NIET (Pharmacy Institute), Greater Noida

2022

UNIT-III (Precipitation Titration)

Ranjeet Kumar Yadav
Assistant Professor, NIET (Pharmacy Institute), Greater Noida
Titration
Titration is a technique used in analytical chemistry to determine the concentration of an
unknown solution by using a solution of known concentration. Solution of known concentration
is known as titrant while the solution of unknown concentration is known as analyte in titration
technique.
Precipitation titration is a type of titration which involves the formation of precipitate
during titration at the endpoint. In this article, we will discuss mainly precipitation titration
definition with example and argentometric titration (a type of precipitation titration), Volhard
method, Fagan's method, Mohr’s method, and the difference between Mohr’s method and
Volhard’s method.
What is Precipitation Titration?
Precipitation titration is a type of titration which involves the formation of precipitate during the
titration technique. In precipitation titration, the titrant reacts with the analyte and forms an
insoluble substance called a precipitate. It continues till the last amount of analyte is consumed.
It is used to determine chloride by using silver ions.
Principle of Precipitation Titration
The principle of precipitation titration can be shown as follows –
Quantity of added precipitating reagent = quantity of substance being precipitated
Basic Requirements of Precipitation Titration
1. Precipation should be produced in rapid manner
2. Reaction must be quantitative
3. End point or equivalence point must be color visible and must not be affected by co-
precipitation
4. Precipitate or product formed should be insoluble
Limitation of precipitation Titration
1. Suitable indicators for detecting precipitation are unavailable
2. The rate of precipitation in dilute solution is too slow
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2022
3. During titration – co-precipitation occurs Which offer difficulty in determining the exact
composition of precipitate formed
4. Precipitation titration are limited to use Ag+ ion to detect the anions
Factors Affecting Solubility of Precipitate
1. Common ion effect: Common ion is one the component ions of the sparingly soluble salt
which increases the solubility of precipitate
Examples: when a solution of AgCl is dissolved in solution of NaCl---Cl - ions formed
upon ionization of NaCl from the common ion with Cl- ion obtained by ionization of
AgCl
2. Complex Formation: Addition of an ion that forms a complex with one of the
component ion of the precipitate- which increases the solubility of precipitate.
3. Temperature: An increases in temperature increases the solubility of precipitate
4. Acids: When certain acids like Sulphuric acid , nitric acid etc are added to sparingly
soluble salt of weak acids results in solvent effect on salt increases their solubility
5. pH: An increase in pH decreases the solubility of salts and vice versa.
6. Solvents: Addition of organic solvents such as alcohol reduces the solubility of most
inorganic compounds.
Precipitation Titration Curve
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2022

Reaction involves is as follows –

AgNO3 + NaCl AgCl + NaNO3
Precipitation Titration Example
Determination of concentration of chloride ions in a solution by using silver ions of a known
solution is an example of precipitation titration. Reactions involved are as follows –
AgNO3+Cl- AgCl + NO3-
(in a solution of NaCl) (White ppt)
Argentometric Titration
It is a type of precipitation titration which involves the use of silver ions. The symbol of silver is
Ag which is taken from its Latin name Argentum. So, the word argentometric is also taken from
the Latin word Argentum.
Methods of Argentometric Titration

 Volhard’s Method
 Fajan’s Method
 Mohr’s Method

Volhard’s Method
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2022
German Chemist- Jacob Volhard
This method was first given by German Chemist Jacob Volhard in 1874. This method involves
the determination of halide (F, Cl, Br, I) ions, anions like phosphate, chromate in acidic medium
by using silver ions. This titration must be performed in an acidic medium otherwise iron ion get
precipitated as hydrated oxide. Iron ions are used as indicators in Volhard’s method. In this
method, 1st analyte (halide ion solution or any other anionic solution) is titrated with a measured
excess of AgNO3.

Reaction – If the analyte contains chloride anions. The reaction will be as follows -
Cl- + Ag+ AgCl + Ag+ (in excess)
Now the unreacted or in excess silver ions are titrated with a standard solution of KSCN using
iron ion (Fe+3) as an indicator which gives red color in the end point.
Reaction – The reaction can be shown as follows-
Ag+ + SCN- AgSCN

Now as the thiocyanate ion will be in excess in the titration mixture, red colour appears which is
due to the formation of the FeSCN(II) compound.
Reaction – Reaction involved can be shown as follows –
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2022

Fe+3 + SCN- FeSCN+2

(Red colored compound)
It is an indirect method of precipitation.

Fajan’s Method
American Chemist – Kazimierz Fajan
This method was given by American chemist Kazimierz Fajan. That’s why it is known as fajan’s
method. This method is also known as the indicator adsorption method because in this method
chloride ions present in excess are adsorbed on silver chloride surface. In this method
dichlorofluorescein is used as an indicator. The end point is determined by green suspension (of
AgCl and indication) turning pink (complex of AgCl and indicator).

Reaction – reaction involved can be written as follows –

Ag+ + Cl- AgCl
Ag+ + AgCl + Indicator AgCl-Ag+ Indicator
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2022
It is a direct method of precipitation.
Mohr’s Method
Karl Friedrich Mohr
This method was given by Karl Friedrich Mohr, a German Chemist. That’s why this method is
called Mohr’s method. It’s a direct titration method. In this method silver nitrate is used as titrant
and chloride ion solution as analyte. Potassium chromate is used as an indicator. At the end
point, when all chloride ions are consumed by silver ions, reddish brown colored precipitate is
formed by reaction of silver ions and chromate ions.

Reaction- Reaction involved can be written as follows –

AgNO3 + Cl- AgCl +NO3-
(in solution of NaCl) (White ppt)
At the end point –
2Ag+ + CrO4-2 Ag2CrO4
(Reddish Brown ppt)
Difference between Mohr’s Method and Volhard’s Method

S.No. Volhard’s Method Mohr’s Method

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2022

1. It is an indirect method of titration. It is a direct method of titration.

In this method, red precipitate of ferric In this method, red precipitate of silver
thiocyanate is formed which indicates the end chromate is formed which indicates the
2. point of the titration. end point.
+3 - +2
Fe + SCN FeSCN 2Ag+ + CrO4-2 Ag2CrO4
(Red colored compound) (Reddish Brown ppt)

Conditions for titration should be acidic. Conditions for titration should be

3.
Otherwise iron ions form hydroxide ions. neutral to alkaline.

By this method, we can determine the By this method, titration of iodide and
4.
concentration of halides. cyanate is not possible.

This titration can be carried out under

5. This titration is carried out below 20℃
room temperature.

Applications of Precipitation Titration

 It is used for the determination of halide ions in the solution.

 It is used to measure salt content in food, beverages and water.
 It is used for Sulphur, thiocyanate, dichromate etc.
 Many drugs such as carbromal, KCl infusion, NaCl infusion etc. can be analyzed by
precipitation titration.
 It can be used for the determination of concentration of anions in the analyte.

Estimation of Sodium Chloride by precipitation titration

Assay in chemistry means the process of determining the composition or quality of a substance.
For the assay of sodium chloride Volhard, the process is used.
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2022
The Volhard method of assay of sodium chloride is described below Weigh accurately
0.1 g of sample and dissolve it in 50 mL water. To this add 50 mL of 0.1 M silver nitrate, 5mL of
2M nitric acid and 2mL of concentrated KMnO4 . Shake well and titrate with 0.1 M ammonium
thiocyanate taken in the burette. 2 ml of ferric ammonium sulphate solution is added as an
indicator. Titrate until the colour become reddish brown.