Oxidation external

Rapp (1961) has confirmed this equation in a study of the oxidation in air of Ag-In alloys at 550°C. The reaction proceeds with tire internal formation of In203 particles over a range of indium concenuations, but at a critical mole fraction of indium in the alloy, external oxidation occurs with the growdr of a layer of In203 covering the alloy. The n airsitioir from internal to external oxidation was found by Rapp to occur at the mole fraction of indium cone-sponding to... 

Maak (1961) has obtained the equation governing the oxidation rate of a metal to form both an external oxide and an internally oxidized dilute solute, as for example in Cu-Be alloys, coiTesponding to tire equation given earlier... 

Another factor that determines the long-term stability of the protective oxide layer is its ability to prevent sulphur penetration which would lead to the eventual formation of chromium sulphide beneath the external oxide layer. With most commercial nickel chromium alloys internal sulphidation... 

For many decades, the standard technique for measuring carotenoids has been high-pressure liquid chromatography (HPLC). This time consuming and expensive chemical method works well for the measurement of carotenoids in serum, but it is difficult to perform in human tissue since it requires biopsies of relatively large tissue volumes. Additionally, serum antioxidant measurements are more indicative of short-term dietary intakes of antioxidants rather than steady-state accumulations in body tissues exposed to external oxidative stress factors such as smoking and UV-light exposure. 

Preliminary observations of the reactions of Fe(II) and Fe(III) in an ultrasonic field revealed conversion of Fe(II) to Fe(III) and vice-versa, even without any external oxidant/reductant, which were subsequently confirmed experimentally and sequentially through the following four qualitative conversions. The details are available in the literature [35]. 

When the results for oxide growth and anion incorporation172,160 are compared with the kinetics of space charge accumulation in barrier and porous alumina films [see Section IV(1)], it can be concluded that anion incorporation modifies the electrostatics of the external oxide interface, thus influencing oxide dissolution and pore formation.172... 

A quite different set of oxidations/reductions, but not fast, were the equilibria which governed the change of the environment, that is external oxidation/reduction potentials. They involve elements such as S, Se and metals but not all C or N couples. Their slow change in value was due to the slow release of oxygen by... 

Cu(0) species. Alternatively, the Cu(n) species may first undergo oxidation by an external oxidant (or internal redox process) to a Cu(m) intermediate, and then undergo reductive elimination to provide the product and a Cu(i) species. Re-oxidation to Cu(n) would then, in theory, complete the catalytic cycle, but in practice, most reactions of this type have been performed with stoichiometric amounts of the copper reagent. 

The above considered reactions model the reductive half cycle of GO where a primary alcohol is oxidized to an aldehyde with concomitant reduction of a (phe-noxyl)copper(II) complex to the reduced (phenol)copper(I) species. In the first two cases, reoxidation of the reduced catalyst was achieved by an external oxidant such as tris(4-bromophenyl)aminium or an electrode but not dioxygen. 

Several articles have reviewed the ongoing work in the photocatalytic degradation of pollutants that involve oxidation or reduction processes (depending on the experimental conditions) [16,18,187,265-273], The addition of external oxidants such as ozone or hydrogen peroxide during the photocatalytic process can improve the degradation of the organic material when they are added in suitable doses [274-275],... 

Internal ligand-to-metal electron transfer may be initiated by the action of an external oxidant on the ligand. This phenomenon of induced electron transfer has received rather scant attention. In the complex 3 shown in (5.82) the one-electron oxidizing center of the Co III) and the two-electron reducing ligand 4-pyridylcarbinol can coexist because of their redox incom-patability . The complex is therefore relatively stable. This situation is upset when a strong one-electron oxidant such as Ce(IV) or Co(III) is added to a solution of the Co(III) complex. The oxidant attacks the carbinol function to generate an intermediate or intermediates the intermediate in this case is oxidized internally by the Co(III) center for example. 

Thus, one equivalent of an external oxidant and one of the Co(III) complex are consumed in oxidizing one equivalent of the alcohol to the aldehyde. Two-equivalent oxidants, Clj, Cr(VI), give no such radical intermediate, and therefore no Co(II), and only the Co III) complex. 

High surface area hexagonal mesoporous Ge also can be prepared with oxidative self-polymerization chemistry of [Ge9] clusters [48]. This synthetic route does not require external oxidants such as ferrocenium or linking Ge(lV) centers and occurs in the presence of cationic surfactant (iV-eicosane-A ,A -dimethyl-A -(2-hydroxyethyl)ammonium bromide, EDMHEABr) as stmcture-directing agent. The polymerization reaction proceeds through the slow oxidative coupling of (Ge9)-clusters and seems to be accompanied by a two-electron process (2). The electron acceptors in this case appear to be the surfactant molecules or the solvent. 

The discussed mechanisms represent a form of intramolecular catalysis of the oxidation of the FeII(CN)5 or Run(edta) centers by the Ruii(NH3)5 moiety. The first two moieties react sluggisly and, on the other hand, the electron in RuII(NH3)5 is readily accessible to the external oxidant and is given up. The rapid electronic isomerization processes aid in the consumption of the full oxidation process. This is not truly catalytic because the catalyst is the reactant itself, which, of course, is consumed in the reaction. A better description involves a net oxidation of the FeII(CN)5 or Run(edta) sites through activation by the facile intramolecular electron transfer between the metal centers. The mechanism is described in Fig. 23, bearing some resemblance to the classical chemical mechanism for inner sphere electron... 

Pyruvate formate-lyase reaction. Anaerobic cleavage of pyruvate to acetyl-CoA and formate (Eq. 15-37) is essential to the energy economy of many cells, including those of E. coli. No external oxidant is needed, and the reaction does not require lipoic acid. 

---