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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 10, Number 3
BKCSDE 10(3)
March 20, 1989 

A Gas Phase Kinetic Study on the Thermal Decomposition of ClCH2CH2CH2Br
Sung Hoon Kim, Kwang Yul Choo*, Kyung-Hoon Jung
The gas phase thermal decomposition of 1-bromo-3-chloropropane in the presence of radical inhibitor was studied by using the conventional static system. The mechanism of unimolecular elimination channel is shown below. [...] In this scheme, the total molecular dissociation rate constant, (k1 + k2), for the decomposition of BrCH2CH2CH2Cl was determined by pyrolyzing the BrCH2CH2CH2Cl in the temperature range of 380-420℃ and in the pressure range of 10∼100 torr. To obtain k3 and k4, and to obtain k1 and k2 independently, the thermal decompositions of allyl chloride and allyl bromide were also studied. The Arrhenius parameters for each step are as follows; log A∞ = 14.20(sec-1), Ea = 56.10(kcal/mol) for reaction path 1; log A∞ = 12.54(sec-1), Ea = 49.75(kcal/mol) for reaction path 2; log A∞ = 13.41(sec-1), Ea = 50.04(kcal/mol) for reaction path 3; log A∞ = 12.43(sec-1), Ea = 52.78(kcal/mol) for reaction path 4; Finally, the experimentally observed pressure dependence of the rate constants in each step is compared with the theoretically predicted values that are obtained by the RRKM calculations.
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