Article

Simulation of Square Wave Voltammetry:  Quasi-Reversible Electrode Processes

Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, OX1 3QZ, United Kingdom
J. Phys. Chem. B, 1999, 103 (42), pp 9020–9028
DOI: 10.1021/jp991508v
Publication Date (Web): October 4, 1999
Copyright © 1999 American Chemical Society

Abstract

Simulations, based on the backward implicit method, for the square wave voltammetry (SWV) experiment are reported for the general case of quasi-reversible Butler−Volmer kinetics and a finite diffusion layer thickness. In the limiting cases of fast electrode kinetics, or semi-infinite diffusion, the results are in excellent agreement with independent calculations confirming the validity of the approach and its implementation. Under the previously unexplored conditions of finite diffusion, the effect of the diffusion layer thickness on the peak characteristicswidth, height, and voltageare identified and quantified, so providing a quantitative basis for the use of SWV at hydrodynamic electrodes for the determination of electrochemical kinetic parameters.

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Article Views: 252 Times
Received 6 May 1999
Published online 4 October 1999
Published in print 1 October 1999
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