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 deter mined. There is good agreement between both sets of values. The ionic transport coefficients of irreversible thermodynamics lij 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 %.