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  • 1
    Electronic Resource
    Electronic Resource
    Gas phase reactions of alkyl nitrates with hydroxyl radicals under tropospheric conditions in comparison with photolysis (1989)
    Springer
    Journal of atmospheric chemistry 9 (1989), S. 419-433 
    Details
    ISSN: 1573-0662
    Keywords: OH radical ; alkyl nitrates ; photolysis frequency ; lifetime
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Rate constants for the reaction of OH radicals with some branched alkyl nitrates have been measured applying a competitive technique. Methyl nitrite photolysis in synthetic air was used as OH radical source at 295±2 K and 1000 mbar total pressure. Using a rate constant of 2.53×10-12 cm3 s-1 for the reaction of OH radicals with n-butane as reference, the following rate constants were obtained (units: 10-12 cm3 s-1): isopropyl nitrate, 0.59±0.22; isobutyl nitrate, 1.63±0.20; 3-methyl-2-butyl nitrate, 1.95±0.15; 2-methyl-1-butyl nitrate, 2.50±0.15; 3-methyl-1-butyl nitrate, 2.55±0.35. These values have been combined with the literature data to recalculate the substituent factors F(X) for the different nitrate groups which can be used to predict OH rate constants for organic nitrates for which experimental data are not available. Preliminary measurements of the photolysis frequency of isopropyl nitrate have shown that for this nitrate as a model substance, OH reactions and direct photolysis are of equal importance under tropospheric conditions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00114754
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  • 2
    Electronic Resource
    Electronic Resource
    Relative-rate study of the gas-phase reaction of hydroxy radicals with difunctional organic nitrates at 298 K and atmospheric pressure (1991)
    Springer
    Journal of atmospheric chemistry 13 (1991), S. 301-311 
    Details
    ISSN: 1573-0662
    Keywords: Organic nitrates ; kinetics ; OH radical ; atmosphere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Rate coefficients for the reactions of difunctional nitrates with atmospherically important OH radicals are not currently available in the literature. This study represents the first determination of rate coefficients for a number of C(3) and C(4) carbonyl nitrates and dinitrates with OH radicals in a 38 l glass reaction chamber at 1000 mbar total pressure of synthetic air by 298±2 K using a relative kinetic technique. The following rate coefficients (in units of 10-12 cm3 molecule-1 s-1) were obtained: 1,2-propandiol dinitrate, 〈0.31; 1,2-butandiol dinitrate, 1.70±0.32; 2,3-butandiol dinitrate, 1.07±0.26; α-nitrooxyacetone, 〈0.43; 1-nitrooxy-2-butanone, 0.91±0.16; 3-nitrooxy-2-butanone, 1.27±0.14; 1,4-dinitrooxy-2-butene, 15.10±1.45; 3,4-dinitrooxy-1-butene, 10.10±0.50. The possible importance of reaction of OH as an atmospheric sink for the compounds compared to other loss processes is considered.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00058137
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