By C. H. Bamford
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Additional resources for Comprehensive Chemical Kinetics Reactions of Non-Metallic Inorganic Compounds
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.
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. ' l 7 carried out a general steady-state treatment of reaction mechanisms of the type occurring in pyrolyses, and arrived at conclusions summarized in Table 11. The overall orders corresponding to the various combinations of possibilities are shown in the last column. The type of termination is indicated by symbols such as P p and PPM; P p means that termination is brought about by reaction between a /l radical and a p radical, and that the conditions are such that the process is in its high-pressure region so that the rate is not proportional to the concentration of a third body.
Eq. 2) on p. 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.
Comprehensive Chemical Kinetics Reactions of Non-Metallic Inorganic Compounds by C. H. Bamford