GRAVIMETRIC ANALYSIS  Number of different kind of ions are present in

the same solution

A. LAW OF MASS ACTION AND REVERSIBLE  Greatest conc any one of them can attain is
REACTIONS determined by the others.
 Under certain conditions may be made to  No great conc of silver can be present in a
continue to completion solution in the presence of chlorine, for the
 Under other condition may attain equilibrium two ions unite to form a precipitate of the
before completion difficulty soluble salt, silver chloride.
 Resulting in erroneous data  Silver chloride is slightly soluble in water
 Three general conditions tend to prevent  The solubility product is thus seen to be an
reversal of reaction ultimate value attained by the ionic product
1. Formation of an insoluble gas when equilibrium has been established
2. Formation of a sparingly soluble solid between the undissolved solid and the difficulty
3. Formation of very slightly ionized molecules. soluble salt in solution.
 According to the law of mass action, rate of  Product of the conc of any pair of ions in
reaction is proportional to the product of the solution is made to exceed in value the
molecular conc. of the reacting substances. solubility product; compound formed by their
 Rate of a reaction depends upon the conc. of union, precipitation of the compound will take
every substance taking part in the reaction. place until the product of the ionic conc is
 Point of equilibrium will depend upon the conc. exactly EQUAL to the solubility product value.
of each of the components of the two opposing  Product of the ionic conc is made LESS THAN
reactions. the solubility product value; compound formed
by their union will dissolved until product of
KNO3 + H2SO4 ↔ KHSO4 + HNO3 ionic conc is equal to the solubility product
 Rate of the reaction of potassium nitrate with value.
sulfuric acid is expressed by the equation. C. COMMON-ION EFFECT
 At definite temp. the equilibrium constant is a  Equilibrium constant does not change, no
fixed value for any given reaction irrespective matter what the conc of the reacting
of the conc of the substances present. substances may be.
 In quantitative analysis, an excess of one  Relative conc of the reacting substances may
component is frequently added to cause the change, but there is no change in the
reaction to go as nearly to completion as equilibrium constant.
possible.  Solution of silver nitrate is added to a solution
B. SOLUBILITY PRODUCT PRINCIPLE of sodium chloride, the chloride ion is
 Solubility product principle is an application of momentarily present in a conc such that its
the law of mass action to equilibria that ionic product with the silver ion exceeds the
generalizes the behavior of difficulty soluble solubility product of AgCl, and insoluble AgCl
salts in their saturated solutions. is precipitated:
 Precipitation occurs, prevented or solution is Ag+ + Cl-  AgCl
affected; solubility product principle is involved.
 The product of the conc of the constituent ions  Equivalent amount of silver nitrate has been
in a saturated solution of a difficulty soluble added, and the system has acquired
salt for any given temp is practically a equilibrium, the conc of silver ions will be
constant, each conc being raised to a power exactly equal to the conc of chloride ions.
equal to the relative number of ions supplied  Supernatant liquid, which is a saturated
by one molecule of the salt upon dissociating. solution of AgCl
 Solubility products of some of the more  Small amount of a soluble silver salt or a
difficulty soluble salts dealt with in soluble chloride is added
pharmaceutical analysis.  Slight further precipitation will take place.
  Conc of silver ion is increased by the addition  Exerts some solvent action on silver halides.
of a soluble silver salt.  Acidified solution should NOT be heated until the
 Concentration of chloride ion must decrease silver nitrate has been added, since chlorine may
and conversely that if the conc of chloride ion be liberated and lost
is increased by adding a soluble chloride NaCl+HNO3HCl+NaNO3
 Conc of silver ion must decrease since their
6HCl+2HNO33Cl2 + 4H2O + 2NO
product remains constant.
 Silver nitrate is added in excess to drive the
reaction to completion through the common-ion
effect
GRAVIMETRIC METHOD
AgNO3 + NaCl  AgCl + NaNO3
Measurement of the weight of a substance in a
 Precipitation must be performed away from strong
sample or calculation of the weight of a light
substance in a sample from the weight of a  Silver chloride is decomposed by sunlight with loss
chemically equivalent amount of some other of chlorine
substance, can be accomplished in various  Diffused light the error chloride which, if present,
ways. would pass through the filter.
 Precipitate is washed to remove soluble salts
Pharmaceutical quantitative analysis, the
present in the solution chiefly sodium nitrate and
substance to be measured gravimetrically is excess AgNO3
separated from other substances composing the  Washing with 0.01N nitric acid prevents loss of
sample by physical methods, purified, and AgCl through its return to colloidal condition
weighed without chemical change. (Peptization).
 AgCl is appreciably VOLATILE when IGNITED, so
NaCl + AgNO3  AgCl + NaNO3 it should be dried at a relatively low temp
 Reaction involved in the calculation of amount of
A chemically equivalent amount of some product silver nitrate solution to be used and of the purity
can be obtained from a reactant of the sample.
Component of the sample being assayed  E.g.
1. It may be precipitated from solution a. NaCl = 58.44
b. AgNO3 = 169.87
2. It may be a decomposition product resulting
 Gravimetric Factor – or a chemical factor by use
from ignition of a compound of which the weight of NaCl in the sample
3. It may be deposited on an electrode by proportionate to the weight of AgCl formed can be
electrolysis. readily calculated.
DETERMINATION OF CHLORINE IN A 𝑊 × 𝐸 × 100
SOLUBLE CHLORIDE %=
𝑆
 Solution of a sample of a soluble chloride is
 Gravimetric method for determination of chlorine
acidified with nitric acid and treated with
in a soluble chloride can also be applied in the
excess silver nitrate solution. assay of most soluble
 Other substances that form insoluble silver  Bromides
salts must be absent from the sample.  Iodides
 Cyanides
ASSAY OF SODIUM CHLORIDE  Thiocyanate
 The solution is acidified with nitric acid to prevent  As well as standardization of HCl solutions
the precipitation of other substances insoluble in and the estimation of silver compounds.
water but soluble in nitric acid, such as  Volumetric precipitation method can be carried
carbonates, oxides, and phosphates. out more rapidly than gravimetric method
 Acid helps to coagulate any colloidal silver
chloride.
 Too great an excess of nitric acid must NOT be
added.
 ASSAY OF SODIUM LAURYL SULFATE FOR ASSAY OF MERCAPTOMERIN SODIUM
SODIUM SULFATE CONTENT
 The hydrogen sulfide reacts with the mercuric salt
 The soln of the sulfate is acidified with HCl to which with the formation of black mercuric sulfide
prevent ppt of carbonate, which are soluble in HCl as hydrogen sulfide is passed into the mixture.
solution.  Mercuric sulfide is insoluble in acids, hydrogen
 Acid also increases the solubility of barium sulfate sulfide may be employed as the precipitating agent
slightly and therefore promotes the growth of large and HCl may be added to suppress the conc of
crystals, since small crystals with greater surface sulfide ion so that metals which form sulfides more
area per unit of weight dissolve more rapidly than soluble than mercuric sulfide and which may be
large one. present as impurities will not be precipitated.
 Larger crystal with smaller surface area exposed  Ppt is washed with water to remove soluble
grow more rapidly than they dissolve. sulfides, then with alcohol to remove water.
 Soln is heated to boiling to expel dissolved CO2  Carbon tetrachloride, is added later and is
 Excess of hot BaCl2 soln is added to ensure immiscible with water but miscible with alcohol,
complete ppt and to decrease the solubility of can permeate the ppt and dissolve any sulfur
BaSO4 by the common-ion effect. formed by the oxidation of hydrogen sulfide.
 Mixture allowed to stand overnight to allow the  Ppt is washed with carbon tetrachloride w/out
larger crystals to grow at the expense of the suction to allow time for the sulfur, which is slowly
smaller ones. soluble, to dissolve.
 BaSO4 is directed to be washed on a filter to  Mercuric sulfide if volatile at high temp (400°C)
remove excess BaCl2 and NaCl formed
 Washing process may be carried out more rapidly HgCl2+H2SHgS+2HCl
by washing once by decantation.
 The filtrate is always acidified with a drop of HNO 3  Same procedure can be adapted for the assay of
in carrying out the test for chlorides. other mercury salts, antimony salts, and a
 Coprecipitation is when BaSO4 exhibits the preliminary oxidative degradation using acid
property of “dragging down” some soluble salts permanganate, for the assay of other
when it is precipitated. organomercury compounds such as meralluride.
 Occluded or coprecipitated salt cannot be removed  The phosphate is ppt as magnesium ammonium
by ordinary washing. phosphate, washed, dried, ignited to the
 Error from this source is reduced largely by pyrophosphate, and weighed.
precipitation from hot dilute soln and by adding the
precipitating reagent slowly with continuous
stirring. ASSAY OF SODIUM PHOSPHATE SOLUTION
 Coprecipitation occur in the presence of nitrates,
 Magnesia mixture TS is a preparation containing
chlorates, and salt of iron, aluminum, chromium
magnesium ions in a buffered ammonium chloride-
and other trivalent element with BaSO4.
ammonium hydroxide soln.
 Addition of a soln containing phosphate ions will
Na2SO4+BaCl22H2OBaSO4+2NaCl+2H2O
form a ppt of magnesium ammonium phosphate if
the pH of the reaction is controlled, through
 It may applied to the estimation of metals that form
buffering and the common-ion effect.
insoluble sulfates such as Ba, Ca, etc.
 Sodium phosphate is dissolved in water, the
 Amount of CaO in MgCo3, Mg2OH, and MgO is
phosphoric acid is ionized
determined by ppt of an equivalent amount of
CaSO4 under conditions such that MgSO4 remains
H3PO4↔H+ + H2PO4-
in soln.
H2PO4-↔H+ + HPO4-2
 Sulfur, free and combined, my be oxidized to
HPO4-2↔H+ + PO4-3
sulfate and subsequently ppt as BaSO4.
 Combustion of sulfobromophthalein sodium in an
 Degree of ionization becomes less for each
oxygen flask combustion with oxidizing agent
successive stage.
before the gravimetric determination as carried out
 Relative amounts of PO4-3, HPO4-2, H2PO4- and
in the assay of sodium lauryl sulfate.
H3PO4 in equilibrium with one another depend on
 Thiosulfates, sulfites, persulfates, etc., may be
the hydrogen-ion conc of the soln.
estimated with similar procedure.
 Basic soln PO4-3 and HPO4-2 ions predominate.
 Phosphate ion which exists in the soln of the  Certain official gold salts are readily assayed
sample reacts with the Mg+2 ions contained in because of the ease of reduction of gold in
magnesia mxt to form the corresponding combination to an equivalent amount of elemental
magnesium salt; all these are more or less gold.
insoluble in water.
 Mg3(PO4)2, MgHPO4, and Mg(H2PO4)2 may be Assayed gravimetrically
formed.  Gold sodium thiomalate
 Addition of a soln NH4OH represses the conc of  Aurothioglucose
H2PO4 and prevent the formation of Mg(H2PO4).
 Zinc eugenol cement and zinc oxide with
 Presence of the ammonium ion, the salt is ppt as
salicylic acid are ignited to yield zinc oxide in
MgNH4PO46H2O
the same way as bismuth subnitrate, yielding
 If the soln is too basic Mg(OH)2 may be
bismuth oxide.
precipitated.
 Aluminum monostearate on ignition yields an
 Precipitation of both Mg3(PO4)2 and Mg(OH)2 is
aluminum oxide residue which is weighed
prevented by the presence of ammonium salts
directly.
which, through the common-ion effect, act as a
 Some miscellaneous gravimetric analyses in which
buffer and prevent the hydroxyl-ion conc from
official compound are converted to insoluble
becoming to great.
residues that are dried and weighed
 The hexahydrate, MgNH4PO46H2O form relatively
 Barium sulfate converted to BaCrO4
coarse crystals on standing for 3hrs or more in
room temp.  Sulfurated potash is determined as CuO
 At temp above 60°C the monohydrate is formed.  Sometimes a loss in weight can be used as basis
 Ppt is washed with aqueous ammonia soln until for analysis
free of chlorides.  Conversion of silicon dioxide, SiO2, to silicon
 Filtrate for chlorides, acidify with HNO3 and add tetrafluoride, a gas, as in the assay of
AgNO3 TS. magnesium trisilicate for SiO2
 Upon ignition the magnesium ammonium  Before extraction of organic medicinal agent, the
phosphate is converted into the pyrophosphate. sample of the powdered tablets is frequently
washed with petroleum benzine to remove
 2MgNH4PO46H2OMg2P2O7+2NH3+13H2O substances such as binders and lubricants that
would be extracted along with the organic
 2Na2HPO47H2O=2MgNH4PO46H2O=Mg2P2O7
medicinal agent by the solvent, chloroform or
( . ) ether, which is used subsequently.
 Each gram of Mg2P2O7 is equivalent to =  Organic medicinal is basic
.
2.409g of Na2HPO47H2O.  Papaverine in papaverine HCl
 Same ppt MgNH4PO46H2O, result when  Or acidic
magnesium ions are treated with a soluble dibasic  Amobarbital in sodium amobarbital tablets
ammonium phosphate.  It is first extracted with an aqueous soln of an acid
 The magnesium pyrophosphate obtained on or base to effect separation from the neutral
ignition is equivalent to the magnesium ammonium substances that might be present.
phosphate.  Aqueous soln of the salt of the organic medicinal
 Magnesium citrate soln was formerly assayed by agent is then made alkaline or acidic, as the case
conversion to Mg2P2O7 and is now assayed by a may be, and the liberated organic base or acid is
procedure involving the use of an organic extracted with chloroform or ether.
precipitant.  If stearic acid or stearates are present, an organic
 The high specificity of organic precipitants, medicinal agent which is acidic (amobarbital)
especially when the pH of the reaction mixture is cannot be extracted with NaOH soln because
controlled, makes possible qualitative and sodium stearate would be extracted along with the
quantitative analyses of certain ions even in the salt of the organic acid.
presence of other ions that interfere in analytical  Saturated soln of barium hydroxide is used, and
procedure in which inorganic precipitating reagent the insol barium stearate can be removed by
are used. filtration.
 The reagent, 8-hydroxyquinoline or oxine
selectively forms a very insoluble precipitate
 Bismuth subnitrate is ignited to the oxide, yielding
an equivalent amount of Bi2O3
  A preparation is acidified with a strong acid such ASH AND WATER DETERMINATION
as HCl, the organic acid is liberated and may be
ASH CONTENT
extracted with an immiscible solvent such as ether
or chloroform.  The ash content of a crude drug is generally
 Organic medicinal agent can sometimes be taken to be the residue remaining after
converted quantitatively to derivatives by reactions incineration.
involving some functional group such as amino,  Usually represents the inorganic salts naturally
carboxyl, aldehyde or ketone carbonyl, phenolic occurring in the drug and adhering to it
hydroxyl, etc.
 An ash determination furnishes a basis for
 Insol salts formed by the reaction of amino or
carboxyl groups may be included in this category. judging the identity and cleanliness of a drug
 Quaternary nitrogen cmpd will form insol salts with and gives information relative to its adulteration
tetraphenylboron. with inorganic matter.
 These nitrogen-containing cmpd, choline chloride,  Ash standards have been established for a
benzethonium chloride, and bethanecol chloride, number of the official drug; usually these
are easily assayed by ppt with sodium
tetraphenylboron.
standards set a maximum limit on the total ash
or on the acid-insoluble ash permitted.
 Total ash is the residue remaining after
R4N++B(C6H5)4-R4NB(C6H5)4
incineration; the acid-insoluble ash is the part of
the total ash which is insoluble in diluted HCl.
 The ash or residue yielded by an organic
SPECIAL METHODS USED IN chemical compound is, as a rule, a measure of
PHARMACEUTICAL ANALYSES the amount of inorganic matter present as
impurity.
 Quantitative analysis of crude drugs and of the  Inorganic matter is present in small amount
products derived from them are made to establish which are difficult to remove in the purification
purity or to determine the amount of process and which are not objectionable if only
therapeutically active constituent present for the traces are present.
purpose of standardization.  Electric furnace is used for ignitions
 Chemical methods, such as those employed in  Very dull-red heat = 500 to 550°C
the determination of ash, moisture, crude fiber,  Dull-red heat = 550 to 700°C
extractive obtained with different solvents, the  Bright-red heat = 800 to 1000°C
estimation of alkaloidal content.  Yellow-red heat = 1000 to 1200°C
 Biological methods, those in which the effect of  White heat = 1200 to 1600°C
drugs upon microbes, animals, or animal tissues  Calcium carbonate is converted to calcium
are measured and which are employed in the oxide at about 825°C
absence of satisfactory chemical methods for  Calcium phosphate is converted to calcium
standardization. pyrophosphate at about 1550°C
 Biological assays or tests for such medicinal  Lithium carbonate form lithium oxide at about
agents as adrenal cortex, corticotropin, digitalis, 600°C
heparin sodium, insulin, oxytocin, parathyroid,  Potassium chloride sublimes at about 1500°C
and vasopressin.
 Microbiological assays are required for TO DETERMINE THE TOTAL AND ACID-
antibiotics, liver, vitamin B12. INSOLUBLE ASH CONTENT OF ACACIA
 Tests are required for the toxicity and potency of
 The crucible in which the drug is to be ignited
serological preparations such as vaccines, should be heated to dull-redness until of constant,
serums, toxoids, and antitoxins. weight, cooled in a desiccator, and weighed.
 Therefore analytical methods for the  This procedure drives off the moisture and the
determination of purity, moisture, and other absorbed gases present on the surface of the
constant are obtained. crucible.
 The drug is incinerated at a temp not to exceed a  Acetazolamide have an upper residue limit of
dull redness. 0.1%
 The ash consists largely of calcium carbonate  Aspirin have an upper residue limit of 0.05%
formed from the calcium oxalate contained in the LOSS ON IGNITION
drug.  This technique provides a means of
 The incineration is carried out at a bright-red heat,
determining the percentage of test material
the calcium oxalate is converted into carbonate,
but when the incineration is carried out at a bright- which is volatilized and driven off under the
red heat, varying amounts of the carbonate are conditions specified.
converted to the oxide with consequent variable  Definite limitations on the amounts of volatile
result. matter they will lose when heated are:
 If the ash contains alkali chlorides, which it
frequently does, there may be loss of some USP
chloride by volatilization when a high ignition
temperature is used.  Calamine (2.0)
 When the ignition residue is not heated above dull  Magnesium sulfate (40.0 – 52.0)
redness, it is frequently very difficult to burn off all  Titanium dioxide (0.5)
the carbon, some of which may become  Zinc oxide (1.0)
surrounded by fused inorganic matter, thereby
keeping it from coming in contact with the oxygen NF
of the air.
 The residue is treated with hot distilled water to  Calcium phosphate tribasic (8.0)
dissolve most of the inorganic matter, and  Kaolin (15.0)
insoluble portion is collected on an ashless filter  Lime (10.0)
and incinerated.
 Magnesium hydroxide (30.0 – 33.0)
 Filtrate is then added to this residue and
evaporated, and the whole is ignited to burn off  Magnesium phosphate (20.0 – 27.0)
any colloidal carbon that may have passed into the  Permitted loss in % weight is given in
filtrate. parenthesis.
WATER CONTENT
Weight of crucible and ash – weight of crucible =  Quantities of water, either as water of
total ash
crystallization (hydrates) or as water in the
 This total ash, which usually contains carbonates, absorbed form
phosphates, sulfates, chlorides, oxides, etc., of  It is necessary that the USP and NF specify
calcium, magnesium, potassium, sodium, certain water-content limits in the drug
aluminum, iron, and other metallic elements monographs.
 The diluted HCl dissolves the calcium carbonates,
 Water content of drugs may also be important
alkali chlorides, etc., leaving an acid-insoluble
residue that consists almost entirely of silica for other reasons.
derived from soil adhering to the drug.  Crude drugs, for example, are sold with
guaranteed assay for active constituent, the
percent active constituent must be calculated
RESIDUE ON IGNITION on the basis of the moisture-free drug.
 The ash content of chemicals is determined by  Moisture or water content of crude drugs and
ignition to dull redness in the same manner as other substances must usually be accurately
in the determination of the ash content of a determined, since variable quantities of
crude drug. moisture would adversely affect the calculated
 The amount of inorganic matter that may be result.
contained in such substances as alkaloidal  Water content is generally determined by one of
salts, especially when the substance is six methods:
intended for hypodermic administration. 1. Gravimetric, for drugs containing no
 Negligible is defined as a quantity not constituents other than water, volatile at
exceeding 500 micrograms. 105°C
 2. Gravimetric, for drugs containing ether- TO DETERMINE THE WATER CONTENT OF
soluble constituent volatile at 105°C ACACIA
3. Azeotropic (Toluene distillation)
 The sample should be ground in order to expose
4. Titrimetric (Karl Fischer) as large a surface of the drug as possible so that
5. Dew point the moisture may be driven off readily.
6. Electrolytic hygrometric  The moisture and any other volatile constituent of
 Most vegetable drugs contain variable amount acacia are driven off.
of volatile substances other than water, such
as essential oils, ethers, esters, and amines, DETERMINATION OF THE MOISTURE CONTENT
this method is not generally applicable. OF DIGITALIS BY THE TOLUENE DISTILLATION
METHOD
Wt. of latter – wt. lost by the drug upon drying =
 Volatile organic substances, such as volatile oils
moisture content
and amines, remain dissolved in the toluene and
 Water is slightly miscible with ether, some of so are not calculated as moisture.
the moisture contained in the drug is extracted
by the anhydrous ether and determined as
volatile ether-soluble extractive.
CONSTANT OF FATS, FATTY OILS, WAXES,
 Xylene method and developed, has been
BALSAMS, RESINS, ETC.
modified and is one of the official methods for
moisture determination.  The methods of analysis of fatty substances,
 Referred to as the azeotropic method in the waxes, resins, etc., usually consist of the
USP and moisture method by toluene determination of a number of physical and
distillation in the NF chemical properties or values commonly known
 This method is specified for the determination as constant, although they are constant only w/in
of moisture content of many vegetable drugs certain limits.
containing 2% or more or moisture.  When taken in conjunction with color, odor, taste,
 Most official chemical compounds are and special identity tests for the given substance
relatively stable with respect to their moisture and for common adulterants, are the basis upon
content at room temp which the purity and quality of these substances
 They neither gain or loss more than slight are judged.
traces of water.
 Some of them are hygroscopic and absorb
water readily (aluminum chloride). ACID VALUE
 Others lose part or all of their water of  Also known as acid number and as the acidity
crystallization unless properly preserved index, is defined as the # of mg of KOH
(copper sulfate) necessary to neutralize the free acids in 1g of
 Control of the amount of water contained in oil, fat, wax, resin, balsam, or similar organic
chemicals is important in making soln of substance of complex composition.
definite conc and in determination of the  It gives the amnt of KOH, expressed in tenths of
dosage of substances used as medicaments. 1%, required to neutralize the free acids in a
 Crystalline cmpds that contain water of substance.
hydration or absorbed water are subjects to  Acidity may also be expressed as the # of mL of
limit test under the heading “water” which 0.1N NaOH required to neutralize the free acid
specifies a determination of the water content in 10g of substance.
by titration with Karl Fischer reagent.  Solid fats and waxes are usually melted on a
water bath and titrated while hot.
 The presence of free acids in oils, fats, and
waxes is due chiefly to the hydrolysis of the
esters composing then and is caused by
 chemical tx, by bacterial action, or by the  Since the natural fats and oils consists of mxt,
catalytic action of light and heat. of glyceryl esters of higher acids, their
 Fresh or recently prepared fatty substances saponification values do not differ greatly.
contain little or no free acids.
 Acid value increases slowly at first and more TO DETERMINE THE SAPONIFICATION VALUE
rapidly later, especially if the substance is not OF COTTONSEED OIL
well protected from the simultaneous action of
 The sx of oil should be introduced into the weighed
light and air.
flask by means of dropper to avoid possibility of a
 Official std if exceeded indicate that the portion of it adhering to the neck of the flask, and
substances have gone hydrolytic decomposition the whole reweighed.
in their preparation or purification.  The alcoholic KOH soln used should not be deeply
 High acid values are not necessarily an colored, since the color would interfere with the
observation of the end point in the titration of the
indication of rancidity.
saponification mxt.
 Minimum acid value is generally given in the  Alcoholic KOH, rather than an aqueous soln is
official std for substances that are balsamic or employed:
resinous in character.  Because oils are more soluble in alcohol than
in water.
TO DETERMINE THE ACID VALUE OF ROSIN  Because the products of saponification are
completely soluble in alcohol
 The rosin is powdered to facilitate its soln.
 Whereas when aqueous soln are used, the
 Commercial alcohol is frequently acid in rxn and
unsaponifiable matter remains insoluble.
should always be tested before the sx is dissolved.
 When saponification is complete, the mxt should
 Adding of phenolphthalein indicator soln to the
be clear and free from oil globules.
alcohol before the rosin is dissolved.
 The glyceryl esters present in fatty oils vary greatly
 If the mxt is found to be acidic, it should be
with respect to their acid components, the
rendered neutral to phenolphthalein by the addition
character of the saponification reaction.
of the std alkali soln.
 In the titration of fatty substances, it is necessary C3H5(C17H33CO2)+3KOHC3H5(OH)3+3C17H33CO2K
to shake the mxt thoroughly after the addition of
each portion of alkali to secure complete extraction  HSO4 should not be substituted for HCl, since
of the fatty acids from the immiscible oily layer. KSO4 would be precipitated from the alcoholic soln
 Rosin is soluble in alcohol and ether, and also in and this would interfere with the observation of the
alkalies. end point.
 The alkali reacts with the dibasic abietic acid
formed from the abietic acid anhydride and with
the other acids contained in the rosin, with the
formation of so-called rosin soaps and water. ESTER VALUE
 Using alcoholic KOH in the titration, since the  Ester #, is defined as the # of mg of KOH
presence of water in the above determination required to saponify the esters in 1g of a fatty or
causes dissociation of the rosin soap with
volatile oil, fat, wax, balsam, resin, or similar
consequent low results.
substance.
 Substances that do not contain free acids, the
ester # is = to the saponification value.
SAPONIFICATION VALUE  Free acids are present, however, the ester
 Saponification # or Koettsdorfer #, as it is value is the difference between the acid and
sometimes called after the originator of the saponification values.
process, is defined as the # of mg of KOH  The ester value is of particular importance in
required to neutralize the free acids and the analysis of yellow and white wax, since it
saponify the esters contained in 1g of fat, fatty serves, in many cases, to indicate the presence
or volatile oil, wax, resin, balsam, or other of adulterants, such as paraffins.
substance of similar composition.
 Considered in conjunction with the acid value,  When iodine # is considered in conjunction w/
the ester value may aid in the detection of such the saponification value of a fat or oil, it serves
adulterants as rosin and stearic acid in the wax. as a means of detecting adulteration, and
frequently it indicates the nature of the
adulterant.
UNSAPONIFIABLE MATTER  Olive oil adulterated with cottonseed oil w/out
 Defined in the USP as the substances present changing saponification value, iodine # of olive
in oils or fats that are not saponified by alkali oil increased.
hydroxides but are soluble in ordinary fat  Castor oil adulterated with olive oil w/out
solvents. changing iodine #, saponification value of
 When oils and fats are saponified, there castor oil increased.
remains a small amnt of residue that may
consist of phytosterol in vegetable oils and fats TO DETERMINE THE IODINE VALUE OF OLIVE
OIL
of cholesterol in animal oils and fats, and in
some cases, of unsaponifiable substances  The oil soluble in carbon tetrachloride
added for the purpose of adulteration.  Iodine alone is not used in this procedure because
 Normal unsaponifiable matter present in most it is absorbed very slowly by the oil.
 Iodine monochloride is readily absorbed.
oils and fats dissolves in the alcoholic soap soln  Unsaturated acids of the oleic and linoleic series
obtained upon saponification. present in olive oil, as well as their glyceryl esters,
 A large amnt of unsaponifiable matter is absorb iodochloride to form addition products.
present, however, it may separate out and float  Oleic acid (C17H33COOH) takes up 1 atom each of
on the surface of the mixture. iodine and chlorine to form the addition product of
stearic acid (C17H33IClCOOH).
 The determination of the amnt of unsaponifiable
 Glass stoppered flask is used to prevent the
matter present in certain oils, such as linseed escape of iodine and chlorine vapors.
oil and cod-liver oil, may be indicative of the  Mxt is protected from light to prevent iodine
quality and purity of the oil. monochloride consumed.
 Corn oil contain not more than 1.5%  Standing for 30min the soln is no longer yellow.
 Cod-liver oil contain not more than 1.3%  Upon the addition of the KI soln, the iodochloride
reacts with KI, liberating iodine until all chlorine is
unsaponifiable matter.
used up:

KI+IClKCl+ I2
IODINE VALUE  An excess of KI is added to ensure the complete
 Is the # of g of iodine absorbed under specified removal of the free chlorine and to prevent
conditions by 100g of oil, fat, wax, or other precipitation of iodine in the aqueous soln.
substance.  Sodium thiosulfate reacts with the excess iodine.
 Value is a quantitative measure of the 2Na2S2O3+I22NaI+Na2S4O6
proportion of unsaturated fatty acids present,
both free and combined as ester, that have the
property of absorbing iodine.
 The determination of the iodine # of fats and HYDROXYL VALUE
oils is important, since it serves to characterize  Hydroxyl #, is the 3 of mg of KOH equivalent to
them and to indicate whether they are pure or the hydroxyl content of 1g of the substance.
admixtures.  This constant gives an indication of the identity
 Determination of the iodine # therefore not only and purity of fatty substances possessing
serves as an aid in the identification of known alcoholic hydroxyl groups.
oils but also serves to indicate in a definite  The hydroxyl value is inversely proportional to
manner the class to w/c an unknown fat or oil the molecular weight
belongs.  An abnormally low value is indicative of
adulteration with higher molecular weight
 alcohols or with nonalcoholic fatty substances
(paraffin, petroleum oil, etc.)

TO DETERMINE THE HYDROXYL NUMBER OF

CETYL ALCOHOL

 Toluene serves as a mutual solvent for the solid

cetyl alcohol, the acetyl chloride, and the cetyl
acetate formed.
 Pyridine acts as condensing agent by reacting with
the hydrogen chloride formed during the
acetylation, w/c proceeds:
CH3(CH2)14CH2OH+CH3COClCH3(CH2)14CH2O2CCH3+HCl

 The excess acetyl chloride is hydrolyzed to acetic

acid by shaking vigorously with water to ensure
contact between the water and the acetyl chloride
dissolved in the oily layer.
 Titration of the acetic acid with 1N sodium
hydroxide, it is again necessary to shake
vigorously to ensure complete neutralization of the
acetic acid.
 The amnt of acetyl chloride that has reacted with
the fatty alcohol can be determined from:

Amnt of 1N NaOH consumed – excess acetyl

chloride in black and actual

ACETYL VALUE OF FATTY ACIDS

 The 3 of mg of KOH required to neutralize the
acetic acid obtained by the saponification of 1g
of acetylated fatty acids.
 The acetyl value of fatty acids corresponds
closely to the hydroxyl value of fatty alcohols,
and the 2 constant have much the same
significance w/ respect to identity and purity of
the substances.
 Acetyl value is found by acetylating hydroxy
fatty acids.

WATER AND SEDIMENT IN FATTY OILS

 Certain fatty oils, particularly those of animal
origin, w/c are not highly refined, frequently
contain some moisture and nonfatty tissue
residues.
 Nondestearinated cod-liver oil must contain not
more then 0.5% by volume of water and
sediment.