Equilibrio líquido-líquido-vapor mediante simulación molecular Monte Carlo.
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Date
2025
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Publisher
Universidad de Concepción
Abstract
El presente trabajo se basa en la simulación molecular mediante el método Monte Carlo para estudiar el equilibrio trifásico líquido-líquido-vapor (VLLE), de las mezclas agua + CPME + alcohol (etanol y 1-butanol). A través del colectivo de Gibbs, se simuló el equilibrio trifásico a una presión de 101.3 kPa para ambas mezclas, comparando los resultados simulados con datos experimentales obtenidos en la literatura.
Se comenzó determinando el equilibrio de los compuestos puros, seguido por los sistemas binarios, y finalmente los ternarios, con el objetivo de evaluar el desempeño del campo de fuerza y las interacciones binarias. Los resultados fueron verificados mediante un análisis gráfico de las propiedades a lo largo de los ciclos de simulación, junto con el gráfico de coexistencia de las fases. Se obtuvieron resultados favorables para la mayoría de los compuestos, excepto para el CPME, el cual presentó errores importantes en la predicción de su equilibrio líquido-vapor (VLE), observados en su densidad y presión de vapor.
Los errores del campo de fuerza del CPME fueron trasladados a los equilibrios binarios y desempeño para simular su fase líquida y con ello el equilibrio líquido-líquido (LLE).
En el sistema ternario, se logró generar un equilibrio trifásico, aunque con diferencias cuantitativas con respecto a los datos experimentales. Finalmente, se llevó a cabo un análisis de sensibilidad de los parámetros σ y ε para evaluar su impacto en las propiedades de equilibrio y determinar ajustes que podr´ıan mejorar los resultados para investigaciones futuras.
This work is based on molecular simulation using the Monte Carlo method to study the liquid liquid- vapor equilibrium (VLLE) of the water + CPME + alcohol (ethanol and 1-butanol) mixtures. Through the Gibbs ensemble, the three-phase equilibrium was simulated at a pressure of 101.3 kPa for both mixtures, comparing the results obtained with experimental data reported in the literature. The study began by determining the equilibrium of the pure compounds, followed by binary systems, and finally ternary systems, with the aim of evaluating the performance of the force field and binary interactions. The results were verified through a graphical analysis of the properties over the simulation cycles, along with the phase coexistence diagram. Favorable results were obtained for most compounds, except for CPME, which showed significant errors in predicting its liquid-vapor equilibrium (VLE), observed in its density and vapor pressure. The errors in the CPME force field carried over to the binary and ternary equilibria involving VLE. However, the CPME force field proved to be better for simulating its liquid phase and, consequently, liquid-liquid equilibrium (LLE). In the ternary system, a three-phase equilibrium was successfully generated, although with quantitative differences compared to experimental data. Finally, a sensitivity analysis of the parameters σ and ε was conducted to evaluate their impact on equilibrium properties and determine adjustments that could improve results for future research.
This work is based on molecular simulation using the Monte Carlo method to study the liquid liquid- vapor equilibrium (VLLE) of the water + CPME + alcohol (ethanol and 1-butanol) mixtures. Through the Gibbs ensemble, the three-phase equilibrium was simulated at a pressure of 101.3 kPa for both mixtures, comparing the results obtained with experimental data reported in the literature. The study began by determining the equilibrium of the pure compounds, followed by binary systems, and finally ternary systems, with the aim of evaluating the performance of the force field and binary interactions. The results were verified through a graphical analysis of the properties over the simulation cycles, along with the phase coexistence diagram. Favorable results were obtained for most compounds, except for CPME, which showed significant errors in predicting its liquid-vapor equilibrium (VLE), observed in its density and vapor pressure. The errors in the CPME force field carried over to the binary and ternary equilibria involving VLE. However, the CPME force field proved to be better for simulating its liquid phase and, consequently, liquid-liquid equilibrium (LLE). In the ternary system, a three-phase equilibrium was successfully generated, although with quantitative differences compared to experimental data. Finally, a sensitivity analysis of the parameters σ and ε was conducted to evaluate their impact on equilibrium properties and determine adjustments that could improve results for future research.
Description
Tesis presentada para optar al título de Ingeniero/a Civil Químico/a.
Keywords
Equilibrio vapor-líquido, Termodinámica, Método de Monte Carlo