PRODUCTS AND MECHANISM OF THE REACTION OF NO3 WITH SELECTED ACYCLIC MONOALKENES

The gas-phase reactions of NO3 with 2-methyl-2-butene, isobutene, trans-butene, l-butene and propene, were investigated in a flow-tube at room temperature. Experiments were performed in the pressure range 1-1000 mbar in synthetic air as well as at a total pressure of 800 mbar with varying concentrations of oxygen in nitrogen. The main products found were oxiranes, nitroxy-carbonyl compounds (ketonitrates) and ketones or aldehydes. The product distribution was a function of pressure. In each case, in synthetic air, the oxirane yield increased with decreasing total pressure up to a value of about 100% at pressures less than 1 mbar. It was concluded that oxirane is a product of the excited adduct radical formed in the electrophilic addition of NO3 to the double bond. Experiments with very low partial pressures of oxygen showed that the quenched adduct radicals also produce the corresponding oxirane. Under tropospheric conditions (1000 mbar synthetic air) the following yields of the corresponding oxiranes were found: 2-methyl-2-butene 9%, isobutene 7%, trans-butene 12%, l-butene 18%, propene 28%. In the case of trans-butene the total oxirane yield consists of 72% trans- and 28% cis-isomer.