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International Journal of Energetic Materials and Chemical Propulsion
ESCI SJR: 0.149 SNIP: 0.16 CiteScore™: 0.29

ISSN Imprimer: 2150-766X
ISSN En ligne: 2150-7678

International Journal of Energetic Materials and Chemical Propulsion

DOI: 10.1615/IntJEnergeticMaterialsChemProp.v5.i1-6.1050
pages 1028-1030

THERMAL DECOMPOSITION OF 1,3,3-TRINITROAZETIDINE IN GAS AND LIQUID PHASE

V. V. Nedelko
Institute of Chemical Physics Problems of Russian Academy of Sciences, (142432 Chemogolovka, Moscow Region, Russia)
B. L. Korsounskii
Institute of Chemical Physics Problems of Russian Academy of Sciences, (142432 Chemogolovka, Moscow Region, Russia)
N. V. Chukanov
Institute of Chemical Physics Problems of Russian Academy of Sciences, (142432 Chemogolovka, Moscow Region, Russia)
T. S. Larikova
Institute of Chemical Physics Problems of Russian Academy of Sciences, (142432 Chemogolovka, Moscow Region, Russia)
N. N. Makhova
Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences (117977 Moscow, Russia)
I. V. Ovchinnikov
Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences (117977 Moscow, Russia)

RÉSUMÉ

1,3,3-Trinitroazetidine (TNAZ) is the prospective high-energy explosive with some practically important properties (low sensitivity, high thermal stability, low melting point). The thermal decomposition kinetics of TNAZ have been investigated by the method of volumetry in gas and liquid phase. The gas-phase reaction (the temperature range was 170−220°C) followed the first order kinetics and obeyed Arrhenius equation k = 1015,67±0,6exp[−(40500 ± 1400)/RT] s−1, where R = 1,987 cal·mol−1·K−1. According to IR-spectrophotometric data the complete TNAZ decomposition at 220°C resulted in the formation of N2, NO2, CO2, O2NCH2CHO and the traces of CO and NO. We explained the formation of nitroacetaldehyde (O2NCH2CHO) by the decomposition of intermediate 3,3-dinitroazetidine. The total quantity of the gaseous products non-condensed at normal conditions was about 4 moles per 1 mole of TNAZ. The more complex kinetics has been measured for TNAZ decomposition in m-dinitrobenzene solution (180−231°C). One could observe the small self-acceleration of the process at low reaction conversions (from 10% up to 25%) and gas-formation level increasing from 4 to 5 moles per 1 mole of TNAZ. Simultaneously, the nitrogen content in the gaseous decomposition products was reduced from 14% in the case of the gas-phase reaction to the traces. TNAZ decomposition in solution was described by the Arrhenius equation:
k (s−1) = 1016.60±1.20 · exp[−(44800 ± 2800)/RT] (R = 1,987 cal/mol , r = 0,998)


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