Simple theoretical model for ion cooperativity in aqueous solutions of simple inorganic salts and its effect on water surface tension

J Phys Chem B. 2011 Nov 3;115(43):12466-72. doi: 10.1021/jp2076512. Epub 2011 Oct 11.

Abstract

Careful analysis of experimental data showed that the salt aqueous solution/air surface tension depends on a rather complicated manner of salt composition and points to the importance of ion cooperativity. In this short article, we include the selective binding of anions over cations at interfaces (as revealed from molecular dynamics simulations, spectroscopic measurements, and Record's analysis of the surface tension data) and the anion-cation association (based on the observation of matching water affinity) in a simple theoretical model to understand salt effects on surface tension. The introduction of the surface effect and ion association provides a qualitative explanation of the experimental data, in particular, the strong anion dependence of the cations' rank according to their ability of increasing water surface tension. We hope that the physical insight provided by this study can be used to point to new directions for more detailed studies.