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

Hongyan Sun, Ghanshyam L. Vaghjiani, Chung K. Law

Research output: Contribution to journalArticle

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.

Original languageEnglish (US)
Pages (from-to)3747-3753
Number of pages7
JournalJournal of Physical Chemistry A
Volume124
Issue number19
DOIs
StatePublished - May 14 2020

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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