On the application of concentrated solution theory to the forced convective flow of excess supporting electrolyte

Abstract

A recent model for electrolysis with forced convection in a channel and an excess of dilute supporting electrolyte is extended using concentrated solution theory. Mean Spherical Approximation theory is used to calculate the necessary Onsager coefficients and ionic activities. Using asymptotic methods, we demonstrate the surprising similarities between the leading order equations for the dilute and concentrated theories. In addition, in deriving the extension, certain omissions in the original work are highlighted: an oversight in the Butler–Volmer law used in the original work is corrected, and the systematic use of similarity-like variables in electrochemical problems that do not have a similarity solution along the entire length of the diffusion layer adjacent to an electrode is demonstrated. This helps to explain the manner in which the solutions for the anode and cathode boundary layers and the bulk region decouple from each other at limiting current, enabling a much simpler solution strategy.