Rate measurements of reactions of OH by resonance absorption. Part 3.—Reactions of OH with H2, D2and hydrogen and deuterium halides

Abstract
The rates of the reactions of OH with H2, D2, HCl and DCl have been determined between 210 and 460 K using time-resolved resonance absorption to monitor removal of OH following creation of the radicals by flash photolysis of mixtures containing H2O or N2O + H2. Arrhenius rate laws are obeyed by all four of these reactions throughout this range of temperature: kOH + H2= 1.8 × 10–11 exp[–19.4 kJ mol–1/RT] cm3 molecule–1 s–1, kOH + D2= 1.25× 10–11 exp[–21.5 kJ mol–1/RT] cm3 molecule–1 s–1, kOH + HCl= 4.1 × 10–12 exp[–4.4 kJ mol–1/RT] cm3 molecule–1 s–1, kOH + DCl= 4.7 × 10–12 exp[–6.5 kJ mol–1/RT] cm3 molecule–1 s–1. The observed kinetic isotope effects are compared with predictions based on 3- and 4-atom models of the transition states using semi-empirical potential functions to estimate the transition state properties. Preliminary measurements on the reactions of OH with HBr and HI are also reported. The rate constants at 298 K are respectively 4.5 × 10–12 and 9 × 10–12 cm3 molecule–1 s–1.