Chambreau Steven D, Popolan-Vaida Denisia M, Kostko Oleg, Lee Jae Kyoo, Zhou Zhenpeng, Brown Timothy A, Jones Paul, Shao Kuanliang, Zhang Jingsong, Vaghjiani Ghanshyam L, Zare Richard N, Leone Stephen R
Jacobs Technology, Inc., Edwards Air Force Base, California 93524, United States.
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
J Phys Chem A. 2022 Jan 27;126(3):373-394. doi: 10.1021/acs.jpca.1c07408. Epub 2022 Jan 11.
To develop chemical kinetics models for the combustion of ionic liquid-based monopropellants, identification of the elementary steps in the thermal and catalytic decomposition of components such as 2-hydroxyethylhydrazinium nitrate (HEHN) is needed but is currently not well understood. The first decomposition step in protic ionic liquids such as HEHN is typically the proton transfer from the cation to the anion, resulting in the formation of 2-hydroxyethylhydrazine (HEH) and HNO. In the first part of this investigation, the high-temperature thermal decomposition of HEH is probed with flash pyrolysis (<1400 K) and vacuum ultraviolet (10.45 eV) photoionization time-of-flight mass spectrometry (VUV-PI-TOFMS). Next, the investigation into the thermal and catalytic decomposition of HEHN includes two mass spectrometric techniques: (1) tunable VUV-PI-TOFMS (7.4-15 eV) and (2) ambient ionization mass spectrometry utilizing both plasma and laser ionization techniques whereby HEHN is introduced onto a heated inert or iridium catalytic surface and the products are probed. The products can be identified by their masses, their ionization energies, and their collision-induced fragmentation patterns. Formation of product species indicates that catalytic surface recombination is an important reaction process in the decomposition mechanism of HEHN. The products and their possible elementary reaction mechanisms are discussed.
为了开发基于离子液体的单推进剂燃烧的化学动力学模型,需要确定诸如硝酸2-羟乙基肼(HEHN)等组分在热分解和催化分解过程中的基元步骤,但目前对此还没有很好的理解。质子型离子液体(如HEHN)的第一步分解通常是质子从阳离子转移到阴离子,从而形成2-羟乙基肼(HEH)和HNO。在本研究的第一部分,采用快速热解(<1400 K)和真空紫外(10.45 eV)光电离飞行时间质谱(VUV-PI-TOFMS)对HEH的高温热分解进行了研究。接下来,对HEHN热分解和催化分解的研究包括两种质谱技术:(1)可调谐VUV-PI-TOFMS(7.4-15 eV)和(2)利用等离子体和激光电离技术的常压电离质谱,将HEHN引入加热的惰性或铱催化表面,并对产物进行探测。产物可以通过其质量、电离能和碰撞诱导碎裂模式来识别。产物物种的形成表明催化表面重组是HEHN分解机理中的一个重要反应过程。讨论了产物及其可能的基元反应机理。