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Vogel Inorg Chem 5ed PDF
Vogel Inorg Chem 5ed PDF
FOURTH EDITION
LONG MANS
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ACCRA, AUCKLAND, IBADAN
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LAHORE, NAIROBI, SALISBURY (RHODESIA)
-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
Rs. 16.50
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
CHAPTER III
REACTIONS OF THE METAL IONS OR CATIONS
III, 1. The analytical classification of the metals 206
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
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
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,
:--. . -: : + =--=~--=-
-- -e-- - :-. .--
- -~---
-- --
-- -- - - --&--
-- + ~----
- -
- --
-
Fig. I, 2, 1
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,---
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.
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
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
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.
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
acid
I
2 X 1O- t 11 d-Tartaric
acid
{KKa 4·55
2
11'04 lo-at
lO-'t
X
X
Tribasic Acids
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
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.
'<;-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
'"
~ 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
= 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
Solubility Solubility
Substance Substance
product product
is disturbed.
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:
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
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
OXIDANTS
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.-
NaG/
A B
Fig. I, 28, 1
or [Zn++] = () + 1037
[Cu++] w
= 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
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
E p-- EO + RT Iog.-
-
aoz. (i)
nF aR,d.
E p-- EO + RT
- o1 g .oz-. C (i/)
nF CRedo
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"
......
,
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:
[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
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
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
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
[Salt]
or pH = pKa + log [Acid] (v)
[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.
~+ =
aru.
- X
cJ. X K •
K • = ----:r- (viii)
aA - C"'A-
"
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:
-'
.... },
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)
_ [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
EXPERIMENTAL TECHNIQUE OF
QUALITATIVE INORGANIC ANALYSIS
Fig. II, 1, 1
Fig. II, 1, 3
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
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.
'.
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.
(6) !
Fig. II, 2, I
Fig. II, 2, 3
(0) (b)
(0) (d)
Fig. II, 2, 4:
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
l,
Fig. 11,3,5
•
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
"", 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
•
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
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.
'.
, .._,_.--~ ..
O~(b)O- a
Fig. II, 3, 15
(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
(b) (c)
Fig. II, 3, 19
(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
•
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;
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
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
flubber stopper
t-
Clamp
/'" A
~~. -Ouler lube 3·5mm. diam.
'i)~
'/
--:r-~'
Outer lube 10 mm. diam.
I
-Inner lube 2 mm. diam.
20mm.
C
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
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:
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.
-,
\
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.
( (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, •
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++.
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).
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.
• 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.
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
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.
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.
(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.
(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.
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<'
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).
A B c
~~
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.
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.
(<(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.
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.
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.
\ J
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 '
\
\
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
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
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.
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)
=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
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
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,
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.
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
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.
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.
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.
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
Treat the ppt. with 0·5 mi. of dilute acetic acid and stir. I
~
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).
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
(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)
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
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.
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.
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' ,-
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.
Treat the dry residue from Group IV with 3-4 mI. of water, stir and
warm for 1 minute. Filter. *
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)
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
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.
Fig. IV, 2, 1.
~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
H°Yy°II~O HOVY 0( 0
V~~~~
~COaH
B)~'~lli
U (I) (II)
-HaN-c\ _ +
-
C=O=NHa CJ
HaND -
I
CH, (I)
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.
,
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.
-
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.
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, 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
Shake the solution with excess of freshly precipitated CdCO., and filter.
Add excess of lead acetate solution to the solution of the alkali metal
salts, and filter cold.
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
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
* 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
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'(
1------------------____________________
Ob8ervation I Inference
1_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _;
Observation Inference
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,
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.
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.
* 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.
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).
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.
Observation Inference
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
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 •.
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 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.
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).
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.
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.
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
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
Ob8ervation Inference
Ob81l'1'vation
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.
~
.........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
!
(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.
,
increases the speed of filtration by retaining part of the precipitate
and thus preventing the clogging of the pores of the filter paper.
(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
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
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.
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.
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.
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 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.
Heat to the boiling point, allow the ppt. to settle, cool and filter. Wash.
the ppt. with 2-3 ml. of N nitric acid.
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.
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
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.
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
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.
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.
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.
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.].
Pt( jC'NH,-C=S )
"'-s-6=NH 2
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.
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.
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.
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.
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.
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.
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
'" 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
/":::---_______
~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.
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.
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.
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.
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
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
)
PAPER CHROMATOGRAPHY
Fig. X, 2, I Fig. X, 2, 2
' :' J
• 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
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.
Ni 0·07 Blue.
Mil 0·3 Brown.
Co 0·6 Brown.
Zn 0·9 Purple.
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.
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.
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,
Th 0·96 Violet-blue.
So 0·17 Violet.
Rare earths 0·00 Violet-blue.
632
2] Appendix 833
A, 1. REAGENTS
CONCENTRATED ACIDS
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
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.
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?
pH at
Solution
12°0 25°0 38°0
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
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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
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
'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.::";:: /,~
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.
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APAlJ C':"~ " 1\1. UhaARY