Real Electrolyte Solutions in the Functionalized Mean Spherical Approximation: A Density Functional Theory for Simple Electrolyte Solutions.

Abstract

The equation of state based on the mean spherical approximation (MSA) can describe electrolyte solutions as a primitive model, where the ions are charged hard-sphere particles and the solvent is a continuum medium. In recent years, many propositions of the classical density functional theory (cDFT) for electrolyte solutions have been presented. One of these is the functionalized MSA (fMSA) which has proven to be a great functional approach of MSA to calculate the electric double layer structures. This work demonstrates how the fMSA theory can describe real electrolyte solutions (e.g., NaCl, KI, and LiBr) where hydration and solvent concentration effects are present. Experimental data of the mean activity coefficients of different simple salts were successfully reproduced. When the hydrated diameter and the electrolyte solution electric permittivity are used, the fMSA predicts a charge inversion on the electrostatic potential near a charged surface at high salt concentrations.