1Max-Planck-Institute für Chemie, Atmospheric Chemistry Division, Mainz, Germany
2EEWRC, Cyprus Institute, Nicosia, Cyprus
3ICTP, Earth System Physics, Trieste, Italy
4King Saud University, Riyadh, Saudi Arabia
Abstract. Recent theoretical calculations showed that reaction with HO2 could be an important sink for acetone (CH3C(O)CH3) and source of acetic acid (CH3C(O)OH) in cold parts of the atmosphere (e.g. the tropopause region). This work details studies of HO2 + CH3C(O)CH3 (CH3)2C(OH)OO (R1) in laboratory-based and theoretical chemistry experiments; the atmospheric significance of Reaction (R1) was assessed in a global 3-D chemical model. Pulsed laser-kinetic experiments were conducted, for the first time, at the low-temperatures representative of the tropopause. Reaction with NO converted HO2 to OH for detection by laser induced fluorescence. Reduced yields of OH at T < 220 K provided indirect evidence for the sequestration of HO2 by CH3C(O)CH3 with a forward rate coefficient greater than 2 × 10−12 cm3 molecule−1 s−1. No evidence for Reaction (R1) was observed at T > 230 K, probably due to rapid thermal dissociation back to HO2 + CH3C(O)CH3. Numerical simulations of the data indicate that these experiments were sensitive to only (R1a) HO2-CH3C(O)CH3 complex formation, the first step in (R1). Rearrangement (R1b) of the complex to form peroxy radicals, and hence the atmospheric significance of (R1) has yet to be rigorously verified by experiment.
Results from new quantum chemical calculations indicate that K1 is characterised by large uncertainties of at least an order of magnitude at T < 220 K. The large predicted values from Hermans et al. lie at the top end of the range of values obtained from calculations at different (higher) levels of theory. Atmospheric modelling studies demonstrated that whilst (R1) chemistry may be a significant loss process for CH3C(O)CH3 near the tropopause, it cannot explain observations of CH3C(O)OH throughout the troposphere.