Ion solvation in liquid mixtures: effects of solvent reorganization.
Using field-theoretic techniques, we study the solvation of salt ions in liquid mixtures, accounting for the permanent and induced dipole moments, as well as the molecular volume of the species. With no adjustable parameters, we predict solvation energies in both single-component liquids and binary liquid mixtures that are in excellent agreement with experimental data. Our study shows that the solvation energy of an ion is largely determined by the local response of the permanent and induced dipoles, as well as the local solvent composition in the case of mixtures, and does not simply correlate with the bulk dielectric constant. In particular, we show that, in a binary mixture, it is possible for the component with the lower bulk dielectric constant but larger molecular polarizability to be enriched near the ion.
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Issei
I
Nakamura
An-Chang
AC
Shi
Zhen-Gang
ZG
Wang
D003102:Colloids / Q000737:chemistry; D007477:Ions / Q000737:chemistry; D008956:Models, Chemical; D016012:Poisson Distribution; D012492:Salts / Q000737:chemistry*; D012995:Solubility; D012997:Solvents / Q000737:chemistry; D013816:Thermodynamics
D003102:Colloids; D007477:Ions; D012492:Salts; D012997:Solvents