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By C. H. Bamford

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I ) P radicals are those that are involved in second-order propagation steps; a hydrogen atom is a /? radical in the ethane decomposition since it undergoes the reaction (ii) p radicals are those that are involved in first-order propagation steps. For example, if in a pyrolysis the C2H5 radical undergoes the propagation reaction and if this reaction is in its first-order (high-pressure) region, the radical is a p radical. It is to be noted that since unimolecular reactions can have kinetics that are between first and second order, radicals may be neither pure P or pure p radicals, but somewhere in between.

7 expresses the rate coefficient of the breakdown of a molecule having energy E in terms of the critical energy E* and the number s of vibrational degrees of freedom. This is the equation given by the RRK and Slater theories when quantum or zero-point effects are neglected. 5 x 10” sec-’. 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.

6 51 58 59 60 + dimethylcyclobutane, which occur according to the following scheme C4Ha cis and trans In contrast to the situation with the cyclopropane derivatives, the &-trans isomerizations are considerably slower than the decompositions. The Arrhenius parameters for the reactions in the above scheme are given in Table 6 . 3 2 R E A C T I O N S OF C Y C L I C H Y D R O C A R B O N S 21 The biradical formed in Process a will be relatively more stable than that formed in b, since the free electrons are both located on secondary carbon atoms; Path a should therefore have a lower activation energy than Path b, in agreement with experiment (cf.

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