Artículos de revistas
Effect of ionic liquid on the thermal decomposition of cyclic organic peroxides
Fecha
2016-06Registro en:
Barreto, Gastón Pablo; Rodríguez, Karla Delgado; Morales, Graciela E.; Enríquez Medrano, Francisco Javier; Cañizo, Adriana Ines; et al.; Effect of ionic liquid on the thermal decomposition of cyclic organic peroxides; Elsevier Science; Arabian Journal of Chemistry; 6-2016; 1-10
1878-5352
CONICET Digital
CONICET
Autor
Barreto, Gastón Pablo
Rodríguez, Karla Delgado
Morales, Graciela E.
Enríquez Medrano, Francisco Javier
Cañizo, Adriana Ines
Eyler, Gladys Nora
Resumen
The thermolysis of cyclic diethylketone triperoxide (3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane, DEKTP) and cyclic pinacolone diperoxide (3,6-diterbutyl-3,6-dimethyl-1,2,4,5-tetraoxacyclohexane, PDP) was studied in neat N,N-dimethylformamide (DMF) and in binary mixtures DMF/Ionic Liquid (1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM+][BF4 -]). The activation parameters for the decomposition of both peroxides in DMF, correspond to a process of homolytic cleavage of one OO bond, generating a biradical in the initial step of radical mechanism. The rate constant values (kd ) are higher for reactions performed in mixtures. A gradual increase of [BMIM+][BF4 -] in the reaction media generates higher kd for both peroxides (i.e. kd , DEKTP in DMF/[BMIM+][BF4 -] 4.0molL-1 is 3.3 times greater than the kd obtained for the mixture with a concentration 1.0molL-1, under the same experimental conditions). The increase in decomposition rate can be associated with a more solvated and stabilized transition state when the ionic liquid is part of the reaction medium.