Rate Constant for the Reaction of OH with H2 between 200 and 480 K

Orkin, V. L., S. N. Kozlov, G. A. Poskrebyshev, and M. J. Kurylo (2006), Rate Constant for the Reaction of OH with H2 between 200 and 480 K, J. Phys. Chem. A, 110, 6978-6985, doi:10.1021/jp057035b.

The rate constant for the reaction of OH radicals with molecular hydrogen was measured using the flash photolysis resonance-fluorescence technique over the temperature range of 200-479 K. The Arrhenius plot was found to exhibit a noticeable curvature. Careful examination of all possible systematic uncertainties indicates that this curvature is not due to experimental artifacts. The rate constant can be represented by the following expressions over the indicated temperature intervals:
kH2(250-479 K) = 4.27 × 10-13 × (T/ 298)^2.406 × exp{-1240/T} cm3 molecule-1 s-1 above T = 250 K and
kH2(200-250 K) = 9.01 × 10-13 × exp{-(1526 ± 70)/T} cm3 molecule-1 s-1 below T = 250 K.
No single Arrhenius expression can adequately represent the rate constant over the entire temperature range within the experimental uncertainties of the measurements. The overall uncertainty factor was estimated to be
fH2(T) = 1.04 × exp{50 × |(1/T) - (1/298)|}.
These measurements indicate an underestimation of the rate constant at lower atmospheric temperatures by the present recommendations. The global atmospheric lifetime of H2 due to its reaction with OH was estimated to be 10 years.

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Upper Atmosphere Research Program (UARP)