Thermal decomposition of 1,3,3-trinitroazetidine in the gas phase, solution, and melt
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1,3,3-Trinitroazetidine (TNAZ) was synthesized using the alternative approach based on the transformation of 3-oximino-1-(p-toluenesulfonyl)azetidine in the reaction with nitric acid through intermediate pseudonitrol. The thermal decomposition of TNAZ in the gas phase, melt and m-dinitrobenzene solution in a wide concentration range (5–80%) was studied by manometry, volumetry, thermogravimetry, IR spectroscopy, and mass spectrometry. In the gas phase in the temperature range from 170 to 220°C the thermal decomposition proceeds according to the first-order kinetic law with the activation energy 40.5 kcal mol−1 and pre-exponential factor 1015.0 s−1. The major gaseous reaction products are N2, NO, NO2, CO2, H2O, and nitroacetaldehyde, and trace amounts of CO and HCN are formed. The rate-determining step of the process is the homolytic cleavage of the N-NO2 bond in the TNAZ molecule. In melt at 170–210 °C the thermal decomposition proceeds with the pronounced self-acceleration and the maximum reaction rates are observed at conversions 53.9–67.4%. The solid decomposition products accelerate the reaction. It is most likely that the autocatalysis of TNAZ decomposition in the liquid phase is due to the autocatalytic decomposition of 1-nitroso-3,3-dinitroazetidine, which is formed by the thermal decomposition of TNAZ. In m-dinitrobenzene TNAZ also decomposes with self-acceleration. The higher the concentration in the solution, the more pronounced the self-acceleration. Additives of picric acid moderately accelerate the thermal decomposition of TNAZ, whereas hexamethylenetetraamine additives exert a strong acceleration.
Key words1,3,3-trinitroazetidine synthesis thermal decomposition thermogravimetry IR spectroscopy mass spectrometry kinetics volumetry
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