ABSTRACT
I begin my chapter by reminding the reader about the beginning of electrode kinetics. This was in a paper presenting an empirical law (the first law of electrode kinetics) that is the basis for our discussion. Of course, there is much else to say apart from this equation, but it plays the same part in electrochemistry as the famous Arrhenius equation, r¼AeE=RT, plays in physical chemistry. Julius Tafel made a very direct contribution to the subject of kinetics at electrodes. In fact, he founded it as a science with equations. Insofar as electrocatalysis concerns the acceleration of electrode reactions by means of the change of substrate, Tafel’s equation is relevant, indeed [1], and, written in the original form, was
h ¼ a b log j (1:1)
where h is the overpotential, the potential of the working electrode, diminished by the reversible potential, for the electrode reaction concerned. hmight well be then renamed the excitation potential, because when it is zero no reaction occurs and when finite, the reaction goes either forward or backward, according to the sign of h, positive for backward, negative for forward.
