TY - JOUR
T1 - Decomposition of ethylamine through bimolecular reactions
AU - Altarawneh, Mohammednoor
AU - Almatarneh, Mansour H.
AU - Marashdeh, Ali
AU - Dlugogorski, Bogdan Z.
N1 - Funding Information:
This study has been supported by grants of computing time from the National Computational Infrastructure (NCI) Australia , and the Pawsey Supercomputing Centre in Perth, as well as funds from the Australian Research Council (ARC) . M. H. A. is grateful to the Atlantic Computational Excellence Network (ACEnet) for computer time. We thank reviewers for their useful and detailed comments that helped us to improve th manuscript.
Publisher Copyright:
© 2015 The Combustion Institute.
PY - 2016/1/1
Y1 - 2016/1/1
N2 - Ethylamine (EA) often serves as a surrogate species to represent aliphatic amines that occur in biofuels. This contribution reports, for the first time, the thermochemical and kinetic parameters for bimolecular reactions of EA with three prominent radicals that form in the initial stages of biomass decomposition; namely, H, CH3 and NH2. Abstraction of a methylene H atom from the EA molecule largely dominates H loss from the two other sites (i.e., methyl and amine hydrogens) for the three considered radicals. We demonstrate that, differences in bond dissociation enthalpies of methylene C-H bonds among EA, ethanol and propane reflect their corresponding HOMO/LUMO energy gaps. At low and intermediate temperatures, the rate of H abstraction from the methylene site in EA exceeds the corresponding values for propane and ethanol. As the temperature rises, matching entropic factors induce comparable rate constants for the three molecules.
AB - Ethylamine (EA) often serves as a surrogate species to represent aliphatic amines that occur in biofuels. This contribution reports, for the first time, the thermochemical and kinetic parameters for bimolecular reactions of EA with three prominent radicals that form in the initial stages of biomass decomposition; namely, H, CH3 and NH2. Abstraction of a methylene H atom from the EA molecule largely dominates H loss from the two other sites (i.e., methyl and amine hydrogens) for the three considered radicals. We demonstrate that, differences in bond dissociation enthalpies of methylene C-H bonds among EA, ethanol and propane reflect their corresponding HOMO/LUMO energy gaps. At low and intermediate temperatures, the rate of H abstraction from the methylene site in EA exceeds the corresponding values for propane and ethanol. As the temperature rises, matching entropic factors induce comparable rate constants for the three molecules.
KW - Ethylamine
KW - H abstraction reactions
KW - Nitrogen content in biomass
KW - Reaction rate constants
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U2 - 10.1016/j.combustflame.2015.10.032
DO - 10.1016/j.combustflame.2015.10.032
M3 - Article
AN - SCOPUS:84949921845
SN - 0010-2180
VL - 163
SP - 532
EP - 539
JO - Combustion and Flame
JF - Combustion and Flame
ER -