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By N. M. Emanuel

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By N. M. Emanuel

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Analogous results were obtained when inhibitor (1-naphthol) was introduced during the oxidation of cyclohexanol. Introduction of inhibitor led to the cessation of the accumulation of cyclohexanone, which only started up again after the inhibitor had been used up completely. TABLE 10 Rate Constant of the Removal of Hydrogen From Different Hydrocarbons by The Action of —1 —1 (98) Tertiary Peroxyl Radicals (£ mol s ). 03 0. 18 0. 65 2. 1 1,1,3,3-Tetramethylbutyl 0-04 0. 32 0. 05 0. 22 0. 15 1. 3 — — 1,1-Diphenylethyl — — 0 18 — 1.

105 [90] 5 [91] [92] - - 9. 10 - - 1. 2 [93] T9ll Mechanism of Liquid Phase Oxidation 37 activation energy for the formation of hydroperoxide varies within a range . The value of the constant k of 4-12 kcal mol is known for a fairly P large number of organic compounds (Table 7 ) . The value of the activation energy k can thus be used to calculate the bond dissociation energies of P the substances being oxidised. 4 . The energy of activation and the pre-exponential factor in the constant k P (95) are related by a simple expression .

Although the value of k" at 145 C is greater than k' by one power of b b magnitude, chain branching in the decomposition of biacetyl into radicals plays an important part in the oxidation of butan-2-one since the concentra­ tion of the latter in this process is considerably greater than that of the keto-hydroperoxide. The mechanism of chain-branching has thus been established for a series of oxygen-containing compounds as well as for various types of hydrocarbons. 3. Chain—propagation Chain-propagation involves the interaction of free radicals with molecules of the original compound.

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