Abstract
cycloHexy1 chloride has been shown to
decompose in the gas phase at 318-385 �C almost exclusively to cyclohexene and
hydrogen chloride. With clean glass-walled reactors the reaction was largely
heterogeneous, but after the walls were coated with a carbonaceous film a
homogeneous first-order reaction was found to predominate. For initial
pressures within the range 4-40 cm mercury the rate coefficients for the
homogeneous reaction were expressible as������� k = 5.88 x 1013exp(-50,000 cal/RT)
sec-1. There was some evidence for
the rate coefficient becoming pressure-dependent below 5-10 mm initial pressure
of reactant.
The reaction exhibited no induction
periods and the velocity was virtually unaffected by the addition of large
amounts of propene or cyclohexene and traces of chlorine or bromine. The
results were consistent with a unimolecular elimination of hydrogen chloride.
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