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Rate Constants for CF3 + H2 → CF3H + H and CF3H + H → CF3 + H2 Reactions in the Temperature Range 1100−1600 K

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Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439
Cite this: J. Phys. Chem. A 1998, 102, 39, 7668–7673
Publication Date (Web):September 9, 1998
https://doi.org/10.1021/jp982432q
Copyright © 1998 American Chemical Society
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    Abstract

    The shock tube technique coupled with H-atom atomic resonance absorption spectrometry has been used to study the reactions (1) CF3 + H2 → CF3H + H and (2) CF3H + H → CF3 + H2 over the temperature ranges 1168−1673 K and 1111−1550 K, respectively. The results can be represented by the Arrhenius expressions k1 = 2.56 × 10-11 exp(−8549K/T) and k2 = 6.13 × 10-11 exp(−7364K/T), both in cm3 molecule-1 s-1. Equilibrium constants were calculated from the two Arrhenius expressions in the overlapping temperature range, and good agreement was obtained with the literature values. The rate constants for reaction 2 were converted into rate constants for reaction 1 using literature equilibrium constants. These data are indistinguishable from direct k1 measurements, and an Arrhenius fit for the joint set is k1 = 1.88 × 10-11 exp(−8185K/T) cm3 molecule-1 s-1. The CF3 + H2 → CF3H + H reaction was further modeled using conventional transition-state theory, which included ab initio electronic structure determinations of reactants, transition state, and products.

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     Author to whom correspondence should be addressed, D-193, Bldg. 200. Phone:  (630) 252-3171. Fax:  (630) 252-4470. E-mail:  Michael@ anlchm.chm.anl.gov.

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