Thermal decomposition of energetic materials. 4. Deuterium isotope effects and isotopic scrambling condensed-phased decomposition of 1,3,5-trinitrohexahydro-s-triazine. Special publication
The inter- versus intra-molecular origin of the products formed in the thermal decomposition of 1,3,5-trinitrohexahydro-S-triazine (RDX) has been traced by isotopic crossover experiments using mixtures of differently labeled analogues of RDX. The isotopic analogues of RDX used in the experiments include 2H, 13C, 15N, and 18O. The fraction of isotopic scrambling and the extent of the deuterium kinetic isotope effect (DKIE) are reported for the different thermal decomposition products. Isotopic scrambling is not observed for the N-N bond in N2O and only in small amounts (7%) in the C-H bonds in CH2O, consistent with a mechanism of their formation through methylene nitramine precursors. A product, oxy-s-triazine (OST, C3H3N3O), does not undergo isotopic scrambling in H/D, 14N/15N, or 13C/18O experiments, and its rate of formation exhibits a DKIE of 1.5. These results are consistent with the formation of OST via unimolecular decomposition of RDX. Another product, 1-nitroso-3,5-dinitrohexahydro-S-triazine (ONDNTA, C3H6N605), is found to be formed with complete scrambling of the N-NO bond, suggesting an N-N bond cleavage and a radical recombination process in its formation. One of the hydrogen containing products, H2O, exhibits a DKIE of 1.5 + or - 0.1. In contrast, CH2O and ONDNTA have DKIEs of 1.05 + or - 0.1 and 1.05 + or - 0.2, respectively, indicating that hydrogen transfer is not involved in the rate-limiting step of the reaction pathway leading to the formation of these products.... RDX, OST, ONDNTA, Isotope effect, Isotopic scrambling, Thermal decomposition.
- Research Organization:
- Sandia Labs., Livermore, CA (United States)
- OSTI ID:
- 6538430
- Report Number(s):
- AD-A-261804/9/XAB
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
360605 -- Materials-- Radiation Effects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
400800 -- Combustion
Pyrolysis
& High-Temperature Chemistry
AZINES
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMBUSTION
DATA
DECOMPOSITION
DEUTERIUM
ELEMENTS
EVALUATION
EXPERIMENTAL DATA
EXPLOSIVES
HETEROCYCLIC COMPOUNDS
HYDROGEN
HYDROGEN ISOTOPES
HYDROGEN TRANSFER
INFORMATION
IONIZATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
MOLECULAR STRUCTURE
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
PHYSICAL PROPERTIES
PROPELLANTS
PYROLYSIS
REACTION KINETICS
STABLE ISOTOPES
THERMAL DEGRADATION
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