Bell, Christopher G. and Anastassiou, Costas A. and O'Hare, Danny and Parker, Kim H. and Siggers, Jennifer H. (2011) Theory of large-amplitude sinusoidal voltammetry for reversible redox reactions. Electrochimica Acta, 56 (24). pp. 8492-8508. ISSN 0013-4686 http://resolver.caltech.edu/CaltechAUTHORS:20111107-102532272
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Sinusoidal voltammetry, where the voltage input is a pure sine wave without any dc ramp, is an effective technique for interrogating electrochemical systems containing reversible redox reactions. In particular, it eliminates the need for baseline subtraction, since purely faradaic information can be obtained from the higher harmonics free from the effects of double layer capacitance. In this article we derive a novel analytical solution for the long-time current response, i.e. as the current approaches a periodic state, using excitation amplitudes of any magnitude. We define a new protocol for deducing the underlying parameters of the electrochemical system, such as bulk concentrations, diffusion coefficients, the half-wave potential, and the double-layer capacitance (if it is linear), from the amplitudes and phases of the different harmonics, and the dc part of the current response. In addition, we show how the Hann window can be used in conjunction with the FFT to derive clean harmonic information from a current signal containing large linear capacitive interference, where leakage in the power spectrum from the fundamental harmonic contaminates the higher harmonics.
|Additional Information:||© 2011 Elsevier Ltd. Received 13 May 2011. Received in revised form 8 July 2011. Accepted 11 July 2011. Available online 23 July 2011. The funding for this project was provided by the Engineering and Physical Sciences Research Council (EPSRC) (grant number EP/F044690/1) and is gratefully acknowledged.|
|Subject Keywords:||Sinusoidal voltammetry Reversible Large-amplitude Double-layer capacitance ac voltammetry|
|Official Citation:||Christopher G. Bell, Costas A. Anastassiou, Danny O’Hare, Kim H. Parker, Jennifer H. Siggers, Theory of large-amplitude sinusoidal voltammetry for reversible redox reactions, Electrochimica Acta, Volume 56, Issue 24, 1 October 2011, Pages 8492-8508, ISSN 0013-4686, 10.1016/j.electacta.2011.07.050. (http://www.sciencedirect.com/science/article/pii/S0013468611010851)|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Ruth Sustaita|
|Deposited On:||07 Nov 2011 18:46|
|Last Modified:||07 Nov 2011 18:46|
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