Production of stabilized Criegee intermediates and peroxides in the gas phase ozonolysis of alkenes 1.: Ethene, trans-2-butene, and 2,3-dimethyl-2-butene

Ozone-alkene reactions generate stabilized Criegee intermediates (of the form R1R2COO), which are believed to react with water molecules to form organic hydroperoxides, hydrogen peroxide and carboxylic acids. These reactions are thought to be significant sources of these environmentally important compounds, yet both the yields of stabilized Criegee intermediates and the branching ratios from their reaction with water are not well known. The formation of hydrogen peroxide and organic hydroperoxides was investigated in the gas phase ozonolysis of ethene, trans-2-butene, and 2,3-dimethyl-2-butene for relative humidities (RH) from 0 and 80% by gas chromatography with flame ionization detection and high-performance liquid chromatography with fluorescence detection. Additionally, yields of acetaldehyde and acetic acid from trans-2-butene and acetone from 2,3-dimethyl-2-butene were measured. The reactions of stabilized Criegee intermediates with water were found to proceed almost entirely via organic hydroperoxide or hydrogen peroxide formation with little acid formation. Stabilized Criegee intermediate yields of 0.39, 0.24, and 0.10 were obtained for ethene, trans-2-butene, and 2,3-dimethyl-2-butene, respectively.