CF3CH3 f HF + CF2CH2: A Non-RRKM Reaction?†

Barker, J., P. J. Stimac, K. D. King, and D. M. Leitner (2006), CF3CH3 f HF + CF2CH2: A Non-RRKM Reaction?†, J. Phys. Chem. A, 110, 2944-2954, doi:10.1021/jp054510x.

The experimental shock tube data recently reported by Kiefer et al. [J. Phys. Chem. A 2004, 108, 24432450] for the title reaction at temperatures between 1600 and 2400 K have been compared to master equation simulations using three models: (a) standard RRKM theory, (b) RRKM theory modified by local random matrix theory, which introduces dynamical corrections arising from slow intramolecular vibrational energy randomization, and (c) an ad hoc empirical non-RRKM model. Only the third model provides a good fit of the Kiefer et al. unimolecular reaction rate data. In separate simulations, all three models accurately reproduce the experimental 300 K chemical activation data of Marcoux and Setser [J. Phys. Chem. 1978, 82, 97-108] when the energy transfer parameters are freely varied to fit the data. When experimental energy transfer parameters for a geometrical isomer (1,1,2-trifluoroethane) are used, the standard RRKM model fits the chemical activation data better than the other models, but if energy transfer in the 1,1,1-trifluoroethane is significantly reduced in comparison to the 1,1,2 isomer, then the empirical ad hoc non-RRKM model also gives a good fit. While the ad hoc empirical non-RRKM model can be made to fit the data, it is not based on theory, and we argue that it is physically unrealistic. We also show that the master equation simulations can mimic the Kiefer et al. vibrational relaxation data, which was the first shock tube observation of double-exponential relaxation. We conclude that, until more data on the trifluoroethanes become available, the current evidence is insufficient to decide with confidence whether non-RRKM effects are important in this reaction, or whether the Kiefer et al. data can be explained in some other way.

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Upper Atmosphere Research Program (UARP)