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

作者：Henstridge Martin C; Rees Neil V; Compton Richard G^*

来源：Journal of Electroanalytical Chemistry, 2012, 687: 79-83.

DOI：10.1016/j.jelechem.2012.10.012

• Steady state voltammetry
• Butler-Volmer kinetics
• Marcus-Hush kinetics
• Channel electrode
• Electrochemical simulation

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.

• 出版日期2012-11-1