Atmospheric Chemistry of 1,3-Dioxolane: Kinetic, Mechanistic, and Modeling Study of OH Radical Initiated Oxidation

C. G. Sauer; I. Barnes; K. H. Becker; H. Geiger; T. J. Wallington; L. K. Christensen; J. Platz; O. J. Nielsen

doi:10.1021/jp991025r

Atmospheric Chemistry of 1,3-Dioxolane: Kinetic, Mechanistic, and Modeling Study of OH Radical Initiated Oxidation

C. G. Sauer, I. Barnes, K. H. Becker, H. Geiger, T. J. Wallington, L. K. Christensen, J. Platz, O. J. Nielsen

Kemisk Institut

17 Citationer (Scopus)

Abstract

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 NO_x 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 NO_x. The results are discussed with respect to the available literature data concerning the atmospheric chemistry of ethers.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry A
Vol/bind	103
Udgave nummer	30
Sider (fra-til)	5959-5966
Antal sider	8
ISSN	1089-5639
DOI	https://doi.org/10.1021/jp991025r
Status	Udgivet - 29 jul. 1999

Adgang til dokumentet

10.1021/jp991025r

Andre filer og links

Link to publication in Scopus

Citationsformater

@article{cc3388ec5c49422aafda11bb83ee3f4f,

title = "Atmospheric Chemistry of 1,3-Dioxolane: Kinetic, Mechanistic, and Modeling Study of OH Radical Initiated Oxidation",

abstract = "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.",

author = "Sauer, {C. G.} and I. Barnes and Becker, {K. H.} and H. Geiger and Wallington, {T. J.} and Christensen, {L. K.} and J. Platz and Nielsen, {O. J.}",

year = "1999",

month = jul,

day = "29",

doi = "10.1021/jp991025r",

language = "English",

volume = "103",

pages = "5959--5966",

journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "30",

}

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

SN - 1089-5639

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

IS - 30

ER -

Atmospheric Chemistry of 1,3-Dioxolane: Kinetic, Mechanistic, and Modeling Study of OH Radical Initiated Oxidation

Abstract

Adgang til dokumentet

Andre filer og links

Fingeraftryk

Citationsformater