Redox systems catalyst

Hydrogen peroxide may react directiy or after it has first ionized or dissociated into free radicals. Often, the reaction mechanism is extremely complex and may involve catalysis or be dependent on the environment. Enhancement of the relatively mild oxidizing action of hydrogen peroxide is accompHshed in the presence of certain metal catalysts (4). The redox system Fe(II)—Fe(III) is the most widely used catalyst, which, in combination with hydrogen peroxide, is known as Fenton s reagent (5). 

This catalyst system is temperature-sensitive and does not function effectively at temperatures below 10°C but at temperatures over 35°C the generation of free radicals can be too prolific, giving rise to incomplete cross-linking formation. Redox systems are preferred for fabrication at temperatures ranging from 20—30°C (Fig. 5). 

The action of redox metal promoters with MEKP appears to be highly specific. Cobalt salts appear to be a unique component of commercial redox systems, although vanadium appears to provide similar activity with MEKP. Cobalt activity can be supplemented by potassium and 2inc naphthenates in systems requiring low cured resin color lithium and lead naphthenates also act in a similar role. Quaternary ammonium salts (14) and tertiary amines accelerate the reaction rate of redox catalyst systems. The tertiary amines form beneficial complexes with the cobalt promoters, faciUtating the transition to the lower oxidation state. Copper naphthenate exerts a unique influence over cure rate in redox systems and is used widely to delay cure and reduce exotherm development during the cross-linking reaction. 

Emulsion Polymerization. In this method, polymerization is initiated by a water-soluble catalyst, eg, a persulfate or a redox system, within the micelles formed by an emulsifying agent (11). The choice of the emulsifier is important because acrylates are readily hydrolyzed under basic conditions (11). As a consequence, the commonly used salts of fatty acids (soaps) are preferably substituted by salts of long-chain sulfonic acids, since they operate well under neutral and acid conditions (12). After polymerization is complete the excess monomer is steam-stripped, and the polymer is coagulated with a salt solution the cmmbs are washed, dried, and finally baled. 

The next step is the insertion of a lattice oxygen into the allylic species. This creates oxide-deficient sites on the catalyst surface accompanied hy a reduction of the metal. The reduced catalyst is then reoxidized hy adsorbing molecular oxygen, which migrates to fill the oxide-deficient sites. Thus, the catalyst serves as a redox system. ... 

The pathway of the metabolic process converting the original nutrients, which are of rather complex composition, to the simple end products of COj and HjO is long and complicated and consists of a large number of intermediate steps. Many of them are associated with electron and proton (or hydrogen-atom) transfer from the reduced species of one redox system to the oxidized species of another redox system. These steps as a rule occur, not homogeneously (in the cytoplasm or intercellular solution) but at the surfaces of special protein molecules, the enzymes, which are built into the intracellular membranes. Enzymes function as specific catalysts for given steps. 

A combination of cat. Ybt and A1 is effective for the photo-induced catalytic hydrogenative debromination of alkyl bromide (Scheme 28) [69]. The ytterbium catalyst forms a reversible redox cycle in the presence of Al. In both vanadium- and ytterbium-catalyzed reactions, the multi-component redox systems are achieved by an appropriate combination of a catalyst and a co-reductant as described in the pinacol coupling, which is mostly dependent on their redox potentials. 

Apart from the above mentioned redox type reactions, we like to consider (in connection with work to be published by us elsewhere) another type of relaxations, due to the possible reorganisations of sorption intermediates on the catalyst surface, as suggested by some investigations in our laboratory. This structuring on the catalyst surface is equivalent to a change in the entropy of the system catalyst surface / adsorbed intermediates and seems to be responsible e.g. for the selectivity change under transient conditions in the oxidation of hydrocarbons. Actually this structural organization of the surface intermediates is also a rate process which can be observed under transient conditions. 

A suspension process using redox initiation in a water medium was developed. The redox system is a combination of persulfatesulfite. Often ferrous or cupric salts were added as a catalyst for the redox reaction. Polymerizations were run in water at low temperature (20-25°C) and low pressure (65-85 psi). Monomer to monomer-plus-water weight ratios of 0.20 to 0.25 were used. Good agitation was required to keep an adequate monomer concentration in the aqueous phase. Yields ofup to 100% were obtained with polymer inherent viscosities of0.4 to 1.5 dl/g in C6F5C1. Reactions were run on both a 1-gal and a 100-gal scale. 

Nippon Steel has developed an interesting liquid-phase process for producing 2-methylpyridine from ethylene and ammonia (74MI1 81MI2, 81MI3). The catalyst is reminiscent of the well-known Wacker process, viz. Pd /Cu redox system [Eq.(5)]. 

The remarkable variety of redox systems which can already be derived from the Weitz type underline the wide scope of the general structure A and C as a basic principle for two step redox systems. The empirical material as well as general rules regarding structural influences on potentials and Ksem have been developed to such an extent, that redox systems can be taylored to meet special purposes. Catalysts for electron transfer, light positive systems and compounds of high electrical conductivity are some fields in which these redox systems could occupy key positions. Some applications have already been discussed in a previous review of wider scope h)... 

In this paper selectivity in partial oxidation reactions is related to the manner in which hydrocarbon intermediates (R) are bound to surface metal centers on oxides. When the bonding is through oxygen atoms (M-O-R) selective oxidation products are favored, and when the bonding is directly between metal and hydrocarbon (M-R), total oxidation is preferred. Results are presented for two redox systems ethane oxidation on supported vanadium oxide and propylene oxidation on supported molybdenum oxide. The catalysts and adsorbates are stuped by laser Raman spectroscopy, reaction kinetics, and temperature-programmed reaction. Thermochemical calculations confirm that the M-R intermediates are more stable than the M-O-R intermediates. The longer surface residence time of the M-R complexes, coupled to their lack of ready decomposition pathways, is responsible for their total oxidation. 

Temperature Programmed Reaction. Examination of another redox system, propylene oxidation on M0O3, provides further insight. It is well accepted that propylene oxidation on molybdenum-based catalysts proceeds through formation of allylic intermediates. From isotopic studies it has been demonstrated that formation of the allylic intermediate is rate-determining (H/D effect), and that a symmetric allylic species is formed ( C labelling). 

In addition, electrode reactions are frequently characterized by an irreversible, i.e., slow, electron transfer. Therefore, overpotentials have to be applied in preparative-scale electrolyses to a smaller or larger extent. This means not only a higher energy consumption but also a loss in selectivity as other functions within the molecule can already be attacked. In the case of indirect electrolyses, no overpotentials are encountered as long as reversible redox systems are used as mediators. It is very exciting that not only overpotentials can be eliminated but frequently redox catalysts can be applied with potentials which are 600 mV or in some cases even up to 1 Volt lower than the electrode potentials of the substrates. These so-called redox reactions opposite to the standard potential gradient can take place in two different ways. In the first place, a thermodynamically unfavorable electron-transfer equilibrium (Eq. (3)) may be followed by a fast and irreversible step (Eq. (4)) which will shift the electron-transfer equilibrium to the product side. In this case the reaction rate (Eq. (5)) is not only controlled by the equilibrium constant K, i.e., by the standard potential difference be-... 

Radical-forming catalysts, such as organic peroxides, hydrogen peiox-ide, aliphatic azo compounds of the type of azoisobutyric acid nitrile, and redox systems arc employed for telomenzation reactions. 

The most studied telogen is certainly CCl3Br initiated either by UV, peroxide or by redox systems. However, we have demonstrated that in this last case, the redox catalyst, especially ferric chloride, induces a disproportionation which leads to a mixture of new telogens as follows [230] ... 

The overwhelming majority of biochemical oxidation processes represent conjugated catalytic (enzymatic) reactions [8], Therefore, of great importance is the ability to distinguish catalyst and inducer, because any mistake would cause an incorrect interpretation of the chemical mechanisms of the reactions proceeding in the biological system. For instance, redox reaction catalysts are often taken for inducers. 

Many other chemical redox systems have been reported as initiators of macrocellulosic radicals and as catalysts for graft polymerization. One variation has been to modify cellulose chemically to increase its reactivity with selected oxidizing and reducing agents which on reaction yield macrocellulosic radicals (14, 15). 

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