The concepts of non-Gibbsian and non-Lewisian properties in chemical thermodynamics

Abstract

The concepts of Gibbsian and non-Gibbsian, Lewisian and non-Lewisian thermodynamic variables are explored with respect to the thermodynamic properties of liquid mixtures and solutions. The general structures of equations for isochoric heat capacities, isentropic compressions and isentropic expansions are compared and contrasted. A simple rule is proposed for transcribing non-Gibbsian equations in terms of non-Lewisian partial molar properties. The bases of equations for partial molar isochoric heat capacities, isentropic compressions and isentropic expansions are examined for (i) components of liquid mixtures, and (ii) solute and solvent in solutions together with the properties of solutes at infinite dilution.