Experimental and Dft Studies of the mechanism of cetone-peroxide formation reaction using Raman and nuclear magnetic resonance spectroscopies
| dc.contributor.advisor | Hernández Rivera, Samuel P. | |
| dc.contributor.author | Espinosa Fuentes, Eduardo A. | |
| dc.contributor.college | College of Arts and Sciences - Sciences | en_US |
| dc.contributor.committee | Román Velázquez, Félix R. | |
| dc.contributor.committee | Mina Camilde, Nairmen | |
| dc.contributor.department | Department of Chemistry | en_US |
| dc.contributor.representative | Briano Peralta, Julio G. | |
| dc.date.accessioned | 2018-04-09T15:09:02Z | |
| dc.date.available | 2018-04-09T15:09:02Z | |
| dc.date.issued | 2009 | |
| dc.description.abstract | A mechanism for the reaction between acetone and hydrogen peroxide leading to the formation of the important homemade explosive Acetone Peroxide is postulated. The proposed mechanistic scheme is based on Raman and Nuclear Magnetic Resonance spectroscopies measurements and is also supported by ab-initio Density Functional Theory calculations using B3LYP 6-311g**d++ method. It was found that for the uncatalized reaction, the proposed mechanism of cyclic organic peroxides formation occurs in three steps: monomer formation, polymerization of the 2-hydroperoxipropan-2- ol monomer and cyclization. Calculated rate constants proved to be in agreement with theoretical calculations. The activation energy obtained confirms that the polymerization step is favored in comparison to other possible pathways. In fact, the activation energy is twofold lower than the acetone-monomer reaction and the peroxide-monomer reaction according to experimental and theoretical measurements, which was previously proposed. | |
| dc.description.abstract | Se postula un mecanismo de reacción entre acetona y peróxido de hidrogeno conduciendo a la formación de explosivos caseros importantes como lo son los peróxidos orgánicos cÃclicos. Esta propuesta está basada en mediciones espectroscópicas Raman y resonancia magnética nuclear y apoyado en cálculos de la TeorÃa del Funcional de la Densidad usando el método B3LYP 6-311g**d++. Se encontró además que el mecanismo propuesto ocurre en tres etapas: formación del monómero, polimerización del monómero 2-hydroperoxipropan-2-ol y ciclación. Las constantes de velocidad encontradas están de acuerdo con las medidas teóricas. La energÃa de activación obtenida para la reacción de polimerización confirmó que este paso es más favorecido energéticamente que otros posibles canales. De hecho la energÃa de activación es tres veces más baja que la reacciones entre el monómero con la acetona y el peróxido de hidrogeno de acuerdo a los resultados teóricos y experimentales, previamente propuesto. | |
| dc.description.graduationYear | 2009 | en_US |
| dc.identifier.uri | https://hdl.handle.net/20.500.11801/380 | |
| dc.language.iso | en | en_US |
| dc.rights.holder | (c) 2009 Eduardo A. Espinosa Fuentes | en_US |
| dc.rights.license | All rights reserved | en_US |
| dc.subject | Raman spectroscopy | en_US |
| dc.subject | Nuclear magnetic resonance | en_US |
| dc.subject | Acetone and hydrogen peroxide formation | en_US |
| dc.subject.lcsh | Acetone. | en_US |
| dc.subject.lcsh | Peroxides. | en_US |
| dc.subject.lcsh | Hydrogen peroxide. | en_US |
| dc.subject.lcsh | Density functionals. | en_US |
| dc.subject.lcsh | Explosives--Detection. | en_US |
| dc.subject.lcsh | Raman spectroscopy. | en_US |
| dc.subject.lcsh | Nuclear magnetic resonance spectroscopy. | en_US |
| dc.title | Experimental and Dft Studies of the mechanism of cetone-peroxide formation reaction using Raman and nuclear magnetic resonance spectroscopies | en_US |
| dc.type | Thesis | en_US |
| dspace.entity.type | Publication | |
| relation.isAuthorOfPublication | 74ec94c8-93b2-439e-a919-9798e1fe997d | |
| relation.isAuthorOfPublication.latestForDiscovery | 74ec94c8-93b2-439e-a919-9798e1fe997d | |
| thesis.degree.discipline | Chemistry | en_US |
| thesis.degree.level | M.S. | en_US |