Precipitation Titration

PHARMACEUTICAL ANALYSIS
SHAMBADITYA GOSWAMI | ASST PROF | 2018
PRECIPITATION TITRATION
PRECIPITATION REACTION
 Precipitation refers to a chemical reaction that occurs in aqueous
solution when two ions bond together to form an insoluble salt, which is
known as the precipitate.
 A precipitation reaction can occur when two solutions containing
different salts are mixed, and a cation/anion pair in the resulting
combined solution forms an insoluble salt; this salt then precipitates out
of solution.
 The following is a common laboratory example of a precipitation
reaction. Aqueous silver nitrate (AgNO3) is added to a solution
containing potassium chloride (KCl), and the precipitation of a white
solid, silver chloride (AgCl), is observed:
AgNO3 (aq) + KCl (aq) → AgCl (s) + KNO3(aq)
 This reaction can be also be written in terms of the individual dissociated
ions in the combined solution. This is known as the completeionic equation:
Ag+ (aq) + NO3−(aq) + K+ (aq) + Cl−(aq) → AgCl(s) + K+ (aq) + NO3−(aq)
PRECIPITATION TITRATION
 In a precipitation titration, the stoichiometric reaction is a reaction

which produces in solution a slightly soluble salt that precipitates out.
To determine the concentration of chloride ion in a particular solution,
one could titrate this solution with a solution of a silver salt, say silver
nitrate, whose concentration is known. The chemical reaction
occurring is
Ag+(aq) + Cl-(aq) AgCl(s).
 A white precipitate of AgClis deposited on the bottom of the flask
during the course of the titration.
 Since the chemical reaction is one silver ion to one chloride ion, we
know that the amount of silver ion used to the equivalence point equals
the amount of chloride ion originally present.
 Since by the definition of molarity n = cV, the number of moles of
either silver ion or chloride ion can be calculated from the number of
moles of the other, and the molar concentration or the volume of
added solution can be calculated for either ion if the other is known.
ARGENTOMETRIC
TITRATION
 In precipitation titration, silver nitrate or silver ions is
involved. As the Latin name of Silver is Argentum, the
precipitation titration is often termed as Argentometric
titration.
 It has been broadly classified into following methods-
1. Mohr’s Method
2. Volhard’s Method
3. Fajan’s Method
4. Gay Lussac Method
MOHR’S METHOD
 Theory:
 In the Mohr titration, the given chloride solution (eg. NaCl) is
titrated with a standard AgNO3 solution when Cl-ions are
precipitated as AgCl.
AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3
 A small amount of K2CrO4 (Potassium Chromate) is added to the
chloride solution which acts as an indicator.
 When AgNO3 is gradually added, the end point is confirmed by
the first permanent appearance of brick red coloured precipitate
of Ag2CrO4.
Ag+(aq) + Cl-(aq) ↔AgCl(s)
2Ag++ CrO42-↔Ag2CrO4
Limitations:
 Ag2CrO4is soluble in acid so, the solution should be always
neutral.
 If the solution is acidic, first neutralize with CaCO3 to
make solution neutral, then start the titration process.
 If the solution is basic, AgNO3is precipitated as Silver
hydroxide. So, first neutralize with HNO3 and then start the
titration.
 The titration is not suitable for iodides. For chloride and
bromide the method is applicable and suitable.
 If BaCl2/BaBr2is used in the process as a sample, slight excess
of K2SO4 is added, otherwise BaSO4 will be precipitated.
Procedure: Determination of Normality of the
given chloride solution by Mohr’s Method
 Preparation of 0.1N AgNO3 solution:
Dissolve 4.248g AgNO3 in 250ml water.
 Titration:
1. Standard Solution: 0.1N AgNO3 in burette.
2. Sample Solution: 25 ml NaCl in clean conical flask.
3. Indicator: 1 ml K2CrO4 (Potassium Chromate) in conical flask
4. End Point: Brick Red Precipitate
5. Blank Titration: Perform the blank titration taking 25 ml
water in place of sample.
Organic Indicators used in Mohr’s Method:
O O
O O Na -
HO O
O O Na -
O OH
O O
Sodium Rhodizonate Tetra hydroxy quinonine
VOLHARD’S METHOD
 Theory
 The method is used for the determination of silver.
 The titration of Ag+ ions in acidic medium is done with a standard
Potassum thiocyanate solution (KSCN).
 Ferric ion is used as indicator.
 When all silver ions have been precipitated, the extra drop of
thiocyanate combines with Fe3+ ion to form a blood-red coloured
complex and it marks the end point.
 Reaction
+ 3+
Ag + SCN- AgCNS
Fe + 3SCN- Fe(CNS) 3
White ppt Blood Red/ Brown ppt

Procedure:
 Titration:
 Standard Solution: KSCN (11g in 1 lit) solution (0.1M) in
burette.
 Sample Solution: 25 ml 0.1N AgNO3 in clean conical flask.
 Acidic Medium: Add 5ml 6N HNO3 in conical flask.
 Indicator: 1 ml Ferric ammonium sulphate (40%) in conical
flask
 End Point: During titration at first white colour precipitate of
AgSCN is formed (the solution appears milky white). At the
end point blood red/ brown colour appears.
Modified Volhard’s Method
 In volhard’s method, if chloride is present, then it can react
with SCN-.
-
AgCl + SCN- AgSCN + Cl
 To prevent this-
 Either filter AgCl before titration with thiocyanate
 Or, add some Nitrobenzene before titration with thiocyanate.
 Nitrobenzene forms an oily coating on the AgCl surface to
prevent the reaction with SCN-.
FAJAN’S METHOD
 Theory:
 This method involves the titration of AgNO3 with any halide
solution in the presence of Adsorption indicator.
 Standard solution of AgNO3is added into unknown
concentration of halide (egNaCl) and a white precipitate of
AgCl is formed.
AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3
 1st Stage: At this stage Cl- ions will make a primary
adsorption layer over the precipitate of AgCl and Na+ will
make a secondary adsorption layer.
Primary Adsorption Layer
Secondary Adsorption Layer

 2nd Stage: Addition of AgNO3 make reaction mixture fuel
with Ag+ and NO3- ion.
 Now, Ag+ ion will make primary adsorption layerand NO3-
ion will make a secondary adsorption layer.
Primary
Adsorption Layer

 3rd Stage: Fluoescein (Adsorption indicator) indicator forms
F- (Fluoreceinate ion) and replace NO3- ion over surface of
AgCl.
Primary Adsorption Layer
 This replacement changes the colour mixture into pink.

Adsorption Indicators:
 Indicators which are used in Fajan’s Method are dyes such as
 Fluorescein, Dichloro-fluorescein, Eosin etc..
 These indicators are weak acidic in nature.
Procedure:
 Titration:
 Standard Solution: 0.1N AgNO3 in burette.
 Sample Solution: 25 ml halide solution in clean conical flask.
 Indicator: 8-10 drops Fluorescein in conical flask
 End Point: During titration at first white colour precipitate is
formed. At the end pointpinkcolour appears.
Assay of Sodium Chloride I.P. 1996
Volhard’s Method
 Take 0.1g of NaCl

 Dissolve in 50 ml of water
 Add 50 ml0.1M Silver Nitrate, 5ml of 2M nitric acid,
2ml of dibutyl phthalate
 Shake well and add 2 ml of ferric ammonium
sulphate as indicator, shake vigorously
 Titrate against 0.1M ammonium thiocyanate until
the colour becomes yellow.

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PHARMACEUTICAL ANALYSIS

SHAMBADITYA GOSWAMI | ASST PROF | 2018

 In a precipitation titration, the stoichiometric reaction is a reaction

White ppt Blood Red/ Brown ppt

Primary Adsorption Layer

Secondary Adsorption Layer

Secondary Adsorption Layer

Secondary Adsorption Layer

 This replacement changes the colour mixture into pink.

 Take 0.1g of NaCl

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