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Effect of the density of nitric acid on thermal behavior during sulfamate nitration

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Abstract

Ammonium dinitramide (ADN) has attracted significant interest as a potential oxidizer for next-generation rocket propellants, since it is a halogen-free alternative to the widely used oxidizer ammonium perchlorate. Because ADN synthesis requires N-nitration generates a very unstable intermediate to form the N–(NO2)2 group, this study used a reaction calorimeter to assess the heat of decomposition during the nitration of potassium sulfamate with various nitration agents (HNO3/H2SO4 and HNO3) by using the HNO3 density between 1.52 and 1.38 gcm−3. The heat of decomposition of potassium sulfamate in HNO3 was found to decrease with decreasing HNO3 density. In contrast, the heat of decomposition did not decrease with density in HNO3/H2SO4, since a significant temperature rise was generated when combining the lower density HNO3 with H2SO4. The heat of decomposition in high-density HNO3 (1.52 gcm−3) was greater than that in the mixed acid, likely because protonation of the potassium sulfate nitrogen by H2SO4 inhibited the subsequent nitration step.

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Authors and Affiliations

  1. Japan Carlit, 1-17-10 Kyobashi, Chuo-ku, Tokyo, 104-0031, Japan

    Yuji Sugie

  2. Yokohama National University, 79-7 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa, 240-8501, Japan

    Atsumi Miyake

Authors
  1. Yuji Sugie
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  2. Atsumi Miyake
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Correspondence to Yuji Sugie.

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Sugie, Y., Miyake, A. Effect of the density of nitric acid on thermal behavior during sulfamate nitration. J Therm Anal Calorim 121, 275–279 (2015). https://doi.org/10.1007/s10973-015-4564-6

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  • DOI: https://doi.org/10.1007/s10973-015-4564-6

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