The role of radical-radical chain-propagating pathways in the phenyl + propargyl reaction

Couch, David E.; Kukkadapu, Goutham; Zhang, Angie J.; Jasper, Ahren W.; Taatjes, Craig A.; Hansen, Nils

doi:10.1016/j.proci.2022.09.012

The role of radical-radical chain-propagating pathways in the phenyl + propargyl reaction

Journal Article · Sat Oct 29 00:00:00 EDT 2022 · Proceedings of the Combustion Institute

DOI:https://doi.org/10.1016/j.proci.2022.09.012· OSTI ID:2217026

^[1]; ^[2]; ^[1]; Jasper, Ahren W. ^[3]; Taatjes, Craig A. ^[1]; ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Well-skipping radical-radical reactions can provide a chain-propagating pathway for formation of polycyclic radicals implicated in soot inception. Here we use controlled pyrolysis in a microreactor to isolate and examine the role of well-skipping channels in the phenyl (C₆H₅) + propargyl (C₃H₃) radical-radical reaction at temperatures of 800-1600 K and pressures near 25 Torr. The temperature and concentration dependence of the closed-shell (C₉H₈) and radical (C₉H₇) products are observed using electron-ionization mass spectrometry. The flow in the reactor is simulated using a boundary layer model employing a chemical mechanism based on recent rate coefficient calculations. Further, comparison between simulation and experiment shows reasonable agreement, within a factor of 3, while suggesting possible improvements to the model. In contrast, eliminating the well-skipping reactions from the chemistry mechanism causes a much larger discrepancy between simulation and experiment in the temperature dependence of the radical concentration, revealing that the well-skipping pathways, especially to form indenyl radical, are significant at temperatures of 1200 K and higher. While most C₉H₇ forms by well-skipping at 25 Torr, an additional simulation indicates that the wellskipping channels only contribute around 3% of the C₉H_x yield at atmospheric pressure, thus indicating a negligible role of the well-skipping pathways at atmospheric and higher pressures.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357; NA0003525

OSTI ID:: 2217026

Alternate ID(s):: OSTI ID: 1984142

Journal Information:: Proceedings of the Combustion Institute, Journal Name: Proceedings of the Combustion Institute Journal Issue: 1 Vol. 39; ISSN 1540-7489

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
indenyl radical
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well-skipping

The role of radical-radical chain-propagating pathways in the phenyl + propargyl reaction

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