Practical Aspects of Cyclic Voltammetry: How to Estimate Reduction Potentials When Irreversibility Prevails

What is the best approach for estimating standard electrochemical potentials, E (0) , from voltammograms that exhibit chemical irreversibility? The lifetimes of the oxidized or reduced forms of the majority of known redox species are considerably shorter than the voltammetry acquisition times, resulting in irreversibility and making the answer to this question of outmost importance. Half-wave potentials, E (1/2) , provide the best experimentally obtainable representation of E (0) . Due to irreversible oxidation or reduction, however, the lack of cathodic or anodic peaks in cyclic voltammograms renders E (1/2) unattainable. Therefore, we evaluate how closely alternative potentials, readily obtainable from irreversible voltammograms, estimate E (0) . Our analysis reveals that, when E (1/2) is not available, inflection-point potentials provide the best characterization of redox couples. While peak potentials are the most extensively used descriptor for irreversible systems, they deviate significantly from E (0) , especially at high scan rates. Even for partially irreversible systems, when the cathodic peak is not as pronounced as the anodic one, the half-wave potentials still provide the best estimates for E (0) . The importance of these findings extends beyond the realm of electrochemistry and impacts fields, such as materials engineering, photonics, cell biology, solar energy engineering and neuroscience, where cyclic voltammetry is a key tool.