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Kinetics and mechanisms of the reaction of OH radicals with dimethyl sulfide
Author(s) -
Barnes I.,
Bastian V.,
Becker K. H.
Publication year - 1988
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550200602
Subject(s) - chemistry , dimethyl sulfide , reaction rate constant , radical , yield (engineering) , torr , analytical chemistry (journal) , sulfone , photodissociation , total pressure , partial pressure , atmospheric pressure , kinetics , sulfur , photochemistry , organic chemistry , oxygen , physics , oceanography , quantum mechanics , thermodynamics , geology , materials science , metallurgy
The rate constant of the reaction of OH with DMS has been measured relative to OH + ethene in a 420 l reaction chamber at 760 torr total pressure and 298 ± 3 K in N 2 + O 2 buffer gas using the 254 nm photolysis of H 2 O 2 as the OH source. In agreement with a recent absolute rate determination of the reaction the measured effective rate constant was found to increase with increasing partial pressure of O 2 in the system, for 760 torr air a rate constant of (8.0 ± 0.5) × 10 −12 cm 3 s −1 was obtained. Product studies have been performed on the reaction in air using FTIR absorption spectrometry for detection of reactants and products. On a molar basis, SO 2 was formed with a yield of 70% and dimethyl sulfone (CH 3 SO 2 CH 3 ) with a yield of approximately 20%. These results are considerably different to those obtained in other product studies which were carried out in the presence of NO x . These differences are compared and their relevance for the atmospheric oxidation mechanisms of DMS is discussed.