CL 610: EXPERIMENTAL METHODS

Report
On
Experiment No: 2
Measurement of moisture content of a sample using Karl Fischer
volumetric titration method

Department of Chemical Engineering

Indian Institute of Technology Bombay

Submitted by: Group No. : M4

Arunima Ghose (133020014)
Madhavi Gupta (133020016)

Submitted to:
Prof. Rajdip Bandyopadhyaya
Prof. Dr. Y.S. Mayya

Date of Experiment: 19-01-2014

Date of submission: 27-01-2014

AIM :
To determine the moisture content of unknown samples by Karl Fischer volumetric titration
technique.

APPARATUS :
1. Karl Fischer Auto titrator
2. Weighing balance
3. Magnetic stirrer
4. Titration flask
5. Spatula & butter paper

CHEMICALS:
1. Karl Fischer reagent,
2. Karl Fischer grade dry methanol,
3. Di-sodium tartrate dihydrate (purified)
4. Samples (KCl and Glycerol)

THEORY:
Karl Fischer titration is an analytical method for determining the moisture content in a variety of
products. The fundamental principle behind it is based on the Bunsen Reaction between iodine and
sulfur dioxide in an aqueous medium.
I2 + SO2 +2H2O 2HI + H2SO4

Karl Fischer discovered that this reaction could be modified to be used for the determination of water
in a non-aqueous system containing an excess of sulfur dioxide. He used a primary alcohol (methanol)
as the solvent, and a base (pyridine) as the buffering agent. The reagents most frequently used today are
pyridine-free and contain imidazole or primary amines instead.

Types of Karl Fischer titration methods :

1) Volumetric Karl Fischer Titration
2) Coulometric Karl Fischer Titration
In our experiment we used the Volumetric Karl Fischer titration technique.

Fig.1. Karl Fischer Auto Titrator

(Ref.- http://labindia-analytical.com/index.php?id=autoatic-karl-fischer-titrator)

Volumetric Karl Fischer Titration :

In this technique the titer value of the Karl Fischer reagent is determined first which is
represented as , mgH2O/ml of KF reagent. Water is quantified on the basis of the volume of Karl
Fischer reagent consumed. Volumetric titration is best suited for determination of water content
in the range of 0.0001% to 100%.
Principle : Iodine present in the Karl-Fisher reagent reacts quantitatively and selectively with
water.
The primary reaction involved in the titration is as follows :
I2 + SO2 + H2O + 3Base + CH3OH 2Base HI + Base HSO4CH3
Water and iodine react in 1:1 ratio in the above reaction.

The amount of water present in the sample is calculated based on the concentration of iodine in
the KF titrating reagent and the amount of KF reagent consumed in the titration.
Iodine first reacts with all the water present in the sample ,then the excess iodine which remains is
detected voltametrically by the titrators indicator electrode. A constant current of 1-30A is applied
between two platinum electrodes. If the titration solution has a relatively high water content, a
polarization voltage of 300-500mV will be produced. As the Karl Fischer titration continues and the
end-point approaches, the voltage suddenly drops to 10-50mV. The endpoint is reached when the
voltage becomes constant for a certain period of time .

Theoretical formula for calculating moisture content:

% moisture = 100S(KF B L/1000) / W
Where , S strength of KF (mg/ml)
KF volume dispensed (ml)
B blank volume (ml)
L leak rate (ml/min)
W weight of sample (mg)

PROCEDURE:

1. Two dessicant tubes are filled with silica gel and molecular sieves and one of them is placed in
the titration flask (which has been properly dried to remove any traces of moisture by
heating it overnight in a hot air oven) and the other is attached to the KF reagent bottle.
2. The dispenser tube containing KF reagent is attached to the titration flask.
3. 40-50 ml (approximately) of KF- grade dry methanol is poured into the titration flask.
4. Priming/ pre- titaration is done to remove old KF reagent that was used before .
5. Standardization:
This is used to determine the strength of KF reagent being used in mg H 2O/ml KF
reagent. A fixed mass of di- sodium tartarate dehydrate is added to the flask and titration
is done to determine the titer value of KF reagent.
6. Titration of sample 1 ( KCl ):
A certain amount of KCl sample is first weighed and then added to the titration flask. The
auto-titration is run and when the end point is reached, the dispensed volume of KF
reagent and % moisture readings are noted down. This is repeated for three different
weights of KCl sample.

7. Titration of sample 2 ( Glycerol ):

A certain amount of glycerol sample is first weighed and then added to the titration flask
using a syringe. The auto-titration is run and when the end point is reached, the dispensed
volume of KF reagent and % moisture readings are noted down. This is repeated for three
different weights of glycerol sample.

OBSERVATIONS & CALCULATIONS:

Standardization:
Weight of di- sodium tartarate dehydrate taken = 83.14mg
Dispensed volume of KF reagent = 3.057 ml
Strength, S = 4.2589 mg H2O/ ml KF
(Function no. : 47 )
Titration of unknown samples :

Sl. No.

1.
2.
3.

Sl. No.

1.
2.
3.

Sample 1( KCl):
( Leak rate = 10 l/min)
Volume of KF
% moisture
dispensed (ml)
(observed)

Weight of
% moisture
sample
(calculated)
(mg)
84.69
0.345
1.7400
1.6846
105.20
0.351
1.4250
1.3805
98.70
0.225
0.9752
0.9277
Coefficient of variation (of observed % moisture) = 0.2785
Sample 2 ( Glycerol)
(Leak rate = 10 l/min)
Weight of
Volume of KF
% moisture
% moisture
sample
dispensed (ml)
(observed)
(calculated)
(mg)
467.48
4.510
4.1088
4.0996
152.77
1.158
3.2283
3.2004
474.95
3.291
2.9511
2.9421
Coefficient of variation (of observed % moisture) = 0.1762

Sample Calculations:
% moisture = 100S(KF B L/1000) / W

For sample 1,
S = 4.2589 mg H2O/ ml KF
KF = 0.345 ml
W = 84.69 mg
B = 0 ml
L = 10 l/min

% moisture = 1.6846 %

Mean %
moisture
(observed)
1.3801

Mean %
moisture
(observed)
3.4294

RESULTS & DISCUSSIONS :

Glycerol has higher % moisture content than KCL.

It is has been observed from the results obtained above that the % moisture determined by
the Karl Fischer auto titrator and that calculated using the formula yield almost the same
values. This small variation in results can be due to improper addition of sample into the
titration flask.

The coefficient of variation for KCL is higher than that for glycerol. Since glycerol is a
liquid addition of sample into the flask was easier in comparison to KCL solid sample.
Glycerol drops did not stick to the walls of the flask whereas while adding KCL sample
some would stick to the walls of the flask and the mass of sample that is actually added is
less than that measured before adding the sample.

ADVANTAGES & DISADVANTAGES OF THIS METHOD :

Advantages:
1. Small sample quantities required.
2. No heating required.
3. Short analysis duration.
4. Nearly unlimited measuring range (1ppm to 100%).
5. High precision and accuracy.
Disadvantage :
The major disadvantage is that the water has to be accessible and easily brought into methanol
solution. Many common substances, especially foods such as chocolate, release water slowly and
with difficulty, and require additional efforts to reliably bring the total water content into contact
with the Karl Fischer reagents.
PRECAUTIONS:

Always check that the titrant, solvent and waste bottles, as well as the titration beaker are
properly assembled.
The beaker system should be properly sealed against atmospheric moisture.
The dessicant should be properly dried.
The titration flask should be dried properly before carrying out the experiment.
Care should be taken while adding the solid sample as it may stick to the walls of the

flask.