Determination of Initial Chemical Steps in the Gas-Phase Decomposition of Energetic Molecules
Abstract
Laser-powered homogeneous pyrolysis (LPHP) has been successfully used to provide conditions where surface-sensitive substrates can be indirectly heated by an infrared laser and allowed to react while remote from potentially catalytic surfaces. The use of the comparative rate technique with LPHP provides and accurate indirect temperature measurement and has made practical the extraction of thermal, decomposition Arrhenius parameters. A laser-heated, GC/ MS-monitored, stirred-flow reaction cell has been used with cyclohexene as the internal temperature standard to determine Arrhenius parameters for the homogeneous gas phase thermal decomposition of nitrotoluene (o-NT), and 2,4- dinitrotoleune (2,4-DNT). In all cases the principal rate-limiting step is the homolysis of the Ar-NO2 bond. The measured Arrhenius parameters for homolysis of the Ar-NO2 bond. The measured Arrhenius parameters for homolysis range from log A = 14.5 to 16.4, and from Ea = 67.0 to 70.0 kcal/mol. The bond dissociation energies derived from the results are 71.4, 73.2, 71.4, 70.2, and 70.6 kcal/mol, respectively, for the above series of compounds.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 09, 1986
- Accession Number
- ADA163751
Entities
People
- David M. Golden
- Donald F. Mcmillen
Organizations
- SRI International