TY - JOUR
T1 - Formation of chlorobenzenes by oxidative thermal decomposition of 1,3-dichloropropene
AU - Ahubelem, Nwakamma
AU - Shah, Kalpit
AU - Moghtaderi, Behdad
AU - Altarawneh, Mohammednoor
AU - Dlugogorski, Bogdan Z.
AU - Page, Alister J.
N1 - Funding Information:
This study was supported by Australian Research Council (ARC) Discovery Project funding and supercomputing grants from The National Computational Infrastructure (NCI) National Facility and INTERSECT. N.A. thanks The University of Newcastle for a postgraduate research scholarship and Prof. Keiji Morokuma (Kyoto University) for useful discussions.
Publisher Copyright:
© 2015 The Combustion Institute.
PY - 2015/6/1
Y1 - 2015/6/1
N2 - We combine combustion experiments and density functional theory (DFT) calculations to investigate the formation of chlorobenzenes from oxidative thermal decomposition of 1,3-dichloropropene. Mono- to hexa-chlorobenzenes are observed between 800 and 1150. K, and the extent of chlorination was proportional to the combustion temperature. Higher chlorinated congeners of chlorobenzene (tetra-, penta-, hexa-chlorobenzene) are only observed in trace amounts between 950 and 1050. K. DFT calculations indicate that cyclisation of chlorinated hexatrienes proceeds via open-shell radical pathways. These species represent key components in the formation mechanism of chlorinated polyaromatic hydrocarbons. Results presented herein should provide better understanding of the evolution of soot from combustion/pyrolysis of short chlorinated alkenes.
AB - We combine combustion experiments and density functional theory (DFT) calculations to investigate the formation of chlorobenzenes from oxidative thermal decomposition of 1,3-dichloropropene. Mono- to hexa-chlorobenzenes are observed between 800 and 1150. K, and the extent of chlorination was proportional to the combustion temperature. Higher chlorinated congeners of chlorobenzene (tetra-, penta-, hexa-chlorobenzene) are only observed in trace amounts between 950 and 1050. K. DFT calculations indicate that cyclisation of chlorinated hexatrienes proceeds via open-shell radical pathways. These species represent key components in the formation mechanism of chlorinated polyaromatic hydrocarbons. Results presented herein should provide better understanding of the evolution of soot from combustion/pyrolysis of short chlorinated alkenes.
KW - 1,3-Dichloropropene
KW - Chlorobenzene
KW - Combustion
KW - Cyclisation
KW - Density functional theory
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U2 - 10.1016/j.combustflame.2015.02.008
DO - 10.1016/j.combustflame.2015.02.008
M3 - Article
AN - SCOPUS:84939940906
SN - 0010-2180
VL - 162
SP - 2414
EP - 2421
JO - Combustion and Flame
JF - Combustion and Flame
IS - 6
ER -