Comprehensive Chemical Kinetics Reactions of Non-Metallic by C. H. Bamford

By C. H. Bamford

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Substitution into eqn. mole-’) leads to a value of 15 for s, the number of effective vibrational degrees of freedom. This value is unreasonably small, the total number of degrees of vibrational freedom in methylcyclobutane being 39. References pp. 138-148 28 D E C OM P 0sI T I 0 N 0 F H Y D R 0 C A R B O N S A more satisfactory relationship between k , and the energy content of the molecule takes into consideration the zero-point energy. An approximate but useful relationship"*86 is ( E-&E*+aEO k , = k' E f E o ) s-' where c0 is the total zero-point energy of the molecule and a = s / ( 3 N - 6 ) where Nis the number of atoms in the molecule.

This effect can arise from interactions between the side groups and the electrons which become unpaired on the twisting of the bond. Such interactions will reduce the energy required to twist the bond, and also the n-bond energy, and will also lead to an increased rigidity of the activated complex and to a reduction in its entropy. In their study of the isomerization of cis-butene-2 to trans-butene-2 Rabinovitch and Michels8 found that the first-order rate coefficient k' fell at pressures below References pp.

Cyclopentane decomposes by two processes, giving (a) cyclopentadiene and hydrogen probably by way of cyclopentene and ( b ) propene and ethylene (ring cleavage), viz. 66,who found them to be apparently homogeneous, and to be unaffected, in their initial stages, by nitric oxide. Added ethylene, propene or cyclopentadiene, however, produce an increase in rate. Further work is required to elucidate the mechanism. 6 CYCLOBUTENES Cyclobutene undergoes a thermal isomerization to butadiene, which is the only product of significance, viz.

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