Multiparameter Estimation in Voltammetry When an Electron Transfer Process Is Coupled to a Chemical Reaction

Alexandr N. Simonov, Graham P. Morris, Elena Mashkina, Blair Bethwaite, Kathryn Gillow, Ruth E. Baker, David J. Gavaghan, Alan M. Bond

Research output: Contribution to journalArticlepeer-review

16 Scopus citations


Estimation of thermodynamic and kinetic parameters in electrochemical studies is usually undertaken via comparison of the experimental results with theory based on a model that mimics the experiment. The present study examines the credibility of transient d.c. and a.c. voltammetric theory-experiment comparisons for recovery of the parameters needed to model the ubiquitous mechanism when an electron transfer (E) reaction is followed by a chemical (C) step in the EC process (A±e-↔E0,k0,αB↔kbkfC). The data analysis has been undertaken using optimization methods facilitated in some cases by grid computing. These techniques have been applied to the simulated (5% noise added) and experimental (reduction of trans-stilbene) voltammograms to assess the capabilities of parameter recovery of E0 (reversible potential for the E step), k0 (heterogeneous electron transfer rate constant at E0), α (charge transfer coefficient for the E step), and kf and kb (forward and backward rate constants for the C step) under different kinetic regimes. The advantages provided by the use of a.c. instead of d.c. voltammetry and data optimization methods over heuristic approaches to "experiment"-theory comparisons are discussed, as are the limitations in the efficient recovery of a unique set of parameters for the EC mechanism. In the particular experimental case examined herein, results for the protonation of the electrochemically generated stilbene dianion demonstrate that, notwithstanding significant advances in experiment and theory of voltammetric analysis, reliable recovery of the parameters for the EC mechanism with a fast chemical process remains a stiff problem.
Original languageEnglish (US)
Pages (from-to)4724-4732
Number of pages9
Issue number9
StatePublished - Apr 4 2016
Externally publishedYes

Bibliographical note

KAUST Repository Item: Exported on 2022-06-02
Acknowledged KAUST grant number(s): KUK-C1-013-04
Acknowledgements: This publication is based on work supported by Award No. KUK-C1-013-04, made by King Abdullah University of Science and Technology (KAUST). Financial support from the Australian Research Council is also gratefully acknowledged.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

ASJC Scopus subject areas

  • Analytical Chemistry


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