Kinetic oxidation

The lubricant oxidation mechanism is free-radical in nature and the additives act on the kinetic oxidation chain by capturing the reactive species either by decomposition of the peroxides, or by deactivation of the metal. 

Organic sulfur compounds such as sulfurized spermaceti oil, terpene sulfides, and aromatic disulfides have been used. Encumbered phenols such as di-tertiary-butylphenols and amines of the phenyl-alphanaphthylamine type are effective stopping the kinetic oxidation chain by creating stable radicals. 

ELECTRODE KINETICS OXIDATION REFERENCE REACTION CATALYTIC PROFICIENCY REGIOSELECTIVITY... 

Hoigne, J. 1990. Formulation and calibration of environmental reaction kinetics Oxidations by aqueous photooxidants as an example. In W. Stumm, ed., Aquatic Chemical Kinetics Reaction Rates of Processes in Natural Waters, pp. 43-70. Wiley-Interscience, New York. 

The application of Eq. 2.35 to chemical reactions in natural waters is described by J. Hoigne, Formulation and calibration of environmental reaction kinetics oxidations by aqueous photo oxidants as an example, pp. 43-70 in W. Stumm, op. cit.6... 

Example 9. Kinetic oxidation of dissolved ferrous iron with oxygen Example 10.—Aragonite-strontianite solid solution Example 11.-Transport and cation exchange Example 12—Advective and diffusive flux of heat and solutes Example 13.-ID transport in a dual porosity column with cation exchange Example 14.-Advective transport, cation exchange, surface complexation, and mineral equilibria... 

Hoignd, J. (1990) Formulation and Calibration of Environmental Reaction Kinetics Oxidations by Aqueous Photooxidants as an Example. In Aquatic Chemical Kinetics, W. Stumm, Ed., Wiley-Interscience, New York. 

FORMULATION AND CALIBRATION OF ENVIRONMENTAL REACTION KINETICS OXIDATIONS BY AQUEOUS PHOTOOXIDANTS AS AN EXAMPLE... 

Swinney, D.C., DE. Ryan, P.E. Thomas, and W. Levin (1988). Evidence for concerted kinetic oxidation of progesterone by purified rat hepatic cytochrome P-450g. Biochemistry 27, 5461-5470. 

Kinetics. Oxidation reactions, such as those enumerated in Sec. I, are accompanied by the formation of water, carbon oxides, or both, or by the introduction of elemental oxygen in the organic molecule, or by the step-down of an oxidizing compound from an unstable state of high oxidation to a more stable state of lower oxidation. These reactions are exothermic and accompanied by a free-energy decrease. Equilibrium, therefore, is favorable, and in practically all cases no means need be provided to force the completion of the reaction. Indeed, in the majority of cases, steps must be taken to limit the extent of the reaction and prevent complete loss of product through continued oxidation. 

Keywords HNO NO Nitroxyl Azanone Nitroxyl anion Nitrosyl Porphyrin Heme Iron Manganese Ruthenium Cobalt Reductive nitrosylation Kinetics Oxidation Protein Myoglobin NOS. 

Keywords Bond strengths Kinetics Oxidative addition Reductive elimination Rhodium Thermodynamics... 

Since the radicals RO and ROj, which are carriers of the kinetic oxidation chains, are formed in the catalytic decomposition of hydroperoxides, the appearance of phenoxyl radicals in such model systems of oxidation [14] gives evidence of stripping of the hydroxyl hydrogen of phenol by the active radicals, as the primary elementary event of inhibition, the reactivity of the OH-bond in the phenol being one of the most important characteristics of the effectiveness of the phenol as an inhibitor. 

Characterizing the mechanism of the action of amines, the overwhelming majority of tiie authors believe that their basic role reduces to the termination of kinetic oxidation chains on account of reaction (3). Actually, stable radicals (CjH5)2NO have been detected by the method of electron paramagnetic resonance as a result of the interaction with peroxide radicals, formed in the liquid-phase oxidation of a hydrocarbon inhibited with diphenylamine [30]. The interaction of certain secondary amines (Ar2NH) with peroxide radicals, prepared by oxidative radiolysis. 

The oxidation of rubbers is substantially accelerated by salts of metals of variable valence (iron, copper, manganese, cobalt, etc.). Figure 169 presents the kinetic oxidation curves illustrating ttie premise stated [23]. Homogeneous catalysis of the chain reaction of rubber oxidation occurs as a result of the reduction of tiie activation energy of initiation, as well as the decomposition of stable peroxide. 

On the basis of these data the program which is aimed at selection of the major oxidation factor for material and allows plotting kinetic oxidation curve for CPM in different conditions of aging has been developed. 

This program allows to obtain graphic plot of kinetic oxidation curve -AP = f(t) under exposure to the voltage and temperature in the range 0 to 60 V and 60 to 160 °C after entering two oxidation factors (Temperature and voltage) for CPM based on SKI-3 and PPMI. 

Recently, a cascade process for the simultaneous preparation of two enantiopure secondary alcohols by the same ADH was investigated [12]. In this work, a kinetic oxidative resolution of different secondary alcohols was coupled with the irreversible asymmetric reduction of selected prochiral activated ketones, that is, a-chloro ketones (Scheme 11.5a). The proposed strategy, named PIKAT (parallel intercoimected kinetic asymmetric transformations), represents an example of redox neutral (or self-sufficient) cascade, with no additional reducing or oxidizing reagents being required. Moreover, the reaction was catalyzed by a single enzyme in the presence of catalytic amounts of the cofactor. As the outcome of the cascade process is a mixture of two different enantioenriched products, substrates were properly selected on the basis of different physical properties. 

Harper, M.R., Van Geem, K.M., Pyl, S.P., Marin, G.B., Green, W.H. Comprehensive reaction mechanism for -butanol p5rrolysis and combustion. Combust. Flame 158,16-41 (2011) Herbinet, O., Pitz, W.J., Westbrook, C.K. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate. Combust. Flame 154, 507—528 (2008)... 

Herbinet O, Pitz WJ, Westbrook CK. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate. Combust Flame. August 2008 154 507-528. 

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