title: The atmospheric photolysis of E-2-hexenal, Z-3-hexenal and E,E-2,4-hexadienal.
abstract: The atmospheric photolysis of E-2-hexenal, Z-3-hexenal and E,E-2,4-hexadienal has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. E-2-Hexenal and E,E-2,4-hexadienal were found to undergo rapid isomerization to produce Z-2-hexenal and a ketene-type compound (probably E-hexa-1,3-dien-1-one), respectively. Both isomerization processes were reversible with formation of the reactant slightly favoured. Values of j(E-2-hexenal)/j(NO(2)) = (1.80 +/- 0.18) x 10(-2) and j(E,E-2,4-hexadienal)/j(NO(2)) = (2.60 +/- 0.26) x 10(-2) were determined. The gas phase UV absorption cross-sections of E-2-hexenal and E,E-2,4-hexadienal were measured and used to derive effective quantum yields for photoisomerization of 0.36 +/- 0.04 for E-2-hexenal and 0.23 +/- 0.03 for E,E-2,4-hexadienal. Although photolysis appears to be an important atmospheric degradation pathway for E-2-hexenal and E,E-2,4-hexadienal, the reversible nature of the photolytic process means that gas phase reactions with OH and NO(3) radicals are ultimately responsible for the atmospheric removal of these compounds. Atmospheric photolysis of Z-3-hexenal produced CO, with a molar yield of 0.34 +/- 0.03, and 2-pentenal via a Norrish type I process. A value of j(Z-3-hexenal)/j(NO(2)) = (0.4 +/- 0.04) x 10(-2) was determined. The results suggest that photolysis is likely to be a minor atmospheric removal process for Z-3-hexenal.
authors.affiliation: Department of Chemistry and Environmental Research Institute, University College Cork, Cork, Ireland.
authors.forename: Margaret P
authors.initials: MP
authors.lastname: O'Connor
authors.forename: John C
authors.initials: JC
authors.lastname: Wenger
authors.forename: Abdelwahid
authors.initials: A
authors.lastname: Mellouki
authors.forename: Klaus
authors.initials: K
authors.lastname: Wirtz
authors.forename: Amalia
authors.initials: A
authors.lastname: Muñoz
mesh_terms: D000447:Aldehydes / Q000032:analysis / Q000737:chemistry* / Q000528:radiation effects; D000466:Alkadienes / Q000032:analysis / Q000737:chemistry* / Q000528:radiation effects; D001272:Atmosphere / Q000032:analysis* / Q000737:chemistry*; D008027:Light; D010777:Photochemistry / Q000379:methods*
chemical_list: D000447:Aldehydes; D000466:Alkadienes; C079389:2,4-hexadienal; C010463:n-hexanal