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  • 1
    Electronic Resource
    Electronic Resource
    Products of the gas-phase reaction of methyl tert-butyl ether with the OH radical in the presence of NOx (1991)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 1003-1015 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The products of the reaction of the hydroxyl (OH) radical with methyl tert-butyl ether (MTBE) in NOx-air systems were identified and measured by Fourier transform infrared absorption spectroscopy and gas chromatography. The products observed, and their yields, were as follows: t-butyl formate, 76 ± 7%; formaldehyde, 37-1+6%; methyl acetate, 17 ± 2%, and acetone, 2.1 ± 0.9%, where the stated error limits represent both random (two standard deviations) and estimated systematic uncertainties. These products account for ca. 95% of the MTBE carbon reacted. Infrared absorption bands which may be due to small amounts of organic nitrate formation were observed, but organic nitrate yields could not be quantified. These data allow a chemical mechanism for the reaction of MTBE with the OH radical in the presence of NOx to be formulated.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550231105
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  • 2
    Electronic Resource
    Electronic Resource
    Gas-phase reactions of azulene with OH and NO3 radicals and O3 at 298 ± 2 K (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 467-480 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Azulene, which is isomeric with naphthalene, was studied to determine whether it behaves like a polycyclic aromatic hydrocarbon or an alkene in its gas-phase reactions with OH and NO3 radicals and O3. Using relative rate methods, rate constants for the reactions of azulene with OH and NO3 radicals and O3 of (2.73 ± 0.56) × 10-10 cm3 molecule-1 s-1, (3.9-1.4+2.0) × 10-10 cm3 molecule-1 s-1, and 〈7 × 10-17 cm3 molecule-1 s-1, respectively, were obtained at 298 ± 2 K. The observation that the NO3 radical reaction did not involve NO2 in the rate determining step indicates that azulene behaves more like an alkene than a polycyclic aromatic hydrocarbon in this reaction. No conclusive evidence for the formation of nitroazulene(s) from either the OH or NO3 radical-initiated reaction of azulene (in the presence of NOx) was obtained.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550240507
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  • 3
    Electronic Resource
    Electronic Resource
    OH radical reaction rate constants for polycyclic alkanes: Effects of ring strain and consequences for estimation methods (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 983-989 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a relative rate method, rate constants for the gas-phase reactions of the OH radical with trans-pinane [(1R, 2R)-2, 6, 6-trimethylbicyclo[3.1.1]heptane], tricyclene (1, 7, 7-trimethyltricyclo[2.2.1.02, 6]heptane), and quadricyclane (quadricyclo[2.2.1.02, 6.03, 5]heptane) of (1.34 ± 0.29) × 10-11 cm3 molecule-1 s-1, (2.86 ± 0.62) × 10-12 cm3 molecule-1 s-1 and (1.83 ± 0.41) × 10-12 cm3 molecule-1 s-1, respectively, have been determined at 296 ± 2 K. These rate constants are compared with values calculated from an empirical estimation method and used to refine this estimation technique for the calculation of OH radical reaction rate constants for polycyclic systems. © John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550241108
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  • 4
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reactions of the OH radical with the cresols and dimethylphenols at 296 ± 2K (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 59-67 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a relative rate technique, rate constants for the gas-phase reactions of the OH radical with the three cresols and the six dimethylphenols have been determined at 296 ± 2 K and atmospheric pressure. The rate constants for the cresols, which range from 4.3 × 10-11 cm3molecule-1 s-1to 6.8 × 10-11 cm3molecule-1 s-1, are in good agreement with previous literature data. The rate constants for 2,3-, 2,4-, 2,5-, 2,6-, and 3,4-dimethylphenol are all in the range (6.6-8.1) × 10-11 cm3 molecule-1 s-1, with the rate constant for 3,5-dimethylphenol being somewhat higher at 1.13 × 10-10 cm3 molecule-1 s-1. Rate constants estimated from the number, identity, and positions of the substituent groups around the aromatic ring agree to within a factor of approximately 2 with these experimentally determined rate constants.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550220105
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics and products of the gas-phase reactions of the OH radical and O3 with allyl chloride and benzyl chloride at room temperature (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 981-998 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase reactions of allyl chloride and benzyl chloride with the OH radical and O3 were investigated at 298 ± 2 K and atmospheric pressure. Direct measurements of the rate constants for reactions with ozone yielded values of k(O3 + allyl chloride) = (1.60 ± 0.18) × 10-18 cm3 molecule-1 s-1 and k(O3 + benzyl chloride) 〈 6 × 10-20 cm3 molecule-1 s-1. With the use of a relative rate technique and ethane as a scavenger of chlorine atoms produced in the OH radical reactions, rate constants of k(OH + allyl chloride) = (1.69 ± 0.07) × 10-11 cm3 molecule-1 s-1 and k(OH + benzyl chloride) = (2.80 ± 0.19) × 10-12 cm3 molecule-1 s-1 were measured. A study of the OH radical reaction with allyl chloride by long pathlength FT-IR absorption spectroscopy indicated that the co-products ClCH2CHO and HCHO account for ca. 44% of the reaction, and along with the other products HOCH2CHO, (ClCH2)2CO, and CH2 = CHCHO account for 84 ± 16% of the allyl chloride reacting. The data indicate that in one atmosphere of air in the presence of NO the chloroalkoxy radical formed following OH radical addition to the terminal carbon atom of the double bond decomposes to yield HOCH2CHO and the CH2Cl radical, which becomes a significant source of the Cl atoms involved in secondary reactions. A product study of the OH radical reaction with benzyl chloride identified only benzaldehyde and peroxybenzoyl nitrate in low yields (ca. 8% and ≤4%, respectively), with the remainder of the products being unidentified.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550220909
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  • 6
    Electronic Resource
    Electronic Resource
    Formation of ring-retaining products from the OH radical-initated reactions of o-, m-, and p-xylene (1991)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 77-97 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ring-retaining products formed from the OH radical-initiated reactions of o-, m-, and p-xylene in the presence of NOx have been identified and their formation yields determined. Experiments were carried out at 298 ± 2 K and in the presence of 740 torr total pressure of air. The products observed, and their yields, were: from o-xylene, o-tolualdehyde, 0.0453; 2-methylbenzyl nitrate, (0.0135 + 5.5 × 10-17 [NO2]); 2,3-dimethylphenol, 0.097; 3,4-dimethyl-phenol, 0.064; 3-nitro-o-xylene, 0.0059; 4-nitro-o-xylene, (0.0111 + 9.9 × 10-17 [NO2]); from m-xylene, m-tolualdehyde, 0.0331; 3-methylbenzyl nitrate, 0.0061; 2,4-dimethylphenol, 0.099; 2,6-dimethylphenol, 0.111; 4-nitro-m-xylene, 0.0018; 5-nitro-m-xylene, (0.0032 + 1.6 × 10-17 [NO2]); from p-xylene, p-tolualdehyde, 0.0701; 4-methylbenzyl nitrate, 0.0082; 2,5-dimethylphenol, 0.188, 2-nitro-p-xylene, (0.0120 + 2.8 × 10-17 [NO2]), where the NO2 concentration is in molecule cm-3 units. The nitro-xylene data are consistent with our recent product study of the corresponding reactions of benzene and toluene and indicate that under the experimental conditions employed the dimethylhydroxycyclohexadienyl radicals reacted with NO2 and not with O2. When combined with literature ring-cleavage product yields, these data show that ca. 55-80% of the reaction pathways are accounted for.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550230108
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  • 7
    Electronic Resource
    Electronic Resource
    Products of the gas-phase reactions of aromatic hydrocarbons: Effect of NO2 concentration (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 929-944 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation yields of selected products of the OH radical-initiated reactions of toluene, o-xylene, and 1,2,3,-trimethylbenzene have been measured in the absence of NOx and in the presence of varying concentrations of NO and NO2. The formation yield of o-cresol from toluene increased from 0.123 ± 0.022 in the absence of NOx to 0.160 ± 0.008 for an average NO2 concentration of 1.7 × 1014 molecule cm3. The formation yield of 2,3-butanedione from o-xylene was 0.092 ± 0.013 in the absence of NOx, and in the presence of NOx decreased from 0.16 at an average NO2 concentration of (7-8) × 1012 molecule cm-3 to 0.09 at an average NO2 concentration of ca. 7 × 1013 molecule cm-3. The formation yield of 2,3-butanedione from 1,2,3-trimethylbenzene increased from 0.18 in the absence of NOx to 0.444 ± 0.053 in the presence of ca. (0.16-3.6) × 1013 molecule cm-3 of NO2. These product data are consistent with literature kinetic data showing that the hydroxycyclohexadienyl radicals formed by OH radical addition to the aromatic ring react with both O2 and NO2 and with the NO2 reaction rate constants being ca. 105 higher than the O2 reaction rate constants at room temperature. Under typical tropospheric conditions the reactions of the hydroxycyclohexadienyl radicals with O2 will dominate over their reactions with NO2. © 1994 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260907
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  • 8
    Electronic Resource
    Electronic Resource
    Gas-phase reactions of 1,4-benzodioxan, 2,3-dihydrobenzofuran, and 2,3-benzofuran with OH radicals and O3 (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 345-358 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase reactions of 1,4-benzodioxan, 2,3-dihydrobenzofuran, and 2,3-benzofuran with OH radicals and O3 have been studied at 298 ± 2 K and atmospheric pressure of air and the products have also been investigated. 1,4-Benzodioxan and 2,3-dihydrobenzofuran were chosen as volatile model compounds for dibenzo-p-dioxin and dibenzofuran, respectively. The rate constants, or upper limits thereof, for the O3 reactions were (in cm3 molecule-1 s-1 units): 1,4-benzodioxan, 〈1.2 × 10-20; 2,3-dihydrobenzofuran, 〈1 × 10-19; and 2,3-benzofuran, (1.83 ± 0.21) × 10-18. Using a relative rate method, the rate constants for the OH radical reactions (in cm3 molecule-1 s-1 units) were: 1,4-dibenzodioxan, (2.52 ± 0.38) × 10-11; 2,3-dihydrobenzofuran, (3.66 ± 0.56) × 10-11; and 2,3-benzofuran, (3.73 ± 0.74) × 10-11. Salicylaldehyde was observed as a product of the OH radical-initiated and O3 reactions of 2,3-benzofuran, with measured formation yields of 0.26 ± 0.05 and 0.13 ± 0.07, respectively.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550240404
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  • 9
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reactions of O3 with a series of monoterpenes and related compounds at 296 ± 2 K (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 871-887 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the gas-phase reactions of O3 with a series of monoterpenes and related compounds have been determined at 296 ± 2 K and 740 torr total pressure of air or O2 using a combination of absolute and relative rate techniques. Good agreement between the absolute and relative rate data was observed, and the rate constants obtained (in units of 10-17 cm3 molecule-1 s-1) were: α-pinene, 8.7; β-pinene, 1.5; Δ3-carene, 3.8; 2-carene, 24; sabinene, 8.8; d-limonene, 21; γ-terpinene, 14; terpinolene, 140; α-phellandrene, 190; α-terpinene, 870; myrcene, 49; trans-ocimene, 56; p-cymene, 〈0.005; and 1,8-cineole, 〈0.015. While these rate constants for α- and β-pinene and sabinene are in good agreement with recent absolute and relative rate determinations, those for the other monoterpenes are generally lower than the literature data by factors of ca. 2-10. The measured rate constants for the monoterpenes are reasonably consistent with predictions based upon the number and positions of the substituent groups around the 〉C=C〈 bond(s).
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550220807
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  • 10
    Electronic Resource
    Electronic Resource
    Formation yields of epoxides and O(3P) atoms from the gas-phase reactions of O3 with a series of alkenes (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 945-950 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of ozone with propene, 1-butene, cis-2-butene, trans-2-butene, 2,3-dimethyl-2-butene, and 1,3-butadiene were carried out in N2 and air diluent at atmospheric pressure and room temperature and, by monitoring the formation of the epoxides and/or a carbonyl compound formed from the reactions of O(3P) atoms with these alkenes, the formation yields of O(3P) atoms from the O3 reactions were investigated. No evidence for O(3P) atom formation was obtained, and upper limits to O(3P) atom formation yields of 〈4% for propene, 〈5% for 1.3-butadiene, and 〈2% for the other four alkenes were derived. The reaction of O3 with 1,3-butadiene led to the direct formation of 3,4-epoxy-1-butene in (2.3 ± 0.4)% yield. These data are in agreement with the majority of the literature data and show that O(3P) atom formation is not a significant pathway in O3 - alkene reactions, and that epoxide formation only occurs to any significant extent from conjugated dienes. © 1994 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260908
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