OH radical formation yield

Chew, A. A., and R. Atkinson, OH Radical Formation Yields from the Gas-Phase Reactions of 03 with Alkenes and Monoterpenes, J. Geophys. Res., 101, 28649-28653 (1996). 

Mark G, Schuchmann MN, Schuchmann H-P, von Sonntag C (1990) The photolysis of potassium peroxodisulphate in aqueous solution in the presence of tert-butanol a simple actinometer for 254 nm radiation. J Photochem Photobiol A Chem 55 157-168 Mark G, Korth H-G, Schuchmann H-P, von Sonntag C (1996) The photochemistry of aqueous nitrate revisited. J Photochem Photobiol A Chem 101 89-103 Mark G, Tauber A, Laupert R, Schuchmann H-P, Schulz D, Mues A, von Sonntag C (1998) OH-radical formation by ultrasound in aqueous solution, part II. Terephthalate and Fricke dosimetry and the influence of various conditions on the sonolytic yield. Ultrason Sonochem 5 41-52 MarkG, Schuchmann H-P, von Sonntag C (2000) Formation of peroxynitrite by sonication of aerated water. J Am Chem Soc 122 3781-3782... 

However, the comparison of the data collected in Tab. 6-4 offers a realistic estimate of process efficiencies. The quantum yield of OH radical formation on Ti02 is only 4 to 10% at best. This is the major reason why Ti02 processes have, in general, not been commercially successful. Pure economic analysis (favored by Bolton) results in an estimate that hydrogen peroxide based photo-initiated AOPs are 50 to 100 times more efficient in their use of electricity than Ti02 photocata-... 

O.C. Zafiriou, R. Bonneau (1987). Wavelength-dependent quantum yield of OH radical formation from photolysis of nitrite ion in water. Photochem. PhotobioL, 45, 723-727. 

Kinetic studies on the gas-phase reactions of O3 with cycloakenes as a function of temperature have provided a reliable kinetic database for these reactions which may be used as an important input into chemical models for the reactions of O3 with alkenes under atmospheric conditions. The relatively high hydroxyl radical formation yields from the 03-cyclohexene reactions indicate that reactions of O3 with alkenes lead to the generation of OH radicals at night and hence allow the... 

There is a report that the quantum yield for OH radical formation is much lower (7 x KT ) than for common photocatalytic reactions (-10" ), and also than that reported for hole generation (5.7 x 10 ) [94]. This suggests that photogenerated holes play a major role in Ti02 photocatalysis, not OH radicals formed by reaction of holes with H2O molecules. 

Cox and Derwent (1976) used NO2 photodecomposition as a reference to estimate the quantum yield of OH radical formation in (I) to be 0.92 0.16. Wollenhaupt et al. (2000) have shown that process (II) is unimportant for photodecomposition within the long-wavelength bands of HONO they measured the resonance fluorescence of H-atoms at 121.6nm to show that (p < 0.01 in photolyses of HONO at 351 nm. Further evidence for the conclusion that 1.0 is given by the direct y(HONO)... 

Koulkes-Pujo and coworkers5 5 studied the formation of methane in the reaction of OH radicals and H atoms with aqueous DMSO in acidic media. In the radiolysis of deaerated acidic aqueous solution of DMSO they found that G(CH4) increases monotonously with CH4 concentration up to 0.8 m DMSO. Similar results were obtained for C2H6 but the yields of C2H6 are much lower than that of CH4. 

In the case of PCSO the addition of N20 leads to increased formation of cysteic acid, alanine and dipropyl sulfide and to a decrease in the yield of dipropyl disulfide. The addition of KBr decreases the yield of all the four products. These findings indicate that cysteic acid and alanine are formed by the reaction of OH radicals in parallel reactions as given in Figure 7. 

In the case of ACSO it was found also that N20 addition reduces the yield of S-allyl-L-cysteine (ACS), indicating that this product is formed by eaq - but not by OH radicals. As a result it can be expected that KBr addition will not reduce the ACS yield. It was found that KBr not only does not reduce the yield of ACS, but it rather increases i ts formation. This is explained as due to ACS formation by reaction of eaq" with ACSO, and its disappearance by reaction with OH radicals to give back ACSO as it is known for the reaction with sulfides. The authors suggest the same reactions for PCSO and PCS (propyl-L-cysteine) although the yield of PCS was not determined. 

Other possible mechanisms have been considered O), but they either predict formation of products which are not observed, do not explain the observed O3/UDMH stoichiometry, or are inconsistent with the results of the UDMH-NO stoichiometry and the formation of nitrosamine and H2O2 in this system. The other products observed, and the fact that the nitrosamine and H2O2 yields are somewhat less than the predicted 100% and 50% of the UDMH consumed, can be attributed to possible secondary reactions of the nitrosamine with the OH radical. 

Interestingly, one-electron oxidants partly mimic the effects of OH radicals in their oxidizing reactions with the thymine moiety of nucleosides and DNA. In fact, the main reaction of OH radicals with 1 is addition at C-5 that yields reducing radicals in about 60% yield [34, 38]. The yield of OH radical addition at C-6 is 35% for thymidine (1) whereas the yield of hydrogen abstraction on the methyl group that leads to the formation of 5-methyl-(2 -de-oxyuridylyl) radical (9) is a minor process (5%). Thus, the two major differences in terms of product analysis between the oxidation of dThd by one-electron oxidants and that by the OH radical are the distribution of thymidine 5-hydroxy-6-hydroperoxide diastereomers and the overall percentage of methyl oxidation products. 

One-electron oxidation of the adenine moiety of DNA and 2 -deoxyadenos-ine (dAdo) (45) gives rise to related purine radical cations 46 that may undergo either hydration to generate 8-hydroxy-7,8-dihydroadenyl radicals (47) or deprotonation to give rise to the 6-aminyl radicals 50. The formation of 8-oxo-7,8-dihydro-2 -deoxyadenosine (8-oxodAdo) (48) and 4,6-diamino-5-formamidopyrimidine (FapyAde) (49) is likely explained in terms of oxidation and reduction of 8-hydroxy-7,8-dihydroadenyl precursor radicals 47, respectively [90]. Another modified nucleoside that was found to be generated upon type I mediated one-electron oxidation of 45 by photoexcited riboflavin and menadione is 2 -deoxyinosine (51) [29]. The latter nucleoside is likely to arise from deamination of 6-aminyl radicals (50). Overall, the yield of formation of 8-oxodAdo 48 and FapyAde 49 upon one-electron oxidation of DNA is about 10-fold-lower than that of 8-oxodGuo 44 and FapyGua 43, similar to OH radical mediated reactions [91]. 

Michael and Hart10 found that the reaction of OH radicals (formed by pulse radiolysis of aqueous solutions saturated with N20) with 1,3- and 1,4-cyclohexadienes leads to formation of an intermediate absorbing at 310 nm. In the case of 1,4-cyclohexadiene, another band at A, < 240 nm was also found. In this system there are both H atoms and OH radicals, however the yield of the OH radicals is 10 times higher than that of the H- atoms. Michael and Hart10 assumed that the band at 310 nm is due to CeWi ... 

Photolytic. Based on data for structurally similar compounds, acenaphthylene may undergo photolysis to yield quinones (U.S. EPA, 1985). In a toluene solution, irradiation of acenaphthylene at various temperatures and concentrations all resulted in the formation of dimers. In water, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, 1,2-epoxyacenaphthylene, and 1-naphthoic acid. In methanol, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, methyl 8-formyl-1-naphthoate, and dimethoxyacetal 1,8-naphthalene dialdehyde (Chen et al., 1979). Acenaphthylene reacts with photochemically produced OH radicals and ozone in the atmosphere. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with OH radicals (500,000/cm ) at 25 °C are 8.44 x lO " cmVmolecule-sec and 5 h, respectively. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with ozone at 25 °C are... 

Titanium dioxide suspended in an aqueous solution and irradiated with UV light X = 365 nm) converted benzene to carbon dioxide at a significant rate (Matthews, 1986). Irradiation of benzene in an aqueous solution yields mucondialdehyde. Photolysis of benzene vapor at 1849-2000 A yields ethylene, hydrogen, methane, ethane, toluene, and a polymer resembling cuprene. Other photolysis products reported under different conditions include fulvene, acetylene, substituted trienes (Howard, 1990), phenol, 2-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol, 2,6-dinitro-phenol, nitrobenzene, formic acid, and peroxyacetyl nitrate (Calvert and Pitts, 1966). Under atmospheric conditions, the gas-phase reaction with OH radicals and nitrogen oxides resulted in the formation of phenol and nitrobenzene (Atkinson, 1990). Schwarz and Wasik (1976) reported a fluorescence quantum yield of 5.3 x 10" for benzene in water. 

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