Journal of Chemical Physics, Vol.103, No.18, 8179-8188, 1995
Static and Transport-Properties of Symmetrical and Asymmetric Electrolytes in Micropores at Fixed Surface-Potential
We study some static and kinetic properties of model electrolyte solutions, confined by two charged plates, for example, ionic exclusion, the force balance between the two plates, and the electrokinetic phenomenological Onsager’s coefficients L(mn). The three point extension hypernetted chain/mean spherical integral equation (TPE-HNC/MSA) was solved to obtain the ionic concentration profiles of a confined restricted primitive model electrolyte and the plate-plate force. We compare the results of this theory with the classically used modified Gouy-Chapman (MGC) point ion theory. It is shown that the properties of the system depend strongly on the charge of the counterions and, hence, the asymmetric 2:1 and 1:2 salts give results similar to those of the symmetric 1:1 and 2:2 salts, respectively. The MGC theory fails to predict the force oscillation between repulsive and attractive and other important features that appear for ultranarrow pores. These discrepancies are enhanced by the presence of doubly charged ions. The TPE-HNC/MSA theory predicts a nonlinear behavior of the capillary conductivity as a function of the slit width.
Keywords:ELECTRICAL DOUBLE-LAYERS;HYPERNETTED CHAIN APPROXIMATION;HYDRATION FORCES;MICA SURFACES;CHARGED SURFACES;INTERFACES;EXTENSION;SALTS;DLVO