Phase equilibrium data and thermodynamic modelling of the system (propane + DMF + methanol) at high pressures

Reported in this work are phase equilibrium data at high pressures for the binary and ternary systems formed by {propane + N,N-dimethylformamide (DMF) + methanol}. Phase equilibrium measurements were performed in a high-pressure, variable-volume view cell, following the static synthetic method for obtaining the experimental bubble and dew points transition data over the temperature range of (363 to 393) K, pressures up to 11.5 MPa and overall mole fraction of the lighter component varying from 0.1 to 0.995. For the systems investigated, vapour–liquid (VLE), liquid–liquid (LLE) and vapour–liquid–liquid (VLLE) phase transitions were visually recorded. Results show that the systems investigated present UCST (upper critical solution temperature) phase transition curves with an UCEP (upper critical end point) at a temperature higher than the propane critical temperature. The experimental data were modelled using the Peng–Robinson equation of state with the Wong–Sandler and the classical quadratic mixing rules, affording a satisfactory representation of the experimental data.     

Phase equilibrium data for the ternary system (propane + chloroform + oryzanol)

The compound oryzanol available in the rice bran (oriza sativa) is well known for its antioxidant activity. Phase equilibrium data involving oryzanol in compressed fluids, hardly found in the literature, are important to provide the basis for the extraction and fractionation processes. In this sense, the aim of this work is to report phase equilibrium measurements for the system (γ-oryzanol + chloroform) in compressed propane. Phase equilibrium experiments were performed using the static synthetic method (cloud points transition data) in a high-pressure variable-volume view cell in the temperature range of 303 K to 353 K, pressures up to 17 MPa, for oryzanol overall mass fractions of 2 wt%, 5 wt% and 10 wt% in (propane + chloroform) mixtures. A complex phase behaviour comprising vapour–liquid, liquid–liquid, vapour–liquid–liquid, solid–liquid, solid–liquid–liquid, solid–liquid–liquid–vapour transitions were visually observed for the system studied.     

Phase equilibrium measurements for semi-clathrate hydrates of the (CO2 + N2 + tetra-n-butylammonium bromide) aqueous solution system

The application of semi-clathrate hydrate formation technology for gas separation purposes has gained much attention in recent years. Consequently, there is a demand for experimental data for relevant semi-clathrate hydrate phase equilibria. In this work, semi-clathrate hydrate dissociation conditions for the system comprising mixtures of {CO₂ (0.151/0.399 mole fraction) + N₂ (0.849/0.601 mole fraction) + 0.05, 0.15, and 0.30 mass fraction tetra-n-butylammonium bromide (TBAB)} aqueous solutions have been measured and are reported. An experimental apparatus which was designed and built in-house was used for the measurements using the isochoric pressure-search method. The range of conditions for the measurements was from 277.1 K to 293.2 K for temperature and pressures up to 16.21 MPa. The phase equilibrium data measured demonstrate the high hydrate promotion effects of TBAB aqueous solutions.     

Phase behavior of (CO2 + methanol + lauric acid) system

In this study the phase equilibrium behaviors of the binary system (CO₂ + lauric acid) and the ternary system (CO₂ + methanol + lauric acid) were determined. The static synthetic method, using a variable-volume view cell, was employed to obtain the experimental data in the temperature range of (293 to 343) K and pressures up to 24 MPa. The mole fractions of carbon dioxide were varied according to the systems as follows: (0.7524 to 0.9955) for the binary system (CO₂ + lauric acid); (0.4616 to 0.9895) for the ternary system (CO₂ + methanol + lauric acid) with a methanol to lauric acid molar ratio of (2:1); and (0.3414 to 0.9182) for the system (CO₂ + methanol + lauric acid) with a methanol to lauric acid molar ratio of (6:1). For these systems (vapor + liquid), (liquid + liquid), (vapor + liquid + liquid), and (solid + fluid) transitions were observed. The phase equilibrium data obtained for the systems were modeled using the Peng–Robinson equation of state with the classical van der Waals mixing rule with a satisfactory correlation between experimental and calculated values.     

Experimental (vapour + liquid) equilibrium data of (methanol + water), (water + glycerol) and (methanol + glycerol) systems at atmospheric and sub-atmospheric pressures

Experimental (vapour + liquid) equilibrium results for the binary systems, (methanol + water) at the local atmospheric pressure of 95.3 kPa and at sub-atmospheric pressures of (15.19, 29.38, 42.66, 56.03, and 67.38) kPa, (water + glycerol) system at pressures (14.19, 29.38, 41.54, 54.72, 63.84, and 95.3) kPa and the (methanol + glycerol) system at pressures (32.02 and 45.3) kPa were obtained over the entire composition range using a Sweitoslwasky-type ebulliometer. The relationship of the liquid composition (x₁) as a function of temperature (T) was found to be well represented by the Wilson model. Computed vapour phase mole fractions, activity coefficients and the measured values along with optimum Wilson parameters are presented.     

Quaternary isobaric (vapor + liquid + liquid) equilibrium and (vapor + liquid) equilibrium for the system (water + ethanol + cyclohexane + heptane) at 101.3 kPa

Experimental isobaric (vapor + liquid + liquid) and (vapor + liquid) equilibrium data for the ternary system {water (1) + cyclohexane (2) + heptane (3)} and the quaternary system {water (1) + ethanol (2) + cyclohexane (3) + heptane (4)} were measured at 101.3 kPa. An all-glass, dynamic recirculating still equipped with an ultrasonic homogenizer was used to determine the VLLE. The results obtained show that the system does not present quaternary azeotropes. The point-by-point method by Wisniak for testing the thermodynamic consistency of isobaric measurements was used to test the equilibrium data.     

Phase equilibrium measurements of (methane + benzene) and (methane + methylbenzene) at temperatures from (188 to 348) K and pressures to 13 MPa

New isothermal pTxy data are reported for (methane + benzene) and (methane + methylbenzene (toluene)) at pressures up to 13 MPa over the temperature range (188 to 313) K using a custom-built (vapor + liquid) equilibrium (VLE) apparatus. The aim of this work was to investigate literature data inconsistencies and to extend the measurements to lower temperatures. For (methane (1) + benzene (2)), measurements were made along six isotherms from (233 to 348) K at pressures to 9.6 MPa. At temperatures below 279 K there was evidence of a solid phase, and thus only vapor phase samples were analyzed at these temperatures. For the (methane (1) + methylbenzene (3)) system, measurements were made along seven isotherms from T = (188 to 313) K at pressures up to 13 MPa. Along the 198 K isotherm, a significant change in the data’s p,x slope was observed indicating (liquid + liquid) equilibria at higher pressures. The data were compared with literature data and with calculations made using the Peng–Robinson (PR) equation of state (EOS). For both binary systems our data agree with much of the literature data that also deviate from the EOS in a similar manner. However, the data of Elbishlawi and Spencer (1951) for both binary systems, which appear to have received an equal weighting to other data in the EOS development, are inconsistent with the results of our measurements and data from other literature sources.     

High-pressure phase equilibrium data for the (carbon dioxide + l-lactide + ethanol) system

Experimental phase equilibrium values (cloud points) for the ternary system involving carbon dioxide, l-lactide and ethanol have been measured in order to provide fundamental values to conduct the polymerization reaction in supercritical carbon dioxide medium. The experiments were performed using a variable-volume view cell over the temperature range from 323 K to 353 K, system pressure between 9 MPa and 25.0 MPa and different mole ratios of ethanol to l-lactide (0.5:1, 1:1 and 1.5:1). Phase transitions of vapour-liquid types were observed. The experimental results were modelled using the Peng–Robinson (PR) equation of state with the Wong–Sandler (PR–WS) mixing rule, providing a good representation of the experimental phase equilibrium values.     

Isobaric (vapor + liquid) equilibrium data for the binary system methanol + 2-butyl alcohol and the quaternary system methyl acetate + methanol + 2-butyl alcohol + 2-butyl acetate at P = 101.33 kPa

In this paper, isobaric (vapor + liquid) equilibrium (VLE) data for the binary system methanol + 2-butyl alcohol and the quaternary system methyl acetate + methanol + 2-butyl alcohol + 2-butyl acetate were determined at P = 101.33 kPa in a modified Rose still. The binary VLE data were found to be thermodynamic consistency by the Herrington method. The VLE data for the binary system were correlated by the Wilson and NRTL equations respectively, which were used to predict the VLE data of the quaternary system. The results showed that the Wilson and NRTL models matched well with the (vapor + liquid) phase equilibrium data. The deviations for the vapor-phase compositions and the equilibrium temperatures are reasonably small and the models are both suitable for these systems.     

(Liquid + liquid) equilibrium of (NaNO3 + PEG 4000 + H2O) ternary system at different temperatures

Phase diagram and (liquid + liquid) equilibrium (LLE) data for the (NaNO₃ + polyethylene glycol 4000 (PEG 4000) + H₂O) system have been determined experimentally at T = (288.15 and 308.15) K. The effects of temperature on the binodal curves and tie-lines have been studied and it was found that an increasing in temperature caused the expansion of two-phase region. The Chen-NRTL, modified Wilson and UNIQUAC models were used to correlate the experimental tie-line data. The results show that the quality of fitting is better with the UNIQUAC model.     

(Liquid + liquid) equilibrium of (NaClO4 + PEG 4000 + H2O) ternary system at different temperatures

Phase diagram and (liquid + liquid) equilibrium (LLE) results for {NaClO₄ + polyethylene glycol 4000 (PEG 4000) + H₂O} have been determined experimentally at T = (288.15, 298.15, and 308.15) K. The Chen-NRTL, modified Wilson and UNIQUAC models were used to correlate the values for the experimental tie-lines. The results show that the quality of fitting is better with the modified Wilson model.     

(Vapor + liquid) equilibrium data for (carbon dioxide + 1,1-difluoroethane) system at temperatures from (258 to 343) K and pressures up to about 8 MPa

Accurate thermo-physical data are of utmost interest for the development of new efficient refrigeration systems. Carbon dioxide (R744) and 1,1-difluoroethane (R152a) are addressed here. Isothermal (vapor + liquid) equilibrium data are reported herein for (R744 + R152a) binary system in the (258–343) K temperature range and in the (0.14 to 7.65) MPa pressure range. A reliable “static-analytic” method taking advantage of two online ROLSI? micro capillary samplers is used for all thermodynamic measurements. The data are correlated using our in-house ThermoSoft thermodynamic model using the Peng–Robinson equation of state, the Mathias–Copeman alpha function, the Wong–Sandler mixing rules, and the NRTL model.     

Phase relations in the system (chromium + rhodium + oxygen) and thermodynamic properties of CrRhO3

Phase relations in the system (chromium + rhodium + oxygen) at T = 1273 K have been determined by examination of equilibrated samples by optical and scanning electron microscopy, powder X-ray diffraction (XRD), and energy dispersive spectroscopy (EDS). Only one ternary oxide, CrRhO₃ with rhombohedral structure ($R\overline{3}$, a = 0.5031, and c = 1.3767 nm) has been identified. Alloys and the intermetallics along the (chromium + rhodium) binary were in equilibrium with Cr₂O₃. The thermodynamic properties of the CrRhO₃ have been determined in the temperature range (900 to 1300) K by using a solid-state electrochemical cell incorporating calcia-stabilized zirconia as the electrolyte. For the reaction,$\begin{array}{cc}\hfill & 1/2{\text{Cr}}_2{\text{O}}_3(\text{solid})+1/2{\text{Rh}}_2{\text{O}}_3(\text{solid})\to {\text{CrRhO}}_3(\text{solid})\text{,}\hfill \\ \hfill & \mathrm{\Delta }{G}^{°}\pm 140/(\text{J}·{\text{mol}}^{-1})=-31967+5.418(T/\text{K})\text{,}\hfill \end{array}$where Cr₂O₃ has the corundum structure and Rh₂O₃ has the orthorhombic structure. Thermodynamic properties of CrRhO₃ at T = 298.15 K have been evaluated. The compound decomposes on heating to a mixture of Cr₂O₃-rich sesquioxide solid solution, Rh, and O₂. The calculated decomposition temperatures are T = 1567 ± 5 K in pure O₂ and T = 1470 ± 5 K in air at a total pressure p^° = 0.1 MPa. The temperature-composition phase diagrams for the system (chromium + rhodium + oxygen) at different partial pressures of oxygen and an oxygen potential diagram at T = 1273 K are calculated from the thermodynamic information.     

Thermodynamic evaluation and optimization of the (NaCl + Na2SO4 + Na2CO3 + KCl + K2SO4 + K2CO3) system

A complete, critical evaluation of all phase diagrams and thermodynamic data was performed for all condensed phases of the (NaCl + Na₂SO₄ + Na₂CO₃ + KCl + K₂SO₄ + K₂CO₃) system, and optimized parameters for the thermodynamic solution models were obtained. The Modified Quasichemical Model in the Quadruplet Approximation was used for modelling the liquid phase. The model evaluates first- and second-nearest-neighbour short-range order, where the cations (Na⁺ and K⁺) were assumed to mix on a cationic sublattice, while anions $({\text{CO}}_3^{2-}\text{,}{\text{SO}}_4^{2-}\text{,}\text{and}{\text{Cl}}^{-})$ were assumed to mix on an anionic sublattice. The thermodynamic properties of the solid solutions of (Na,K)₂(SO₄,CO₃) were modelled using the Compound Energy Formalism, and (Na,K)Cl was modelled using a substitutional model in previous studies. Phase transitions in the common-cation ternary systems (NaCl + Na₂SO₄ + Na₂CO₃) and (KCl + K₂SO₄ + K₂CO₃) were studied experimentally using d.s.c./t.g.a. The experimental results were used as input for evaluating the phase equilibrium in the common-cation ternary systems. The models can be used to predict the thermodynamic properties and phase equilibria in multicomponent heterogeneous systems. The experimental data from the literature are reproduced within experimental error limits.     

Phase equilibrium measurements and modelling of ternary system (carbon dioxide + ethanol + palmitic acid)

This work reports phase equilibrium measurements for the ternary system (palmitic acid + ethanol + CO₂). The motivation of this research relies on the fact that palmitic acid is the major compound of several vegetable oils. Besides, equilibrium data for palmitic acid in carbon dioxide using ethanol as co-solvent are scarce in the literature. Phase equilibrium experiments were performed using a high-pressure variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 20 MPa and mole fraction of palmitic acid from 0.0199 to 0.2930. Vapour–liquid and solid–fluid transitions were visually observed for the system studied. The Peng–Robinson equation of state, with the classical van der Waals quadratic mixing rule was employed for thermodynamic modelling of the system investigated with a satisfactory agreement between experimental and calculated values.     

Phase equilibria for H2 + CO2 + H2O system containing gas hydrates

Isothermal phase equilibrium (pressure–composition in the gas phase) for the ternary system of H₂ + CO₂ + H₂O has been investigated in the presence of gas hydrate phase. Three-phase equilibrium pressure increases with the H₂ composition of gas phase. The Raman spectra suggest that H₂ is not enclathrated in the hydrate-cages and behaves only like the diluent gas toward the formation of CO₂ hydrate. This fact is also supported by the thermodynamic analysis using Soave–Redlich–Kwong equation of state.     

(Liquid + liquid) equilibrium for the system {ethyl stearate(1) + ethanol(2) + glycerol(3)}

This paper reports the results of a new experimental study on the (liquid + liquid) equilibrium of the system {ethyl stearate(1) + ethanol(2) + glycerol(3)} at atmospheric pressure and at T = (313.15 and 323.15) K. The equilibrium compositions were measured by gas chromatography. Ternary diagrams were obtained for each temperature and the equilibrium data were compared to the system in the presence of salt (NaCl) at T = 323.15 K. The experimentally determined (liquid + liquid) equilibrium data were satisfactorily correlated with NRTL and UNIQUAC equations. A comparative analysis was performed using the UNIFAC-LLE group contribution method. From the results presented herein good predictions were obtained for this ternary system.     

The precise measurement of the (vapour + liquid) equilibrium properties for (CO2 + isobutane) binary mixtures

Recently, it has been suggested that natural working fluids, such as CO₂, hydrocarbons, and their mixtures, could provide a long-term alternative to fluorocarbon refrigerants. (Vapour + liquid) equilibrium (VLE) data for these fluids are essential for the development of equations of state, and for industrial process such as separation and refinement. However, there are large inconsistencies among the available literature data for (CO₂ + isobutane) binary mixtures, and therefore provision of reliable and new measurements with expanded uncertainties is required. In this study, we determined precise VLE data using a new re-circulating type apparatus, which was mainly designed by Akico Co., Japan. An equilibrium cell with an inner volume of about 380 cm³ and two optical windows was used to observe the phase behaviour. The cell had re-circulating loops and expansion loops that were immersed in a thermostatted liquid bath and air bath, respectively. After establishment of a steady state in these loops, the compositions of the samples were measured by a gas chromatograph (GL Science, GC-3200). The VLE data were measured for CO₂/propane and CO₂/isobutane binary mixtures within the temperature range from 300 K to 330 K and at pressures up to 7 MPa. These data were compared with the available literature data and with values predicted by thermodynamic property models.     

Measurement and modeling of high-pressure (vapour + liquid) equilibria of (CO2 + alcohol) binary systems

An apparatus based on a static-analytic method assembled in this work was utilized to perform high pressure (vapour + liquid) equilibria measurements with uncertainties estimated at <5%. Complementary isothermal (vapour + liquid) equilibria results are reported for the (CO₂ + 1-propanol), (CO₂ + 2-methyl-1-propanol), (CO₂ + 3-methyl-1-butanol), and (CO₂ + 1-pentanol) binary systems at temperatures of (313, 323, and 333) K, and at pressure range of (2 to 12) MPa. For all the (CO₂ + alcohol) systems, it was visually monitored to insure that there was no liquid immiscibility at the temperatures and pressures studied. The experimental results were correlated with the Peng–Robinson equation of state using the quadratic mixing rules of van der Waals with two adjustable parameters. The calculated (vapour + liquid) equilibria compositions were found to be in good agreement with the experimental values with deviations for the mol fractions <0.12 and <0.05 for the liquid and vapour phase, respectively.     

Measurement and modeling of high-pressure (vapor + liquid) equilibria of (CO2 + alkanol) binary systems

Complementary isothermal (vapor + liquid) equilibria data are reported for the (CO₂ + 3-methyl-2-butanol), (CO₂ + 2-pentanol), and (CO₂ + 3-pentanol) binary systems at temperatures of (313, 323, and 333) K, and at pressure range of (2 to 11) MPa. For all (CO₂ + alcohol) systems, it was visually monitored that there was no liquid immiscibility at the temperatures and pressures studied. The experimental data were correlated with the Peng–Robinson equation of state using the quadratic mixing rules of van der Waals with two adjustable parameters. The calculated (vapor + liquid) equilibria compositions were found to be in good agreement with the experimental data with deviations for the mole fractions <8% and <2% for the liquid and vapor phase, respectively.