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  • 1980-1984  (3)
  • 1
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of sulfur compounds. Part III: n-butyl 2-propenyl sulfide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 131-142 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of n-butyl 2-propenyl sulfide has been investigated in a static system in the initial pressure range of 50-350 torr. The reaction was found to be homogeneous and first order. The rate coefficients are given by the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ k{\rm}(s^{- 1}) = 10^{11.42 \pm 0.28} \exp [(- 155 \pm 3){\rm kJ/mol/}RT] $$\end{document} between 262 and 293°C. The rate of the reaction remains unchanged in the presence of cyclohexene as radical inhibitor. The main reaction products were propene and a trimer of n-butyl thioaldehyde. The results are interpreted in terms of a molecular mechanism involving a cyclic six-centered transition state. This mechanism is supported by the pyrolysis of 1,1-dideutero-n-butyl 2-propenyl sulfide at 281°C. The kinetic deuterium isotope effect had a value of 2.7 ± 0.2. Nuclear magnetic resonance and mass spectroscopic analysis of the reaction products showed the deuterium to be distributed as expected from the proposed reaction mechanism.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140203
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  • 2
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of sulfur compounds. Part IV. n-propyl allyl sulfide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 605-612 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of n-propyl allyl sulfide has been studied in static and stirred-flow systems at temperatures between 270 and 400°C. Propene and 2,4,6-triethyl-1,3,5-trithiane were the only reaction products. The order of the reaction was 0.99 ± 0.05 at 377°C. The first-order rate coefficients followed the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$k{\rm (s}^{- 1} {\rm) = 10}^{{\rm 11}{\rm .52} \pm {\rm 0}{\rm .16}} {\rm exp[(- 157} \pm {\rm 2) kJ/mol/R}T]$$\end{document} The rate coefficients and the product distribution remained unchanged when cyclohexene was used as carrier gas. A molecular mechanism involving a six-centered cyclic transition state is proposed to explain the present results. This mechanism is further supported by the pyrolysis of 4-thia-5-dideutero-1-heptene at 377°C, where only 3-deuteropropene is formed. The kinetic deuterium isotope effect had a value of 2.6 ± 0.3 at this temperature. The results are compared with those obtained in the pyrolysis of n-butyl allyl sulfide previously reported.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140602
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    Gas phase thermolysis of sulfur compounds. II. Ditertiary butyl sulfide (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 699-716 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of di-tert-butyl sulfide has been investigated in static and stirred-flow systems at subambient pressures. The rate of consumption of the sulfide was measured in some experiments, and the rate of pressure increase was followed in others. The results suggest that the reaction is essentially homogeneous in a seasoned reactor and proceeds through a free radical mechanism. In the initial stages, the decomposition rate follows first-order kinetics, and the rate coefficient in the absence of an inhibitor is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{^u} (\sec ^{ - 1}) = 10^{15.1 \pm 0.6} \exp \left[{\left({ - 229 \pm 8} \right){\rm kJ/mol/RT}} \right] $$\end{document} between 360 and 413°C. The stoichiometry of the uninhibited reaction at 380°C and 50% decomposition is approximately \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm t}^{\rm \_} {\rm C}_{\rm 4} {\rm H}_{{\rm 9}^{\rm -}} {\rm S}_{\rm -} {\rm t}_{\rm -} {\rm C}_{\rm 4} {\rm H}_{\rm 9} = 1.72i_ - {\rm C}_{\rm 4} {\rm H}_{\rm 8} + 0.88{\rm H}_{\rm 2} {\rm S} + 0.29i_ - {\rm C}_{\rm 4} {\rm H}_{{\rm 10}} + 0.11t_ - {\rm C}_{\rm 4} {\rm H}_{\rm 9} {\rm SH} $$\end{document} between 360 and 413°C. The stoichiometry of the uninhibited reaction at 380°C and 50% decomposition is approximately.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550121004
    Library Location Call Number Volume/Issue/Year Availability
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    Paper (German National Licenses)
    Fulltext
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