A comparison of the Butler-Volmer and asymmetric Marcus-Hush models of electrode kinetics at the channel electrode

Journal article

We report a theoretical study of steady-state voltammetry at the channel electrode comparing the Butler-Volmer and Marcus-Hush (both symmetric and asymmetric) models of electrode kinetics. The latter model is shown, for small values of both reorganisation energy and standard rate constant, to exhibit a kinetically-limited steady-state current which is smaller than the mass-transport limiting current given by the Levich equation. However, the combination of parameters required to observe this kinetically-limited current is unlikely to occur in a 'real' system. We conclude that the Butler-Volmer model is sufficient to accurately model voltammetry under these conditions. © 2012 Elsevier B.V. All rights reserved.

Authors: Henstridge, M; Rees, N; Compton, R

• Publication status: Published
• Journal: JOURNAL OF ELECTROANALYTICAL CHEMISTRY
• Volume: 687
• Pages: 79-83
• Publication date: 2012-11-01
• DOI: 10.1016/j.jelechem.2012.10.012
• ISSN: 1572-6657
• Language: English
• Keywords: Marcus-Hush kinetics; Butler-Volmer kinetics; Electrochemical simulation; Steady state voltammetry; Channel electrode