TY - JOUR
T1 - Ab Initio Kinetics of Methylamine Radical Thermal Decomposition and H-Abstraction from Monomethylhydrazine by H-Atom
AU - Sun, Hongyan
AU - Vaghjiani, Ghanshyam L.
AU - Law, Chung K.
N1 - Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/5/14
Y1 - 2020/5/14
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85084694223&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85084694223&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.0c02389
DO - 10.1021/acs.jpca.0c02389
M3 - Article
C2 - 32299215
AN - SCOPUS:85084694223
SN - 1089-5639
VL - 124
SP - 3747
EP - 3753
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 19
ER -