Abstract
An important requirement of any mechanism for the low temperature oxidation of alkanes at 300° to 400°C is shown to be inclusion of processes for the conversion of HO 2 to OH radicals. This conversion must involve the co-oxidation of the olefin, A B, which is the primary oxidation product of most alkanes. The key to the conversion mechanism is the sequenceAB→ABOOH→OOABOOH The complete mechanism explains the major features of alkane and olefin oxidation in the low temperature régime. It explains the existence of the negative temperature coefficient in terms of the instability of the ABOOH radical and the effect of structure on the ease of oxidation. The paper includes ( a) thermochemical data on peroxides, peroxy radicals and hydroperoxide radicals, ( b) estimates of the equilibrium constants and lifetimes of peroxy and hydroperoxide radicals.
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