CARBONYL PRODUCTS OF THE OZONE-UNSATURATED ALCOHOL REACTION

被引:29
作者
GROSJEAN, D
GROSJEAN, E
机构
关键词
D O I
10.1029/95JD02094
中图分类号
P4 [大气科学(气象学)];
学科分类号
0706 ; 070601 ;
摘要
Carbonyl products of the gas phase reaction of ozone with four monosubstituted and three 1,2-disubstituted unsaturated alcohols that are relevant to biogenic emissions have been identified in laboratory experiments involving unsaturated alcohol-ozone mixtures in the dark. Cyclohexane was added to scavenge the hydroxyl radical, which forms as a product of the ozone-unsaturated alcohol reaction. Major carbonyl products included formaldehyde and hydroxyacetaldehyde from allyl alcohol, acetaldehyde, and hydroxyacetaldehyde from 2-buten-1-ol, propanal, and hydroxyacetaldehyde from cis-2-penten-1-ol, formaldehyde from 3-buten-2-ol, 1-penten-3-ol, and 2-methyl-3-buten-2-ol, and hydroxyacetaldehyde from 2-buten-1,4 diol. Yields of the primary carbonyls (ozone + unsaturated alcohol --> 2 primary carbonyls + 2 biradicals) averaged 0.91 +/- 0.29, which compares to a theoretical value of 1.0. Yields of carbonyls that are not hydroxy substituted averaged 0.38 +/- 0.13, which compares to a theoretical value of 0.50 if one assumes that the alkyl-substituted and the hydroxyalkyl-substituted biradicals are formed in equal yields. The corresponding reaction mechanisms are outlined with focus on similarities between unsaturated alcohols and alkene structural homologues. Possible decomposition pathways for hydroxyalkyl-substituted biradicals are examined. The atmospheric persistence and the fate of unsaturated alcohols from biogenic emissions and of their carbonyl products are briefly discussed.
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页码:22815 / 22820
页数:6
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