Surface ECE mechanism in protein film voltammetry—a theoretical study under conditions of square-wave voltammetry

Gulaboski, Rubin (2009) Surface ECE mechanism in protein film voltammetry—a theoretical study under conditions of square-wave voltammetry. Journal of Solid State Electrochemistry, 13. pp. 1015-1024. ISSN 1432-8488

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Abstract

For the first time, the features of a surface electron
transfer–chemical reaction–electron transfer (ECE) mechanism,
relevant to protein-film set-up, have been studied
theoretically under conditions of square-wave voltammetry.
The considered surface ECE mechanism is presented by
following reaction scheme:AðadsorbedÞ þ ne� !B adsorbed ð Þþ
YYk
f C adsorbed ð Þþ ne� !D adsorbed ð Þ. The mathematical solutions
of this complex redox mechanism are given in form
of integral equations, and they can be applied to any chronoamperometric
technique. Attention is given to two frequently
met situations: (a) case where the energy for the
reduction in the second electron transfer step is lower or
equal to that of the first reduction step and (b) case where
the energy for the reduction of the second electron transfer
step is much higher than that of the first reduction step. The
theoretical square-wave voltammograms feature various
shapes, depending mainly on the energy difference between
the two electron transfer steps, but they also depend on the
kinetics of the first and the second electron transfer, as well
as on the rate of the chemical reaction. Hints are given for
qualitative recognition of the surface ECE mechanism and for its distinguishing from similar surface redox systems.
Reliable methods are proposed for the estimation of kinetic
parameters of the electron transfer steps and that of the
chemical reaction. Since many biological compounds undergo
this redox mechanism, the theoretical results presented
in this work can be of help for the people dealing with
organic electrochemistry or protein-film voltammetry.

Item Type: Article
Subjects: Natural sciences > Biological sciences
Natural sciences > Chemical sciences
Natural sciences > Physical sciences
Divisions: Faculty of Agriculture
Depositing User: Rubin Gulaboski
Date Deposited: 25 Dec 2012 13:04
Last Modified: 25 Dec 2012 13:04
URI: https://eprints.ugd.edu.mk/id/eprint/4397

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