β-Bond Scission and the Yields of H and CH3 in the Decomposition of Isobutyl Radicals.

The relative rates of C-C and C-H β-scission reactions of isobutyl radicals (2-methylprop-1-yl, C4H9) were investigated with shock tube experiments at temperatures of (950 to 1250) K and pressures of (200 to 400) kPa. We produced isobutyl radicals from the decomposition of dilute mixtures of isopentylbenzene and observed the stable decomposition products, propene and isobutene. These alkenes are characteristic of C-C and C-H bond scission, respectively. Propene was the main product, approximately 30 times more abundant than isobutene, indicating that C-C β-scission is the primary pathway. Uncertainty in the ratio of [isobutene]/[propene] from isobutyl decomposition is mainly due to a small amount of side chemistry, which we account for using a kinetics model based on JetSurF 2.0. Our data are well-described after adding chemistry specific to our system and adjusting some rate constants. We compare our data to other commonly used kinetics models: JetSurF 2.0, AramcoMech 2.0, and multiple models from Lawrence Livermore National Laboratory (LLNL). With the kinetics model, we have determined an upper limit of 3.0% on the branching fraction for C-H β-scission in the isobutyl radical for the temperatures and pressures of our experiments. While this agrees with previous high quality experimental results, many combustion kinetics models assume C-H branching values above this upper limit, possibly leading to large systematic inaccuracies in model predictions. Some kinetics models additionally assume contributions from 1,2-H shift reactions-which for isobutyl would produce the same products as C-H β-scission-and our upper limit includes possible involvement of such reactions. We suggest kinetics models should be updated to better reflect current experimental measurements.