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+ Conductivity
+ Chemistry
+ Electrochemistry
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Adelaida de Lumen

Determination of Cell constant

Andy Cairns  Follow

Conductivity measurements were done in late 1800s by Friedrich Kohlrausch, who painstakingly measured the conductivities of solutions so accurately that they are still valid today. Most of his work is in German was published in relatively unknown journals. In his time, conductivity theory was not advanced enough to predict the conductivity of simple salt solutions in water, so there was no a priori theoretical prediction of conductivity, from the first principles. I don't think it is doable today after 100 years (may well be wrong(.

However, the accurate measurement of resistance was well established in physics. See below.

A paper in the J. Am. Chem. Soc. 1933, 55, 5, 1780 describes what Kohlrausch and his meticulous colleagues they did. Note the level of details which is remarkably missing from papers today.

After Kohlrausch had developed his method of measuring the electricalconductance of solutions by means of an alternating current bridge, heundertook with the aid of Holborn and Diesselhorst’ the determinationof the specific conductance of seven standard reference solutions inabsolute units in order that the results might be available to himselfand to other experimenters for the calibration of conductance cells.For this purpose they used two cells whose cross sectional areas, a,and length, l, were determined mechanically. The cell constant,l/a, could then be computed in absolute units (cm$^{-1}$) from the measured dimensions.

The cell constants of a considerable number of other cells withsealed-in electrodes of the usual type were determined electrically bycomparison with the primary cells by measurements of resistance whenfilled with a common solution. These cells, whose cell constants werethus determined indirectly, were then used for the determination ofthe specific conductance of the seven standard reference solutions atapproximately 0, 9, 18, 27 and 36 C. The specific conductance of eachof these solutions for every degree between 0 and 36 C was obtained byinterpolation. No actual measurements were made at either 20 or at25’. The water-bath used to fix the temperature of the cells was notprovided with an automatic thermostatic control. The majority of thedata on conductance in the literature are based on the values ascribedto these standard reference solutions by Kohlrausch, especially the 1N and 0.1 N potassium chloride solutions.

In the original paper by Kohlrausch, Holborn and Diesselhorst it isstated that the normal potassium chloride solution was prepared bydissolving 74.555 g. of potassium chloride weighed in air and makingup to 1 liter at 18 C. The 0.1, 0.02, and 0.01 normal solutions wereprepared by dilution by volume. The book “Das Leitvermogen derElektrolyte” by Kohlrausch and Holborn, which was published in thesame year as the paper referred to, contains alternative directionsfor the preparation of these solutions by weight. This book hasprobably been used by other experimenters more than the original paperbecause it is more generally available.

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