Isobaric vapour–liquid equilibria for binary systems of 2-butanone with ethanol, 1-propanol, and 2-propanol at 20 and 101.3 kPa

Consistent isobaric vapour–liquid equilibrium data have been measured for 2-butanone + ethanol, 2-butanone + 1-propanol, and 2-butanone + 2-propanol at 20 and 101.3 kPa. The binary systems 2-butanone + ethanol and 2-butanone + 2-propanol present a minimum boiling azeotrope at both pressures, and show that the azeotropic compositions is strongly dependent on pressure. The equilibrium data were correlated using the Wilson, NRTL, and UNIQUAC models for which the parameters are reported.     

Vapor–liquid equilibria for binary and ternary mixtures of ethanol, 2-butanone,and 2,2,4-trimethylpentane at 101.3 kPa

Vapor–liquid equilibrium (VLE) at 101.3 kPa have been determined for the ternary system ethanol + 2-butanone + 2,2,4-trimethylpentane (isooctane) and its constituent binary systems: ethanol + 2,2,4-trimethylpentane, ethanol + 2-butanone, and 2-butanone + 2,2,4-trimethylpentane. Minimum boiling azeotropes were observed for all these binary systems. No azeotropic behavior was found for the ternary system. Thermodynamic consistency tests were performed for all VLE data. The activity coefficients of the binary mixtures were satisfactorily correlated with the Wilson, NRTL, and UNIQUAC models. The models with their best-fitted binary parameters were used to predict the ternary vapor–liquid equilibrium.     

Liquid-liquid equilibria of water + 3-hydroxy-2-butanone + ethyl ethanoate

(Liquid-liquid) equilibrium (LLE) data of the solubility curves and tie-line compositions have been determined for mixtures of (water + 3-hydroxy-2-butanone + ethyl ethanoate) at 298.15 K, 308.15 K and 318.15 K and 101.3 kPa. Distribution coefficients and separation factors have been evaluated for the immiscibility region. The reliability of the experimental tie-lines has been confirmed by using Othmer-Tobias correlation. The LLE data of the ternary systems have been predicted by UNIFAC method.     

Isobaric (vapour + liquid) equilibrium for (2-propanol + water + ammonium thiocyanate): Fitting the data by an empirical equation

Isobaric (vapour + liquid) equilibrium (VLE) data for {2-propanol (1) + water (2) + ammonium thiocyanate (3)} were obtained at 101.3 kPa experimentally. An all-glass Fischer-Labodest type still capable of handling pressures from (0.25 to 400) kPa and temperatures up to 523.15 K was used. (Vapour + liquid) equilibrium data of (2-propanol + water) were also obtained at 101.3 kPa experimentally. An equation is proposed to fit the data of salt-containing systems using dimensionless groups called relative ratio. The proposed model was also tested for the salt-containing systems given from the literature.     

Multiphase equilibria for mixtures containing water, isopropanol, propionic acid, and isopropyl propionate

Vapor pressures of isopropyl propionate and isobaric vapor-liquid equilibrium (VLE) properties of isopropyl propionate + isopropanol and propionic acid + isopropyl propionate were measured. Isothermal vapor-liquid-liquid equilibrium (VLLE) data were also determined experimentally for water + isopropyl propionate and water + isopropyl propionate + isopropanol at temperatures from 323.24 K to 373.15 K. The binary VLE and VLLE data can be correlated well with the NRTL-HOC and the UNIQUAC-HOC models. The ternary VLLE data were used to test the validity of two versions of the UNIFAC model and the NRTL-HOC and the UNIQUAC-HOC models with the parameters determined from the phase equilibrium data of the constituent binaries. The ternary VLLE data were also correlated with the NRTL-HOC and the UNIQUAC-HOC models and the Soave-Redlich-Kwong equation of state with the Wong-Sandler mixing rule.     

Vapor–liquid equilibrium data for the nitrogen + n-octane system from (344.5 to 543.5) K and at pressures up to 50 MPa

A static-analytical apparatus with visual sapphire windows and pneumatic capillary samplers has been used to obtain new vapor–liquid equilibrium data for the N₂ + n-octane system over the temperature range from (344.5 to 543.5) K and at pressures up to 50 MPa. Equilibrium phase compositions and vapor–liquid equilibrium ratios are reported. The new results were compared with solubility data reported by other authors. The comparison showed that the solubility data reported in this work at 344.5 K are in good agreement with those determined by others at 344.3 K. The experimental data were modeled with the PR and PC-SAFT equations of state by using one-fluid mixing rules and a single temperature-independent interaction parameter. Results from the modeling effort showed that the PC-SAFT equation was superior to the PR equation in correlating the experimental data of the N₂ + n-octane system.     

Isothermal vapour-liquid equilibria in the binary and ternary systems composed of 2,2,4-trimethylpentane, 2-methyl-1-propanol, and 4-methyl-2-pentanone

Vapour-liquid equilibrium data in the three binary 2,2,4-trimethylpentane + 2-methyl-1-propanol, 2-methyl-1-propanol + 4-methyl-2-pentanone, 2,2,4-trimethylpentane + 4-methyl-2-pentanone systems, and in the ternary 2,2,4-trimethylpentane + 2-methyl-1-propanol + 4-methyl-2-pentanone system are reported. The data were measured isothermally at 333.15, 348.15 and 364.15 K covering the pressure range 12-100 kPa. The binary vapour-liquid equilibrium data were correlated using the Wilson and NRTL equations by means of a robust algorithm for processing all isotherms together; resulting parameters were then used for calculation of phase behaviour in the ternary system and for subsequent comparison with experimental data.     

Isobaric vapour–liquid equilibria for the binary systems 4-methyl-2-pentanone + 1-butanol and + 2-butanol at 20 and 101.3 kPa

Isobaric vapour–liquid equilibrium (VLE) measurements for the binary systems 4-methyl-2-pentanone + 1-butanol and 4-methyl-2-pentanone + 2-butanol are reported at 20 and 101.3 kPa. The system 4-methyl-2-pentanone + 1-butanol presents a minimum boiling point azeotrope at both pressures (20 and 101.3 kPa) and the system 4-methyl-2-pentanone + 2-butanol presents only a minimum boiling azeotrope at 20 kPa. In both systems, which deviate positively from ideal behaviour, the azeotropic composition is strongly dependent on pressure. The activity coefficients and boiling points of the solutions were correlated with its composition by the Wilson, UNIQUAC, and NRTL models for which the parameters are reported.     

Vapor-liquid and liquid-liquid equilibrium properties of ethane + methanol system at ambient temperature

The liquid-liquid and vapor-liquid equilibrium data for the binary system of ethane + methanol were measured at ambient temperature over a wide range of pressures using a designed PVT apparatus. The experimental liquid-liquid and vapor-liquid equilibrium data were compared with the modeling results obtained using the Peng Robinson and Soave-Redlich-Kwong equations of state.     

Measurement and correlation of (liquid + liquid) equilibrium of the azeotrope (cyclohexane + 2-butanone) with different ionic liquids at T = 298.15 K

Experimental densities, speeds of sound, and refractive indices of the binary mixtures of 2-butanone with cyclohexane and OMIM PF₆ (1-methyl-3-octylimidazolium hexafluorophosphate) were determined from T = (293.15 to 303.15) K, since they are necessary to determine the (liquid + liquid) equilibrium. Excess molar volumes, changes of refractive index on mixing, and deviations in isentropic compressibility for the above systems were calculated. Experimental (liquid + liquid) equilibrium of the ternary mixtures {cyclohexane + 2-butanone + 1-hexyl-3-methylimidazolium hexafluorophosphate (HMIM PF₆)} and (cyclohexane + 2-butanone + OMIM PF₆) were carried out to assess the suitability of HMIM PF₆ and OMIM PF₆ as azeotrope breaker of the mixture cyclohexane and 2-butanone. Selectivity and distribution ratio values, derived from the tie lines data, were presented in order to analyze the best separation solvent in a liquid extraction process. Experimental (liquid + liquid) equilibrium data were compared with the correlated values obtained by means of the NRTL and UNIQUAC models.     

Solubility of carbon dioxide in aqueous solution of 2-amino-2-methyl-1-propanol and piperazine

In this work, new experimental results of the vapour-liquid equilibrium (VLE) of CO₂ in aqueous 2-amino-2-methyl-1-propanol (AMP) and piperazine (PZ) have been presented in the temperature range of 298-328 K and PZ concentration range of 2-8 mass%, keeping the total amine concentration in the solution at 30 mass%. The partial pressures of CO₂ were in the range of 0.1-1450 kPa. A thermodynamic model was developed to correlate and predict the VLE of CO₂ in aqueous AMP + PZ. The electrolyte nonrandom two liquid (ENRTL) theory has been used to develop the VLE model for the quaternary system (CO₂ + AMP + PZ + H₂O) to describe the equilibrium behaviour of the solution. The experimental data from this work and data available in the literature were used to regress the ENRTL interaction parameters. The model predictions are in good agreement with the experimental data of CO₂ solubility in aqueous blends of this work as well as those reported in the literature. The current model can also predict speciation, heat of absorption, pH of the CO₂ loaded solution, and amine volatility.     

Vapour–liquid equilibrium for β-myrcene and carbon dioxide and/or hydrogen and the volume expansion of β-myrcene or limonene in CO2 at 323.15 K

Vapour–liquid equilibrium measurements for binary and ternary (carbon dioxide + β-myrcene and carbon dioxide + β-myrcene + hydrogen) systems have been carried out at 323.15 K and pressures in the range from 7 MPa to the critical pressure of the binary mixture and at pressures from 10 to 14 MPa for the investigated ternary systems. Samples from the coexisting phases were taken, and compositions were determined experimentally. Results were correlated using the Peng–Robinson and the Soave–Redlich–Kwong equations of state with the Mathias–Klotz–Prausnitz mixing rule. The set of interaction parameters for the employed equations of state and applied mixing rule for the system of CO₂ + β-myrcene and of CO₂ + β-myrcene + H₂ were obtained. Additionally, the volume expansion of the liquid phase for the binary mixtures (carbon dioxide + β-myrcene and carbon dioxide + limonene) were measured at 323.15 K and at pressures from 4 MPa up to very close to the critical pressure of the mixture. The ratio of liquid phase total volumes at the given pressure and at 4 MPa was calculated.     

Ethanoled gasoline bubble pressure determination: Experimental and Monte Carlo modeling

In this work, we present some experimental and modeling studies of ethanoled gasoline bubble pressures (ethanol + gasoline blends) at various temperatures and ethanol contents. Modelings are carried out using Monte Carlo simulations in a specific bubble-point pseudo ensemble and using the AUA4 force field. This method is first validated on the prediction of binary mixture bubble pressures (ethanol + n-hexane, ethanol + propylene, ethanol + toluene, ethanol + isooctane). It is shown that a good accuracy is reached without introducing empirical binary interaction parameter, demonstrating the predictivity of the approach. Then, simulations of ethanoled gasolines have been performed. The molecular representation of the gasoline is obtained using a lumping scheme from the detailed composition of a commercial gasoline. Simulation results are compared to experimental bubble pressures measured in this work on this commercial gasoline in which various proportions of ethanol have been added. From a qualitative point of view, the azeotropic behavior of such fuels is observed both experimentally and by simulations. From a quantitative point of view, an average deviation of 15% between experimental and simulation data is found. Such results show that Monte Carlo simulation using an accurate force field is an efficient method to predict phase equilibrium of complex mixtures such as oxygenated gasolines. This methodology can thus be seen as an efficient tool that can be used by engineers for fuel formulation or for equation of state or process model calibration.     

Phase equilibrium for the systems diisopropyl ether,isopropyl alcohol + 2,2,4-trimethylpentane and +n-heptane at 101.3 kPa

Consistent vapour–liquid equilibrium data for the ternary systems diisopropyl ether + isopropyl alcohol + 2,2,4-trimethylpentane and diisopropyl ether + isopropyl alcohol + n-heptane are reported at 101.3 kPa. The vapour–liquid equilibrium data have been correlated by Wilson, NRTL and UNIQUAC equations. The ternary systems do not present ternary azeotropes.     

Liquid-liquid equilibria for mixtures of (ethylene carbonate + aromatic hydrocarbon + cyclohexane)

Liquid-liquid equilibrium data for mixtures of (ethylene carbonate + benzene + cyclohexane) at temperatures 303.15 and 313.15 K and (ethylene carbonate + BTX + cyclohexane) at temperature 313.15 K are reported, where the BTX is benzene, toluene and m-xylene. The compositions of liquid phases at equilibrium were determined by gas liquid chromatography. The selectivity factors and partition coefficients of ethylene carbonate for the extraction of benzene, toluene and m-xylene from (ethylene carbonate + BTX + cyclohexane) are calculated and presented. The obtained results are compared with the selectivity factors and partition coefficients of ethylene carbonate for the extraction of benzene from (ethylene carbonate + benzene + cyclohexane). The liquid-liquid equilibrium data were correlated with the UNIQUAC and NRTL activity coefficient models. The phase diagrams for the studied mixtures are presented and the correlated tie line results have been compared with the experimental data. The comparisons indicate the applicability of the UNIQUAC and NRTL activity coefficients model for liquid-liquid equilibrium calculations of the studied mixtures. The tie line data of the studied mixtures also were correlated using the Hand method.     

Isothermal vapor–liquid equilibrium at 303.15 K and excess molar volumes at 298.15 K for the ternary system of propyl vinyl ether + 1-propanol + 2,2,4-trimethyl-pentane and its binary sub-systems

Isothermal vapor–liquid equilibrium data determined by the static method at 303.15 K are reported for the binary systems propyl vinyl ether + 1-propanol, 1-propanol + 2,2,4-trimethylpentane and propyl vinyl ether + 2,2,4-trimethylpentane and also for the ternary system propyl vinyl ether + 1-propanol + 2,2,4-trimethyl-pentane. Additionally, new excess volume data are reported for the same systems at 298.15 K. The experimental binary and ternary vapor–liquid equilibrium data were correlated with different G^E models and excess molar volume data were correlated with the Redlich–Kister equation for the binary systems and the Cibulka equation for the ternary system, respectively.     

Prediction of vapor-liquid equilibrium data of the system MTBE + methanol + ethanol by PRSV2 EOS

The Stryjek and Vera (1986) [9] modification of Peng-Robinson (PRSV2) equation of state has been applied for modeling vapor-liquid equilibrium of the systems MTBE + methanol, MTBE + ethanol and methanol + ethanol. Binary interaction parameters for mixing rules have been estimated by using experimental data at the atmospheric pressure. The calculated binary interaction parameters were used for predicting azeotropic behavior at high pressure and also for isobaric equilibrium points which showed an excellent agreement with experimental data. In addition, estimated binary interaction parameters for binary systems were used for ternary system (MTBE + methanol + ethanol). The predictions deviated only slightly from the experimental data. The results show PRSV2 can be used for VLE prediction of polar systems.     

Equation of state for square-well chain molecules with variable range II. Extension to mixtures

An equation of state (EOS) developed in our previous work for square-well chain molecules with variable range is further extended to the mixtures of non-associating fluids. The volumetric properties of binary mixtures for small molecules as well as polymer blends can well be predicted without using adjustable parameter. With one temperature-independent binary interaction parameter, satisfactory correlations for experimental vapor–liquid equilibria (VLE) data of binary normal fluid mixtures at low and elevated pressures are obtained. In addition, VLE of n-alkane mixtures and nitrogen + n-alkane mixtures at high pressures are well predicted using this EOS. The phase behavior calculations on polymer mixture solutions are also investigated using one-fluid mixing rule. The equilibrium pressure and solubility of gas in polymer are evaluated with a single adjustable parameter and good results are obtained. The calculated results for gas + polymer systems are compared with those from other equations of state.     

Bubble-point measurements for the system CO2 + aqueous ethanol solutions of boldo leaf antioxidant components (boldine and catechin) at high pressures

The bubble-points pressures of solute(s) + ethanol + water + CO₂ mixtures were determined visually using a synthetic method in an experimental apparatus that included a variable-volume equilibrium cell. Tested solutes included boldo leaf tincture, a boldine + catechin mixture, pure boldine, and pure catechin. Uncertainties in bubble-point pressures were estimated to be <5%, based on comparisons with literature values and replicate measurements. The largest effect we observed was an average increase of 205% in the bubble-point pressure when decreasing the ethanol-to-water ratio from 63:37 to 37:63 (w/w). The bubble-point pressure increased 11% when increasing the temperature from 313 to 343 K, and decreased 8.2% when increasing the concentration of solids from 400 to 1500 ppm. The bubble-point pressure was higher for boldo leaf tincture than for a boldine + catechin mixture having the same boldine-to-catechin weight ratio, but this was partially due to a lower content of solids in the tincture. On the other hand, bubble-point pressures of the boldine + catechin mixture were marginally (0.33%) higher than the weighed average of the bubble-point pressures for pure boldine and pure catechin.     

High pressure vapor–liquid equilibria for carbon dioxide + tetrahydrofuran mixtures

Vapor–liquid equilibria and saturated density for carbon dioxide + tetrahydrofuran mixtures at high pressures were measured by the analytical method at the temperatures 298.15 and 313.15 K. The experimental apparatus equipped with three Anton Paar DMA 512S vibrating tube density meters was previously developed for measuring vapor–liquid–liquid equilibrium at high pressures. The equilibrium composition and saturated density of each phase were determined by gas chromatograph and vibrating tube density meters, respectively. The bubble point pressure at the temperature 313.15 K was further measured by the synthetic method. The experimental data were correlated with Soave–Redlich–Kwong (SRK) equation of state and the pseudocubic equation of state.