Abstract
Derivative-extremum analysis (DEA) of j-E curves is a newly proposed method of half wave potential (E1/2) and activation feature extraction from steady-state voltammetry. Here, the DEA is demonstrated to be valid in the full range of reversibility using numerical simulations with a derived universal electrode equation, providing a novel perspective of electrochemical kinetics in the reversibility domain. The results reveal that E1/2 is a better choice of the reference potential instead of equilibrium potential (Eeq) in electrode equations, especially since Eeq is meaningless in an irreversible case. The equations referenced with standard potential, E1/2 and Eeq, are summarized in three tables, and their applications in parameter determinations are specified. Finally, reversibility is proved to be a relative measure between kinetic slowness and mass transport of electroactive species, and the reversibility classifications are proposed according to the DEA feature in the reversibility domain. This work, based on the DEA principle, refines the electrode equation forms and generalizes their applicability in the full range of reversibility.
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