Phosphorous and Sulfur and the Related Elements · 1982 · 25 citations · 11 references
Natural SciencesChemistryChemical KineticsOrganic ChemistryPhysical ChemistryChemical Reaction KineticsChemical ThermodynamicsGas-phase Reaction KineticsSulfur ChemistrySulfur CompoundsArrhenius EquationArrhenius KineticsFirst-order KineticsPseudo-first-order KineticsReaction Rate CoefficientsUnimolecular Reaction KineticsUnimolecular Reaction RatesUnimolecular Reactions
Abstract The title compounds have been pyrolyzed in a stirred-flow system, at temperatures within the range 315–418°C and pressures between 2 and 15 torr. Under these conditions, the products observed were propene and the polymers of thiomethanal, allyl thioaldehyde and benzyl thioaldehyde. Diallyl sulfide was further studied in a static system, over the temperature range of 227–256°C and initial pressures between 90 and 255 torr. The reactions showed first-order kinetics and the rate coefficients yielded the following Arrhenius equations Methyl Allyl Sulfide: k (sec−1) = 1011.23±0.25 exp(-160 ± 3 kJ/mol. RT) Diallyl Sulfide: k (sec−1) = 1011.01±0.06 exp(-138.2 ± 0.7 kJ/mol. RT) Benzyl Allyl Sulfide: k (sec−1) = 1010.93±0.18 exp(-141 ± 2 kJ/mol. RT) The Arrhenius parameters are consistent with a unimolecular mechanism involving six-centered cyclic transition states yielding propene and thioaldehyde. The results are discussed in relation to allyl ethers and amines reported in the literature.
11