Atmospheric chemistry of enols: a theoretical study of the vinyl alcohol + OH + O(2) reaction mechanism.
Enols are emerging as trace atmospheric components that may play a significant role in the formation of organic acids in the atmosphere. We have investigated the hydroxyl radical ((•)OH) initiated oxidation chemistry of the simplest enol, vinyl alcohol (ethenol, CH2═CHOH), using quantum chemical calculations and energy-grained master equation simulations. A lifetime of around 4 h was determined for vinyl alcohol in the presence of tropospheric levels of (•)OH. The reaction proceeds by (•)OH addition at both the α (66%) and β (33%) carbons of the π-system, yielding the C-centered radicals (•)CH2CH(OH)2, and HOCH2C(•)HOH, respectively. Subsequent trapping by O2 leads to the respective peroxyl radicals. About 90% of the chemically activated population of the major peroxyl radical adduct (•)O2CH2CH(OH)2 is predicted to undergo fragmentation to produce formic acid and formaldehyde, with regeneration of (•)OH. The minor peroxyl radical HOCH2C(OO(•))HOH is even less stable and undergoes almost exclusive HO2(•) elimination to form glycolaldehyde (HOCH2CHO). Formation of the latter has not been proposed before in the oxidation of vinyl alcohol. A kinetic mechanism for use in atmospheric modeling is provided, featuring phenomenological rate coefficients for formation of the three main product channels ((•)O2CH2CH(OH)2 [8%]; HC(O)OH + HCHO + (•)OH [56%]; HOCH2CHO + HO2(•) [37%]). Our study supports previous findings that vinyl alcohol should be rapidly removed from the atmosphere by reaction with (•)OH and O2 with glycolaldehyde being identified as a previously unconsidered product. Most importantly, it is shown that direct chemically activated reactions can lead to (•)OH and HO2(•) (HOx) recycling.
Department of Chemical and Biomolecular Engineering, The University of Melbourne , Victoria 3010, Australia.
Sui
S
So
Uta
U
Wille
Gabriel
G
da Silva
D000438:Alcohols / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry*; D003198:Computer Simulation; D017665:Hydroxyl Radical / Q000737:chemistry*; D007536:Isomerism; D007700:Kinetics; D008962:Models, Theoretical; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D013816:Thermodynamics
D000438:Alcohols; D017665:Hydroxyl Radical; D010100:Oxygen