Semiempirical equation of state for the infinite dilution thermodynamic functions of hydration of nonelectrolytes over wide ranges of temperature and pressure

The recently proposed model [Geochim. Cosmochim. Acta 64 (2000) 495; Geochim. Cosmochim. Acta 64 (2000) 2779] for correlating the infinite dilution partial molar properties of aqueous nonelectrolytes is briefly outlined. The approach is fundamentally based on the A12=V20/κRT parameter, related to the infinite dilute solute–water direct correlation function integral. The A12 parameter is considered as a semiempirical function of temperature and density. At supercritical temperatures thermodynamic integrations of this function allow calculation of all thermodynamic functions of hydration (V20, ΔhG0, ΔhH0 and ΔhCp0) of a solute. An extension to subcritical conditions is done using an auxiliary ΔhCp0(T, Pr)-function, which describes the temperature course of the heat capacity of hydration of a solute at Pr=28 MPa and subcritical temperatures. The variations of the ΔhCp0(T, Pr)-function are constrained by known values of ΔhG0, ΔhH0 and ΔhCp0 at ambient and supercritical conditions. This model, which was used earlier to correlate properties of a few dissolved gases, is successfully employed here to describe V20, ΔhG0, ΔhH0 and ΔhCp0 experimental results for a number of aqueous nonelectrolytes, including ones of high polarity (alcohols, amines, acids and amides) and/or large size (hexane and benzene).