The Correlated States Theory of Nonpolar Solvation in Normal van der Waals Liquids

Abstract In the present work, we developed a new thermodynamic theory of solvation of nonpolar molecules in nonpolar van der Waals liquids, built as a limiting case of nonpolar solvation in polar liquid at the enthalpy/entropy convergence temperatures tending to infinity. Expressions for the full set of thermodynamic functions of solvation (ΔG, ΔH, ΔS, ΔCP), corrected for the Kuhn-like segment, were derived in closed analytical form and demonstrated a good match with the extended experimental data set for nonpolar solvation in own neat liquids (branched alkanes, linear alkanes/alkenes, aromatics). It was shown that the enthalpy–entropy compensation phenomenon, Trouton’s law, and zero transfer energy between different van der Waals liquids, known from previous empirical studies, stem as partial cases from the equations of the developed theory.