A Model of Electrochemical Kinetics from Statistical Mechanics

The Butler-Volmer model is widely applied to describe and explain electrochemical kinetics. As it is phenomenological by nature, much effort has been devised to develop more insightful theories which to this date have failed to deliver a consistent model of electrochemical reactions. In this work, I provide an alternative view on electrochemical kinetics without explicitly considering specifics of the electron transfer. This model predicts that the Butler-Volmer equation is only valid if the electron transfer occurs outside of the electrochemical double layer. Key features of this model are testable and explain why the proton transfer facilitating the formation of forming underpotential deposited hydrogen must largely be independent of the concentration of proton donors and acceptors.