The thermal decomposition of phenyl chloride (C6H5Cl) has been investigated in a diaphragmless shock tube using laser schlieren densitometry, at pressures of 30–224 Torr and temperatures ranging from 1760–2520 K, and time-of-flight mass spectrometry, at pressures ranging from 160–678 Torr and temperatures ranging from 1604–1963 K. A model has been developed that simulates the experimental density gradient profiles over a broad range of conditions that is supported by high-level ab initio calculations. Direct C–Cl bond scission is the major decomposition channel for C6H5Cl, with a minor roaming mediated pathway that yields ortho-benzyne (o–C6H4) + HCl products. The C6H5Cl decomposition mechanism and secondary chemistry associated with C6H5 and o–C6H4 radicals reported here are consistent with previous studies of phenyl halide pyrolysis.
