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.

The perturbation of the temperature field caused by a quartz sampling probe has been investigated in a fuel-rich low-pressure premixed ethylene/oxygen/argon/krypton flame using Xray fluorescence. The experiments were performed at the 7-BM beamline at the Advanced Photon Source (APS) at the Argonne National Laboratory where a continuous beam of X-rays at 15 keV was used to excite krypton atoms that were added to the unburnt flame gases in a concentration of 5% (by volume). The resulting krypton X-ray fluorescence at 12.65 keV was collected and the spatially resolved signal was subsequently converted into the local temperature of the imaged spot. One and two dimensional scans of the temperature field were obtained by translating the entire flame chamber through a pre-programmed sequence of positions on high precision translation stages and measuring the X-ray fluorescence at each location. Multiple measurements were performed at various separations between the burner surface and probe tip, representing sampling positions from the preheat, reaction, and postflame zones of the lowpressure flame. Distortions of up to 1000 K of the burner-probe centerline flame temperature were found with the tip of the probe in the preheat zone and distortions of up to 500 K were observed with it in the reaction and postflame zones. Furthermore, perturbations of the temperature field have been revealed that reach radially as far as 20 mm from the burner-probe centerline and about 3 mm in front of the probe tip. These results clearly reveal the limitations of one-dimensional models for predicting flame-sampling experiments and comments are made with regard to model developments and validations based on quantitative speciation data from low-pressure flames obtained via intrusive sampling techniques.

No abstract

length: 155 (word processor count) Main text length: 3639 (word processor count) References length: 647 (given formula) Equation 1: 23 (given formula) Equation 2: 23 (given formula) Total text length: 6030(Method I

Improvements to equipment lifetime and measurement reproducibility have been made by modifying the actuating mechanism of a diaphragmless shock tube that is used for high temperature gas kinetic studies. The modifications have two major benefits while retaining the simplicity of the original apparatus. First, the reproducibility of shock wave generation has been greatly improved and is demonstrated with 50 nearly identical experiments on the dissociation of cyclohexene at T2 = 1765 ± 13 K and P2 = 120 ± 1 Torr, demonstrating the capability for signal averaging over many experiments. Second, the lifetime of the bellows which forms the heart of the actuator is considerably improved, significantly increasing the time between replacements.