Estudio experimental y computacional de la termólisis de isoprenol en solución de m-xileno
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Resumen: Se llevó a cabo un estudio cinético de la reacción de descomposición térmica de unos β-hidroxialquenos: el 3-buten-1-ol a 553.2, 573.2 y 593.2 K y el isoprenol a cinco temperaturas diferentes en el rango de 513.2 – 563.2 K, ambas reacciones en solución de m-xileno. Un análisis mediante cromatografía gaseosa permitió observar la desaparición de los reactantes en el medio de reacción e identificar los compuestos: propeno y formadehído como los productos de descomposición térmica del 3-buten-1-ol e isobuteno y formaldehído como los productos para la reacción de descomposición del isoprenol. Adicional a ello se realizó un estudio computacional mediante métodos de perturbación y de la teoría del funcional de la densidad. La implementación de técnicas computacionales permitió un análisis detallado respecto a los cambios geométricos y de energía durante el transcurso de la reacción. Se encontró que las reacciones estudiadas se ajustan a una cinética de primer orden y presentan una dependencia del tipo Arrhenius de la constante de velocidad con la temperatura. La evidencia experimental y computacional permite proponer para los β-hidroxialquenos estudiados, un mecanismo de reacción de una etapa, ligeramente asincrónico, que procede a través de un estado de transición cíclico de seis miembros.
Abstract: It was conducted a kinetic study of the reaction of thermal decomposition of some β –hydroxy alkenes: 3-buten-1-ol at 553.2, 573.2 and 593.2 K and isoprenol at five different temperatures in the range of 513.2 - 563.2 K, both reactions in m-xylene solution. An analysis by gas chromatography allowed to observe the disappearance of the reactants in the reaction medium and to identify the compounds: propene and formaldehyde as thermal decomposition products of the 3-buten- 1-ol and isobutene and formaldehyde as the product to the reaction of isoprenol decomposition. In addition a computational study was carried out by methods of perturbation and density functional theory. Computational techniques implementation allowed a detailed analysis regarding geometric and energy changes during the course of the reaction. It is found that the reactions studied fit a first-order kinetics and exhibit an Arrhenius type dependence of the rate constant with temperature. Experimental and computational evidence allowed us to propose a reaction mechanism of a one-step, slightly asynchronous, which proceeds through a six-membered cyclic transition state for β-hydroxy alkenes studied.
Abstract: It was conducted a kinetic study of the reaction of thermal decomposition of some β –hydroxy alkenes: 3-buten-1-ol at 553.2, 573.2 and 593.2 K and isoprenol at five different temperatures in the range of 513.2 - 563.2 K, both reactions in m-xylene solution. An analysis by gas chromatography allowed to observe the disappearance of the reactants in the reaction medium and to identify the compounds: propene and formaldehyde as thermal decomposition products of the 3-buten- 1-ol and isobutene and formaldehyde as the product to the reaction of isoprenol decomposition. In addition a computational study was carried out by methods of perturbation and density functional theory. Computational techniques implementation allowed a detailed analysis regarding geometric and energy changes during the course of the reaction. It is found that the reactions studied fit a first-order kinetics and exhibit an Arrhenius type dependence of the rate constant with temperature. Experimental and computational evidence allowed us to propose a reaction mechanism of a one-step, slightly asynchronous, which proceeds through a six-membered cyclic transition state for β-hydroxy alkenes studied.