Multi-step electrode reactions

T. Iwasita-Vielstich shows how modem spectroscopic techniques enable us to analyze the mechanism of catalyzed multi-step electrode reactions of organic molecules by detecting intermediates. This demonstrates the current general trend in electrochemical research involving the development of techniques that provide information on the atomic or molecular scale. 

The Frumkin epoch in electrochemistry [i-iii] commemorates the interplay of electrochemical kinetics and equilibrium interfacial phenomena. The most famous findings are the - Frumkin adsorption isotherm (1925) Frumkin s slow discharge theory (1933, see also - Frumkin correction), the rotating ring disk electrode (1959), and various aspects of surface thermodynamics related to the notion of the point of zero charge. His contributions to the theory of polarographic maxima, kinetics of multi-step electrode reactions, and corrosion science are also well-known. An important feature of the Frumkin school was the development of numerous original experimental techniques for certain problems. The Frumkin school also pioneered the experimental style of ultra-pure conditions in electrochemical experiments [i]. A list of publications of Frumkin until 1965 is available in [iv], and later publications are listed in [ii]. 

It should be remembered that Eq. 6E is applicable only for a single-step electrode reaction. The corresponding equation for multi step electrode reactions is Eq. 51F in Section 14.7. 

Monolayer adsorption, 261, 280, 312, 420, Multi-step electrode reactions, 130... 

In a more general description one can define an electrode reaction with n electrons, whereupon either the elementary electrode reaction occurs n times or there is a more complex situation of multi-step electrode reactions for which there is much treatment in the literatiue. ... 

Most electrode reactions encountered in the field of corrosion involve the transfer of more than one electron. Such reactions take place in steps, of which the slowest, called the rate-determining step, abbreviated RDS, determines the overall reaction rate. In simple cases, one can identify the rate-determining step by an analysis of the measured Tafel slopes. In the so-called quasi-equilibrium approach one assumes that with the exception of the rate-limiting step, all other steps are at equilibrium. This greatly simplifies the mathematical equations for the reaction rate. More realistic approaches require numerical simulation and shall not be discussed here. To illustrate the quasi equilibrium approach to the study of multi-step electrode reactions we shall look at proposed mechanisms for the dissolution of copper and of iron. 

Specific Examples of Multi-Step Electrode Reactions... 

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