Chemical potential of electrolytes adsorbed in porous media with charged obstacles: application of the continuum replica methodology

Abstract

A theoretical study is reported of a quenched-annealed system where both components were modelled as size symmetric +1: −1 primitive model electrolytes. The partly quenched system was studied by using the replica Ornstein-Zernike (ROZ) integral equation theory in the hypernetted chain (HNC) approximation and grand canonical Monte Carlo (GCMC) simulations. The primary interest was the excess Gibbs free energy (logarithm of the mean activity coefficient) of the adsorbed electrolyte and an expression for this quantity, valid within the ROZ/HNC formalism, was derived. The effects of the concentration of matrix ions, pre-quenching conditions, and the electrolyte and solvent conditions (concentration, temperature, dielectric constant) on the structure and thermodynamics of the adsorbed electrolyte were examined. The numerical results indicated that the mean activity of the adsorbed electrolyte differs substantially from the corresponding quantity for the bulk electrolyte. The excess chemical potential depends strongly on the concentration of charged obstacles and matrix preparation, and also on the temperature and dielectric constant of the annealed electrolyte solution. Newly generated computer simulation results for the structural and thermodynamic parameters, obtained by the grand canonical Monte Carlo method, were used to assess the validity of the ROZ/HNC approximation. It was shown that the ROZ/HNC theory yields good agreement with the computer simulations.