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Ab Initio Kinetics of Methylamine Radical Thermal Decomposition and H-Abstraction from Monomethylhydrazine by H-Atom

Author(s): Sun, Hongyan; Vaghjiani, Ghanshyam L; Law, Chung K

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Abstract: Methylamine radicals (CH3NH) and amino radicals (NH2) are major products in the early pyrolysis/ignition of monomethylhydrazine (CH3NHNH2). Ab initio kinetics of thermal decomposition of CH3NH radicals was analyzed by RRKM master equation simulations. It was found that β-scission of the methyl H-atom from CH3NH radicals is predominant and fast enough to induce subsequent H-abstraction reactions in CH3NHNH2 to trigger ignition. Consequently, the kinetics of H-abstraction reactions from CH3NHNH2 by H-atoms was further investigated. It was found that the energy barriers for abstraction of the central amine H-atom, two terminal amine H-atoms, and methyl H-atoms are 4.16, 2.95, 5.98, and 8.50 kcal mol–1, respectively. In units of cm3 molecule–1 s–1, the corresponding rate coefficients were found to be k8 = 9.63 × 10–20T2.596 exp(−154.2/T), k9 = 2.04 × 10–18T2.154 exp(104.1/T), k10 = 1.13 × 10–20T2.866 exp(−416.3/T), and k11 = 2.41 × 10–23T3.650 exp(−870.5/T), respectively, in the 290–2500 K temperature range. The results reveal that abstraction of the terminal amine H-atom to form trans-CH3NHNH radicals is the dominant channel among the different abstraction channels. At 298 K, the total theoretical H-abstraction rate coefficient, calculated with no adjustable parameters, is 8.16 × 10–13 cm3 molecule–1 s–1, which is in excellent agreement with Vaghjiani’s experimental observation of (7.60 ± 1.14) × 10–13 cm3 molecule–1 s–1 ( J. Phys. Chem. A 1997, 101, 4167−4171, DOI: 10.1021/jp964044z).
Publication Date: 2020
Citation: Sun, Hongyan, Ghanshyam L. Vaghjiani, and Chung K. Law. "Ab Initio Kinetics of Methylamine Radical Thermal Decomposition and H-Abstraction from Monomethylhydrazine by H-Atom." The Journal of Physical Chemistry A 124, no. 19 (2020): 3747-3753. doi:10.1021/acs.jpca.0c02389
DOI: 10.1021/acs.jpca.0c02389
ISSN: 1089-5639
EISSN: 1520-5215
Pages: 3747 - 3753
Type of Material: Journal Article
Journal/Proceeding Title: Journal of Physical Chemistry A
Version: Author's manuscript

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