Kinetics and Mechanism of Thermal Decomposition of Malonaldehyde Peroxide (DPM) in Solution

In this paper, the kinetics of the thermal decomposition reaction of 3,6-diethanal-1,2,4,5 tetroxane (malonaldehydeperoxide, DPM) is investigated in methanol solvents at different temperatures. In the temperature range of 130.0-166.0 ° C studied and at the concentration of 2 x 10-2 M, it follows a f...

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Detalles Bibliográficos
Autores: Reguera, Mónica Beatriz, Galante, Nadia Soledad, Varela, Noelia Melina, Profeta, Mariela Inés, Jorge, Maria Josefa, Jorge, Lilian Cristina, Romero, Jorge Miguel, Jorge, Nelly Lidia
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/173577
Acceso en línea:http://hdl.handle.net/11336/173577
Access Level:acceso abierto
Palabra clave:DIPEROXIDE
KINETIC MECHANISM
GAS CHROMATOGRAPHY
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descripción
Sumario:In this paper, the kinetics of the thermal decomposition reaction of 3,6-diethanal-1,2,4,5 tetroxane (malonaldehydeperoxide, DPM) is investigated in methanol solvents at different temperatures. In the temperature range of 130.0-166.0 ° C studied and at the concentration of 2 x 10-2 M, it follows a first order kinetic law up to at least 60% DPM conversion. The organic products observed were malonaldehyde. A stepwise mechanism of decomposition was proposed where the first step is the homolytic unimolecular rupture of the O-O bond. The activation enthalpy and activation entropy for DPM in methanol were calculated (ΔH0# = 86.1 ± 2.7 kJ mol-1 y ΔS0# = -65.2 ± 6.0 J mol-1 K-1).