Science and Technology of Energetic Materials

Vol.76, No.3 (2015)

Research paper

Effect of nitration agent and water on thermal behavior during the nitration of sulfamates
Yuji Sugie and Atsumi Miyake


Ammonium dinitramide (ADN) has attracted significant interest as a potential oxidizer for next-generation rocket propellants because it is a halogen-free alternative to the widely used ammonium perchlorate. During the synthesis of ADN, N-nitration is required to form the N-(NO2)2 group, in conjunction with the decomposition of sulfamate. The study reported herein used calorimetry to assess thermal variations during the nitration of both K and NH4 sulfamates, applying a number of different nitration agents (HNO3/H2SO4, HNO3/H2SO4+H2O, HNO3/AcOH and HNO3). It was determined that the heat of decomposition of the sulfamates in HNO3/H2SO4 at 0℃ was greater than at 20℃, although the similar trend was not observed in HNO3/AcOH and HNO3. The heats of decomposition in HNO3/AcOH and in HNO3 were greater than in HNO3/H2SO4 because of how the nitration reagent affects the relative contributions of different pathways to the decomposition process. The heat of decomposition in HNO3/H2SO4+H2O was less than that in HNO3/H2 SO4 because the addition of water inhibits both nitration and decomposition by HNO3. Under such conditions, however, a second exothermic peak is observed, due to the hydrolysis of potassium sulfamate.

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ammonium dinitramide, sulfamate, nitration, reaction calorimetry, hydrolysis

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