Kinetic solvent effects on the thermal decomposition reaction of acetone triperoxide

The kinetic data of the thermal decomposition reaction of acetone cyclic triperoxide (3,3,6,6,9,9‐hexamethyl‐1,2,4,5,7,8‐hexaoxacyclononane, ACTP) are reported for a wide range of organic solvents (acetone, toluene, 2‐propanol, 2‐methoxyethanol, n‐butylamine, diethylamine, triethylamine, and chlorobenzene) at 0.02 M initial concentration and in the temperature range of 135.0–172.0 °C. The thermolysis reaction follows pseudo first‐order kinetic laws up to at least ca. 70% ACTP conversion. The results indicate the importance of solvent polarity and specific solvent‐peroxide interactions in governing the rates of the reactions. The activation enthalpy and entropy of the thermal decomposition reaction of this triperoxide in several organic solvents were correlated through “isokinetic relationships” to verify the existence of a genuine solvent effect on this reaction. Other cyclic organic di‐ and triperoxides and some cyclic trioxanes showed a similar behavior, in contrast to the pinacolone cyclic diperoxide (PDP), probably due to a relatively great steric hindrance of this molecule.