Cyclic voltammetry in weakly supported media The reduction of the cobaltocenium cation in acetonitrile - Comparison between theory and experiment

Journal article

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.

Authors: Limon-Petersen, J; Dickinson, E; Belding, SR; Rees, N; Compton, R

• Publication status: Published
• Journal: JOURNAL OF ELECTROANALYTICAL CHEMISTRY
• Volume: 650
• Issue: 1
• Pages: 135-142
• Publication date: 2010-12-15
• DOI: 10.1016/j.jelechem.2010.08.011
• ISSN: 1572-6657
• Language: English
• Keywords: Migration; Cobaltocenium; Weakly supported voltammetry; Ohmic drop; Supporting electrolyte; Nernst-Planck-Poisson equations