Experimental comparison of the Butler-Volmer and Marcus-Hush-Chidsey formalisms of electrode kinetics: The reduction of cyclooctatetraene at mercury hemispherical electrodes via cyclic and square wave voltammetries

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 pla...

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Main Authors: Suwatchara, D, Rees, N, Henstridge, M, Laborda, E, Compton, R
Format: Journal article
Language:English
Published: 2012
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author Suwatchara, D
Rees, N
Henstridge, M
Laborda, E
Compton, R
author_facet Suwatchara, D
Rees, N
Henstridge, M
Laborda, E
Compton, R
author_sort Suwatchara, D
collection OXFORD
description 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. © 2011 Elsevier B.V. All rights reserved.
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spelling oxford-uuid:b2f5af43-0c29-458e-9f16-7a2042dc7aa32022-03-27T04:15:29ZExperimental comparison of the Butler-Volmer and Marcus-Hush-Chidsey formalisms of electrode kinetics: The reduction of cyclooctatetraene at mercury hemispherical electrodes via cyclic and square wave voltammetriesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:b2f5af43-0c29-458e-9f16-7a2042dc7aa3EnglishSymplectic Elements at Oxford2012Suwatchara, DRees, NHenstridge, MLaborda, ECompton, RCritical 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. © 2011 Elsevier B.V. All rights reserved.
spellingShingle Suwatchara, D
Rees, N
Henstridge, M
Laborda, E
Compton, R
Experimental comparison of the Butler-Volmer and Marcus-Hush-Chidsey formalisms of electrode kinetics: The reduction of cyclooctatetraene at mercury hemispherical electrodes via cyclic and square wave voltammetries
title Experimental comparison of the Butler-Volmer and Marcus-Hush-Chidsey formalisms of electrode kinetics: The reduction of cyclooctatetraene at mercury hemispherical electrodes via cyclic and square wave voltammetries
title_full Experimental comparison of the Butler-Volmer and Marcus-Hush-Chidsey formalisms of electrode kinetics: The reduction of cyclooctatetraene at mercury hemispherical electrodes via cyclic and square wave voltammetries
title_fullStr Experimental comparison of the Butler-Volmer and Marcus-Hush-Chidsey formalisms of electrode kinetics: The reduction of cyclooctatetraene at mercury hemispherical electrodes via cyclic and square wave voltammetries
title_full_unstemmed Experimental comparison of the Butler-Volmer and Marcus-Hush-Chidsey formalisms of electrode kinetics: The reduction of cyclooctatetraene at mercury hemispherical electrodes via cyclic and square wave voltammetries
title_short Experimental comparison of the Butler-Volmer and Marcus-Hush-Chidsey formalisms of electrode kinetics: The reduction of cyclooctatetraene at mercury hemispherical electrodes via cyclic and square wave voltammetries
title_sort experimental comparison of the butler volmer and marcus hush chidsey formalisms of electrode kinetics the reduction of cyclooctatetraene at mercury hemispherical electrodes via cyclic and square wave voltammetries
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