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Author(s):   Sheng, L.; Li, Z.-S.; Liu, J.-Y.; Xiao, J.-F.; Sun, C.-C.
Title:   Ab initio direct dynamics studies on the reactions of H atoms with CCl4 and CHCl3
Journal:   J. Phys. Chem. A
Volume:   106
Page(s):   12292 - 12298
Year:   2002
Reference type:   Journal article
Squib:   2002SHE/LI12292-12298

Reaction:   CHCl3 + CHCl2 + HCl
Reaction order:   2
Temperature:   200 - 5000 K
Rate expression:   4.38x10-12 [cm3/molecule s] (T/298 K)1.59 e-24519 [J/mole]/RT
Category:  Theory
Data type:   Ab initio
Comments:   Used density functional theory (DFT) and ab initio quantum calculations to determine reaction pathways for reactions of H atoms with CCl4 and CHCl3. Employed BH&HLYP/6-311G(d,p) geometries/frequencies and PM4/6-311+G(3df,2p) energies. Rate expressions calculated using Truhlars Polyrate program employing CVT/SCT tunneling correction.

The calculated barrier for CCl4+H = CCl3+HCl was about 6.5 kcal/mol. For reaction with CHCl3, there are two reaction channels, abstraction of H atom with a barrier of about 6.8 kcal/mol and abstraction of Cl with a barrier of about 8.0 kcal/mol. The H atom abstraction channel dominates at low temperature, at about 670 K the two channels are about equal, and at high temperatures (2000 K) the Cl atom abstraction is about 65% of the total rate.

For CCl4+H, the calculated rate expression is about 2-3 lower than experimental rate constants (2001 Bryukov, Slagle, and Knyazev) and for CHCl3, the calculated total rate expression is only about 10-30% lower than the experimental values (same reference).

View full bibliographic record.


Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
200 9.17E-19
300 2.38E-16
400 4.40E-15
500 2.74E-14
600 9.78E-14
700 2.52E-13
800 5.28E-13
900 9.59E-13
1000 1.57E-12
1100 2.39E-12
1200 3.44E-12
1300 4.72E-12
1400 6.24E-12
1500 8.01E-12
1600 1.00E-11
1700 1.23E-11
1800 1.49E-11
1900 1.76E-11
2000 2.07E-11
2100 2.40E-11
2200 2.75E-11
2300 3.13E-11
2400 3.54E-11
2500 3.96E-11
2600 4.41E-11
2700 4.89E-11
2800 5.38E-11
2900 5.90E-11
3000 6.45E-11
3100 7.01E-11
3200 7.60E-11
3300 8.20E-11
3400 8.83E-11
3500 9.48E-11
3600 1.01E-10
3700 1.08E-10
3800 1.15E-10
3900 1.23E-10
4000 1.30E-10
4100 1.38E-10
4200 1.46E-10
4300 1.54E-10
4400 1.62E-10
4500 1.70E-10
4600 1.79E-10
4700 1.88E-10
4800 1.97E-10
4900 2.06E-10
5000 2.15E-10