Journal
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
Volume 673, Issue -, Pages 13-23Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jelechem.2012.03.008
Keywords
Weakly supported media; Background electrolyte; Square wave voltammetry; Differential multipulse voltammetry; Formal potential
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Funding
- St. Johns College
- EPSRC
- Fundacion SENECA [08813/PI/08]
- Direccion General de Investigacion Cientifica y Tecnica [CTQ2009-13023]
- EPSRC [EP/H002413/1, EP/I029095/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/H002413/1, EP/I029095/1] Funding Source: researchfish
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Square wave voltammetry (SWV) and differential multipulse voltammetry (DMPV) in weakly supported media are investigated. The numerical simulation procedures reported in literature (Streeter et al., J. Phys. Chem. C 112 (2008) 13716-13728: Limon-Petersen et al.. J. Phys. Chem. C 114 (2010) 2227-2236) for electrochemical experiments in low conductivity solutions is applied with success. From this theory, the influence of the concentration of supporting electrolyte on the voltammograms is discussed for different redox couples and at electrodes of different size. The variation of the peak current and peak potential due to migration and ohmic drop effects are reported. The theory is applied to the experimental study of the one-electron reduction processes of cobaltocenium and cobalt (III) sepulchrate at mercury hemispherical electrodes of 25 mu m radius. The kinetic parameters and formal potential are obtained in a wide range of support ratio from the SWV and DMPV voltammograms. Possible changes of the kinetic and thermodynamic properties of the electrode reactions are analyzed as a function of the level of support. (C) 2012 Elsevier B.V. All rights reserved.
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