NH2与二甲醚和乙醚反应的理论动力学研究:动力学模型的意义

IF 1.5 4区 化学 Q4 CHEMISTRY, PHYSICAL
Binod Raj Giri, Tam V.-T. Mai, Krishna Prasad Shrestha, Sushant Giri, R. Thirumaleswara Naik, Rakhi Verma, Fabian Mauss, Lam K. Huynh
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引用次数: 0

摘要

氨(NH3)和氢(H2)已成为有望通过减少温室气体排放来帮助缓解全球变暖的无碳燃料。我们目前正在进行的研究重点是了解NH3与含氧化合物和碳氢化合物混合物的燃烧特性,揭示碳氮交叉反应在准确模拟其燃烧行为中的关键作用。氨基(NH2)自由基在氨和富氮环境中大量存在,对nh3 -烃/氧混合物的低温反应性产生强烈影响,影响其整体反应性和排放特性。认识到NH2自由基的重要性,我们研究了NH2与二甲醚(DME, CH3OCH3)和乙醚(DEE, CH3CH2OCH2CH3)的反应动力学,采用适当的高级从头算和统计速率理论方法。我们计算了CCSD(T)/cc-pV(T, Q)Z//M06-2X/aug-cc-pVTZ理论能级的势能分布,分析了这些醚在不同C─H位上NH2自由基的反应活性。结合这些新导出的速率参数,我们更新的动力学模型成功捕获了以前的实验数据,解决了我们早期研究中遇到的建模挑战。我们的发现,包括对NH2自由基影响的见解,有助于理解氨燃烧及其在实现碳中和能源系统中的潜力。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Theoretical Kinetic Study of NH2 Reactions With Dimethyl Ether and Diethyl Ether: Implications for Kinetic Modeling

Theoretical Kinetic Study of NH2 Reactions With Dimethyl Ether and Diethyl Ether: Implications for Kinetic Modeling

Ammonia (NH3) and hydrogen (H2) have emerged as promising carbon-free fuels to help mitigate global warming by reducing greenhouse gas emissions. Our ongoing research currently focuses on understanding the combustion characteristics of NH3 blends with oxygenates and hydrocarbons, uncovering the critical role of carbon–nitrogen cross-reactions in accurately modeling their combustion behavior. Amino (NH2) radicals, which are abundant in ammonia and nitrogen-rich environments, strongly influence the low-temperature reactivity of NH3-hydrocarbon/oxygenate mixtures, affecting overall reactivity and emission characteristics. Recognizing the importance of NH2 radicals, we investigated the reaction kinetics of NH2 with dimethyl ether (DME, CH3OCH3) and diethyl ether (DEE, CH3CH2OCH2CH3) using appropriate high-level ab initio and statistical rate theory methods. We computed the potential energy profiles at the CCSD(T)/cc-pV(T, Q)Z//M06-2X/aug-cc-pVTZ level of theory, analyzing the reactivity of NH2 radicals at various C─H sites of these diethers. Incorporating these newly derived rate parameters, our updated kinetic model successfully captures previous experimental data, addressing the modeling challenges encountered in our earlier studies. Our findings, including insights into the impact of NH2 radicals, contribute to an understanding of ammonia combustion and its potential in achieving carbon-neutral energy systems.

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来源期刊
CiteScore
3.30
自引率
6.70%
发文量
74
审稿时长
3 months
期刊介绍: As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.
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