Time- and isomer-resolved measurements of sequential addition of acetylene to the propargyl radical

Savee, John D.; Selby, Talitha M.; Welz, Oliver; Taatjes, Craig A.; Osborn, David L.

doi:10.1021/acs.jpclett.5b01896

Time- and isomer-resolved measurements of sequential addition of acetylene to the propargyl radical

Journal Article · Tue Oct 06 00:00:00 EDT 2015 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.5b01896· OSTI ID:1329623

Savee, John D. ^[1]; Selby, Talitha M. ^[1]; Welz, Oliver ^[1]; Taatjes, Craig A. ^[1]; Osborn, David L. ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Soot formation in combustion is a complex process in which polycyclic aromatic hydrocarbons (PAHs) are believed to play a critical role. Recent works concluded that three consecutive additions of acetylene (C₂H₂) to propargyl (C₃H₃) create a facile route to the PAH indene (C₉H₈). However, the isomeric forms of C₅H₅ and C₇H₇ intermediates in this reaction sequence are not known. We directly investigate these intermediates using time- and isomer-resolved experiments. Both the resonance stabilized vinylpropargyl (vp-C₅H₅) and 2,4-cyclopentadienyl (c-C₅H₅) radical isomers of C₅H₅ are produced, with substantially different intensities at 800 K vs 1000 K. In agreement with literature master equation calculations, we find that c-C₅H₅ + C₂H₂ produces only the tropyl isomer of C₇H₇ (tp-C₇H₇) below 1000 K, and that tp-C₇H₇ + C₂H₂ terminates the reaction sequence yielding C₉H₈ (indene) + H. Lastly, this work demonstrates a pathway for PAH formation that does not proceed through benzene.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1329623

Report Number(s):: SAND--2016-10081J; 648116

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 20 Vol. 6; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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