title: Experimental and theoretical investigation of the self-reaction of phenyl radicals.
abstract: A combination of experiment and theory is applied to the self-reaction kinetics of phenyl radicals. The dissociation of phenyl iodide is observed with both time-of-flight mass spectrometry, TOF-MS, and laser schlieren, LS, diagnostics coupled to a diaphragmless shock tube for temperatures ranging from 1276 to 1853 K. The LS experiments were performed at pressures of 22 +/- 2, 54 +/- 7, and 122 +/- 6 Torr, and the TOF-MS experiments were performed at pressures in the range 500-700 Torr. These observations are sensitive to both the dissociation of phenyl iodide and to the subsequent self-reaction of the phenyl radicals. The experimental observations indicate that both these reactions are more complicated than previously assumed. The phenyl iodide dissociation yields approximately 6% C(6)H(4) + HI in addition to the major and commonly assumed C(6)H(5) + I channel. The self-reaction of phenyl radicals does not proceed solely by recombination, but also through disproportionation to benzene + o-/m-/p-benzynes, with comparable rate coefficients for both. The various channels in the self-reaction of phenyl radicals are studied with ab initio transition state theory based master equation calculations. These calculations elucidate the complex nature of the C(6)H(5) self-reaction and are consistent with the experimental observations. The theoretical predictions are used as a guide in the development of a model for the phenyl iodide pyrolysis that accurately reproduces the observed laser schlieren profiles over the full range of the observations.
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, USA. tranter@anl.gov
authors.forename: Robert S
authors.initials: RS
authors.lastname: Tranter
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Klippenstein
authors.forename: Lawrence B
authors.initials: LB
authors.lastname: Harding
authors.forename: Binod R
authors.initials: BR
authors.lastname: Giri
authors.forename: Xueliang
authors.initials: X
authors.lastname: Yang
authors.forename: John H
authors.initials: JH
authors.lastname: Kiefer