Transport in polymer-electrolyte membranes - I. Physical model

In this paper, a physical model is developed that is semiphenomenological and takes into account Schroeder's paradox. Using the wealth of knowledge contained in the literature regarding polymer-electrolyte membranes as a basis, a novel approach is taken in tying together all of the data into a single coherent theory. This approach involves describing the structural changes of the membrane due to water content, and casting this in terms of capillary phenomena. By treating the membrane in this fashion, Schroeder's paradox can be elucidated. Along with the structural changes, two different transport mechanisms are presented and discussed. These mechanisms, along with the membrane's structural changes, comprise the complete physical model of the membrane. The model is shown to agree qualitatively with different membranes and different membrane forms, and is applicable to modeling perfluorinated sulfonic acid and similar membranes. It is also the first physically based comprehensive model of transport in a membrane that includes a physical description of Schroeder's paradox, and it bridges the gap between the two types of macroscopic models currently in the literature. (C) 2003 The Electrochemical Society.