Atmospheric chemistry of dimethyl sulfide: UV spectra and self-reaction kinetics of CH3SCH2 and CH3SCH2O2 radicals and kinetics of the reactions CH3SCH2 + O2 → CH3SCH2O2 and CH3SCH2O2 + NO → ...

Timothy J. Wellington; Thomas Ellermann; Ole J. Nielsen

Atmospheric chemistry of dimethyl sulfide: UV spectra and self-reaction kinetics of CH₃SCH₂ and CH₃SCH₂O₂ radicals and kinetics of the reactions CH₃SCH₂ + O₂ → CH₃SCH₂O₂ and CH₃SCH₂O₂ + NO → ...

Timothy J. Wellington^*, Thomas Ellermann, Ole J. Nielsen

^*Corresponding author af dette arbejde

28 Citationer (Scopus)

Abstract

Full title: Atmospheric chemistry of dimethyl sulfide: UV spectra and self-reaction kinetics of CH₃SCH₂ and CH₃SCH₂O₂ radicals and kinetics of the reactions CH₃SCH₂ + O₂ → CH₃SCH₂O₂ and CH₃SCH₂O₂ + NO → CH₃SCH₂O + NO₂. A pulse radiolysis technique has been used to measure the UV spectra of CH₃SCH₂ and CH₃SCH₂O₂ radicals over the range 225-350 nm. At 285 nm, σ(CH₃SCH₂) = (9.8 ± 1.7) × 10^-8; at 250 nm, σ(CH₃SCH₂O₂) = (4.3 ± 0.7) × 10^-18 cm² molecule^-1. Observed self-reaction rate constants, defined as -d[CH₃SCH₂]/dt = 2k₆[CH₃SCH₂]² and -d[CH₃SCH₂O₂[/dt = 2k_7obs[CH₃SCH₂O₂]², were k₆ = (3.0 ± 0.6) × 10^-11 and k_7obs = (7.9 ± 1.4) × 10^-12 cm³ molecule^-1 s^-1. Errors are statistical (2 standard deviations) plus our estimate of potential systematic uncertainty (15%). A rate constant, k₂ = (5.7 ± 0.4) × 10^-12 cm³ molecule^-1 s^-1, was derived for the addition reaction CH₃SCH₂ + O₂ → CH₃SCH₂O₂. A rate constant, k₃ = (1.9 ± 0.6) × 10^-11 cm³ molecule^-1 s^-1, is reported for the reaction of CH₃SCH₂O₂ radicals with NO, producing NO₂. Errors for k₂ and k₃ are 2 standard deviations. Results are discussed with respect to the atmospheric chemistry of dimethyl sulfide.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry
Vol/bind	97
Udgave nummer	32
Sider (fra-til)	8442-8449
Antal sider	8
ISSN	0022-3654
Status	Udgivet - 1 dec. 1993

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Citationsformater

Atmospheric chemistry of dimethyl sulfide : UV spectra and self-reaction kinetics of CH₃SCH₂ and CH₃SCH₂O₂ radicals and kinetics of the reactions CH₃SCH₂ + O₂ → CH₃SCH₂O₂ and CH₃SCH₂O₂ + NO → ... / Wellington, Timothy J.; Ellermann, Thomas; Nielsen, Ole J.

I: Journal of Physical Chemistry, Bind 97, Nr. 32, 01.12.1993, s. 8442-8449.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

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title = "Atmospheric chemistry of dimethyl sulfide: UV spectra and self-reaction kinetics of CH3SCH2 and CH3SCH2O2 radicals and kinetics of the reactions CH3SCH2 + O2 → CH3SCH2O2 and CH3SCH2O2 + NO → ...",

abstract = "Full title: Atmospheric chemistry of dimethyl sulfide: UV spectra and self-reaction kinetics of CH3SCH2 and CH3SCH2O2 radicals and kinetics of the reactions CH3SCH2 + O2 → CH3SCH2O2 and CH3SCH2O2 + NO → CH3SCH2O + NO2. A pulse radiolysis technique has been used to measure the UV spectra of CH3SCH2 and CH3SCH2O2 radicals over the range 225-350 nm. At 285 nm, σ(CH3SCH2) = (9.8 ± 1.7) × 10-8; at 250 nm, σ(CH3SCH2O2) = (4.3 ± 0.7) × 10-18 cm2 molecule-1. Observed self-reaction rate constants, defined as -d[CH3SCH2]/dt = 2k6[CH3SCH2]2 and -d[CH3SCH2O2[/dt = 2k7obs[CH3SCH2O2]2, were k6 = (3.0 ± 0.6) × 10-11 and k7obs = (7.9 ± 1.4) × 10-12 cm3 molecule-1 s-1. Errors are statistical (2 standard deviations) plus our estimate of potential systematic uncertainty (15%). A rate constant, k2 = (5.7 ± 0.4) × 10-12 cm3 molecule-1 s-1, was derived for the addition reaction CH3SCH2 + O2 → CH3SCH2O2. A rate constant, k3 = (1.9 ± 0.6) × 10-11 cm3 molecule-1 s-1, is reported for the reaction of CH3SCH2O2 radicals with NO, producing NO2. Errors for k2 and k3 are 2 standard deviations. Results are discussed with respect to the atmospheric chemistry of dimethyl sulfide.",

author = "Wellington, {Timothy J.} and Thomas Ellermann and Nielsen, {Ole J.}",

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journal = "Journal of Physical Chemistry",

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TY - JOUR

T1 - Atmospheric chemistry of dimethyl sulfide

T2 - UV spectra and self-reaction kinetics of CH3SCH2 and CH3SCH2O2 radicals and kinetics of the reactions CH3SCH2 + O2 → CH3SCH2O2 and CH3SCH2O2 + NO → ...

AU - Wellington, Timothy J.

AU - Ellermann, Thomas

AU - Nielsen, Ole J.

PY - 1993/12/1

Y1 - 1993/12/1

N2 - Full title: Atmospheric chemistry of dimethyl sulfide: UV spectra and self-reaction kinetics of CH3SCH2 and CH3SCH2O2 radicals and kinetics of the reactions CH3SCH2 + O2 → CH3SCH2O2 and CH3SCH2O2 + NO → CH3SCH2O + NO2. A pulse radiolysis technique has been used to measure the UV spectra of CH3SCH2 and CH3SCH2O2 radicals over the range 225-350 nm. At 285 nm, σ(CH3SCH2) = (9.8 ± 1.7) × 10-8; at 250 nm, σ(CH3SCH2O2) = (4.3 ± 0.7) × 10-18 cm2 molecule-1. Observed self-reaction rate constants, defined as -d[CH3SCH2]/dt = 2k6[CH3SCH2]2 and -d[CH3SCH2O2[/dt = 2k7obs[CH3SCH2O2]2, were k6 = (3.0 ± 0.6) × 10-11 and k7obs = (7.9 ± 1.4) × 10-12 cm3 molecule-1 s-1. Errors are statistical (2 standard deviations) plus our estimate of potential systematic uncertainty (15%). A rate constant, k2 = (5.7 ± 0.4) × 10-12 cm3 molecule-1 s-1, was derived for the addition reaction CH3SCH2 + O2 → CH3SCH2O2. A rate constant, k3 = (1.9 ± 0.6) × 10-11 cm3 molecule-1 s-1, is reported for the reaction of CH3SCH2O2 radicals with NO, producing NO2. Errors for k2 and k3 are 2 standard deviations. Results are discussed with respect to the atmospheric chemistry of dimethyl sulfide.

AB - Full title: Atmospheric chemistry of dimethyl sulfide: UV spectra and self-reaction kinetics of CH3SCH2 and CH3SCH2O2 radicals and kinetics of the reactions CH3SCH2 + O2 → CH3SCH2O2 and CH3SCH2O2 + NO → CH3SCH2O + NO2. A pulse radiolysis technique has been used to measure the UV spectra of CH3SCH2 and CH3SCH2O2 radicals over the range 225-350 nm. At 285 nm, σ(CH3SCH2) = (9.8 ± 1.7) × 10-8; at 250 nm, σ(CH3SCH2O2) = (4.3 ± 0.7) × 10-18 cm2 molecule-1. Observed self-reaction rate constants, defined as -d[CH3SCH2]/dt = 2k6[CH3SCH2]2 and -d[CH3SCH2O2[/dt = 2k7obs[CH3SCH2O2]2, were k6 = (3.0 ± 0.6) × 10-11 and k7obs = (7.9 ± 1.4) × 10-12 cm3 molecule-1 s-1. Errors are statistical (2 standard deviations) plus our estimate of potential systematic uncertainty (15%). A rate constant, k2 = (5.7 ± 0.4) × 10-12 cm3 molecule-1 s-1, was derived for the addition reaction CH3SCH2 + O2 → CH3SCH2O2. A rate constant, k3 = (1.9 ± 0.6) × 10-11 cm3 molecule-1 s-1, is reported for the reaction of CH3SCH2O2 radicals with NO, producing NO2. Errors for k2 and k3 are 2 standard deviations. Results are discussed with respect to the atmospheric chemistry of dimethyl sulfide.

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M3 - Journal article

AN - SCOPUS:0000525746

SN - 0022-3654

VL - 97

SP - 8442

EP - 8449

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 32

ER -

Atmospheric chemistry of dimethyl sulfide: UV spectra and self-reaction kinetics of CH3SCH2 and CH3SCH2O2 radicals and kinetics of the reactions CH3SCH2 + O2 → CH3SCH2O2 and CH3SCH2O2 + NO → ...

Abstract

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Atmospheric chemistry of dimethyl sulfide: UV spectra and self-reaction kinetics of CH₃SCH₂ and CH₃SCH₂O₂ radicals and kinetics of the reactions CH₃SCH₂ + O₂ → CH₃SCH₂O₂ and CH₃SCH₂O₂ + NO → ...