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dc.contributor.author
Nesprias, Rosa Karina
dc.contributor.author
Iglesias, Mariángeles
dc.contributor.author
Rivas, Sonia
dc.contributor.author
Alvarez, Elida
dc.contributor.author
Barreto, Gastón Pablo
dc.contributor.author
Eyler, Gladys Nora
dc.contributor.author
Cañizo, Adriana Ines
dc.date.available
2022-12-01T13:02:05Z
dc.date.issued
2011-07
dc.identifier.citation
Nesprias, Rosa Karina; Iglesias, Mariángeles; Rivas, Sonia; Alvarez, Elida; Barreto, Gastón Pablo; et al.; 4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution; John Wiley & Sons Inc.; International Journal of Chemical Kinetics; 43; 11; 7-2011; 657-666
dc.identifier.issn
0538-8066
dc.identifier.uri
http://hdl.handle.net/11336/179747
dc.description.abstract
Cyclic organic peroxides have interesting pharmacological properties and are used at industrial level as polyfunctional initiators of polymerization, and so their preparation through novel methods has attracted the attention of numerous researchers. White crystals of 4-heptanone cyclic diperoxide (HDP) can be obtained in acidic media at −1°C by a reaction between 4-heptanone and hydrogen peroxide. Its thermal decomposition was studied in acetone, cyclohexane, acetonitrile, ethyl acetate, ethanol, 2-propanol, 2-butanol, and 1,4-dioxane at temperatures higher than 120°C, showing a behavior accordingly with a pseudo-first-order kinetic law up to at least 80% HDP conversion. It was demonstrated that an increase in solvent polarity is accompanied by an increase in reaction rates. The effect of solvent polarity on the thermal decomposition rate constant values can be associated with a reaction mechanism involving a more dipolar-activated complex than the diperoxide initial molecule. The activation parameters varied widely from 31.2 to 46.6 kcal mol−1 and −1.33 to 31.7 cal mol−1 K−1 when going from ethanol to cyclohexane as reaction solvents, respectively. An enthalpy–entropy compensation effect was observed in all solvents. Specific interactions between the oxygen atoms from the peroxidic bond and the hydrogen atom bonded to C2 and/or from the OH group can be taken into account to explain that the existence of the compensation effect does not mean that an isokinetic relationship consequently can be established. The kinetic results showed that an isokinetic relationship is observed only for a group of solvents.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
John Wiley & Sons Inc.
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
CYCLIC PEROXIDE
dc.subject
KINETICS IN SOLUTION
dc.subject
SOLVENT EFFECT
dc.subject.classification
Química Orgánica
dc.subject.classification
Ciencias Químicas
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CIENCIAS NATURALES Y EXACTAS
dc.title
4-Heptanone cyclic diperoxide: Improved preparation method and solvent effect on its thermolysis in solution
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2021-06-07T16:59:00Z
dc.journal.volume
43
dc.journal.number
11
dc.journal.pagination
657-666
dc.journal.pais
Estados Unidos
dc.journal.ciudad
New York
dc.description.fil
Fil: Nesprias, Rosa Karina. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
dc.description.fil
Fil: Iglesias, Mariángeles. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
dc.description.fil
Fil: Rivas, Sonia. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
dc.description.fil
Fil: Alvarez, Elida. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
dc.description.fil
Fil: Barreto, Gastón Pablo. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
dc.description.fil
Fil: Eyler, Gladys Nora. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina
dc.description.fil
Fil: Cañizo, Adriana Ines. Universidad Nacional del Centro de la Provincia de Buenos Aires. Facultad de Ingeniería Olavarría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
dc.journal.title
International Journal of Chemical Kinetics
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/full/10.1002/kin.20600
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/https://doi.org/10.1002/kin.20600
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