Spectrokinetic study of SF5 and SF5O2 radicals and the reaction of SF5O2 with NO
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Spectrokinetic study of SF5 and SF5O2 radicals and the reaction of SF5O2 with NO. / Sehested, Jens; Ellermann, Thomas; Nielsen, Ole John; Wallington, Timothy J.
In: International Journal of Chemical Kinetics, Vol. 26, No. 6, 01.01.1994, p. 615-629.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - Spectrokinetic study of SF5 and SF5O2 radicals and the reaction of SF5O2 with NO
AU - Sehested, Jens
AU - Ellermann, Thomas
AU - Nielsen, Ole John
AU - Wallington, Timothy J.
PY - 1994/1/1
Y1 - 1994/1/1
N2 - UV spectra of SF5 and SF5O2 radicals in the gas phase at 295 K have been quantified using a pulse radiolysis UV absorption technique. The absorption spectrum of SF5 was quantified from 220 to 240 nm. The absorption cross section at 220 nm was (5.5 ± 1.7) × 10−19 cm2. When SF5 was produced in the presence of O2 an equilibrium between SF5, O2, and SF5O2 was established. The rate constant for the reaction of SF5 radicals with O2 was (8 ± 2) × 10−13 cm3 molecule−1 s−1. The decomposition rate constant for SF5O2 was (1.0 ± 0.5) × 105 s−1, giving an equilibrium constant of Keq = [SF5O2]/[SF5][O2] = (8.0 ± 4.5) × 10−18 cm3 molecule−1. The SF5O2 bond strength is (13.7 ± 2.0) kcal mol−1. The SF5O2 spectrum was broad with no fine structure and similar to the UV spectra of alkyl peroxy radicals. The absorption cross section at 230 nm was found to (3.7 ± 0.9) × 10−18 cm2. The rate constant of the reaction of SF5O2 with NO was measured to (1.1 ± 0.3) × 10−11 cm3 molecule−1 s−1 by monitoring the kinetics of NO2 formation at 400 nm. The rate constant for the reaction of F atoms with SF4 was measured by two relative methods to be (1.3 ± 0.3) × 10−11 cm3 molecule−1 s−1. © 1994 John Wiley & Sons, Inc.
AB - UV spectra of SF5 and SF5O2 radicals in the gas phase at 295 K have been quantified using a pulse radiolysis UV absorption technique. The absorption spectrum of SF5 was quantified from 220 to 240 nm. The absorption cross section at 220 nm was (5.5 ± 1.7) × 10−19 cm2. When SF5 was produced in the presence of O2 an equilibrium between SF5, O2, and SF5O2 was established. The rate constant for the reaction of SF5 radicals with O2 was (8 ± 2) × 10−13 cm3 molecule−1 s−1. The decomposition rate constant for SF5O2 was (1.0 ± 0.5) × 105 s−1, giving an equilibrium constant of Keq = [SF5O2]/[SF5][O2] = (8.0 ± 4.5) × 10−18 cm3 molecule−1. The SF5O2 bond strength is (13.7 ± 2.0) kcal mol−1. The SF5O2 spectrum was broad with no fine structure and similar to the UV spectra of alkyl peroxy radicals. The absorption cross section at 230 nm was found to (3.7 ± 0.9) × 10−18 cm2. The rate constant of the reaction of SF5O2 with NO was measured to (1.1 ± 0.3) × 10−11 cm3 molecule−1 s−1 by monitoring the kinetics of NO2 formation at 400 nm. The rate constant for the reaction of F atoms with SF4 was measured by two relative methods to be (1.3 ± 0.3) × 10−11 cm3 molecule−1 s−1. © 1994 John Wiley & Sons, Inc.
UR - http://www.scopus.com/inward/record.url?scp=0028456905&partnerID=8YFLogxK
U2 - 10.1002/kin.550260604
DO - 10.1002/kin.550260604
M3 - Journal article
AN - SCOPUS:0028456905
VL - 26
SP - 615
EP - 629
JO - International Journal of Chemical Kinetics
JF - International Journal of Chemical Kinetics
SN - 0538-8066
IS - 6
ER -
ID: 228193478