Theoretical and experimental study of the surface redox reaction involving interactions between the adsorbed particles under conditions of square-wave voltammetry

Mirceski, Valentin and Lovrić, Milivoj and Gulaboski, Rubin (2001) Theoretical and experimental study of the surface redox reaction involving interactions between the adsorbed particles under conditions of square-wave voltammetry. Journal of Electroanalytical Chemistry, 515 (1-2). pp. 91-100. ISSN 15726657

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Official URL: http://dx.doi.org/10.1016/S0022-0728(01)00609-X

Abstract

A surface redox reaction of a strongly adsorbed redox couple involving interactions between the adsorbed particles was analyzed theoretically under conditions of square-wave voltammetry (SWV). If uniform interactions act between the adsorbed particles, the effect of interaction forces is represented through the product of the relative surface coverage and Frumkin interaction parameter �a. The kinetics of the redox reaction in the presence of uniform interactions are a function of the apparent rate constant defined as ks,app.=ks exp(−2a�), where ks is a real standard rate constant. The apparent reversibility of the redox reaction is determined solely by a dimensionless kinetic parameter defined as the ratio of the apparent rate constant and the signal frequency, �=ks,app/f. This dimensionless kinetic parameter unifies the effects of both the interaction forces and the charge transfer rate. The height of the dimensionless response depends parabolically on the kinetic parameter �, as a consequence of the phenomenon known as a ‘quasireversible maximum’. Based on this peculiarity, a method for estimating the real standard rate constant ks and Frumkin interaction parameter a is proposed. The theoretical results are compared qualitatively with the experimental SW voltammograms of probucole.

Item Type: Article
Subjects: Natural sciences > Chemical sciences
Natural sciences > Physical sciences
Divisions: Faculty of Agriculture
Depositing User: Rubin Gulaboski
Date Deposited: 31 Oct 2012 13:13
Last Modified: 05 Nov 2012 11:12
URI: http://eprints.ugd.edu.mk/id/eprint/154

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