Atmospheric chemistry of CF2BrH: Kinetics and mechanism of reaction with F and Cl atoms and fate of CF2BrO radicals
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Atmospheric chemistry of CF2BrH : Kinetics and mechanism of reaction with F and Cl atoms and fate of CF2BrO radicals. / Bilde, Merete; Sehested, Jens; Møgelberg, Trine E.; Wallington, Timothy J.; Nielsen, Ole J.
I: Journal of Physical Chemistry, Bind 100, Nr. 17, 25.04.1996, s. 7050-7059.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Atmospheric chemistry of CF2BrH
T2 - Kinetics and mechanism of reaction with F and Cl atoms and fate of CF2BrO radicals
AU - Bilde, Merete
AU - Sehested, Jens
AU - Møgelberg, Trine E.
AU - Wallington, Timothy J.
AU - Nielsen, Ole J.
PY - 1996/4/25
Y1 - 1996/4/25
N2 - A pulse radiolysis technique was used to investigate the kinetics and products of the reaction of CF2BrH with fluorine atoms at 296 K. This reaction forms an adduct which is in dynamic equilibrium with CF2BrH and fluorine atoms. The UV absorption spectrum of the adduct was measured relative to the UV spectrum of the CH3O2 radical over the range 230-380 nm. At 280 nm, an absorption cross section of (1.3 ± 0.3) × 10-17 cm2 molecule-1 was determined. From the absorption at 280 nm the equilibrium constant K5 = [adduct]/ ([F][CF2BrH]) was measured to be (1.59 ± 0.13) × 10-17 cm3 molecule-1. In 1 atm of SF6, the forward rate constant k5 = (1.4 ± 0.5) × 10-11 cm3 molecule-1 s-1 and the backward rate constant k-5 = (8.8 ± 3.0) × 105 s-1 were determined by monitoring the rate of formation and loss of the adduct. As part of the present work a relative rate technique was used to measure k(Cl+CF2BrH) = (5.8 ± 1.0) × 10-15 cm3 molecule-1 s-1 at 296 K and 700 Torr of N2. The fate of the oxy radical, CF2BrO, in the atmosphere is bromine atom elimination and formation of COF2.
AB - A pulse radiolysis technique was used to investigate the kinetics and products of the reaction of CF2BrH with fluorine atoms at 296 K. This reaction forms an adduct which is in dynamic equilibrium with CF2BrH and fluorine atoms. The UV absorption spectrum of the adduct was measured relative to the UV spectrum of the CH3O2 radical over the range 230-380 nm. At 280 nm, an absorption cross section of (1.3 ± 0.3) × 10-17 cm2 molecule-1 was determined. From the absorption at 280 nm the equilibrium constant K5 = [adduct]/ ([F][CF2BrH]) was measured to be (1.59 ± 0.13) × 10-17 cm3 molecule-1. In 1 atm of SF6, the forward rate constant k5 = (1.4 ± 0.5) × 10-11 cm3 molecule-1 s-1 and the backward rate constant k-5 = (8.8 ± 3.0) × 105 s-1 were determined by monitoring the rate of formation and loss of the adduct. As part of the present work a relative rate technique was used to measure k(Cl+CF2BrH) = (5.8 ± 1.0) × 10-15 cm3 molecule-1 s-1 at 296 K and 700 Torr of N2. The fate of the oxy radical, CF2BrO, in the atmosphere is bromine atom elimination and formation of COF2.
UR - http://www.scopus.com/inward/record.url?scp=0010801838&partnerID=8YFLogxK
M3 - Journal article
AN - SCOPUS:0010801838
VL - 100
SP - 7050
EP - 7059
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 17
ER -
ID: 227487807