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  • Articles: DFG German National Licenses  (11)
  • 1990-1994  (11)
  • Chemistry  (11)
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  • Articles: DFG German National Licenses  (11)
Material
Years
Year
Keywords
  • 1
    Electronic Resource
    Electronic Resource
    Rate coefficients for the reaction of OH with HONO between 298 and 373 K (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 711-725 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate coefficients, k1, for the reaction OH + HONO → H2O + NO2, have been measured over the temperature range 298 to 373 K. The OH radicals were produced by 266 nm laser photolysis of O3 in the presence of a large excess of H2O vapor. The temporal profiles of OH were measured under pseudo-first-order conditions, in an excess of HONO, using time resolved laser induced fluorescence. The measured rate coefficient exhibits a slight negative temperature dependence, with k1 = (2.8 ± 1.3) × 10-12 exp((260 ± 140)/T) cm3 molecule-1 s-1. The measured values of k1 are compared with previous determinations and the atmospheric implications of our findings are discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550240805
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of Cl atoms with CH3Br and CH2Br2 (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 719-728 
    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 reactions of Cl atoms with CH3Br, (k1) and CH2Br2, (k2) were measured as functions of temperature by generating Cl atoms via 308 nm laser photolysis of Cl2 and measuring their temporal profiles via resonance fluorescence detection. The measured rate coefficients were: k1 = (1.55 ± 0.18) × 10-11 exp{(-1070 ± 50)/T} and k2 = (6.37 ± 0.55) × 10-12 exp{(-810 ± 50)/T} cm3 molecule-1 s-1. The possible interference of the reaction of CH2Br product with Cl2 in the measurement of k1 was assessed from the temporal profiles of Cl at high concentrations of Cl2 at 298 K. The rate coefficient at 298 K for the CH2Br + Cl2 reaction was derived to be (5.36 ± 0.56) × 10-13 cm3 molecule-1 s-1. Based on the values of k1 and k2, it is deduced that global atmospheric lifetimes for CH3Br and CH2Br2 are unlikely to be affected by loss via reaction with Cl atoms. In the marine boundary layer, the loss via reaction (1) may be significant if the Cl concentrations are high. If found to be true, the contribution from oceans to the overall CH3Br budget may be less than what is currently assumed. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260705
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  • 3
    Electronic Resource
    Electronic Resource
    The yield of CH3S from the reaction of OH with CH3SSCH3 (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 943-951 
    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 OH with CH3SSCH3 (DMDS) were investigated at 298 K using a flow tube reactor coupled to a photoionization mass spectrometer and a pulsed photolysis-pulsed laser induced fluorescence apparatus. The results from the former apparatus were semi-quantitative and showed that CH3S and CH3SOH are produced in the title reaction. The latter apparatus was used to quantify the yield of CH3S in the title reaction. The measured yield was 0.28 ± 0.20, independent of pressure and buffer gas, suggesting that products other than CH3S and CH3SOH are also important in this reaction. The quoted uncertainty is at the 95% confidence level and includes estimated systematic errors. © John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550241104
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetics of the reaction of H(2S) with HBr (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 973-982 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants for the reaction H + HBr → H2 + Br were measured between 217 and 383 K using pulsed laser photolysis of HBr and cw resonance fluorescence detection of H(2S). The temporal profiles of the product Br atoms were also monitored to obtain the rate constant at 298 K. The yield of Br from the reaction was determined to be unity. The rate coefficient as a function of temperature is given by the Arrhenius expression, k 1 = (2.96 ± 0.44) × 10-11 exp(-(460 ± 40)/T) cm3 molecule-1 s-1. The quoted errors are at the 95% confidence level and include estimated systematic errors. Our results are compared with those from previous direct measurements. © John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550241107
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  • 5
    Electronic Resource
    Electronic Resource
    The rate coefficient for the reaction of O(3P) with CH3OOH at 297 K (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 351-358 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute second-order rate coefficient for the reaction, O(3P) + CH3OOH → products, was measured to be k1 = (1.06 ± 0.26) × 10-14 cm3 molec-1 s-1 at 297 K, where the quoted error is 2σ including precision and estimated systematic errors. The possible presence of (CH3CH2)2O in our sample of CH3OOH leads to a large error in k1 which reflects the relatively large uncertainty indicated. O(3P) was generated in excess CH3OOH by photolyzing a small amount of O3 at 532 nm, where CH3OOH does not photolyze. The rate of removal of O(3P) in the experiments was monitored by resonance fluorescence detection. The increased reactivity of O(3P) with CH3OOH relative to H2O2 is interpreted as due to H abstraction from the CH3 group.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550220404
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  • 6
    Electronic Resource
    Electronic Resource
    Atmospheric oxidation of reduced sulfur species (1991)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 483-527 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of elementary gas phase reactions involved in the oxidation of reduced sulfur species, H2S, CS2, OCS, CH3SH, CH3SCH3, and CH3SSCH3, to SO2 (or other products) are reviewed. The reactions with OH and NO3 which are the processes that initiate the degradation of the above compounds have been evaluated. Reactions of key intermediates, HS, HSO, CH3S, and CH3SO, are discussed. Whenever possible, recommendations for the rate coefficients are made and the need for further work indicated. The review has been carried out with the atmospheric chemistry in mind by looking at the laboratory based kinetics data. This review also provides information that will help model the Earth's sulfur cycle.
    Additional Material: 19 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550230604
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  • 7
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of OH with alkanes (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 973-990 
    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 reactions of OH with ethane (k1), propane (k2), n-butane (k3), iso-butane (k4), and n-pentane (k5) have been measured over the temperature range 212-380 K using the pulsed photolysis-laser induced fluorescence (PP-LIF) technique. The 298 K values are (2.43±0.20) × 10-13, (1.11 ± 0.08) × 10-12, (2.46 ± 0.15) × 10-12, (2.06 ± 0.14) × 10-12, and (4.10 ± 0.26) × 10-12 cm3 molecule-1 s-1 for k1, k2, k3, k4, and k5, respectively. The temperature dependence of k1 and k2 can be expressed in the Arrhenius form: k1 = (1.03 ± 0.07) × 10-11 exp[-(1110 ± 40)/T] and k2 = (1.01 ± 0.08) × 10-11 exp[-(660 ± 50)/T]. The Arrhenius plots for k3 - k5 were clearly curved and they were fit to three parameter expressions: k3 = (2.04 ± 0.05) × 10-17 T2 exp[(85 ± 10)/T] k4 = (9.32 ± 0.26) × 10-18 T2 exp[(275 ± 20)/T]; and k5 = (3.13 ± 0.25) × 10-17 T2 exp[(115 ± 30)/T]. The units of all rate constants are cm3 molecule-1 s-1 and the quoted uncertainties are at the 95% confidence level and include estimated systematic errors. The present measurements are in excellent agreement with previous studies and the best values for atmospheric calculations are recommended. © 1994 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550261003
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  • 8
    Electronic Resource
    Electronic Resource
    Kinetics of O(1D) reactions with bromocarbons (1993)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 479-487 
    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 removal of O(1D) by reaction with the following seven bromocarbons were measured using time-resolved vacuum UV atomic resonance fluorescence detection of O(3P): CH3Br, CH2Br2, CHBr3, CF3Br (Halon-1301), CF2Br2 (Halon-1202), CF2ClBr (Halon-1211), and CF2BrCF2Br (Halon-2402). The branching ratios for the quenching of O(1D) to O(3P) by the above molecules were also determined. From these measurements, the rate coefficients for reactive and nonreactive loss of O(1D) were calculated. These results are discussed in terms of their atmospheric relevance and trends in reactivity of O(1D) with hydrocarbons upon halogen substitution. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550250607
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  • 9
    Electronic Resource
    Electronic Resource
    Kinetics of Cl(2P) reactions with CF3CHCl2, CF3CHFCl, and CH3CFCl2 (1993)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 833-844 
    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 removal of Cl atoms by reaction with three HCFCs, CF3CHCl2 (HCFC-123), CF3CHFCl (HCFC-124), and CH3CFCl2 (HCFC 141b), were measured as a function of temperature between 276 and 397 K. CH3CF2Cl (HCFC-142b) was studied only at 298 K. The Arrhenius expressions obtained are: k1 = (3.94 ± 0.84)× 10-12 exp[-(1740 ± 100)/T] cm3 molecule-1 s-1 for CF3CHCl2 (HCFC 123); k2 = (1.16 ± 0.41) × 10-12 exp[-(1800 ± 150)/T] cm3 molecule-1 s-1 for CF3CHFCl (HCFC 124); and k3 = (1.6 ± 1.1) × 10-12 exp[-(1800 ± 500)/T] cm3 molecule-1 s-1 for CH3CFCl2 (HCFC 141b). In case of HCFC 141b, non-Arrhenius behavior was observed at temperatures above ca. 350 K and is attributed to the thermal decomposition of CH2CFCl2 product into Cl + CH2CFCl. In case of HCFC-142b, only an upper limit for the 298 K value of the rate coefficient was obtained. The atmospheric significance of these results are discussed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550251005
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  • 10
    Electronic Resource
    Electronic Resource
    Does the HO2 radical react with H2S, CH3SH, and CH3SCH3? (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 355-365 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the title reactions were investigated in a discharge flow tube by using laser magnetic resonance detection of HO2. The upper limits for the bimolecular rate constants for the reactions of HO2 with H2S (k1), CH3SH (k2), and CH3SCH3 (k3) are 〈3 × 10-15, 〈4 × 10-15, and 〈5 × 10-15 cm3 molecule-1 s-1, respectively, at 298 K. Our upper limit for k1 is three orders of magnitude lower than the previously reported value.Measurements at higher temperatures also yield similar upper limits. Our results suggest that HO2 is not an important oxidant for these reduced compounds in the atmosphere. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260306
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