Reactions with hydroxyl radical

FIGURE 3 12 Possible initial steps for ozone, atomic oxygen, nitrogen dioxide, and hydroxyl-radical reaction with aromatic hydrocarbons. 

Good, D.A., Hanson,]., Francisco, ].S., Li, Z., andjeong, G.-R. Kinetics and reaction mechanism of hydroxyl radical reaction with methyl formate, J. Phys. Chem. A, 103(50) 10893-10898, 1999. 

Photolysis, molecular ozone reactions, or hydroxyl radical reactions with the target compound can be quantified by ... 

Salomon J, Elad D (1973) Photochemical reactions of nucleic acid constituents. Peroxide-initiated reactions of purines with alcohols. J Org Chem 38 3420-3421 Salomon J, Elad D (1974) Ultraviolet and y-ray-induced reactions of nucleic acid constituents. Reactions of purines with amines. Photochem Photobiol 19 21-27 Samuni A, Neta P (1973) Hydroxyl radical reaction with phosphate esters and the mechanism of phosphate cleavage. J Phys Chem 77 2425-2429... 

Lindsey, M. E., and M. A. Tarr. 2000. Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter. Environmental Science and Technology 34 444. 

Lee, J.H., Tang, I.N. (1983) Absolute rate constants for the hydroxyl radical reactions with CH3SH and C2H5SH at room temperature. J. Chem. Phys. 78, 6646-6649. 

III. HYDROXYL RADICAL REACTIONS WITH ORGANIC COMPOUNDS... 

Figure 1 Generic mechanisms for hydroxyl radical reaction with organic compounds.

Figure 2 Proposed reaction pathways for hydroxyl radical reaction with benzene. (From Refs. 3, 4, 105, and 106.)...

Michael BD, Hart EJ. The rate constants of hydrated electron, hydrogen atom, and hydroxyl radical reactions with benzene, 1,3-cyclohexadiene, 1,4-cyclo-hexadiene, and cyclohexene. J Phys Chem 1970 74 2878-2884. 

Arif, M., Dellinger, B., Taylor P.H. (1997) Rate coefficients of hydroxyl radical reaction with dimethyl ether and methyl fert-butyl ether over an extended temperature range. J. Phys. Chem. A 101, 2436-2441. 

Mohan H, Mittal JP. (2002) Different channels of hydroxyl radical reaction with aryl sulfides Effect of the substituents./P/tyr Chem A 106 6574-6580. 

Ervens B., S. GUgorovski and H. Herrmann Temperature-dependent rate constants for hydroxyl radical reactions with organic corrrpormds in aqueous phase, Phys. Chem. Chem. Phys., 5 (2003) 1811-1824. 

The most important daytime loss process for the biogenics is reaction with OH radicals. Rate constants for the OH reaction with isoprene, a-and /3-pinene are 1.01 X 10-10 cm3 molecule-1 s-1, 5.37 X 10-11 cm3 molecule-1 s-1, and 7.89 X 10 11 cm3 molecule-1 s-1, respectively. Hydroxyl radical reactions with dialkenes and monoterpenes proceed primarily via OH addition across the double bond. Subsequent addition of oxygen to the radical produces a peroxy radical. The reactions of the resulting peroxy radical proceed in a manner similar to those of alkyl peroxy radicals. 

Hydroxyl radical reaction with aldehydes involves H-atom abstraction to produce the corresponding acyl (RCO) radical... 

Table IX.4 gives the distribution of isopentane hydroxylation products in various systems, including photochemical hydroxylation by hydrogen peroxide, where free hydroxyl radicals are known to be formed as intermediates. It is clear that the ratios of selectivities with respect to the site of attack (1° 2° 3°) in the systems involving and ions are very close to each other and to the selectivity observed for the attack by hydroxyl. This leads to the conclusion [47c] that the same active species (presumably hydroxyl radicals) participates in all these systems. This is also supported by a low isotope effect (kuJkn 1.2-1.3, when comparing reactions of C6H12 and C6D12). The yield of cyclohexane hydroxylation products depends on the nature of the solvent. The high yields in acetonitrile as compared with the other solvents are to be expected, provided the hydroxyl radicals are the intermediate active species. The rate constant of the hydroxyl radical reaction with cyclohexane is 5 lO dm mol s , with...

Gery, M. W., Fox, D. L., Kamens, R. M., and Stockburger, L. (1987) Investigation of hydroxyl radical reactions with o-xylene and w-xylene in continuous. stirred tank reactor. Environ. Sci. Technoi. 21, 339-348. 

Hydroxyl radical reactions with volatile organic compounds under simulated tropospheric conditions tropospheric lifetimes,... 

Dual-level direct dynamics of the hydroxyl radical reaction with ethane and haloethanes Toward a general reaction parameter method ... 

Hydroxyl radical reactions with phenol as a model for generation of biologically... 

Neeb, P. (2000), Structure-reactivity based estimation of the rate constants for hydroxyl radical reactions with hydrocarbons, J. Atmos. Chem., 35, 295-315. 

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