Kinetics of the thermal decomposition reaction of diethylketone cyclic triperoxide in acetone–toluene and acetone–1‐propanol binary solvent mixtures

Abstract

The thermal decomposition reaction of diethylketone triperoxide (DEKT) ca. 0.02 M was studied in binary mixtures of acetone–toluene and acetone–1‐propanol at 150 °C. Products of DEKT thermolysis in solution, detected by GC analysis, were diethylketone, bibenzyl and butane. The reactions were explored by GC at different solvent compositions and in each case the reactions followed a pseudo first order kinetic law, up to at least 90% peroxide conversion. The rate coefficient value of the reaction is affected by the solvent properties, showing an increase in the kobs values with increases in the polarity of the solvent mixture in acetone–toluene systems. Changes in the rate coefficient values are probably caused by the presence of the apolar toluene solvent, which dominates the preferential solvation around the DEKT molecule through non‐specific interactions. In acetone–1‐propanol mixtures the solvation effect is slightly dominated by the specific interactions between the 1‐propanol and a polar intermediate specie represented by the biradical, initially formed. The rate coefficient value increases ca. 6% in the mixture with 0.1 mole fraction of 1‐propanol in comparison with the value in pure acetone; but no more changes in rate coefficient values are observed when the amount of the alcohol increases. The critical state of the reaction (intermediate biradical) is preferentially solvated by the 1‐propanol instead of acetone, but in mixtures of different composition, it is not possible to detect any effect on the reactivity for homolytic rupture of the OO bond. Copyright © 2008 John Wiley & Sons, Ltd.

Thermal decomposition of diethyl ketone triperoxide in methyl methacrylate: Theoretical and experimental study of the initial solvation state and its influence on the polymerization process

“…The thermal decomposition reaction of DEKTP at the different evaluated temperatures followed a pseudo first‐order kinetic law until at least 52% of the cyclic triperoxide conversion. The obtained k d values were in reasonable agreement within the typical experimental error of this kind of studies (3%) . As it was expected k d values increased with temperature (Table ).…”

“…The obtained k d values were in reasonable agreement within the typical experimental error of this kind of studies (3%). 27 As it was expected k d values increased with temperature ( The Arrhenius equation plot for k d was linear (r 5 0.9987) (see Figure S3 in Supporting Information) in a relatively wide temperature range (ca. 308C), which suggested that the calculated activation parameters for the DEKTP reaction corresponded to a single process, that would be certainly the thermolysis to The kinetic parameters obtained from the Eyring equation were compared with those published for other solvents in related works, (Table II) 10,13,18 where it can be observed that DEKTP reactivity increased when monomers (MMA and St) were employed as the reaction medium instead of organic solvents (ethylbenzene and chlorobenzene).…”

Effect of ionic liquid on the thermal decomposition of cyclic organic peroxides

“…The kinetic data obtained in this work, and other results previously described by various authors for different cyclic peroxides (Cafferata et al, 1984;Cafferata et al, 1990;Cafferata et al, 1991;Eyler et al, 1994;Eyler et al, 2000;Barreto and Cañizo, 2004;Sheng et al, 2004;Cañizo, 2006;Iglesias et al, 2009), allowed to associate the rate constants with the unimolecular rupture process of one peroxidic bond as the rate-determining step of the decomposition route (Scheme 2).…”

Research on the Thermal Decomposition Reaction Kinetics and Mechanism of Pyridinol-Blocked Isophorone Diisocyanate

“…From the value of the slope and activation energy, the reaction order can be calculated [24]. The reaction order n can be calculated from the value of the slope with the average activation energy E calculated by FRL and FWO method.…”