Bockris and Matthews

However, quantal and molecular treatments of proton transfer reactions at an electrode are rare. This treatment incorporates the major effect of an electric field as well as some of the important concepts reported earlier by Bockris and Matthews concerning proton transfer reactions at an electrode. 

Bockris and Matthews measured the separation factor at -71°C by using concentrated HCl solutions. During this work, they accidentally observed an important effect, namely, the considerable variation of the separation factor with potential (Figure 4). 

An interesting development from Gurney s paper(16) and from a paper of Bell(20) published soon after, was the application of quantum-mechanical tunneling concepts to the transfer of the proton in the H2 evolution reaction by a tunneling mechanism, as treated in a paper by Bawn and Ogden(21). Further treatments of this kind were made later by Conway(22), Conway and Salomon(23), Christov(24), and Bockris and Matthews(25). However, despite attempts to detect proton transfer by the tunneling mechanism by means of electrochemical experiments at low temperatures(23) (e.g. down to 180 K), no clear... 

Bockris, Khan, and Matthews pointed out that if one plots the value of calculated on the solvent fluctuation theory for a number of redox reactions in solution, against the corresponding value, calculated from experiment, with the transmission coefficient assumed to be unity, one obtains no correlation, except that the values theoretically predicted are generally below those observed experimentally. 

Source Reprinted with the permission of the Royal Society of Chemistry from J. O M. Bockris, S. Srinivasan, and D. B. Matthews, Discuss. Faraday Soc. 39 239,1965, Table 5. 

J. O M. Bockris, D. B. Matthews, and S. U. M. Khan, J. Res. Inst. Catal. 22 1 (1974). The AG°X calculated from the electrostatic model of Weiss-Marcus is discrepant with experimental trends, but a vibrational energy based theory fits well. 

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