A test of the theory of the steady-state properties of an ion exchange membrane with mobile sites and dissociated counterions

Abstract

An experimental model system, formally equivalent to a liquid ion exchange membrane having completely dissociated sites and counterions, has been devised in order to test the steady-state properties recently deduced theoretically for such a membrane by Conti and Eisenman, (1966). In this system we have obtained quantitative experimental confirmation of the following theoretical expectations. (a) The current-voltage relationship is nonlinear and exhibits finite limiting currents with strong applied fields. (b) The mobile sites rearrange within the "membrane" under applied electric field to give a linear concentration profile and a logarithmic electric potential profile in the steady state. We have also extended the theory to consider the instantaneous conductance in the steady state. Theory and experiment indicate that in a mobile site membrane the instantaneous conductance in the steady state is not given by the chord conductance of the steady-state current-voltage relationship, in contrast to the situation in a fixed site membrane. This finding suggests a way of testing whether ions permeate across an unknown membrane by a fixed site or a dissociated mobile site mechanism.