ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction of hydrogen atoms with methyl nitrite was studied in a fast-flow system using photoionization mass spectrometry and excess atomic hydrogen. The associated bimolecular rate coefficient can be expressed by \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (4.3 \pm 0.9) \times 10^{- 13}\, {\rm exp\,}[- (1900 \pm 110){\rm cal}/{\rm mol} \cdot RT]\,{\rm cm}^3 /{\rm molecule} \cdot {\rm sec} $$\end{document} in the temperature range of 223-398°K. NO, CH3OH, CH4, C2H6, CH2O, and H2O are the main products; OH and CH3 radicals were detectable intermediates. The mechanism was deduced from the observed product yields using normal and deuterated reactants. The primary reaction steps were identified as followed by a rapid unimolecular decomposition of CH2ONO into CH2O and NO. Since the extent of reaction channel (1b) could not be determined independently, only extreme limits could be obtained for the individual contributions of the two channels of reaction (3) which follows the generation of CH3O radicals: The most probable values, k3a/k3 = 0.31 ± 0.30 and k3b/k3 = 0.69 ± 0.30, support the previous results on this reaction, although the range of uncertainties is much greater here.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550090209
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