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Microelectrode voltammetry as a high accuracy method for determination of diffusion coefficients

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Abstract

Stripping voltammetry analysis using a hemispheroidal mercury microelectrode has been previously assessed theoretically as a possible candidate ‘primary method’ for amount of substance measurement. It was shown that the measurement methodology can be described completely by a set of measurement equations when a novel quantification process is employed to measure the steady-state diffusion-limited deposition current over an optimum sampling time, instead of employing an analyte stripping step. The corollary is that, for solutions of known composition, the method may be used for highly accurate determination of diffusion coefficients. This investigation uses experimental data from steady-state diffusion-limited current measurements with sampling periods optimised using Allan deviation techniques, together with a full uncertainty analysis to estimate feasibility and likely accuracy of this method.

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Acknowledgements

The authors are very grateful to Alistair Forbes (NPL) for providing numerical solutions to Eq. 3, and to NPL’s Exploratory Strategic Research Programme for funding.

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Authors and Affiliations

  1. Analytical Science Team, National Physical Laboratory, Teddington, Middlesex, TW11 0LW, UK

    Richard J. C. Brown

  2. Department of Chemical Engineering, University College London, London, WC1E 7JE, UK

    Dan J. L. Brett

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  1. Richard J. C. Brown
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  2. Dan J. L. Brett
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Correspondence to Richard J. C. Brown.

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Brown, R.J.C., Brett, D.J.L. Microelectrode voltammetry as a high accuracy method for determination of diffusion coefficients. Microchim Acta 164, 337–344 (2009). https://doi.org/10.1007/s00604-008-0062-x

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  • DOI: https://doi.org/10.1007/s00604-008-0062-x

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