Thermal decomposition of benzaldehyde cyclic diperoxide in benzene solution

In the temperature range of 130-166 degrees C, the thermolysis of 3,6-diphe nyl-1,2,4,5-tetroxane in benzene solution in the initial concentration rang e of 1.32-1.68 x 10(-2) moi kg(-1); follows first order kinetic lawas up to 40% diperoxide conversion. The activation parameters for the DFT unimolecu lar decomposition reaction are DH# = 132,7 +/- 1,7 kJ mol(-1) and DS# = -21 ,8 +/- 5,0 J mol(-1) K-1. Support for an homolytic stepwise mechanism -inst ead of a concerted process- is proposed on the basis of the comparison of t hese values with those corresponding to the unimolecular thermolysis of oth er similar cyclic diperoxides in solution.