TY - JOUR
T1 - Atmospheric Chemistry of 1,3-Dioxolane
T2 - Kinetic, Mechanistic, and Modeling Study of OH Radical Initiated Oxidation
AU - Sauer, C. G.
AU - Barnes, I.
AU - Becker, K. H.
AU - Geiger, H.
AU - Wallington, T. J.
AU - Christensen, L. K.
AU - Platz, J.
AU - Nielsen, O. J.
PY - 1999/7/29
Y1 - 1999/7/29
N2 - An absolute rate pulse radiolysis technique was used to measure k(OH + 1,3-dioxolane) = (8.8 ± 0.9) × 10-12 cm3 molecule-1 s-1 at 295 K in 1000 mbar of Ar. Relative rate techniques were used to study the reactions of OH radicals and Cl atoms with 1,3-dioxolane and Cl atoms with ethylene carbonate and methylene glycol diformate at 300 K in 1 bar of synthetic air. Rate coefficients were k(OH + 1,3-dioxolane) = (1.04 ± 0.16) × 10-11, k(Cl + 1,3-dioxolane) = (1.6 ± 0.3) × 10-10, k(Cl + ethylene carbonate) = (7.1 ± 1.7) × 10-12, and k(Cl + methylene glycol diformate) = (5.6 ± 0.7) × 10-13 cm3 molecule-1 s-1. OH radical and chlorine atom initiated oxidation of 1,3-dioxolane in 1 bar of N2/O2 mixtures at 298 K in the presence of NOx gives ethylene carbonate and methylene glycol diformate. Molar yields of ethylene carbonate and methylene glycol diformate were 0.48 ± 0.07 and 0.50 ± 0.14 for OH radical initiation and 0.43 ± 0.07 and 0.53 ± 0.07 for Cl atom initiation. Product yields were independent of O2 partial pressure over the range studied (60-800 mbar). A photochemical mechanism was developed to describe the OH-initiated degradation of 1,3-dioxolane in the presence of NOx. The results are discussed with respect to the available literature data concerning the atmospheric chemistry of ethers.
AB - An absolute rate pulse radiolysis technique was used to measure k(OH + 1,3-dioxolane) = (8.8 ± 0.9) × 10-12 cm3 molecule-1 s-1 at 295 K in 1000 mbar of Ar. Relative rate techniques were used to study the reactions of OH radicals and Cl atoms with 1,3-dioxolane and Cl atoms with ethylene carbonate and methylene glycol diformate at 300 K in 1 bar of synthetic air. Rate coefficients were k(OH + 1,3-dioxolane) = (1.04 ± 0.16) × 10-11, k(Cl + 1,3-dioxolane) = (1.6 ± 0.3) × 10-10, k(Cl + ethylene carbonate) = (7.1 ± 1.7) × 10-12, and k(Cl + methylene glycol diformate) = (5.6 ± 0.7) × 10-13 cm3 molecule-1 s-1. OH radical and chlorine atom initiated oxidation of 1,3-dioxolane in 1 bar of N2/O2 mixtures at 298 K in the presence of NOx gives ethylene carbonate and methylene glycol diformate. Molar yields of ethylene carbonate and methylene glycol diformate were 0.48 ± 0.07 and 0.50 ± 0.14 for OH radical initiation and 0.43 ± 0.07 and 0.53 ± 0.07 for Cl atom initiation. Product yields were independent of O2 partial pressure over the range studied (60-800 mbar). A photochemical mechanism was developed to describe the OH-initiated degradation of 1,3-dioxolane in the presence of NOx. The results are discussed with respect to the available literature data concerning the atmospheric chemistry of ethers.
UR - http://www.scopus.com/inward/record.url?scp=0000938934&partnerID=8YFLogxK
U2 - 10.1021/jp991025r
DO - 10.1021/jp991025r
M3 - Journal article
AN - SCOPUS:0000938934
VL - 103
SP - 5959
EP - 5966
JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
SN - 1089-5639
IS - 30
ER -