General Theory of Cathodic and Anodic Stripping Voltammetry at Solid Electrodes:  Mathematical Modeling and Numerical Simulations

Abstract

Theory is presented to describe the voltammetric signals associated with the stripping phase of stripping voltammetry at solid electrodes. Three mathematical models are considered, and the importance of the hemispherical diffusion associated with electrochemical dissolution of particles in the micrometer range is investigated. Model A considers a "monolayer" system where the coverage at a specific point cannot exceed a maximum value. Model B considers a thin layer of metal or metal oxide, but in contrast to model A, the maximum surface coverage is not restricted. Model C represents the stripping of a "thick layer" where the deposition is also unrestricted.

The mathematical models of the stripping voltammetry metal deposition/dissolution process

“…The total current, identically as in model I, can be calculated as the algebraic sum of currents for the two charge transfer reactions (9). Fig.…”

“…The total current is calculated as the algebraic sum of currents for the two charge transfer reactions, identical in form as for oneplate model (9).…”

“…Such a response is often met in stripping analysis of metals. In models presented in literature the authors report about "nucleation loop" which "cannot be simulated" [10] or the problem of loop is not considered [9]. In our model, elementary kinetic parameters method is used [42,14].…”

“…Advanced mathematical models of respective stripping analysis are described in recent papers by Compton and co-workers [9,10]. In paper [9] there are three A, B and C models described, respectively, for monolayer system, thin layer system where maximum electrode coverage is not restricted, and thick layer system.…”

Stripping Voltammetry at Microdisk Electrode Arrays: Theory

“…Whilst the theory of ASV has been well developed for macroelectrodes under planar diffusion using solid electrodes [26] and for mercury films under convective conditions [10,27], the response of mercury film microelectrodes and arrays of these electrodes is essentially unexplored. Accordingly, this paper addresses the issue of ASVat such electrodes.…”