Irreversible thermodynamics and the transference numbers of aqueous cadmium chloride solutions

Abstract

A comparison of Hittorf and cell transference numbers provides a means of testing the validity of the Onsager reciprocal relation for electrochemical systems with transference. Cell transference numbers of aqueous cadmium chloride solutions at 25°C have been determined at concentrations from 0.1 to 6 mol kg^–1. Hittorf transference numbers for the same system have also been determined. There is good agreement between both sets of values. The ionic transport coefficients of irreversible thermodynamics l_ij have been calculated for concentrations from 0.1 to 1.0 mol kg^–1 and in this region the Onsager reciprocal relation is shown to be valid to within about 1 %.