Catalyst, oxidation-reduction

The equilibration in this case is believed to involve oxidation-reduction at the alcohol center, rather than reversal of the addition. (See Section 5.3.2 for a discussion of Ti(0-i-Pr)4 as an oxidation-reduction catalyst.)... 

The Incentive to modify our existing continuous-flow microunit to incorporate the square pulse capability was provided by our work on perovskite-type oxides as oxidation-reduction catalysts. In earlier work, it had been inferred that oxygen vacancies in the perovskite structure played an important role in catalytic activity (3). Pursuing this idea with perovskites of the type Lai-xSrxFeg 51 10 503, our experiments were hampered by hysteresis effects which we assumed to be due to the response of the catalyst s oxygen stoichiometry to the reaction conditions. 

Biological fuel cells have a long history in the literature,but in recent years, they have come to prominence as more conventional fuel cell technologies have approached mass-market acceptance. Driving the recent ascendance of biofuel cells are the aspects of biocatalysis that are unmatched by conventional low-temperature oxidation—reduction catalysts, namely, activity at near-room temperatures and neutral pH and, more importantly, selective catalytic activity. 

Another approach to wards photocatalysis is to use dy as a sensitizer instead of a semiconductor as in photosynthesis. It is not the aim of this book to cover all the aspects of the sensitized photochemical conversion system, but typical sensitized systems for photocatalytic reactions of water are described in Chapter 18 The concept of a photochemical conversion system using a sensitizer and water oxidation/reduction catalysts is mentioned in Chapter 19, accompanied by a discussion on the sensitization of semiconductors. 

A dietary factor that must be present in the diet of humans to prevent scurvy. It cures scurvy and increases resistance to infection. Ascorbic acid presumably acts as an oxidation-reduction catalyst in the cell. It is readily oxidized citrus juices should not be exposed to air for more than a few minutes before use. 

The interaction of oxygen with perovskites has been studied mainly because of the importance of these materials as oxidation-reduction catalysts. Data of oxygen adsorption on LaM03 (M = Cr, Mn, Fe, Co, Ni) oxides were reported by Kremenid et al. (136). The adsorption profile at 25°C showed two maxima for Mn and Co (Fig. 12) that coincide with the maxima observed by Iwamoto et al. (137) for the respective simple oxides... 

Voorhoeve, R.J.H., 1977, Perovskite-Related Oxides as Oxidation-Reduction Catalysts, in Advanced Materials in Catalysis, eds. I.I. Burton and R.L. Garten (Academic Press, New York) ch. 5. 

If one considers the hypothetical possibilities for an interaction or a shielding effect of tocopherols and other quinonoid compounds on reactive sulfhydryl sites in enzyme molecules, two modes of action come to mind. In its capacity to act as an oxidation-reduction catalyst, tocopherol, in the form of an oxidized derivative, could interact with sulfhydryl groups and shift the equilibrium from the sensitive, reduced sulfhydryl toward the... 

Iron, as mentioned above, is an electron dealer it facilitates electron transfer or oxidation reduction reactions. Several other elements also function as oxidation-reduction catalysts. They include copper, manganese, and molybdenum. The basic common character is that they can readily change their oxidation states. 

Reactivity (oxidation/reduction. catalysts) Inhibitors may be required... 

Manufacture. Hydroxypivalyl hydroxypivalate may be produced by the esterification of hydroxypivaUc acid with neopentyl glycol or by the intermolecular oxidation—reduction (Tishchenko reaction) of hydroxypivaldehyde using an aluminum alkoxide catalyst (100,101). 

CaniZZaro Reaction. Both 2- and 4-hydroxybenzaldehydes undergo this self-oxidation—reduction reaction, but much less readily than benzaldehyde the reaction requires metal catalysts such as nickel, cobalt, or silver to yield the corresponding hydroxybenzoic acids and hydroxybenzyl alcohols (47—48). 

Catalysts. Silver and silver compounds are widely used in research and industry as catalysts for oxidation, reduction, and polymerization reactions. Silver nitrate has been reported as a catalyst for the preparation of propylene oxide (qv) from propylene (qv) (58), and silver acetate has been reported as being a suitable catalyst for the production of ethylene oxide (qv) from ethylene (qv) (59). The solubiUty of silver perchlorate in organic solvents makes it a possible catalyst for polymerization reactions, such as the production of butyl acrylate polymers in dimethylformamide (60) or the polymerization of methacrylamide (61). Similarly, the solubiUty of silver tetrafiuoroborate in organic solvents has enhanced its use in the synthesis of 3-pyrrolines by the cyclization of aHenic amines (62). 

For more selective hydrogenations, supported 5—10 wt % palladium on activated carbon is preferred for reductions in which ring hydrogenation is not wanted. Mild conditions, a neutral solvent, and a stoichiometric amount of hydrogen are used to avoid ring hydrogenation. There are also appHcations for 35—40 wt % cobalt on kieselguhr, copper chromite (nonpromoted or promoted with barium), 5—10 wt % platinum on activated carbon, platinum (IV) oxide (Adams catalyst), and rhenium heptasulfide. Alcohol yields can sometimes be increased by the use of nonpolar (nonacidic) solvents and small amounts of bases, such as tertiary amines, which act as catalyst inhibitors. 

The sampling system consists of a condensate trap, flow-control system, and sample tank (Fig. 25-38). The analytical system consists of two major subsystems an oxidation system for the recovery and conditioning of the condensate-trap contents and an NMO analyzer. The NMO analyzer is a gas chromatograph with backflush capabihty for NMO analysis and is equipped with an oxidation catalyst, a reduction catalyst, and an FID. The system for the recovery and conditioning of the organics captured in the condensate trap consists of a heat source, an oxidation catalyst, a nondispersive infrared (NDIR) analyzer, and an intermediate collec tion vessel. 

On reduction with sodium amalgam the acid adds on two atoms of hydrogen the resulting amorphous aeid yields a crystalline dimethyl ester, C2iH2gOgN2, colourless prisms, m.p. 143-7° dec.). On hydrogenation in presenee of platinic oxide as catalyst 2 mols, of hydrogen are absorbed to form the acid, CjgHjgOgNj, colourless prisms, [ajo - -17-7° (HjO). On oxidation with chromic acid the Cjg acid is converted into Wieland s Ci7 acid and Hanssen s Cjg acid. ... 

The (ZZ-ephedrine was resolved into its components by the use of d-and Z-mandelic acids. In 1921 Neuberg and Hirsch showed that benz-aldehyde was reduced by yeast, fermenting in suerose or glueose solution to benzyl aleohol and a phenylpropanolone, which proved to be Z-Ph. CHOH. CO. CH3. This ean be simultaneously, or consecutively, eondensed with methylamine and then eonverted to Z-ephedrine by reduction, e.g., with aluminium amalgam in moist ether, or by hydrogen in presenee of platinic oxide as catalyst (Knoll, Hildebrant and Klavehn ). 

The modes of thermal decomposition of the halates and their complex oxidation-reduction chemistry reflect the interplay of both thermodynamic and kinetic factors. On the one hand, thermodynamically feasible reactions may be sluggish, whilst, on the other, traces of catalyst may radically alter the course of the reaction. In general, for a given cation, thermal stability decreases in the sequence iodate > chlorate > bromate, but the mode and ease of decomposition can be substantially modified. For example, alkali metal chlorates decompose by disproportionation when fused ... 

Metals are most active when they first deposit on the catalyst. With time, they lose their initial effectiveness through continuous oxidation-reduction cycles. On average, about one third of the nickel on the equilibrium catalyst will have the activity to promote dehydrogenation reactions. 

Palladium catalyst foe partial ee DUCTION OF ACETYLENES, 46, 89 Palladium on charcoal, catalyst for reductive methylation of ethyl p-mtrophenylacetate, 47, 69 in reduction of l butyl azidoacetate to glycine J-butyl ester 4B, 47 Palladium oxide as catalyst for reduction of sodium 2 nitrobenzene sulfinate, 47, S... 

The final authority on the durability of catalysts is performance in road vehicles. Such data have been rapidly accumulated by the various automobile manufacturers in recent months. This data takes into consideration all the accidents of everyday usage, serving to test how much abuse the catalyst can withstand and still perform its duty. Experience has shown that fresh oxidation and reduction catalysts by a large variety of formulations from many manufacturers would indeed perform their duty. Many oxidation catalysts perform well enough at 25,000 accumulated miles to satisfy the requirement of 0.41 g hydrocarbon/mile and 3.4 g CO/mile, but few would perform well enough at 50,000 miles without maintenance and adjustment of the engine. Many such vehicle endurance tests have to be terminated because of malfunction of the engine or the auxiliary equipment. 

Most of the NO reducing catalysts in pellet or monolithic form begin to lose their activity at 2000 miles and fail to be effective at 4000 miles. This lack of durability may well be connected to the usage of the NO bed for oxidation purposes during the cold start, which exposes the NOx catalysts to repeated oxidation-reduction cycles. Better catalyst durability can be anticipated in the single bed redox catalyst with a tightly controlled air-to-fuel ratio, since this oxidation-reduction cycle would not take place. Recent data indicates that the all metal catalysts of Questor and Gould may be able to last 25,000 miles. 

Transition metal catalysts arc characterized by their redox ehemistry (catalysts can be considered as one electron oxidants/reductants). They may also be categorized by their halogen affinity. While in the initial reports on ATRP (and in most subsequent work) copper266,267 or ruthenium complexes267 were used, a wide range of transition metal complexes have been used as catalysts in ATRP. 

Hydrogen cyanide reactions catalysts, 6,296 Hydrogen ligands, 2, 689-711 Hydrogenolysis platinum hydride complexes synthesis, 5, 359 Hydrogen peroxide catalytic oxidation, 6, 332, 334 hydrocarbon oxidation iron catalysts, 6, 379 reduction... 

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