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  • Physical Chemistry  (5)
  • 1
    Electronic Resource
    Electronic Resource
    Rate coefficients for the reactions of OH radicals with Methylglyoxal and Acetaldehyde (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 1009-1020 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate coefficients have been measured for the reaction of OH radicals with methylglyoxal from 260 to 333 K using the discharge flow technique and laser-induced fluorescence detection of OH. The rate coefficient was found to be (1.32±0.30) × 10-11 cm3 molecule-1 s-1 at room temperature, with a distinct negative temperature dependence (E/R of -830 ± 300 K). These are the first measurements of the temperature dependence of this reaction. The reaction of OH with acetaldehyde was also investigated, and a rate coefficient of (1.45 ± 0.25) × 10-11 cm3 molecule-1 s-1 was found at room temperature, in accord with recent studies. Experiments in which O2 was added to the flow showed regeneration of OH following the reaction of CH3CO radicals with O2. However, chamber experiments at atmospheric pressure using FTIR detection showed no evidence for OH production. FTIR experiments have also been used to investigate the chemistry of the CH3COCO radical formed by hydrogen abstraction from methylglyoxal. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550271006
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  • 2
    Electronic Resource
    Electronic Resource
    Rate coefficients for the reactions of O(3P) with selected biogenic Hydrocarbons (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 997-1008 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate coefficients for the reaction of O(3P) with the biogenic hydrocarbons Δ3-carene, α-pinene, and isoprene have been measured using a direct method for the first time. O(3P) was generated from the pulsed photolysis of NO2 or O3 at 308 nm, and measured by resonance fluorescence at 131 nm. Rate coefficients at room temperature for the biogenics are similar: (3.4 ± 0.6) × 10-11, (3.7 ± 0.6) × 10-11, and (3.5 ± 0.6) × 10-11 cm3 molec-1 s-1, for Δ3-carene, α-pinene, and isoprene, respectively. The rate coefficients for the reaction of O(3P) with NO2 and ethene were also measured with the same method, and these values are within 4% and 10% of the currently recommended values, respectively. The correlation between OH and O(3P)-alkene reaction rate coefficients is updated and discussed. © 1995 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550271005
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    Atmospheric chemistry of acetone: Kinetic study of the CH3C(O)CH2O2+NO/NO2 reactions and decomposition of CH3C(O)CH2O2NO2 (1998)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 475-489 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pulse radiolysis was used to study the kinetics of the reactions of CH3C(O)CH2O2 radicals with NO and NO2 at 295 K. By monitoring the rate of formation and decay of NO2 using its absorption at 400 and 450 nm the rate constants k(CH3C(O)CH2O2+NO)=(8±2)×10-12 and k(CH3C(O)CH2O2+NO2)=(6.4±0.6)×10-12 cm3 molecule-1 s-1 were determined. Long path length Fourier transform infrared spectrometers were used to investigate the IR spectrum and thermal stability of the peroxynitrate, CH3C(O)CH2O2NO2. A value of k-6≈3 s-1 was determined for the rate of thermal decomposition of CH3C(O)CH2O2NO2 in 700 torr total pressure of O2 diluent at 295 K. When combined with lower temperature studies (250-275 K) a decomposition rate of k-6=1.9×1016 exp (-10830/T) s-1 is determined. Density functional theory was used to calculate the IR spectrum of CH3C(O)CH2O2NO2. Finally, the rate constants for reactions of the CH3C(O)CH2 radical with NO and NO2 were determined to be k(CH3C(O)CH2+NO)=(2.6±0.3)×10-11 and k(CH3C(O)CH2+NO2)=(1.6±0.4)×10-11 cm3 molecule-1 s-1. The results are discussed in the context of the atmospheric chemistry of acetone and the long range atmospheric transport of NOx. © John Wiley & Sons, Inc. Int J Chem Kinet: 30: 475-489, 1998
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Atmospheric chemistry of CH2BR2: Rate coefficients for its reaction with Cl atoms and OH and the chemistry of the CHBr2O radical (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 433-442 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate coefficients for the reaction of OH radicals and Cl atoms with dibromomethane OH + CH2Br2 → CHBr2 + H2O (1) and Cl + CH2 Br2 → CHBr2 + HCL (3) and for the reaction of Cl atoms with methyl bromide, Cl + CH3Br → HCl + CH2Br (4), have been obtained using relative rate techniques. At 298 K, the value of k1 was determined to be (1.2 ± 0.31) × 10-13 cm3 molec-1 s-1. The rate coefficients k3 and k4 were determined at a series of temperatures ranging from 228 K to 296 K and combined with the measurements of Gierczak et al., yielding the following Arrhenius expressions for k3 and k4; k3 = (6.35 ± 0.6) × 10-12 exp(-807 ± 50/T) cm3 molec-1 s-1 and k4 = (1.49 ± 0.2) × 10-11 exp(-1056 ± 50/T) cm3 molec-1 s-1.In addition, the Cl atom initiated oxidation mechanism of CH2Br2 in air has been studied at 298 K. The products observed were HC(O)Br and small amounts of CO. The dominant atmospheric fate of the alkoxy radical, CHBr2O is elimination of a Br atom, which occurs at a rate estimated to be greater than 4 × 106 s-1 in 700 torr of O2 at 298 K. © 1996 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.5
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  • 5
    Electronic Resource
    Electronic Resource
    Pressure dependence of the rate coefficients and product yields for the reaction of CH3CO radicals with O2 (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 655-663 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate coefficients for the reaction of acetyl (CH3CO) radicals with O2 (k4) and Cl2 (k7) have been obtained at 298 K and 228 K as a function of total pressure, using FTIR/environmental chamber techniques. Measured values of k4/k7 were placed on an absolute basis using k7=2.8×10-11 exp(-47/T) cm3 molec-1 s-1. At 298 K, the value of k4 is constant ((7±2)×10-13 cm3 molec-1 s-1) at pressures from 0.1 to 2 torr, then increases to a high pressure limiting value of (3.2±0.6)×10-12 cm3 molec-1 s-1, which is approached at pressures above 300 torr. At 228 K, the low-pressure value of k4 increases by about 20-30%, while the high pressure value remains unchanged. Experiments designed to elucidate the products of reaction (4) as a function of pressure at 298 K indicate that the reaction occurs via a concerted mechanism in which CH3CO radicals combine with O2 to give an excited acetylperoxy radical (CH3COO2*) which is increasingly stabilized at high pressure at the expense of a low pressure decomposition channel. The yield of acetylperoxy radicals from reaction (4) decreases from 〉95% at pressures above 100 torr, to about 90% at 60 torr, and 50% at 6 torr. Indirect evidence for formation of OH radicals from the low pressure decomposition is presented, although the carbon-containing coproduct(s) of this channel could not be identified. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 655-663, 1997.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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