Cyclic voltammetry in weakly supported media The reduction of the cobaltocenium cation in acetonitrile - Comparison between theory and experiment
Experimental cyclic voltammetry at a hemispherical mercury microelectrode in acetonitrile solution, containing 3 mM cobaltocenium hexafluorophosphate and different concentrations of supporting electrolyte, is compared with theoretical simulations using the Nernst-Planck-Poisson system of equations,...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
2010
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| Summary: | Experimental cyclic voltammetry at a hemispherical mercury microelectrode in acetonitrile solution, containing 3 mM cobaltocenium hexafluorophosphate and different concentrations of supporting electrolyte, is compared with theoretical simulations using the Nernst-Planck-Poisson system of equations, without the assumption of electroneutrality, and is found in to be in good agreement. Deviations from diffusion-only theory are analyzed in terms of migration and potential drop in the solution as a function of the concentration of supporting electrolyte. We are unaware of previous reports in which non-steady-state cyclic voltammetry without supporting electrolyte has been quantitatively and fully simulated, so this work opens up a new area for voltammetry. © 2010 Published by Elsevier B.V. |
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