β-Ionone reactions with ozone and OH radical: Rate constants and gas-phase products

The bimolecular rate constants, k OH + β -ionone (118±30)×10 −12 cm 3 molecule −1 s −1 and k O 3 + β ‐ ionone , (0.19±0.05)×10 −16 cm 3 molecule −1 s −1, were measured using the relative rate technique for the reaction of the hydroxyl radical (OH) and ozone (O 3) with 4-(2,6,6-trimethyl-1-cyclohexen...

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Veröffentlicht in:Atmospheric environment (1994) Jg. 41; H. 38; S. 8758 - 8771
Hauptverfasser: Forester, Crystal D., Ham, Jason E., Wells, J. Raymond
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Oxford Elsevier Ltd 01.12.2007
Elsevier Science
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ISSN:1352-2310, 1873-2844
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Zusammenfassung:The bimolecular rate constants, k OH + β -ionone (118±30)×10 −12 cm 3 molecule −1 s −1 and k O 3 + β ‐ ionone , (0.19±0.05)×10 −16 cm 3 molecule −1 s −1, were measured using the relative rate technique for the reaction of the hydroxyl radical (OH) and ozone (O 3) with 4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one ( β-ionone) at 297±3 K and 1 atm total pressure. To more clearly define part of β-ionone's indoor environment degradation mechanism, the products of the β-ionone+OH and β-ionone+O 3 reactions were also investigated. The identified β-ionone+OH reaction products were: glyoxal (ethanedial, HC(=O)C(=O)H), and methylglyoxal (2-oxopropanal, CH 3C(=O)C(=O)H) and the identified β-ionone+O 3 reaction product was 2-oxopropanal. The derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N, O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) were used to propose 2,6,6-trimethylcyclohex-1-ene-1-carbaldehyde as the other major β-ionone+OH and β-ionone+O 3 reaction product. The elucidation of this other reaction product was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible β-ionone+OH and β-ionone+O 3 reaction mechanisms based on previously published volatile organic compound+OH and volatile organic compound+O 3 gas-phase reaction mechanisms. The additional gas-phase products observed from the β-ionone+OH reaction are proposed to be the result of cyclization through a radical intermediate.
Bibliographie:ObjectType-Article-2
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ISSN:1352-2310
1873-2844
DOI:10.1016/j.atmosenv.2007.07.047