Shock Tube cis-trans Isomerization Studies - Journal of the American

Peter M. Jeffers, and Walter Shaub. J. Am. Chem. Soc. , 1969, 91 (27), pp 7706– ... E. W. Kaiser and David S. Pierce. The Journal of Physical Chemis...
0 downloads 0 Views 493KB Size
7706

Maccoll, et a1.,3 for the hydrogen halide catalyzed dehydration of alcohols,6 for the hydrogen bromide cata. lyzed isomerization of but-l-ene, l1 and for the pyrolysis, of l-chloro-cis-but-2-ene. l7 Transition states of this. type may be quasi-heterolytic3 as represented by I1 in the case of the 1,l-dimethylcyclopropanereaction.

c1-

The Arrhenius preexponential factor for the catalyzed isomerization ( A = 2.3 X 10l8sec-l ml moleT1) is significantly larger than for most bimolecular reactions. High A factors are not uncommon for the gas-phase reactions of cyclopropane compounds (e.g., A = 2.6 X 10’6 sec-’ for trans- to cis-1,2-dideuteriocyclopropane,lE and A = 2.8 X 10’5 sec-l for methylcycl~propane~~ to a (17) P. G. Rodgers, Ph.D. Thesis, University of London, 1966. (18) B. S. Rabinovitch, F. W. Schlag, and I