By L.I. Krishtalik
The mechanism of an effortless act is definitely essentially the most basic difficulties of chemical and, particularly, electro chemical kinetics. even though this challenge has involved scientists for rather many years, it used to be purely within the overdue fifties and early sixties that it all started to be actively investigated for cost move reactions. because of the improvement of latest equipment within the research of this challenge, major developments have been made in theoretical in addition to experimental experiences. those investigations confirmed that the actual mechanism of cost move in all procedures together with heterogeneous electrochemical and homogeneous chemical and bio chemical strategies is largely an analogous. consequently, the consequences ob tained within the box of electrochemical kinetics are suitable to the certainty of homogeneous chemical reactions in addition. This publication endeavors to summarize the result of investigations performed over the past 20 years. it really is in response to the author's monograph "Electrode Reactions: The Mechanism of an hassle-free Act" (Nauka, 1979). in comparison to the 1st model, the booklet has been significantly revised and enlarged not just to incorporate a wide physique of knowledge released among 1978 and 1982, but additionally to investigate intimately the hyperlinks among electrochemical and homogeneous, specifically enzymatic, kinetics. consequently, a brand new bankruptcy has been extra to the e-book. The swap within the identify displays the truth that the fabric inside the ebook isn't really constrained to an research of in simple terms electrochemical problems.
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Additional info for Charge Transfer Reactions in Electrochemical and Chemical Processes
Since in acidic solutions at low current densities the process of electrode self-dissolution may play a significant role, we chose a mercury electrode since mercury is the noblest of all cathodic materials with a high hydrogen overpotential. 1The results of these investigations were briefly mentioned for the first time in Reference 101. 39 40 CHAPTER 2 Bowden and Grew and Mituja[106, 107] have studied the hydrogen overpotential for rather low current densities at mercury cathodes, while Kolotyrkin and Frumkin carried out similar investigations with spon~y lead.
E. in the region approximately corresponding to that predicted theoretically. e. 5 times less than the slope of the theoretical curve. Mituja's results, however, cannot be considered as conclusive, since the values of the overpotential and capacity obtained by him are in sharp contradiction with the data available in the literature for comparable values of current density (in all probability, this is due to the proximity of the platinum anode and the cathode[109-111]. A serious drawback of the experimental techniques, like the one proposed in Reference 105, lies in that neither the cathode nor the solution can be replaced in the course of the experiment, and hence it is impossible to verify the reproducibility of the results.
It can be seen that a quantitative relation between the two quantities under investigation does not exist, since practically identical overpotentials may correspond to essentially different solvation energies. Moreover, for dimethylsulfoxide, the changes in the solvation energy and overpotential have opposite signs. The effect of the nature of a solvent on the kinetics of electrode reactions will be discussed in Chapter 6. 4. THE BR0NSTED RELATION AND THE ACTIVITY COEFFICIENT OF AN ACTIVATED COMPLEX In the absolute rate theory, the reaction rate is proportional to the concentration of the activated complex.