Reduction of oxygen

The Huron-Dow Process. The Huron-Dow (H-D) process is a refinement of the cathodic reduction of oxygen in an alkaline electrolyte yielding low strength hydrogen peroxide directiy. Earlier attempts reHed on neutralizing the excess caustic or forming insoluble metal peroxides (92). The two reactions involved are... 

Ghromium(II) Compounds. The Cr(II) salts of nonoxidizing mineral acids are prepared by the dissolution of pure electrolytic chromium metal ia a deoxygenated solution of the acid. It is also possible to prepare the simple hydrated salts by reduction of oxygen-free, aqueous Cr(III) solutions using Zn or Zn amalgam, or electrolyticaHy (2,7,12). These methods yield a solution of the blue Cr(H2 0)g cation. The isolated salts are hydrates that are isomorphous with and compounds. Examples are chromous sulfate heptahydrate [7789-05-17, CrSO 7H20, chromous chloride hexahydrate... 

Reduction of oxygen is one of the predominant cathodic reactions contributing to corrosion. Awareness of the importance of the role of oxygen was developed in the 1920s (19). In classical drop experiments, the corrosion of iron or steel by drops of electrolytes was shown to depend on electrochemical action between the central relatively unaerated area, which becomes anodic and suffers attack, and the peripheral aerated portion, which becomes cathodic and remains unattacked. In 1945 the linear relationship between rate of iron corrosion and oxygen pressure from 0—2.5 MPa (0—25 atm) was shown (20). 

Alternatives to Arresters Alternatives to the use of flame arresters include fast-ac ting isolation valves, vapor suppression systems, velocity-type devices in which gas velocity is designed to exceed flashback velocity, and control of the flammable mixture (NFPA 69 standard, Explosion Prevention Systems ). The latter alternative frequently involves reduction of oxygen concentration to less than the limiting oxygen concentration (LOC) of the gas stream. 

Now the formation and solution of Fe is analogous to the formation and diffusion of M" in an oxide film under dry oxidation and the formation of OH is closely similar to the reduction of oxygen on the surface of an oxide film. However, the much faster attack found in wet corrosion is due to the following ... 

The reduction of oxygen in Complex IV is accompanied by transport of protons across the inner mitochondrial membrane. Transfer of four electrons through this complex drives the transport of approximately four protons. The mechanism of proton transport is unknown but is thought to involve the steps from state P to state O (Figure 21.20). Four protons are taken up on the matrix side for every two protons transported to the cytoplasm (see Figure 21.17). 

When dezincification occurs in service the brass dissolves anodically and this reaction is electrochemically balanced by the reduction of dissolved oxygen present in the water at the surface of the brass. Both the copper and zinc constituents of the brass dissolve, but the copper is not stable in solution at the potential of dezincifying brass and is rapidly reduced back to metallic copper. Once the attack becomes established, therefore, two cathodic sites exist —the first at the surface of the metal, at which dissolved oxygen is reduced, and a second situated close to the advancing front of the anodic attack where the copper ions produced during the anodic reaction are reduced to form the porous mass of copper which is characteristic of dezincification. The second cathodic reaction can only be sufficient to balance electrochemically the anodic dissolution of the copper of the brass, and without the support of the reduction of oxygen on the outer face (which balances dissolution of the zinc) the attack cannot continue. 

In sea-water, the increase of pH adjacent to the surface of cathodes brought about by the reduction of oxygen leads to the deposition of films of calcium carbonate and magnesium hydroxide . Such film deposition often results in a gradual decrease in the rate of galvanic corrosion of the more negative members of couples immersed in sea-water. 

These data have been obtained by anodic polarisation work and might therefore be more relevant when cathodic reduction of oxygen takes place that can increase the corrosion potential to high positive values. 

Multiphase gold or palladium-based alloys never show dissolution of Au or Pd but often exhibit progressive surface ennoblement due to selective dissolution of copper or silver from the outer 2-3 atomic layers Heat treatment often decomposes multicomponent alloys into a Pd-Cu rich compound and an Ag-rich matrix with corrosion of the latter phase in deaerated artificial saliva and S -containing media . Au-Cu-rich lamellae have similarly been observed, again with preferential attack on Ag-rich phases or matrix. These effects presumably arise from the ability of the noble alloy phases to catalyse the cathodic reduction of oxygen . 

The explicit aims of boiler and feed-water treatment are to minimise corrosion, deposit formation, and carryover of boiler water solutes in steam. Corrosion control is sought primarily by adjustment of the pH and dissolved oxygen concentrations. Thus, the cathodic half-cell reactions of the two common corrosion processes are hindered. The pH is brought to a compromise value, usually just above 9 (at 25°C), so that the tendency for metal dissolution is at a practical minimum for both steel and copper alloys. Similarly, by the removal of dissolved oxygen, by a combination of mechanical and chemical means, the scope for the reduction of oxygen to hydroxyl is severely constrained. 

Table 21.16 Exchange current densities for several noble metals and a platinum-rhodium alloy in the reduction of oxygen from perchloric acid solution ...

Any chemical (such as zinc hydroxide) that suppresses the reduction of oxygen to hydroxyl ion. A cathodic inhibitor suppresses that part of the electrolytic corrosion process at the cathodic sites on a metal surface. 

The electrochemical reduction of oxygen usually proceeds via two well-separated two-electron steps. The first step corresponds to the formation of hydrogen peroxide ... 

What is the standard potential for the reduction of oxygen to water in (a) an acidic solution (b) a basic solution ... 

The first reported electroorganic synthesis of a sizeable amount of material at a modified electrode, in 1982, was the reduction of 1,2-dihaloalkanes at p-nitrostyrene coated platinum electrodes to give alkenes. The preparation of stilbene was conducted on a 20 pmol scale with reported turnover numbers approaching 1 x 10. The idea of mediated electrochemistry has more frequently been pursued for inorganic electrode reactions, notably the reduction of oxygen which is of eminent importance for fuel cell cathodes Almost 20 contributions on oxygen reduction at modified... 

The elemental reaction used to describe a redox reaction is the half reaction, usually written as a reduction, as in the following case for the reduction of oxygen atoms in O2 (oxidation state 0) to H2O (oxidation state —2). The half-cell potential, E°, is given in volts after the reaction ... 

Reduced nicotinamide-adenine dinucleotide (NADH) plays a vital role in the reduction of oxygen in the respiratory chain [139]. The biological activity of NADH and oxidized nicotinamideadenine dinucleotide (NAD ) is based on the ability of the nicotinamide group to undergo reversible oxidation-reduction reactions, where a hydride equivalent transfers between a pyridine nucleus in the coenzymes and a substrate (Scheme 29a). The prototype of the reaction is formulated by a simple process where a hydride equivalent transfers from an allylic position to an unsaturated bond (Scheme 29b). No bonds form between the n bonds where electrons delocalize or where the frontier orbitals localize. The simplified formula can be compared with the ene reaction of propene (Scheme 29c), where a bond forms between the n bonds. 

From biochemical synthesis to bioenergetics, redox reactions are fundamental parts of the life process. Molecular oxygen is the oxidizing agent in most of these redox reactions. It has been estimated that the reduction of oxygen... 

Xanthate compounds are widely used as collectors in flotation. Their function is to render the mineral surface hydrophobic and thus facilitate bubble attachment. The adsorption of xanthates onto sulfide minerals occurs via an electrochemical mechanism involving the reduction of oxygen and the anodic adsorption of xanthate. 

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