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Consistent diffusion coefficients of ferrocene in some non-aqueous solvents: electrochemical simultaneous determination together with electrode sizes and comparison to pulse-gradient spin-echo NMR results

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Abstract

Cyclic voltammetry data recorded at disk macro- (millimeter dimension) and microelectrodes (10 and 100 μm) at various scan rates are used to simultaneously determine the diffusion coefficient D of ferrocene (fc) and the electroactive surfaces A and/or radii r of the electrodes. A case study with three electrodes of different sizes in CH3CN- and propylene carbonate (PC)-based electrolytes shows the possibly large effect of incorrect D values. Diffusion coefficients of fc are determined for PC, CH3CN, CH2Cl2, DMF, and DMSO electrolytes and (except for PC) compared to those from pulse-gradient spin-echo nuclear magnetic resonance experiments in the presence of supporting electrolyte in the respective deuterated solvents. The dependence of D fc on solvent viscosity is shown to follow the Stokes–Einstein relation.

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Notes

  1. In the following, we will use the term “microelectrode” not only for electrodes conforming to Heinze’s definition (d ≤ 20 μm) [4] but also for those of a larger diameter if used under conditions where a hemispherical diffusion steady-state can be achieved.

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Acknowledgments

The authors thank Jürgen Heinze, Universität Freiburg, and Gunther Wittstock, Universität Oldenburg, for discussions. We are indebted to Jörg Henig and David Degler, Universität Tübingen, for preliminary experiments. Adrian Ruff thanks the Universität Tübingen for an LGFG fellowship.

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Authors and Affiliations

  1. Institut für Organische Chemie, Auf der Morgenstelle 18, 72076, Tübingen, Germany

    Janina Janisch, Adrian Ruff, Bernd Speiser, Christian Wolff, Jonas Zigelli & Steffi Benthin

  2. Institut für Anorganische Chemie, Auf der Morgenstelle 18, 72076, Tübingen, Germany

    Verena Feldmann & Hermann A. Mayer

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  1. Janina Janisch
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  2. Adrian Ruff
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  3. Bernd Speiser
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Correspondence to Bernd Speiser.

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This article is dedicated to Professor Fritz Pragst on the occasion of his 70th birthday.

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Janisch, J., Ruff, A., Speiser, B. et al. Consistent diffusion coefficients of ferrocene in some non-aqueous solvents: electrochemical simultaneous determination together with electrode sizes and comparison to pulse-gradient spin-echo NMR results. J Solid State Electrochem 15, 2083–2094 (2011). https://doi.org/10.1007/s10008-011-1399-3

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  • DOI: https://doi.org/10.1007/s10008-011-1399-3

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