Measurement of membrane potential and estimation of effective fixed-charge density in membranes.

Electrical potentials Em arising across cross-linked phenolsulfonate membrane separating NaCl solutions of molality M1 and M2 have been measured at 25 degrees C. These values of Em have been used in the Nernst equation to calculate values for the apparent transport number ti(app) for the counterion or the co-ion in the membrane. Values of ti(app) together with the limiting value for the cation transport number in the aqueous phase have been used in the equation developed by Kobatake and co-workers to evaluate the membrane permselectivity Ps as a function of external electrolyte concentration. With the help of the equation relating Ps to phiX, the effective fixed-charge density in the membrane (where phi is a constant, 0 less than phi less than 1, and X is the membrane stochiometric charge density and can be evaluated by chemical analysis of the membrane phase), values for phiX and phi have been determined. Values of phi were low in dilute solutions and increased with increase in the concentration of the external solution. Similar behavior was noted in the case of another membrane system, cross-linked polymethacrylic acid in contact with KOH solutions. On the other hand, the membrane system, "untreated" collodion in contact with KCl solutions, exhibited a behavior in which the values of phi, low in dilute solutions, increased and then decreased following a gradual increase in the external concentration. This slight divergence in its behavior was attributed to the heterogeneity of the collodion membrane structure. The reliability of this potentiometric method to estimate effective fixed-charge density in membranes has been discussed in relation to a similar but old method due to Teorell, Meyer and Sievers. Also the significance of the values derived for phi has been pointed out.