Bell, Christopher G. and Anastassiou, Costas A. and O’Hare, Danny and Parker, Kim H. and Siggers, Jennifer H. (2012) Theoretical treatment of high-frequency, large-amplitude ac voltammetry applied to ideal surface-confined redox systems. Electrochimica Acta, 64 . pp. 71-80. ISSN 0013-4686 http://resolver.caltech.edu/CaltechAUTHORS:20120409-145854607
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Large-amplitude ac voltammetry, where the applied voltage is a large-amplitude sinusoidal waveform superimposed onto a dc ramp, is a powerful method for investigating the reaction kinetics of surface-confined redox species. Here we consider the large-amplitude ac voltammetric current response of a quasi-reversible, ideal, surface-confined redox system, for which the redox reaction is described by Butler–Volmer theory. We derive an approximate analytical solution, which is valid whenever the angular frequency of the sine-wave is much larger than the rate of the dc ramp and the standard kinetic rate constant of the redox reaction. We demonstrate how the third harmonic and the initial transient of the current response can be used to estimate parameters of the electrochemical system, namely the kinetic rate constant, the electron transfer coefficient, the adsorption formal potential, the initial proportion of oxidised molecules and the linear double-layer capacitance.
|Additional Information:||© 2011 Elsevier Ltd. Received 6 October 2011. Revised 23 November 2011. Accepted 20 December 2011. Available online 29 December 2011. The authors gratefully acknowledge the funding for this project that was provided by the Engineering and Physical Sciences Research Council (EPSRC) (Grant Number EP/F044690/1).|
|Subject Keywords:||ac voltammetry; Quasi-reversible; Large-amplitude; Adsorbed; Surface-confined|
|Official Citation:||Christopher G. Bell, Costas A. Anastassiou, Danny O’Hare, Kim H. Parker, Jennifer H. Siggers, Theoretical treatment of high-frequency, large-amplitude ac voltammetry applied to ideal surface-confined redox systems, Electrochimica Acta, Volume 64, 1 March 2012, Pages 71-80, ISSN 0013-4686, 10.1016/j.electacta.2011.12.088.|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Tony Diaz|
|Deposited On:||10 Apr 2012 21:35|
|Last Modified:||10 Apr 2012 21:35|
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