TY - JOUR
T1 - Voltammetry involving amalgam formation and anodic stripping in weakly supported media
T2 - Theory and experiment
AU - Limon-Petersen, J.G.
AU - Dickinson, E.J.F.
AU - Doneux, T.
AU - Rees, N.V.
AU - Compton, R.G.
N1 - Copyright 2010 Elsevier B.V., All rights reserved.
PY - 2010/4/22
Y1 - 2010/4/22
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?partnerID=yv4JPVwI&eid=2-s2.0-77951137729&md5=6ac7ae1936d5542c79e561e09e3bfe43
U2 - 10.1021/jp100845n
DO - 10.1021/jp100845n
M3 - Article
AN - SCOPUS:77951137729
SN - 1932-7447
VL - 114
SP - 7120
EP - 7127
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 15
ER -