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Study of the Formation of the First Aromatic Rings in the Pyrolysis of Cyclopentene

Identifieur interne : 000013 ( Main/Merge ); précédent : 000012; suivant : 000014

Study of the Formation of the First Aromatic Rings in the Pyrolysis of Cyclopentene

Auteurs : Olivier Herbinet [France] ; Anne Rodriguez [France] ; Benoit Husson [France] ; Frédérique Battin-Leclerc [France] ; Zhandong Wang [République populaire de Chine] ; Zhanjun Cheng [République populaire de Chine] ; Fei Qi [République populaire de Chine]

Source :

RBID : Hal:hal-01305110

English descriptors

Abstract

The thermal decomposition of cyclopentene was studied in a jet-stirred reactor operated at constant pressure and temperature to provide new experimental information about the formation of the first aromatic rings from cyclic C5 species. Experiments were carried out at a residence time of 1 s, a pressure of 106.7 kPa, temperatures ranging from 773 to 1073 K and under diluted conditions (cyclopentene inlet mole fraction of 0.04). Species were quantified using three analytical methods: gas chromatography, synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS), and single photon laser ionization mass spectrometry (SPI-MS). Several species could be quantified using both methods allowing comparison of experimental data obtained with the three apparatuses. Discrepancies observed in mole fraction profiles of some large aromatics suggest that the direct sampling in the gas phase (with a molecular beam or a capillary tube) provide more reliable results. The main reaction products are 1,3-cyclopentadiene and hydrogen. The formation of many unsaturated C2–C6 olefins, diolefins and alkynes was also observed but in smaller amounts. Benzene, toluene, styrene, indene, and naphthalene were detected from 923 K. SVUV-PIMS data allowed the identification of another C6H6 isomer which is 1,5-hexadien-3-yne rather than fulvene. The quantification of the cyclopentadienyl radical was obtained from SVUV-PIMS and SPI-MS data with some uncertainty induced by the possible contribution to the signal for m/z 65 of a fragment from the decomposition of a larger ion. This is the first time that a radical is quantified in a jet-stirred reactor using non-optical techniques. SPI-MS analyses allowed the detection of species likely being combination products of allyl and cyclopentadienyl radicals. A model was developed for the pyrolysis of cyclopentene. This model includes routes of formation of aromatics from the cyclopentadienyl radical. The comparison of experimental and computed data is overall satisfactory for primary reaction products whereas discrepancies are still observed for aromatics.

Url:
DOI: 10.1021/acs.jpca.5b09203

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<name sortKey="Husson, Benoit" sort="Husson, Benoit" uniqKey="Husson B" first="Benoit" last="Husson">Benoit Husson</name>
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<name sortKey="Battin Leclerc, Frederique" sort="Battin Leclerc, Frederique" uniqKey="Battin Leclerc F" first="Frédérique" last="Battin-Leclerc">Frédérique Battin-Leclerc</name>
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<name sortKey="Wang, Zhandong" sort="Wang, Zhandong" uniqKey="Wang Z" first="Zhandong" last="Wang">Zhandong Wang</name>
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<country>République populaire de Chine</country>
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<author>
<name sortKey="Cheng, Zhanjun" sort="Cheng, Zhanjun" uniqKey="Cheng Z" first="Zhanjun" last="Cheng">Zhanjun Cheng</name>
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<country>République populaire de Chine</country>
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<author>
<name sortKey="Qi, Fei" sort="Qi, Fei" uniqKey="Qi F" first="Fei" last="Qi">Fei Qi</name>
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<orgName>National Synchrotron Radiation Laboratory</orgName>
<orgName type="acronym">NSRL</orgName>
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<addrLine>University of Science and Technology of China National Synchrotron Radiation Laboratory‎ Hezuohua South Road Shushan, Hefei, Anhui</addrLine>
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<country>République populaire de Chine</country>
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<idno type="DOI">10.1021/acs.jpca.5b09203</idno>
<series>
<title level="j">Journal of Physical Chemistry A</title>
<idno type="ISSN">1089-5639</idno>
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<date type="datePub">2016</date>
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<keywords scheme="mix" xml:lang="en">
<term> AB INITIO/RRKM</term>
<term> CROSS-SECTIONS</term>
<term> FLAME CHEMISTRY</term>
<term> GAS JETS</term>
<term> HIGH-TEMPERATURE</term>
<term> HYDROCARBON FORMATION</term>
<term> RATE CONSTANTS</term>
<term> SHOCK-TUBE</term>
<term> THERMAL-DECOMPOSITION</term>
<term>PHOTOIONIZATION MASS-SPECTROMETRY</term>
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<front>
<div type="abstract" xml:lang="en">The thermal decomposition of cyclopentene was studied in a jet-stirred reactor operated at constant pressure and temperature to provide new experimental information about the formation of the first aromatic rings from cyclic C5 species. Experiments were carried out at a residence time of 1 s, a pressure of 106.7 kPa, temperatures ranging from 773 to 1073 K and under diluted conditions (cyclopentene inlet mole fraction of 0.04). Species were quantified using three analytical methods: gas chromatography, synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS), and single photon laser ionization mass spectrometry (SPI-MS). Several species could be quantified using both methods allowing comparison of experimental data obtained with the three apparatuses. Discrepancies observed in mole fraction profiles of some large aromatics suggest that the direct sampling in the gas phase (with a molecular beam or a capillary tube) provide more reliable results. The main reaction products are 1,3-cyclopentadiene and hydrogen. The formation of many unsaturated C2–C6 olefins, diolefins and alkynes was also observed but in smaller amounts. Benzene, toluene, styrene, indene, and naphthalene were detected from 923 K. SVUV-PIMS data allowed the identification of another C6H6 isomer which is 1,5-hexadien-3-yne rather than fulvene. The quantification of the cyclopentadienyl radical was obtained from SVUV-PIMS and SPI-MS data with some uncertainty induced by the possible contribution to the signal for m/z 65 of a fragment from the decomposition of a larger ion. This is the first time that a radical is quantified in a jet-stirred reactor using non-optical techniques. SPI-MS analyses allowed the detection of species likely being combination products of allyl and cyclopentadienyl radicals. A model was developed for the pyrolysis of cyclopentene. This model includes routes of formation of aromatics from the cyclopentadienyl radical. The comparison of experimental and computed data is overall satisfactory for primary reaction products whereas discrepancies are still observed for aromatics.</div>
</front>
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