ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The thermal decomposition of azomethane (A) has been studied in a static system at temperatures between 250° and 320°C and at pressures between 5 and 402 torr, with particular attention to identification of products. Major products, in decreasing order of importance, were nitrogen, methane, ethane, methylethyldiimide, dimethylhydrazone, propane, tetramethylhydrazine, ethylene, methylpropyldiimide, and methylethylhydrazone. Carbon balance at the lowest pressure and highest temperature was 92%, but decreased with increasing pressure and decreasing temperature owing to the formation of a polymer. A fairly simple mechanism accounts reasonably well for a short chain in the decomposition, propagated by the radical CH3N2CH2 (B), and for the five most abundant products, except ethane. It turns out that there is a second source of ethane, arising by C2H5 + A → C2H6 + B; this explains an anomalously high apparent activation energy for the reaction CH3 + A → CH4 + B. Ethyl radicals are also shown to be responsible for the formation of propane, ethylene, methylethylhydrazone, and methylpropyldiimide. The radical B decomposes to CH3 + CH2 + N2, and the methylene radical (probably both singlet and triplet) is shown to yield C2H5 at low pressure and high temperature, and mostly polymer at high pressure and low temperature.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550050418
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