es505860s_si_001.pdf (3.02 MB)

Multiphase Chemistry of Glyoxal: Revised Kinetics of the Alkyl Radical Reaction with Molecular Oxygen and the Reaction of Glyoxal with OH, NO3, and SO4 in Aqueous Solution

Download (3.02 MB)
journal contribution
posted on 06.01.2015, 00:00 by T. Schaefer, D. van Pinxteren, H. Herrmann
The rate constant for the reaction of the hydrated glyoxyl radical (CH­(OH)2-C­(OH)2· with O2 has been determined as k298 K = (1.2 ± 0.3) × 109 L mol–1 s–1 at pH 4.8. This experimental value is considerably higher than a widely used estimated value of about k = 1 × 106 L mol–1 s–1. As the aqueous phase conversion of glyoxal is of wide interest for aqSOA formation, we suggest that the newly determined rate constant should be applied in multiphase models. The formation of the dimerization product tartaric acid has as well been studied. This product is found, however in significant yields only when the oxygen content of the solution is reduced. The formation of dimers from the recombination of alkyl radicals in the atmospheric aqueous phase should hence be treated with great care. Finally, the reactions of the free radicals OH, NO3, and SO4 with glyoxal have been investigated and rate constants of k298 K (OH) = (9.2 ± 0.5) × 108 L mol–1 s–1, k298 K (SO4) = (2.4 ± 0.2) × 107 L mol–1 s–1 and k298 K (NO3) = (4.5 ± 0.3) × 106 L mol–1 s–1 were obtained.