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Author(s):   Zhu, L.; Bozzelli, J.W.
Title:   Kinetics and Mechanism for the Thermal Chlorination of Chloroform in the Gas Phase: Inclusion of HCl Elimination from CHCl3
Journal:   Int. J. Chem. Kinet.
Volume:   35
Page(s):   647 - 660
Year:   2003
Reference type:   Journal article
Squib:   2003ZHU/BOZ647-660

Reaction:   CHCl3CCl2 (X 1A1) + HCl
Reaction order:   1
Temperature:   300 - 2000 K
Rate expression:   1.74x1019 [s-1] (T/298 K)-8.70 e-267358 [J/mole]/RT
Category:  Theory
Data type:   Ab initio
Pressure dependence:   Rate constant is high pressure limit
Comments:   The authors have calculated the rate of the reaction CHCl3 = 1CCl2 + HCl at the G3, G3//MP2/6-311G(d,p) and G3//B3LYP/6-311G(d,p) levels and estimated k as a function of pressure and temperature using QRRK-master equation analysis. Their calculated results are in agreement with data from previous experimental studies.

The authors have additionally modeled the chlorination of chloroform by adding 30 reversible reactions to a 10-step chemical kinetic model published previously (Huybrechts, G.; Hubin, Y.; Van Mele, B. Int J Chem Kinet 2000, 32, 466). The present model provides a good fit to the experimental data of Huybrechts et al. for [Cl2] decay, unless the recently published* abstraction reaction 1CCl2 + Cl2 = CCl3 + Cl is included in the mechanism.
*Kostina, S. A.; Shestov, A. A.; Knyazev, V. D. In Proceedings of the 3rd Joint Meeting of the U.S. Section of the Combustion Institute, Chicago, March 16?9, 2003.

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [s-1]
300 4.63E-28
400 1.64E-17
500 2.27E-11
600 2.10E-7
700 1.16E-4
800 1.13E-2
900 3.53E-1
1000 5.03E0
1100 4.08E1
1200 2.19E2
1300 8.57E2
1400 2.63E3
1500 6.67E3
1600 1.45E4
1700 2.80E4
1800 4.87E4
1900 7.78E4
2000 1.16E5