Article

Anodic Stripping Voltammetry at Hydrodynamic Mercury Electrodes. Square Wave Voltammetry:  Numerical Theory for Electrochemically Reversible Systems

Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, OX1 3QZ U.K.
J. Phys. Chem. B, 1998, 102 (20), pp 3967–3973
DOI: 10.1021/jp980749k
Publication Date (Web): April 28, 1998
Copyright © 1998 American Chemical Society

Abstract

Numerical simulations exploiting the time-dependent backward implicit method are used to develop the theory of square wave voltammetry as applied to electrochemically reversible processes undergoing anodic stripping at planar mercury electrodes having arbitrary film and diffusion layer thicknesses. Computations made using a time scale distorted to reflect the Cottrellian character of the transient response at short times are found to be extremely efficient when applied to this problem. For the limiting case of semi-infinite diffusion in the solution phase, excellent agreement with existing analytical theory is noted (Kounaves et al. Anal. Chem. 1987, 59, 386). The effects of the pulse frequency are investigated and, in particular, the effect of diffusion layer thickness characterized. Deviations from semi-infinite theory are predicted and rationalized for the case when the magnitude of the latter is comparable to the diffusion length of the solution-phase species during a single pulse width as might occur when measurements are made using hydrodynamic electrodes or sonotrodes.

Citation data is made available by participants in Crossref's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search inSciFinder.

Explore by:

Metrics

Article Views: 125 Times
Received 12 January 1998
Published online 28 April 1998
Published in print 1 May 1998
+
Altmetric Logo Icon More Article Metrics

This website uses cookies to improve your user experience. By continuing to use the site, you are accepting our use of cookies. Read the ACS privacy policy.

CONTINUE