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  • Physical Chemistry  (3)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 867-875 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative rate technique has been used to determine the rate constants for the reaction of chlorine atoms with a series of oxygenated organic species. Experiments were performed at 295 ± 2 K and atmospheric pressure of synthetic air or nitrogen. The decay rates of the organic species were measured relative to that of ethane or n-butane. Using rate constants of 5.7 × 10-11 cm3 molecule-1 s-1, and 2.25 × 10-10 cm3 molecule-1 s-1 for the reaction of Cl with ethane and n-butane respectively the following rate constants were derived, in units of 10-11 cm3 molecule-1 s-1: propane, (16.0 ± 0.4);i-butane, (15.1 ± 0.9) n-pentane, (31.0 ± 1.6); n-hexane, (34.5 ± 2.3); cyclohexane, (36.1 ± 1.5); methanol, (4.57 ± 0.40); ethanol, (8.45 ± 0.91); n-propanol, (14.4 ± 1.2); t-butylalcohol, (3.26 ± 0.19); acetaldehyde, (8.45 ± 0.79); propionaldehyde, (11.3 ± 0.9); dimethylether, (20.5 ± 0.8); diethylether, (35.6 ± 2.8); and methyl-t-butylether, (16.6 ± 1.2). Quoted errors represent 2σ, and do not include any errors due to uncertainties in the rate constants used to place our relative measurements on an absolute basis. The results are discussed with respect to the mechanisms of these reactions and to previous literature data.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 993-1001 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethers are being increasingly used as motor fuel additives to increase the octane number and to reduce CO emissions. Since their reaction with hydroxyl radicals (OH) is a major loss process for these oxygenated species in the atmoshpere, we have conducted a relative rate study of the kinetics of the reactions of OH radicals with a series of ethers and report the results of these measurements here. Experiments were performed under simulated atmospheric conditions; atmospheric pressure (≃ 740 torr) in synthetic air at 295 K. Using rate constants of 2.53 × 10-12, and 1.35 × 10-11 cm3 molecule-1 s-1 for the reaction of OH radicals with n-butane and diethyl ether, the following rate constants were derived, in units of 10-11 cm3 molecule-1 s-1: dimethylether, (0.232 ± 0.023); di-n-propylether, (1.97 ± 0.08); di-n-butylether, (2.74 ± 0.32); di-n-pentylether, (3.09 ± 0.26); methyl-t-butylether, (0.324 ± 0.008); methyl-n-butylether, (1.29 ± 0.03); ethyl-n-butylether, (2.27 ± 0.09); and ethyl-t-butylether, (0.883 ± 0.026). Quoted errors represent 2σ from the least squares analysis and do not include any systematic errors associated with uncertainties in the reference rate constants used to place our relative measurements on an absolute basis. The implications of these results for the atmospheric chemistry of ethers are discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1069-1076 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative rate technique has been used to determine rate constants for the reaction of bromine atoms with a variety of organic compounds. Decay rates of the organic species were measured relative to i-butane or acetaldehyde or both. Using rate constants of 1.74 × 10-15 and 3.5 × 10-12 cm3 molecule-1 s-1 for the reaction of Br with i-butane and acetaldehyde respectively, the following rate constants were derived, in units of cm3 molecule-1 s-1: 2, 3-dimethylbutane, (6.40 ± 0.77) × 10-15; cyclopentane, (1.16 ± 0.18) × 10-15, ethene, (≤2.3 × 10-13); propene, (3.85 ± 0.41) × 10-12; trans-2-butene, (9.50 ± 0.76) × 10-12, acetylene, (5.15 ± 0.19) × 10-15; and propionaldehyde, (9.73 ± 0.91) × 10-12. Quoted errors represent 2σ and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295 ± 2 K and atmospheric pressure of synthetic air or nitrogen. The results are discussed with respect to the mechanisms of these reactions and their utility in serving as a laboratory source of alkyl and alkyl peroxy radicals.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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