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  • 1
    Electronic Resource
    Electronic Resource
    Arrhenius parameters for the decomposition of the t-butoxy radical (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1053-1055 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140910
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  • 2
    Electronic Resource
    Electronic Resource
    Reaction of methoxy radicals with oxygen. I. Using dimethyl peroxide as a thermal source of methoxy radicals (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1045-1053 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using dimethyl peroxide as a thermal source of methoxy radicals overthe temperature range of 110-160°C, and the combination of methoxy radicals and nitrogen dioxide as a reference reaction: a value was determined of the rate constant for the reaction of methoxy radicals with oxygen: is independent of nitrogen dioxide or oxygen concentration and added inert gas (carbon tetrafluoride). No heterogeneous effects were detected. The value of k4 is given by the expression \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }k_4 {\rm = 9}{\rm .0} \pm {\rm 0}{\rm .6 - 4}{\rm .8 } \pm {\rm 1}{\rm .1/}\theta {\rm (M}^{{\rm - 1}} \cdot \sec ^{ - 1}) $$\end{document} In terms of atmospheric chemistry, this corresponds to a value of 105.6 M-1·sec-1 at 298 K. Extrapolation to temperatures where the combustion of organic compounds has been studied (813 K) produces a value of 107.7 M-1·sec-1 for k4. Under these conditions, reaction (4) competes with hydrogen abstraction or disproportionation reactions of the methoxy radical and its decomposition (3): In particular k3 is in the falloff region under these conditions. It is concluded that reaction (4) takes place as the result of a bimolecular collision process rather than via the formation of a cyclic complex.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111003
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  • 3
    Electronic Resource
    Electronic Resource
    Decomposition of the t-butoxy radical  -  I. Studies over the temperature range 402-443 K (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 391-400 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By allowing the t-butoxy radical to decompose in the presence of nitric oxide, it has been possible to determine rate constants for decomposition by the measurements of the relative rates (2) and (3) Process (3) is clearly pressure dependent. The value of k3(∞) has been determined in the presence of several inert gases (CF4, SF6, N2, and Ar) and a value of k3 interpolated for atmospheric conditions. The results may be compared with those for other relevant alkoxy radicals at room temperature. Extrapolated values for k3 in the presence of CF4 lead to the result \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 (\infty)/s^{ - 1} = 10^{14.6 \pm 0.6} \exp (- 8052 \pm 604/T) $$\end{document}
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190502
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