alpha-Terpineol reactions with the nitrate radical: Rate constant and gas-phase products

作者：Jones Brian T; Ham Jason E^*

来源：Atmospheric Environment, 2008, 42(27): 6689-6698.

DOI：10.1016/j.atmosenv.2008.04.017

• alpha-Terpineol
• Nitrate radical
• Kinetics
• Reaction products
• Oxygenated organic compounds

The bimolecular rate constant of kNO(3)*(1 alpha-terpineol) (16 +/- 4) 10(-12) cm(3) molecule(-1) s(-1) was measured using the relative rate technique for the reaction of the nitrate radical (NO3*) with a-terpineol (2-(4-methyl-1-cycloliex-3-enyl)propan-2-ol) at 297 +/- 3 K and 1 atmosphere total pressure. To more clearly define part of alpha-terpineol's indoor environment degradation mechanism, the products of alpha-terpineol + NO3* reaction were investigated. The identified reaction products were: acetone, glyoxal (HC(=O)C(=O)H), and methylglyoxal (CH3C(=O)C(=O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobellzyl)-hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose the other major reaction products: 6-hydroxyhept-5-en-2-one, 4-(1-hydroxy-1-methylethyl)-1-methyl-2-oxocyclohexyl nitrate, 5-(1-hydroxy-1-methylethyl)-2-oxocyclohexyl nitrate, 1-formyl-5-hydroxy-4-(hydroxymethyl)-1,5-dimethylhexyl nitrate, and 1,4-diformyl-5-hydroxy-1,5-dimethylhexyl nitrate. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products Coupled with plausible alpha-terpineol + NO3* reaction mechanisms based oil previously published volatile organic compound + NO3* gas-phase mechanisins. The additional gas-phase products (2,6,6-trimethyltetrahydro-2H-pyran-2,5-dicarbalaldehyde and 2,2-dimethylcyclohexane-1,4-dicarbaldehyde) are proposed to be the result of cyclizition through a reaction intermediate. Published by Elsevier Ltd.

• 出版日期2008-9