THE DECOMPOSITION OF BENZOYL PEROXIDE IN BENZENE

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Abstract
A kinetic study has been made of the decomposition of benzoyl peroxide in benzene. Kinetic data for this study have been obtained from three separate sets of measurements. Rate measurements from evolved carbon dioxide and direct iodometric measurements of peroxide are in good agreement. Alkali-metric determinations of the product, benzoic acid, have also been made during the course of the reaction.Gravimetric determinations show that the total evolved carbon dioxide from the reaction is a function of the temperature, and indicate that the mechanism involves two parallel fast reactions, one of which evolves one mole of carbon dioxide per mole of peroxide and the other two moles of carbon dioxide per mole of peroxide. The latter reaction predominates at higher temperatures.A kinetic analysis is included and provides for a slow reaction involving the rupture of the peroxide bond, followed by free radical reactions.[Formula: see text]The secondary free radical reactions would probably form hydrogen radicals, but there is evidence to support the view that these hydrogen radicals are not eliminated by mutual termination.The reaction is first order and the energy of activation was found to be 31,000 cal. per mole.

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