Rate constants for the removal of O(bΣ) by collisions with O, N, CO, and HO have been determined over the temperature range from 297 to 800 K. O(bΣ) was excited by pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the bΣ-XΣ fluorescence. The removal rate constants for CO, N, and HO were not strongly dependent on temperature and could be represented by the expressions k = (1.18 ± 0.05) × 10 × T × exp[Formula: see text], k = (8 ± 0.3) × 10 × T × exp[Formula: see text], and k = (1.27 ± 0.08) × 10 × T × exp[Formula: see text] cm molecule s. Rate constants for O(bΣ) removal by O(X), being orders of magnitude lower, demonstrated a sharp increase with temperature, represented by the fitted expression k = (7.4 ± 0.8) × 10 × T × exp[Formula: see text] cm molecule s. All of the rate constants measured at room temperature were found to be in good agreement with previously reported values.
Rate constants for the removal of O bΣ by collisions with species relevant to combustion, H, CO, NO, CH and CH have been measured in the temperature range 297-800 K. O(bΣ) was produced from ground-state molecular oxygen by photoexcitation pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the bΣ-XΣ fluorescence. The removal rate constants for H, CO, NO, CH, and CH could be represented by the modified Arrhenius expressions k = (1.44 ± 0.02) × 10 T exp[(0 ± 10)/ T], k = (6.9 ± 0.4) × 10 T exp[(939 ± 33)/ T], k = (2.63 ± 0.14) × 10 T exp[(590 ± 26)/ T], k = (3.5 ± 0.2) × 10 T exp[(-220 ± 24)/ T], and k = (2.34 ± 0.10) × 10 T exp[(680 ± 16)/ T] cm molecule s, respectively. All of the rate constants measured at room temperature were found to be in good agreement with previously reported values, whereas the values at elevated temperatures up to 800 K were systematically measured for the first time.
Quantum chemical calculations, computational fluid dynamics (CFD) simulations, and isothermal approximation were applied for the interpretation of experimental measurements of the reaction of С6Н5 + O2 in the high-temperature microreactor and of the pressure drop in the flow tube of the reactor.
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