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The thermal decomposition of azomethane‐d 6
Author(s) -
Chang DoRen,
Rice O. K.
Publication year - 1969
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550010205
Subject(s) - chemistry , arrhenius equation , thermal decomposition , activation energy , decomposition , extrapolation , analytical chemistry (journal) , stereochemistry , organic chemistry , mathematical analysis , mathematics
The thermal decomposition of azomethane‐d 6 has been studied. There is a short chain reaction, and measurements have been made of the rate of production of N 2 , CD 4 , and C 2 D 6 . 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 N 2 production, extrapolated to zero NO pressure, measures the rate of the initial step CD 3 N 2 CD 3 → 2 CD 3 + N 2 . This has an activation energy at high pressures of 50.7 kcal per mole and an Arrhenius A ·factor of 10 15.49 sec −1 . This is to be compared to values of 55.5 and 10 17.3 found by Forst and Rice for CH 3 N 2 CH 3 → 2 CH 3 + N 2 . The pressure fall‐off behavior for CD 3 N 2 CD 3 → 2 CD 3 + N 2 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 CH 3 N 2 CH 3 → 2 CH 3 + N 2 . It is suggested that the extrapolation to zero NO pressure may not be entirely correct in the CH 3 N 2 CH 3 case where the chain is longer than with CD 3 N 2 CD 3 . It is believed that the decomposition of azomethane‐d 6 is a better example for unimolecular‐rate theory than is that of azomethane.