The determination of the standard potential of the cell PbxHg - PbC12 25 Mol% MeOH, 75 Mol% H2O - AgCl - Ag and derived thermodynamic functions (1949)
AuthorsFoster, P. K.show all
The problem of electrolytic solutions involves the correct representation of their microscopic states. However, due to the development of electrochemical thermodynamics by Gibbs, it is possible to obtain from experimental data, derived functions which are independent of any assumptions as to a model of the system, or the mechanism of the process considered. From a knowledge of the standard free energy change and its temperature coefficient, the standard entropy, standard heat content, and standard heat capacity changes can be readily evaluated. The value of the tabulated functions built up in this way, is twofold. Trends in the values of a function as certain variables, such as solvent or electrolyte, are in turn fixed, may lead to a postulated model or mechanism which would enable the theoretical calculation of the function. Conversely, any significant theory of solutions and solution processes must be able to reconcile its predictions with available experimental data. The present work is concerned with the evaluation of these functions for a moderately strong electrolyte in a mixed solvent by measuring the potential of a suitable galvanic cell ranges of temperature and concentration.