CF3CH3 --> HF + CF2CH2: a non-RRKM reaction?

The Journal of Physical Chemistry. a
John R BarkerDavid M Leitner

Abstract

The experimental shock tube data recently reported by Kiefer et al. [J. Phys. Chem. A 2004, 108, 2443-2450] 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...Continue Reading

References

May 30, 1998·Proceedings of the National Academy of Sciences of the United States of America·R BigwoodP G Wolynes
Jan 8, 1996·Physical Review Letters·D M Leitner, P G Wolynes
Oct 14, 2000·Annual Review of Physical Chemistry·J C Keske, B H Pate
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Citations

Aug 21, 2007·The Journal of Chemical Physics·Johnson K AgboKenneth D Jordan
Apr 14, 2015·The Journal of Physical Chemistry. a·John R BarkerDavid M Golden
Dec 6, 2014·The Journal of Physical Chemistry. a·Akira MatsugiHiroumi Shiina
Jan 19, 2013·The Journal of Physical Chemistry. a·Baptiste SirjeanMatthew A Oehlschlaeger
Oct 9, 2009·Journal of the American Chemical Society·Jingjing ZhengDonald G Truhlar
Aug 10, 2007·Physical Chemistry Chemical Physics : PCCP·Hui XuRobert S Tranter
Oct 22, 2008·Physical Chemistry Chemical Physics : PCCP·Binod R GiriRobert S Tranter
Mar 6, 2008·The Journal of Physical Chemistry. a·Philip J Stimac, John R Barker
Feb 14, 2007·The Journal of Physical Chemistry. a·Binod R Giri, Robert S Tranter

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