EFFECT OF PRESSURE ON THE DECOMPOSITION OF 2-TERT-BUTYL PEROXIDE IN SOLUTION

Article abstract of DOI:10.1007/BF00961517

A study was carried out on the effect of pressure up to 1400 MPa on the homolytic decomposition of di-tert-butyl peroxide (DTBP) at 403 K in 2-methoxy- (I) and 2-ethoxytetrahydropyran (II) as well as in a mixture of 30 mole percent (I) and 70 mole percent benzene.Spline approximation of the experimental pressure dependence of the logarithm of the decomposition rate constant (k_d) gave the continuous dependence of the volumetric activation effect (ΔV excit.) on pressure.The value of ΔV excit. at atmospheric pressure (ΔV excit.₀) and the nature of the change of ΔV excit. with increasing pressure were found to depend on the nature of the solvent.This dependence is difficult to explain in the framework of the accepted transition state theory.