The data presented here demonstrate that mixtures may react differently than the sum of their individual components. By investigating the chemistry of mixtures of chemicals in contrast to the chemistry of individual compounds, a better assessment can be made of the overall impact cleaning products have on indoor environments.
Chamber studies to quantify formation yields of oxygenated organic reaction products were performed for gas-phase reactions of the hydroxyl radical (OH*) and ozone (03) with the common cleaning product terpene compounds limonene, alpha-terpineol, and geraniol. The reaction products observed were identified and quantified using derivatization by O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and gas chromatography/mass spectrometry. Limonene rate constants and product mechanisms have been examined previously. Several of these investigations have measured productyields from limonene reactions and those results are compared with the results presented here. Although rate constants and product mechanisms have previously been investigated for alpha-terpineol and geraniol, yields of oxygenated organic reaction products have not been measured. Reactions from the fragrance compounds in this study produced several dicarbonyl reaction products such as glyoxal, methylglyoxal, and 4-oxopentanal which were observed from all three terpenes. Total carbonyl yields ranged from 5.1% for the limonene + O3 reaction to 92% for the geraniol + O3 reaction.
A bimolecular rate constant, k OH + dihydromyrcenol , of (38± 9) × 10 −12 cm 3 molecule −1 s −1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol,) at 297 ± 3 K and 1 atm total pressure. Additionally, an upper limit of the bimolecular rate constant, k O 3 + dihydromyrcenol, of approximately 2 × 10 −18 cm 3 molecule −1 s −1 was determined by monitoring the decrease in ozone (O 3 ) concentration in an excess of dihydromyrcenol. To more clearly define part of dihydromyrcenol's indoor environment degradation mechanism, the products of the dihydromyrcenol + OH and dihydromyrcenol + O 3 reactions were also investigated. The positively identified dihydromyrcenol/OH and dihydromyrcenol/O 3 reaction products were acetone, 2-methylpropanal (O CHCH(CH 3 ) 2 ), 2-methylbutanal (O CHCH(CH 3 )CH 2 CH 3 ), O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) clearly indicated that several other reaction products were formed. The elucidation of these other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible dihydromyrcenol/OH and dihydromyrcenol/O 3 reaction mechanisms based on previously published volatile organic compound/OH and volatile organic compound/O 3 gas-phase reaction mechanisms. C 2006 Wiley Periodicals, Inc.
ethanedial (glyoxal, HC( O)C( O)H), 2-oxopropanal (methylglyoxal, CH 3 C( O)C( O)H). The use of derivatizing agents
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