The pyrolysis of dimethyl sulfide, kinetics and mechanism

Shum, Lilian G. S.; Benson, Sidney W.

doi:10.1002/kin.550170705

Cited by 45 publications

(39 citation statements)

References 19 publications

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“…It was successfully used to determine accurate thermodynamic and kinetic data for reactions involving unsaturated oxygenates,5 peroxy radicals,6 and carbonyl‐containing compounds such as aldehydes and ketones 7. The contribution of Benson’s group‐additivity method in studying atmospheric8 and free‐radical chemistry of several processes such as pyrolysis9 and oxidation and combustion10 is also distinguished. The techniques used are very powerful, and most of them are easily applied by hand on a specific reaction, depending on the available data.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Modeling of α‐Hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Carbon‐Centered Radicals

et al. 2014

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Hydrogen abstractions are important elementary reactions in a variety of reacting media at high temperatures in which oxygenates and hydrocarbon radicals are present. Accurate kinetic data are obtained from CBS-QB3 ab initio (AI) calculations by using conventional transition-state theory within the high-pressure limit, including corrections for hindered rotation and tunneling. From the obtained results, a group-additive (GA) model is developed that allows the Arrhenius parameters and rate coefficients for abstraction of the α-hydrogen from a wide range of oxygenate compounds to be predicted at temperatures ranging from 300 to 1500 K. From a training set of 60 hydrogen abstractions from oxygenates by carbon-centered radicals, 15 GA values (ΔGAV°s) are obtained for both the forward and reverse reactions. Among them, four ΔGAV°s refer to primary contributions, and the remaining 11 ΔGAV°s refer to secondary ones. The accuracy of the model is further improved by introducing seven corrections for cross-resonance stabilization of the transition state from an additional set of 43 reactions. The determined ΔGAV°s are validated upon a test set of AI data for 17 reactions. The mean absolute deviation of the pre-exponential factors (log A) and activation energies (E(a)) for the forward reaction at 300 K are 0.238 log(m(3) mol(-1) s(-1)) and 1.5 kJ mol(-1), respectively, whereas the mean factor of deviation <ρ> between the GA-predicted and the AI-calculated rate coefficients is 1.6. In comparison with a compilation of 33 experimental rate coefficients, the <ρ> between the GA-predicted values and these experimental values is only 2.2. Hence, the constructed GA model can be reliably used in the prediction of the kinetics of α-hydrogen-abstraction reactions between a broad range of oxygenates and oxygenate radicals.

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Section: Introductionmentioning

confidence: 99%

Kinetic Modeling of α‐Hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Carbon‐Centered Radicals

et al. 2014

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“…[15][16][17] Previous conversion processes showed that the gaseous oxidation of DMS at 473 K yielded SO 2 and aldehydes as the primary products; the gas-phase pyrolysis of DMS generated the major products methane (CH 4 ), ethylene (C 2 H 4 ), H 2 S, and CS 2 , with small amounts of C 2 H 5 SH and yellowish compounds. 18,19 However, our previous study showed that CH 3 SH could be destroyed successfully at room temperature by rf plasma, and S atoms were converted into SO 2 and CS 2 , which were less odorous. No extremely toxic and odorous H 2 S was produced in the CH 3 SH plasmolysis process, which would otherwise have prevented the use of post-treatment processes.…”

Section: Discussionmentioning

confidence: 97%

“…This differs greatly from H 2 S being the major product (28%) in the process of DMS pyrolysis. 19 Moreover, sulfuric acid (H 2 SO 4 ) was also not produced, avoiding the corrosion problem. Small deposits formed on the wall of the glow-discharge zone and afterglow zone could be eliminated using O 2 plasma or liquid solvent.…”

Section: Important Factors For the Removal Of Odorous Dmsmentioning

confidence: 99%

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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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“…8 kJ mol Ϫ1 . [37] The substituent effects on the parent cyclopropane suggest a slightly larger figure (ca. 12 kJ mol Ϫ1 ), which is well within the margin of error.…”

Section: -Substituted Ethenylcyclopropanes (1-x)mentioning

confidence: 99%

On the Substituent Effects of the Thermal Ethenylcyclopropane-to-Cyclopentene Rearrangement: Gas-Phase Kinetics of Ethoxy-, Methylthio- and Trimethylsilyl-Substituted Ethenylcyclopropanes

et al. 2001

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The pyrolysis of dimethyl sulfide, kinetics and mechanism

Cited by 45 publications

References 19 publications

Kinetic Modeling of α‐Hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Carbon‐Centered Radicals

Kinetic Modeling of α‐Hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Carbon‐Centered Radicals

Deodorization of Dimethyl Sulfide Using a Discharge Approach at Room Temperature

On the Substituent Effects of the Thermal Ethenylcyclopropane-to-Cyclopentene Rearrangement: Gas-Phase Kinetics of Ethoxy-, Methylthio- and Trimethylsilyl-Substituted Ethenylcyclopropanes

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