TY - JOUR
T1 - UV absorption spectra and kinetics of the self reaction of CFCl2CH2O2 and CF2ClCH2O2 radicals in the gas phase at 298 K
AU - Wallington, Timothy J.
AU - Nielsen, Ole J.
PY - 1991/1/1
Y1 - 1991/1/1
N2 - The ultraviolet absorption spectra of the peroxy radicals derived from hydrochlorofluorocarbons 141b and 142b, (CFCl2CH2O2 and CF2ClCH2O2, respectively), and the kinetics of their self reactions have been studied in the gas phase at 298 K using a pulse radiolysis technique. Absorption cross sections were quantified over the wavelength range 220–300 nm. Measured absorption cross sections at 250 nm were indistinguishable within the experimental uncertainties (≈10%) and yield; (Formula Presented.) Errors represent the sum of statistical uncertainty and our estimate of potential systematic errors. Our absorption cross section data were then used to derive the observed self reaction rate constants for reactions (1) and (2), defined as −d[RO2]/dt = 2k[RO2]2 (R = CFCl2CH2 or CF2ClCH2), (Formula Presented.) of k1obs = (4.36 ± 0.64) × 10−12 and k2obs = (4.13 ± 0.58) × 10−12 cm3 molecule−1 s−1, quoted errors represent 2σ. These results are discussed with respect to previous studies of the absorption spectra and kinetics of peroxy radicals.
AB - The ultraviolet absorption spectra of the peroxy radicals derived from hydrochlorofluorocarbons 141b and 142b, (CFCl2CH2O2 and CF2ClCH2O2, respectively), and the kinetics of their self reactions have been studied in the gas phase at 298 K using a pulse radiolysis technique. Absorption cross sections were quantified over the wavelength range 220–300 nm. Measured absorption cross sections at 250 nm were indistinguishable within the experimental uncertainties (≈10%) and yield; (Formula Presented.) Errors represent the sum of statistical uncertainty and our estimate of potential systematic errors. Our absorption cross section data were then used to derive the observed self reaction rate constants for reactions (1) and (2), defined as −d[RO2]/dt = 2k[RO2]2 (R = CFCl2CH2 or CF2ClCH2), (Formula Presented.) of k1obs = (4.36 ± 0.64) × 10−12 and k2obs = (4.13 ± 0.58) × 10−12 cm3 molecule−1 s−1, quoted errors represent 2σ. These results are discussed with respect to previous studies of the absorption spectra and kinetics of peroxy radicals.
UR - http://www.scopus.com/inward/record.url?scp=0026220317&partnerID=8YFLogxK
U2 - 10.1002/kin.550230905
DO - 10.1002/kin.550230905
M3 - Journal article
AN - SCOPUS:0026220317
SN - 0538-8066
VL - 23
SP - 785
EP - 798
JO - International Journal of Chemical Kinetics
JF - International Journal of Chemical Kinetics
IS - 9
ER -