Precipitation Titration

Important terminologies
• Saturated solution – solution that contains the maximum amount of
solute dissolved in a given amount solvent at a specific temperature
• Solubility – the maximum amount of solute dissolved in a given solvent at
a specific temperature
• Solutions that contain dissolved solute less than the maximum are called
unsaturated while those that contain dissolved solute more than the
maximum are called supersaturated solutions

Solubility product constant (KSP) • Consider an aqueous saturated solution

of a sparingly soluble salt represented by the equation:
 Argentometric titrations
• One of the oldest analytical techniques that started in the mid–1800’s
• Silver nitrate (AgNO3) is commonly used as titrant and the end point are
observed as follows:
a. Formation of a secondary colored precipitate – Mohr method
• Developed by Karl Friedrich Mohr (1806-1879) in 1865

•In practice, the indicator concentration is kept between 0.002 M to 0.005 M

• Titration is done at a pH of 8 to avoid precipitation of silver as hydroxide
(above pH of 10) and eliminate formation of HCrO4 –1 (below pH of 6) which
results to consumption of more titrant
• Usually a low concentration of chromate is desired to detect the end point
clearly since a chromate ion imparts an intense yellow color.
B. Formation of a colored complex– Volhard method
• Developed by Jacob Volhard (1834-1910) in 1874

• Titration is done in acidic medium using HNO3 with indicator

concentration of about 0.01 M
• For the titration of chloride, the resulting precipitate is filtered off before
the back titration since it reacts with the titrant and is more soluble than
AgSCN
• For the titration of iodide, the indicator is not added until all iodide is
precipitated since the dissolved iodide is oxidized by the ferric ion
c. Formation of a colored adsorption complex – Fajans Method
• Developed by Kazimierz Fajans (1887-1975) in 1926

• Before the equivalence point, chloride anion adsorbs to the precipitate in

the primary adsorption layer and drives the adsorption dye anion away by
electrostatic repulsion and the dye imparts a greenish-yellow color in
solution
• As soon as the equivalence point is just exceeded with the presence of
excess silver ion, this ion now adsorbs to the precipitate in the primary
adsorption layer where the oppositely-charged adsorption dye anion
adsorbs to the counter-ion layer and imparts a pink color in solution
• For titration of chlorides, fluorescein may be used at an optimum pH
range between 7-10 while dichlorofluorescein is used in acidic solution of
pH greater than 4.4
• For bromides, iodides and thiocyanates, eosin is used for titration in
acidic medium of pH between 1-2 imparting magenta color at the end point
• Dextrin is added to prevent excessive coagulation of the AgCl precipitate.