Formation of chlorobenzenes by oxidative thermal decomposition of 1,3-dichloropropene

Nwakamma Ahubelem; Kalpit Shah; Behdad Moghtaderi; Mohammednoor Altarawneh; Bogdan Z. Dlugogorski; Alister J. Page

doi:10.1016/j.combustflame.2015.02.008

Formation of chlorobenzenes by oxidative thermal decomposition of 1,3-dichloropropene

Nwakamma Ahubelem, Kalpit Shah, Behdad Moghtaderi, Mohammednoor Altarawneh, Bogdan Z. Dlugogorski, Alister J. Page

Research output: Contribution to journal › Article › peer-review

12 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	2414-2421
Number of pages	8
Journal	Combustion and Flame
Volume	162
Issue number	6
DOIs	https://doi.org/10.1016/j.combustflame.2015.02.008
Publication status	Published - Jun 1 2015
Externally published	Yes

Keywords

1,3-Dichloropropene
Chlorobenzene
Combustion
Cyclisation
Density functional theory

ASJC Scopus subject areas

Chemistry(all)
Chemical Engineering(all)
Fuel Technology
Energy Engineering and Power Technology
Physics and Astronomy(all)

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10.1016/j.combustflame.2015.02.008

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title = "Formation of chlorobenzenes by oxidative thermal decomposition of 1,3-dichloropropene",

abstract = "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.",

keywords = "1,3-Dichloropropene, Chlorobenzene, Combustion, Cyclisation, Density functional theory",

author = "Nwakamma Ahubelem and Kalpit Shah and Behdad Moghtaderi and Mohammednoor Altarawneh and Dlugogorski, {Bogdan Z.} and Page, {Alister J.}",

note = "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: {\textcopyright} 2015 The Combustion Institute.",

year = "2015",

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doi = "10.1016/j.combustflame.2015.02.008",

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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

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KW - Combustion

KW - Cyclisation

KW - Density functional theory

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Formation of chlorobenzenes by oxidative thermal decomposition of 1,3-dichloropropene

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