Abstract
The current is considered at a stationary reversible spherical electrode whose potential E(t) as a function of time is given, such that E(t) determines the ratio of oxidized to reduced species at the electrode surface. Writing the current as that for planar geometry, I0, plus corrections for sphericity, we derive formulae for the corrections. The first two are expressed as integrals over I0, with no explicit dependence on the potential, for any form of E(t), and whether the reduced species diffuses into the electrode or into the solution. If the ratio of diffusion constants for oxidized and reduced species is taken as unity, and if oxidized and reduced species are both in the solution, the corrections become extremely simple (no integrations or differentiations), regardless of the form of E(t). The first correction is evaluated in several cases where this does not obtain.
Highlights
To compute the current at a reversible stationary spherical microelectrode with changing potential E(t), one must solve the diffusion equation for oxidized and reduced species in the solution, coupled by the Nernst equilibrium conditions on the concentrations at the electrode surface
Some authors [2,6] have solved the problem for spherical diffusion directly in certain cases, and the diffusion problems themselves have been studied in detail [4,7,8]
We present here a general procedure for obtaining the leading corrections to the planar result for any variation of electrode potential E with time, for any ratio of diffusion coefficients of oxidized and reduced species, and for diffusion of reduced species into the electrode or into the solution
Summary
Follow this and additional works at: https://surface.syr.edu/che Part of the Chemistry Commons. Recommended Citation Goodisman, Jerry, "General Correction for Electrode Sphericity in Voltammetry of Nernstian Systems" (1983). This is an author-produced, peer-reviewed version of this article. The published version of this document can be found online in the [Journal of Electroanalytical Chemistry and Interfacial and Electrochemistry] (http://www.sciencedirect.com/science/article/pii/S0022072883801417 ) published by Elsevier. The official page numbers are noted in brackets throughout the article
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