Theory of electrolytes including steric, attractive, and hydration interactions

We present a continuum theory of electrolytes composed of a waterlike solvent and univalent ions. First, we start with a density functional F for the coarse-grained solvent, cation, and anion densities, including the Debye-Hückel free energy, the Coulombic interaction, and the direct interactions among these three components. These densities fluctuate obeying the distribution ∝exp(-F/k_BT). Eliminating the solvent density deviation in F, we obtain the effective non-Coulombic interactions among the ions, which consist of the direct ones and the solvent-mediated ones. We then derive general expressions for the ion correlation, the apparent partial volume, and the activity and osmotic coefficients up to linear order in the average salt density n_s. Second, we perform numerical analysis using the Mansoori-Carnahan-Starling-Leland model [J. Chem. Phys. 54, 1523 (1971)] for three-component hardspheres. The effective interactions sensitively depend on the cation and anion sizes due to competition between the steric and hydration effects, which are repulsive between small-large ion pairs and attractive between symmetric pairs. These agree with previous experiments and Collins' rule [Biophys. J. 72, 65 (1997)]. We also give simple approximate expressions for the ionic interaction coefficients valid for any ion sizes.