Alpha-Terpineol Reactions with the Nitrate Radical: Rate Constant and Gas-Phase Products

Details

• Personal Author:
  Ham JE ; Jones BT
• Description:
  The bimolecular rate constant of kNO3+a-terpineol (16 +/- 4) × 10-12 cm3 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-cyclohex-3-enyl)propan-2-ol) at 297 +/- 3 K and 1 atmosphere total pressure. To more clearly define part of a-terpineol's indoor environment degradation mechanism, the products of a-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-pentafluorobenzyl)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 a-terpineol + NO3* reaction mechanisms based on previously published volatile organic compound + NO3* gas-phase mechanisms. The additional gas-phase products (2,6,6-trimethyltetrahydro-2H-pyran-2,5-dicarbaldehyde and 2,2-dimethylcyclohexane-1,4-dicarbaldehyde) are proposed to be the result of cyclization through a reaction intermediate. [Description provided by NIOSH]
• Subjects:
  Air Pollutants, Occupational Air Pollution Air Pollution, Indoor Chemistry Environmental Health Occupational Health Safety
• Keywords:
  Air-quality Author Keywords: A-Terpineol Chemical-binding Chemical-composition Chemical-deposition Chemical-properties Chemical-reactions Chemical-synthesis Gases Indoor-environmental-quality Kinetics Nitrate Radical Organic-chemicals Organic-compounds Organic-vapors Oxygenated Organic Compounds Quantitative-analysis Reaction Products Sampling-methods

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• ISSN:
  1352-2310
• Document Type:
  Text
• Genre:
  Journal Article
• Place as Subject:
  OSHA Region 3 ; West Virginia
• CIO:
  National Institute for Occupational Safety and Health (NIOSH)
• Division:
  HELD - Health Effects Laboratory Division
• Topic:
  Workplace Safety & Health
• Location:
  North America
• Volume:
  42
• Issue:
  27
• NIOSHTIC Number:
  nn:20034618
• Citation:
  Atmos Environ 2008 Sep; 42(27):6689-6698
• Contact Point Address:
  Jason E. Ham, Exposure Assessment Branch, Health Effects Laboratory Division, National Institute for Occupational Safety and Health, 1095 Willowdale Road, Morgantown, WV 26505
• Email:
  bvo2@cdc.gov
• CAS Registry Number:
  Acetone (CAS RN 67-64-1) ; Glyoxal (CAS RN 107-22-2) ; Methylglyoxal (CAS RN 78-98-8)
• Federal Fiscal Year:
  2008
• NORA Priority Area:
  Services
• Peer Reviewed:
  True
• Source Full Name:
  Atmospheric Environment
• Collection(s):
  National Institute for Occupational Safety and Health
• Main Document Checksum:
  urn:sha-512:2e6878755acebe7519ac4562414cde7c8945803b60bbc55ec18cb8ba8e40230fba91b4668cf4d6236e0fc6610381b5be49d40381bb0b67bd5c0086bb99237377
• Download URL:
  https://stacks.cdc.gov/view/cdc/186761/cdc_186761_DS1.pdf
• File Type:
  [PDF - 735.84 KB ]