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Author(s):   Xiao, J.-F.; Li, Z.-S.; Liu, J.-Y.; Sheng, L.; Sun, C.-C.
Title:   Theoretical Study of the Hydrogen-Abstraction Reactions for CH3CX3 + Cl -> CH2CX3 + HCl (X=Cl and F)
Journal:   J. Phys. Chem. A
Volume:   107
Page(s):   267 - 271
Year:   2003
Reference type:   Journal article
Squib:   2003XIA/LI267-271

Reaction:   CH3CCl3 + ClHCl + CCl3CH2
Reaction order:   2
Temperature:   200 - 1200 K
Rate expression:   1.44x10-12 [cm3/molecule s] (T/298 K)3.53 e-12630 [J/mole]/RT
Category:  Theory
Data type:   Ab initio
Pressure dependence:   Rate constant is pressure independent
Comments:   The authors have used ab initio calculations to investigat the hydrogen abstractions by chlorine atom from the 1,1,1-trichloroethane 1,1,1-trifluoroethane. The minimum energy paths (MEPs) of both reactions are calculated at the BH&H-LYP/6-311+G(d,p) level, and the energies along the MEPs are further refined at the CCSD(T)/6-311+G(2df,2p) (single-point) level. Theoretical rate constants were obtained over the temperature range 200-1200 K using POLYRATE 8.4.1 (Truhlar and co-workers) which uses improved canonical variational transition-state theory (ICVT) incorporating the smallcurvature tunneling correction (SCT) method proposed by Truhlar and co-workers.

Transition state properties are provided and results are compared with available experimental data. Variational effect were found to be small over the considered temperature range and the small-curvature tunneling effect was important only at lower temperatures.

The listed rate expression is a fit derived at NIST to the calculated rate constants reported by the authors for temperatures between 200 and1200 K. The fitted expression reproduces the calculated rates within 5%.

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
200 1.77E-16
300 9.32E-15
400 9.13E-14
500 4.29E-13
600 1.36E-12
700 3.36E-12
800 7.06E-12
900 1.32E-11
1000 2.27E-11
1100 3.65E-11
1200 5.57E-11