The surface as a limiting factor in the slow combustion of hydrocarbons

Abstract
With special reaction vessels, varying widely in diameter while maintaining approximately constant volume, and employing several refinements in technique, a study has been made of the effect of surface on the slow oxidation of several hydrocarbons, both saturated and unsaturated. All reactions were of the degenerate branching type, and were found to be principally homogeneous in character. When the diameter of the reaction vessel was sufficiently reduced, the reaction rate was observed to drop abruptly toward zero, while the corresponding induction period increased toward infinity. Data so obtained have demonstrated that in narrow vessels surface deactivation can predominate over other processes of deactivation, while in wider vessels surface and volume deactivation occur to a comparable extent over a considerable range of pressure. When the vessel diameter is decreased to a critical value, the surface deactivation almost alone can suppress the factors leading to chain branching, and from the reactions investigated the existence of such a critical diameter appears to be a general property of hydrocarbon oxidations in conformity with the theory of degenerate branching.

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