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  • Chemistry  (3)
  • 1
    Electronic Resource
    Electronic Resource
    Gas-phase chlorine-initiated photooxidation of methanol and isopropanol (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 173-182 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of CH3OH/Cl2/air, CH3OH/Cl2/NO2/air, and (CH3)2CHOH/Cl2/NO2/air at 28 ± 2°C was studied using the long-path FTIR method. The primary reactions of methanol and isopropanol with Cl atoms were α-hydrogen abstraction (100%), and α hydrogen (85%), and α-hydrogen abstraction (15%), respectively. The failure to detect hydroxyalkyl-peroxy nitrates suggested that the oxygen addition to α-hydroxy radicals is not important. From the product distribution an upper limit of the ratio of oxygen addition to CH2OH and CH3CHOH was estimated to be about 6 and 7%, respectively. The oxygen addition ratio to (CH3)2COH was very low. The reaction mechanism is also discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140207
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Products and mechanism for the OH radical initiated oxidation of acrylonitrile, methacrylonitrile, and allylcyanide in the presence of NO (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1385-1399 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photooxidation of acrylonitrile, methacylonitrile, and allylcyanide in the presence of NO was studied in parts per million concentration using the long-path Fourier transform IR spectroscopic method. The stoichiometry of the OH radical initiated oxidation of methacrylonitrile was established as \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {{\rm OH}} \right) + {\rm CH}_{\rm 2} = {\rm C}\left( {{\rm CH}_{\rm 3} } \right){\rm CN + 2NO + 2O}_{\rm 2} \mathop {\hbox to 20pt{\rightarrowfill}}\limits^{1.0} {\rm HCHO + CH}_{\rm 3} {\rm COCN + 2NO}_{{\rm 2}} + \left( {{\rm OH}} \right) $\end{document}. The yield of HCHO for acrylonitrile and allylcyanide was found to be ca. 100 and 80%, and the stoichiometric reactions were assessed to proceed, \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {{\rm OH}} \right) + {\rm CH}_{\rm 2} = {\rm CHCN + 2NO + 2O}_{\rm 2} \mathop {\hbox to 20pt{\rightarrowfill}}\limits^{1.0} {\rm HCHO + HCOCN + 2NO}_{\rm 2} + \left( {{\rm OH}} \right) $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {{\rm OH}} \right) + {\rm CH}_{\rm 2} = {\rm CHCH}_{\rm 2} {\rm CN + 2NO + 2O}_{\rm 2} \mathop {\hbox to 20pt{\rightarrowfill}}\limits^{0.8} {\rm HCHO + HCOCH}{\rm 2} {\rm CN + 2NO}_{\rm 2} + \left( {{\rm OH}} \right) $\end{document}, respectively. These results revealed that the reaction mechanism for these unsaturated organic cyanides are analogous to that of olefins.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550161110
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetic measurements of methyl and ethyl nitrate reactions with OH radicals (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 933-941 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction rate coefficients of methyl and ethyl nitrates with OH radicals were determined by the relative rate method in 1 atmosphere of oxygen. Reactions were initiated by the photochemical formation of OH radicals utilizing the reaction: H2O+O(1D)→2OH. O(1D) was obtained through a stationary photolysis of excess ozone in an experimental system under black light irradiation. Measurements were carried out for various combinations with different reference materials. Rate coefficients obtained were (0.30±0.032 (2σ)×10-13 cm3molecule-1s-1 (Temp.: 304-310 K) for methyl nitrate and (2.0±0.70)× 10-13 cm3molecule-1s-1 (298-310 K) for ethyl nitrate. For methyl nitrate, this data indicates the preference of a smaller rate coefficient between the two values reported in the literature [1,2], which have shown large discrepancies of more than one order of magnitude. For ethyl nitrate, only one measurement has been reported [2]. However, the present result suggests that the reported value was overestimated by a factor of more than two. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet: 29: 933-941, 1997.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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    Paper (German National Licenses)
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