Solubility determination and comparison of β-HMX and RDX in two binary mixed solvents (acetonitrile + water, nitric acid + water)

doi:10.1016/j.cjche.2023.12.016

摘要/Abstract

摘要： In order to remove hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), the main impurity, in process of polymorphic transformation of octrahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), the solubility of β-HMX and RDX in acetonitrile (ACN) + water in the temperature range of 288.15-333.15 K and in nitric acid (HNO₃) + water in the temperature range of 298.15-333.15 K were measured by laser dynamic method. The results showed that the solubility of both β-HMX and RDX in binary mixed solvents increased monotonously as the temperature increase at a given solvent composition or with increasing of mole fraction of solvent (ACN and nitric acid). Solubility data were well correlated by the modified Apelblat equation, Jouyban-Acree model, Yaws equation and van't Hoff equation, and the Yaws equation achieved the best fitting results according to the relative error and the mean square error root. Furthermore, the solubility of β-HMX and RDX in binary mixed solvent was compared, based on the solubility difference and the solvent's own properties, the best separation degree of β-HMX and RDX was found when the mole fraction of nitric acid was 0.22 at room temperature, which provided data support for HMX crystallization in mixed solvent. The solubility differences between RDX and β-HMX in mixed solvents were explained from the formation of intermolecular and intramolecular hydrogen bonds.

关键词: Solubility, Octrahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, Hexahydro-1,3,5-trinitro-1,3,5-triazine, Separation, Model, Hydrogen bond

Abstract: In order to remove hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), the main impurity, in process of polymorphic transformation of octrahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), the solubility of β-HMX and RDX in acetonitrile (ACN) + water in the temperature range of 288.15-333.15 K and in nitric acid (HNO₃) + water in the temperature range of 298.15-333.15 K were measured by laser dynamic method. The results showed that the solubility of both β-HMX and RDX in binary mixed solvents increased monotonously as the temperature increase at a given solvent composition or with increasing of mole fraction of solvent (ACN and nitric acid). Solubility data were well correlated by the modified Apelblat equation, Jouyban-Acree model, Yaws equation and van't Hoff equation, and the Yaws equation achieved the best fitting results according to the relative error and the mean square error root. Furthermore, the solubility of β-HMX and RDX in binary mixed solvent was compared, based on the solubility difference and the solvent's own properties, the best separation degree of β-HMX and RDX was found when the mole fraction of nitric acid was 0.22 at room temperature, which provided data support for HMX crystallization in mixed solvent. The solubility differences between RDX and β-HMX in mixed solvents were explained from the formation of intermolecular and intramolecular hydrogen bonds.

Key words: Solubility, Octrahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, Hexahydro-1,3,5-trinitro-1,3,5-triazine, Separation, Model, Hydrogen bond

Yuehua Yao, Fan Wang, Yinguang Xu, Zishuai Xu, Lizhen Chen, Jianlong Wang. Solubility determination and comparison of β-HMX and RDX in two binary mixed solvents (acetonitrile + water, nitric acid + water)[J]. 中国化学工程学报, 2024, 69(5): 238-249.

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