title: Kinetic study of the OH radical reaction with phenylacetylene.
abstract: The reaction of the OH radical with phenylacetylene is studied over the 298-423 K temperature range and 1-7.5 Torr pressure range in a quasi-static reaction cell. The OH radical is generated by 266 nm photolysis of hydrogen peroxide (H2O2) or 355 nm photolysis of nitrous acid (HONO), and its concentration monitored using laser-induced fluorescence. The measured reaction rates are found to strongly depend on laser fluence at 266 nm. The 266 nm absorption cross-section of phenylacetylene is measured to be 1.29 (±0.71) × 10(-17) cm(2), prohibiting any accurate kinetic measurements at this wavelength. The rates are independent of laser fluence at 355 nm with an average value of 8.75 (±0.73) × 10(-11) cm(3) s(-1). The reaction exhibits no pressure or temperature dependence over the studied experimental conditions and is much faster than the estimated values presently used in combustion models. These results are consistent with the formation of a short lifetime intermediate that stabilizes by collisional quenching with the buffer gas. The structures of the most likely formed products are discussed based on both the computed energies for the OH-addition intermediates and previous theoretical investigations on similar chemical systems.
authors.affiliation: Department of Chemistry, West Virginia University , Morgantown, West Virginia 26506, United States.
authors.forename: Ranjith Kumar
authors.initials: RK
authors.lastname: Abhinavam Kailasanathan
authors.forename: Juddha
authors.initials: J
authors.lastname: Thapa
authors.forename: Fabien
authors.initials: F
authors.lastname: Goulay