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Photochemical Sources of Organic Acids. 2. Formation of C₅−C₉ Carboxylic Acids from Alkene Ozonolysis under Dry and Humid Conditions

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Grazyna E. Orzechowska,^†^‡ Ha T. Nguyen,^† and Suzanne E. Paulson*^†

Departments of Atmospheric and Oceanic Sciences and Chemistry and Biochemistry, University of California at Los Angeles, Los Angeles, California 90095-1565

J. Phys. Chem. A, 2005, 109 (24), pp 5366–5375

DOI: 10.1021/jp050167k

Publication Date (Web): May 28, 2005

Section:

Physical Organic Chemistry

Abstract

The dependence of organic acid generation by alkene ozonolysis on relative humidity, thermalized Criegee intermediate scavengers, and alkene structure is investigated. Carboxylic acids generated from the ozonolysis of 1-hexene, 1-octene, 1-decene, trans-3-octene, and 1-methylcyclohexene were analyzed as trimethylsilyl (TMS) derivatives. Experiments were performed under dry (relative humidity (RH) < 1%) and humid (RH = 65%) conditions with cyclohexane or n-butyl ether as an OH scavenger. Pentanoic acid is produced from 1-hexene and trans-3-octene with yields 8.5 ± 2.6 and 5.0 ± 1.5% under dry conditions and 5.1 ± 1.5 and 2.8 ± 0.8% under humid conditions, respectively. Heptanoic acid yields from 1-octene are 8.3 ± 2.5 and 4.4 ± 1.3% under dry and humid conditions, respectively. Ozonolysis of 1-methylcyclohexene produced six C₅−C₇ multifunctional carboxylic acids, with a total yield of 7%. Several other acids and aldehydes were also monitored and quantified. An additional set of experiments with added stabilized Criegee intermediate (SCI) scavengers was performed for 1-octene ozonolysis under dry conditions. The results indicate that SCIs and their reaction with water are minor contributors to acid formation in the atmosphere and suggest that many of the acids are formed directly.

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This article has been cited by 2 ACS Journal articles (2 most recent appear below).

2,3-Dimethyl-2-butene (TME) Ozonolysis: Pressure Dependence of Stabilized Criegee Intermediates and Evidence of Stabilized Vinyl Hydroperoxides
Greg T. Drozd, Jesse Kroll, and Neil M. Donahue
The Journal of Physical Chemistry A2011 115 (2), 161-166
- 2,3-Dimethyl-2-butene (TME) Ozonolysis: Pressure Dependence of Stabilized Criegee Intermediates and Evidence of Stabilized Vinyl Hydroperoxides
  Greg T. Drozd, Jesse Kroll, and Neil M. Donahue
  The Journal of Physical Chemistry A2011 115 (2), 161-166
  We present measurements of the pressure dependence of stabilized Criegee intermediate (SCI) formation utilizing a hexafluoroacetone scavenger. SCI yields in the ozonolysis of 2,3-dimethyl-2-butene (TME) were measured in a high pressure flow reactor within ...
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Photolysis of Heptanal
Suzanne E. Paulson, De-Ling Liu, and Grazyna E. Orzechowska, Luis M. Campos and K. N. Houk
The Journal of Organic Chemistry2006 71 (17), 6403-6408
- Photolysis of Heptanal
  Suzanne E. Paulson, De-Ling Liu, and Grazyna E. Orzechowska, Luis M. Campos and K. N. Houk
  The Journal of Organic Chemistry2006 71 (17), 6403-6408
  Photolysis of heptanal is investigated from an experimental and theoretical point of view. Photoexcited heptanal is believed to undergo rapid intersystem crossing to the triplet manifold and from there undergoes internal H-abstraction to form biradical ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links