ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The thermal decomposition of azomethane-d6 has been studied. There is a short chain reaction, and measurements have been made of the rate of production of N2, CD4, and C2D6. A mechanism is suggested which accounts for these results fairly well. A comparison is made with some similar results of Forst for azomethane. Measurements have also been made of the reaction inhibited by NO. It is believed that the N2 production, extrapolated to zero NO pressure, measures the rate of the initial step CD3N2CD3 → 2 CD3 + N2. This has an activation energy at high pressures of 50.7 kcal per mole and an Arrhenius A·factor of 1015.49 sec-1. This is to be compared to values of 55.5 and 1017.3 found by Forst and Rice for CH3N2CH3 → 2 CH3 + N2. The pressure fall-off behavior for CD3N2CD3 → 2 CD3 + N2 has also been investigated and compared to the theoretical curves, which seem to fit satisfactorily except at the lowest pressure, where experimental errors may be large. Unexpectedly, the fall-off curve crosses that for CH3N2CH3 → 2 CH3 + N2. It is suggested that the extrapolation to zero NO pressure may not be entirely correct in the CH3N2CH3 case where the chain is longer than with CD3N2CD3. It is believed that the decomposition of azomethane-d6 is a better example for unimolecular-rate theory than is that of azomethane.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550010205
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