A Theoretical Study of the Photoisomerization of Glycolaldehyde and Subsequent OH Radical-Initiated Oxidation of 1,2-Ethenediol.
It has recently been discovered that carbonyl compounds can undergo UV-induced isomerization to their enol counterparts under atmospheric conditions. This study investigates the photoisomerization of glycolaldehyde (HOCH2CHO) to 1,2-ethenediol (HOCH═CHOH) and the subsequent (•)OH-initiated oxidation chemistry of the latter using quantum chemical calculations and stochastic master equation simulations. The keto-enol tautomerization of glycolaldehyde to 1,2-ethenediol is associated with a barrier of 66 kcal mol(-1) and involves a double-hydrogen shift mechanism to give the lower-energy Z isomer. This barrier lies below the energy of the UV/vis absorption band of glycolaldehyde and is also considerably below the energy of the products resulting from photolytic decomposition. The subsequent atmospheric oxidation of 1,2-ethenediol by (•)OH is initiated by addition of the radical to the π system to give the (•)CH(OH)CH(OH)2 radical, which is subsequently trapped by O2 to form the peroxyl radical (•)O2CH(OH)CH(OH)2. According to kinetic simulations, collisional deactivation of the latter is negligible and cannot compete with rapid fragmentation reactions, which lead to (i) formation of glyoxal hydrate [CH(OH)2CHO] and HO2(•) through an α-hydroxyl mechanism (96%) and (ii) two molecules of formic acid with release of (•)OH through a β-hydroxyl pathway (4%). Phenomenological rate coefficients for these two reaction channels were obtained for use in atmospheric chemical modeling. At tropospheric (•)OH concentrations, the lifetime of 1,2-ethenediol toward reaction with (•)OH is calculated to be 68 h.
Department of Chemical and Biomolecular Engineering, The University of Melbourne , Melbourne, Victoria 3010, Australia.
Sui
S
So
School of Chemistry and Bio21 Institute, The University of Melbourne , Melbourne, Victoria 3010, Australia.
Uta
U
Wille
Department of Chemical and Biomolecular Engineering, The University of Melbourne , Melbourne, Victoria 3010, Australia.
Gabriel
G
da Silva
D000079:Acetaldehyde / Q000031:analogs & derivatives* / Q000737:chemistry; D005030:Ethylenes / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D007700:Kinetics; D008962:Models, Theoretical; D010084:Oxidation-Reduction; D010777:Photochemistry; D011789:Quantum Theory; D013237:Stereoisomerism; D013816:Thermodynamics
D005030:Ethylenes; D017665:Hydroxyl Radical; D000079:Acetaldehyde; C010972:glycolaldehyde