Thermal Decomposition of Dimethylnitramine and Dimethylnitrosamine by Pulsed Laser Pyrolysis

Article abstract of DOI:10.1021/j100340a020

Pyrolysis of dimethylnitramine (DMNA) and dimethylnitrosamine (DMNO) was carried out in a flow system over the temperature range 800-900 K using pulsed infrared laser heating, via SF6 in a 250-Torr bath of CO2 and radical scavanger.Arrhenius parameters for DMNO and DMNA composition were log k(s^-1)=(15.8+/-1.1)-(50.0+/-3.4)/2.3RT and (13.5+/-0.6)-(37.4+/-2.5)/2.3RT, respectively.The former set of parameters is consistentwith simple bond scission as the rate-limiting step; the latter set, which was produced with different scavengers, temperature standards, and varying amounts of added NO as a radical trap, is not consistent with simple bond scission.The experimental reaults can be reproduced via a mechanistic numerical model in which N-NO2 bond scission and nitro-nitrite rearrangement are competitive initial steps and the displacement of NO2 from DMNA by NO is included as a low-temperature route to DMNO.