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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:   CCl4 + ·CCl3 + HCl
Reaction order:   2
Temperature:   200 - 5000 K
Rate expression:   7.98x10-12 [cm3/molecule s] (T/298 K)1.43 e-19747 [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 3.14E-17
300 2.94E-15
400 3.21E-14
500 1.45E-13
600 4.14E-13
700 9.09E-13
800 1.68E-12
900 2.77E-12
1000 4.19E-12
1100 5.96E-12
1200 8.08E-12
1300 1.05E-11
1400 1.34E-11
1500 1.65E-11
1600 2.00E-11
1700 2.38E-11
1800 2.79E-11
1900 3.23E-11
2000 3.70E-11
2100 4.20E-11
2200 4.73E-11
2300 5.28E-11
2400 5.86E-11
2500 6.46E-11
2600 7.08E-11
2700 7.73E-11
2800 8.41E-11
2900 9.10E-11
3000 9.82E-11
3100 1.06E-10
3200 1.13E-10
3300 1.21E-10
3400 1.29E-10
3500 1.37E-10
3600 1.45E-10
3700 1.54E-10
3800 1.63E-10
3900 1.72E-10
4000 1.81E-10
4100 1.90E-10
4200 1.99E-10
4300 2.09E-10
4400 2.18E-10
4500 2.28E-10
4600 2.38E-10
4700 2.48E-10
4800 2.59E-10
4900 2.69E-10
5000 2.80E-10