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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|
|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|
|Publisher Link: ||http://dx.doi.org/10.1039/c0cp02471f|
|Appears in Collections:||Published Articles (Chemistry)|
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