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The thermal decomposition reactions of aliphatic peroxy acids containing from 8 to 16 carbon atoms in a molecule were studied. It was found that the carbon radical length had no effect on the thermal stability of peroxide groups. The apparent rate constants of thermolysis of peroxydecanoic acid in various solvents and the activation energies of the test reaction were found. The thermal degradation of peroxy acids involved secondary reactions of induced chain degradation in addition to the primary homolysis of the peroxide group. The rate constants of induced chain degradation were found. [ABSTRACT FROM AUTHOR]

The catalytic decomposition of peroxy acids is studied in various solvents in the presence of manganese, cobalt, chromium, nickel, and copper acetates and cerium benzoate. The catalytic activity of the salts in peroxy acid decomposition decreases in the order Mn2+ > Co2+ > Ce3+ > Cr3+ > Ni2+ > Cu2+. The apparent activation energies of the catalytic decomposition of peroxydecanoic acid range between 45.9 and 88.0 kJ/mol. The reaction medium has an effect both on the apparent rate constant and on the activation energy of the reaction. The reaction mechanism includes the fast formation of a catalyst-peroxy acid intermediate complex, which decomposes to release a catalyst molecule and forms the reaction products. The oxidation state of the metal ion of the catalyst can change. The introduction of compounds capable of forming complexes with metal ions of the catalyst substantially slows down the catalytic decomposition. [ABSTRACT FROM AUTHOR]