Kinetics of the reactions of CF[sub 3]O[sub x] radicals with NO, O[sub 3], and O[sub 2]

Journal Article · Thu Apr 28 04:00:00 EDT 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100068a019· OSTI ID:7165859

Turnipseed, A A; Barone, S B; Ravishankara, A R ^[1]

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1. National Oceanic and Atmospheric Administration, Boulder, CO (United States) Univ. of Colorado, Boulder, CO (United States)

The technique of pulsed laser photolysis/pulsed laser-induced fluorescence detection of CF[sub 3]O was used to study the stratospherically important reactions of CF[sub 3]O radicals with NO (k[sub 5]), O[sub 3] (k[sub 4]), and O[sub 2] (k[sub 6]) and that of CF[sub 3]-OO with NO (k[sub 2]) and O[sub 3](k[sub 3]). Over the temperature range 233-360, K, k[sub 5](T) = (3.34 [+-] 0.68) x 10[sup [minus]11] exp[(160 [+-] 45)/T] cm[sup 3] molecule[sup [minus]1] s[sup [minus]1]. At 298 K, k[sub 2] = (1.57 [+-] 0.38) x 10[sup [minus]11] cm[sup 3] molecule[sup [minus]1] s[sup [minus]1] in agreement with past work. The reactions of CF[sub 3]O and CF[sub 3]OO with O[sub 3] were found to be slow with rate coefficients at 298 K of k[sub 4] = (2.5[sub [minus]1.5][sup 0.7]) x 10[sup [minus]14] cm[sup 3] molecule[sup [minus]1] s[sup [minus]1] and k[sub 3] [le] 7 x 10[sup [minus]15] cm[sup 3] molecule[sup [minus]1] s[sup [minus]1], respectively. No reaction of CF[sub 3]O with O[sub 2] was observed at 298 or 373 K, leading to an upper limit of k[sub 6] [le] 4 x 10[sup [minus]17] cm[sup 3] molecule[sup [minus]1] s[sup [minus]1] at 373 K. The implications of these results to the chemistry of CF[sub 3]O[sub x] radicals and O[sub 3] in the stratosphere are discussed. 32 refs., 7 figs., 1 tab.

• OSTI ID: 7165859
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:17; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
54 ENVIRONMENTAL SCIENCES
540110
ATMOSPHERIC CHEMISTRY
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
EARTH ATMOSPHERE
ELEMENTS
EXCIMER LASERS
FLUIDS
FLUORESCENCE
GAS LASERS
GASES
HELIUM
INFORMATION
KINETICS
LASERS
LUMINESCENCE
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN OXIDES
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXIDES
OXYGEN
OXYGEN COMPOUNDS
OZONE
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
RARE GASES
REACTION KINETICS
STRATOSPHERE
THEORETICAL DATA