The C7H5 fulvenallenyl radical as a combustion intermediate: Potential new pathways to two- and three-ring PAHs

Document Type

Article

Publication Date

11-5-2009

Abstract

This study proposes the existence of a new, highly resonantly stabilized free radical, fulvenallenyl (C7H5). Fulvenallenyl forms from dissociation or abstraction of the weak H atoms in the C7H 6 compounds fulvenallene and 1-ethynylcyclopentadiene, which were recently identified as intermediates in the combustion of aromatic fuels and in sooting flames. The fulvenallenyl radical shares properties of the propargyl and cyclopentadienyl radicals, and like these species, we propose that fulvenallenyl has a significant resonance stabilization energy. This resonance energy is lost upon further reaction, making the fulvenallenyl radical resistant to oxidation and thermal decomposition. As with the resonantly stabilized radicals propargyl and cyclopentadienyl, fulvenallenyl is expected to react with other radicals in molecular weight growth reactions. Several pathways are proposed for self-reaction and cross-reactions of fulvenallenyl that directly produce two- and three-ring PAHs like naphthalene, diphenyl, and phenanthrene. Rate constants are calculated for H atom abstraction from fulvenallene and 1-ethynylcyclopentadiene by the common radicals H, OH, and CH3, to facilitate the inclusion of fulvenallenyl in kinetic models. © 2009 American Chemical Society.

Identifier

77649169681 (Scopus)

Publication Title

Journal of Physical Chemistry A

External Full Text Location

https://doi.org/10.1021/jp907230b

e-ISSN

15205215

ISSN

10895639

First Page

12045

Last Page

12048

Issue

44

Volume

113

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