NIST Chemical Kinetics Database

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 + H· → ·OH + HCl
Reaction order:   2
Temperature:   220 - 2000 K
Rate expression:   4.91x10^-12 [cm³/molecule s] (T/298 K)^1.20 e^{-1557 [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.

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Rate constant values calculated from the Arrhenius expression:

T (K)	k(T) [cm³/molecule s]
220	1.46E-12
300	2.65E-12
400	4.37E-12
500	6.28E-12
600	8.32E-12
700	1.05E-11
800	1.27E-11
900	1.50E-11
1000	1.74E-11
1100	1.98E-11
1200	2.23E-11
1300	2.49E-11
1400	2.75E-11
1500	3.01E-11
1600	3.28E-11
1700	3.55E-11
1800	3.83E-11
1900	4.11E-11
2000	4.39E-11