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Title: Beyond the Butler–Volmer equation. Curved Tafel slopes from steady-state current–voltage curves
Authors: Fletcher, Stephen
Varley, Thomas S.
Keywords: Symmetry factor
Butler-Volmer equation
Tafel slope
Electron transfer
Reaction coordinate
Issue Date: 2011
Publisher: Royal Society of Chemistry (© The Owner Societies)
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.
Abstract: 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.
Description: This article was published in the journal, Physical Chemistry Chemical Physics: http://pubs.rsc.org/en/journals/journalissues/cp
Version: Accepted for publication
DOI: 10.1039/c0cp02471f
URI: https://dspace.lboro.ac.uk/2134/8384
Publisher Link: http://dx.doi.org/10.1039/c0cp02471f
ISSN: 1463-9076
Appears in Collections:Published Articles (Chemistry)

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