OH-radical

A very different nucleation scheme by Grieser and co-workers employs ultrasonic irradiation of salt solutions to create H- and OH- radicals in solution [73]. These radicals proceed to nucleate growth of quantum-sized (Q-state) particles of cadmium sqlfide. Similar initiation has been used for polymer latices [74]. 

Sinks, chemical species, or method OH, reaction with OH radical S, sedimentation P, precipitation scavenging NO, reaction with NO radical uv, photolysis by ultraviolet radiation Sr, destmction at surfaces O, adsorption or destmction at oceanic surface. 

The more efficient system of genera ting OH radicals in the homogeneous phase is H2O2/uv, where the quantum yield, < >254 0.50 (20,21). There... 

A debate centers on the mechanistic details of heterogeneous photocatalysis. The goal is to improve the photocatalytic activity of Ti02, and understand the role and importance of mineralisation by (/) free versus surface bound oxidising radicals, OH, and (2) by surface OH radicals versus direct hole oxidation. 

Rapid e / h recombination, the reverse of equation 3, necessitates that D andM be pre-adsorbed prior to light excitation of the Ti02 photocatalyst. In the case of a hydrated and hydroxylated Ti02 anatase surface, hole trapping by interfacial electron transfer occurs via equation 6 to give surface-bound OH radicals (43,44). The necessity for pre-adsorbed D andM for efficient charge carrier trapping calls attention to the importance of adsorption—desorption equihbria in... 

Product identification does not distinguish OH versus hole oxidation, because the products are identical. For example, the products identified in the photo oxidation of phenol (qv) (Fig. 7) may originate either by OH radical attack of the phenol ring, or by direct hole oxidation to give the cation radical which subsequendy undergoes hydration in solvent water. 

Pulse radiolysis results (74) have led other workers to conclude that adsorbed OH radicals (surface trapped holes) are the principal oxidants, whereas free hydroxyl radicals probably play a minor role, if any. Because the OH radical reacts with HO2 at a diffusion controlled rate, the reverse reaction, that is desorption of OH to the solution, seems highly unlikely. The surface trapped hole, as defined by equation 18, accounts for most of the observations which had previously led to the suggestion of OH radical oxidation. The formation of H2O2 and the observations of hydroxylated intermediate products could all occur via... 

Radiolysis creates oxidants such as the OH radical and reductants such as e (aq), which oxidize or reduce plutonium ions. Self-radiolysis of Pu... 

Atmosphere—Water Interaction. Although water is a very minor component of the atmosphere, less than 10 vol % of the atmosphere consisting of water, many important reactions occur ki the water droplets of cloud, fog, and rain. The atmosphere is an oxic environment ki its water phase, gigantic quantities of reductants, such as organic substances, Fe(II), SO2, CH SCH (dimethyl sulfide), and nitrogen oxides, are oxidized by oxidants such as oxygen, OH radicals, H2O2, and Fe(III). 

Combustion chemistry in diffusion flames is not as simple as is assumed in most theoretical models. Evidence obtained by adsorption and emission spectroscopy (37) and by sampling (38) shows that hydrocarbon fuels undergo appreciable pyrolysis in the fuel jet before oxidation occurs. Eurther evidence for the existence of pyrolysis is provided by sampling of diffusion flames (39). In general, the preflame pyrolysis reactions may not be very important in terms of the gross features of the flame, particularly flame height, but they may account for the formation of carbon while the presence of OH radicals may provide a path for NO formation, particularly on the oxidant side of the flame (39). 

The effect of increasing pressure is to move the average hydrocarbon content towards the heavier species, but increasing temperature seems to favour the production of lighter species. The final proportions are also determined by the state of the catalyst, and the physical anangement of tire reactor. The formation of the oxygenated compounds could also involve reactions between the H2O content of tire gas in the form of adsorbed OH radicals and hydrocarbon radicals since the production of these molecules is also well beyond the thermodynamic expectation. 

Aldehydes undergo two primary reactions photolysis and reaction with OH radicals. These reactions lead to formation of CO, H, and R radicals. 

Under the influence of thermal motion and on endothermic electron transition from the OH ion to the Me ion in alkali metal hydroxides the formation of the Me. and OH. radicals takes place. As a result, free va-... 

The OH radical formed during the decomposition of hydroperoxy groups is very reactive and can either terminate a reaction (39) or may attack the weak bond of the backbone polymer resulting in the formation of a new radical (40). 

The OH radicals may initiate grafting via abstraction of the hydrogen atom from cellulose or may also initiate homopolymerization. 

Freeman, A. J., J. Chem. Phys. 28, 230, "Configuration interaction study of the electronic structure of the OH radical by the atomic and molecular methods."... 

This is one of the most universal techniques for obtaining hydrogels from water-soluble polymers. Crosslinked PEO, PVA, PAAm, PAAc and its salts, as well as some polymer blends were obtained by this method. Although all polymers mentioned above have their own specific features, in most cases the gelation doses do not exceed 1-2 Mrad, i.e. they are substantially lower than for the same polymer in bulk. This is due to the fact that in aqueous media crosslinking occurs indirectly, namely because of the OH radical formation and their attack on the macromolecules. There exists a developed theory of these processes [73],... 

In the mass spectrum of 10-propyl-3-amino-7,9-dichlorophenothiazine-5-sulfone (67) the molecular ion is quite intense, but the base peak is formed by the loss of Et from the propyl side-chain16. The other primary and secondary fragmentations are summarized in equation (31). The loss of two OH radicals (H2Oz) can occur favorably from the extra configuration of 67 (cf. Section II.D). 

The pKa value of the equilibrium was found to be equal to 10.2. Meissner and coworkers36 studied also the reaction of OH radicals with DMSO, however, the product of this reaction has no optical absorption in the range 270-800 nm and they measured only the rate of this reaction by a competition method and obtained k = 4.2 x 109m-1s-1. 

The reaction of OH radicals with dimethyl sulfoxide in aqueous solution was studied already in 1964 by Norman and coworkers37 38. They used the system T1m-H202 to produce OH radicals and using ESR/rapid mixing techniques they were able to demonstrate elimination of a methyl radical during the OH induced oxidation. Further studies showed the formation of sulfmic radicals in this reaction either directly or by spin trapping experiments39-44. 

Gilbert and co workers42 found the same behavior of OH radicals with other aliphatic sulfoxides. In many of these cases the OH adduct is decomposed to the sulfonyl radical. 

G(CH3S02 ) is the yield of CH3S02 radicals, AOH- and AH+ are the decrease and increase of the conductivity in basic and acidic solutions respectively, l is the specific conductivity and l(Haq+) and i(OH ) are known to be 315 and 178 fl-1 cm2, respectively. For dimethyl sulfoxide G(RS02 ) was found to be 5.46 comparing this to G(OH) = 6.0 for N20 -saturated aqueous solution leads to the conclusion that 91% of the OH radicals were added to the sulfoxide bond. There is no proof for the fate of the other 9% it is probable that they abstract hydrogen atoms from the methyl groups. 

In the case of diaryl sulfoxides the formation of both the aryl radical and the hydroxycyclohexadienyl radical was observed optically. Veltwisch and coworkers45 studied also the reaction of OH radicals from radiolysis of aqueous solutions of mixed (alkyl phenyl) sulfoxides (PhSOR). They found the formation of both alkylsulfinic and phenylsulfinic acids. 

The total yield of sulfinic acid from the mixed sulfoxides is higher than that from diphenyl sulfoxides (31%) but lower than that from the corresponding dialkyl sulfoxides, and accounts for about 45% of the OH radicals (Table 1). 

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