Experimental and theoretical studies of the reaction of the OH radical with alkyl sulfides: 3. Kinetics and mechanism of the OH initiated oxidation of dimethyl, dipropyl, and dibutyl sulfides: reactivity trends in the alkyl sulfides and development of a predictive expression for the reaction of OH with DMS

M. B. Williams, P. Campuzano-Jost, Anthony J Hynes, A. J. Pounds

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Abstract

A pulsed laser photolysis-pulsed laser-induced fluorescence technique has been employed to measure rate coefficients for the OH-initiated oxidation of dimethyl sulfide (DMS), its deuterated analog (DMS-d 6). dipropyl sulfide (DPS), and dibutyl sulfide (DBS). Effective rate coefficients have been measured as a function of the partial pressure of O 2 over the temperature range of 240-295 K and at 200 and 600 Torr total pressure. We report the first observations of an O 2 enhancement in the effective rate coefficients for the reactions of OH with DPS and DBS. All observations are consistent with oxidation proceeding via a two-channel oxidation mechanism involving abstraction and addition channels. Structures and thermochemistry of the DPSOH and DBSOH adducts were calculated. Calculated bond strengths of adducts increase with alkyl substitution but are comparable to that of the DMSOH adduct and are consistent with experimental observations. Reactivity trends across the series of alkyl sulfide (C 2-C 8) reactions are analyzed. All reactions proceed via a twochannel mechanism involving either an H-atom abstraction or the formation of an OH adduct that can then react with O 2. Measurements presented in this work, in conjunction with previous measurements, have been used to develop a predictive expression for the OH-initiated oxidation of DMS. This expression is based on the elementary rate coefficients in the two-channel mechanism. The expression can calculate the effective rate coefficient for the reaction of OH with DMS over the range of 200-300 K, 0-760 Torr, and 0-100% partial pressure of O 2. This expression expands on previously published work but is applicable to DMS oxidation throughout the troposphere.

Original languageEnglish (US)
Pages (from-to)6697-6709
Number of pages13
JournalJournal of Physical Chemistry A
Volume113
Issue number24
DOIs
StatePublished - Jun 18 2009

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Sulfides
sulfides
reactivity
trends
Oxidation
oxidation
Kinetics
kinetics
Pulsed lasers
Partial pressure
adducts
Thermochemistry
coefficients
Troposphere
Photolysis
partial pressure
pulsed lasers
Substitution reactions
Fluorescence
dipropyl sulfide

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Experimental and theoretical studies of the reaction of the OH radical with alkyl sulfides: 3. Kinetics and mechanism of the OH initiated oxidation of dimethyl, dipropyl, and dibutyl sulfides: reactivity trends in the alkyl sulfides and development of a predictive expression for the reaction of OH with DMS",
abstract = "A pulsed laser photolysis-pulsed laser-induced fluorescence technique has been employed to measure rate coefficients for the OH-initiated oxidation of dimethyl sulfide (DMS), its deuterated analog (DMS-d 6). dipropyl sulfide (DPS), and dibutyl sulfide (DBS). Effective rate coefficients have been measured as a function of the partial pressure of O 2 over the temperature range of 240-295 K and at 200 and 600 Torr total pressure. We report the first observations of an O 2 enhancement in the effective rate coefficients for the reactions of OH with DPS and DBS. All observations are consistent with oxidation proceeding via a two-channel oxidation mechanism involving abstraction and addition channels. Structures and thermochemistry of the DPSOH and DBSOH adducts were calculated. Calculated bond strengths of adducts increase with alkyl substitution but are comparable to that of the DMSOH adduct and are consistent with experimental observations. Reactivity trends across the series of alkyl sulfide (C 2-C 8) reactions are analyzed. All reactions proceed via a twochannel mechanism involving either an H-atom abstraction or the formation of an OH adduct that can then react with O 2. Measurements presented in this work, in conjunction with previous measurements, have been used to develop a predictive expression for the OH-initiated oxidation of DMS. This expression is based on the elementary rate coefficients in the two-channel mechanism. The expression can calculate the effective rate coefficient for the reaction of OH with DMS over the range of 200-300 K, 0-760 Torr, and 0-100{\%} partial pressure of O 2. This expression expands on previously published work but is applicable to DMS oxidation throughout the troposphere.",
author = "Williams, {M. B.} and P. Campuzano-Jost and Hynes, {Anthony J} and Pounds, {A. J.}",
year = "2009",
month = "6",
day = "18",
doi = "10.1021/jp9010668",
language = "English (US)",
volume = "113",
pages = "6697--6709",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
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T1 - Experimental and theoretical studies of the reaction of the OH radical with alkyl sulfides

T2 - 3. Kinetics and mechanism of the OH initiated oxidation of dimethyl, dipropyl, and dibutyl sulfides: reactivity trends in the alkyl sulfides and development of a predictive expression for the reaction of OH with DMS

AU - Williams, M. B.

AU - Campuzano-Jost, P.

AU - Hynes, Anthony J

AU - Pounds, A. J.

PY - 2009/6/18

Y1 - 2009/6/18

N2 - A pulsed laser photolysis-pulsed laser-induced fluorescence technique has been employed to measure rate coefficients for the OH-initiated oxidation of dimethyl sulfide (DMS), its deuterated analog (DMS-d 6). dipropyl sulfide (DPS), and dibutyl sulfide (DBS). Effective rate coefficients have been measured as a function of the partial pressure of O 2 over the temperature range of 240-295 K and at 200 and 600 Torr total pressure. We report the first observations of an O 2 enhancement in the effective rate coefficients for the reactions of OH with DPS and DBS. All observations are consistent with oxidation proceeding via a two-channel oxidation mechanism involving abstraction and addition channels. Structures and thermochemistry of the DPSOH and DBSOH adducts were calculated. Calculated bond strengths of adducts increase with alkyl substitution but are comparable to that of the DMSOH adduct and are consistent with experimental observations. Reactivity trends across the series of alkyl sulfide (C 2-C 8) reactions are analyzed. All reactions proceed via a twochannel mechanism involving either an H-atom abstraction or the formation of an OH adduct that can then react with O 2. Measurements presented in this work, in conjunction with previous measurements, have been used to develop a predictive expression for the OH-initiated oxidation of DMS. This expression is based on the elementary rate coefficients in the two-channel mechanism. The expression can calculate the effective rate coefficient for the reaction of OH with DMS over the range of 200-300 K, 0-760 Torr, and 0-100% partial pressure of O 2. This expression expands on previously published work but is applicable to DMS oxidation throughout the troposphere.

AB - A pulsed laser photolysis-pulsed laser-induced fluorescence technique has been employed to measure rate coefficients for the OH-initiated oxidation of dimethyl sulfide (DMS), its deuterated analog (DMS-d 6). dipropyl sulfide (DPS), and dibutyl sulfide (DBS). Effective rate coefficients have been measured as a function of the partial pressure of O 2 over the temperature range of 240-295 K and at 200 and 600 Torr total pressure. We report the first observations of an O 2 enhancement in the effective rate coefficients for the reactions of OH with DPS and DBS. All observations are consistent with oxidation proceeding via a two-channel oxidation mechanism involving abstraction and addition channels. Structures and thermochemistry of the DPSOH and DBSOH adducts were calculated. Calculated bond strengths of adducts increase with alkyl substitution but are comparable to that of the DMSOH adduct and are consistent with experimental observations. Reactivity trends across the series of alkyl sulfide (C 2-C 8) reactions are analyzed. All reactions proceed via a twochannel mechanism involving either an H-atom abstraction or the formation of an OH adduct that can then react with O 2. Measurements presented in this work, in conjunction with previous measurements, have been used to develop a predictive expression for the OH-initiated oxidation of DMS. This expression is based on the elementary rate coefficients in the two-channel mechanism. The expression can calculate the effective rate coefficient for the reaction of OH with DMS over the range of 200-300 K, 0-760 Torr, and 0-100% partial pressure of O 2. This expression expands on previously published work but is applicable to DMS oxidation throughout the troposphere.

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JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

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