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Toluene is an interesting case as C-H homolysis t o form t h e benzyl radical is 2 1 A 2 2 6 1 A 1 A 36 faster than C-C homolysis to give the phenyl radical, due t o the 50 kJ m o l energy in the benzyl radical. 6x10-! 5 1 * Units s ' , reactions as specified in Table 9 ** N o t e kj A values for C-H homolysis in C H 3 group 7. 1. General introduction It has long been established that conjugate alkenes are the major initial p r o d u c t s in the reaction of alkyl radicals with 0 (where structurally possible) above ca 550 Κ [30, 4 5 , 6 3 .

A full range of possible reactions are considered for each radical intermediate involved. Their calculated rate constants are in g o o d agreement with experimental data [75,80], and they conclude that there is n o evidence for a direct bimolecular C H 0 * reaction below 1000 K. Bozzelli and Dean comment that "the energised hydroperoxy radical C H O O H * , if formed, dissociates t o C H and H 0 almost completely at l o w pressures due t o the high βscission A factor (compared t o that for reverse isomerisation), whilst at high pressures large fractions can be stabilised.

Only, therefore, by modelling the rate of oxidation in the very early stages of reaction can an accurate value of k be obtained. However, in their modelling studies E m d e e et al had n o experimental data for the first 1 0 - 1 5 % o f toluene oxidation. Beyond this stage, the relative importance of primary initiation may well b e markedly diminished. (iii) Finally, it is necessary to consider the comment made by E m d e e et al that an accurate value of k can b e obtained because the calculated rate is so sensitive t o k .

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Absorption of Ultra-Sonic Waves by Hydrogen and Carbon Dioxide by Abello T.P.


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