We report a shock-tube, laser-schlieren investigation of the molecular dissociation of the title trifluoroethane, CF3CH3 → CH2CF2 + HF, over very high temperatures, 1600−2400 K, and a wide range of sub-atmospheric pressures, 15−550 Torr. The density gradients are well fit by a simple two-reaction mechanism and accurate dissociation rates obtained. The results are compared with a k ∞ calculated from a G3 TS for this molecular elimination, which is a superb fit to the available lower-T data and a reliable extrapolation of k ∞ to high temperatures. The derived rate constants show a very deep falloff from this extrapolation but surprisingly little variation with pressure. This peculiarity is so severe that RRKM calculations dramatically fail to account for the behavior. The dissociation seems to be a clear example of an intrinsic non-RRKM process (nonstatistical dissociation). This conclusion is strongly supported by the observation of double vibrational relaxation at both dissociating and nondissociating temperatures, an unambiguous demonstration of slow IVR. Using a simple model with division into two groups of states, the deep falloff is found to be consistent with a rate-controlling slow IVR, not with low collision efficiency. The model suggests an IVR rate of ∼108 s-1 for dissociation energies.

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.

The thermal decomposition of nitromethane provides a classic example of the competition between roaming mediated isomerization and simple bond fission. A recent theoretical analysis suggests that as the pressure is increased from 2 to 200 Torr the product distribution undergoes a sharp transition from roaming dominated to bond-fission dominated. Laser schlieren densitometry is used to explore the variation in the effect of roaming on the density gradients for CH3NO2 decomposition in a shock tube for pressures of 30, 60, and 120 Torr at temperatures ranging from 1200 to 1860 K. A complementary theoretical analysis provides a novel exploration of the effects of roaming on the thermal decomposition kinetics. The analysis focuses on the roaming dynamics in a reduced dimensional space consisting of the rigid-body motions of the CH3 and NO2 radicals. A high-level reduced-dimensionality potential energy surface is developed from fits to large-scale multireference ab initio calculations. Rigid body trajectory simulations coupled with master equation kinetics calculations provide high-level a priori predictions for the thermal branching between roaming and dissociation. A statistical model provides a qualitative/semiquantitative interpretation of the results. Modeling efforts explore the relation between the predicted roaming branching and the observed gradients. Overall, the experiments are found to be fairly consistent with the theoretically proposed branching ratio, but they are also consistent with a no-roaming scenario and the underlying reasons are discussed. The theoretical predictions are also compared with prior theoretical predictions, with a related statistical model, and with the extant experimental data for the decomposition of CH3NO2, and for the reaction of CH3 with NO2.

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