Simplifications in the theory of step experiments at microelectrodes

Theoretical studies of the chronoamperometry of the reaction O+ n e − ⇄ R often consider (1) the diffusion-limited reaction, (2) the totally irreversible reaction, and (3) the reversible reaction (governed by the Nernst equation), and these can all be considered as special limiting cases of (4) quas...

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Bibliographic Details
Published in:Journal of electroanalytical chemistry and interfacial electrochemistry 1987-10, Vol.235 (1), p.97-106
Main Authors: Cope, D.K., Tallman, D.E.
Format: Article
Language:English
Subjects:
Chemistry
Electrochemistry
Exact sciences and technology
General and physical chemistry
Kinetics and mechanism of reactions
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Summary:Theoretical studies of the chronoamperometry of the reaction O+ n e − ⇄ R often consider (1) the diffusion-limited reaction, (2) the totally irreversible reaction, and (3) the reversible reaction (governed by the Nernst equation), and these can all be considered as special limiting cases of (4) quasi-reversible reactions, electron transfer kinetics governed by the general current-potential characteristic. Cases (1) and (2) simplify to one-component diffusion systems for the concentration of O; cases (3) and (4) are necessarily two-component diffusion systems involving the concentrations of both O and R. We show that, when O and R have equal diffusion coefficients, the solution for the reversible reaction (3) can be expressed in terms of the solution for the diffusion-limited reaction (1) and that the solution for the quasi-reversible reaction (4) can be expressed in terms of the solution for the totally irreversible reaction (2). These results hold for arbitrary electrode geometries.
ISSN:0022-0728
DOI:10.1016/0022-0728(87)85200-2