Thermal Decomposition of Benzyl Radicals: Kinetics and Spectroscopy in a Shock Tube.

Understanding the mechanism of high-temperature reactions of aromatic hydrocarbons and radicals is essential for the modeling of hydrocarbon growth processes in combustion environments. In this study, the thermal decomposition reaction of benzyl radicals was investigated using time-resolved broadband cavity-enhanced absorption spectroscopy behind reflected shock waves at a postshock pressure of 100 kPa and temperatures of 1530, 1630, and 1740 K. The transient absorption spectra during the decomposition were recorded over the spectral range of 282-410 nm. The spectra were contributed by the absorption of benzyl radicals and some transient and residual absorbing species. The temporal behavior of the absorption was analyzed using a kinetic model to determine the rate constant for benzyl decomposition. The obtained rate constants can be represented by the Arrhenius expression k1 = 1.1 × 1012 exp(-30 500 K/T) s-1 with an estimated logarithmic uncertainty of Δlog10 k = ±0.2. Kinetic simulation of the secondary reactions indicated that fulvenallenyl radicals are potentially responsible for the transient absorption that appeared around 400 nm. This assignment is consistent with the available spectroscopic information of this radical. Possible candidates for the residual absorbing species are presented, suggesting the potential importance of ortho-benzyne as a reactive intermediate.