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The pyrolysis of trimethylene sulfide. A unimolecular decomposition
Author(s) -
Jeffers P.,
Dasch C.,
Bauer S. H.
Publication year - 1973
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.550050405
Subject(s) - chemistry , pyrolysis , reaction rate constant , decomposition , cyclopropane , isomerization , thermal decomposition , propene , ethylene , enthalpy , sulfide , kinetics , cyclohexene , atmospheric temperature range , organic chemistry , thermodynamics , catalysis , ring (chemistry) , physics , quantum mechanics
The kinetics of decomposition of trimethylene sulfide to ethylene and thioformaldehyde was investigated in a single‐pulse shock tube using the «relative rate» technique. The extent of reaction was measured in the reflected shock regime from 860° to 1170°K, but experimental difficulties limited the useful data to the temperature range of 980°–1040°K. The first‐order rate constant was found to be k = 10 13.0 exp (−48,200/ RT ) sec −1 . This result sets an upper limit of 50 kcal/mole for the standard enthalpy of formation of CH 2 S, with 35 kcal/mole as a more likely value. The isomerization of cyclopropane to propene was used for the reference reaction; in turn, this was checked, in a relative rate experiment, against the pyrolysis of cyclohexene.