TY - JOUR
T1 - Experimental comparison of the Butler-Volmer and Marcus-Hush-Chidsey formalisms of electrode kinetics
T2 - The reduction of cyclooctatetraene at mercury hemispherical electrodes via cyclic and square wave voltammetries
AU - Suwatchara, D.
AU - Rees, N.V.
AU - Henstridge, M.C.
AU - Laborda, E.
AU - Compton, R.G.
N1 - Copyright 2012 Elsevier B.V., All rights reserved.
PY - 2012/1/15
Y1 - 2012/1/15
N2 - Critical analysis of the Butler-Volmer and Marcus-Hush-Chidsey kinetic models is carried out through the study of the first one-electron reduction of cyclooctatetraene in DMSO at mercury hemispherical microelectrodes. This is an atypically slow process due to the conformational distortion taking place from the tub-shaped neutral species to the planar radical anion. Cyclic and square wave voltammetries are employed with the aim of examining the consistency of the results extracted from each model. Whereas the experimental results in cyclic voltammetry are adequately fitted by both models, the fit of square wave voltammograms at high frequency are not satisfactory when the Marcus-Hush-Chidsey formalism is employed.
AB - Critical analysis of the Butler-Volmer and Marcus-Hush-Chidsey kinetic models is carried out through the study of the first one-electron reduction of cyclooctatetraene in DMSO at mercury hemispherical microelectrodes. This is an atypically slow process due to the conformational distortion taking place from the tub-shaped neutral species to the planar radical anion. Cyclic and square wave voltammetries are employed with the aim of examining the consistency of the results extracted from each model. Whereas the experimental results in cyclic voltammetry are adequately fitted by both models, the fit of square wave voltammograms at high frequency are not satisfactory when the Marcus-Hush-Chidsey formalism is employed.
UR - http://www.scopus.com/inward/record.url?partnerID=yv4JPVwI&eid=2-s2.0-84855204809&md5=fe5b65e235b7d49c3859060dce03a050
U2 - 10.1016/j.jelechem.2011.11.009
DO - 10.1016/j.jelechem.2011.11.009
M3 - Article
AN - SCOPUS:84855204809
SN - 1572-6657
VL - 665
SP - 38
EP - 44
JO - Journal of Electroanalytical Chemistry
JF - Journal of Electroanalytical Chemistry
ER -