Atmospheric Chemistry of Trimethoxymethane, (CH3O)3CH; Laboratory Studies

J. Platz; J. Sehested; O. J. Nielsen; T. J. Wallington

Atmospheric Chemistry of Trimethoxymethane, (CH₃O)₃CH; Laboratory Studies

J. Platz, J. Sehested, O. J. Nielsen, T. J. Wallington

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Abstract

A pulse radiolysis technique was used to measure the UV absorption spectra of (CH₃O)₂CHOCH₂(.) and (CH₃O)₂CHOCH₂O₂(.) radicals derived from trimethoxymethane over the range 220-320 nm, σ_{250 nm} (CH₃O)_2- CHOCH₂(.) = (2.8 ± 0.4) × 10^-18 and σ_250nm (CH₃O)₂CHOCH₂O₂(.) = (3.5 ± 0.4) × 10^-18 cm² molecule^-1. The self-reaction rate constants for (CH₃O)₂CHOCH₂(.) and (CH₃O)₂CHOCH₂O₂(.) radicals, defined as -d[(CH₃O)₂CHOCH₂(.)]/dt = 2k₅[(CH₃O)₂CHOCH₂(.)]² and -d[(CH₃O)₂CHOCH₂O₂(.)]/dt = 2k₆, _obS[(CH₃O)₂-CHOCH₂O ₂(.)]² were k₅ = (3.5 ± 0.5) × 10^-11 and k_{6 obs} = (1.3 ± 0.2) × 10^-11 cm³ molecule^-1 s^-1. Rate constants for reactions of (CH₃O)₂CHOCH₂O₂(.) radicals with NO and NO₂ were k₇ = (9.0 ± 1.2) × 10^-12 and k₈ = (1.0 ± 0.2) × 10^-11 cm³ molecule^-1 s^-1, respectively. Rate constants for the reaction of OH radicals and F atoms with trimethoxymethane and the reaction of (CH₃O)₂CHOCH₂(.) radicals with O₂ were k₁ = (6.0 ± 0.5) × 10^-12, k³ = (3.0 ± 0.7) × 10^-10, and k₂ = (9.2 ± 1.5) × 10^-12 cm³ molecule^-1 s^-1, respectively. Relative rate techniques were used to measure k(Cl + trimethoxymethane) = (1.5 ± 0.2) × 10^-1 cm³ molecule^-1 s^-1. OH-radical-initiated oxidation of trimethoxymethane in air gives dimethyl carbonate in a molar yield of 81 ± 10%. These results are discussed with respect to the atmospheric chemistry of automotive fuel additives.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry A
Vol/bind	103
Udgave nummer	15
Sider (fra-til)	2632-2640
Antal sider	9
ISSN	1089-5639
Status	Udgivet - 1 dec. 1999

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@article{d041a0c263d743a186ff95765e2cb8eb,

title = "Atmospheric Chemistry of Trimethoxymethane, (CH3O)3CH; Laboratory Studies",

abstract = "A pulse radiolysis technique was used to measure the UV absorption spectra of (CH3O)2CHOCH2(.) and (CH3O)2CHOCH2O2(.) radicals derived from trimethoxymethane over the range 220-320 nm, σ250 nm (CH3O)2- CHOCH2(.) = (2.8 ± 0.4) × 10-18 and σ250nm (CH3O)2CHOCH2O2(.) = (3.5 ± 0.4) × 10-18 cm2 molecule-1. The self-reaction rate constants for (CH3O)2CHOCH2(.) and (CH3O)2CHOCH2O2(.) radicals, defined as -d[(CH3O)2CHOCH2(.)]/dt = 2k5[(CH3O)2CHOCH2(.)]2 and -d[(CH3O)2CHOCH2O2(.)]/dt = 2k6, obS[(CH3O)2-CHOCH2O 2(.)]2 were k5 = (3.5 ± 0.5) × 10-11 and k6 obs = (1.3 ± 0.2) × 10-11 cm3 molecule-1 s-1. Rate constants for reactions of (CH3O)2CHOCH2O2(.) radicals with NO and NO2 were k7 = (9.0 ± 1.2) × 10-12 and k8 = (1.0 ± 0.2) × 10-11 cm3 molecule-1 s-1, respectively. Rate constants for the reaction of OH radicals and F atoms with trimethoxymethane and the reaction of (CH3O)2CHOCH2(.) radicals with O2 were k1 = (6.0 ± 0.5) × 10-12, k3 = (3.0 ± 0.7) × 10-10, and k2 = (9.2 ± 1.5) × 10-12 cm3 molecule-1 s-1, respectively. Relative rate techniques were used to measure k(Cl + trimethoxymethane) = (1.5 ± 0.2) × 10-1 cm3 molecule-1 s-1. OH-radical-initiated oxidation of trimethoxymethane in air gives dimethyl carbonate in a molar yield of 81 ± 10%. These results are discussed with respect to the atmospheric chemistry of automotive fuel additives.",

author = "J. Platz and J. Sehested and Nielsen, {O. J.} and Wallington, {T. J.}",

year = "1999",

month = dec,

day = "1",

language = "English",

volume = "103",

pages = "2632--2640",

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

issn = "1089-5639",

publisher = "American Chemical Society",

number = "15",

}

TY - JOUR

T1 - Atmospheric Chemistry of Trimethoxymethane, (CH3O)3CH; Laboratory Studies

AU - Platz, J.

AU - Sehested, J.

AU - Nielsen, O. J.

AU - Wallington, T. J.

PY - 1999/12/1

Y1 - 1999/12/1

N2 - A pulse radiolysis technique was used to measure the UV absorption spectra of (CH3O)2CHOCH2(.) and (CH3O)2CHOCH2O2(.) radicals derived from trimethoxymethane over the range 220-320 nm, σ250 nm (CH3O)2- CHOCH2(.) = (2.8 ± 0.4) × 10-18 and σ250nm (CH3O)2CHOCH2O2(.) = (3.5 ± 0.4) × 10-18 cm2 molecule-1. The self-reaction rate constants for (CH3O)2CHOCH2(.) and (CH3O)2CHOCH2O2(.) radicals, defined as -d[(CH3O)2CHOCH2(.)]/dt = 2k5[(CH3O)2CHOCH2(.)]2 and -d[(CH3O)2CHOCH2O2(.)]/dt = 2k6, obS[(CH3O)2-CHOCH2O 2(.)]2 were k5 = (3.5 ± 0.5) × 10-11 and k6 obs = (1.3 ± 0.2) × 10-11 cm3 molecule-1 s-1. Rate constants for reactions of (CH3O)2CHOCH2O2(.) radicals with NO and NO2 were k7 = (9.0 ± 1.2) × 10-12 and k8 = (1.0 ± 0.2) × 10-11 cm3 molecule-1 s-1, respectively. Rate constants for the reaction of OH radicals and F atoms with trimethoxymethane and the reaction of (CH3O)2CHOCH2(.) radicals with O2 were k1 = (6.0 ± 0.5) × 10-12, k3 = (3.0 ± 0.7) × 10-10, and k2 = (9.2 ± 1.5) × 10-12 cm3 molecule-1 s-1, respectively. Relative rate techniques were used to measure k(Cl + trimethoxymethane) = (1.5 ± 0.2) × 10-1 cm3 molecule-1 s-1. OH-radical-initiated oxidation of trimethoxymethane in air gives dimethyl carbonate in a molar yield of 81 ± 10%. These results are discussed with respect to the atmospheric chemistry of automotive fuel additives.

AB - A pulse radiolysis technique was used to measure the UV absorption spectra of (CH3O)2CHOCH2(.) and (CH3O)2CHOCH2O2(.) radicals derived from trimethoxymethane over the range 220-320 nm, σ250 nm (CH3O)2- CHOCH2(.) = (2.8 ± 0.4) × 10-18 and σ250nm (CH3O)2CHOCH2O2(.) = (3.5 ± 0.4) × 10-18 cm2 molecule-1. The self-reaction rate constants for (CH3O)2CHOCH2(.) and (CH3O)2CHOCH2O2(.) radicals, defined as -d[(CH3O)2CHOCH2(.)]/dt = 2k5[(CH3O)2CHOCH2(.)]2 and -d[(CH3O)2CHOCH2O2(.)]/dt = 2k6, obS[(CH3O)2-CHOCH2O 2(.)]2 were k5 = (3.5 ± 0.5) × 10-11 and k6 obs = (1.3 ± 0.2) × 10-11 cm3 molecule-1 s-1. Rate constants for reactions of (CH3O)2CHOCH2O2(.) radicals with NO and NO2 were k7 = (9.0 ± 1.2) × 10-12 and k8 = (1.0 ± 0.2) × 10-11 cm3 molecule-1 s-1, respectively. Rate constants for the reaction of OH radicals and F atoms with trimethoxymethane and the reaction of (CH3O)2CHOCH2(.) radicals with O2 were k1 = (6.0 ± 0.5) × 10-12, k3 = (3.0 ± 0.7) × 10-10, and k2 = (9.2 ± 1.5) × 10-12 cm3 molecule-1 s-1, respectively. Relative rate techniques were used to measure k(Cl + trimethoxymethane) = (1.5 ± 0.2) × 10-1 cm3 molecule-1 s-1. OH-radical-initiated oxidation of trimethoxymethane in air gives dimethyl carbonate in a molar yield of 81 ± 10%. These results are discussed with respect to the atmospheric chemistry of automotive fuel additives.

UR - http://www.scopus.com/inward/record.url?scp=0001272146&partnerID=8YFLogxK

M3 - Journal article

AN - SCOPUS:0001272146

SN - 1089-5639

VL - 103

SP - 2632

EP - 2640

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 - 15

ER -

Atmospheric Chemistry of Trimethoxymethane, (CH3O)3CH; Laboratory Studies

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Atmospheric Chemistry of Trimethoxymethane, (CH₃O)₃CH; Laboratory Studies