Binary liquid-liquid equilibria for systems of mono or disubstituted haloakanes (Cl,Br) and pyiridinium based ionic liquids. Advances in the experimentation and interpretation of results

[EN]This work presents the measurements made to define the temperature−composition curves for a set of binary systems composed of several pyridinium-based ionic liquids (ILs) [bpy][BF4] and [bYmpy][BF4] (Y = 2,3,4) with mono- and dihaloalkanes (Cl and Br) in the temperature interval [280−473] K and at atmospheric pressure. With the exception of the short chain dichloroalkanes (1,1- and 1,2-), all the compounds present some degree of immiscibility with the ionic liquids selected.

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.

Effects of potential models in the vapor-liquid equilibria and adsorption of simple gases on graphitized thermal carbon black

In this paper, we investigate the effects of various potential models in the description of vapor–liquid equilibria (VLE) and adsorption of simple gases on highly graphitized thermal carbon black. It is found that some potential models proposed in the literature are not suitable for the description of VLE (saturated gas and liquid densities and the vapor pressure with temperature). Simple gases, such as neon, argon, krypton, xenon, nitrogen, and methane are studied in this paper. To describe the isotherms on graphitized thermal carbon black correctly, the surface mediation damping factor introduced in our recent publication should be used to calculate correctly the fluid–fluid interaction energy between particles close to the surface. It is found that the damping constant for the noble gases family is linearly dependent on the polarizability, suggesting that the electric field of the graphite surface has a direct induction effect on the induced dipole of these molecules. As a result of this polarization by the graphite surface, the fluid–fluid interaction energy is reduced whenever two particles are near the surface. In the case of methane, we found that the damping constant is less than that of a noble gas having the similar polarizability, while in the case of nitrogen the damping factor is much greater and this could most likely be due to the quadrupolar nature of nitrogen.

Models of gas-liquid solubilities

A recent method for phase equilibria, the AGAPE method, has been used to predict activity coefficients and excess Gibbs energy for binary mixtures with good accuracy. The theory, based on a generalised London potential (GLP), accounts for intermolecular attractive forces. Unlike existing prediction methods, for example UNIFAC, the AGAPE method uses only information derived from accessible experimental data and molecular information for pure components. Presently, the AGAPE method has some limitations, namely that the mixtures must consist of small, non-polar compounds with no hydrogen bonding, at low moderate pressures and at conditions below the critical conditions of the components. Distinction between vapour-liquid equilibria and gas-liquid solubility is rather arbitrary and it seems reasonable to extend these ideas to solubility. The AGAPE model uses a molecular lattice-based mixing rule. By judicious use of computer programs a methodology was created to examine a body of experimental gas-liquid solubility data for gases such as carbon dioxide, propane, n-butane or sulphur hexafluoride which all have critical temperatures a little above 298 K dissolved in benzene, cyclo-hexane and methanol. Within this methodology the value of the GLP as an ab initio combining rule for such solutes in very dilute solutions in a variety of liquids has been tested. Using the GLP as a mixing rule involves the computation of rotationally averaged interactions between the constituent atoms, and new calculations have had to be made to discover the magnitude of the unlike pair interactions. These numbers have been seen as significant in their own right in the context of the behaviour of infinitely-dilute solutions. A method for extending this treatment to "permanent" gases has also been developed. The findings from the GLP method and from the more general AGAPE approach have been examined in the context of other models for gas-liquid solubility, both "classical" and contemporary, in particular those derived from equations-of-state methods and from reference solvent methods.

A New Technique for Studying Vapour–liquid Equilibria of Multi-Component Systems

A Fourier transform infrared gas-phase method is described herein and capable of deriving the vapour pressure of each pure component of a poorly volatile mixture and determining the relative vapour phase composition for each system. The performance of the present method has been validated using two standards (naphthalene and ferrocene), and a Raoult’s plot surface of a ternary system is reported as proof-of-principle. This technique is ideal for studying solutions comprising two, three, or more organic compounds dissolved in ionic liquids as they have no measurable vapour pressures.

Phase equilibrium studies at moderate pressures

The theory of vapour-liquid equilibria is reviewed, as is the present status or prediction methods in this field. After discussion of the experimental methods available, development of a recirculating equilibrium still based on a previously successful design (the modified Raal, Code and Best still of O'Donnell and Jenkins) is described. This novel still is designed to work at pressures up to 35 bar and for the measurement of both isothermal and isobaric vapour-liquid equilibrium data. The equilibrium still was first commissioned by measuring the saturated vapour pressures of pure ethanol and cyclohexane in the temperature range 77-124°C and 80-142°C respectively. The data obtained were compared with available literature experimental values and with values derived from an extended form of the Antoine equation for which parameters were given in the literature. Commissioning continued with the study of the phase behaviour of mixtures of the two pure components as such mixtures are strongly non-ideal, showing azeotopic behaviour. Existing data did not exist above one atmosphere pressure. Isothermal measurements were made at 83.29°C and 106.54°C, whilst isobaric measurements were made at pressures of 1 bar, 3 bar and 5 bar respectively. The experimental vapour-liquid equilibrium data obtained are assessed by a standard literature method incorporating a themodynamic consistency test that minimises the errors in all the measured variables. This assessment showed that reasonable x-P-T data-sets had been measured, from which y-values could be deduced, but that the experimental y-values indicated the need for improvements in the design of the still. The final discussion sets out the improvements required and outlines how they might be attained.

An interesting feature of the vapour pressure curve

There exists a maximum in the products of the saturation properties such as T(p(c) - p) and p(T-c - T) in the vapour-liquid coexistence region for all liquids. The magnitudes of those maxima on the reduced coordinate system provide an insight to the molecular complexity of the liquid. It is shown that the gradients of the vapour pressure curve at temperatures where those maxima occur are directly given by simple relations involving the reduced pressures and temperatures at that point. A linear relation between the maximum values of those products of the form [p(r)(1 - T-r)](max) = 0.2095 - 0.2415 [T-r(1 - p(r))](max) has been found based on a study of 55 liquids ranging from non-polar monatomic cryogenic liquids to polar high boiling point liquids.

Simple three parameter equations for correlating liquid phase compositions in subcritical and supercritical systems

Two Chrastil type expressions have been developed to model the solubility of supercritical fluids/gases in liquids. The three parameter expressions proposed correlates the solubility as a function of temperature, pressure and density. The equation can also be used to check the self-consistency of the experimental data of liquid phase compositions for supercritical fluid-liquid equilibria. Fifty three different binary systems (carbon-dioxide + liquid) with around 2700 data points encompassing a wide range of compounds like esters, alcohols, carboxylic acids and ionic liquids were successfully modeled for a wide range of temperatures and pressures. Besides the test for self-consistency, based on the data at one temperature, the model can be used to predict the solubility of supercritical fluids in liquids at different temperatures. (C) 2014 Elsevier B.V. All rights reserved.

1-Ethyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide as solvent for the separation of aromatic and aliphatic hydrocarbons by liquid extraction - extension to C-7- and C-8-fractions

The ionic liquid 1-ethyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide ([C(2)mim][NTf2]) was tested as solvent for the separation of aromatic and aliphatic hydrocarbons containing 7 or 8 carbon atoms (the C-7- and C-8-fractions). The liquid-liquid equilibria (LLE) of the ternary systems (heptane + toluene + [C(2)mim][NTf2]) and (octane + ethylbenzene + [C(2)mim][NTf2]), at 25 degrees C, were experimentally determined. The performance of the ionic liquid as the solvent in such systems was evaluated by means of the calculation of the solute distribution ratio and the selectivity. The results were compared to those previously reported for the extraction of benzene from its mixtures with hexane by using the same ionic liquid, therefore analysing the influence of the size of the hydrocarbons. It was found that the ionic liquid is also good for the extraction of C-7- and C-8- fraction aromatic compounds, just a greater amount of ionic liquid being needed to perform an equivalently efficient separation than for the C-6-fraction. It is also discussed how [C(2)mim][NTf2] performs comparably better than the conventional solvent sulfolane. The original 'Non-Random Two-Liquid' (NRTL) equation was used to adequately correlate the experimental LLE data.

Deep separation of benzene from cyclohexane by liquid extraction using ionic liquids as the solvent

Separation of benzene and cyclohexane is one of the most important and difficult processes in the petrochemical industry, especially for low benzene concentration. In this work, three ionic liquids (ILs), [Bmim][BF ₄], [Bpy][BF ₄], and [Bmim][SCN], were investigated as the solvent in the extraction of benzene from cyclohexane. The corresponding ternary liquid-liquid equilibria (LLE) were experimentally determined at T = 298.15 K and atmospheric pressure. The LLE data were correlated with the nonrandom two-liquid model, and the parameters were fitted. The separation capabilities of the ILs were evaluated in terms of the benzene distribution coefficient and solvent selectivity. The effect of the IL structure on the separation was explained based on a well-founded physical model, COSMO-RS. Finally, the extraction processes were defined, and the operation parameters were analyzed. It shows that the ILs studied are suitable solvents for the extractive separation of benzene and cyclohexane, and their separation efficiency can be generally ranked as [Bmim][BF ₄] > [Bpy][BF ₄] > [Bmim][SCN]. The extraction process for a feed with 15 mol % benzene was optimized. High product purity (cyclohexane 0.997) and high recovery efficiency (cyclohexane 96.9% and benzene 98.1%) can be reached. © 2012 American Chemical Society.

Multiproperty correlation of experimental data of the binaries propyl ethanoate+alkanes (pentane to decane). New experimental information for vapor-liquid equilibrium and mixing properties

[EN]A thermodynamic study is carried out on binary systems composed of propyl ethanoate with six alkanes, from pentane to decane. Vapor pressures of the ester and the isobaric vapor−liquid equilibria of these six mixtures were measured at 101.32 kPa in a small-capacity ebulliometer and also the mixing properties yE = vE,hE over a range of temperatures and at atmospheric pressure. Adequate correlations are drawn for the surfaces yE = yE(x,T) with an interpretation on the behavior of the mixtures and also using cp E data from literature.

Isothermal (liquid + liquid) equilibrium data at T = 313.15 K and isobaric (vapor + liquid + liquid) equilibrium data at 101.3 kPa for the ternary system (water + 1-butanol + p-xylene)

The (vapor + liquid), (liquid + liquid) and (vapor + liquid + liquid) equilibria of the ternary system (water + 1-butanol + p-xylene) have been determined. (Water + 1-butanol + p-xylene) is a type 2 heterogeneous ternary system with partially miscible (water + 1-butanol) and (water + p-xylene) pairs. By contrast, (1-butanol + p-xylene) is totally miscible under atmospheric conditions. This paper examines the (vapor + liquid) equilibrium in both heterogeneous and homogeneous regions at 101.3 kPa of pressure. (Liquid + liquid) equilibrium data at T = 313.15 K have also been determined, and for comparison, the obtained experimental data have been calculated by means of several thermodynamic models: UNIQUAC, UNIFAC and NRTL. Some discrepancies were found between the (vapor + liquid + liquid) correlations; however, the models reproduced the (liquid + liquid) equilibrium data well. The obtained data reveal a ternary heterogeneous azeotrope with mole fraction composition: 0.686 water, 0.146 1-butanol and 0.168 p-xylene.

Simultaneous chemical reaction and distillation of formaldehyde

The thesis is concerned with the development and testing of a mathematical model of a distillation process in which the components react chemically. The formaldehyde-methanol-water system was selected and only the reversible reactions between formaldehyde and water giving methylene glycol and between formaldehyde and methanol producing hemiformal were assumed to occur under the distillation conditions. Accordingly the system has been treated as a five component system. The vapour-liquid equilibrium calculations were performed by solving iteratively the thermodynamic relationships expressing the phase equilibria with the stoichiometric equations expressing the chemical equilibria. Using optimisation techniques, the Wilson single parameters and Henry's constants were calculated for binary systems containing formaldehyde which was assumed to be a supercritical component whilst Wilson binary parameters were calculated for the remaining binary systems. Thus the phase equilibria for the formaldehyde system could be calculated using these parameters and good accuracy was obtained when calculated values were compared with experimental values. The distillation process was modelled using the mass and energy balance equations together with the phase equilibria calculations. The plate efficiencies were obtained from a modified A.I.Ch.E. Bubble Tray method. The resulting equations were solved by an iterative plate to plate calculation based on the Newton Raphson method. Experiments were carried out in a 76mm I.D., eight sieve plate distillation column and the results were compared with the mathematical model calculations. Overall, good agreement was obtained but some discrepancies were observed in the concentration profiles and these may have been caused by the effect of limited physical property data and a limited understanding of the reactions mechanism. The model equations were solved in the form of modular computer programs. Although they were written to describe the steady state distillation with simultaneous chemical reaction of the formaldehyde system, the approach used may be of wider application.