title: Quantum Chemical Molecular Dynamics Simulations of 1,3-Dichloropropene Combustion.
abstract: Oxidative decomposition of 1,3-dichloropropene was investigated using quantum chemical molecular dynamics (QM/MD) at 1500 and 3000 K. Thermal oxidation of 1,3-dichloropropene was initiated by (1) abstraction of allylic H/Cl by O2 and (2) intra-annular C-Cl bond scission and elimination of allylic Cl. A kinetic analysis shows that (2) is the more dominant initiation pathway, in agreement with QM/MD results. These QM/MD simulations reveal new routes to the formation of major products (H2O, CO, HCl, CO2), which are propagated primarily by the chloroperoxy (ClO2), OH, and 1,3-dichloropropene derived radicals. In particular, intra-annular C-C/C-H bond dissociation reactions of intermediate aldehydes/ketones are shown to play a dominant role in the formation of CO and CO2. Our simulations demonstrate that both combustion temperature and radical concentration can influence the product yield, however not the combustion mechanism.
authors.affiliation: Newcastle Institute for Energy and Resources, The University of Newcastle , Callaghan, NSW 2308, Australia.
authors.forename: Nwakamma
authors.initials: N
authors.lastname: Ahubelem
authors.affiliation: Newcastle Institute for Energy and Resources, The University of Newcastle , Callaghan, NSW 2308, Australia.
authors.forename: Kalpit
authors.initials: K
authors.lastname: Shah
authors.affiliation: Newcastle Institute for Energy and Resources, The University of Newcastle , Callaghan, NSW 2308, Australia.
authors.forename: Behdad
authors.initials: B
authors.lastname: Moghtaderi
authors.affiliation: Newcastle Institute for Energy and Resources, The University of Newcastle , Callaghan, NSW 2308, Australia.
authors.forename: Alister J
authors.initials: AJ
authors.lastname: Page
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D006843:Hydrocarbons, Chlorinated; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory
chemical_list: D000498:Allyl Compounds; D006843:Hydrocarbons, Chlorinated; C023891:1,3-dichloro-1-propene