Atmospheric chemistry of unsaturated oxygenates: Alcohols, aldehydes, ketones and esters

Conference · Sat Dec 31 04:00:00 EST 1994

OSTI ID:197478

Grosjean, D; Grosjean, E ^[1]

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1. DGA, Inc., Ventura, CA (United States)

The authors have measured ozone reaction rate constants for a number of unsaturated alcohols, esters and carbonyls. Using these rate constants together with structure-reactivity relationships, rate constants have been estimated for the reaction of the hydroxyl radical with the unsaturated biogenic oxygenates of interest. From these kinetic data, estimates could be made of the atmospheric lifetimes for a number of unsaturated alcohols, esters and carbonyls. They have also investigated, in laboratory experiments carried out under conditions that are relevant to the atmosphere, the oxidation of the unsaturated alcohols cis-3-hexen-1-ol, 3-buten-1-ol, and allyl alcohol. Two types of experiments have been performed, one involving sunlight irradiations of unsaturated alcohol-NO mixtures and the other involving the reaction of ozone with the unsaturated alcohol in the dark. Carbonyl and peroxyacyl nitrate products of the alcohol-NO reaction in sunlight have been identified and their concentrations measured. Peroxypropionyl nitrate (PPN, CH{sub 3}CH{sub 2}C(O)OONO{sub 2}) was a major product of cis-3-hexen-1-ol and accounted for 14--20% of the initial NO. Atmospheric persistence of unsaturated alcohols and implications for the formation of propanal and PPN from biogenic emissions of cis-3-hexen-1-ol will be discussed.

• OSTI ID: 197478
• Report Number(s): CONF-9405167--
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
AIR POLLUTION
ALCOHOLS
ALDEHYDES
ATMOSPHERIC CHEMISTRY
ESTERS
KETONES
OZONE
PEROXYACETYL NITRATE
PHOTOCHEMICAL REACTIONS