Gas-phase chemistry of citronellol with ozone and OH radical: Rate constants and products

A bimolecular rate constant, k OH+citronellol, of (170±43)×10 −12 cm 3 molecule −1 s −1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 3,7-dimethyl-6-octen-1-ol (citronellol) at (297±3) K and 1 atmosphere total pressure. Additionally, a bimolecular...

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Vydáno v:Atmospheric environment (1994) Ročník 40; číslo 4; s. 726 - 735
Hlavní autoři: Ham, Jason E., Proper, Steven P., Wells, J.R.
Médium: Journal Article
Jazyk:angličtina
Vydáno: Oxford Elsevier Ltd 01.02.2006
Elsevier Science
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ISSN:1352-2310, 1873-2844
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Abstract A bimolecular rate constant, k OH+citronellol, of (170±43)×10 −12 cm 3 molecule −1 s −1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 3,7-dimethyl-6-octen-1-ol (citronellol) at (297±3) K and 1 atmosphere total pressure. Additionally, a bimolecular rate constant, k O 3 + citronellol , of (2.4±0.1)×10 −16 cm 3 molecule −1 s −1, was measured by monitoring the decrease in ozone (O 3) concentration in an excess of citronellol. To more clearly define part of citronellol's indoor environment degradation mechanism, the products of the citronellol+OH and citronellol+O 3 reactions were also investigated. The positively identified citronellol/OH and citronellol/O 3 reaction products were: acetone, ethanedial (glyoxal, HC( O)C( O)H), and 2-oxopropanal (methylglyoxal, CH 3C( O)C( O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N, O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose 6-hydroxy-4-methylhexanal as the other major citronellol/OH and citronellol/O 3 reaction product. The elucidation of this other reaction product was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible citronellol/OH and citronellol/O 3 reaction mechanisms based on previously published volatile organic compound/OH and volatile organic compound/O 3 gas-phase reaction mechanisms.
AbstractList A bimolecular rate constant, k sub(OH+citronellol), of (170+/-43)x10 super(- 12) cm super(3) molecule super(-1) s super(-1) was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 3,7-dimethyl-6- octen-1-ol (citronellol) at (297+/-3) K and 1 atmosphere total pressure. Additionally, a bimolecular rate constant, k sub(O) sub(3+citronellol), of (2.4+/-0.1)x10 super(-16) cm super(3) molecule super(-1) s super(-1), was measured by monitoring the decrease in ozone (O sub(3)) concentration in an excess of citronellol. To more clearly define part of citronellol's indoor environment degradation mechanism, the products of the citronellol+OH and citronellol+O sub(3) reactions were also investigated. The positively identified citronellol/OH and citronellol/O sub(3) reaction products were: acetone, ethanedial (glyoxal, HC(O)C(O)H), and 2-oxopropanal (methylglyoxal, CH sub(3)C(O)C(O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose 6-hydroxy-4-methylhexanal as the other major citronellol/OH and citronellol/O sub(3) reaction product. The elucidation of this other reaction product was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible citronellol/OH and citronellol/O sub(3) reaction mechanisms based on previously published volatile organic compound/OH and volatile organic compound/O sub(3) gas-phase reaction mechanisms.
A bimolecular rate constant, k OH+citronellol, of (170±43)×10 −12 cm 3 molecule −1 s −1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 3,7-dimethyl-6-octen-1-ol (citronellol) at (297±3) K and 1 atmosphere total pressure. Additionally, a bimolecular rate constant, k O 3 + citronellol , of (2.4±0.1)×10 −16 cm 3 molecule −1 s −1, was measured by monitoring the decrease in ozone (O 3) concentration in an excess of citronellol. To more clearly define part of citronellol's indoor environment degradation mechanism, the products of the citronellol+OH and citronellol+O 3 reactions were also investigated. The positively identified citronellol/OH and citronellol/O 3 reaction products were: acetone, ethanedial (glyoxal, HC( O)C( O)H), and 2-oxopropanal (methylglyoxal, CH 3C( O)C( O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N, O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose 6-hydroxy-4-methylhexanal as the other major citronellol/OH and citronellol/O 3 reaction product. The elucidation of this other reaction product was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible citronellol/OH and citronellol/O 3 reaction mechanisms based on previously published volatile organic compound/OH and volatile organic compound/O 3 gas-phase reaction mechanisms.
Author Ham, Jason E.
Proper, Steven P.
Wells, J.R.
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  givenname: Steven P.
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  surname: Wells
  fullname: Wells, J.R.
  email: ozw0@cdc.gov
  organization: Exposure Assessment Branch, Health Effects Laboratory Division, National Institute for Occupational Safety and Health, 1095 Willowdale Road, Morgantown, WV 26505, USA
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Issue 4
Keywords Reaction products
Oxygenated organic compounds
Citronellol
Kinetics
3,7-dimethyl-6-octen-1-ol
Chemical analysis
Pollutant behavior
Reaction initiator
Reaction product
Alcohol
Ozone
Volatile organic compound
Chemical reaction kinetics
3.7-dimethyl-6-octen-1-ol: Reaction products
Reaction mechanism
Indoor pollution
Hydroxyl radicals
Qualitative analysis
Gaseous phase reaction
Organic compounds
Language English
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Snippet A bimolecular rate constant, k OH+citronellol, of (170±43)×10 −12 cm 3 molecule −1 s −1 was measured using the relative rate technique for the reaction of the...
A bimolecular rate constant, k sub(OH+citronellol), of (170+/-43)x10 super(- 12) cm super(3) molecule super(-1) s super(-1) was measured using the relative...
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StartPage 726
SubjectTerms 3,7-dimethyl-6-octen-1-ol
Applied sciences
Atmospheric pollution
Buildings. Public works
Citronellol
Exact sciences and technology
Indoor pollution and occupational exposure
Kinetics
Oxygenated organic compounds
Pollution
Pollution indoor buildings
Reaction products
Title Gas-phase chemistry of citronellol with ozone and OH radical: Rate constants and products
URI https://dx.doi.org/10.1016/j.atmosenv.2005.10.004
https://www.proquest.com/docview/17239042
Volume 40
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