Atmospheric Oxidation of Furan and Methyl-Substituted Furans Initiated by Hydroxyl Radicals.

Abstract

The atmospheric oxidation mechanism of furan and methylfurans (MFs) initiated by OH radicals is studied using high-level quantum chemistry and kinetic calculations. The reaction starts mainly with OH addition to the C2/C5-position, forming highly chemically activated adduct radical R2*/R5*, which would either be stabilized by collision or promptly isomerize to R2B*/R5B* by breaking the C2-O/C5-O bond and then isomerize to other conformers of R2B/R5B by internal rotations. Under the atmospheric conditions, the ring-retaining radical R2/R5 would recombine with O2 and be converted to a 5-hydroxy-2-furanone compound and a compound containing epoxide, ester, and carbonyl functional groups, while the ring-opening radicals R2B/R5B would react with O2 and form unsaturated 1,4-dicarbonyl compounds. RRKM-ME calculations on the fate of R2*/R5* from the addition of OH and furans predict that the fractions of R2B/R5B formation, i.e., the molar yields of the corresponding dicarbonyl compounds, are 0.73, 0.43, 0.26, 0.07, and 0.28 for furan, 2-MF, 3-MF, 2,3-DMF, and 2,5-DMF, respectively, at 298 K and 760 Torr when using the RHF-UCCSD(T)-F12a/cc-pVDZ-F12 reaction energies and barrier heights. The predicted yields for dicarbonyl compounds agree reasonably with recent experimental measurements. Calculations here also suggest high yields of ring-retaining 5-hydroxy-2-furanone compounds, which might deserve further study.