Oxidation-reduction reactions quantitative aspects

This review is concerned with the quantitative aspects of metal-catalysed oxyradical reactions. As such one will find discussions of structures of metal complexes, rate constants and reduction potentials, not unlike our review of 1985 [34], Two areas related to the role of transition metals in radical chemistry and biology have been reviewed recently these are the metal-ion-catalysed oxidation of proteins [35] and the role of iron in oxygen-mediated toxicities [36]. These topics will not be discussed in detail in this review. Related to this work is a review on the role of transition metals in autoxidation reactions [37]. Additional information can be obtained from Afanas ev s two volumes on superoxide [38,39], This subject is also treated in a more general and less quantitative manner by Halliwell and Gutteridge [40],... 

An understanding of the operation of the SECM and an appreciation of the quantitative aspects of measurements with this instrument depends upon an understanding of electrochemistry at small electrodes. The behavior of ultramicroelectrodes in bulk solution (far from a substrate) has been the subject of a number of reviews (17-21). A simplified experimental setup for an electrochemical experiment is shown in Figure 1. The solution contains a species, O, at a concentration, c, and usually contains supporting electrolyte to decrease the solution resistance and insure that transport of O to the electrode occurs predominantly by diffusion. The electrochemical cell also contains an auxiliary electrode that completes the circuit via the power supply. As the power supply voltage is increased, a reduction reaction, O + ne — R, occurs at the tip, resulting in a current flow. An oxidation reaction will occur at the auxiliary electrode, but this reaction is usually not of interest in SECM, since this electrode is placed sufficiently far from the UME... 

Abstract Corrosion is basically the oxidation of metals, where electrons are transferred between oxidant and reductant. Therefore, corrosion is generally composed of redox reactions and should be analyzed from the viewpoint of electrochemistry. In this chapter, we describe the basic concept of electrochemistry and how various corrosion aspects can be explained by this discipline. We focus particularly on the equilibrium side because it could suggest possibilities that might be useful for corrosion prediction. The close relationship between redox reactions and corrosion are explained and stressed qualitatively and quantitatively. 

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