Conductimetry

As its name implies, conductimetry is concerned with the electrical conductivity of electrolytes. Measurements are made indirectly across the resistance of the solution with alternating current, since direct current would alter the composition of the sample solution by electrolysis. Experience has shown that for reasons related to the measuring technique (polarisation phenomena) better results are obtained when the measuring frequency is adapted to the range of measurement. The conductivity of a solution depends on: The quantity of ions. The more ions a solution contains, the higher will be its conductivity. The kind of ions. The smaller and more mobile an ion, the better will be its electrical conductivity. Thus H3O+, OH-, K+ and Cl- ions all conduct very well. The solvent. The more polar the solvent, the better the ionisation of the solutes it contains. In relation to this, water is an ideal solvent, while methyl alcohol is also good. The temperature. Ionic mobility increases with rising temperature. According to the type of ion, the conductivity increases by 1-3% / C. To avoid measuring errors (change in field distribution), measurements should always be carried out in a definite volume. For this reason, immersion cells are always surrounded by a glass bell.

Figure 1. A modern conductivity meter with cell and standard KCl solution for determination of cell constant

The measuring cell is calibrated with KCl solution and cell constant c allocated to it. The value of the size of the cell refers to a distance of 1 cm between electrodes and an area of 1 cm2. The unit is thus the cm-1. Conductance is quoted in mS or S units, and conductivity in mS cm-1 or S cm-1. The measuring temperature should be given or, failing this, the value converted for the reference temperature of 20 C by means of the temperature coefficient.

Conductance G = 1/R unit S (siemens) = 103 mS = 106 S Conductivity = G . c where c is the cell constant

A measured conductivity should be correctly reported as a follows: S.cm-1 (20 C)

In conductimetric titrations, the cell constant does not usually need to be known, since only the change in conductance during the titration is tracked.

Conductivity meter

Conductivity cell

Magnetic stirrer

Figure 2. A simple conductimetric titration system

Some typical conductimetric titration curves are shown in Fig. 3. (a)-(d).

Figure 3. (a)-(d) Typical conductimetric titration curves Strong acid with a strong base (a) Line 1-2 Strong acid with a weak base (a) Line 1-3 Weak acid with a strong base (b) Weak acids with weak bases (c) Mixture of a strong acid and a weak acid with a strong base (d)

Author: Vmos Istvn Institution: Petrik Lajos Vocational School for Chemistry, Environmental Sciences and Information Technology, Budapest, Hungary

For further information see: http://global.com/story_e/conductivity Reference textbooks: D. A. Skoog - D. M. West - F. J. Holler: Fundamentals of Analytical Chemistry, Saunders College Publishing, Fort Worth, 1992. J. Kenkel: Analytical Chemistry for Technicians, Lewis Publishers, Boca Raton (Florida), 1994.