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dc.contributor.advisorHernández-Rivera, Samuel P.
dc.contributor.authorRuiz-Caballero, Jose L.
dc.date.accessioned2018-04-09T15:07:41Z
dc.date.available2018-04-09T15:07:41Z
dc.date.issued2010
dc.identifier.urihttps://hdl.handle.net/20.500.11801/377
dc.description.abstractThe solubility of 1,3,5-trinitrohexahydro-s-triazine (RDX) in different alcohols were measured by HPLC, DSC, GC/MS, and NMR. The conformation of RDX in acetone-D6 solution was verified by vibrational studies using Raman spectroscopy. The thermodynamic parameters and conformations were calculated using density functional theory, Hartree-Fock, and the polarized continuum model. Raman studies suggest that the RDX molecule has approximate C3v symmetry in solution, with alteration of the attached NO2 groups. The solubility of RDX in alcohols (ethyl alcohol, 2-methyl-1-propanol, 2-propanol and 1-butanol) has been determined at six different temperatures, 15, 20, 25, 30, 35, 40°C. From the solubility data, the values of thermodynamic functions such as Enthalpy (ΔsolvH), Entropy (ΔsolvS) and free energies of solutions or solvation (ΔsolvG) were obtained. In the calculation, different basis sets for DFT and HF methods are reported for the geometry, energy, and Gibbs solvation energy of the high explosive in the gas phase and dissolved in alcohols, as previously mentioned. The Polarizable Continuum model (PCM) has been applied to investigate the effect of the alcohols medium on these AAARDX, AAE-RDX and EEE-RDX conformers. The inclusion of a solvent reaction field has a strong influence on the Gibbs free energy of solvation and on calculation of molecular properties. The PCM model was consistent with the experimental observations, the RDX in AAA conformation was predicted to be strongly favored in a condensed dielectric medium excluding that the distortion associated with the NO2 groups has not been found.
dc.description.abstractLa solubilidad del 1,3,5-trinitrohexahydro-s-triazina (RDX) y sus propiedades termodinámicas en diferentes alcoholes fueron medidos por HPLC, DSC, GC/MS y RMN. La conformación de RDX en solución de acetona-d6 fue verificada usando espectroscopía Raman. Los parámetros termodinámicos y las conformaciones fueron calculados utilizando la teoría del funcional de la densidad (DFT), HF y el modelo continuo de polarización (PCM). El estudio Raman sugiere que la molécula de RDX tiene simetría C3V en solución, con modificación asociada en los grupos nitro (NO2). La solubilidad de RDX en los alcoholes (alcohol etílico, 2-metil-1-propanol, 2-propanol y nbutanol) se ha determinado a seis diferentes temperaturas, 15, 20, 25, 30, 35, 40°C. De los datos de solubilidad, los valores de las funciones termodinámicas tales como entalpía (ΔsolvH), entropía (ΔsolvS) y la energía libre en solución (ΔsolvG) fueron derivadas. En el cómputo ejecutado a distintas funciones de base usando como método DFT y HF se reporta para la geometría, la energía y la energía Gibbs de solvatación del material energético (RDX) en la fase gaseosa y en solución alcohólica, mencionados previamente. El modelo continuo polarizable (PCM) se ha ejecutado para investigar el efecto del medio en los confórmeros AAA-, AAE- y EEE-RDX. La inclusión de un campo de reacción de disolvente ejerce una fuerte influencia en la energía libre de Gibbs de solvatación, y en las propiedades moleculares. El modelo PCM ha sido consistente con observaciones experimentales afirmando que el RDX en un medio dieléctrico condensado tiene conformación AAA-RDX (o β-RDX) exceptuando la distorsión asociada con los grupos nitros (NO2).
dc.language.isoenen_US
dc.subjectRaman spectroscopyen_US
dc.subjectPolarized continuum modelen_US
dc.subjectGibbs energy of solvationen_US
dc.subject.lcshRDX (Cyclonite)--Solubilityen_US
dc.subject.lcshExplosives--Detectionen_US
dc.titleExperimental and theoretical study of solubility of 1, 3, 5-trinitrohexahydro-S-triazine (Rdx) In alcoholsen_US
dc.typeThesisen_US
dc.rights.licenseAll rights reserveden_US
dc.rights.holder(c) 2010 Jose L. Ruiz-Caballeroen_US
dc.contributor.committeeRoman-Velazquez, Felix
dc.contributor.committeeMina-Camilde, Nairmen
dc.contributor.committeeSantana, Alberto
dc.contributor.representativeBriano, Julio
thesis.degree.levelM.S.en_US
thesis.degree.disciplineChemistryen_US
dc.contributor.collegeCollege of Arts and Sciences - Sciencesen_US
dc.contributor.departmentDepartment of Chemistryen_US
dc.description.graduationYear2010en_US


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