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Kinetics of the thermal isomerization of 1,1-dimethylcyclopropane

✍ Scribed by Bansi L. Kalra; David K. Lewis

Publisher
John Wiley and Sons
Year
2001
Tongue
English
Weight
132 KB
Volume
33
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

Rate constants for the unimolecular thermal isomerization of gaseous 1,1‐dimethylcyclopropane to isomeric methylbutenes have been measured, and Arrhenius parameters determined, over a wide temperature range, 683–1132 K, using a single‐pulse shock tube and a static reactor. For the overall reaction, E~a~ = 61.8 ± 0.4 kcal/mol, and log~10~(A, s^−1^) = 15.04 ± 0.10. These values are in good agreement with previously reported values obtained over a much narrower temperature range. Rate constants for formation of the two major products, 2‐methylbut‐2‐ene and 3‐methylbut‐1‐ene, are given by E~a~ = 61.9 kcal/mol, log A = 14.80 and E~a~ = 61.1 kcal/mol, log A = 14.54, respectively. A comparison of the activation parameters for structural isomerizations of cyclopropane, methylcyclopropane, and 1,1‐dimethylcyclopropane confirms a trend toward lower activation energy values as hydrogen atoms in cyclopropane are replaced by CH~3~ groups. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 853–858, 2001

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