PRECIPITATION TITRATION

A precipitation titration is one in which the titrant forms a precipitate with the
analyte.
The important precipitating reagent is silver nitrate.
Titrimetric methods base upon silver nitrate are sometimes termed as
argentometric methods. Potassium chromate can serve as an end point
indicator for the argentometric determination of chloride, bromide and cyanide
ions by reacting with silver ions to form a brick red silver chromate precipitate
in the equivalence point region.
In the detection of chlorides, sodium chloride is estimated on the basis of its
chloride ions by titration with silver nitrate solution.
Requirements for Precipitation titration.
1. The rate of reaction between the precipitant and the substance to be
precipitated must be fast.
2. There should be no coprecipitation. The titration results should not be
affected by co-precipitation effects.
3. The precipitate should be insoluble.
4. A suitable indicator should be used to locate the end point of the
titration.
Solubility product
The process of precipitation titration is completely based on the concept of
solubility product. When the ionic compounds dissolve in water, they go into
solution as ions. When the solution becomes saturated with ions, that is
unable to hold anymore, the excess solid settles to the bottom of the
container and equilibrium is established between the undissolved solid and
the dissolved ions.
It is defined as the product of the concentration of ions in a saturated
solution of an electrolyte at a given temperature.
Example: consider the equilibrium reaction of AgCl,

AgCl Ag+ + Cl-

Where Ag+ and Cl- represent the ionic concentration,
 According to law of mass action, K = [Ag+] [Cl-]
[AgCl]
The concentration of AgCl remains constant, hence the above equation
becomes,
K = [Ag+] [Cl-], this is the solubility constant product. (Ksp)
Factors affecting the solubility of the precipitate
1. Effect of temperature
As the temperature increases, the solubility of the precipitate also
increases.
The solubility of AgCl at 10oc is 1.72 mg/L
100oc is 21.1 mg/L
2. Effect of the solvent on solubility
The solubility of most of the organic compounds is reduced by the
addition of organic solvent such as methanol, ethanol and n-propanol
etc.
3. Effect of electrolyte on solubility
The precipitate tends to be more soluble in an electrolyte solution ,
provided that the electrolytes contain no ions in common with the
precipitate.
4. Common ion effect
The solubility of a salt can be decreased by adding an excess of either
of its ions and the precipitate dissolves more easily in water than in
solution containing common ions.
Titration curve explaination
To understand the titration curve of precipitation titration, a stepwise titration
of precipitation titration at different stages will be useful.
Let us consider the titration of 50ml of 0.1 M
sodium chloride (NaCl) against 0.1M silver
nitrate (AgNO3) .
The main four regions of the titration curve are
as follows:
1) Beginning of the titration.
2) Just before the equivalence point.
 3) The equivalence point.
4) The excess point of the titrant.

[Cl-] = volume of NaCl unreacted * molarity of NaCl

Total volume

1) At the beginning of the titration, no AgNO3 is added to NaCl. Hence the

AgNO3 consumed is 0, and pCl-= 1.
2) As the titration continues, part of Cl- is precipitated as AgCl
pCl- = - log [Cl-] remaining
on calculation, pCl- = 2.27.
3) At the equivalence point, volume of AgNO3 = Volume of NaCl
[Ag+] = [Cl-]
pCl- = 4.96
4) Excess addition of AgNO3, [Ag+] increases and [Cl-] decreases
pCl- = 7.59
Indicators used in Fajan’s method
1. Fluorescein.
2. Dichloro-fluorescein.
3. Eosin.(tetra-bromofluorescein)
4. Erythrosine (tetra-iodofluorescein)
Conditions for the selection of adsorption indicators
 The indicator should have a charge opposite to that of the precipitate.
 The indicator should be secondarily adsorbed only after the equivalence
point.
 Sharp colour change is desired.
 Multivalent ions and other factors which have coagulating effects should
be avoided as a colloidal state of the precipitate is desired.
 Precipitate particles should be of colloidal dimension to maximise the
quantity of indicator adsorbed on these particles.

1. Estimation of Sodium chloride (volhard’s method)

Weigh accurately about 0.1g sodium chloride and dissolved in 50ml of
water in glass stoppered flask. Add 50ml of 0.1M AgNO3, 5ml of 2M nitric
acid and 5ml of nitrobenzene. Add 1ml of ferric ammonium sulphate as
 an indicator and titrate with 0.1 M ammonium thiocyanate. Observe
formation of red-brown colour indicating the end point.
Factor calculation :
1 Mole of AgNO3 ≡ 1 Mole of sodium chloride
1000 ml of 1M AgNO3 ≡ 58.44g of NaCl (23 + 35)
1mL of 0.1 M AgNO3 ≡ 0.005844g of NaCl.