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Beyond the Butler–Volmer equation. Curved Tafel slopes from steady-state current–voltage curves

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journal contribution
posted on 19.05.2011 by Stephen Fletcher, Thomas S. Varley
We report the discovery and analysis of curved Tafel slopes from the electrochemical reduction of hexamminecobalt(III) under steady-state conditions. In order to confirm the existence of the curvature, random assemblies of carbon microelectrodes (RAM™ electrodes) were employed to obtain experimental data over more than three orders of magnitude, without significant double layer charging currents and without ohmic distortion. Since the rate-determining step in the reduction reaction is electron transfer, and no ligand substitution reactions occur on the timescale of experiments, the curvature of the Tafel plot is attributed to the dependence of the symmetry factor on electrode potential.

History

School

  • Science

Department

  • Chemistry

Citation

FLETCHER, S. and VARLEY, T.S., 2011. Beyond the Butler–Volmer equation. Curved Tafel slopes from steady-state current–voltage curves. Physical Chemistry, Chemical Physics, 13, pp. 5359-5364.

Publisher

Royal Society of Chemistry (© The Owner Societies)

Version

AM (Accepted Manuscript)

Publication date

2011

Notes

This article was published in the journal, Physical Chemistry Chemical Physics: http://pubs.rsc.org/en/journals/journalissues/cp

ISSN

1463-9076

Language

en

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