Reflected Shock Tube and Theoretical Studies of High-Temperature Rate Constants for OH + CF3H ⇆ CF3 + H2O and CF3 + OH → Products

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 111; no. 29; pp. 6822 - 6831
• Main Authors: Srinivasan, N. K, Su, M.-C, Michael, J. V, Klippenstein, S. J, Harding, L. B
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 26.07.2007
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp0706228

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm, using either 36 or 60 optical passes corresponding to total path lengths of 3.25 or 5.25 m, respectively, has been used to study the bimolecular reactions, OH + CF3H → CF3 + H2O (1) and CF3 + H2O → OH + CF3H (−1), between 995 and 1663 K. During the course of the study, estimates of rate constants for CF3 + OH → products (2) could also be determined. Experiments on reaction −1 were transformed through equilibrium constants to k 1, giving the Arrhenius expression k 1 = (9.7 ± 2.1) × 10-12 exp(−4398 ± 275K/T) cm3 molecule-1 s-1. Over the temperature range, 1318−1663 K, the results for reaction 2 were constant at k 2 = (1.5 ± 0.4) × 10-11 cm3 molecule-1 s-1. Reactions 1 and −1 were also studied with variational transition state theory (VTST) employing QCISD(T) properties for the transition state. These a priori VTST predictions were in good agreement with the present experimental results but were too low at the lower temperatures of earlier experiments, suggesting that either the barrier height was overestimated by about 1.3 kcal/mol or that the effect of tunneling was greatly underestimated. The present experimental results have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range of 252−1663 K. The three parameter expression k 1 = 2.08 × 10-17 T 1.5513 exp(−1848 K/T) cm3 molecule-1 s-1 describes the rate behavior over this temperature range. Alternatively, the expression k 1,th = 1.78 × 10-23 T 3.406 exp(−837 K/T) cm3 molecule-1 s-1 obtained from empirically adjusted VTST calculations over the 250−2250 K range agrees with the experimental evaluation to within a factor of 1.6. Reaction 2 was also studied with direct CASPT2 variable reaction coordinate transition state theory. The resulting predictions for the capture rate are found to be in good agreement with the mean of the experimental results and can be represented by the expression k 2,th = 2.42 × 10-11 T -0.0650 exp(134 K/T) cm3 molecule-1 s-1 over the 200−2500 K temperature range. The products of this reaction are predicted to be CF2O + HF.