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Gas‐phase thermolysis of sulfur compounds. Part IV. n ‐propyl allyl sulfide
Author(s) -
Martin Gonzalo,
Ropero Marcos
Publication year - 1982
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.550140602
Subject(s) - chemistry , pyrolysis , thermal decomposition , arrhenius equation , propene , sulfide , kinetic isotope effect , decomposition , cyclohexene , deuterium , carbonyl sulfide , hydrogen sulfide , sulfur , medicinal chemistry , organic chemistry , activation energy , catalysis , physics , quantum mechanics
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.