Partial Solvation Parameters and Mixture Thermodynamics

Abstract

The recently introduced partial solvation parameters (PSPs) are molecular descriptors that combine elements from quantum mechanics with the QSPR/LSER/solvatochromic and solubility parameter approaches. Basic regularities and universalities exhibited by PSPs are examined in this work and the concepts of homosolvation, heterosolvation and solvation energy density are quantified. A simple consistent thermodynamic framework is developed, through which the validity of the PSP approach is tested. The predictions are compared with experimental phase equilibrium data that span the full composition range from the pure fluid state to infinite dilution. They include vapor-liquid equilibria of fluids interacting with strong specific forces, dissolution of solids/liquids in various solvents and probe/oligomer or probe/polymer interactions as typically determined by inverse gas-chromatography. These applications show the potential of the PSP approach not only to reasonably predict a variety of properties of classes of complex systems but, also, to shed light to challenging aspects of intermolecular interactions. The perspectives of this unified approach to solution thermodynamics are discussed.