Solubility, Density, Refractive Index, and Viscosity for the Polyhydric Alcohol + CsBr + H2O Ternary Systems at Different Temperatures

The solubility, density, refractive index, and viscosity data for the ethylene glycol + CsBr + H2O, 1,2-propanediol + CsBr + H2O, and glycerin + CsBr + H2O ternary systems have been determined at (288.15, 298.15, and 308.15) K. In all cases, the solubility of CsBr in aqueous solutions was decreased significantly due to the presence of polyhydric alcohol. The liquid–solid equilibrium experimental data were correlated using the NRTL (nonrandom two-liquid) activity coefficient model, considering nondissociation of the dissolved salt in the liquid phase, and new interaction parameters were estimated. The mean deviations between calculated and experimental compositions were low, showing the good descriptive quality and applicability of the NRTL model. The refractive indices, densities, and viscosities for the unsaturated solutions of the three ternary systems have also been measured at three temperatures. Values for all of the properties were correlated with the salt concentrations and proportions of polyhydric alcohol in the solutions.

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.

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.

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.

Geometrical study of the three-dimensional temperature–composition diagrams. An important aid to understand the behavior of the liquid–vapour equilibrium in ternary systems

In this work the usefulness of qualitatively studying and drawing three-dimensional temperature–composition diagrams for ternary systems is pointed out to understand and interpret the particular behavior of the liquid–vapour equilibrium of non-ideal ternary systems. Several examples have been used in order to highlight the interest and the possibilities of this tool, which should be an interesting support not only for lecturers, but also for researchers interested in experimental equilibrium data determination.

Gibbs Energy of Mixing Function: Topological Analysis in Azeotropic Systems

ESAT 2014. 27th European Symposium on Applied Thermodynamics, Eindhoven University of Technology, July 6-9, 2014.

Liquid–Liquid Equilibria of Water + Ethanol + 1-Butyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Ternary System: Measurements and Correlation at Different Temperatures

In this work authors present the experimental liquid–liquid equilibria (LLE) data of water + ethanol + 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([bmim][Tf2N]) system at different temperatures. The LLE of the system was obtained in the temperature range from 283.2 to 323.2 K. The nonrandom two liquid (NRTL) and universal quasichemical (UNIQUAC) models were used to correlate ternary systems. The equilibrium compositions were successfully correlated by the interaction parameters from both models, however UNIQUAC gave a more accurate correlation. Finally, a study about the solvent capability of ionic liquid was made in order to evaluate the possibility of separating the mixture formed by ethanol and water using that ionic liquid.

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.

Influence of thymol and silver nanoparticles on the degradation of poly(lactic acid) based nanocomposites: thermal and morphological properties

Biopolymers, such as poly(lactic acid) (PLA), have been proposed as environmentally-friendly alternatives in applications such as food packaging. In this work, silver nanoparticles and thymol were used as active additives in PLA matrices, combining the antibacterial activity of silver with the antioxidant performance of thymol. The combined action of both additives influenced PLA thermal degradation in ternary systems. DSC results showed that the addition of thymol resulted in a clear decrease of the glass transition temperature (Tg) of PLA, suggesting its plasticizing effect in PLA matrices. Slight modifications in mechanical properties of dog-bone bars were also observed after the addition of the active components, especially in the elastic modulus. FESEM analyses showed the good distribution of active additives through the PLA matrix, obtaining homogenous surfaces and highlighting the presence of silver nanoparticles successfully embedded into the bulk matrix. Degradation of these PLA-based nanocomposites with thymol and silver nanoparticles in composting conditions indicated that the inherent biodegradable character of this biopolymer was improved after this modification. The obtained nanocomposites showed suitable properties to be used as biodegradable active-food packaging systems with antioxidant and antimicrobial effects.

Nano-biocomposite films with modified cellulose nanocrystals and synthesized silver nanoparticles

Ternary nano-biocomposite films based on poly(lactic acid) (PLA) with modified cellulose nanocrystals (s-CNC) and synthesized silver nanoparticles (Ag) have been prepared and characterized. The functionalization of the CNC surface with an acid phosphate ester of ethoxylated nonylphenol favoured its dispersion in the PLA matrix. The positive effects of the addition of cellulose and silver on the PLA barrier properties were confirmed by reductions in the water permeability (WVP) and oxygen transmission rate (OTR) of the films tested. The migration level of all nano-biocomposites in contact with food simulants were below the permitted limits in both non-polar and polar simulants. PLA nano-biocomposites showed a significant antibacterial activity influenced by the Ag content, while composting tests showed that the materials were visibly disintegrated after 15 days with the ternary systems showing the highest rate of disintegration under composting conditions.

Combined effects of cellulose nanocrystals and silver nanoparticles on the barrier and migration properties of PLA nano-biocomposites

Poly(lactic acid) (PLA)-based high performance nano-biocomposites were prepared to be used in active food packaging. Pristine (CNC) and surfactant modified cellulose nanocrystals (s-CNC) with silver (Ag) nanoparticles were used as the matrix modifiers. Binary and ternary systems were prepared. Morphological investigations revealed the good distribution of silver nanoparticles in PLA ternary systems. The combination of s-CNC and Ag nanoparticles increased the barrier effect of the produced films while the results of overall migration for the PLA nano-biocomposites revealed that none of the samples exceeded the overall migration limit, since results were well below 60 mg kg−1 of simulant.

The influence of promoters (Zr, La, Tb, Pr) on the catalytic performance of CuO-CeO2 systems for the preferential oxidation of CO in the presence of CO2 and H2O

CuO supported on CeO2 and Ce0.9X0.1O2, where X is Zr, La, Tb or Pr, were synthesized using nitrate precursors, giving rise ceria based materials with a small particle size which interact with CuO species generating a high amount of interfacial sites. The incorporation of cations to the ceria framework modifies the CeO2 lattice parameter, improving the redox behavior of the catalytic system. The catalysts were characterized by X-ray fluorescence spectrometry (XRFS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, thermoprogrammed reduction with H2 (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The catalysts were tested in the preferential oxidation of CO under a H2-rich stream (CO-PROX), reaching conversion values higher than 95% between 115 and 140 °C and being the catalyst with 6 wt.% of Cu supported on Ce0.9Zr0.1O2 (sample 6CUZRCE) the most active catalyst. The influence of the presence of CO2 and H2O was also studied simulating a PROX unit, taking place a decrease of the catalytic activity due to the inhibitor effect both CO2 and H2O.

Electrocatalytic activity of Ni-doped nanoporous carbons in the electrooxidation of propargyl alcohol

Herein, we explore the immobilization of nickel on various carbon supports and their application as electrocatalysts for the oxidation of propargyl alcohol in alkaline medium. In comparison with massive and nanoparticulated nickel electrode systems, Ni-doped nanoporous carbons provided similar propargyl alcohol conversions for very low metallic contents. Nanoparticulated Ni on various carbon supports gave rise to the highest electrocatalytic activity in terms of product selectivity, with a clear dependence on Ni content. The results point to the importance of controlling the dispersion of the Ni phase within the carbon matrix for a full exploitation of the electroactive area of the metal. Additionally, a change in the mechanism of the propargyl alcohol electrooxidation was noted, which seems to be related to the physicochemical properties of the carbon support as well. Thus, the stereoselectivity of the electrooxidative reaction can be controlled by the active nickel content immobilized on the anode, with a preferential oxidation to (Z)-3-(2-propynoxy)-2-propenoic acid with high Ni-loading, and to propiolic acid with low loading of active Ni sites. Moreover, the formation of (E)-3-(2-propynoxy)-2-propenoic acid was discriminatory irrespective of the experimental conditions and Ni loadings on the carbon matrixes.