Pitfalls on computing liquid-liquid phase equilibria using the k-value method

Poster presented in the 11th Mediterranean Congress of Chemical Engineering, Barcelona, October 21-24, 2008.

Phase equilibria of the water + 1-butanol + toluene ternary system at 101.3 kPa

Isobaric vapour–liquid and vapour–liquid–liquid equilibrium data for the water + 1-butanol + toluene ternary system were measured at 101.3 kPa with a modified VLE 602 Fischer apparatus. In addition, the liquid–liquid equilibrium data at 313.15 K were measured and compared with data from other authors at different temperatures. The system exhibits a ternary heterogeneous azeotrope whose temperature and composition have been determined by interpolation. The thermodynamic consistency of the experimental vapour–liquid and vapour–liquid–liquid data was checked by means of the Wisniak’s Li/Wi consistency test. Moreover, the vapour–liquid and the liquid–liquid equilibrium correlation for the ternary system with NRTL and UNIQUAC models, together with the prediction made with the UNIFAC model, were studied and discussed.

X lberoamerican Conference on Phase Equilibria and Fluid Properties for Process Design (EQUIFASE): June 28-July 1, 2015 - Alicante (Spain): Book of Abstracts

The general purpose of the EQUIFASE Conference is to promote the Scientific and Technologic exchange between people from both the academic and the industrial environment in the field of Phase Equilibria and Thermodynamic Properties for the Design of Chemical Processes. Topics: Measurement of Thermodynamic Properties. Phase Equilibria and Chemical Equilibria. Theory and Modelling. Alternative Solvents. Supercritical Fluids. Ionic Liquids. Energy. Gas and oil. Petrochemicals. Environment and sustainability. Biomolecules and Biotechnology. Product and Process Design. Databases and Software. Education.

GE models and algorithms for condensed phase equilibrium data regression in ternary systems: limitations and proposals

Phase equilibrium data regression is an unavoidable task necessary to obtain the appropriate values for any model to be used in separation equipment design for chemical process simulation and optimization. The accuracy of this process depends on different factors such as the experimental data quality, the selected model and the calculation algorithm. The present paper summarizes the results and conclusions achieved in our research on the capabilities and limitations of the existing GE models and about strategies that can be included in the correlation algorithms to improve the convergence and avoid inconsistencies. The NRTL model has been selected as a representative local composition model. New capabilities of this model, but also several relevant limitations, have been identified and some examples of the application of a modified NRTL equation have been discussed. Furthermore, a regression algorithm has been developed that allows for the advisable simultaneous regression of all the condensed phase equilibrium regions that are present in ternary systems at constant T and P. It includes specific strategies designed to avoid some of the pitfalls frequently found in commercial regression tools for phase equilibrium calculations. Most of the proposed strategies are based on the geometrical interpretation of the lowest common tangent plane equilibrium criterion, which allows an unambiguous comprehension of the behavior of the mixtures. The paper aims to show all the work as a whole in order to reveal the necessary efforts that must be devoted to overcome the difficulties that still exist in the phase equilibrium data regression problem.

Vapor-liquid equilibria using the Gibbs energy and the common tangent plane criterion

Phase thermodynamics is often perceived as a difficult subject that many students never become fully comfortable with. The Gibbsian geometrical framework can help students to gain a better understanding of phase equilibria. An exercise to interpret the vapor-liquid equilibrium of a binary azeotropic mixture, using the equilibrium condition based on the common tangent plane criterion (the Gibbs stability test), is presented in this paper. From a T-composition phase diagram for the mixture, the temperature is set at different values: above, intermediate to, and below the boiling temperatures of the pure components, to intersect different regions of the system. Students prepare an Excel spreadsheet where the Gibbs energy of mixing of the vapor and liquid mixtures are calculated and represented over the whole range of compositions and then, apply the Gibbs stability test to ascertain the aggregation state of the system and to calculate the VL phase equilibrium compositions. Finally, Matlab is used to generate the 3D Gibbs energy of mixing surfaces for both phases over the whole range of temperatures which facilitates the geometrical interpretation of the vapor-liquid equilibrium.

Modelling liquid–liquid equilibria for island type ternary systems

Closed miscibility gaps in ternary liquid mixtures, at constant temperature and pressure, are obtained if phase separations occur only in the ternary region, whilst all binary mixtures involved in the system are completely miscible. This type of behaviour, although not very frequent, has been observed for a certain number of systems. Nevertheless, we have found no information about the applicability of the common activity coefficient models, as NRTL and UNIQUAC, for these types of ternary systems. Moreover, any of the island type systems published in the most common liquid–liquid equilibrium data collections, are correlated with any model. In this paper, the applicability of the NRTL equation to model the LLE of island type systems is assessed using topological concepts related to the Gibbs stability test. A first attempt to correlate experimental LLE data for two island type ternary systems is also presented.

Mapping Binary Liquid-Vapor or Liquid-Liquid-Vapor Equilibria Regions, including the Different Azeotropic Behaviours, as a Function of the NRTL Binary Parameters

13th Mediterranean Congress of Chemical Engineering (Sociedad Española de Química Industrial e Ingeniería Química, Fira Barcelona, Expoquimia), Barcelona, September 30-October 3, 2014

Correlation of the liquid–liquid equilibrium data for specific ternary systems with one or two partially miscible binary subsystems

This paper presents the results of a liquid–liquid equilibrium data correlation for 11 ternary systems which have not been previously fitted using the NRTL model or, when they have, the results presented in the literature are inconsistent with the experimental behavior of the system. These ternary systems include mixtures with one or two partially miscible pairs. During the correlation process, new restrictions were imposed on the values for the NRTL binary parameters to ensure correct prediction of the total or partial miscibility for the binary pairs involved. In addition, topological concepts related to the Gibbs stability test have been applied in order to validate the results in the whole range of compositions.

Absorption cross-sections of hole polarons in glassy and β-phase polyfluorene

Absorption induced by electrochemically injected holes is studied in poly-9,9-dioctylfluorene (PFO) films. Injected charges form positive polarons which are delocalised over four fluorene units in the glassy phase and about seven fluorene units in its β-phase. Polaron absorption cross-sections at the 640 nm peak are similar to the published values of chemically reduced oligofluorenes in solution. The absorption cross-section of polaron in the β-phase at 470 nm is about eight times smaller than the stimulated emission cross-section derived from published data. This indicates that β-phase-rich PFO is an attractive candidate for a light-emitting layer in double-heterostructure organic laser diodes.

Astrophysical parameters and orbital solution of the peculiar X-ray transient IGR J00370+6122

Context. BD + 60° 73 is the optical counterpart of the X-ray source IGR J00370+6122, a probable accretion-powered X-ray pulsar. The X-ray light curve of this binary system shows clear periodicity at 15.7 d, which has been interpreted as repeated outbursts around the periastron of an eccentric orbit. Aims. We aim to characterise the binary system IGR J00370+6122 by deriving its orbital and physical parameters. Methods. We obtained high-resolution spectra of BD + 60° 73 at different epochs. We used the fastwind code to generate a stellar atmosphere model to fit the observed spectrum and obtain physical magnitudes. The synthetic spectrum was used as a template for cross-correlation with the observed spectra to measure radial velocities. The radial velocity curve provided an orbital solution for the system. We also analysed the RXTE/ASM and Swift/BAT light curves to confirm the stability of the periodicity. Results. BD + 60° 73 is a BN0.7 Ib low-luminosity supergiant located at a distance ~3.1 kpc, in the Cas OB4 association. We derive Teff = 24 000 K and log gc = 3.0, and chemical abundances consistent with a moderately high level of evolution. The spectroscopic and evolutionary masses are consistent at the 1-σ level with a mass M∗ ≈ 15 M⊙. The recurrence time of the X-ray flares is the orbital period of the system. The neutron star is in a high-eccentricity (e = 0.56 ± 0.07) orbit, and the X-ray emission is strongly peaked around orbital phase φ = 0.2, though the observations are consistent with some level of X-ray activity happening at all orbital phases. Conclusions. The X-ray behaviour of IGR J00370+6122 is reminiscent of “intermediate” supergiant X-ray transients, though its peak luminosity is rather low. The orbit is somewhat wider than those of classical persistent supergiant X-ray binaries, which when combined with the low luminosity of the mass donor, explains the low X-ray luminosity. IGR J00370+6122 will very likely evolve towards a persistent supergiant system, highlighting the evolutionary connection between different classes of wind-accreting X-ray sources.

Pulse phase-coherent timing and spectroscopy of CXOU J164710.2−45521 outbursts

We present a long-term phase-coherent timing analysis and pulse-phase resolved spectroscopy for the two outbursts observed from the transient anomalous X-ray pulsar CXOU J164710.2−455216. For the first outburst we used 11 Chandra and XMM–Newton observations between 2006 September and 2009 August, the longest baseline yet for this source. We obtain a coherent timing solution with P = 10.61065583(4) s, Ṗ = 9.72(1) × 10−13 s s−1 and P̈ = –1.05(5) × 10−20 s s−2. Under the standard assumptions this implies a surface dipolar magnetic field of ∼1014 G, confirming this source as a standard B magnetar. We also study the evolution of the pulse profile (shape, intensity and pulsed fraction) as a function of time and energy. Using the phase-coherent timing solution we perform a phase-resolved spectroscopy analysis, following the spectral evolution of pulse-phase features, which hints at the physical processes taking place on the star. The results are discussed from the perspective of magnetothermal evolution models and the untwisting magnetosphere model. Finally, we present similar analysis for the second, less intense, 2011 outburst. For the timing analysis we used Swift data together with 2 XMM–Newton and Chandra pointings. The results inferred for both outbursts are compared and briefly discussed in a more general framework.

Removal of 8-quinolinecarboxylic acid pesticide from aqueous solution by adsorption on activated montmorillonites

Sodium montmorillonite (Na-M), acidic montmorillonite (H-M), and organo-acidic montmorillonite (Org-H-M) were applied to remove the herbicide 8-quinolinecarboxylic acid (8-QCA). The montmorillonites containing adsorbed 8-QCA were investigated by transmission electron microscopy, FT-IR spectroscopy, X-ray diffraction analysis, X-ray fluorescence thermogravimetric analysis, and physical adsorption of gases. Experiments showed that the amount of adsorbed 8-QCA increased at lower pH, reaching a maximum at pH 2. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The Langmuir model provided the best correlation of experimental data for adsorption equilibria. The adsorption of 8-QCA decreased in the order Org-H-M > H-M > Na-M. Isotherms were also used to obtain the thermodynamic parameters. The negative values of ΔG indicated the spontaneous nature of the adsorption process.