Redox systems obeying Marcus-Hush-Chidsey electrode kinetics do not obey the Randles-Sevcik equation for linear sweep voltammetry

被引：54

作者：

Henstridge, Martin C. ^{[1
]}

Laborda, Eduardo ^{[1
]}

Dickinson, Edmund J. F. ^{[1
]}

Compton, Richard G. ^{[1
]}

机构：

[1] Univ Oxford, Dept Chem, Phys & Theoret Chem Lab, Oxford OX1 3QZ, England

来源：

JOURNAL OF ELECTROANALYTICAL CHEMISTRY | 2012年 / 664卷

基金：

英国工程与自然科学研究理事会;

关键词：

Randles-Sevcik equation; Marcus-Hush-Chidsey kinetics; Butler-Volmer kinetics; Surface-bound species; Cyclic voltammetry; REDUCTION;

D O I：

10.1016/j.jelechem.2011.10.015

中图分类号：

O65 [分析化学];

学科分类号：

070302 ; 081704 ;

摘要：

The cyclic voltammetry of the reaction of a solution-phase species at a macroelectrode under semi-infinite diffusion is simulated assuming irreversible electrode kinetics within the Marcus-Hush-Chidsey model. The resulting peak currents are shown to deviate from the square root dependence on voltage scan rate predicted by the Randles-Sevcik equation. Simulated voltammetry of a surface-bound redox couple also shows deviations from the expected linear dependence of peak current on scan rate. These numerical findings are supported by analytical arguments and they provide simple method for a critical analysis of the kinetic model. In particular the sheer extent of published experimental work containing linear Randles-Sevcik plots suggests the need for significant refinement of the Marcus-Hush-Chidsey model before it is suitable for the analysis of experimental voltammetry. (C) 2011 Elsevier B.V. All rights reserved.

引用

页码：73 / 79

页数：7

共 13 条

[1] [Anonymous], 2001, ELECTROCHEMICAL METH
[2] Extraction of electrode kinetic parameters from microdisc voltammetric data measured under transport conditions intermediate between steady-state convergent and transient linear diffusion as typically applies to room temperature ionic liquids
Barnes, Alexander S.
Rogers, Emma I.
Streeter, Ian
Aldous, Leigh
Hardacre, Christopher
Compton, Richard G.
[J]. JOURNAL OF PHYSICAL CHEMISTRY B, 2008, 112 (25) : 7560 - 7565
[3] Britz D., 2005, Digital simulation in electrochemistry, V3rd
[4] FREE-ENERGY AND TEMPERATURE-DEPENDENCE OF ELECTRON-TRANSFER AT THE METAL-ELECTROLYTE INTERFACE
CHIDSEY, CED
[J]. SCIENCE, 1991, 251 (4996) : 919 - 922
[5] Compton RG, 2011, UNDERSTANDING VOLTAMMETRY, 2ND EDITION, P1
[6] THEORY OF IRREVERSIBLE WAVES IN OSCILLOGRAPHIC POLAROGRAPHY
DELAHAY, P
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1953, 75 (05) : 1190 - 1196
[7] How Much Supporting Electrolyte Is Required to Make a Cyclic Voltammetry Experiment Quantitatively "Diffusional"? A Theoretical and Experimental Investigation
Dickinson, Edmund J. F.
Limon-Petersen, Juan G.
Rees, Neil V.
Compton, Richard G.
[J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2009, 113 (25) : 11157 - 11171
[8] Implications of Marcus-Hush Theory for Steady-State Heterogeneous Electron Transfer at an Inlaid Disk Electrode
Feldberg, Stephen W.
[J]. ANALYTICAL CHEMISTRY, 2010, 82 (12) : 5176 - 5183
[9] Quantitative weaknesses of the Marcus-Hush theory of electrode kinetics revealed by Reverse Scan Square Wave Voltammetry: The reduction of 2-methyl-2-nitropropane at mercury microelectrodes
Laborda, Eduardo
Wang, Yijun
Henstridge, Martin C.
Martinez-Ortiz, Francisco
Molina, Angela
Compton, Richard G.
[J]. CHEMICAL PHYSICS LETTERS, 2011, 512 (1-3) : 133 - 137
[10] On the evaluation and analysis of the Marcus-Hush-Chidsey integral
Oldham, Keith B.
Myland, Jan C.
[J]. JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 2011, 655 (01) : 65 - 72

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