Shock-initiation chemistry of nitroarenes
- DX-1, Mail Stop P-952, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States)
- Department of Chemistry, New Mexico Institute of Mining and Technology, Socorro, New Mexico 87801 (United States)
We present evidence that the shock-initiation chemistry of nitroarenes is dominated by the intermolecular hydrogen transfer mechanism discussed previously. The acceleration by pressure, kinetic isotope effect, and product distribution are consistent with the bimolecular transition state rather than rate-determining C-N homolysis. GC-MS analysis of samples which were subjected to a shock wave generated by detonation of nitromethane shows that nitrobenzene produces aniline and biphenyl, and {ital o}-nitrotoluene forms aniline, toluene, {ital o}-toluidine and {ital o}-cresol, but not anthranil, benzoxazinone, or cyanocyclopentadiene. In isotopic labeling experiments {ital o}-nitrotoluene and TNT show extensive H-D exchange on their methyl groups, and C-N bond rupture is not consistent with the formation of aniline from nitrobenzene or nitrotoluene, nor the formation of {ital o}-toluidine from {ital o}-nitrotoluene. Recent work incorporating fast TOF mass spectroscopy of samples shocked and quenched by adiabatic expansion indicates that the initial chemical reactions in shocked solid nitroaromatic explosives proceed along this path. {copyright} {ital 1998 American Institute of Physics.}
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 295481
- Report Number(s):
- CONF-970707-; ISSN 0094-243X; TRN: 9902M0046
- Journal Information:
- AIP Conference Proceedings, Vol. 429, Issue 1; Conference: Meeting of the topical group on shock compression of condensed matter of the American Physical Society, Amherst, MA (United States), 27 Jul - 1 Aug 1997; Other Information: PBD: Jul 1998
- Country of Publication:
- United States
- Language:
- English
Similar Records
Structural Insight into the Dioxygenation of Nitroarene Compounds: the Crystal Structure of Nitrobenzene Dioxygenase
STUDY OF MECHANISMS OF CERTAIN OXIDATION-REDUCTION REACTIONS BY ISOTOPE METHODS