The thermal decomposition of some organic solids. Part II. m-Nitroperoxybenzoic acid and related peroxyacids

Abstract

The thermal decomposition of m-nitroperoxybenzoic acid has been studied in a static system in the temperature range 66·5–90°. m-Nitrobenzoic acid, carbon dioxide, water, and nitrogen are the principal products, with dinitrodiphenyls, nitrobenzoates, and oxygen as minor products. The reaction is autocatalytic; its course may be represented by two expressions of the form logV//_V∞–V=kt+ C, where V_∞ is the volume of gas evolved at complete decomposition, V, the volume of gas evolved at t minutes and k the rate constants. The activation energy for both processes is 30 ± 3 kcal./mole. A reaction mechanism involving the rupture of the peroxy bond and subsequent reactions of the two radicals formed has been proposed. Substituted benzoic acids and oxalic acid catalyse the decomposition.

The investigation was extended to include the thermal decomposition of p-peroxytoluic acid and p-chloroperoxybenzoic acid.