Conductometric Titrations

Definition:

The determination of the end point of a titration by means of conductivity measurement is

termed as conductometric titration.

In a conductometric titration the titrant is added from the burette and the conductivity readings
corresponding to various increments of titrant are plotted against the volume of titrant. Two curves will
be obtained which will intersect each other at appoint called “end point” or “equivalence point”.

When the reaction is not quantitative, there is some curvature in the curve near the end point
which may be due to hydrolysis, dissociation of the product or appreciable solubility in case of
precipitation reactions.

It should be borne in mind that the resistance, and thus the conductance of an electrolytic
solution is profoundly affected by changes in temperature. The resistance decreases by about 1% to 2%
for each degree increase in temperature and for this reason it is desirable to carry out a conductometric
titration at an approximately constant temperature. If absolute measurements are to be made a
constant temperature bath is, of course, necessary.

The concentration of the titrant must be 10 times as the solution being titrated. This is done to
keep the volume charge small. If it cannot be done, a correction to the reading must be applied, i.e,

Actual conductivity = ( v +V
V )
x observed conductivity where v is the volume of titrant or reagent added

and V is the original volume.

Advantages of conductometric titrations:

The following are the advantages of conductometric titrations
1) They are particularly useful in the case of coloured or turbid liquids, where ordinary indicators
cannot function.
2) They can be employed for the analysis of dilute solutions and also for very weak acids.
3) No special precautions are necessary as the titration approaches the equivalence point, since
the latter is found graphically.
4) It is not necessary to measure the actual conductance, as we any use any quantity that is
proportional to it, e.g., the reading on a Wheatstone bridge or resistance box. The same can be
directly plotted against the volume of the alkali solution used up.

Apparatus for conductometric Titrations:

1. Measuring circuits: To prevent concentration changes due to reaction at the electrodes.
2. Commercial apparatus: Convenient and can be used without knowledge of electricity or
electronics.
3. Electrodes and cells: The simplest titration cell consists of a dipping electrode, a beaker of the
appropriate size and a mechanical stirring device. The electrodes are platinised to decrease cell
capacitance and to absorb substances from solution.
4. Special methods: Though conductance is measured by means of a.c. apparatus, Eastmen
showed that direct current method is capable of yielding results that agree to 10% with those
obtained with usual a.c. method.
Differential conductance titration:
Daval and Duval used two cells connected in two branches of a Wheatstone bridge, both
cells contained identical sample solution and both were titrated with the same reagent, but one
cell always had 0.05 to 0.1ml. more titrant in it than the other. The titration curves for each cell
were plotted on graph and their point of intersection gave one point.