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Author(s):   Wang, L.; Liu, J.-y.; Li, Z.-s.; Huang, X.-r.; Sun, C.-c.
Title:   Theoretical Study and Rate Constant Calculation of the Cl + HOCl and H + HOCl Reactions
Journal:   J. Phys. Chem. A
Volume:   107
Page(s):   4921 - 4928
Year:   2003
Reference type:   Journal article
Squib:   2003WAN/LIU4921-4928

Reaction:   HOCl + ·ClHCl + ClO
Reaction order:   2
Temperature:   220 - 2000 K
Rate expression:   6.92x10-15 [cm3/molecule s] (T/298 K)4.07 e1412 [J/mole]/RT
Category:  Theory
Data type:   Ab initio
Pressure dependence:   None reported
Comments:   The authors have used ab initio calculations to investigate the reactions Cl + HOCl = PRODUCTS and H + HOCl = PRODUCTS. The geometries, harmonic vibrational frequencies, energies, and enthalpies of all of the stationary points are calculated at the MP2/6-311+G(2d, 2p) level of theory. Minimum energy paths were calculated by IRC theory at the MP2/6-311+G(2d,2p) level, and dynamics calculations carried out at the G3//MP2 level. Rate constants were evaluated with POLYRATE 8.4.1 (Truhlar and co-workers) using improved canonical variational transition-state theory (ICVT) with a small-curvature tunneling correction (SCT). Temperatures between 220-2000 K were considered and results were compared with experiment where data was available.

For the HOCl + Cl system, the calculations indicate formation of two lower energy intermediate complexes along the Cl and H abstraction channels.

View full bibliographic record.


Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
220 4.35E-15
300 1.25E-14
400 3.51E-14
500 7.99E-14
600 1.59E-13
700 2.85E-13
800 4.76E-13
900 7.51E-13
1000 1.13E-12
1100 1.64E-12
1200 2.31E-12
1300 3.17E-12
1400 4.24E-12
1500 5.57E-12
1600 7.19E-12
1700 9.15E-12
1800 1.15E-11
1900 1.42E-11
2000 1.75E-11