Journal
CHEMICAL PHYSICS LETTERS
Volume 517, Issue 1-3, Pages 29-35Publisher
ELSEVIER
DOI: 10.1016/j.cplett.2011.10.004
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Funding
- EPSRC [EP/H002413/1]
- St. John's College
- Fundacion SENECA
- EPSRC [EP/H002413/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/H002413/1] Funding Source: researchfish
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We present a comparative experimental evaluation of the Butler-Volmer and Marcus-Hush models using cyclic voltammetry at a microelectrode. Numerical simulations are used to fit experimental voltammetry of the one electron reductions of europium (III) and 2-methyl-2-nitropropane, in water and acetonitrile, respectively, at a mercury microhemisphere electrode. For Eu (III) very accurate fits to experiment were obtained over a wide range of scan rates using Butler-Volmer kinetics, whereas the Marcus-Hush model was less accurate. The reduction of 2-methyl-2-nitropropane was well simulated by both models, however Marcus-Hush required a reorganisation energy lower than expected. (C) 2011 Elsevier B.V. All rights reserved.
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