360 2366 2371 2377 2382 2388 2393 1 1 2 2 3 3 4 4
·as 2399 2404 2410 2415 2421 2427 2432 2438 2443 2449 1 1 2 2 3 3 4 4
'39 2455 2460 2466 2472 2477 2483 2489 2495 2500 2506 1 1 2 2 3 3 4 Ii
'40 2512 2518 2523 2529 2535 2541 2547 2553 2559 2564 I 1 2 2 3 4 4 6
'-- 1--
·41 2570 2576 2582 2588 2594 2600 2606 2612 2618 2624 1 1 2 2 3 4 4 5
·42 2630 2636 2642 2f)49 2655 2661 2667 2673 2679 2685 1
·43 2692 2698 2704 2710 2716 2723 2729 2735 2742 2748 1
1
1
2 2 3 4 4
4 "Ii5
·44 2754 2761 2767 2773 2780
_-
2786 2793 2799 2805 2812 1
'45 2818 2825 2831 2838 2844 2851 2858 2864 2871 2877 1 1 2 3
1
2
2
3
3
3
3
3
4
4
4
4
5 Ii
·46 2884 2891 2897 2904 2911 2917 2924 2931 2938 2944 1 1 2 3 S 4 5 5
·47 2951 2958 2965 2972 2979 2985 2992 2999 3006 3013 1 I 2 3 S 4 Ii 5
-48 3020 3027 3031 3041 3048 3055 3062 I 3069 3076 3083 I I 2 3 4 4 6 6
..s 3090 3097 3105 Sl12 S119 3126 3133 I 3Hl lIl48 SUi I I ! I 4 4 Ii 6
 ANTILOGARITHMS

0 1 2 3 4 6 6 7 8 9 12 34 6 6 '1 8 9
·50 3162 3170 BI17 8184 11911 8199 3206 3214 8221 3228 1 1 , , , • 5 6 7
'1>1 3236 3243 32U S268 stSB 3273 3281 3289 3296 3304 1 2 2 S 4 6 6 8 7
'52 3311 3319 3321 8334 S342 3350 8357 3365 3873 3381 1 2 2 3 4 6 6 6 7
·53 3388 3396 3404 5412 8420 3428 3436 8443 3451 3459 1 2 2 3 4 6 6 6 1
oM 3467 3475 3483 8491 3499 3508 3516 3524 3532 3540 1 2 2 3 4 ~ 6 6 7
'55 S648 3556 3565 S573 3581 3589 8597 3606 3614 3622 1 2 2 3 4 6 6 7 7
'56 3651 3639 8648 S656 S664 3G73 3681 8690 3698 3707 1 2 3 3 4 6 6 1 8
'57 S7I5 3724 3733 3741 5750 3758 3767 3776 3784 5793 1 2 3 3 4 6 6 7 8
'58 3802 8811 3819 3828 3837 3846 3855 3864 3873 3882 1 2 3 4 4 ); 6 7 8
'59 3890 8899 3908 3917 3926 3936 3945 3954 3963 3972 1 2 B 4 5 6 6 1 8

'60 3981 3990 3999 4009

--140i8 -- - -- 4027 4036 4046 40~5 4064 1 2 3 4 6 6 6 1 9

'61 4074 4083 4093 4102 4111 4121 41S0 4140 4150 4159 1 2 S 4 5 6 1 8 9
·62 4169 4178 4188 4198 4207 4217 4227 4236 4246 4256 1 :I S 4 5 6 7 8 9
·63 4266 4276 4285 4295 4305 431~ 4325 4336 4345 4355 1 2 S 4 5 6 7 8 9
'64 4365 4375 4385 4395 4406 4416 4426 4436 4446 4457 1 2 S 4 5 6 7 8 9
I---
-65 4467 4477 4487 4498 4508 4519 4529 4539 4550 4560 1 2
-- 3 4 5 6 7 8 9
--- '--- -
-66 4571 4581 4592 460S 4613 ~624 4634 4645 4656 4667 1 2
---- S 4 5 6 7 9 10
-67 4677 4688 4699,4710 4721 4732 4742 4753 4764 4775 1 2 3 4 5 7 8 9 10
·68 4786 4797 4808 4819 4831 4842 4853 4864 4875 4887 1 2 & 4- 6 7 8 9 10
-69 4898 4909 4920 4932 49-131955 4966 4977 4989 5000 1 2 8 6' 6 1 8 9 10
f--- - ----- r----
·70 5012 5023 5035 5047 5058 5070 5082 5093 5105 5117 1
---- 2 40 6 6 T g
9 II
''11 IH29 5140 0152 5164 5176 5188 1\200 0212 5224 0236 1 2 40 6 6
----
7 8 1011
'72 6248 6260 5272 5284 5297 5309 5321 5333 5346 5358 1 2 4 5 6 7 9 10 11
'i3 6370 5383 5395 6408 0420 5433 5445 5158 5470 5483 1 8 4 5 6 8 9 10 11
'74 6495 5508 5521 5534 6546 5559 5572 5585 5598 5610 1 3 4 5 6 8 9 10 12
-- -- -- --
'75 6623 6636 0649 6662 0675 5689 0702 5715 5728 5741 1
-- 3 , 5 7 8 91012
'76 6754 5768 6781 6194 5808 5821 5834 6848 5861 5815 I 8 4 5 7 8 9 11 12
'77 5888 5902 5916 6929 5943 5957 5970 5984 5998 6012 1 3 4 5 7 8 10 11 12
'78 6026 6039 6053 6067 6081 6095 6109 6124 6138 6152 1 3 4 6 7 8 10 11 13
'79 6166 6180 6194 6209 6223 6237 6252 6266 6281 6295 1 3 4 6 7 9 10 11 13
-- -- --
·80 163iO 6324 4339 6353 6368 6383 6397 6412 6421 6442 1 S , 6 1 9 10 12 13
--. - -- f--- --
-81 6457 6471 6486 6501 6516 6531 6546 6561 6577 6692 2 S 6 6 8
-----
9 II 12 U
'82 6607 fl622 6637 6653 6668 6683 6699 6714 6730 6745 2 S I; ~ 8 9 11 12 14
-83 ti761 6776 6792 6808 6823 6839 681)5 687l 6887 6902 2 3 5 6 B 9 11 13 14
-84 691S 6934 6950 6966 6982 6998 7015 7031 7047 7063 2 3 6 6 8 10 11 13 16

'85 7079 7096 7112 1129 7145 7161 7178 7194 7211 7228 2 3
-- ~ 1 8 10 12 13 15
- - --I - ---- - -
'86 7244 7261 7278 7295 7311 7328 7345 7362 7379 7396 2 3 5 7 8 10 12 13 16
''il7 7413 7430 1447 7464 7482 7499 7516 7634 7551 75('8 :I 3 6 1 9 10 12 14 16
-S8 n86 7603 7621 7638 7656 7674 7Bn 7709 7727 7745 2 4 5 7 9 11 12 14 16
'89 7762 7780 7798 7816 7834 7852 7870 7889 7907 7925 2 4 6 7 9 11 IS 14 16
-
'110 7943 7962 7980 7998 B017 8035 BO:;4 8072 8091 BUO 2 9 11 13 U 17
-- - - -
·91 8128 8147 8166 81B5 8204 8222 8241 8260 8279 8299 2
-- - - "
4
6

6
7

8 9 11 13 16 17
'92 8318 8337 8MB 8375 8395 M14 8433 8453 8472 84~2 2 4 6 8 10 12 14 15 17
·93 8511 8531 8551 8570 8590 8610 8630 8650 8670 8li90 :I 4 6 8 10 12 14 16 18
·94 B710 8730 8750 8770 8790 8810 8831 8851 8872 8892 2 10 12 14 16 18

·95 8913 8933 8954 8974 8995 9016 9036 9007 9078 9099 2
" 6 8
10 12 15 17 19
.1)6 9120 91419162 9183 9204 9226 9247 9268
--
9290 9311 :I
"
4
8
6
8
8 11
_----
13 16 17 19
'97 9338 9354 9376 9397 9419 9441 9462 9484 9506 9528 1I 11
'98 9550 9572 9594
·99 9712 9795 9817
9616
9840
9638
9863
9661
9886
9683
9908
9705
9931
9721
9954
9750
9977
2
2
"
4
5
7
1
7
9
9
9
11
11
13 16 17 20
13 16 18 20
l4 16 18 20
 INDEX
Acetate ions, effect upon ionisation Ammonium ion, acid dissociation
of acetic acid, 30. of, 126; nlactions of, 318.
Acetates, reactions of, 397. Ammonium mercurithiocyanate
Acetone, 399, 492, 615. reagent, 228, 294, 295; prep.
Acetylacetone test, 597. of, 228, 294.
Acetylene, 498. • Ammonium mercurithiocyanate-
Acid radicals (anions), classifica· cobalt Fulphate test, 295;
tion of, 325; confirmatory -copper sulphate test, 2!l!.
test for, 442 (elementary), Ammonium molybdate reagent,
471 (semimicro), 549; in solu· 386; prep. of, 637.
tion, examination for. 438 Ammonium molybdate-quinine
(elementary), 467 ("emi. sulphate reagent, 389; prep.
micro), 534; preliminary tests of, 389.
for, 496; reactions of. 325; Ammonium radical, preliminary
special testfl for mixtures of, tests for, 436 (elementary),
416, 444 (elementary), 475 463 (Bemimicro), 495; re-
(semirnicro), 541. action;; of, 318.
Acids, Bronsted-Lowry definition Ampholytes, 10.
of, 9; cation 9; concentrated, Analysis, macro, 141; micro, 141;
strength of, 633; dilute, semimicro, 141; of alloys, 449;
strength of, 633; dissociation of liquids (solutions). 455
of, 16; polybasic, 7, 28; (elementary), 487 (semirnicro),
strengths of, 27; strong, 7, 11; 553: of insoluble substances,
theory of, 6; weak, 7, II. 556; of solid and non-metallic
Activity, 22, 32. substanees, 489; spot, 189;
Activity coeffiCient, 22, 23, 32, 33; technique of, macro, 143,
. and ionic strength, 24, 33; micro, 189, semimicro. 165.
table of mean, 25. Analytical operations, macro, 143;
Activity product constant, 32. micro, ]89; semimicro, 165.
Adsorption, 136. Anions, see Acid radicals.
Alizarin reagent, 270; prep. of, 270. Anthranilic acid reagent, 609.
Alizarin-S reagent, 271, 60:l; prep. Antilogarithms, table of, 650.
of, 271, 603. Antimony, 246; antimonie, re-
Alloys, analysis of, 554: com- actions of, 249; antimonious,
position of, 556. reactions of, 247: special tests
Aluminium, 267; reactions of, 267. for small amounts of, 250.
Aluminium hydroxide, precipita. Apparatus, for spot test analysis,
tion and solution of, 42. 194; macro, 155; micro, 189;
Aluminon reagent, 269; prep. of, semimiero, 165, 187. /'
270. Aqua, 21; regia, 448.
Ammonia, tests for, 318, 319, 320, Arsenate, reactions of, 392: reduc·
321,463 (semimicro). tion of (in analysis), 4;,2, 484
Ammonia solution, 126, 206. (semimicro),507.
Ammoniacal silver nitrate reagent, Arsenic, 237; arsenic, reactions of,
608; prep. of, 608. 240: arsenious, reactions of,
Ammoniacal silver sulphate solu- 237; special tests for small
tion, prep. of, 417. amounts of, 241.
Arsenite, reactions of, 392. Centrifugate, 170, 207; transfer "f,
Atomic weights, table of, 632. micro, 190.
Auric compounds, reactions of, 579. Centrifugation, 170; ad vanta 'lS
of, 170.
Barium, reactions of, 299. Centrifuge, 169; electric, I ~;
Bases, 8; anion, 9; Bronsted- hand, 171; theory of, I'll;
Lowry definition of, 8; con· use of, 172.
centration of, 633; strength Centrifuge tubes, 165, 174; cle"11-
of, 26; strong, 7; theory of, 7; ing of, micro, 193; heating ·jf
weak,7. solutions in, 192; micro, 1'·:1.
Beakers, 155, 187 (semimicro). Ceric compounds, reactions of, 6' "I.
Benzidine reagent, 210, 351; prep. Cerous compounds, reactions f,
of, 211, 351, 370, 380. 607.
Benzoates, reactions of, 410. Charcoal block, 143; reducti, is
a-Benzoin oxime reagent, see upon, 144, 433, 462 (seldi-
Cupron reagent. micro), 493.
Beryllium compounds, reactions Chemical equations, see Equatioll>l.
of, 595. Chemical formulae, see Formulae.
Bettendorff's test, 239. Chloramine-T, 446.
Bicarbonates, test for, 328. Chlorates, reactions of, 366, 540.
Bismuth, 221; reactions of, 222. Chlorides, reactions of, 352.
Blowpipe tests, 143, 433, 462, 493. Chlorine water, 635; equivalent
Boiling tube, 155, 166 (semimicro). solution, 358, 420.
Borates, reactions of, 373; removal Chloroplatinates, reactions of, 581.
in analysis, 486 (semimicro), Chloroplatinic acid reagent, 3 l5,
508, 566; test for, 50 l. 320; prep. of, 316.
Borax bead tests, 150, 435, 463, Chromate, reactions of, 393; test
494, 615. for, 547.
Bromates, reactions of, 369, 540. Chromatograms, paper, 616, 622.
Bromides, reactions of, 355. Chromium, 272; chromic, reactiolls
Brown ring test, 363, 473 (semi. of, 272; oxidation to chro-
micro). mate, 274.
Buffer action, 109. "Chromotrope 2B" reagent, 371);
Buffer solutions, 102, 109; calcula· prep. of, 376, 600.
tions involving, 114; effect of Chromotropic acid reagent, 2'- :;,
dilution upon, 112, 113; pre· 600; prep. of, 275.
paration of, 112, 643. Chromyl chloride test, 353, 419.
Bunsen flame, structure of, 145. Cinchonine-potassium iodide re-
agent, 224; prep. of, 224.
Citrates, reactions of, 407.
('11ass;neation~ Ull.aJ~l>i;.~nl <:>or ' e
1'1l'",r-r__.1.9. 2f'.).'lo_
CY-.a~ oJ'" ~ _/~ _/.~
(,~ror::>"?;rZ2?~",,#''\C'''/_
~~..J;f.'?;-.
Coagu1ation. ISo; v~J,luo~ 138.
Cobalt, 279; reactions of, 279.
Cobalt acetate-ammouium. \~~..

~\1\)I.)'t\m~\\1\\, \)~Il.
\~\,~\\~\,t1\,
C()\)\\\\\)\u~~\\lS'" ~\1, ~'2~.
Cells, calculation of e.mJ. of Cobalt nitrate, colour reacti"llS
voltaic, 90; concentration, 90; with, 387, 494.
oxidation-reduction, 91. Cobalticyanide, 500.
 Index
Colloidal state, 134, 135. p-Dimethylaminobenzene-a
Colloids, 135; lyophilic, 137; lyo- phenylarsonic acid reagl
phobic, 137. 603; prep. of, 603.
Colour, 'changes of, by heating, p-Dimethylaminobenzylide
491; reactions with cobalt rhodanine reagent, 215, 5
nitrate, 387, 494. prep. of, 216, 580.
Coloured compounds, commonly Dimethylgiyoxime reagent,
occurring, 490. 262, 285, 583, 594; prep.
Common ion effect, 29. 253. 262, 286, 637.
Comparator, 105; Lovibond, 105. ,8,8-Dinaphthol reagent, 407; prep.
Complex cyanides, decomposition of, 407.
of, 500, 559. Dinitro-p-diphenylcarbazide re-
Complex hydroxide ions, 55. agent, 230; prep. of, 231.
Complex ions, 51; calculations in- Diphenylamine reagent, 365; prep.
volving, 57; instability con- of, :365.
stants of, 52; table of Diphenylcarbazide reagent, 274,
instability constants of, 57. 312,395; prep. of, 275, 312.
Concentration limit, 195. Diphenylcarbazone reagent, 220;
Concentration of reagents, 633. prep. of, 221.
Conductance, 12; equivalent, 12; Diphenylthiocarbazone (or Dithi-
equivalent, and dissociation zone) reagent, 211; prep. of,
constant, 21, 22; limiting, 13; 212.
specific, 12. Dipicrylamine reagent, 316; prep.
Conjugate acid-base pair, 9, 125. of, 316.
Copper, 224; hydroxide test, 406; 0:0:' -Dipyridyl reagent, 261; prep.
reactions of cupric, 225; sul- of, 316.
phide suspension, prep. of, Dioxan, 615.
343. Disperse medium, 136; phase, 136;
Coprecipitation, 45, 140. system, 136.
Counter ions, 137. Dissociation, Arrhenius theory of
Course of instruction, abbreviated electrolytic, 4; experimental
for elementary students, 431, determination of approximate
459 (semimicro). degree of, 12, 13, 14; of poly-
Cupferron reagent, 264, 599; prep. basic acids, 28; theory of
of,265. complete, 17.
Cupric sulphate-pyridine reagent,' Dissociation constant, acid, 20 ;
347. ._ basic, 22; primary, 28;
Cupron reagent, 227, 577; prep. of, secondary, 28; tertiary, 28;
227. thermodynamic, 23; table of,
Cyanates, reactions of, 344. for acids and bases, 27.
C!yanides. rN",t;on" of. ~4-0: arldi- Distribution coefficient, 131.
tjOHHi losl; f(~r~ 41'5~ 408,. 546.
~~... •9'sa :I.9..:!: Dlatr:ibution 1~l1V~ 131; npplioations
_ .z?" ",-/_?~,.3Y.::";:: /,~

.Decaz:~ru~o~ w •...,.hfng k,'. IDS. I;-~ ~I~~~."..~,," %.o#.,~.. of. ..?..>.r.

(seIlllmJCfO). .o.Jt0r_O.llltes. reactIons of, ,/,15.
Def~c~z reaction, 575. DJthlOxami~e . reagent, see
\~.~\~\~~~~ , RubeaulC aCId reagent.
'",,-~ ~ ~~~ ~~~~\~\, ~~~~\\~~\~~:~,\.~\
\\\~~\~I\~)',\~\.,\\\,\\\,\\\, Th.'I'~\'~~, "\~"\, \c\~\ ~~"\\.\,
1)1.)l. \ u\); ca,\itl1:aticm, 0t, \ \)1 .. cot\..
Dialysis, 136. struction of, 161, 431.
Dichromates, reactions of, 393. Dropping bottle, semimicro, 168,
Digestion, 140. 196; T.R .• 168.
654
Arsenite, reactions of, 392. Centrifugate, 170, 207; transfer' ,f,
Atomic weights, table of, 632. micro, 190.
Auric compounds, reactions of, 579. Centrifugation, 170; advanta -0S
of, 170.
Barium, reactions of, 299. Centrifuge, 169; electric, -'.
0,
Bases, 8; anion, 9 ; Bronsted- hand, 171; theory of, 'I ;
Lowry definition of, 8; con· use of, 172_
centration of, 633; strength Centrifuge tubes, 165, 174; cle" n-
of, 26; strong, 7; theory of, 7; ing of, micro, 193; heating: )f
weak,7. solutions in, 192; micro, I - I.
Beakers, 155, 187 (semimicro). Ceric compounds, reactions of, 6' "I.
Benzidine reagent, 210, 351; prep. Cerous compounds, reactions f,
of, 211, 351, 370, 380. 607.
Benzoates, reactions of, 410. Charcoal block, 143; reducti, ,s
a-Benzoin oxime reagent, see upon, 144, 433, 462 (sel"I-
Cupron reagent. micro), 493.
Beryllium compounds, reactions Chemical equations, see Equatioll>!.
of,595. Chemical formulae, see Formulae.
Bettendorff's test, 239. Chloramine-T, 446.
Bicarbonates, test for, 328. Chlorates, reactions of, 366, 540_
Bismuth, 221; reactions of, 222. Chlorides, reactions of, 352.
Blowpipe tests, 143, 433, 462, 493. Chlorine water, 635; equivalent
Boiling tube, 155, 166 (semimicro). solution, 358, 420.
Borates, reactions of, 373; removal Chloroplatinates, reactions of, 581.
in analysis, 486 (semimicro), Chloroplatinic acid reagent, 3 I ::>,
508,566; test for, 50l. 320; prep. of, 316.
Borax bead tests, 150, 435, 463, Chromate, reactions of, 393; tp"t
494, 615. for, 547.
Bromates, reactions of, 369, 540. Chromatograms, paper, 616, 622.
Bromides, reactions of, 355. Chromium, 272; chromic, reactiolls
Brown ring test, 363, 473 (semi- of, 272; oxidation to chro-
micro). mate, 274.
Buffer action, 109. "Chromotrope 2B" reagent, 3'iG;
Buffer solutions, 102, 109; calcula- prep. of, 376, 600.
tions involving, 114; effect of Chromo tropic acid reagent, 2 ~ ;>,
dilution upon, 112, 113; pre- 600; prep. of, 275.
paration of, 112, 643. Chromyl chloride test, 353, 419.
Bunsen fiame, structure of, 145. Cinchonine-potassium iodide re-
agent, 224; prep. of, 224.
Cacodyl oxide test, 399. Citrates, reactions of, 407.
Cacotheline reagent, 253; prep. of, Classification, analytical of t he
253. metals, 205.
"Cadion 2B" reagent, 231; prep. Cleaning of apparatus, 162, I ~2
of, 23l. (semimicro).
Cadmium, 229; dry test for, 231; Co agel, 137.
reactions of, 229. Coagulation, 135; value, 138.
Calcium, 303; reactions of, 303. Cobalt, 279; reactions of, 279.
Carbide, 498. Cobalt acetate-ammonium thio-
Carbonate, reactions of, 326. cyanate reagtlnt, 22l.
Carborundum, 562. Cobalt blue glass, 317, 323.
Cells, calculation of e.m.f. of Cobalt nitrate, colour reactiulls
voltaic, 90; concentration, 90; with, 387, 494.
oxidation-reduction, 91. Cobalticyanide, 500.
 Index
Colloidal state, 134, 135. p-Dimethylamino benzene-azo-
Colloids, 135; lyophilic, 137; lyo. phenylarsonic acid reagent,
phobic, 137. 603; prep. of, 603.
Colour, .changes of, by heating, p-Dimethylaminobenzylidene-
491; reactions with cobalt rhodanine reagent, 215, 580;
nitrate, 387, 494. prep. of, 216, 580.
Coloured compounds, commonly Dimethylglyoxime reagent, 253,
occurring, 490. 262, 285, 583, 594; prep. of,
Common ion effect, 29. 253. 262, 286, 637.
Comparator, 105; Lovihond, 105. j3j3-Dinaphthol reagent, 407; prep.
Complex cyanides, decomposition of, 407.
of, 500, 559. Dinitro-p-diphenylcarbazide re-
Complex hydroxide ions, 55. agent, 230; prep. of. 231.
Complex ions, 51; calculations in· Diphenylamine reagent, 365; prep.
volving, 57; instability con· of, :365.
stants of, 52; table of Diphenylcarbazide reagent, 274,
instability constants of, 57. 312. 395; prep. of, 275, 312.
Concentration limit, 195. Diphenylcarbazone reagent, 220;
Concentration of reagents, 633. prep. of, 221.
Conductance, 12; equivalent, 12; Diphenylthiocarbazone (or Dithi-
equivalent, and dissociation zone) reagent, 211; prep. of,
constant, 21, 22; limiting, 13; 212.
specific, 12. Dipicrylamine reagent, 316; prep.
Conjugate acid-base pair, 9, 125. of, 316.
Copper, 224; hydroxide test, 406; ococ'-Dipyridyl reagent, 261; prep.
reactions of cupric, 225; sul· of, 316.
phide suspension, prep. of, Dioxan, 615.
343. Disperse medium, 136; phase, 136;
Coprecipitation, 45, 140. system, 136.
Counter ions, 137. Dissociation, Arrhenius theory of
Course of instruction, abbreviated electrolytic, 4; experimental
for elementary students, 431, determination of approximate
459 (semimicro). degree of, 12, 13, 14; of poly.
Cupferron reagent, 264, 599; prep. basic acids, 28; theory of
of, 265. complete, 17.
Cupric sulphate-pyridine reagent, Dissociation constant, acid, 20 ;
347. • basic, 22; primary, 28;
Cupron reagent, 227, 577; prep. of, secondary, 28; tertiary, 28;
227. thermodynamic, 2:1; table of.
Cyanates, reactions of. 344. for acids and bases, 27.
Cyanides, reactions of, 340; addi· Distribution coefficient, 131.
tional test for, 465, 498, 546. Distribution law, 131; applications
Cyanogen, 350, 492. in analysis, 132.
Dithiol reagent, 254; prep. of, 254.
Decantation, washing by, 158, 174 Dithionites, reactions of, 415.
(semimicro) . Dithioxamide reagent, see
Defacqz reaction, 575. Hubeanic acid reagent.
Deniges reagent, 408; prep. of, 409. Droppers, 166, 430; capillary, 167;
Devarda's alloy, 364, 417, 436, 464, modicine, 167, 430; reagent,
501. 166; calibration of, 167; con·
Dialysis, 136. struction of, 167, 431.
Dichromates, reactions of, 393. Dropping bottle, semimicro, 168,
Digestion, 140. 196; T.R., 168.
 6 Index
'op reaction paper, 184, 197, 204. Ferrocyanides, reactions of, 348;
'Y reactions, 143. removal in analysis, 500, 540.
Filter cone, 160; pipette (micro),
ectrode, calomel, 106; hydrogen, 200; stick (Emich), 201; sup-
85,86,106; quinhydrone, 107. port, 160; tube (micro), 200.
ectrode potentials, 83, 84; appli- Filter paper, impregnated, 199;
cation to calculation of equi- macerated, 139, 158, 427; for
librium constants, 89; cal- spot reactions, 197, 204.
culation of, 88; standard, 86, Filtration, 158; accelerator, 139,
89; table of standard, 87. 158, 427; aids to, 159.
ectro}ysis. 2. Flame, non-luminous Bunsen, 145;
ectrolytes, 2. oxidising, 143, 145; reducing,
ectrolytic dissociation, theory of, 143, 145; spectra, 147; tests,
2,4, 17. 145, 435, 462 (semimicro),
ectrolytic solution pressure, 83. 492.
ementary students, abbreviated Flasks, conical or Erlenmeyer,
course of instruction, 431, 155, 187 (semimicro).
459 (semimicro). Fleitmann's test, 245.
luations, chemical, 59; balancing Flocculation, 135; value, 138.
by ion-electron method, 68; Fluorescein reagent, prep. of, 357.
balancing by oxidation num- Fluorescein test, 356 (for bromine),
ber method, 64; balancing of, 412 (for succinate), 412.
61. Fluorides, reactions of, 360;
luilibrium between a sparingly removal in analysis, 487
soluble salt and a liquid, 38. (semimicro), 505, 508; test
luilibrium constants, 19, 20, 89; for, 546.
of oxidation-reduction re- Fluosilicates, reactions of, 384.
actions, 94, 95. Formaldoxime reagent, 291; prep.
luivalent weight, 77; of an acid, of, 291.
77; of a base, 77; of acid and Formates, reactions of, 400.
double salts, 78; of a normal Fuchsin bisulphite reagent, prep.
salt, 78; of an oxidising of, 358; test, 357.
agent, 78; of n re~ucing agent, Fuchsin reagent, 331; prep. of,
79; ionic equations for use in 331, 638.
calculation of, oxidising and Funnel, Buchner, 160; "slit sieve" ,
reducing agents, 80; variation 161; sintered glass, 161.
with reaction, SO. ct-Furil-dioxime reagent, 286; prep.
;ching test, 361. of,286.
;hylenediamine reagent, 220;
prep. of, 220.
rap oration, 161; anti-bumping Gallate, 428, 500, 545.
device for, 162. Gallocyanine reagent, 2 I I; prep.
of, 211.
Ihling's solution, 225; prep. of, Gamma (y), 195.
638. ' Gases, identification, in micro
Inton's test, 406. analysis, 193, 202; in 5emi·
Irric chloride, "neutral" solution, micro analysis, 181.
prep. of, 442, 471, 545, 568. Gas reactions in spot analysis, 193,
IrriC periodate reagent, 614; prep. 202.
of, 614. Gel, 137.
!rricyanides, reactions of, 350; Gold, see Auric compounds.
removal in analysis, 500, 540. Gram equivalent weight, see Equi-
i'eni-thiocyanate" test, 342. valent weight.
 Index 657
Group separation (advanced), Group UIB (Table SM. V),
general scheme in presence 298; Group IV (Table S2'I'l.VI),
of phosphates, etc. (Table I), 308 or (Table SM.VIA), 309;
505; (Table II), 511. Group V (Table SM. VII),
Group separation tables (advanced): 324.
Group I (Table III), 512; Groups, divi:-;ion of acid radicals
Group II, separation of sub- (or anions) into, 325; division
groups (Table IV, Method A), of metal ions (or cations) into,
513 or (Table IVA, Method 205.
B), 515; Group IIA (Table V), Gutzeit's test, 244, 251.
517; Group lIB (Table VI),
519 or (Table VIA), 521;
Group IlIA (Table VIl), 523; Heat on SUbstance, action of, 143,
Group IIlB (Table VIII), 524 433, 460, 490.
or (Table VIllA), 527; Group Hepar reaction, 378.
IV (Table IX), 529 or Hexanitro-diphenylamine reagent,
(Table IXA), 532; Group V see Dipicrylamine reagent.
(Table X), 533. Hofmann's test, 244.
Group separation tables (advanced, Hydrogen ion concentration, deter-
including "rarer" elements): mination of, by buffer solu-
Group I in presence of TI and tion method, 102; by com-
W (Table I), 576; Group II parator (or permanent colour
in presence of Mo, Au, Pt, standard) method, 10"1; by
Pd, Se and Te (Table II, III electrometric method, 106.
and IV), 589, 590, 591 and Hydrogen ion exponent (pH), 99;
592; Group IlIA in presence adjustment for precipitation
of Ti, Zr, Ce, Th, U and V with H 2S, 451 (elementary),
(Table V), 611; Group IIIB, 483 (selUimicro), 506.
notes on precipitation in pre- Hydrogen peroxide, reactions of,
sence of TI, V and Mo, 612; 413.
Group V, notes on detection Hydrogen sulphide, details of use
of Li in, 615. of, macro 156, micro 193,
Group separation (elementary), semimicro 179; generator,
general scheme (Table S), 450. semimicro, 181; poisonous
Group separation tables (element- character of, 210; sulphide
ary): Group I (Table I), 217; ion concentration in solution
Group IIA (Table II), 233 or of, 29, 30.
(Table IIA), 224; Group lIB Hydrolysis, 116, 117, 128; and
(Table III), 256 or (Table proton theory of acids and
IIIA), 257; Group IlIA bases, 125; constant, 117 ;
(Table IV), 277; Group IHB constant and degree of hydro-
(Table V), 297; Group IV lysis, 117; calculations in-
(Table VI), 307; Group V volving, 119, 120, 121, 122,
(Table VII), 323. 124; degree of, 118; of metal-
Group separation (semimicro), lic ions, 130; of salts, 114, 116;
general scheme (Table SM.S), pH of hydrolysed salts, 119,
482. 122, 124.
Group separation tables (semi- Hydrosulphites, reactions of, 415.
micro): Group I (Table SM.I), Hydroxonium ion, 6.
217; Group IIA (Table S-Hydroxyquinoline reagent, see
SM.HA), 258; Group lIB Oxine reagent.
(Table SM.IIIA), 258; Group Hypochlorites, reactions of, 351.
IlIA (Table SM.IV), 278; Hypophosphites, reactions ()f, 391.
 ;8 Index
:uition tube, 14.3, 4~3, 460 (semi- \ Magnesium, 310; reactions of, 311.
micro), 490. I Magnesium nitrate reagent, 239,
npregnated reagent paper, 198. , 241, 386; prep. of, 638.
lCrustation, 144. Magneson I reagent, 313; prep. of,
ldicator, 10 I; narrow range, 102; 313.
universal, 102; wide range, Magneson II reagent, 313.
102; table of colour changes Manganese, 287; manganous, re-
and pH ranges of, 103. actions of, 288.
uIigo solution, prep. of, 416, 638; Manganous nitrate--sil\rer nitrate
test, 399. reagent, 321; prep. of, 322.
ldole reagent, 340; prep. of, 340. Manganous sulphate~phosphoric
lfusible white precipitate, 212. acid reagent, 368; prep. of,
lSoluble substances, analysis of, 369.
556; preparing a solution of, Mannitol-bromothymol blue test,
56!. 376; reagent, prep. of, 377.
lStability constants of complex Marsh's test, 242, 250.
ions, 52; table of, 57. Mass action, law of, 18, 19; appli-
,dates, reactions of, 370, 539; test cation to solutions of weak
for, 547. electrolytes, 20, 21, 22.
lllides, reactions of, 358. Mercuric chloride paper, prep. of,
,dine, distribution between water 245.
and an organic. solvent, ]31, Mercury. 212, 2J8; mercuric, re-
134; solution, prep. of, 636. actions of, 219 ; mercurous,
,nic mobilities, 16; strength, 23, reactions of, 212.
24. Metal ions, analytical classification
,nic product of water, 97; at of, 205.
various temperatures, 99. Metallic hydroxides, as weak bases,
mis~tion. theory of complete, 17, 130.
>::.:~~T,-.:~;_.:: _;:,-'.' '_i_ :'_;_:_'~__·_;.;.~,~~t.~~~.t.~_-_;_.
g;~~~~:.,~~. '1.;: _~- ____ -:-"_~~-:.t
::!:'r::_~,;;_~~·,;:~t,:----.- - .. ___ -~~~_

~~~f{:~~~~:~~~:: ~~~~~::.~~~~~~ . ,~~::-~

~......-.hC">o ..... d ....... ~><.._,,_p~_to ..... JO,-_ 1 .~ ... _

f=~~_i~~~?~~:~::'9:~: 1~ ~::~n ~
 Index 659
Micro distillation, 203. Nitton reagent, 366; prep. of, 366.
Microcosmic salt bead tests, 153, oc-Nitroso-~-naphthol reagent, 281,
382, 495; colours of, 154. 583; prep. of, 282.
Micron. 135. Nitroso-R-salt reagent, 282; prep.
Microscope tests. acetylacetone (for of,282.
Be), 597; ammonium carbon- Normal solution. 76, 77.
ate solution (for Li), 614;
calcium sulphate dihydrate Oil of winter-green test, 409.
(for Cal, 305, 529. Organic acids, removed in analysis,
Millimicron, 136. 486 (semirnicro), 505, 508,
Modification of the analysis in the 566; table of separation of,
presence of: borate and fluo- 427,428.
ride, 505, 508, 566; organic Orthophosphate~. reactions of, 385,
acids, 508, 566; phosphate, 390.
454 (elementary), 486 (semi- Osmotic pressure. 84.
micro), 505, 508, 511, 566; Ostwald's dilution law. 21.
silicate, 505, 508, 566. Oxalates, reactions of, 401.
Molar solutions. 76. Oxidation, 61, 62, 63.
Molybdates. reactions of, 577. Oxidation number method. 64.
Molybdenum blue. 249. Oxidation numbers, determination
.. of. 64 •
Nernst equation, 130. Oxidation potential. 91; calculation
Nessler's reagent. 319, 496; prep. of, 93; staQdard, 92; table of,
of,319. 92.
Neutral solution. "Na 2CO a practi- Oxidation-reduction cells, 91; dis-
cally". prep. of, 427, 441, 470 cussion of, 61; reactions,
(semimicro), 544. equilibrium constants of, 95;
Nickel. detection of traces in cobalt theory of, 82.
_..
~~~tl_~- non )l:~~~;~~W~:~~~:~Z~=E!:
--ur--~7:--: .' .. r; :-;-T'<=~';:-~
O ....;iI;l'i~_':",..a,,,.~t;\~,,_~;!;_ "nP'lFl.'.'f'~ 'if.t
c::>O"'"'~i::-:;,:~~;_':' 2. ~_~~;~~ '" -;:~£.,:~~':' :-;:.,_:~!~
- ..... . 1;;:. . . :"_--_

~E:)~~t~j
~ ~;_:~i,=:'::"t~
~- -'",,'J'- ~- ---- - ,--:---;"-,,~_,.-,,,,~

SIi~f(~!ti~~~~~I~~illr;i~~
."_1''''_ ~"' ..~ OC-7.
!=t:U~-= j_~:::,I_n-:J.-~"~_~:':i__ "i'>~'"
_ • • _)_~>""F'I" :&~M_
I.-.
 ;0 Index
\
lPtisation, 137, 139. (semimicro); washing of, 158,
llerchromic acid", 394, 413. 174 (semimicro), 191 (micro).
lrchlorates, reactions of, 372. Precipitation, 156; fractional, 47;
lriodate, distinction from iodate, of hydroxides, 4'2; with
548; test for, 548. hydrogen sulphide, technique
lrmanganates, reactions of, 395. of, 156, 179 (sem.imicro), 193
)roxides, removal from diethyl (micro), 452, 484, 506.
ether, 413. Preliminary tests, 433 (elementary),
)r-salts, 437, 498. 460 (semimicro), 490.
B:, 99; calculations involving, Prepared solution, "Na 2 CO S '" prep.
100; determination of, by of, 427, 439 (elementary), 467
buffer solution method 102, (semimicro), 535.
by comparator (or permanent n-Propylarsonic acid reagent. 602;
colour standard) method 104, prep. of, 603.
by electrometric method 106. Protolytic reactions, 10.
H of a solution of a hydrolysed Prussian blue, 261, 263.
salt, 119, 122, 124. Prussian blue test. for cyanides,
henylarsonic acid reagent, 602; 341, 498, 546.
prep. of, 602. Pyrocatechol reagent, 600; prep.
henylhydrazine reagent, 578; of, 600.
prep. of, 578. Pyrogallol reagent, 223; prep. of,
hosphate bead tests, 153; colours 223.
of. J154-, PpDpnospn.ates. react~Dns of, 389,
Phosphate separations" : by 390.
acetate buffer-ferric chloride Pyrrole reagent, 585; prep. of, 386.
method, 568; by stannic
chloride method, 570; by Quinaldinic acid reagent, 294;
zirconyl nitrate method, 454 prep. of, 294.
(elementary), 487 (semimicro), Quinalizarin reagent. 271, 314,
511. 596; prep. of, 271, 314.
hosphates, see Orthophosphates. Quinhydrone. 108, 109.
hosphine, 388, 391 392, 393,
hosphites, reaction\ of, 390. "Rarer" elements. reactions of
'hosphomolybdic acid reagent, some, 571.
249; prep. of, 249. Reactions, on a semirnicro scale,
'icrolonic acid reagent, 305. 207, 458; seleQtive, 204;
'ipette, dropper, 166, 195; filter specific, 204.
for spot analysis, 200; trans- Reagent bottles, seminlicro, 168.
fer capillary, 190. Reagent paper. impre~ated", 198,
'latinum, Bee Chloroplatinates. 199.
'latinum wire, cleaning of, 147, Reagents, concentration of, 76;
152; loops, 195; tests, 146, preparation of, 633; prepara-
435, 462, 492. tion of special, 637; semi-
'Policeman", 155. micro, 169; side shelf, 169;
'olysulphide, 498. solid, 640; specific, 204; see
~ost-precipitation, 45, 140. also under individ1lal reagents.
~otassium, reactions of, 315. Redox processes, 63.
~otassium cobalticyanide test Reducing agents. 63, 64; examples
paper, prep. of, 296. of, 74; table of common, 75;
?otassium xanthate, 578. tests for, in an.a1ysis, 489
~recipitate, drying of, 162; (elementary), {68 (semi-
removal from filter, 159; micro), 537.
transfer of, 191 (micro), 176 Reduction, 62, 63, 68.
 Index 661
Reinsch's test. 246, 251. of evolved gases in 181;
Resorcinol test. 406. practical hints on, 185;
RF values. 616. technique o~ 165, 458;
Rhodamine-B reagent. 248; prep. transferring of precipitate in,
of, 249. 176; washing of precipitate
Rhodanine reagent. 215; prep. of, in, 174.
216. Sensitivity. 195.
Riegler's solution, 321. Silica "skeleton", 153, 382.
Rinmann's green test, 295. Silicates, reactions of, 381; re-
Rubeanic acid reagent, 227, 282, moval in analysis, 505, 508,
287, 582; prep. of, 228, 283, 566; test for, 545.
287,582. Silicides, 562.
Silicotluol'ides, reactions of, 384.
Salicylaldoxime reagent, 227, 583; Silicon tetrafluoride test, 382.
prep. of, 227. Silver, 214; reactions of, 214.
Salicylate, reactions of, 409; in Silver mirror test, 404.
analysis, dangers attending, Silver nitrate solution, tests with.
410. 440 (elementary), 469 (semi-
Salt effect. 33. micro), 540.
Salt solutions, strength of, 634. Sodium, 317; reactions of, 317.
Salts, pH of hydrolysed, 119, 122, Sodium alizarin sulphonate, see
124; structure of, 11. Alizarin-S.
Sebacic acid. 604. Sodium azide-iodine reagent, prep.
Selective reaction or reagent, 204. of, 335, 337, 347.
Selenates, reactions of, 586. Sodium carbonate bead tests, 154.
Selenites, reactions of, 584. Sodium carbonate-phenolphthalein
Selenium, 584. reagent, 328; prep. of, 328.
Semimicro, air bath, 179; Sodium cobaItinitrite reagent, 315,
apparatus, cleaning of, 183; 320, 572; prep. of, 638.
apparatus, list of 187; boiling Sodium dihydroxytartrate osazone
tube, 166; centrifuge, 169; reagent, 304.
centrifuge, electric, 172; cen- Sodium hypochlorite solution, 358,
trifuge, hand, 171; centrifuge, _ 420,639.
use of, 172; centrifuge tube, Sodium I-nitroso-2-hydroxynaph-
165; droppers, 166; drop re- thalene-3 : 6-disulphonate re-
action paper, 184; evapora- agent, see Nitroso-R-salt re-
tion, 177, 179; filter tubes, agent.
182; flasks, 187; HzS genera- Sodium rhodizonate reagent, 301,
tor, 180; precipitations with 302; prep. of, 301.
HzS, 179; reagent bottles, Sodium stannite reagent, 222 ;
168; reagents, 169; Bpot prep. of, 222, 223.
plates, Ij4; spatulas, 176; Sols, 137; hydrophilic, 138; hydro-
stirring rods, 166; test-tubes, phobic, 138.
165; test-tube brushes, 183; Solubilities of salts, 496; table of,
test-tube holders, 178; wash 647.
bottles, 175; water baths, 177, Solubility, of Ag 2S0 4 and TICI,
178. influence of various salts
Semimicro analysis, 141, 457 ; upon, 33, 34; of sparingly
advantages of, 141; calcula- soluble salts of weak acids in
tion of volume of precipitating strong mineral acids, 46.
reagents in, 184; dissolving of Solubility product, 31; examples of
precipitate in, 179; heating of calculations involving, 35;
eolution in, 176; identification table of, 37.
662 Index
Solubility product principle (rela- Sulphide ion concentration in,
tion), 32; applications of, 38: 0'25MHClsaturated wi <tH,S,
to precipitation of hydroxides, 30; in saturated HIS s( 'ltion,
42; to precipitation of sul- 29.
phides, 40; to solubility of Sulphides, reactions of, 335.
sparingly soluble salts of weak Sulphites, reactions of, 329;
acids in strong mineral acids, fuchsin test for, 331.
46. Sulphur dioxide, test for, 32!1, 331,
Solutions of solid for analysis, prep. 332.
of, 448 (elementary), 479
(semimicro), 502. Tannate, 428, 500, 545.
Solution of "insoluble substances", Tannic acid-silver nitrate test. 320.
56!. Tannin test, 5940.
Solutions, preparation of, 49; some Tartaric acid-ammonium VI ,lyb-
properties of, 3; see Buffer date reagent, prep. of, 3b!J.
solutions. Tartrates, reactions of, 404.
Solvents, 639: amphiprotic, 125; Tellurates, reactions of, 588.
aprotic, 125; protogenic, 125; Tellurites, reaotions of, 587.
protophilic, 125; for paper Tellurium, 587.
chromatography, 621, 622. Test solutions, prep. of, 640.
Solvolysis, 128. Test-tubes, 155, 165 (semimicro).
Specific reactions or reagents, 204. Tetrafluoride test, 361, 362, 540.
Spectroscope, 147; direct vision, Tetramethyldiamino·diphenyl-
148. methane (or "tetra-base" re-
Spectroscopic tests, 147. &gent, 210; prep. of, 210.
Spectrum lines, diagrall\ of, 151; Thallic compounds, reaction,· of,
table of, 150. 673.
Spot plates, 184, 196. , Thallous compounds. reaction of,
spot test analysis, 189;' apparatus 672.
for, 194; apparatus for diges- Thenard's blue, 272.
tion, 196; apparatus for gas Thiocyanates, reactions of, :,15,
reactions in, 202; filter paper 641.
for, 197, 204; filter pipette for, Thiosulphates, reactions of, ::;13,
200, 201; heating of filter 638.
paper in, 197, 201; impreg- Thiourea reagent. 224 ; prep. of, ~"'4.
nated reagent paper for, 198, Thorium compounds, reactions rlf,
199; removal and addition of 606.
drops in, 195, 196; separation Tin, 251; stannic, reactions f,
of solid and liquid phases in, 254; stannous, reactions f,
200; technique of, 196. 252.
Spray, glass, 199. Titan yellow reagent, 314; pr, p.
Stannous chloride reagent, prep. of, of, 314.
220. Titanic compounds, reactions "f,
Starch reagent, prep. of, 360, 639. 598.
Stirring rods, Hi5, 166 (semimicro). Titanic sulphate solution, prep. (Jf,
Strontium, 302; reactions of, 302. 414, 598.
Sublimate, 434, 461, 491. Titanium chloride reagent, 349;
Succinates, reactions of, 412. prep. of, 349.
Sulphantic acid, for removal of Transfer capillary pipette, 190.
nitrites, 339, 417. Transport number. 15.
Sulphanilic acid-IX-naphthylamine Triethanolamine, 307, 308, 52 '.
reagent, 340; prep. of, 340. 531.
Sulphates, reactions of, 377. Tungstates, reactions Df, 574.
 lndez 663
Turmeric paper test, 375. Washing, by rre"cBniation, 158.
Tyndall effect, 135. Wet reactions, 154.
Whatman filtration accelerator,
Ultra-filtration, 136. 139, 158, 427.
Ultramicroscope, 135. Working hints, 163, 185 (semi.
Uranyl compounds, reactions of, micro).
604.
'Uranyl magnesium acetate reagent, Zinc, 291; hy,iroxide, precipita-
317; prep. of, 317. tion and solution of, 44; re-
Uranyl zinc acetate reagent, 317; actions of, 292.
prep. of, 318. Zirconium-alizarin lake test, 362.
Urea, 251, 417. Zirconium-alizarin-S test paper,
Vanadates, reactions of, 592. prep. of, 363.
Vanadium. 592. Zirconium compounds, reactions
of, 601.
Walpole technique, for pH, 104. Zirconyl nitrate reagent, 387, 455,
Wash bottle, 156. 175 (semimicro). 487,511; prep. of, 639.

-
APAlJ C':"~ " 1\1. UhaARY

A CC I ; " (I. I0 6I '

Date' -<63____...l
LI ~?:__..:.....
 INDEX TO TABLES-continUtd
O. ADVANCED ANALYSIS
PA.GE
?reliminary dry tests • • 490
t>reliminary tests for acid radicals (anions) • • 496
t>repara.tion of a solution of the solid . • 502
H.:xamination for acid radicals (anions) in solution. • 534
Jonfirmatory tests for acid radicals (anions) • • 549
3pecial tests for mixtures of acid radicals (anions) • • 416
3eparation of organic acids. • 428
rable I.-Separation of Cations into Groups (Organic
Acids, Boric, Hydrofluoric, Silicic and P1waphoric
Acids being pre.sent) • 505
rable II.-Phosphate Separation Table (Zirconyl Nitrate
Method) 511
Phosphate Separation Table (Acetate Buffer-.Fe013 Method) 568
Table lil.-Analysis of Group I (Silver Group) • 512
Table IV.-Analysis of Group n (Copper and Arsenic
Groups). Separation of Group lIA (Copper Group)
and Group lIB (Arsenic Group)-Ammonium Poly-
8Ulphide Method • • 513
Table IVA.-Separation of Group llA and Group IIB-
Pota88ium Hydroxide Method 515
Table V.-Analysis of Group IIA (Copper Group) • 517
Table VI.-Analysis of Group lIB (Arsenic Group)-
Method A • 519
or Table VIA.-Analysis of Group TIB (Arsenio Group)
-Method B • 521
Ta.ble VIl.-Analysis of Group nIA (Iron Group). • 523
[Oontinued
 INDEX TO TABLES-continued
PAGB
Table VllI.-Analysis of Group IIIB (Zinc Qroup)-
M etlwd A . • 524
or Table VIIIA.-Analysis of Group IIIB (Zino Group)
-Metlwd B 527
Table IX.-Analysis of Group IV (Calcium Group)-
M etlwd A • • 529
or Table lXA.-Analysis of Group IV (Calcium Group)
-Metlwd B 532
Table X.-Analysis of Group V (Alkali Group) 533
Analysis of a liquid (solution) 553
Analysis of So metal or an alloy • 554
Analysis of insoluble substances .• .556
I
D. ADVANCED ANALYSIS INCLUDING" RARER"
ELEMENTS '"
Additional to, or modifications of, Tables ~iven bod
j'. C
Table I.-Analysis of Group I (Silver Group) in the pre-
sence of TI and W 5n
Table II.-Analysis of Group II (Copper and Arsenio
Groups) in the presence of Mo, Au, Pt, Pd, Se and Te 58~
Table lII.-Analysis of Group IIA (Copper Group) 590
Table IV.-Analysis of Group IIB (Arsenic Group) 591-2
Table V.-Analysis of Group ilIA in the presence of Ti,
Zr, Ce, Th, U and V • • 611
Table VI.-Borax Bead Tests - 615