Ideal Gas Reference for Association and Dissociation Reactions: II. Kinetic Reference Potentials and Concentration Bias in Electrolysis

The ideal gas reference for association and dissociation reactions, developed in the first part of this series, is applied to electrochemical reactions. We obtain an ideal Nernst equation that quantifies the unspecific voltage contribution arising from an imbalance between the reactant and product concentrations of an electrochemical reaction for the given conditions. Subtracting this concentration bias from the equilibrium voltage/potential, we define the "kinetic reference voltage/potential" where the reactant and product states are "aligned" within the potential energy landscape of the system. The kinetic reference voltage/potential is a fundamental descriptor for a given electrochemical reaction, providing an intrinsic reference point which is most relevant in cases where the (standard) equilibrium voltage/potential is biased by large concentration differences between the reactant and product side. This is most dramatic for the case of water electrolysis, where the gaseous H₂ and O₂ product concentrations are several orders of magnitude smaller than the liquid water reactant concentration. The respective equilibrium voltage is strongly biased by the low H₂ and O₂ concentrations, although the latter do not directly influence the forward water splitting rate. The unbiased kinetic reference voltage agrees remarkably well with the experimentally observed onset of macroscopic water splitting rates. We further extend our analysis to the kinetic reference potentials of the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and lattice oxygen evolution reaction (LOER), providing an unconventional perspective on pH-dependent overpotentials, anticipated electrocatalysis improvements, and kinetic stabilization of electrocatalyst materials.