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Published on: February 7, 2017
Reaction Kinetics of Methyl Vinyl Ketone Oxide with Carboxylic Acids: Experimental and Theoretical Insights into
Shoma Hoshino1,2, Hiroo Hata3,4, Yusuke Yoshigoe5
1Department of Chemistry, School of Science, Kitasato University, 1-15-1 Kitazato, Minami, Sagamihara, Kanagawa252-0373, Japan.
Abstract:
Criegee intermediates (CIs) formed via alkene ozonolysis play an important role in tropospheric oxidation chemistry. Methyl vinyl ketone oxide (MVKO), an isoprene-derived CI, is expected to have a significant impact in regions with high biogenic emissions; however, quantitative kinetic data for reactions with organic acids remain limited. Here, the reaction kinetics of MVKO with acetic acid (CH3COOH) and propionic acid (CH3CH2COOH) were investigated using time-resolved cavity ring-down spectroscopy (TR-CRDS) at 298 K under low pressure conditions. The measured bimolecular rate coefficients are (2.7 ± 0.1) × 10-10 and (3.6 ± 0.1) × 10-10 cm3 molecule-1 s-1 for CH3COOH and CH3CH2COOH, respectively, indicating near-collision-limited reactivity. Complementary quantum chemical calculations combined with variational transition state theory identify barrierless reaction pathways for MVKO reactions with carboxylic acids, driven by the formation of strong hydrogen-bonding interactions. The calculated high-pressure-limit rate coefficients are in good agreement with the experimental values, with small deviations attributable to falloff effects. Incorporating the derived kinetics into a chemical transport model indicates that reactions with organic acids provide an efficient sink for MVKO in isoprene-rich regions, leading to a maximum reduction of approximately 3% in the carboxylic acid concentration. These results provide robust kinetic constraints for MVKO-acid reactions and improve the representation of isoprene-derived CI chemistry in atmospheric models.
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