PRECIPITATION TITRATIONS

 It is a type of volumetric analysis that depends on the formation of a precipitate.

 The most important precipitating agent used in precipitation titration is Silver nitrate
(AgNO3). Titrations based on the use of silver nitrate are called Argentometric
titration.
 Argentometry is derived from a latin word Argentum which means silver.
 Argentometric titrations are mainly used for determination of halides (Cl, Br & I).
These are also used for the determination of SCN, CN and other compounds which
form insoluble products (precipitate) with Silver nitrate.

Detection of the end point: Indicators

 Two types of indicators are generally used.

 The first type forms a coloured precipitate with the titrant which is present in
excess.
 The second type, called an adsorption indicator, suddenly becomes adsorbed on
the precipitate at the equivalence point owing to a change in property of the
precipitate at the equivalence point, and the colour of the indicator changes when
it is adsorbed.

Mohr’s method

 The Mohr’s method involves the use of a silver nitrate solution as the titrant for the
determination of chlorides and bromides.
 When a chloride containing solution reacts with a standard solution of silver nitrate, it
results in the formation of silver chloride.
 When all the chloride existing in solution is completely precipitated in this manner,
the next excess drop of the titrant leads to reaction between silver and the indicator
ions.
 In this method Potassium chromate (K2CrO4) is used as an indicator. Chromate is
yellow in neutral and alkaline conditions. At the endpoint the chromate ions combine
with Silver ions to form red coloured Silver chromate.
 Silver chromate will form only after all the chloride ions (from NaCl) had been
precipitated. The next extra drop of Silver nitrate causes precipitation of Silver
chromate (red coloured).

AgCl + AgNO3 AgCl + NaNO3

(white)

2AgNO3 + K2CrO4 AgCrO4 + 2KNO3

(red)

 Errors are introduced due to the need of addition of extra titrant before the endpoint
colour is visible. To overcome this error it is necessary to carry out blank titrations,
where only indicator is present. It is also important to use a constant amount (1 ml) of
indicator in all titrations.
  Mohr’s

method works in the pH region of 6-9 only.
Above this pH, Silver will form a precipitate with hydroxide.

+ -
Ag + OH → AgOH ↓

Below this pH chromate converts to dichromate, a bright orange colour
thereby delaying the endpoint. Calcium carbonate is often added to reduce the
acidity of the solution.
2- + 4- 2-
2CrO4 + 2H → 2HCrO → Cr2O7 + H2O

Volhard’s method

 Volhard’s method involves the titration of chlorides, bromides and iodides in an acidic
medium.
 A known excess of silver nitrate solution is added to the sample and the excess is back
titrated with standard thiocyanate solution. This method uses back titration with
potassium thiocyanate.
 The titration uses iron (III) chloride as an indicator. This indicator works by forming
the coloured complex with an excess of ammonium thiocyanate.
 The solution must be acidic, with a concentration of about 1 M nitric acid so that the
complex formed is stable.
 The method is suitable for the direct determination of silver.

NaCl + AgNO3 AgCl + NaNO3

(Excess) (white)

AgNO3 + NH4SCN AgSCN + NH4NO3

2+ 2+ +
Fe + NH4SCN [FeSCN] + NH4
(reddish-brown)

Fajan’s method

 With adsorption indicators, the indicator reaction takes place on the surface of the
precipitate. The indicator, which is a dye, exists in solution in the ionized form,
usually an anion (In−).
 Adsorption indicators are organic compounds that tend to be adsorbed onto the
surface of the solid precipitate in a precipitation titration.
 Consider the titration of NaCl with AgNO 3. Before the equivalence point, Cl− is in
excess, and the primary adsorbed layer is Cl −. This repels the indicator anion, and the
+
more loosely bound secondary layer of adsorbed ions is cations, such as Na . [Fig (a)]
+
 Beyond the equivalence point, Ag is in excess, and the surface of the precipitate
becomes positively charged, with the primary layer being Ag+. This will attract the
indicator anion (having negative charge) and adsorbs it in the counter layer. [Fig (b)]
  A possible explanation for this colour change is that the indicator forms a coloured
complex with Ag+, whose formation is facilitated by adsorption on the surface of the
precipitate (it becomes “insoluble”).
 Examples of adsorption indicators: Fluorescein, Dichlorofluorescein, Bromcresol
green, Eosin, Methyl violet, Rhodamine 6 G, Orthochrome T, Bromphenol blue,
Thorin.

Estimation of Sodium chloride: (Volhard’s method)

 The assay of Sodium chloride can be performed by Volhard’s method.

 Weigh accurately about 0.1 g Sodium chloride and dissolve in 50 ml of water in a
glass-stoppered flask.
 Add 50.0 ml of 0.1M Silver nitrate, 5 ml of 2M Nitric acid and 2 ml of Dibutyl
phthalate, shake well and titrate with 0.1M Ammonium thiocyanate using 2 ml of
Ferric ammonium sulphate solution as indicator, until the colour becomes reddish
yellow.
 Each ml of 0.1M Silver nitrate is equivalent to 0.005844 g of NaCl.

Sr. No. Mohr’s method Volhard’s method

1. It is a direct titration of sample This is an indirect method in which sample is
with Silver nitrate. precipitated with the excess Silver nitrate and it
is back titrated with Ammonium thiocyanate.
2. Potassium chromate is used as Ferric ammonium sulphate is used as an
an indicator. indicator.
3. At the end point red ppt of Silver At the end point red solution of Ferric
chromate is formed. thiocyanate is formed.
4. This reaction is carried out in the This reaction is carried out in the acidic pH.
pH range of 6-9.
5. This method works on the This method works on the principle of
principle of formation of formation of coloured solution of complex.
coloured precipitate.
- - - - -
6. Titration of I , CN is not Determination of Cl , Br , I is possible with this
possible with this method. method.