Temperature dependence of rate constants for the reactions of oxygen atoms, O(3P), with HBr and HI

Rate constants for the reactions O(3P) + HX → OH + X (X = Br, I) have been determined by a phase shift technique. Oxygen atoms were generated by modulated mercury photosensitized decomposition of nitrous oxide, and were monitored by the chemiluminescence from the reaction with nitric oxide. Over the temperature interval 298–554 K, the rate constants are satisfactorily represented by the Arrhenius expressions kO+HBr = (8.09 ± 0.86) × 109 exp (−3.59 ± 0.08)/RT and kO+HI = (2.82 ± 0.27) × 1010 exp (−1.99 ± 0.07)/RT, where the units are ℓ mol−1 s−1 and kcal mol−1. The indicated uncertainties are one standard deviation. The results of bond energy–bond order calculations, incorporating recently proposed modifications, are discussed.