PHOTOCHEMICAL AND THERMOCHEMICAL DECOMPOSITION OF 3-NITRO-1,2,4-TRIAZOL-5-ONE AND PERDEUTERIO-3-NITRO-1,2,4-TRIAZOL-5-ONE IN NEAT AND MIXED SYSTEMS

被引:51
作者
MENAPACE, JA [1 ]
MARLIN, JE [1 ]
BRUSS, DR [1 ]
DASCHER, RV [1 ]
机构
[1] ALBANY COLL PHARM,ALBANY,NY 12208
关键词
D O I
10.1021/j100167a028
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Electron paramagnetic resonance spectroscopy (EPR) and high performance liquid chromatography (HPLC) are used to examine the decomposition of 3-nitro-1,2,4-triazol-5-one (NTO), NTO-d2, NTO (NTO-d2) in acetone (acetone-d6), and NTO (NTO-d2) in 2,4,6-trinitrotoluene (TNT) (TNT-d5) under photochemical and thermochemical decomposition conditions. Room-temperature photochemical decomposition of NTO (NTO-d2)/acetone (acetone-d6) solutions monitored by EPR shows that the NTO nitro group abstracts hydrogen atoms from other NTO species and/or acetone as evidenced by the observation of EPR spectra associated with NTO hydroxy nitroxide radicals. The aryl hydroxy nitroxide and aryl benzyl nitroxide radical spectra observed in the NTO (NTO-d2)/TNT (TNT-d5) thermochemical decompositions at 370 K also show that nitro group/hydrogen abstraction reactions are operative in these systems. The hydrogen abstraction reactivity order present in these systems is found to be NO2,TNT/H(NTO) > NO2,NTO/CH3,TNT > NO2,NTO/NH(NTO), NO2,TNT/CH3,TNT almost-equal-to 0. These experiments also indicate that the mixtures undergo accelerated decomposition relative to the neat materials due to contributions from cross reactions occurring between NTO and TNT. The HPLC global kinetics studies conducted between 498 and 518 K show that the loss of NTO (NTO-d2) proceeds by a solid-state global autocatalytic reaction scheme for which initiation and propagation reactions contribute to the observed kinetic behavior. The decompositions are found to possess an average global activation energy of 88.0 kcal/mol. A primary kinetic deuterium isotope effect of 1.67 (2.44 at 298 K) is also observed which indicates that nitrogen-hydrogen bond cleavage plays a significant role in the loss of NTO (NTO-d2).
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页码:5509 / 5517
页数:9
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