Diagnostics of Anodic Stripping Mechanisms under Square-Wave Voltammetry Conditions Using Bismuth Film Substrates

Mirceski, Valentin and Hocevar, Samo B. and Ogorevc, Bozidar and Gulaboski, Rubin and Drangov, Ivan (2012) Diagnostics of Anodic Stripping Mechanisms under Square-Wave Voltammetry Conditions Using Bismuth Film Substrates. Analytical Chemistry, 84 (10). pp. 4429-4436. ISSN 0003-2700

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A mechanistic study to provide diagnostics of anodic
stripping electrode processes at bismuth-film electrodes is presented from
both theoretical and experimental points of view. Theoretical models for
three types of electrode mechanisms are developed under conditions of
square-wave voltammetry, combining rigorous modeling based on
integral equations and the step function method, resulting in derivation
of a single numerical recurrent formula to predict the outcome of the
voltammetric experiment. In the course of the deposition step, it has been
assumed that a uniform film of the metal analyte is formed on the
bismuth substrate, in situ deposited onto a glassy carbon electrode
surface, without considering mass transfer within either the bismuth or
the metal analyte film. Theoretical data are analyzed in terms of dimensionless critical parameters related with electrode kinetics,
mass transfer, adsorption equilibria, and possible lateral interactions within the deposited metal particles. Theoretical analysis
enables definition of simple criteria for differentiation and characterization of electrode processes. Comparing theoretical and
experimental data, anodic stripping processes of zinc(II), cadmium(II), and lead(II) are successfully characterized, revealing
significant differences in their reaction pathways. The proposed easy-to-perform diagnostic route is considered to be of a general
use while the bismuth film exploited in this study served as a convenient nonmercury model substrate surface.

Item Type: Article
Subjects: Natural sciences > Chemical sciences
Natural sciences > Matematics
Natural sciences > Physical sciences
Divisions: Faculty of Agriculture
Depositing User: Rubin Gulaboski
Date Deposited: 31 Oct 2012 23:10
Last Modified: 31 Oct 2012 23:10
URI: https://eprints.ugd.edu.mk/id/eprint/224

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