화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.111, No.33, 8126-8138, 2007
Temperature dependence of the HO2+ClO reaction. 2. Reaction kinetics using the discharge-flow resonance-fluorescence technique
The total rate coefficient, k(3), for the reaction HO2 + ClO -> products has been determined over the temperature range of 220-336 K at a total pressure of approximately 1.5 Torr of helium using the discharge-flow resonance-fluorescence technique. Pseudo-first-order conditions were used with both ClO and HO2 as excess reagents using four different combinations of precursor molecules. HO2 molecules were formed by using either the termolecular association of H atoms in an excess of O-2 or via the reaction of F atoms with an excess of H2O2. ClO molecules were formed by using the reaction of Cl atoms with an excess of O-3 or via the reaction of Cl atoms with Cl2O. Neither HO2 nor ClO were directly observed during the course of the experiments, but these species were converted to OH or Cl radicals, respectively, via reaction with NO prior to their observation. OH fluorescence was observed at 308 nm, whereas Cl fluorescence was observed at approximately 138 nm. Numerical simulations show that under the experimental conditions used secondary reactions did not interfere with the measurements; however, some HO2 was lost on conversion to OH for experiments in excess HO2. These results were corrected to compensate for the simulated loss. At 296 K, the rate coefficient was determined to be (6.4 +/- 1.6) x 10(-12) cm(3) molecule(-1) s(-1). The temperature dependence expressed in Arrhenius form is (1.75 +/- 0.52) x 10(-12) exp[(368 +/- 78)/T] cm(3) molecule(-1) s(-1). The Arrhenius expression is derived from a fit weighted by the reciprocal of the measurement errors of the individual data points. The uncertainties are cited at the level of two standard deviations and contain contributions from statistical errors from the data analysis in addition to estimates of the systematic experimental errors and possible errors from the applied model correction.