THERMAL-DECOMPOSITION OF ENERGETIC MATERIALS .3. TEMPORAL BEHAVIORS OF THE RATES OF FORMATION OF THE GASEOUS PYROLYSIS PRODUCTS FROM CONDENSED-PHASE DECOMPOSITION OF 1,3,5-TRINITROHEXAHYDRO-S-TRIAZINE
THERMAL-DECOMPOSITION OF ENERGETIC MATERIALS .3. TEMPORAL BEHAVIORS OF THE RATES OF FORMATION OF THE GASEOUS PYROLYSIS PRODUCTS FROM CONDENSED-PHASE DECOMPOSITION OF 1,3,5-TRINITROHEXAHYDRO-S-TRIAZINE
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DOI：
10.1021/j100201a036
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发表时间：
1992-10-29
影响因子：
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通讯作者：
BULUSU, S
中科院分区：
文献类型：
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作者：
BEHRENS, R;BULUSU, S
通过同时热重调制束质谱（STMBMS）测量、飞行时间（TOF）速度谱分析和H-2、C-13、N-15和O-18标记的1，3，5-三硝基六氢均三嗪（RDX）类似物，确定了RDX的热分解产物为H_2O、HCN、CO、CH_2O、NO、N_2O、NH_2CHO、NO_2、HONO，（CH_3）NHCHO、氧代均三嗪（OST）和1-亚硝基-3，5-二硝基六氢均三嗪（ONDNTA）以及它们所有的气体生成速率都已被测量为时间的函数。从这些结果中，控制RDX在固相和液相中的分解的主要反应途径已被发现。四个主要的反应途径控制RDX在200和215摄氏度之间的液相中的分解。两个途径都是一级反应，只在RDX中。一种主要产生OST、NO和H2O，约占分解RDX的30%，另一种主要产生N2 O和CH 2 O，以及少量的NO2、CO和NH 2CHO，约占分解RDX的10%。第三种途径是NO和RDX反应生成ONDNTA，然后ONDNTA分解为CH 2 O和N2 O。第四种反应途径包括通过与由先前分解的RDX的分解产物形成的催化剂反应来分解RDX。第三和第四反应通道各占分解的RDX的约30%。固相RDX的实验表明，其分解速率比液相RDX慢得多。ONDNTA是唯一的产品，似乎是在固态RDX分解的早期阶段形成的。随着固相分解的进行，N2 O和较少量的CH 2 O开始析出，并且它们的析出速率增加，直到与液相RDX分解相关的产物出现，并且所有产物的气体形成速率迅速增加。这种行为强烈表明，固体RDX的分解发生通过在晶格内形成ONDNTA，随后在晶格内分解为N2 O和CH 2 O，然后CH 2 O分散在RDX中，导致其最终液化和液相分解反应的开始。
Through the use of simultaneous thermogravimetry modulated beam mass spectrometry (STMBMS) measurements, time-of-flight (TOF) velocity-spectra analysis, and H-2, C-13, N-15, and O-18 labeled analogues of 1,3,5-trinitrohexahydro-s-triazine (RDX), the thermal decomposition products of RDX have been identified as H2O, HCN, CO, CH2O, NO, N2O, NH2CHO, NO2, HONO, (CH3)NHCHO, oxy-s-triazine (OST), and 1-nitroso-3,5-dinitrohexahydro-s-triazine (ONDNTA) and all of their gas formation rates have been measured as a function of time. From these results the primary reaction pathways that control the decomposition of RDX in both the solid and liquid phases have been discovered. Four primary reaction pathways control the decomposition of RDX in the liquid phase between 200 and 215-degrees-C. Two pathways are first-order reactions solely in RDX. One produces predominantly OST, NO, and H2O and accounts for approximately 30% of the decomposed RDX, and the other produces predominantly N2O and CH2O with smaller amounts of NO2, CO, and NH2CHO and accounts for 10% of the decomposed RDX. The third pathway consists of formation of ONDNTA by reaction between NO and RDX, followed by the decomposition of ONDNTA to predominantly CH2O and N2O. The fourth reaction pathway consists of decomposition of RDX through reaction with a catalyst that is formed from the decomposition products of previously decomposed RDX. The third and fourth reaction channels each account for approximately 30% of the decomposed RDX. Experiments with solid-phase RDX have shown that its decomposition rate is very much slower than that of liquid-phase RDX. ONDNTA is the only product that appears to be formed during the early stages of the decomposition of RDX in the solid phase. As the solid-phase decomposition progresses, N2O and lesser amounts of CH2O start to evolve and their rates of evolution increase until products associated with the liquid-phase RDX decomposition appear and the rates of gas formation of all products rapidly increase. This behavior strongly suggests that the decomposition of solid RDX occurs through formation of ONDNTA within the lattice, the subsequent decomposition of it within the lattice to N2O and CH2O, followed by the dispersion of CH2O in the RDX, leading to its eventual liquefaction and the onset of the liquid-phase decomposition reactions.