The rate and mechanism of the gas-phase oxidation of hydroxyacetone

The rate and mechanism for gas-phase destruction of hydroxyacetone, CH₃C(O)CH₂OH, by reaction with OH, Cl-atoms, and by photolysis have been determined. The first quantitative UV absorption spectrum of hydroxyacetone is reported over the wavelength range 235 to 340 nm; the spectrum is blue- shifted by about 15 nm relative to that of acetone and peaks at 266 nm, with a maximum absorption cross section of (6.7 ± 0.6) x 10^-20 cm² molecule^{- 1}. Measurable absorption extends out to about 330 nm. The quantum yield for photolysis of hydroxyacetone in the region relevant to the troposphere (λ > 290 nm) was found to be significantly less than unity. Rate coefficients for the reaction of hydroxyacetone with OH radicals and Cl-atoms were determined at 298 K using the relative rate technique. The rate coefficient for reaction with OH was found to be (3.0 ± 0.7) x 10^-12 cm³ molecule^-1 s^-1, while the rate coefficient for reaction with Cl-atoms was found to be (5.6 ± 0.7) x 10^-11 cm³ molecule^-1 s^-1. Both values agree well with previous studies. The data were used to determine the lifetime of hydroxyacetone in the troposphere. Reaction with OH is the major gas-phase destruction mechanism for this compound, limiting its lifetime to about 4 days, while photolysis is found to be only of minor importance.