TY - JOUR
T1 - Atmospheric chemistry of CF3COx radicals
T2 - Fate of CF3CO radicals, the UV absorption spectrum of CF3C(O)O2 radicals, and kinetics of the reaction CF3C(O)O2 + NO → CF3C(O)O + NO2
AU - Wallington, Timothy J.
AU - Hurley, Michael D.
AU - Nielsen, Ole J.
AU - Sehested, Jens
PY - 1994/12/1
Y1 - 1994/12/1
N2 - The atmospheric fate of CF3CO radicals has been studied using a pulse radiolysis technique to provide kinetic data and FTIR-smog chamber system to provide product data. In 1 atm of SF6 at 296 ± 2 K, CF3CO radicals decompose to give CF3 radicals and CO with a rate of (1.2 ± 0.8) × 105 s-1 and react with O2 to form CF3C(O)O2 radicals with a rate constant of (7.3 ± 1.1) × 10-13 cm3 molecule-1 s-1. In 1 atm of N2 at 296 ± 2 K, the rate constant ratio k(CF3CO + O2 → CF3C(O)O2)/k(CF3CO → CF3 + CO) = (7.4 ± 0.6) × 10-18 cm3 molecule-1. Reaction with O2 accounts for 99.5% of the loss of CF3CO radicals in the atmosphere. The ultraviolet absorption spectrum of CF3C(O)O2 radicals has been studied over the wavelength range 220-300 nm, and at 230 nm, σCF3C(O)O2 = (3.78 ± 0.43) × 10-18 cm2 molecule-1. Monitoring the rate of NO2 formation at 400 nm allowed a lower limit of k4 > 9.9 × 10-12 cm3 molecule-1 s-1 to be derived for the rate constant of the reaction of CF3C(O)O2 radicals with NO. Reaction of CF3C(O)O2 radicals with NO produces the alkoxy radical CF3C(O)O, which undergoes C-C bond scission rapidly with a rate greater than 6 × 104 s-1. Results are discussed with respect to the atmospheric chemistry of CF3COx radicals. As part of the present work, a rate constant k6 = (2.3 ± 0.4) × 10-11 cm3 molecule-1 s-1 was determined for the reaction of F atoms with CF3CHO.
AB - The atmospheric fate of CF3CO radicals has been studied using a pulse radiolysis technique to provide kinetic data and FTIR-smog chamber system to provide product data. In 1 atm of SF6 at 296 ± 2 K, CF3CO radicals decompose to give CF3 radicals and CO with a rate of (1.2 ± 0.8) × 105 s-1 and react with O2 to form CF3C(O)O2 radicals with a rate constant of (7.3 ± 1.1) × 10-13 cm3 molecule-1 s-1. In 1 atm of N2 at 296 ± 2 K, the rate constant ratio k(CF3CO + O2 → CF3C(O)O2)/k(CF3CO → CF3 + CO) = (7.4 ± 0.6) × 10-18 cm3 molecule-1. Reaction with O2 accounts for 99.5% of the loss of CF3CO radicals in the atmosphere. The ultraviolet absorption spectrum of CF3C(O)O2 radicals has been studied over the wavelength range 220-300 nm, and at 230 nm, σCF3C(O)O2 = (3.78 ± 0.43) × 10-18 cm2 molecule-1. Monitoring the rate of NO2 formation at 400 nm allowed a lower limit of k4 > 9.9 × 10-12 cm3 molecule-1 s-1 to be derived for the rate constant of the reaction of CF3C(O)O2 radicals with NO. Reaction of CF3C(O)O2 radicals with NO produces the alkoxy radical CF3C(O)O, which undergoes C-C bond scission rapidly with a rate greater than 6 × 104 s-1. Results are discussed with respect to the atmospheric chemistry of CF3COx radicals. As part of the present work, a rate constant k6 = (2.3 ± 0.4) × 10-11 cm3 molecule-1 s-1 was determined for the reaction of F atoms with CF3CHO.
UR - http://www.scopus.com/inward/record.url?scp=0039044470&partnerID=8YFLogxK
M3 - Journal article
AN - SCOPUS:0039044470
SN - 0022-3654
VL - 98
SP - 5686
EP - 5694
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 22
ER -