CHINESE JOURNAL OF ENERGETIC MATERIALS
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CL-20/1,4-DNI共晶形成的热力学
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1.西南科技大学环境友好能源材料国家重点实验室,四川 绵阳 621010;2.四川临港五洲工程设计有限公司,四川 泸州 646003

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国家自然基金(11572270);环境友好能源材料国家重点实验室自主课题资助(18fksy0217)


Thermodynamic on the Formation of CL-20/1,4-DNI Cocrystal
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1.State Key Laboratory of Environment-feriendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, China;2.Sichuan Lingang Wuzhou Engineering Design Co., Ltd., Luzhou 646003, China

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    摘要:

    为了获得共晶形成的热力学判据,为结晶溶剂和过程参数的筛选和优化提供理论指导,开展了六硝基六氮杂异戊兹烷(CL-20)/1,4-二硝基咪唑(1,4-DNI)共晶形成的热力学研究。分别以丙酮、乙酸乙酯和甲醇为结晶溶剂,采用高效液相色谱(HPLC)测定了CL-20和1,4-DNI在纯溶剂的溶解度,以及CL-20在不同浓度(0.04,0.06,0.08,0.10,0.12,0.16,0.20,0.24 g·mL-1)1,4-DNI溶液中的溶解度,绘制得到CL-20/1,4-DNI/溶剂三元相图;基于溶液化学中的平衡理论,通过对溶解度数据的拟合,计算得到共晶的溶度积Ksp、络合常数K11及反应自由能ΔG0等热力学参数。结果表明,共晶组分在溶剂中的溶解度越大且组分间溶解度差异越小,其三元相图中的共晶区域越大、形状越对称。三种溶剂中共晶区域由大到小的顺序为:丙酮>乙酸乙酯>甲醇,且在丙酮和乙酸乙酯中共晶区域形状更对称;热力学参数的计算结果显示,在三种溶剂中,丙酮最有利于CL-20/1,4-DNI共晶的形成,其次是乙酸乙酯;不同温度下丙酮溶剂中的三元相图和热力学参数表明,降低结晶温度有利于CL-20/1,4-DNI共晶的析出。

    Abstract:

    In order to provide the thermodynamic criterion for the cocrystal formation and give theoretical basis for the screening and optimization of crystallization solvents and parameters, the thermodynamic of hexanitrohexaazaisowurtzitane (CL-20)/1,4-dinitroimidazole (1,4-DNI) cocrystal formation has been investigated. Taking acetone, ethyl acetate and methanol as solvents, the solubility data of CL-20, 1,4-DNI in pure solvents and CL-20 in 1,4-DNI solutions with different concentrations (0.04, 0.06, 0.08, 0.10, 0.12, 0.16, 0.20, 0.24 g·mL-1) were achieved with the help of high performance liquid chromatography. The ternary phase diagrams of CL-20/1,4-DNI solvents were built. The thermodynamic parameters of the solubility product Ksp, the complexation constant K11, and the reaction free energy ΔG0 were obtained through fitting the solubility data based on the mathematical models of solution chemistry theory. The results show that if the solubilities of CL-20 and 1,4-DNI are larger and their discrepency is less in a solvent, the cocrystal region is larger and its shape is more symmetrical. The order of the cocrystal regions in the three solvents from large to small is acetone > ethyl acetate > methanol, and the shape of the cocrystal region in the acetone and ethyl acetate is more symmetrical. The calculated thermodynamic parameters indicate that the acetone is the most beneficial to the formation of CL-20/1,4-DNI cocrystal among the three solvents, followed by ethyl acetate. The ternary phase diagram and thermodynamic parameters in acetone solvent at different temperatures show that lowering the crystallization temperature is beneficial to the precipitation of the CL-20/1,4-DNI cocrystal.

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引用本文

董海燕,龙义强,周婷婷,等. CL-20/1,4-DNI共晶形成的热力学[J].含能材料, 2020, 28(9):819-825. DOI:10.11943/CJEM2020057.
DONG Hai-yan, LONG Yi-qiang, ZHOU Ting-ting, et al. Thermodynamic on the Formation of CL-20/1,4-DNI Cocrystal[J]. Chinese Journal of Energetic Materials, 2020, 28(9):819-825. DOI:10.11943/CJEM2020057.

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  • 收稿日期: 2020-03-16
  • 最后修改日期: 2020-06-17
  • 录用日期: 2020-05-26
  • 在线发布日期: 2020-06-17
  • 出版日期: 2020-09-25