Unidimensional Approximation of the Diffuse Electrical Layer in the Inner Volume of Solid Electrolyte Grains in Absence of Background Ions

Abstract

In this paper we continue working on our theory of electrical double layers resulting exclusively from dissociation of a solid electrolyte, which we previously proposed as a medium for catalytic interaction between solid cellulose and solid acid catalysts of hydrolysis. Two theoretical unidimensional models of the inner grain volume are considered: an infinitely long cylindrical pore, and a gel electrolyte near a grain outer surface. Despite the model simplicity, the predictions for the cylindrical pore case are in semi‐quantitative agreement with literature data on electroosmotic experiments, adequately explaining high proton selectivity of sulfonic membranes, and decline of such selectivity at high background acid concentration. The gel model predicts less concentrated diffuse layer in comparison to electrolytes with impenetrable skeleton (e.g., sulfonated carbons). This suggests limited suitability of gel electrolytes as catalysts if a substrate cannot diffuse into the gel bulk and the reaction is thereby spatially limited to the near‐surface region, for example if a substrate is solid like aforementioned cellulose.