GENERAL LINEARIZED MATRIX THEORY OF ELECTROCHEMICAL MASS TRANSFER WITH APPLICATIONS TO ELECTRODE PROCESSES AND ION EXCHANGE

Abstract

A general linearized matrix theory for electrochemical mass transfer is presented. The accuracy of the theory when applied to cases where electric current exists is tested by comparing results with exact calculations of the effect of ionic migration on limiting currents at a rotating disk electrode with laminar flow and at a flat plate electrode adjacent to a stagnant fluid film. Application of the theory is further illustrated by using it to calculate the effect of ionic migration on limiting currents in a turbulent, law-of-the-wall boundary layer. Finally, the theory is used to evaluate commonly used “film-model” methods for generalizing binary mass-transfer correlations to multicomponent nonideal mixtures. For this last purpose, a film-model generalization method was developed for nonideal electrolyte mixtures. The method is equivalent to that used by Krishnamurthy and Taylor (1985) for mass-transfer in nonideal nonelectrolyte mixtures. Results using the film-model method are compared to matrix calculations of multicomponent ion-exchange mass transfer across a laminar boundary layer and in fixed and fluidized beds.

KEYWORDS:

• Mass transfer
• Electrolytes
• Matrix theory

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