title: Understanding the Phase Behavior of Tetrahydrofuran + Carbon Dioxide, + Methane, and + Water Binary Mixtures from the SAFT-VR Approach.
abstract: The high-pressure phase diagrams of the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) mixtures are examined using the SAFT-VR approach. Carbon dioxide molecule is modeled as two spherical segments tangentially bonded, water is modeled as a spherical segment with four associating sites to represent the hydrogen bonding, methane is represented as an isolated sphere, and tetrahydrofuran is represented as a chain of m tangentially bonded spherical segments. Dispersive interactions are modeled using the square-well intermolecular potential. In addition, two different molecular model mixtures are developed to take into account the subtle balance between water-tetrahydrofuran hydrogen-bonding interactions. The polar and quadrupolar interactions present in water, tetrahydrofuran, and carbon dioxide are treated in an effective way via square-well potentials of variable range. The optimized intermolecular parameters are taken from the works of Giner et al. (Fluid Phase Equil. 2007, 255, 200), Galindo and Blas (J. Phys. Chem. B 2002, 106, 4503), Patel et al. (Ind. Eng. Chem. Res. 2003, 42, 3809), and Clark et al. (Mol. Phys. 2006, 104, 3561) for tetrahydrofuran, carbon dioxide, methane, and water, respectively. The phase diagrams of the binary mixtures exhibit different types of phase behavior according to the classification of van Konynenburg and Scott, ranging from types I, III, and VI phase behavior for the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) binary mixtures, respectively. This last type is characterized by the presence of a Bancroft point, positive azeotropy, and the so-called closed-loop curves that represent regions of liquid-liquid immiscibility in the phase diagram. The system exhibits lower critical solution temperatures (LCSTs), which denote the lower limit of immiscibility together with upper critical solution temperatures (UCSTs). This behavior is explained in terms of competition between the incompatibility with the alkyl parts of the tetrahydrofuran ring chain and the hydrogen bonding between water and the ether group. A minimum number of unlike interaction parameters are fitted to give the optimal representation of the most representative features of the binary phase diagrams. In the particular case of tetrahydrofuran(1) + water(2), two sets of intermolecular potential model parameters are proposed to describe accurately either the hypercritical point associated with the closed-loop liquid-liquid immiscibility region or the location of the mixture lower- and upper-critical end-points. The theory is not only able to predict the type of phase behavior of each mixture, but also provides a reasonably good description of the global phase behavior whenever experimental data are available.
authors.affiliation: Laboratoire des Fluides Complexes et Leurs Reservoirs, Université de Pau et des Pays de l'Adour , CNRS, TOTAL - UMR 5150, Avenue de l'Université, B.P. 1155 - PAU, F-64013 Pau, France.
authors.forename: J M
authors.initials: JM
authors.lastname: Míguez
authors.affiliation: Departamento de Física Aplicada, Universidade de Vigo , E36310 Vigo, Spain.
authors.forename: M M
authors.initials: MM
authors.lastname: Piñeiro
authors.affiliation: Laboratorio de Simulación Molecular y Química Computacional, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Física Aplicada, Universidad de Huelva , 21007 Huelva, Spain.
authors.forename: J
authors.initials: J
authors.lastname: Algaba
authors.affiliation: Laboratoire des Fluides Complexes et Leurs Reservoirs, Université de Pau et des Pays de l'Adour , CNRS, TOTAL - UMR 5150, Avenue de l'Université, B.P. 1155 - PAU, F-64013 Pau, France.
authors.forename: B
authors.initials: B
authors.lastname: Mendiboure
authors.affiliation: Laboratoire des Fluides Complexes et Leurs Reservoirs, Université de Pau et des Pays de l'Adour , CNRS, TOTAL - UMR 5150, Avenue de l'Université, B.P. 1155 - PAU, F-64013 Pau, France.
authors.forename: J P
authors.initials: JP
authors.lastname: Torré
authors.affiliation: Laboratorio de Simulación Molecular y Química Computacional, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Física Aplicada, Universidad de Huelva , 21007 Huelva, Spain.
authors.forename: F J
authors.initials: FJ
authors.lastname: Blas