Thesis MEASURING AND MODELING OF THERMODYNAMIC SOLUBILITY OF BIOACTIVE PHYTOCHEMICALS COMPOUNDS IN SUPERCRITICAL CARBON DIOXIDE: NOBILETIN + CO2 AND MENADIONE + CO2
Date
2016
Authors
CABRERA PALACIOS, ADOLFO LUIS
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Abstract
Se realizaron mediciones de isotermas de solubilidad de 2-(3,4-Dimethoxyphenyl)-5,6,7,8-tetramethoxychromen-4-one (nobiletina) y 2-methyl-1,4-naphthoquinone (menadiona) en dióxido de carbono supercrítico a temperaturas de (313, 323 y 333) K y presiones de (9 a 32) MPa usando una metodología analítica con recirculación, con determinación directa de la composición molar de la fase rica en dióxido de carbono usando cromatografía líquida de alto rendimiento. Los resultados indican que el rango de la solubilidad de nobiletina medida fue de 107 · 10-6 mol · mol-1 a 333 K y 18.35 MPa a 182 · 10-6 mol · mol-1 a 333 K y 31.40 MPa. Similarmente, la solubilidad de menadiona medida varió de 630 · 10-6 mol · mol-1 a 333 K y 9.72 MPa a 1057 · 10-6 mol · mol-1 a 333 K y 13.43 MPa. La validación de los datos de solubilidad experimentales se realizó usando tres enfoques, a saber, estimación de la incertidumbre combinada expandida para cada punto de solubilidad a partir de valores de parámetros experimentales (=23 · 10-6 mol · mol-1 y =111 · 10-6 mol · mol-1 para nobiletina y menadiona, respectivamente); consistencia termodinámica, verificada utilizando un test adaptado de herramientas basadas en la ecuación de Gibbs-Duhem y datos de solubilidad obtenidos de modelación; y auto-consistencia, demostrada mediante la correlación de los datos de solubilidad con un modelo semi-empírico como una función de la temperatura, presión y densidad de CO2 puro.
Isothermal solubility of 2-(3,4-Dimethoxyphenyl)-5,6,7,8-tetramethoxychromen-4-one (nobiletin) and 2-methyl-1,4-naphthoquinone (menadione) in supercritical carbon dioxide at temperatures of (313, 323 and 333) K and pressures from (9 to 32) MPa was measured using an analytic-recirculation methodology, with direct determination of the molar composition of the carbon dioxide-rich phase by using high performance liquid chromatography. Results indicated that the range of the measured nobiletin solubility was between 107 · 10-6 mol · mol-1 at 333 K and 18.35 MPa to 182 · 10-6 mol · mol-1 at 333 K and 31.40 MPa. Similarly, the measured menadione solubility ranged from 630 · 10-6 mol · mol-1 at 333 K and 9.72 MPa to 1057 · 10-6 mol · mol-1 at 333 K and 13.43 MPa. The validation of the experimental solubility data was carried out using three approaches: estimation of combined expanded uncertainty for each solubility data point from experimental parameters values (=23 · 10-6 mol · mol-1 and =111 · 10-6 mol · mol-1 for nobiletin and menadione, respectively); thermodynamic consistency, verified utilizing a test adapted from tools based on Gibbs–Duhem equation and solubility modeling results; and self-consistency, proved by correlating the solubility data with a semi-empirical model as a function of temperature, pressure and pure CO2 density.
Isothermal solubility of 2-(3,4-Dimethoxyphenyl)-5,6,7,8-tetramethoxychromen-4-one (nobiletin) and 2-methyl-1,4-naphthoquinone (menadione) in supercritical carbon dioxide at temperatures of (313, 323 and 333) K and pressures from (9 to 32) MPa was measured using an analytic-recirculation methodology, with direct determination of the molar composition of the carbon dioxide-rich phase by using high performance liquid chromatography. Results indicated that the range of the measured nobiletin solubility was between 107 · 10-6 mol · mol-1 at 333 K and 18.35 MPa to 182 · 10-6 mol · mol-1 at 333 K and 31.40 MPa. Similarly, the measured menadione solubility ranged from 630 · 10-6 mol · mol-1 at 333 K and 9.72 MPa to 1057 · 10-6 mol · mol-1 at 333 K and 13.43 MPa. The validation of the experimental solubility data was carried out using three approaches: estimation of combined expanded uncertainty for each solubility data point from experimental parameters values (=23 · 10-6 mol · mol-1 and =111 · 10-6 mol · mol-1 for nobiletin and menadione, respectively); thermodynamic consistency, verified utilizing a test adapted from tools based on Gibbs–Duhem equation and solubility modeling results; and self-consistency, proved by correlating the solubility data with a semi-empirical model as a function of temperature, pressure and pure CO2 density.
Description
Catalogado desde la version PDF de la tesis.
Keywords
EQUILIBRIO SOLIDO-FLUIDO , EXPERIMENTAL , EXTRACCION SUPERCRITICA , TERMODINAMICA