Periodic Kinetics in Diffusion-Controlled Electrochemical Reactions

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Abstract
Periodic processes are often encountered in electrode reactions, particularly in the case of anodic oxidations. Analogous effects have been found by other workers in systems of biological interest, e.g., with processes involving membranes and enzymes. The general problem is to account for why no chemical steady‐state arises under conditions of controlled potential (potentiostatic) or controlled over‐all current or rate (galvanostatic). Here, a diffusion‐controlled process with a coupled adsorption–electrochemical oxidation reaction (e.g., oxidation of C2H4) is examined and the special conditions which can lead to unstable steady states, and hence periodicity, are established under simplifying assumptions.