Atmospheric chemistry of 1,4-dioxane. Laboratory studies
Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
Standard
Atmospheric chemistry of 1,4-dioxane. Laboratory studies. / Platz, J.; Sehested, J.; Møgelberg, T.; Nielsen, O. J.; Wallington, T. J.
I: Journal of the Chemical Society - Faraday Transactions, Bind 93, Nr. 16, 21.08.1997, s. 2855-2863.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
Harvard
APA
Vancouver
Author
Bibtex
}
RIS
TY - JOUR
T1 - Atmospheric chemistry of 1,4-dioxane. Laboratory studies
AU - Platz, J.
AU - Sehested, J.
AU - Møgelberg, T.
AU - Nielsen, O. J.
AU - Wallington, T. J.
PY - 1997/8/21
Y1 - 1997/8/21
N2 - A pulse radiolysis technique was used to measure the UV absorption spectra of c-C4H7O2 and (c-C4H7O2)O2 radicals over the range 220-320 nm, σ(c-C4H7O2)250 nm = (5.9 ± 0.6) × 10-18 and σ[(c-C4H7O2)O2]240 nm = (4.8 × 0.8) × 10-18 cm2 molecule-1. The observed self-reaction rate constants for the c-C4H7O2 and (c-C4H7O2)O2 radicals, defined as -d[c-C4H7O2]/dt = 2k4[c-C4H7O2]2 and -d[(c-C4H7O2)O2]/dt = 2k5 obs[(c-C4H7O2)O2]2 were k4 = (3.3 ± 0.4) × 10-11 and k5 obs = (7.3 ± 1.2) × 10-12 cm3 molecule-1 s-1. The rate constants for reactions of (c-C4H7O2)O2 radicals with NO and NO2 were k6 (1.2 ± 0.3) × 10-11 and k7 = (1.3 ± 0.3) × 10-11 cm3 molecule-1 s-1, respectively. The rate constants for the reaction of F atoms with 1,4-dioxane and the reaction of c-C4H7O2 radicals with O2, were k3 = (2.4 ± 0.7) × 10-10 and k2 = (8.8 ± 0.9) × 10-12 cm3 molecule-1 s-1, respectively. A relative rate technique was used to measure the rate constant for the reaction of Cl atoms with 1,4-dioxane, k17 = (2.0 ± 0.3) × 10-10 cm3 molecule-1 s-1. A long-pathlength FTIR spectrometer coupled to a smog chamber system was used to show that the sole atmospheric fate of the alkoxy radical (c-C4H7O2)O is decomposition via C-C bond scission leading to the formation of H(O)COCH2CH2OC(O)H (ethylene glycol diformate).
AB - A pulse radiolysis technique was used to measure the UV absorption spectra of c-C4H7O2 and (c-C4H7O2)O2 radicals over the range 220-320 nm, σ(c-C4H7O2)250 nm = (5.9 ± 0.6) × 10-18 and σ[(c-C4H7O2)O2]240 nm = (4.8 × 0.8) × 10-18 cm2 molecule-1. The observed self-reaction rate constants for the c-C4H7O2 and (c-C4H7O2)O2 radicals, defined as -d[c-C4H7O2]/dt = 2k4[c-C4H7O2]2 and -d[(c-C4H7O2)O2]/dt = 2k5 obs[(c-C4H7O2)O2]2 were k4 = (3.3 ± 0.4) × 10-11 and k5 obs = (7.3 ± 1.2) × 10-12 cm3 molecule-1 s-1. The rate constants for reactions of (c-C4H7O2)O2 radicals with NO and NO2 were k6 (1.2 ± 0.3) × 10-11 and k7 = (1.3 ± 0.3) × 10-11 cm3 molecule-1 s-1, respectively. The rate constants for the reaction of F atoms with 1,4-dioxane and the reaction of c-C4H7O2 radicals with O2, were k3 = (2.4 ± 0.7) × 10-10 and k2 = (8.8 ± 0.9) × 10-12 cm3 molecule-1 s-1, respectively. A relative rate technique was used to measure the rate constant for the reaction of Cl atoms with 1,4-dioxane, k17 = (2.0 ± 0.3) × 10-10 cm3 molecule-1 s-1. A long-pathlength FTIR spectrometer coupled to a smog chamber system was used to show that the sole atmospheric fate of the alkoxy radical (c-C4H7O2)O is decomposition via C-C bond scission leading to the formation of H(O)COCH2CH2OC(O)H (ethylene glycol diformate).
UR - http://www.scopus.com/inward/record.url?scp=33748635809&partnerID=8YFLogxK
U2 - 10.1039/a700598i
DO - 10.1039/a700598i
M3 - Journal article
AN - SCOPUS:33748635809
VL - 93
SP - 2855
EP - 2863
JO - Journal of the Chemical Society - Faraday Transactions
JF - Journal of the Chemical Society - Faraday Transactions
SN - 0956-5000
IS - 16
ER -
ID: 225756051