Journal of Physical Chemistry B, Vol.103, No.25, 5361-5369, 1999
Structure and thermodynamics of asymmetric electrolytes adsorbed in disordered electroneutral charged matrices from replica Ornstein-Zernike equations
The replica Ornstein-Zernike equations, supplemented by the hypernetted chain approximation, were solved for size and/or charge asymmetric electrolytes adsorbed in a disordered matrix of charged species that are electroneutral in total. More precisely, the matrix was represented as a symmetric +1:-1 electrolyte. To obtain the numerical solution of the replica Ornstein-Zernike equations, renormalization of the initial equations was performed. Both the matrix and adsorbed fluid were modeled as charged hard spheres in a dielectric continuum. As a result of the numerical calculation, we obtained pair distribution functions. The effect of charge and size asymmetry of the annealed fluid was investigated. We present the results for charge asymmetric +2:-1 and +3:-1 electrolytes, and for a solution with asymmetries in charge of +3:-1 (+6:-1) and asymmetries in diameter of 7 Angstrom:4 Angstrom, (20 Angstrom:4:4 Angstrom). Ln addition to the structural properties, the isothermal compressibility and the excess internal energy of the adsorbed electrolyte were calculated.