Kinetics of the Gas-Phase Reaction of OH with HCl

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: k1 = 3.20 x 10(-15)T0.99 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: k1 = 8.81 x 10(-16)T1.16 exp(58 K/T) cm3 molecule(-1) s(-1) for the temperature range 200-1015 K and k1 = 6.84 x 10(-19)T2.12 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.