Kinetics Database Logo

Kinetics Database Resources

Simple Reaction Search

Search Reaction Database

Search Bibliographic Database

Set Unit Preferences


Rate Our Products and Services


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


Administrative Links

NIST home page

MML home page

Chemical Sciences Division

  NIST Logo Home
©NIST, 2020
Accessibility information
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