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The kinetics of the reaction: Br + C3H6 ⇌ HBr + C3H5

✍ Scribed by Osamu Kondo; Roger M. Marshall; Sidney W. Benson

Publisher
John Wiley and Sons
Year
1988
Tongue
English
Weight
449 KB
Volume
20
Category
Article
ISSN
0538-8066

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✦ Synopsis

Studies of the reaction of Br + propylene to produce HBr and ally1 radical were made using VLPR (Very Low Pressure Reactor) over the range 263-363 K. Apparent bimolecular rate constants k;PP were found to vary in an inverse manner with the initial concentration of bromine atoms introduced into the reactor. Plots of k;pp against [Brl;' give straight lines whose intercepts were taken to be the true bimolecular, metathesis rate constant k,. The reaction scheme is Br + C3H6 & HBr + allyl Br t allyl A HBr + allene where kz * k , and k -, [HBrl is negligibly small under our conditions.

shown to give excellent fits to the observed intercepts. Arrhenius parameters for k 1 were assigned for linear and bent transition states and linear: bent: log(kl/cm3 mol-' s-') = 12.1 -3 . 5 / 0 log(kl/cm3 m o l -' ~-~) = 12.7 -4.4/0 where 0 = 2.303 R T (kcal mol-'). The dependence of k;pp on [Brl;' is accounted for in terms of the reactivity of Br* t2P1 2 )

produced in the microwave discharge. The activation energy for the metathesis reaction of Br* with propylene is shown to be very small.

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