Abstract
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: k(H2)(250-479 K) = 4.27 x 10(-13) x (T/298)2.406 x exp[-1240/T] cm3 molecule(-1) (s-1) above T = 250 K and k(H2)(200-250 K) = 9.01 x 10(-13) x 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 f(H2)(T) = 1.04 x exp[50 x /(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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