Kinetics of the Gas-Phase Reaction of OH with HCl

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2006-01, Vol.110 (3), p.936-943
• Main Authors: Bryukov, Mikhail G, Dellinger, Barry, Knyazev, Vadim D
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp053615x

The reaction of hydroxyl radicals with hydrogen chloride (reaction 1) has been studied experimentally using a pulsed-laser photolysis/pulsed-laser-induced fluorescence technique over a wide range of temperatures, 298−1015 K, and at pressures between 5.33 and 26.48 kPa. The bimolecular rate coefficient data set obtained for reaction 1 demonstrates no dependence on pressure and exhibits positive temperature dependence that can be represented with modified three-parameter Arrhenius expression within the experimental temperature range:  k 1 = 3.20 × 10-15 T 0.99 exp(−62 K/T) cm3 molecule-1 s-1. The potential-energy surface has been studied using quantum chemical methods, and a transition-state theory model has been developed for the reaction 1 on the basis of calculations and experimental data. The model results in modified three-parameter Arrhenius expressions:  k 1 = 8.81 × 10-16 T 1.16 exp(58 K/T) cm3 molecule-1 s-1 for the temperature range 200−1015 K and k 1 = 6.84 × 10-19 T 2.12 exp(646 K/T) cm3 molecule-1 s-1 for the temperature dependence of the reaction 1 rate coefficient extrapolation to high temperatures (500−3000 K). A temperature dependence of the rate coefficient of the Cl + H2O → HCl + OH reaction has been derived on the basis of the experimental data, modeling, and thermochemical information.