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  • 11
    Electronic Resource
    Electronic Resource
    Rate constant for the reaction of OH radicals with isopropylcyclopropane at 298 ± 2 K: Effects of ring strain on substituted cycloalkanes (1988)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 339-342 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550200407
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  • 12
    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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  • 13
    Electronic Resource
    Electronic Resource
    Products of the gas-phase OH radical-initiated reactions of 4-methyl-2-pentanone and 2,6-dimethyl-4-heptanone (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 261-275 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reactions of the OH radical with 4-methyl-2-pentanone and 2,6-dimethyl-4-heptanone have been investigated in the presence of NOx. Acetone and 2-methylpropanal were identified and qualified as products of both reactions. The acetone yield from 2,6-dimethyl-4-heptanone increased after addition of NO to reacted mixtures, indicating that acetone is formed through the intermediary of an acyl radical. The acetone and 2-methylopropanal formation yields were determined to be 0.78 ± 0.06 and 0.071 ± 0.011, respectively, from 4-methyl-2-pentanone and 0.68 ± 0.11 and 0.385 ± 0.034, respectively, from 2,6-dimethyl-4-heptanone. The possible reaction mechanisms are discussed and compared with these product data, and it is concluded that the experimental data provide direct evidence for isomerization of the (CH3)2CHCH2C(O)CH2C(O) (CH3)2 alkoxy radical formed from 2,6-dimethyl-4-heptanone. However, the isomerization rates of the alkoxy radicals formed from the ketones depend on whether the H-atom abstracted is on a carbon atom α or β to the 〉C=O group, with H-atom abstraction from C—H bonds on the β carbon atoms being significantly faster than from C—H bonds on the α carbon atoms. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550270305
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  • 14
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reactions of alkanes with Cl atoms at 296 ± 2 K (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 613-622 
    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 the Cl atom with a series of alkanes have been determined at 296 ± 2 K using a relative rate method. Using a rate constant for the Cl atom reaction with n-butane of 1.94 × 10-10 cm3 molecule-1 s-1, the rate constants obtained (in units of 10-11 cm3 molecule-1 s-1) were: 2-methylpentane, 25.0 ± 0.8; 3-methylpentane, 24.8 ± 0.6; cyclohexane, 30.8 ± 1.2; cyclohexane-d12, 25.6 ± 0.8; 2,4-dimethylpentane, 25.6 ± 1.2; 2,2,3-trimethylbutane, 17.9 ± 0.7; methylcyclohexane, 34.7 ± 1.2; n-octane, 40.5 ± 1.2; 2,2,4-trimethylpentane, 23.1 ± 0.8; 2,2,3,3-tetramethylbutane, 15.6 ± 0.9; n-nonane, 42.9 ± 1.2; n-decane, 48.7 ± 1.8; and cis-bicyclo[4.4.0]decane, 43.1 ± 0.8, where the indicated errors are two least-squares standard deviations and do not include the uncertainties in the n-butane rate constant. These data have been combined with rate constants obtained previously for ten C2—C7 alkanes and this entire data set has been used to develop an estimation method allowing the room temperature rate constants for the reactions of the Cl atom with alkanes to be calculated. © 1995 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550270611
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  • 15
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reactions of cis-3-Hexen-1-ol, cis-3-Hexenylacetate, trans-2-Hexenal, and Linalool with OH and NO3 radicals and O3 at 296 ± 2 K, and OH radical formation yields from the O3 reactions (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 941-955 
    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 the four oxygenated biogenic organic compounds cis-3-hexen-1-ol, cis-3-hexenylacetate, trans-2-hexenal, and linalool with OH radicals, NO3 radicals, and O3 have been determined at 296 ± 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained were (in cm3 molecule-1 s-1 units): cis-3-hexen-1-ol: (1.08 ± 0.22) × 10-10 for reaction with the OH radical; (2.72 ± 0.83) × 10-13 for reaction with the NO3 radical; and (6.4 ± 1.7) × 10-17 for reaction with O3; cis-3-hexenylacetate: (7.84 ± 1.64) × 10-11 for reaction with the OH radical; (2.46 ± 0.75) × 10-13 for reaction with the NO3 radical; and (5.4 ± 1.4) × 10-17 for reaction with O3; trans-2-hexenal: (4.41 ± 0.94) × 10-11 for reaction with the OH radical; (1.21 ± 0.44) × 10-14 for reaction with the NO3 radical; and (2.0 ± 1.0) × 10-18 for reaction with O3; and linalool: (1.59 ± 0.40) × 10-10 for reaction with the OH radical; (1.12 ± 0.40) × 10-11 for reaction with the NO3 radical; and (4.3 ± 1.6) × 10-16 for reaction with O3. Combining these rate constants with estimated ambient tropospheric concentrations of OH radicals, NO3 radicals, and O3 results in calculated tropospheric lifetimes of these oxygenated organic compounds of a few hours. © 1995 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550271002
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  • 16
    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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  • 17
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reactions of selected dibasic esters with the OH radical (1998)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 471-474 
    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 have been measured for the gas-phase reactions of the OH radical with the dibasic esters dimethyl succinate [CH3OC(O)CH2CH2C(O)OCH3], dimethyl glutarate [CH3OC(O)CH2CH2CH2C(O)OCH3], and dimethyl adipate [CH3OC(O)CH2CH2CH2CH2C(O)OCH3] at 298±3 K. The rate constants obtained were (in units of 10-12 cm3 molecule-1 s-1): dimethyl succinate, 1.4±0.6; dimethyl glutarate, 3.3±1.1; and dimethyl adipate, 8.4±2.5, where the indicated errors include the estimated overall uncertainty of ±25% in the rate constant for cyclohexane, the reference compound. The calculated tropospheric lifetimes of these dibasic esters due to gas-phase reaction with the OH radical range from 1.4 days for dimethyl adipate to 8.3 days for dimethyl succinate for a 24 h average OH radical concentration of 1.0×106 molecule cm-3. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 471-474, 1998
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 18
    Electronic Resource
    Electronic Resource
    Effects of ring strain on gas-phase rate constants. 2. OH radical reactions with cycloalkenes (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1161-1177 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the gas-phase reactions of OH radicals with a series of cycloalkenes have been determined at 298 ± 2 K using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with isoprene of 9.60 × 10-11 cm3 molecule-1 s-1, the rate constants obtained were (X 1011 cm3 molecule-1 s-1): cyclopentene 6.39 ± 0.23, cyclohexene 6.43 ± 0.17, cycloheptene 7.08 ± 0.22, 1,3-cyclohexadiene 15.6 ± 0.5, 1,4 cyclohexadiene 9.48 ± 0.39, bicyclo[2.2.1]-2-heptene 4.68 ± 0.39, bicyclo[2.2.1] 2,5 heptadiene 11.4 ± 1.0, and bicyclo[2.2.2] 2 octene 3.88 ± 0.19. These data show that the rate constants for the nonconjugated cycloalkenes studied depend on the number of double bonds and the degree of substitution per double bond, and indicate that there are no obvious effects of ring strain energy on these OH radical addition rate constants. A predictive technique for the estimation of OH radical rate constants for alkenes and cycloalkenes is presented and discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151105
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  • 19
    Electronic Resource
    Electronic Resource
    Rate constants for the reaction of OH radicals with a series of alkenes and dialkenes at 295 ± 1 K (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1175-1186 
    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 n-butane, n-hexane, and a series of alkenes and dialkenes, relative to that for propene, have been determined in one atmosphere of air at 295 ± 1 K. The rate constant ratios obtained were (propene = 1.00): ethene, 0.323 ± 0.014; 1-butene, 1.19 ± 0.06; 1-pentene, 1.19 ± 0.05; 1-hexene, 1.40 ± 0.04; 1-heptene, 1.51 ± 0.06; 3-methyl-1-butene, 1.21 ± 0.04; isobutene, 1.95 ± 0.09; cis-2-butene, 2.13 ± 0.05; trans-2-butene, 2.43 ± 0.05; 2-methyl-2-butene, 3.30 ± 0.13; 2,3-dimethyl-2-butene, 4.17 ± 0.18; propadiene, 0.367 ± 0.036; 1,3-butadiene, 2.53 ± 0.08; 2-methyl-1,3-butadiene, 3.81 ± 0.15; n-butane, 0.101 ± 0.012; and n-hexane, 0.198 ± 0.017. From a least-squares fit of these relative rate data to the most reliable literature absolute flash photolysis rate constants, these relative rate constants can be placed on an absolute basis using a rate constant for the reaction of OH radicals with propene of 2.63 × 10-11 cm3 molecule-1 s-1. The resulting rate constant data, together with previous relative rate data from these and other laboratories, lead to a self-consistent data set for the reactions of OH radicals with a large number of organics at room temperature.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550161002
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  • 20
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of naphthalene, 2-methylnaphthalene, and 2,3-dimethylnaphthalene with OH radicals and with O3 at 295 ± 1 K (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 569-573 
    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 naphthalene, 2-methylnaphthalene, and 2,3-dimethylnaphthalene with O3 and with OH radicals have been studied at 295 ± 1 K in one atmosphere of air. Upper limit rate constants for the O3 reactions of 〈3 × 10-19, 〈4 × 10-19, and 〈4 × 10-19 cm3 molecule-1 s-1 were obtained for naphthalene, 2-methylnaphthalene, and 2,3-dimethylnaphthalene, respectively. For the OH radical reactions, rate constants of (in units of 10-11 cm3 molecule-1 s-1) 2.59 ± 0.24, 5.23 ± 0.42, and 7.68 ± 0.48 were determined for naphthalene, 2±methylnaphthalene, and 2,3-dimethylnaphthalene, respectively. These data show that under atmospheric conditions these naphthalenes will react mainly with the OH radical, with life-times due to this reaction ranging from ca. 11 h for naphthalene to ca. 4 h for 2,3-dimethylnaphthalene.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180507
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