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  • 1995-1999  (6)
  • 1
    Electronic Resource
    Electronic Resource
    Laser flash photolysis studies of radical–radical reaction kinetics: The O(3PJ)+BrO reaction (1995)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 4131-4142 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A novel dual laser flash photolysis-long path absorption-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reaction O(3PJ)+BrO→k1Br(2PJ)+O2 as a function of temperature (231–328 K) and pressure (25–150 Torr) in N2 buffer gas. The experimental approach preserves the principal advantages of the flash photolysis method, i.e., complete absence of surface reactions and a wide range of accessible pressures, but also employs techniques which are characteristic of the discharge flow method, namely chemical titration as a means for deducing the absolute concentration of a radical reactant and use of multiple detection axes. We find that k1 is independent of pressure, and that the temperature dependence of k1 is adequately described by the Arrhenius expression k1(T)=1.91×10−11 exp(230/T) cm3 molecule−1 s−1; the absolute accuracy of measured values for k1 is estimated to vary from ±20% at T∼230 K to ±30% at T∼330 K. Our results demonstrate that the O(3PJ)+BrO rate coefficient is significantly faster than previously "guesstimated,'' and suggest that the catalytic cycle with the O(3PJ)+BrO reaction as its rate-limiting step is the dominant stratospheric BrOx odd-oxygen destruction cycle at altitudes above 24 km. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.468541
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    A Mechanistic Study of the Reaction of OH with Dimethyl-d6 Sulfide. Direct Observation of Adduct Formation and the Kinetics of the Adduct Reaction with O2 (1995)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 16967-16975 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100046a024
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    The atmospheric chemistry of dimethylsulfoxide (DMSO) kinetics and mechanism of the OH+DMSO reaction (1996)
    Springer
    Journal of atmospheric chemistry 24 (1996), S. 23-37 
    Details
    ISSN: 1573-0662
    Keywords: hydroxyl radical ; dimethylsulfoxide ; kinetics ; sulfur cycle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with dimethylsulfoxide and its deuterated analogue. A rate coefficient of (1.0±0.3)×10-10 cm3 molecule-1 s-1 was obtained ar room temperature. The rate coefficient was independent of pressure over the range 25–700 Torr, showed no dependence on the nature of the buffer gas and showed no kinetic isotope effect. A limited study of the temperature dependence indicated that the reaction displays a negative activation energy. The gas phase ultraviolet absorption spectrum was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross-section at 205 nm, the absorption peak, is (1.0±0.3)×10-17 cm2, where the large uncertainty results from experimental difficulties associated with the low vapor pressure and ‘stickiness’ of DMSO.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00053821
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetics of the reaction of O(3P) with CF3NO (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 369-377 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the reaction of O(3P) with CF3NO (k2) as a function of temperature. Our results are described by the Arrhenius expression k2(T) = (4.54 ± 0.70) × 10-12 exp[(-560± 46)/T] cm3molecule-1 s-1 (243 K ≤ T ≤ 424 K); errors are 2σ and represent precision only. The O(3P) + CF3NO reaction is sufficiently rapid that CF3NO cannot be employed as a selective quencher for O2(a1Δg) in laboratory systems where O(3P) and O2(a1Δg) coexist, and where O(3P) kinetics are being investigated. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550270408
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  • 5
    Electronic Resource
    Electronic Resource
    Branching ratios for BrO production from reactions of O(1D) with HBr, CF3Br, CH3Br, CF2ClBr, and CF2HBr (1998)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 555-563 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Laser-flash photolysis of RBr/O3/SF6/He mixtures at 248 nm has been coupled with BrO detection by time-resolved UV absorption spectroscopy to measure BrO product yields from O(1D) reactions with HBr, CF3Br, CH3Br, CF2ClBr, and CF2HBr at 298±3 K. The measured yields are: HBr, 0.20±0.04; CF3Br, 0.49±0.07; CH3Br, 0.44±0.05; CF2ClBr, 0.31±0.06; and CF2HBr, 0.39±0.07 (uncertainties are 2σ and include estimates of both random and systematic errors). The results are discussed in light of other available information or O(1D)+RBr reactions. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 555-563, 1998
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 6
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of atomic chlorine with H2S, D2S, CH3SH, and CD3SD (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 359-368 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Time-resolved resonance fluorescence detection of atomic chlorine following 266-nm laser flash photolysis of Cl2CO/RSR'/N2 mixtures has been employed to study the kinetics of Cl reactions with H2S(k1), CH3SH(k2), D2S(k3), and CD3SD(k4) as a function of temperature (193-431 K) and pressure (25-600 torr). Arrhenius expressions which describe our results are (units are 10-11 cm3molecule-1s-1; uncertainties are 2σ, precision only) k1 = (3.69 ± 0.33) exp[(208 ± 24)/T], k2 = (11.9 ± 1.7) exp[(151 ± 38)/T], and k3 = (1.93 ± 0.32) exp[(168 ± 42)/T]. The Cl + CD3SD reaction has been studied at 299 K and 396 K; values for k4 at these two temperatures are essentially the same as those measured for k2. Our results are compared with earlier studies and the mechanistic implications of observed negative activation energies and H—D kinetic isotope effects are discussed. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550270407
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