Gas-phase reactions of O(3P) atoms with methanethiol, ethanethiol, methyl sulfide, and dimethyl disulfide. 2. Reaction products and mechanisms

Cvetanović, R. J.; Singleton, D. L.; Irwin, R. S.

doi:10.1021/ja00402a046

Cited by 42 publications

(35 citation statements)

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“…The results are given in Table 3. The consumption of CH3SSCH3 is not as great as in the absence of CH3SH, and in most cases the final amount of CH3SSCH3 exceeds the initial amount, i.e., CH3SSCH3 is actually formed from the added CH3SH in the course of the reaction as has been observed in our earlier work (5). Addition of 80 pmol of CH,SH decreases the yield of CH3S(0),SCH3 to about 30% of its value in the absence of CH3SH.…”

Section: Resultssupporting

confidence: 66%

“…Thus, for the very fast radical-radical reactions, the statistical ratios (k, + k3dl + k,,,?) = 2k2 = 2(k4 + kJdl + kJ,IZ) = 2kI7 are adopted as was done previously (5). Sensitivity tests showed that appreciable variations in the absolute values of these and some of the other rate constants had only a minor effect on the results.…”

Section: Irradiation Time (Minlmentioning

confidence: 99%

“…We have recently carried out an extensive study of (he kinetics (4) and (5) of oxygen atom In either case, on the basis of the postulated secondary reacreactions with several organic sulfur compounds including tions, it was expected that CH,S(O)?SCH, would be the final CH3SH, C2H5SH, CH,SCH3, and CH,SSCH,. From a detailed stable oxidation product.…”

Section: Introductionmentioning

confidence: 99%

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Mechanism of the reaction of oxygen atoms, O(³P) with dimethyl disulfide

Singleton¹,

Irwin²,

Cvetanović³

1983

Can. J. Chem.

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The mechanism of the reaction of ground state oxygen atoms, O(3P), with CH3SSCH3 was studied by analysis of the final products. Oxygen atoms were generated by mercury photosensitized decomposition of N2O such that [Formula: see text]. The only detected product was CH3S(O)2SCH3, which accounted for close to 70% of the oxygen atoms reacted. Isomerization of small amounts of cis- or trans-2-butene added to the reaction mixture indicated the presence of CH3S radicals. The results are consistent with the primary reaction O + CH3SSCH3 → CH3SO + CH3S. The effect of small amounts of CH3SH and H2S on the yields of CH3S(O)2SCH3 and the products formed provide further information on the nature of the secondary chemistry. A comprehensive reaction mechanism has been proposed.

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Section: Resultssupporting

confidence: 66%

Section: Irradiation Time (Minlmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Mechanism of the reaction of oxygen atoms, O(³P) with dimethyl disulfide

Singleton¹,

Irwin²,

Cvetanović³

1983

Can. J. Chem.

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“…4,[22][23][24][25] Other odorless products detected were CO, CO 2 , H 2 , CH 4 , C 2 H 4 , C 2 H 2 , formaldehyde (CH 2 O), and methanol (CH 3 OH). The yield and selectivity of products were primarily dependent on the applied rf power and the O 2 /DMS ratio.…”

Section: Conversion Of Dms Species Of Odorous S Compounds and Odorlesmentioning

confidence: 99%

“…32 The O-initiated oxidation also decomposes DMS and produces CH 3 SO, dimethyoxythio (CH 3 SCH 2 O), and HSO radicals, and so on, and then further converts them into stable products. 22,33 DMS ϩ ͑O, O*͒ 3 3 ͑CH 3 SO, CH 3 SCH 2 O· · ·͒…”

Section: Postulated Pathways For Dms Destruction and Sulfur Atommentioning

confidence: 99%

Deodorization of Dimethyl Sulfide Using a Discharge Approach at Room Temperature

Tsai

Huang

Chen

et al. 2003

Journal of the Air & Waste Management Association

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The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH 3 SCH 3 , or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS 2 ) or sulfur dioxide (SO 2 ). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O 2 )/DMS molar ratio slightly improved the removal efficiency. In an O 2 -free environment, DMS was converted primarily to CS 2 , methane (CH 4 ), acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), and hydrogen (H 2 ), with traces of hydrogen sulfide (H 2 S), methyl mercaptan (CH 3 SH), and dimethyl disulfide. In an O 2 -containing environment, the species detected were SO 2 , CS 2 , carbonyl sulfide, carbon dioxide (CO 2 ), CH 4 , C 2 H 4 , C 2 H 2 , H 2 , formaldehyde, and methanol. Differences in yield of products were functions of the amounts of added O 2 and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes. INTRODUCTIONDimethyl sulfide (CH 3 SCH 3 , or DMS) is an odorous organosulfur pollutant subject to strong public criticism. Natural sources of DMS include oceanic emissions, marine biogenic sources, and terrestrial biogenic sources. 1 In industry, DMS is emitted to the atmosphere from the incomplete combustion of coal and oil, synthetic fibers and resins, petroleum refining process, Kraft paper mills, synthetic polymer spinning, tannery process, and so on. 2,3 The olfactory detection threshold of DMS is ϳ0.001 ppm, fairly close to that of methyl mercaptan (CH 3 SH) (0.002 ppm), ethyl mercaptan (C 2 H 5 SH) (0.001 ppm),

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Scavenging of Radicals from the Gas Phase by Freezing with Dimethyl Disulfide

Schottler¹,

Homann²

1987

Ber Bunsenges Phys Chem

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Elementary Reactions J Methods and Systems J Molecular Beams J RadicalsH and 0 atoms and methyl radicals produced in microwave discharges of H2/He, Oz/He and CH4/He mixtures, respectively, were scavenged by supersonic nozzle probing with subsequent freezing and reaction with dimethyl disullide on a liquid nitrogen cooled wall. The main reaction products for the three kinds of radicals were CH3SH, CH3S(0)SCH3 and CH3SCH3, respectively. Side products were CH3SCH2SSCH3 and CH3SSSCH3 for H atoms and CH3S(0)?SCH3 for 0 atoms. -The scavenging efficiencies for the different radicals were determined and measured as a function of the gas phase radical concentration, the flow of scavenger molecules, the pressure in the vacuum chamber, and the conditions of the discharge and the flow through the sampling nozzle. It is concluded that this method is suitable for light radicals with reservations in the case of H atoms and can probably be used with still better success for heavier radicals.

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Gas-phase reactions of O(3P) atoms with methanethiol, ethanethiol, methyl sulfide, and dimethyl disulfide. 2. Reaction products and mechanisms

Cited by 42 publications

References 3 publications

Mechanism of the reaction of oxygen atoms, O(³P) with dimethyl disulfide

Mechanism of the reaction of oxygen atoms, O(³P) with dimethyl disulfide

Deodorization of Dimethyl Sulfide Using a Discharge Approach at Room Temperature

Scavenging of Radicals from the Gas Phase by Freezing with Dimethyl Disulfide

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Gas-phase reactions of O(3P) atoms with methanethiol, ethanethiol, methyl sulfide, and dimethyl disulfide. 2. Reaction products and mechanisms

Cited by 42 publications

References 3 publications

Mechanism of the reaction of oxygen atoms, O(3P) with dimethyl disulfide

Mechanism of the reaction of oxygen atoms, O(3P) with dimethyl disulfide

Deodorization of Dimethyl Sulfide Using a Discharge Approach at Room Temperature

Scavenging of Radicals from the Gas Phase by Freezing with Dimethyl Disulfide

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Product

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Mechanism of the reaction of oxygen atoms, O(³P) with dimethyl disulfide

Mechanism of the reaction of oxygen atoms, O(³P) with dimethyl disulfide