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Voltammetric Peak Heights of the Proton–Hydrogen Redox Couple: A Comprehensive Analysis

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Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford University, Oxford OX1 3QZ, United Kingdom
Cite this: J. Phys. Chem. C 2015, 119, 40, 23203–23210
Publication Date (Web):August 7, 2015
https://doi.org/10.1021/acs.jpcc.5b06040
Copyright © 2015 American Chemical Society

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    Abstract

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    We present a comprehensive analysis of the voltammetric peak heights of the proton–hydrogen redox couple. To this end, we first reconcile conflicting literature that provides deviating solutions for the one-dimensional problem of a macrodisk electrode under reversible conditions, and numerically verify the correct solution. We then compare one-dimensional theory with two-dimensional simulations of commonly used, standard-size macroelectrodes and establish the loss of electrochemical reversibility as a result of high diffusion coefficients. We further explore the magnitude of the standard electrochemical rate constant needed for “Nernstian” behavior in such systems.

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    Cited By

    This article is cited by 6 publications.

    1. Rachel L. Pindar, Christopher Batchelor-McAuley, Minjun Yang, Richard G. Compton. Towards Direct Electroanalysis in Seawater: Understanding the Role of the Buffer Capacity of Seawater in Proton-Coupled Electron Transfer Reactions. The Journal of Physical Chemistry C 2021, 125 (51) , 27949-27958. https://doi.org/10.1021/acs.jpcc.1c09142
    2. José María Gómez-Gil, Eduardo Laborda, Angela Molina. General Explicit Mathematical Solution for the Voltammetry of Nonunity Stoichiometry Electrode Reactions: Diagnosis Criteria in Cyclic Voltammetry. Analytical Chemistry 2020, 92 (5) , 3728-3734. https://doi.org/10.1021/acs.analchem.9b05023
    3. Eduardo Laborda, Joaquín González, Francisco Martínez-Ortiz, Angela Molina. Voltammetry at microelectrodes of reversible electrode reactions with complex stoichiometry: A general analytical theoretical framework. Journal of Electroanalytical Chemistry 2020, 872 , 113932. https://doi.org/10.1016/j.jelechem.2020.113932
    4. Eduardo Laborda, José María Gómez-Gil, Manuela López-Tenés, Angela Molina. Cyclic square wave voltammetry of electrode reactions with nonunity stoichiometry. Journal of Electroanalytical Chemistry 2020, 873 , 114421. https://doi.org/10.1016/j.jelechem.2020.114421
    5. Pitchnaree Kraikaew, Eden E. L. Tanner, Stanislav V. Sokolov, Christopher Batchelor‐McAuley, Jennifer Holter, Neil P. Young, Richard G. Compton. Nanoparticle Surface Coverage Controls the Speciation of Electrochemically Generated Chlorine. ChemElectroChem 2016, 3 (11) , 1794-1798. https://doi.org/10.1002/celc.201600449
    6. Christopher Batchelor-McAuley, Minjun Yang, Elise M. Hall, Richard G. Compton. Correction factors for the analysis of voltammetric peak currents measured using staircase voltammetry. Journal of Electroanalytical Chemistry 2015, 758 , 1-6. https://doi.org/10.1016/j.jelechem.2015.10.004

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