单甲基肼与四氧化二氮液相反应的Ab - Inito化学动力学模型。

IF 2.8 2区 化学 Q3 CHEMISTRY, PHYSICAL
The Journal of Physical Chemistry A Pub Date : 2025-05-08 Epub Date: 2025-04-23 DOI:10.1021/acs.jpca.5c00893
Dan Liu, Lidong Zhang, Peng Zhang
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引用次数: 0

摘要

单甲基肼(MMH)和四氧化二氮(NTO)作为自燃双推进剂应用于航天器发动机已有多年,但液相MMH/NTO的反应机理尚不清楚。本理论研究探讨了MMH与NTO的液相反应。采用隐式溶剂模型,在CCSD(T)/CBS//M06-2X/6-311++G(d,p)/SMD理论水平上进行了高精度量子化学计算,得到了NTO异构化反应、MMH与T - onono2反应以及MMH与NO2反应的反应路径。在CCSD(T)/CBS//M06-2X/6-311++G(d,p)理论水平下,计算了相应的气相反应路径。结果表明,由于溶剂的作用,液相反应的能垒低于气相反应的能垒。利用过渡态理论计算了速率常数。我们建立了动力学模型,并应用该模型模拟了液相MMH/NTO在预混合和绝热条件下的早期反应。结果表明,从初始温度(-13℃)上升到MMH沸点温度(87.5℃)所需的时间约为0.05 μs,与前人在跌落试验中观察到的结果一致。动力学分析表明,反应步骤N2O4→t-ONONO2和CH3NHNH2 + t-ONONO2→CH3NH2 + N2O + HNO3对后续反应的触发起关键作用,从而决定了升温速率。本研究不仅为液相MMH/NTO反应提供了新的动力学模型,而且阐明了液相反应在MMH/NTO自燃过程中的作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Ab Inito Chemical Kinetics Modeling of Liquid-phase Reactions of Monomethylhydrazine and Nitrogen Tetroxide.

Monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) have been utilized as hypergolic bipropellants in spacecraft engines for many years, but the liquid-phase MMH/NTO reaction mechanism remains underexplored. This theoretical study investigates the liquid-phase reactions between MMH and NTO. By employing an implicit solvent model and conducting high-accuracy quantum chemical calculations at the CCSD(T)/CBS//M06-2X/6-311++G(d,p)/SMD theoretical level, we obtained the reaction paths for the isomerization reactions of NTO, for the reactions between MMH and t-ONONO2, and for the reactions between MMH and NO2. The corresponding reaction pathways in the gas phase were also computed for comparison at the CCSD(T)/CBS//M06-2X/6-311++G(d,p) theoretical level. The results indicate that the energy barriers for the liquid-phase reactions are lower than their gas-phase counterparts due to the solvent effects. The rate constants were calculated using the transition state theory. We established a kinetic model and applied it to simulate the early stage of the liquid-phase MMH/NTO reactions under premixed and adiabatic conditions. The results indicate that the required time for temperature rising from the initial temperature (-13 °C) to the boiling point temperature of MMH (87.5 °C) is approximately 0.05 μs, consistent with previous experimental observations in drop tests. In addition, the kinetic analysis revealed that the reaction steps N2O4t-ONONO2 and CH3NHNH2 + t-ONONO2 → CH3NH2 + N2O + HNO3 play critical roles in triggering the subsequent reactions, thereby dictating the rate of temperature rise. This work not only provides a new kinetic model for liquid-phase MMH/NTO reactions but also clarifies the role of liquid-phase reactions in the hypergolic ignition of MMH/NTO.

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来源期刊
The Journal of Physical Chemistry A
The Journal of Physical Chemistry A 化学-物理:原子、分子和化学物理
CiteScore
5.20
自引率
10.30%
发文量
922
审稿时长
1.3 months
期刊介绍: The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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