Reaction of HO2 with O3 and the effect of water vapor on HO2 kinetics

The effects of temperature and water vapor concentration on the ratio of the rate constant of the reaction HO2 + O3 yields OH + 2(O2) to the square root of the rate constant for the reaction HO2 + HO2 yields H2O2 + O2 are determined. Photolysis of H2-O2-O3 mixtures at 253.7 nm was carried out with H2O pressures in the range 0 to 15 torr at a temperature range of -42.5 to 61 C along with 184.9 nm photolysis of H2O-O2-O3 mixtures. It is shown that the rate of O3 photolysis is suppressed by the addition of water vapor and it is suggested that this effect is realized in the HO2 + HO2 yields H2O2 + O2 reaction. The calculated expression for the temperature dependence of the rate constant ratio is found to be in good agreement with that calculated from separate rate constants. Rate constants determined for the reaction OH + HO2 yields H2O + O2 are found to be higher than those previously determined, presumably due to increased pressure, indicating that atmospheric models should take into account the possible pressure dependences of the reactions considered.