Theoretical treatment of high-frequency, large-amplitude ac voltammetry applied to ideal surface-confined redox systems
Abstract
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).Additional details
- Eprint ID
- 30041
- Resolver ID
- CaltechAUTHORS:20120409-145854607
- EP/F044690/1
- Engineering and Physical Sciences Research Council (EPSRC)
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2012-04-10Created from EPrint's datestamp field
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2023-03-16Created from EPrint's last_modified field