Kinetic and mechanistic studies of the OH-initiated oxidation of dimethylsulfide at low temperature - A reevaluation of the rate coefficient and branching ratio

M. B. Williams; P. Campuzano-Jost; D. Bauer; A. J. Hynes

doi:10.1016/S0009-2614(01)00764-3

Kinetic and mechanistic studies of the OH-initiated oxidation of dimethylsulfide at low temperature - A reevaluation of the rate coefficient and branching ratio

M. B. Williams, P. Campuzano-Jost, D. Bauer, A. J. Hynes

Atmospheric Sciences

Research output: Contribution to journal › Article › peer-review

41 Scopus citations

Abstract

The pulsed laser photolysis-pulsed laser induced fluorescence (PLP-PLIF) technique has been used to study the reactions of OH with DMS and DMS-d₆. The effective rate coefficient for the reaction of OH with DMS-d₆ has been determined as a function of O₂ partial pressure at 600 Torr total pressure in N₂/O₂ mixtures at 298 and 261 K and for both DMS and DMS-d₆ at 240 K. Currently recommended rates are based on an empirical fit to a two-channel mechanism. This work shows that at low temperatures the currently recommended expression underestimates both the effective rate coefficient for reaction together with the branching ratio between addition and abstraction.

Original language	English (US)
Pages (from-to)	61-67
Number of pages	7
Journal	Chemical Physics Letters
Volume	344
Issue number	1-2
DOIs	https://doi.org/10.1016/S0009-2614(01)00764-3
State	Published - Aug 17 2001

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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10.1016/S0009-2614(01)00764-3

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title = "Kinetic and mechanistic studies of the OH-initiated oxidation of dimethylsulfide at low temperature - A reevaluation of the rate coefficient and branching ratio",

abstract = "The pulsed laser photolysis-pulsed laser induced fluorescence (PLP-PLIF) technique has been used to study the reactions of OH with DMS and DMS-d6. The effective rate coefficient for the reaction of OH with DMS-d6 has been determined as a function of O2 partial pressure at 600 Torr total pressure in N2/O2 mixtures at 298 and 261 K and for both DMS and DMS-d6 at 240 K. Currently recommended rates are based on an empirical fit to a two-channel mechanism. This work shows that at low temperatures the currently recommended expression underestimates both the effective rate coefficient for reaction together with the branching ratio between addition and abstraction.",

author = "Williams, {M. B.} and P. Campuzano-Jost and D. Bauer and Hynes, {A. J.}",

note = "Funding Information: This work was funded by the Office of Naval Research through grant N000149910032.",

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T1 - Kinetic and mechanistic studies of the OH-initiated oxidation of dimethylsulfide at low temperature - A reevaluation of the rate coefficient and branching ratio

AU - Williams, M. B.

AU - Campuzano-Jost, P.

AU - Bauer, D.

AU - Hynes, A. J.

N1 - Funding Information: This work was funded by the Office of Naval Research through grant N000149910032.

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AB - The pulsed laser photolysis-pulsed laser induced fluorescence (PLP-PLIF) technique has been used to study the reactions of OH with DMS and DMS-d6. The effective rate coefficient for the reaction of OH with DMS-d6 has been determined as a function of O2 partial pressure at 600 Torr total pressure in N2/O2 mixtures at 298 and 261 K and for both DMS and DMS-d6 at 240 K. Currently recommended rates are based on an empirical fit to a two-channel mechanism. This work shows that at low temperatures the currently recommended expression underestimates both the effective rate coefficient for reaction together with the branching ratio between addition and abstraction.

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Kinetic and mechanistic studies of the OH-initiated oxidation of dimethylsulfide at low temperature - A reevaluation of the rate coefficient and branching ratio

Abstract

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