The thermal decomposition of azomethane-d6

✍ Scribed by Do-Ren Chang; O. K. Rice

• Publisher: John Wiley and Sons
• Year: 1969
• Tongue: English
• Weight: 962 KB
• Volume: 1
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550010205

✦ Synopsis

Ihe 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 N, , CD, , and C,D, . .\ mechanism is suggested which accounts for these results fairly well. A com- parison 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, production, extrapolated to zero N O pressure, measures the rate of the initial step CD,N,CD, + 2 CDzi + N, . This has an activation energy at high pressures of 50.7 kcal per mole and an Arrhenius A.factor of 101s,49 sec-l. This is to be compared to values of 55.5 and found by Forst and Rice for CH,N,CH, + 2 CH, + N, . The pressure fall-off behavior for CD,N,CD, + 2 CD, + hT2 has also been investigated and compared to the theoretical curses, which seem to fit satisfactorily except a t the lowest pressure, where experimental errots may be large. Unexpectedly, the fall-off curve crosses that for CH,N,CH, + 2 CH, + N,. I t is suggested that the extrapolation to zero N O pressure may not be entirely correct in the CH,K,CH, case where the chain is longer than with CD,N,CD, .

It is believed that the decomposition of azomethane-d, is a better example for unimolecular-rate theory than is that of azomethane.