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A kinetics and mechanistic study of the atmospherically relevant reaction between molecular chlorine and dimethyl sulfide (DMS)

A kinetics and mechanistic study of the atmospherically relevant reaction between molecular chlorine and dimethyl sulfide (DMS)
A kinetics and mechanistic study of the atmospherically relevant reaction between molecular chlorine and dimethyl sulfide (DMS)
A gas-phase kinetics study of the atmospherically important reaction between Cl2 and dimethyl sulfide (DMS)1Cl2+ CH3SCH3 productshas been made using a flow-tube interfaced to a photoelectron spectrometer. The rate constant for this reaction has been measured at 1.6 and 3.0 torr at T=(294 ± 2) K as (3.4 ± 0.7)× 10–14 cm3 molecule–1 s–1. Reaction (1) has been found to proceed via an intermediate, (CH3)2SCl2, to give CH3SCH2Cl and HCl as the products. The mechanism of this reaction and the structure of the intermediate were investigated using electronic structure calculations. A comparison of the mechanisms of the reactions between Cl atoms and DMS, and Cl2 and DMS has been made and the relevance of the results to atmospheric chemistry is discussed
1463-9076
866-873
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Ghosh, M.V.
210ab8df-8389-4bf5-9622-9931cc4a9f81
Kinnison, David
a33126d6-9711-4b41-a6a2-a46e097fa19d
Levita, Giacomo
57b647e5-eec3-489b-ac4d-837829042ff9
Morris, Alan
e70d7160-c9d9-4035-90b8-9006a1052551
Shallcross, Dudley
f706d4ac-11ea-4f20-b0d9-644ae8611dc5
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Ghosh, M.V.
210ab8df-8389-4bf5-9622-9931cc4a9f81
Kinnison, David
a33126d6-9711-4b41-a6a2-a46e097fa19d
Levita, Giacomo
57b647e5-eec3-489b-ac4d-837829042ff9
Morris, Alan
e70d7160-c9d9-4035-90b8-9006a1052551
Shallcross, Dudley
f706d4ac-11ea-4f20-b0d9-644ae8611dc5

Dyke, John M., Ghosh, M.V., Kinnison, David, Levita, Giacomo, Morris, Alan and Shallcross, Dudley (2005) A kinetics and mechanistic study of the atmospherically relevant reaction between molecular chlorine and dimethyl sulfide (DMS). Physical Chemistry Chemical Physics, 7 (5), 866-873. (doi:10.1039/b415566a).

Record type: Article

Abstract

A gas-phase kinetics study of the atmospherically important reaction between Cl2 and dimethyl sulfide (DMS)1Cl2+ CH3SCH3 productshas been made using a flow-tube interfaced to a photoelectron spectrometer. The rate constant for this reaction has been measured at 1.6 and 3.0 torr at T=(294 ± 2) K as (3.4 ± 0.7)× 10–14 cm3 molecule–1 s–1. Reaction (1) has been found to proceed via an intermediate, (CH3)2SCl2, to give CH3SCH2Cl and HCl as the products. The mechanism of this reaction and the structure of the intermediate were investigated using electronic structure calculations. A comparison of the mechanisms of the reactions between Cl atoms and DMS, and Cl2 and DMS has been made and the relevance of the results to atmospheric chemistry is discussed

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Published date: 2005

Identifiers

Local EPrints ID: 147211
URI: http://eprints.soton.ac.uk/id/eprint/147211
ISSN: 1463-9076
PURE UUID: e0930ed7-b823-4e4d-acc0-0d5c530e9064
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X
ORCID for David Kinnison: ORCID iD orcid.org/0000-0001-6103-8502

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Date deposited: 20 May 2010 07:47
Last modified: 29 Aug 2019 00:55

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Contributors

Author: John M. Dyke ORCID iD
Author: M.V. Ghosh
Author: David Kinnison ORCID iD
Author: Giacomo Levita
Author: Alan Morris
Author: Dudley Shallcross

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