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Two-stage decomposition of 2-hydroxyethylhydrazinium nitrate (HEHN)
Combustion and Flame ( IF 4.4 ) Pub Date : 2020-10-01 , DOI: 10.1016/j.combustflame.2020.06.028
Alan A. Esparza , Steven D. Chambreau , Ghanshyam L. Vaghjiani , Evgeny Shafirovich

Abstract The hydrazine-derived ionic liquid 2-hydroxyethylhydrazinium nitrate (HEHN) is a promising fuel component of green monopropellants. For successful implementation of these propellants, it is necessary to understand the kinetics and mechanism of HEHN decomposition, but the available data are scarce. The objective of the present work was to investigate the kinetics of HEHN thermal decomposition using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) as well as to identify the evolved gas products with mass spectrometry (MS) and Fourier-transform infrared (FTIR) spectroscopy. Both TGA and DSC have revealed that the decomposition of high-purity HEHN has two distinct stages. The effective kinetic parameters of both stages were determined using the Ozawa-Wall-Flynn, Kissinger, and model-based methods. The model-based analysis has shown autocatalytic behaviour of the involved reactions and produced apparent activation energies of 113.7 ± 1.7 kJ/mol at the first stage and 123.6 ± 2.5 kJ/mol at the second stage, close to the literature data (124.8 kJ/mol) on the autocatalytic reaction between HEHN and HNO3. The evolved gas analysis has shown that the first stage generates H2O, N2, NH3, NO, N2O, and NO2, while the second stage also generates HNO3 and CO2. The observed existence of two stages in the thermal decomposition of HEHN could be explained by the formation of a condensed by product, which, in turn, decomposes via a highly activated reaction during the second (high-temperature) stage.

中文翻译:

2-羟乙基肼硝酸盐(HEHN)的两阶段分解

摘要 肼衍生的离子液体硝酸 2-羟乙基肼 (HEHN) 是一种很有前途的绿色单组元推进剂燃料组分。为了成功实施这些推进剂,有必要了解 HEHN 分解的动力学和机制,但可用数据很少。本工作的目的是使用热重分析 (TGA) 和差示扫描量热法 (DSC) 研究 HEHN 热分解的动力学,并使用质谱法 (MS) 和傅里叶变换红外 (FTIR) 鉴定释放的气体产物。 ) 光谱学。TGA 和 DSC 都表明高纯度 HEHN 的分解有两个不同的阶段。使用 Ozawa-Wall-Flynn、Kissinger 和基于模型的方法确定两个阶段的有效动力学参数。基于模型的分析显示了相关反应的自催化行为,并在第一阶段产生了 113.7 ± 1.7 kJ/mol 的表观活化能,在第二阶段产生了 123.6 ± 2.5 kJ/mol,接近文献数据 (124.8 kJ/mol)。 mol) 关于 HEHN 和 HNO3 之间的自催化反应。逸出气体分析表明,第一阶段产生 H2O、N2、NH3、NO、N2O 和 NO2,而第二阶段也产生 HNO3 和 CO2。在 HEHN 的热分解中观察到的两个阶段的存在可以通过形成冷凝副产物来解释,该副产物反过来在第二(高温)阶段通过高度活化的反应分解。在第二阶段为 6 ± 2.5 kJ/mol,接近 HEHN 与 HNO3 之间自催化反应的文献数据(124.8 kJ/mol)。逸出气体分析表明,第一阶段产生 H2O、N2、NH3、NO、N2O 和 NO2,而第二阶段也产生 HNO3 和 CO2。在 HEHN 的热分解中观察到的两个阶段的存在可以通过形成冷凝副产物来解释,该副产物反过来在第二(高温)阶段通过高度活化的反应分解。在第二阶段为 6 ± 2.5 kJ/mol,接近 HEHN 与 HNO3 之间自催化反应的文献数据(124.8 kJ/mol)。逸出气体分析表明,第一阶段产生 H2O、N2、NH3、NO、N2O 和 NO2,而第二阶段也产生 HNO3 和 CO2。在 HEHN 的热分解中观察到的两个阶段的存在可以通过形成冷凝副产物来解释,该副产物反过来在第二(高温)阶段通过高度活化的反应分解。
更新日期:2020-10-01
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