Solvation: Effects of molecular size and shape

摘要

Sharpetal. have raised the question: If a solute and its solvent have different molecular sizes, how should solvation interaction energies be extracted from transfer experimentsquest; Is the chemical potential more appropriately given by lsquo;lsquo;classicalrsquo;rsquo; solution theory or by Floryndash;Huggins theoryquest; We study a general statistical mechanical treatment of solvation, a generalized Floryndash;Huggins theory, and related treatments by Hildebrand and by Sharpetal. to determine the physical basis for sizehyphen;dependent terms in the chemical potential, and their limitations and applicabilities. We find that the extra entropy in the Floryndash;Huggins theory does not arise from the disparity of sizes of solute and solvent, from free volume, or from artifacts of approximations. Rather, when solutes and solvents have sufficient complexity that they can lsquo;lsquo;interferersquo;rsquo; with each other in solution, there is an lsquo;lsquo;entropy of couplingrsquo;rsquo; of translational freedom to excluded volume or internal or rotational degrees of freedom. The Floryndash;Huggins theory approximates this coupling entropy for polymeric solutes or solvents, but not for other systems. Proper extraction of contact free energies requires proper subtraction of the coupling term. This study rationalizes several experimental and simulation studies, and indicates that coupling entropies that depend on molecular size and shape are often needed to treat complex solvation processes.