Effect of concentration polarization on permselectivity

In this paper, the variation of permselectivity in the course of concentration polarization is systematically analyzed for a three-layer membrane system consisting of a nonperfectly permselective ion exchange membrane, homogeneous or heterogeneous, flanked by two diffusion layers of a binary univalent electrolyte. For a heterogeneous membrane, an ionic transport model is proposed, which is amenable to analytical treatment. In this model, assuming a constant fixed charge in the membrane and disregarding water splitting, the entire transport problem is reduced to solution of a single algebraic equation for the counterion transport number. It is concluded that for both types of membrane the concentration polarization may significantly affect the permselectivity of the system through the effects of the induced nonuniformity of the coion diffusion flux in the membrane (convexity of the coion concentration profile) and varying membrane-solution interface concentration. While the former is significant for low membrane fixed charge density, for a heterogeneous membrane, the latter might be considerably affected by the flux focusing effect at the permeable membrane segments.