A Theory of Electron Transfer Processes at Electrodes

Chemical and electrochemical redox reactions have many characteristics in common from the point of view of the experimental results and theory. A quantitative theory of the rates of electron transfer reactions in solution has been formulated (1) and related concepts used to develop an analogous treatment of electrode processes (2). In this chapter we consider the foundations of this theory, their relation to quantum mechanical principles, and the relation between the electron transfer mechanism and other mechanisms of electrode processes. The quantitative development has been presented elsewhere (2). The theoretical equations themselves have been used to interpret some of the data (3). In the interpretation, the relation to chemical electron transfers has been emphasized.