Abstract
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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