ANALYTICAL

CHEMISTRY
(Precipitation
Titrations)
Dr.S.SURESH
Assistant Professor
Email:avitsureshindia@gm
ail.com

Precipitation
titration
Titrations with precipitating agents are useful for
determining certain analyte. Example: Cl can be
determined when titrated with AgNO 3

Determination of chloride
Principle
Chlorides are present in all types of water
resources
at
a
varying
concentration
depending on the geo-chemical conditions in
the form of CaCl2, MgCl2 and NaCl.
Chlorides are introduced into the water
resources from the discharge of effluents from
chemical industries, sewage disposal and
seawater intrusion in coastal region.
The concentration of chloride ions more than
250 ppm is not desirable for drinking purpose.
The total chloride ions can be determined by
argentometric method. (Mohrs Method)

Estimation of chloride (by

Mohrs method)
In this method Cl ion solution is directly titrated
against AgNO3 using potassium chromate (K 2CrO4 )
as the indicator.
AgNO3

Cl
(in water)

AgCl
+
NO3
(White precipitate)

At the end point, when all the chloride ions are

removed. The yellow colour of chromate changes
into reddish brown due to the following reaction.

2AgNO3 +
2KNO3

K2CrO4
(yellow)

Ag2CrO4

(Reddish brown)

Estimation of chloride
Titration
Estimation of Chloride ion:
20 ml of the given water sample is
pipette out into a clean conical
flask. 1 ml of freshly prepared
potassium chromate solution is
added as an indicator and titrated
against standard AgNO3 solution
taken in the burette. The end point
is the change of colour from yellow
to reddish brown colour. Repeat the
titration for concordant values.

Calculation:
Volume of AgNO3 used
Normality of AgNO3

V1
N1

= -------- ml (Burette Reading)

= -------- N (From

Standardisation)

Volume of water sample

V2

Normality of water sample

N2

= 20 ml
N2 =

= V1 x N 1

V2
Normality of water sample(chloride ion) N2 = ------ N
Amount of Cl ions present in 1 litre
Equivalent
weight
Amount of Cl ions present in 100 ml
the given water sample
= ----------- gms.

= Normality (N 1) X

100
1000

= Normality X 35.46 X

Estimation of chloride
(Volhards Method)
Volhards method is used in the estimation of
chloride ions with standard solution of AgNO 3
It is an example of titration in which indicator
forms a coloured complex ion with the
titrant(i.e) silver nitrate.

Determination of chloride by Volhard Method

This
is
an
indirect
method
for
chloride
determination where an excess amount of standard
Ag+ is added to the chloride solution containing Fe 3+
as an indicator. The excess Ag + is then titrated with
standard SCN- solution until a reddish brown color
is obtained which results from the reaction:
NaCl

AgNO3 AgCl

Excess Ag+

SCN-

NaNO3 + excess Ag+

Fe3+ (Yellow) + SCN- =

brown)

AgSCN
Fe(SCN)2+ (Reddish

Determination of Chloride ion

Preparation of standard ammonium
thiocyanate
By weighing appropriate quantity of
ammonium thiocyanate, its 250ml of 0.1M
solution is prepared in distilled water.

Determination of unknown chloride ions

Given chloride solution is diluted to 250ml
using distilled water. From this 20ml solution is
pipetted out into a conical flask to which 20ml
of 0.1M AgNO3 is added.
After shaking the solution,2ml of nitrobenzene
and 5ml of 30% HNO3 and ferric alum are added
as indicator.
It is then titrated with standard NH 4SCN till
reddish
brown
colour
is
obtained
to
supernatant solution. Suppose the reading is
x ml, Then (20-x)ml will be the amount of
NH4SCN required to precipitate Cl ions.
Then the amount of Cl ions in given solution
can be calculated.