Peroxide pathway, oxygen

The addition of thiols to C—C multiple bonds may proceed via an electrophilic pathway involving ionic processes or a free radical chain pathway. The main emphasis in the literature has been on the free radical pathway, and little work exists on electrophilic processes.534-537 The normal mode of addition of the relatively weakly acidic thiols is by the electrophilic pathway in accordance with Markovnikov s rule (equation 299). However, it is established that even the smallest traces of peroxide impurities, oxygen or the presence of light will initiate the free radical mode of addition leading to anti-Markovnikov products. Fortunately, the electrophilic addition of thiols is catalyzed by protic acids, such as sulfuric acid538 and p-toluenesulfonic acid,539 and Lewis acids, such as aluminum chloride,540 boron trifluoride,536 titanium tetrachloride,540 tin(IV) chloride,536 540 zinc chloride536 and sulfur dioxide.541... 

Nowadays, it has been demonstrated that the reaction is indeed structure sensitive with a multielectron transfer process that involves several steps and the possible existence of several adsorption intermediates [93-96]. The main advantage that we have with the new procedures with respect to cleanliness is that we have well-ordered surfaces to study a complex mechanism such as the oxygen electroreduction reaction [96-99]. In aqueous solutions, the four-electron oxygen reduction appears to occur by two overall pathways a direct four-electron reduction and a peroxide pathway. The latter pathway involves hydrogen peroxide as an intermediate and can undergo either further reduction or decomposition in acid solutions to yield water as the final product. This type of generic model of a reaction has been extensively studied since the early 1960s by different authors [100-108]. 

The reduction of oxygen is itself a complex electrochemical process. As described in Section 9.2, O2 reduction is considered to proceed along two parallel pathways, the direct four-electron pathway and the peroxide pathway (Eq. 9-9). Both pathways... 

In spite of the considerable effort expended in trying to unravel the fundamental aspects of the O2 electroreduction reaction, many details about the mechanism are not fully understood. The electrochemical reduction of oxygen is a multielectron reaction that occurs via two main pathways one involving the transfer of two electrons to give peroxide, and the so-called direct four-electron pathway to give water. The latter involves the rupture of the 0-0 bond. The nature of the electrode strongly influences the preferred pathway. Most electrode materials catalyze the reaction via two electrons to give peroxide Peroxide pathway in acid... 

Figure 1 shows electrochemical oxygen reduction mechanism in alkaline system. Oxygen reduction in alkaline system is cmisidered to proceed by two overall pathways. One is the direct 4-electron pathway (O2 + 4e + 2H2O = 40H ), and the other one is the peroxide pathway (O2 + 2e + H2O = H02 + OH ), which produces hydrogen peroxide as an intermediate product. The H02 is further reduced to OH by either electrochemical reaction or catalytical decomposition reaction. The reactions are dependent on the kind of electrocatalysts [4]. 

While the cathodic pathway of oxygen reduction to water proceeds through a peroxide pathway, the rate quantification of several parallel steps has been investigated and mechanisms have been explained by multi-parallel pathways (Damjanovic et al, 1966). Following is the overall reaction proposed in an acidic medium... 

The luminescence reaction of coelenterazine is initiated by the peroxidation of coelenterazine at its C2 carbon by molecular oxygen (Fig. 3.3.4). Then, the peroxidized coelenterazine decomposes into coelenteramide plus CO2, producing the energy needed for the light emission. For the mechanism of the decomposition of peroxide that produces the energy, two different pathways can be considered. 

Nifurtimox, a nitrofuran, is a prodrug that is reduced to unstable nitroanion radicals, which react to produce highly toxic oxygen metabolites, such as superoxide and peroxide. Oxidative stress subsequently kills the parasite, which seems to lack effective enzymatic pathways to detoxify oxygen metabolites. 

Two major pathways exist for this reaction, one bypassing hydrogen peroxide (first pathway) and the other involving intermediate peroxide formation via reaction (15.21) (second pathway). The peroxide formed is either electrochemically reduced to water via reaction (15.22) or decomposed catalytically on the electrode surface via reaction (15.23), in which case half of the oxygen consumed to form it reemerges [in both cases the overall reaction corresponds to Eq. (15.20)]. 

In the reaction following the second pathway, the 0-0 bond is not broken while the first two electrons are added it is preserved in the HjOj produced as an intermediate, and breaks in a later step, when the hydrogen peroxide is reduced or cat-alytically decomposed. An analog for this pathway does not exist in anodic oxygen evolution. 

The second pathway is seen distinctly at mercury and graphite electrodes. These electrodes are quite inactive in the catalytic decomposition of H2O2. Moreover, at them the potential where the peroxide is reduced further is more negative than the potential where it is formed from oxygen. Hence, within a certain range of not too negative potentials, the reaction can occur in such a way that the hydrogen peroxide formed accumulates in the solution. 

The resulting unstable molecular ion Oj) rapidly adds another electron and protons to yield hydrogen peroxide. In alkaline solutions the same pathway is followed, but owing to the much lower polarization, the reaction becomes practically reversible (b = 0.03 V) its rate then is determined by oxygen transport to the surface, and polarization is of the concentration type (Bagotsky and Yablokova, 1953). 

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