Voltammetry Involving Amalgam Formation and Anodic Stripping in Weakly Supported Media: Theory and Experiment

Journal article

The voltammetric behavior of the Tl(I)/Tl(Hg) redox couple at a small mercury hemisphere (45 -m radius) is theoretically and experimentally investigated in the presence of various concentrations of supporting electrolyte, covering the range between "self-supported" (no electrolyte) to "fully supported" (very large excess of supporting electrolyte). A theoretical model is described, implementing the Nernst-Planck-Poisson equations, to account for both diffusional and migrational contributions to the mass transport, as well as for the potential distribution in solution. The model accurately reproduces the experimental results and then is used to predict the cathodic and anodic peak potentials and intensities for a wide range of supporting conditions, potential sweep rates, and electrode sizes. The influence of diffusion (linear vs spherical, semi-infinite vs finite), electrode size, and potential drop in solution are discussed in light of the theoretical and experimental results. © 2010 American Chemical Society.

Authors: Limon-Petersen, J; Dickinson, E; Doneux, T; Rees, N; Compton, R

• Publication status: Published
• Journal: JOURNAL OF PHYSICAL CHEMISTRY C
• Volume: 114
• Issue: 15
• Pages: 7120-7127
• Publication date: 2010-04-22
• DOI: 10.1021/jp100845n
• EISSN: 1932-7455
• ISSN: 1932-7447
• Language: English