Organic acid formation in the gas-phase ozonolysis of α,β-unsaturated ketones

Abstract

Organic acids are key species in determining the radiative properties of the atmosphere due to their contribution to particle formation. Reported discrepancies between field measurements and modelling suggest significant missing sources. Herein, we present a mechanistic investigation on the gas-phase ozonolysis of ethyl vinyl ketone (EVK, 1-penten-3-one), which we chose as a model compound for α,β-unsaturated ketones. Experiments were performed in a 1080 L quartz-glass reaction chamber (QUAREC) at 990 ± 15 mbar and 298 ± 2 K (r. h. ≪ 0.1%) and analysed via long-path FTIR spectrometry and PTR-ToF-MS. The experiments were performed in the presence of an excess of CO to suppress the chemistry of OH radicals. For a comprehensive picture, in selected experiments, SO₂ was also added to the reaction system to scavenge the stabilized Criegee intermediates (sCIs) and to investigate their formation yield. Combining the results of both set-ups allowed us to quantify 2-oxobutanal, for which we report vapour-phase FTIR spectra. In addition, we introduce the first-ever infrared spectra of perpropionic acid, which was also positively identified in the EVK + O₃ system. A detailed analysis of the experimental findings allowed us to link the identified reaction products (acetaldehyde, ethyl hydroperoxide, and perpropionic acid) to known bimolecular reactions of RO₂ radicals. Thereby, it is shown that the EVK + O₃ reaction yields formic acid, HC(O)OH, and propionic acid, C₂H₅C(O)OH, and their formation is not covered by mechanisms reported in the literature. Three different pathways accounting for their formation from chemically activated CIs are proposed and possible implications for the ozonolysis of α,β-unsaturated ketones in the atmosphere are discussed.