Published online by Cambridge University Press: 15 February 2011
The effects of physical properties and molecular conformation on the thermal decomposition kinetics of several cyclic nitramines are examined and compared to the decomposition of RDX. The compounds used in the study are: octahydro-1,3,5,7-tetranitro- 1,3,5,7-tetrazocine (HMX), hexahydro-l-nitroso-3,5-dinitro-s-triazine (ONDNTA), 1,3,5- trinitro- 1,3,5-triazacycloheptane (TNCHP), and 2-oxo-1,3,5-trinitro-1,3,5-triazacyclohexane (K6). The decomposition pathways of HMX in the liquid phase are similar to the four parallel decomposition pathways that control the decomposition of RDX in the liquid phase. The products formed during the thermal decomposition of ONDNTA arise from multiple reaction pathways. The identities and temporal behaviors of the ONDNTA decomposition products are discussed. TNCHP is thermally stable in the liquid phase. The decomposition products from TNCHP are formed via multiple reaction pathways. One decomposition pathway for TNCHP is through its mononitroso intermediate. TNCHP does not form a stable product that is analogous to oxy-s-triazine (OST) formed in RDX or the smaller ring fragments formed in the liquid-phase decomposition of HMX. K6 is less thermally stable and the decomposition mechanism is much simpler than that of RDX, HMX and TNCHP. The thermal decomposition of K6 occurs between 150 and 180 °C. The products formed during the decomposition of K6 are mainly CH2O and N2O with minor amounts or HCN, CO, NO, and NO2.
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