Can the Tafel equation be derived from first principles?

A century ago, Tafel disapproved the attempts to derive the empirical equation named after him by thermodynamic methods. He noted that his observations referred to irreversible electrochemical reactions, where thermodynamics is inapplicable. This statement seems to remain valid until today. Indeed, it is impossible as yet to predict the kinetic parameters for chemical processes by determining rate constants and reaction orders from "first principles", unless strictly specialized and, to a great extent, artificial models are developed. Nevertheless, in this paper an attempt to derive the kinetic law of mass action from "first principles" is made in macroscopic formulation. It has turned out to be possible owing to the methods of thermodynamics of irreversible processes that were unknown in Tafel's time. (c) 2005 Elsevier Ltd. All rights reserved.