화학공학소재연구정보센터
Fluid Phase Equilibria, Vol.183-184, 133-142, 2001
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 A(12) = V-2(0)/kappa RT 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 (V-2(0), Delta (h)G(0), Delta H-h(0) and Delta hC(p)(0)) of a solute. An extension to subcritical conditions is done using an auxiliary Delta C-h(p)0(T, P-r)-function, which describes the temperature course of the heat capacity of hydration of a solute at P-r = 28 MPa and subcritical temperatures. The variations of the Delta C-h(p)0(T, Pr)-function are constrained by known values of Delta hG(0), Delta H-h(0) and Delta C-h(p)0 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 V-2(0), Delta (h)G(0), Delta H-h(0) and Delta C-h(p)0 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).