Parameter Interpretation and Reduction for a Unified Statistical Mechanical Surface Tension Model.

Surface properties of aqueous solutions are important for environments as diverse as atmospheric aerosols and biocellular membranes. Previously, we developed a surface tension model for both electrolyte and nonelectrolyte aqueous solutions across the entire solute concentration range (Wexler and Dutcher, J. Phys. Chem. Lett. 2013, 4, 1723-1726). The model differentiated between adsorption of solute molecules in the bulk and surface of solution using the statistical mechanics of multilayer sorption solution model of Dutcher et al. (J. Phys. Chem. A 2013, 117, 3198-3213). The parameters in the model had physicochemical interpretations, but remained largely empirical. In the current work, these parameters are related to solute molecular properties in aqueous solutions. For nonelectrolytes, sorption tendencies suggest a strong relation with molecular size and functional group spacing. For electrolytes, surface adsorption of ions follows ion surface-bulk partitioning calculations by Pegram and Record (J. Phys. Chem. B 2007, 111, 5411-5417).