Theory and computer simulation of solute effects on the surface tension of liquids.

A complete description of the thermodynamics of planar mixed solute-solvent interfaces suitable for the analysis of computer simulation data is provided. The approach uses surface probability distributions to characterize the interface regions, coupled with radial distribution functions and the Kirkwood-Buff theory of solutions to characterize the bulk solution properties. The approach is then used to understand the relationship between changes in the surface tension, the degree of surface adsorption or depletion, and the bulk solution properties of two aqueous solute systems. The first, aqueous NaCl solutions, provides an example of a surface excluded solute. The second, aqueous methanol solutions, provides an example of a surface adsorbed solute. The numerical results support the theoretical relationships described here and provide a consistent picture of the thermodynamics of solution interfaces involving any number of components which can be applied to a wide variety of systems.