Determination by reactive absorption of the rate constant of the ozone reaction with the hydroperoxide anion

Abstract : The reaction rate constant between the hydroperoxide anion (HO2−) and molecular ozone was evaluated from the reactive absorption method in the range of temperature from 20 to 35 °C. This reaction is crucial in the initiation step of the ozone decomposition, especially using the peroxone process which combines ozone and hydrogen peroxide in solution. A stirred-cell operated semi-continuously was used for this purpose. A high initial concentration of tert-butanol (0.05 mol L−1) was applied to efficiently scavenge all radicals and to avoid any parasite reaction. Based on the dissolved H2O2 concentration decreasing and the outlet ozone concentration time-course, the stoichiometry of the initiation reaction was determined, with one mol of H2O2 consumed per mol of ozone transferred. The chemical conditions were thoroughly selected to reach a fast pseudo-first order absorption regime. The reaction rate constant increased from 1.91 × 106–2.40 × 106 L mol−1 s−1 at 20 °C to 5.68 × 106–7.31 × 106 L mol−1 s−1 at 35 °C.