Multi-ionic potential and membrane permeability matrix. III. Diffusion and concentration of ions within membrane phase as a controlling factor to ion permselectivity.

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Membrane concentrations of cations in the NaCl–CsCl and NaCl–CaCl2 systems with a highly selective cation-exchange membrane were measured under the extensive external electrolyte conditions. The modes of membrane/solution distribution and diffusion of cations, as a controlling factor to the membrane permselectivity, were correlated consistently with the electrochemical and cation flux data, as well as with the estimated membrane permselectivity parameters. The NaCl–CsCl uni-uni valent cation system was characterized well by the Na+/Cs+ concentration ratio of external solution, since the Na+/Cs+ concentration ratio in the membrane phase was related directly to the external ratio. Na+/Cs+ diffusion coefficient ratio varied from 0.5 to 3 with increasing external Na+/Cs+ concentration ratio from 1/100 to 100. While in the NaCl–CaCl2 uni-bi valent cation system, the high and constant membrane concentration of Ca2+ regulated the transport process. The Na+/Ca2+ diffusion coefficient ratio ranged from 0.5 to 500 with external Na+/Ca2+ ratio from 1/100 to 100. Analyses on the phenomenological coefficients, describing the inter-cationic correlations within the membrane phase, as a function of the external cation concentration ratio were also carried out.
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