A further view on the calculation of the enthalpy of cavity formation in liquids. The influence of the cavity size and shape

Abstract

A reformulation of the Sinanoglu–Reisse semi-empirical approach to describe the cavity formation process in liquids is proposed. The energy of cavity formation is regarded as a strictly potential energy corrected for short range order effects in the liquid state. Deviations from the Corresponding States Principle quantified by the Pitzer acentric factor are considered to describe these short range order effects.The influence of the cavity shape on the calculation of its energetics is emphasized as well as the need for a realistic description of the dependence of the microscopic surface tension on the size and shape of the cavities. The proposed method is successfully applied to binary mixtures of n-alkanes at infinite dilution.