Journal
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
Volume 650, Issue 1, Pages 135-142Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jelechem.2010.08.011
Keywords
Ohmic drop; Migration; Nernst-Planck-Poisson equations; Cobaltocenium; Weakly supported voltammetry; Supporting electrolyte
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Funding
- CONACYT Mexico
- St John s College Oxford
- EPSRC [EP/H002413/1]
- Engineering and Physical Sciences Research Council [EP/H002413/1] Funding Source: researchfish
- EPSRC [EP/H002413/1] Funding Source: UKRI
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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 (C) 2010 Elsevier B V All rights reserved
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