title: Study of the Formation of the First Aromatic Rings in the Pyrolysis of Cyclopentene.
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.
authors.affiliation: Laboratoire Réactions et Génie des Procédés, Université de Lorraine, UMR 7274 , BP 20451, 1 rue Grandville, Nancy, F-54000, France.|Laboratoire Réactions et Génie des Procédés, CNRS, UMR 7274 , BP 20451, 1 rue Grandville, Nancy, F-54000, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Herbinet
authors.affiliation: Laboratoire Réactions et Génie des Procédés, Université de Lorraine, UMR 7274 , BP 20451, 1 rue Grandville, Nancy, F-54000, France.|Laboratoire Réactions et Génie des Procédés, CNRS, UMR 7274 , BP 20451, 1 rue Grandville, Nancy, F-54000, France.
authors.forename: Anne
authors.initials: A
authors.lastname: Rodriguez
authors.affiliation: Laboratoire Réactions et Génie des Procédés, Université de Lorraine, UMR 7274 , BP 20451, 1 rue Grandville, Nancy, F-54000, France.|Laboratoire Réactions et Génie des Procédés, CNRS, UMR 7274 , BP 20451, 1 rue Grandville, Nancy, F-54000, France.
authors.forename: Benoit
authors.initials: B
authors.lastname: Husson
authors.affiliation: Laboratoire Réactions et Génie des Procédés, Université de Lorraine, UMR 7274 , BP 20451, 1 rue Grandville, Nancy, F-54000, France.|Laboratoire Réactions et Génie des Procédés, CNRS, UMR 7274 , BP 20451, 1 rue Grandville, Nancy, F-54000, France.
authors.forename: Frédérique
authors.initials: F
authors.lastname: Battin-Leclerc
authors.affiliation: National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230029, P. R. China.
authors.forename: Zhandong
authors.initials: Z
authors.lastname: Wang
authors.affiliation: National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230029, P. R. China.
authors.forename: Zhanjun
authors.initials: Z
authors.lastname: Cheng
authors.affiliation: National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230029, P. R. China.
authors.forename: Fei
authors.initials: F
authors.lastname: Qi