化学
线性扫描伏安法
循环伏安法
伏安法
工作(物理)
氧化还原
扩散
水平扫描速率
热力学
动力学
电极
动能
相(物质)
分析化学(期刊)
电化学
物理化学
无机化学
量子力学
色谱法
物理
有机化学
作者
Martin C. Henstridge,Eduardo Laborda,Edmund J. F. Dickinson,Richard G. Compton
标识
DOI:10.1016/j.jelechem.2011.10.015
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–Ševčík 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–Ševčík plots suggests the need for significant refinement of the Marcus–Hush–Chidsey model before it is suitable for the analysis of experimental voltammetry.
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