The enthalpy and entropy of cavity formation in liquids and Corresponding States Principle

A new method to calculate the enthalpy and entropy of cavity formation in liquids is proposed. The reference cavity formation process is identified with the vaporization of liquid in the absence of order and Corresponding States Principle is used to eliminate the order contribution to vaporization enthalpy. The proposed method agrees very well with Claverie's modification of the Pierotti's method but strongly disagrees with the Sinanoglu's method, particularly in the context of entropy of cavity formation.The new method is checked by applying it to the description of solution process in alkane binary mixtures at infinite dilution and is used to study the solvent effect on the solvolysis of t-butyl chloride and bromide. Keywords: cavity formation, enthalpy and entropy of cavity formation, Corresponding States Principle, alkanes, intermolecular interactions, acentric factor, solvent effect.