Course Name: Volumetric and Gravimetric

Analytical Chemistry

Course Code: 4022133-3

Lecture 9 contents

Precipitation Titration
-Mohr’s method
-Fajan’s method
-Volhard’s method
 Precipitation reaction

A reaction in which a precipitate is formed (sparingly

soluble compound).

As in that titration of silver ion with chloride ion. NO

change in oxidation state.

Volumetric analysis using precipitation reaction

Based on using silver nitrate as titrant is called
argentometric titration
The Solubility Product, Ksp

Ag + + Cl - ⇌ AgCl (s)
white ppt

Ksp = [Ag +] [Cl -]

 Precipitation titration curve

A titration curve for this method usually consists of a

plot of PAg versus the volume of silver nitrate added

We have three region in the titration curve :

1- Before reaching the eq. point:
2- At the eq. Point
3- After the eq. Point
Additional data points calculations:
Detection of end point in precipitation titration

Indicators
reacting with the
1- Mohr’s method titrant
2-Volhard΄s method
3-Fajan’s method

Adsorption
indicators
 Mohr Method

formation of a colored precipitate (reddish brown

Ag2CrO4)

Titrant : AgNO3 (secondary standard solution)

Ag+(aq) + Cl-(aq) → AgCl(s) (titration reaction)

Indicator: 5% potassium chromate salt (K2CrO4)

2Ag+(aq) + CrO42-(aq) → Ag2CrO4(s) (indicator reaction)

yellow red
 Mohr Method
-Has to be performed at a neutral or weak basic
solution
of pH 7-9 (or 6-10)
- In a lower pH (acid solution)
CrO42-(aq) + 2H+(aq) Cr2O7-2 + H2O
The end point (formation of Ag2CrO4) is delayed.
-In a high pH (basic solution)
Formation of ppt of silver hydroxide
2Ag+(aq) + 2OH-(aq) 2AgOH(s) Ag2O + H2O
So, we must avoid this by doing the titration in slightly
alkaline solution to determine chloride and bromide
Mohr Method
 Volhard Method

formation of a colored complex (reddish colour)

Titrant : KSCN
Indicator: Ferric alum (NH4) Fe(SO4)2

-The titration must be carried out in acidic medium to

prevent the precipitation of Fe+3 as Fe(OH)3

-The advantage of this method is the possibility of

titration in very acidic solution.
 Volhard Method
Determination of Cl- requires a back-titration
– First, Cl- is precipitated by excess AgNO3
Ag+ (aq) + Cl-(aq) AgCl(s)

– Excess Ag+ is titrated with KSCN in the presence of Fe3+

Ag+(aq) + SCN-(aq) AgSCN(s) (Indicator’s reaction)

– When Ag+ has been consumed, a red complex forms

Fe3+(aq) + SCN-(aq) [FeSCN]2+(aq) (Indicator’s reaction)
Volhard Method
 Fajan’s Method
Adsorption indicator organic dyes adsorbed at end point
on the surface of the precipitate to give it a different
colour than a free precipitate, e.g. (dichlorofluroscien)

(Weak organic acid)

Medium should be natural where acid medium decrease the

concentration of indicator ion so, render detection the end point.

HIn H+ +In-
 Home Work

Chloride in a brine solution is determined by the

Volhard method. A 10 ml aliquot of the solution is
treated with 15 ml of standard 0.1182 M AgNO3
solution. The excess silver is titrated with standard
0.101 M KSCN solution, requiring 2.38 ml to reach
the red end point. Calculate the concentration of
chloride in the brine solution, in g/L