On the Theory of Overvoltage for Electrode Processes Possess ing Electron Transfer Mechanisms. I.

Abstract

The following article was first prepared as the above Office of Naval Research Technical Report, and is being reproduced here in its entirety. The results were applied in subsequent papers on electrode kinetics [I], and the Report itself has been widely cited in the literature. Originally intended for journal publication, the article was never submitted because of the efforts of the author towards generalization. The generalization was published some years later [2], but in some respects the approach of the 1957 Technical Report is more readable. The principal generalizations are the inclusion of inner coordination shell contributions and the use of statistical mechanics for inner and outer contributions [2,3]. The 1957 Report and a predecessor [4] had as their aims the treatment of the outer shell contribution; their equation for the dielectric continuum calculation of that contribution is the same as that in the later publication [2]. The Report draws upon some derivations in ONR Technical Report No.11, and this latter Report is included also. The generalization of those results may be found in Ref. [5]. Elsewhere in this book we comment on more recent developments.