Thermal decomposition of CF3 and the reaction of CF2 + OH --> CF2O + H.
The reflected shock tube technique with multipass absorption spectrometric detection (at a total path length of approximately 1.75 m) of OH-radicals at 308 nm has been used to study the dissociation of CF3-radicals [CF3 + Kr --> CF2 + F + Kr (a)] between 1,803 and 2,204 K at three pressures between approximately 230 and 680 Torr. The OH-radical concentration buildup resulted from the fast reaction F + H2O --> OH + HF (b). Hence, OH is a marker for F-atoms. To extract rate constants for reaction (a), the [OH] profiles were modeled with a chemical mechanism. The initial rise in [OH] was mostly sensitive to reactions (a) and (b), but the long time values were additionally affected by CF2 + OH --> CF2O + H (c). Over the experimental temperature range, rate constants for (a) and (c) were determined from the mechanistic fits to be kCF3+Kr = 4.61 x 10-9 exp(-30,020 K/T) and kCF2+OH = (1.6 +/- 0.6) x 10-10, both in units of cm3 molecule-1 s-1. Reaction (a), its reverse recombination reaction reaction (-a), and reaction (c) are also studied theoretically. Reactions (c) and (-a) are studied with direct CASPT2 variable reaction coordinate transition state theory. A master equation analysis for reaction (a) incorporating the ab initio determined reactive flux for reaction (-a) suggests that this reaction is close to but not quite in the low-pressure limit for the pressures studied experimentally. In contrast, reaction (c) is predicted to be in the high-pressure limit due to the high exothermicity of the products. A comparison with past and present experimental results demonstrates good agreement between the theoretical predictions and the present data for both (a) and (c).
Srinivasan
N K
NK
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Su
M-C
MC
Michael
J V
JV
Jasper
A W
AW
Klippenstein
S J
SJ
Harding
L B
LB