Faradaic rectification results

The present chapter will cover detailed studies of kinetic parameters of several reversible, quasi-reversible, and irreversible reactions accompanied by either single-electron charge transfer or multiple-electrons charge transfer. To evaluate the kinetic parameters for each step of electron charge transfer in any multistep reaction, the suitably developed and modified theory of faradaic rectification will be discussed. The results reported relate to the reactions at redox couple/metal, metal ion/metal, and metal ion/mercury interfaces in the audio and higher frequency ranges. The zero-point method has also been applied to some multiple-electron charge transfer reactions and, wheresoever possible, these results have been incorporated. Other related methods and applications will also be treated. 

Thus, thallium ion discharge on thallium amalgam was investigated, using the impedance method, by Randles, and it was shown that log ks changes linearly with the change of the reversible potential as indicated by Eq. (25). The plot rendered (3 = 0.52 (similar results were obtained from Faradaic rectification measurements by Barker et... 

By the use of a variety of polarographic and allied techniques, reaction half-times down to about 10 s can be studied, and a recent technique, known as high level Faradaic rectification extends this range to about 10 s. However, there are some problems in interpreting kinetic results for proton-transfer reactions derived from electrochemical studies. In the first place, the relation between the observed quantities and chemical rate constants is a complicated one, and its derivation usually involves physical or mathematical approximations and corrections. Secondly, the informa-... 

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