Competition between redox reaction and

Competition Between Redox Reactions and Anodic Decomposition. 136... 

Competition between redox reactions and anodic decomposition... 

Competition between Redox Reaction and Anodic Dis.iolution... 

The competition between redox reaction and anodic dissolution became very important in the development of stable regenerative solar cells on the basis of semiconductor-liquid junctions. As shown in the previous section, it is determined by the thermodynamic and kinetic properties of the processes involved. Information on the competitions between these reactions cannot be obtained entirely from current-potential curves, because in many cases they do not look very different upon addition of a redox system, especially if the current is controlled by the light intensity. Therefore, a rotating ring disc electrode (RRDE) assembly consisting of a semiconductor disc and a Pt ring is usually applied, i.e. a technique which makes it possible to determine separately the current corresponding to the oxidation of a redox system [62, 63]. 

Competition between Redox Processes and Other Reactions... 

Inasmuch as flavins can accommodate two electrons but possess a relatively stable one-electron intermediate, an obvious question which can be asked of any flavin-mediated two electron redox reaction is whether or not the mechanism includes the radical species on a direct line between reactants and products. The mere observation of semiquinones in a reaction mixture is not sufficient evidence for their intermediacy, due to the existence of side reactions such as comproportionation (F -I- FH2 2 FH-) which can generate radicals rapidly. Bruice has discussed this question from a physical-organic point of view and concluded that there must exist a competition between one-electron and two-electron processes and that the actual mechanism should be determined mainly by the free energy of formation of substrate radical and the nucleophilicity of the substrate. Bruice has analyzed a variety of systems which he feels should proceed via one-electron mechanisms among these are quinone and carbonyl group reduction by FH2... 

However, the competition between Srn 1 and polar abstraction mechanisms is complicated in certain reactions by the formation of disulfides which is inhibited by radical and radical anion traps, and requires photolysis [23, 24]. These results implicate a third possibility, the chain SET redox mechanism (Srt2, i.e. substitution, electron transfer, bimolecular), Scheme 10.34. This alternative mechanism occurs when the intermediate radical anion can be intercepted by the thiolate (Equation 10.23) prior to the dissociation required in the SrnI mechanism (Equation 10.17 in Scheme 10.29). It becomes possible when either... 

Competition between electron transfer and radical abstraction, along with the greater ability of water and methanol to solvate the ions help complete the rationalization. Methanesulfmic acid 258 is thought to participate in further redox reactions and is not isolated. 

Transient Techniques In transient electrochemical measurements involving a solution phase redox couple, one seeks to create a competition between the reaction of interest, that is, electron transfer at the electrode surface or coupled homogeneous steps, and diffusion of the species to and from the electrode surface [139]. 

Carbonate formation from an alcohol and carbon monoxide is known to take place in the presence of a number of metal and non-metal redox couples, e.g. palladium, platinum, cobalt, copper, nickel, rhodium, mercury, selenium, and bromine. Most of these are also active in the oxidation of CO to CO2 in water, due to the similarity of the reaction pathways for CO2 and carbonate formation, which involve intermediate hydroxy carbonyl and alkoxy carbonyl species, respectively. Competition between carbon dioxide and carbonate formation is a major factor that has to be considered when catalyst re-oxidation is carried out by oxygen, as in most technical developments, since in this case water is co-produced in the reaction system. 

The charge carriers may reduce or oxidize the semiconductor itself leading to decomposition. This poses a serious problem for practical photoelectrochemical devices. Absolute thermodynamic stability can be achieved if the redox potential of oxidative decomposition reaction lies below the valence band and the redox potential of the reductive decomposition reaction lies above the conduction band. In most cases, usually one or both redox potentials lie within the bandgap. Then the stability depends on the competition between thermodynamically possible reactions. When the redox potentials of electrode decomposition reactions are thermodynamically more favored than electrolyte redox reactions, the result is electrode instability, for example, ZnO, Cu20, and CdS in an aqueous electrolyte. 

Although no good quantitative correlation between redox potentials of flavonoids and their prooxidant activities still was not documented, a relationship between the prooxidant toxicity of flavonoids to HL-60 cells and redox potentials apparently takes place [176]. However, there is a simple characteristic of possible prooxidant activity of flavonoids, which increases with an increase in reactive hydroxyl groups in the B ring. From this point of view, the prooxidant activity of flavonoids should increase in the range kaempferol < quercetin < myricetin (Figure 29.7). Thus, for many flavonoids the ratio of their antioxidant and prooxidant activities must depend on the competition between Reactions (14) and (15) and Reaction (17). 

Case 1 appears to accurately predict the observed dependence on persulfate concentration. Furthermore, as [Q]+otal approaches [KX], the polymerization rate tends to become independent of quat salt concentration, thus qualitatively explaining the relative insensitivity to [Aliquat 336]. The major problem lies in explaining the observed dependency on [MMA]. There are a number of circumstances in free radical polymerizations under which the order in monomer concentration becomes >1 (18). This may occur, for example, if the rate of initiation is dependent upon monomer concentration. A particular case of this type occurs when the initiator efficiency varies directly with [M], leading to Rp a [M]. Such a situation may exist under our polymerization conditions. In earlier studies on the decomposition of aqueous solutions of potassium persulfate in the presence of 18-crown-6 we showed (19) that the crown entered into redox reactions with persulfate (Scheme 3). Crematy (16) has postulated similar reactions with quat salts. Competition between MMA and the quat salt thus could influence the initiation rate. In addition, increases in solution polarity with increasing [MMA] are expected to exert some, although perhaps minor, effect on Rp. Further studies are obviously necessary to fully understand these polymerization systems. 

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