Kinetics Database Logo

Kinetics Database Resources

Simple Reaction Search

Search Reaction Database

Search Bibliographic Database

Set Unit Preferences

Feedback

Rate Our Products and Services

Help


Other Databases

NIST Standard Reference Data Program

NIST Chemistry Web Book

NDRL-NIST Solution Kinetics Database

NIST Computational Chemistry Comparison and Benchmark Database

The NIST Reference on Constants, Units, and Uncertainty

More...


Administrative Links

NIST home page

MML home page

Chemical and Biochemical Reference Data Division

MML home page

Chemical and Biochemical Reference Data Division

  NIST Logo Home
©NIST, 2013
Accessibility information
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.

View full bibliographic record.


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