Photooxidation of methylhydroperoxide and ethylhydroperoxide in the aqueous phase under simulated cloud droplet conditions

The photooxidation of methylhydroperoxide (MHP) and ethylhydroperoxide (EHP) was studied in the aqueous phase under simulated cloud droplet conditions. The kinetics and the reaction products of direct photolysis and OH-oxidation were studied for both compounds. The photolysis frequencies obtained were J_MHP=4.5 (±1.0)×10^?5 s^?1 and J_EHP=3.8 (±1.0)×10^?5 s^?1 for MHP and EHP respectively at 6 °C. The rate constants of OH-oxidation of MHP at 6 °C were 6.3 (±2.6)×10⁸ M^?1 s^?1 and 5.8 (±1.9)×10⁸ M^?1 s^?1 relative to ethanol and 2-propanol respectively, and the rate constant of OH-oxidation of EHP was 2.1 (±0.6)×10⁹ M^?1 s^?1 relative to 2-propanol at 6 °C. The reaction products obtained were not only the corresponding aldehydes, but also the corresponding acids, and hydroxyhydroperoxides as primary reaction products. The yields for these products were sensitive to the pH value. The carbon balance was higher than 85% for all experiments, showing that most reaction products were detected. A chemical mechanism was proposed for each reaction, and the atmospheric implications were discussed.