Faradaic rectification applications

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. 

Faradaic rectification polarographic studies have been carried out for a mixture containing several metal ions together and also for individual inorganic depolarizers so as to explore the applicability and limitations of the method and to determine kinetic parameters for some of them. For comparison, some of the dc and ac polarograms have also been recorded simultaneously. In the following, the details of the experimental technique used will be described and the potentiality of the technique in qualitative and quantitative analysis will be examined. The applicability of the method in the... 

Thus, the contributions of several orders can be accessed experimentally by means of a detection device tuned to the proper frequency. Applications of this principle have thus far been limited to the so-called second-order techniques second harmonic a.c. polarography [25], faradaic rectification [26], and the recently developed demodulation technique [27],... 

Refs. [i] Delahay P (1961) Fast electrode processes by relaxation methods. In Delahay P (ed) Advances in electrochemistry and electrochemical engineering, vol. 1. Interscience, New York, Chap. 5 [ii] Reinmuth WH (1964) Anal Chem 36 211R [Hi] Bond AM (1980) Modernpolarographic methods in analytical chemistry. Marcel Dekker, New York, pp 296,298, 361 [iv] Agarwal HP (1974) Faradaic rectification method and its applications in the study of electrode processes. In Bard A (ed) Electroanalyt-ical chemistry, vol. 7. Marcel Dekker, New York, pp 161... 

I. lami and P. Delahay [1962] Faradaic Rectification and Electrode Processes. IH. Experimental Methods for High Frequencies and Application to the Discharge of Mercurous Ion, J. Phys. Chem. 66, 1108-1113. 

Organometallic Electrochemistry, Michael D. Morris Faradaic Rectification Method and Its Applications in the Study of Electrode Processes, H. P. Agarwal... 

Due to the nonlinearity of the I c — Eac relation also direct current component may be detected (faradaic rectification) without any analytical application. Improvement may be achieved by following the second harmonic current response. The main reason for the use of this technique ensues from the fact that the faradaic-to-charging current ratio is extremely favorable in this case. The double-layer charging current, unlike the faradaic component, does not practically involve higher harmonic contributions [4]. 

Faradaic Rectification Method and Its Applications in the Study of Electrode... 

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