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Planar diffusion to macro disc electrodes—what electrode size is required for the Cottrell and Randles-Sevcik equations to apply quantitatively?

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Abstract

Simulations and experiments are reported which investigate the size of a macro disc electrode necessary to quantitatively show the chronoamperometric or voltammetric behaviour predicted by the Cottrell equation or the Randles-Sevcik equation on the basis of exclusive one-dimensional diffusional mass transport. For experimental time scales of several seconds, the contribution of radial diffusion is seen to be measurable even for electrodes of millimetres in radius. Recommendations on the size of macro electrodes for quantitative study are given and should exceed 4 mm radius in aqueous solution.

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Notes

  1. The Arrhenius relation is ln D = constant − E aR−1  T −1; hence, the slope of the linear fit shown in Fig. 2b provides the activation energy for the diffusion of [Fe(CN)6]4− in the electrolyte upon multiplication by −R.

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Acknowledgments

KT was supported by a Marie Curie Intra European Fellowship (Grant Agreement no. 327706) within the 7th European Community Framework Programme. SE and RGC acknowledge funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. 320403.

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Authors and Affiliations

  1. Department of Chemistry Physical & Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QZ, UK

    Kamonwad Ngamchuea, Shaltiel Eloul, Kristina Tschulik & Richard G. Compton

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  1. Kamonwad Ngamchuea
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  2. Shaltiel Eloul
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  3. Kristina Tschulik
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  4. Richard G. Compton
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Correspondence to Richard G. Compton.

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Paper submitted for the ‘Fletcher Festschrift’ issue of Journal of Solid State Electrochemistry in admiration of an outstanding scientist and much valued electrochemistry colleague.

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Ngamchuea, K., Eloul, S., Tschulik, K. et al. Planar diffusion to macro disc electrodes—what electrode size is required for the Cottrell and Randles-Sevcik equations to apply quantitatively?. J Solid State Electrochem 18, 3251–3257 (2014). https://doi.org/10.1007/s10008-014-2664-z

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  • DOI: https://doi.org/10.1007/s10008-014-2664-z

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