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.

Infrared spectroscopy in superfluid helium droplets

“…Early spectroscopic works in He droplets containing N He = 10 3 -10 4 atoms focused on several small single molecules and molecular cluster targets such as SF 6 [5,6,32,57], OCS [33,34,58,59], HCCCN [60], CH 3 OH [61], HCN [62], HF [63,64], HCl [65,66], H 2 O [67,68], C 2 H 6 [69], CO 2 [70,71], NH 3 [72][73][74], CH 4 [75][76][77], and NO [78,79]. It was discovered that, contrary to the spectra in ordinary matrices, vibrational bands of dopants in superfluid droplets often demonstrate well-resolved rotational structure [32][33][34]57].…”

“…Later, infrared absorption experiments in free 4 He clusters revealed that the rotational structure is observed in even smaller clusters containing one molecule (OCS, CO, CO 2 , N 2 O, HCCCNN) and up to~100 attached 4 He atoms [92][93][94][95][96][97][98]. The clusters are formed via co-expansion of the molecules and He gas at low T ≈50-100 K. Figure 5(a) shows the dependence of the ground state rotational constant (B) in OCS-He N clusters vs N He (red circle) [92].…”

Formation of persistent organic pollutants from 2,4,5-trichlorothiophenol combustion: a density functional theory investigation

“…There is close correlation between the concentrations of PCDT and PCTA, and their dioxin analogues, indicating that similar chemical mechanisms dictate their formation during combustion [13]. Furthermore, since chlorinated hydrocarbons (1,3-dichloropropene [14][15][16] and particularly chlorophenols [17]) are known to be key precursors of PCDD and PCDF during combustion, it is likely that chlorothiophenol is a precursor for the formation of the PCDT and PCTA analogues. A previous report has demonstrated that the presence of sulfur in the precursor moiety, as opposed to oxygen, lowers enthalpic barriers in this respect [18].…”