Effect of Electron-Transfer Rate and Reorganization Energy on the Cyclic Voltammetric Response of Redox Adsorbates

Autor:	Michael J. Honeychurch
Rok vydání:	1999
Předmět:	Tafel equation Chemistry Kinetics Finite difference Thermodynamics Surfaces and Interfaces Condensed Matter Physics Kinetic energy Electrochemistry Redox Electron transfer Physical chemistry General Materials Science Cyclic voltammetry Spectroscopy
Zdroj:	Langmuir. 15:5158-5163
ISSN:	1520-5827 0743-7463
DOI:	10.1021/la990169u
Popis:	The theory of cyclic voltammetry of redox adsorbates based on the nonadiabatic kinetic models of Levich and Dogonadze (GMLD kinetics) is re-examined. It is shown that if generalized predictions of cyclic voltammetric behavior are sought, the model is applicable only over a small range of reorganization energies. It is well-known that at high reorganization energies Tafel plots simulated using both Butler−Volmer and GMLD kinetics give similar results; however, cyclic voltammograms simulated from GMLD kinetics at high reorganization energies do not reduce to the generalized Butler−Volmer model for cyclic voltammogram of redox adsorbates derived by Laviron (J. Electroanal. Chem. 1979, 101, 19). Two methods of solution to the cyclic voltammogram equation are considered: a finite difference numerical solution and an analytical approximation. The analytical approximation enables a more rapid simulation of cyclic voltammograms. Methods for applying the model to real systems are suggested which include an equati...
Databáze:	OpenAIRE
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