jp011546q_si_001.pdf (157.87 kB)

The Kinetics of the Reaction of H Atoms with C4F6

Download (157.87 kB)
journal contribution
posted on 16.11.2001, 00:00 by Xiaohua Hu, A. Goumri, Paul Marshall
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•−CFCF2 and/or CF2H−CF•−CFCF2. 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·-CFCF2, 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.