ABSTRACT
Measurements of the rate constants for the gas phase reactions of OH radicals with bromoform (CHBr3) and epichlorohydrin (C3H5ClO) were performed using a flash photolysis resonance-fluorescence technique over the temperature range 230-370 K. The temperature dependences of the rate constants can be represented by the following expressions: kBF(230-370 K) = (9.94 ± 0.76) × 10(-13) exp[-(387 ± 22)/T] cm(3) molecule(-1) s(-1) and kECH(230-370 K) = 1.05 × 10(-14)(T/298)(5.16) exp(+1082/T) cm(3) molecule(-1) s(-1). Rate constants for the reactions of OH with CHCl2Br and CHClBr2 were measured between 230 and 330 K. They can be represented by the following expressions: kDCBM(230-330 K) = (9.4 ± 1.3) × 10(-13) exp[-(513 ± 37)/T] cm(3) molecule(-1) s(-1) and kCDBM(230-330 K) = (9.0 ± 1.9) × 10(-13) exp[-(423 ± 61)/T] cm(3) molecule(-1) s(-1). The atmospheric lifetimes due to reactions with tropospheric OH were estimated to be 57, 39, 72, and 96 days, respectively. The total atmospheric lifetimes of the Br-containing methanes due to both reaction with OH and photolysis were calculated to be 22, 50, and 67 days for CHBr3, CHClBr2, and CHCl2Br, respectively.
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.
