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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 11, Number 5
BKCSDE 11(5)
May 20, 1990 

 
Title
Gas Phase Thermal cis-trans Isomerization Reaction of 1-Bromopropene
Author
Do Sung Huh, Jae Young Um, Sun Jin Yun, Kwang Yul Choo, Kyung-Hoon Jung*
Keywords
Abstract
The kinetics of thermnal cis-trans isomerization reaction of 1-bromopropene(1-BP) was studied at temperatures from 620.8 to 753.15 K over the pressure range 0.17-50.3 Torr. Both the inhibition effect by cyclohexene or propene and the catalytic effect by HBr showed a radical process as the main mechanism of the isomerization. In the suppression of the radical process by the inhibitors, the molecular process also contributed to overall reaction rate. The reactions demonstrated the first order kinetics under both uninhibited and inhibited conditions and could be represented by the expressions (R = 1.987 cal/mol/K) kun/s-1 = (3.45±1.50)×1011exp[(- 48100± 2000)/RT] kinhs-1 = (2.98±1.40)×1012exp[(- 55800± 1800)/RT] where kun is the observed rate constant of cis-1-bromopropene(1-BPc) to trans-1-bromopropene(1-BPt) under uninhibited condition at initial pressure of 50 Torr and kinh is the rate constant under maximal inhibition by cyclohexene. The ratio of rate constants for bromine atom elimination from the allylic hydrogen of reactant(1-BP) and from the inhibitors, propene and cyclohexene, were measured from the observed rates of the uninhibited and inhibited reactions. The inhibition efficiencies of cyclohexene and propene were compared kinetically from the rate constants and shown to give good agreement with the previous results reported from other alkyl bromide pyrolyses.
Page
391 - 395
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