The kinetics of the reaction of H atoms with C₄F₆

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Article on the kinetics of the reaction of H atoms with C₄F₆.

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6 p.

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Hu, Xiaohua; Goumri, Abdellatif & Marshall, Paul November 16, 2001.

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Article on the kinetics of the reaction of H atoms with C₄F₆.

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6 p.

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Abstract: The rate constant k for the gas-phase reaction of atomic hydrogen with 1,1,2,3,4,4-hexafluoro-1,3-butadiene has been measured over the temperature range 290−1010 K by time-resolved atomic resonance fluorescence using H2O and NH3 as precursors, at argon pressures of about 30−140 mbar. Over the range 290−620 K a positive activation energy was observed, k = (3.40 ± 0.34) × 10-11 exp[(−16.7 ± 0.4) kJ mol-1/RT] cm3 molecule-1 s-1, and k dropped rapidly between 620 and 700 K. Over the range 700−1010 K, k = (1.83 ± 0.53) × 10-10 exp[(−34.1 ± 2.1) kJ mol-1/RT] cm3 molecule-1 s-1 where the statistical uncertainties are 1σ. Confidence limits for k are ± 16%. Several isomers of C4F6H were characterized by ab initio methods. Below about 600 K the dominant pathway is suggested to be addition of H atoms to form CF2H−CF•−CFCF2 and/or CF2H−CF•−CFCF2. These adducts dissociate at elevated temperatures, and on the assumption that the major addition product at around 670 K is the more stable CF2H−CF·-CFCF2, the C−H bond dissociation enthalpy is estimated via a third-law method to be about −111 kJ mol-1, with an estimated uncertainty of ± 7 kJ mol-1.

Reprinted with permission from the Journal of Physical Chemistry A. Copyright 2001 American Chemical Society.

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  • Journal of Physical Chemistry A, 2001, Washington D.C.: American Chemical Society, pp. 11220-11225

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  • Publication Title: Journal of Physical Chemistry A
  • Volume: 105
  • Issue: 50
  • Page Start: 11220
  • Page End: 11225
  • Pages: 6
  • Peer Reviewed: Yes

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  • November 16, 2001

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  • March 17, 2015, 10:38 a.m.

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Hu, Xiaohua; Goumri, Abdellatif & Marshall, Paul. The kinetics of the reaction of H atoms with C₄F₆, article, November 16, 2001; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc501384/: accessed September 25, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.