Capacitive and Solution Resistance Effects on Voltammetric Responses at a Disk Microelectrode Covered with a Self-Assembled Monolayer in the Presence of Electron Hopping

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TitleCapacitive and Solution Resistance Effects on Voltammetric Responses at a Disk Microelectrode Covered with a Self-Assembled Monolayer in the Presence of Electron Hopping
Publication TypeJournal Article
Year of Publication2009
AuthorsAmatore, C, Oleinick A, Klymenko OV, Svir I
JournalAnalytical Chemistry
Volume81
Issue20
Pagination8545-8556
Date PublishedOct
ISBN Number0003-2700
Accession NumberISI:000270670600037
Abstract

This article extends our previous works (Amatore, C.; Oleinick, A.; Svir, 1. Anal. Chem. 2008, 80,7947-7956; 7957-7963.) about the effects of resistive and capacitive distortions in voltammetry at disk microelectrodes. The particular case of voltammetry of a self-assembled monolayer carrying one redox site per molecule is investigated here. In addition, the effect of an uneven distribution of the effective electrochemical potential on the possibility of electron hopping (EH) contributions is examined. An original model of EH has been developed considering both diffusion-type (i.e., related to concentration giradients) and migration-type (i.e., imposed by an uneven distribution of the electrical potential due to an ohmic drop and capacitance charging) contributions. This predicts that as soon as the system performs out of thermodynamic equilibrium and provided that the EH rate constants are not too small the system tends to re-establish its out-of-equilibrium state through EH. Hence, EH somewhat tries to compensate the voltammetric distortions that would be enforced by the uneven distribution of the electrochemical driving force incurred by the system due to an ohmic drop and capacitive charging. However, this rigorous analysis established that, though EH may be effective under specific circumstances particularly near the electrode edge, its overall influence on voltammetric waves remains negligible for any realistic experimental situation.

URL<Go to ISI>://000270670600037
DOI10.1021/ac901513x
Short TitleCapacitive and Solution Resistance Effects on Voltammetric Responses at a Disk Microelectrode Covered with a Self-Assembled Monolayer in the Presence of Electron Hopping
Unit: 
UMR 8640