Organic photochemistry. 20. A method for estimating gas-phase rate constants for reactions of hydroxyl radicals with organic compounds from their relative rates of reaction with hydrogen peroxide under photolysis in 1,1,2-trichlorotrifluoroethane solution

Journal Article · Thu Dec 01 04:00:00 EST 1988 · Environ. Sci. Technol.; (United States)

DOI:https://doi.org/10.1021/es00177a010· OSTI ID:6158426

Dilling, W L; Gonsior, S J; Boggs, G U; Mendoza, C G

The reaction with hydroxyl radicals appears to be the major transformation route for many organic compounds in the atmosphere. To avoid the difficulties of measuring the rate constants for these reactions in the gas phase for some compounds, we have developed a solution-phase system for measuring relative rates. This system involves photolysis of continuously extracted 90% hydrogen peroxide into 1,1,2-trichlorotrifluoroethane solution, which contains two or more organic compounds, one of which serves as a reference standard whose gas-phase rate constant is known. Reasonable correlations (r/sup 2/ = 0.84, 0.87) were obtained between the relative solution-phase rates and the absolute gas-phase rate constants, which varied over 4 orders of magnitude for n-hexane, 2,2,4-trimethylpentane, cyclohexane, 1,1,1,-trichloroethane, cyclohexene, trichloroethene, tetra-chloroethene, ethyl acetate, toluene, n-propylbenzene, o-xylene, p-isopropyltoluene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, biphenyl, naphthalene, hexafluorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2,4-trichlorobenzene, anisole, and nitrobenzene. This method allows estimations of the gas-phase rate constants to within 1 order of magnitude or better.

• Research Organization: Dow Chemical Company, Midland, MI (USA)
• OSTI ID: 6158426
• Journal Information: Environ. Sci. Technol.; (United States), Journal Name: Environ. Sci. Technol.; (United States) Vol. 22:12; ISSN ESTHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500 -- Photochemistry
500200* -- Environment
Atmospheric-- Chemicals Monitoring & Transport-- (-1989)
54 ENVIRONMENTAL SCIENCES
ALKANES
ALKYLATED AROMATICS
ANISOLE
AROMATICS
ATMOSPHERIC CHEMISTRY
BIPHENYL
CHEMICAL REACTIONS
CHEMISTRY
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINATED AROMATIC HYDROCARBONS
CONDENSED AROMATICS
DECOMPOSITION
ETHERS
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENATED AROMATIC HYDROCARBONS
HEXANE
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN PEROXIDE
HYDROXYL RADICALS
MEASURING METHODS
NAPHTHALENE
NITRO COMPOUNDS
NITROBENZENE
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
PHASE STUDIES
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
RADICALS
TOLUENE
XYLENES