The products of the Cl‐atom‐initiated oxidation of hydroxyacetone (HYAC, CH3C(O)CH2OH) have been examined under conditions relevant to the earth's lower atmosphere. Over the range of temperatures studied (252‐298 K), in the absence of NOx, methylglyoxal (CH3C(=O)CH=O, MGLY) was formed with a primary yield >84% (96 ± 9% at 298 K), while in the presence of elevated NOx, MGLY and formic acid were both formed as major primary products. In contrast to a previous study, acetic acid was not identified as a major primary product under the conditions studied. The results are quantitatively interpreted from a consideration of the formation of a stabilized CH3C(O)CH(OH)OO• radical, either in a ≈50% yield from the addition of O2to CH3C(O)CH•(OH) or in 100% yield from the addition of HO2to MGLY. At high temperature and low NOx, decomposition of the stabilized CH3C(O)CH(OH)OO• radical to MGLY is favored, while lower temperatures and conditions of high NOxfavor bimolecular reactions of the stabilized radical, with subsequent production of formic acid. Analysis of the data allows for a semiquantitative determination of
Improved computational modeling of the kinetics of the acetylperoxy + HO 2 reaction
The acetylperoxy + HO 2 reaction has multiple impacts on the troposphere, with a triplet pathway leading to peracetic acid + O 2 (reaction (1a)) competing with singlet pathways leading to acetic acid + O 3 (reaction (1b)) and acetoxy + OH + O 2 (reaction (1c)). A recent experimental study has reported branching fractions for these three pathways ( α 1a , α 1b , and α 1c ) from 229 K to 294 K. We constructed a theoretical model for predicting α 1a , α 1b , and α 1c using quantum chemical and Rice–Ramsperger–Kassel–Marcus/master equation (RRKM/ME) simulations. Our main quantum chemical method was Weizmann-1 Brueckner Doubles (W1BD) theory; we combined W1BD and equation-of-motion spin-flip coupled cluster (SF) theory to treat open-shell singlet structures. Using RRKM/ME simulations that included all conformers of acetylperoxy–HO 2 pre-reactive complexes led to a 298 K triplet rate constant, k 1a = 5.11 × 10 −12 cm 3 per molecule per s, and values of α 1a in excellent agreement with experiment. Increasing the energies of all singlet structures by 0.9 kcal mol −1 led to a combined singlet rate constant, k 1b+1c = 1.20 × 10 −11 cm 3 per molecule per s, in good agreement with experiment. However, our predicted variations in α 1b and α 1c with temperature are not nearly as large as those measured, perhaps due to the inadequacy of SF theory in treating the transition structures controlling acetic acid + O 3 formation vs. acetoxy + OH + O 2 formation.
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- NSF-PAR ID:
- 10422847
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Faraday Discussions
- Volume:
- 238
- ISSN:
- 1359-6640
- Page Range / eLocation ID:
- 589 to 618
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract K 3 = (2.9 ± 0.4) × 10−16cm3molecule−1, for the HO2+ MGLY ↔ CH3C(O)CH(OH)OO• equilibrium process at 298 K and a roughly order of magnitude increase inK 3at 252 K. -
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