On the thermodynamic framework of solutions (with special reference to aqueous electrolyte solutions)

Abstract

Thermodynamic consistency relations arising from the properties of equations that are homogeneous in the sense of Euler are examined, and alternative minimum tests for demonstrating full consistency of semi-empirical model equations for activity coefficients are established. Inconsistencies of this type can be avoided by the "differentiate down' approach. A problem peculiar to aqueous solutions is the usage in the literature of two distinct definitions of thermodynamic ideality: one consistent with the notion of unit mole fraction or rational activity coefficients, the other with the notion of unit molal activity coefficients for the solute components. -from Author