Selective solvation in aqueous mixtures: Interface deformations and instability

Abstract

We briefly review the effects of selective solvation of ions in aqueous mixtures, where the ion densities and the composition fluctuations are strongly coupled. We then examine the surface tension \gamma of a liquid-liquid interface in the presence of ions. We show that \gamma can be decreased drastically due to the electrostatic and solvation interactions near the interface. We calculate how the free energy is changed due to small surface undulations in the presence of an electric double layer. A surface instability occurs for negative \gamma, which can easily be realized for antagonistic ion pairs near the solvent criticality. Three-dimensional simulation shows how the surface instability is induced.Comment: 16 pages, 4 figure