Kinetics of the gas-phase reactions of NO/sub 3/ radicals with a series of dialkenes, cycloalkenes, and monoterpenes at 295 +/- 1 K

Journal Article · Tue May 01 04:00:00 EDT 1984 · Environ. Sci. Technol.; (United States)

DOI:https://doi.org/10.1021/es00123a016· OSTI ID:7023787

Atkinson, R; Aschmann, S M; Winer, A M; Pitts, Jr, J N

Rate constants for the gas-phase reactions of the NO/sub 3/ radical, an important reactive constituent of nighttime ambient atmospheres, have been determined for the first time for a series of dialkenes, cycloalkenes, and monoterpenes by using a relative rate technique. By use of a rate constant for the reaction of NO/sub 3/ radicals with trans-2-butene of (2.11 +/- 0.24) x 10 /sup -13/ cm/sup 3/ molecule /sup -1/s/sup -1/, the rate constants obtained at 295 +/- 1 K were the following (in cm/sup 3/ molecule/sup -1/s/sup -1/ units): 1,3-butadiene, (5.34 +/- 0.62) x 10/sup -14/; isoprene, (3.23 +/- 0.38) x 10/sup -13/; cyclohexene, (2.87 +/- 0.34) x 10/sup -13/; 1,3-cyclohexadiene, (7.2 +/- 1.7) x 10/sup -12/; 1,4-cyclohexadiene, (2.89 +/- 0.35) x 10/sup -13/; 1,3-cycloheptadiene, (3.8 +/- 0.9) x 10/sup -12/; ..cap alpha..-pinene, (3.4 +/- 0.8) x 10/sup -12/; ..beta..-pinene, (1.4 +/- 0.3) x 10/sup -12/; ..delta../sup 3/-carene, (5.9 +/- 1.3) x 10/sup -12/; d-limonene, (7.7 +/- 1.7) x 10/sup -12/. These NO/sub 3/ radical rate constants for the naturally emitted hydrocarbons isoprene and the monoterpenes, in conjunction with measured ambient NO/sub 3/ radical concentrations, show that nighttime reaction with the NO/sub 3/ radical can be an important, if not dominant, loss process for these organics. Similarly, these reactions can also be an important loss process for NO/sub 3/ radicals, and hence for NO/sub x/, during nighttime hours. 43 references.

• Research Organization: Univ. of California, Riverside
• OSTI ID: 7023787
• Journal Information: Environ. Sci. Technol.; (United States), Journal Name: Environ. Sci. Technol.; (United States) Vol. 18:5; ISSN ESTHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
ATMOSPHERIC CHEMISTRY
BUTADIENE
CHEMICAL REACTION KINETICS
CHEMISTRY
CYCLOALKENES
DAILY VARIATIONS
DIENES
HYDROCARBONS
ISOPRENE
KINETICS
MEASURING METHODS
MEDIUM TEMPERATURE
NITRATES
NITROGEN COMPOUNDS
NITROXYL RADICALS
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
POLYENES
RADICALS
REACTION KINETICS
VARIATIONS