Phase equilibria for four binary systems containing propylene

Isothermal vapor—liquid equilibria (P−x, y) for four binary systems of propylene with methanol, acetone, diethyl ether and propylene oxide were measured using a swing method at 25°C. Also, the saturated molar volume of the liquid phase for each system was obtained by a weighing method. The data obtained were correlated by use of the Soave-Redlich-Wong equation. The P-x, y relations were described satisfactorily, except for the methanol—propylene     

Phase equilibria in binary mixtures with monoethyl succinate

Monoethyl succinate was produced by partial esterification of succinic anhydride with ethanol using Amberlyst 15^® as catalyst. After separation and purification, the purity of monoethyl succinate was confirmed by nuclear magnetic resonance (NMR). Vapor pressure of monoethyl succinate was measured and correlated with Antoine equation. Vapor-liquid equilibria at constant temperature were measured for the binary systems ethyl acetate + monoethyl succinate, acetic acid + monoethyl succinate, and water + monoethyl succinate at 323.15 K, and ethanol + monoethyl succinate at 313.15 K. Binary parameters for the NRTL equations were obtained by fitting experimental data using the regression tool in ASPEN Plus^® using the Hayden-O’Connell method for vapor phase fugacities. The model agrees reasonably well with the experimental data.     

Phase equilibria in binary mixtures of ethane and hexadecane

This paper reports experimental results of a study of the phase behaviour of binary mixtures of ethane + hexadecane. In the near-critical region of ethane liquid + vapour and solid hexadecane + liquid two-phase boundaries have been measured. Also the three-phase equilibrium solid hexadecane + liquid + vapour has been determined experimentally. The experimental data cover the complete mole fraction range. Pressures up to 18 MPa were applied and the investigation was performed in a temperature region from about 260 K up to 450 K.     

Phase equilibria on binary systems containing diethyl sulfide

Isothermal vapor-liquid equilibrium (VLE) of the following systems was measured with a recirculation still: diethyl sulfide + ethanol at 343.15 K, diethyl sulfide + 1-propanol at 358.15 K, and diethyl sulfide + propyl acetate at 363.15 K. Diethyl sulfide + ethanol at 343.15 K and diethyl sulfide + 1-propanol at 358.15 K systems exhibit positive deviation from Raoult's law, whereas diethyl sulfide + propyl acetate at 363.15 K system exhibits only slight positive deviation from Raoult's law. A maximum pressure azeotrope was found in the systems diethyl sulfide + ethanol (x₁ = 0.372, P = 88.4 kPa, T = 343.15 K) and diethyl sulfide + 1-propanol (x₁ = 0.640, P = 96.8 kPa, T = 358.15 K). No azeotropic behavior was found in diethyl sulfide + propyl acetate system at 363.15 K. The experimental results were correlated with the Wilson model and compared to COSMO-SAC predictive model. Liquid and vapor phase compositions were determined with gas chromatography. All measured data sets passed the thermodynamic consistency tests. The activity coefficients at infinite dilution are also presented.     

Phase equilibria in binary mixtures of propane + acenaphthene

In the near-critical region of propane, phase equilibria of binary mixtures of propane + acenaphthene have been investigated experimentally. Apart from the three-phase equilibrium solid acenaphthene + liquid + vapour, two-phase boundaries liquid + vapour and solid acenaphthene + liquid have been investigated over the entire mole fraction range. The measurements were performed in the temperature region 350–420 K with pressures up to 10 MPa.     

Phase equilibria on four binary systems containing 3-methylthiophene

Isothermal vapor–liquid equilibrium (VLE) for 3-methylthiophene + 2,2,4-trimethylpentane at 368.15 K, 3-methylthiophene + 2,4,4-trimethyl-1-pentene at 368.15 K, 3-methylthiophene  + cyclohexane at 348.15 K, and 3-methylthiophene + 1-hexene at 333.15 K were measured with a recirculation still. All systems exhibit positive deviation from ideality. No azeotropic behavior was found in all systems. The experimental results were correlated with the Wilson model and also compared with the original UNIFAC and UNIFAC-Dortmund predictive models. Analyses of liquid and vapor-phase composition were determined with gas chromatography (GC). All VLE measurements passed the used thermodynamic consistency tests (integral, infinite dilution and point test). The activity coefficients at infinite dilution are also presented.     

Phase equilibria in binary systems containing N-monosubstituted amides and hydrocarbons

The binary vapour-liquid equilibrium of seven systems of -caprolactam + octane, + decane, + dodecane, octane, + decane, + dodecane, of N-methylacetamide + octane, of N-ethylacetamide of N-methylpropionamide + octane and of N-methylpropionamid + -caprolactam was measured in the temperature range from 363 to 423 K and in the low pressure region. A static equilibrium apparatus for the measurements was constructed.

In the system N-methylpropionamide + octane measurements of liquid-liquid equilibrium were carried out in the temperature range from 310 K up to the critical solution temperature.

The experimental results were correlated applying activity coefficients models such as NRTL. The data obtained from our measurements were used to estimate UNIFAC interaction parameters for the groups CH₂/CONHCH₂, CH₂/C₅H₁₀CONH and CONHCH₂/C₅H₁₀CONH.     

Phase equilibria for mixtures containing nonionic surfactant systems: Modeling and experiments

Surfactants are important materials with numerous applications in the cosmetic, pharmaceutical, and food industries due to inter-associating and intra-associating bond. We present a lattice fluid equation-of-state that combines the quasi-chemical nonrandom lattice fluid model with Veytsman statistics for (intra + inter) molecular association to calculate phase behavior for mixtures containing nonionic surfactants. We also measured binary (vapor + liquid) equilibrium data for {2-butoxyethanol (C₄E₁) + n-hexane} and {2-butoxyethanol (C₄E₁) + n-heptane} systems at temperatures ranging from (303.15 to 323.15) K. A static apparatus was used in this study. The presented equation-of-state correlated well with the measured and published data for mixtures containing nonionic surfactant systems.     

On the thermodynamics of alcohol solutions. Phase equilibria of binary and ternary mixtures containing any number of alcohols

Nagata, I., 1985. On the thermodynamics of alcohol solutions. Phase equilibria of binary and ternary mixtures containing any number of alcohols. Fluid Phase Equilibria, 19: 153–174.Binary vapor—liquid and liquid—liquid equilibrium data for alcohol solutions includin one or two alcohols are correlated with the UNIQUAC associated solution theory (Nagata and Kawamura). The theory uses pure liquid association constants determined by the method of Brandani and a single value of the enthalpy of the hydrogen bond equal to ?23.2 kJ mol ^?1 for pure alcohols. For alcohol-active nonassociating component mixtures and alcohol—alcohol mixtures the theory involves additional solvation constants. The theory is extended to contain ternary mixtures with any number of alcohols. Ternary predictions of vapor—liquid and liquid—liquid equilibria are performed using only binary parameters. Good agreement is obtained between calculated and experimental results for many representative mixtures.     

On the gas—gas equilibria of polar—non-polar binary mixtures from a polarizable hard-sphere dipole model

Perturbation theory is applied to a polarizable hard-sphere dipole model mixture. It is shown that for increasing values of the reduced polarizability of the non-polar component. gas—gas equilibria of the first and second kind can be described for a polar—non-polar binary mixture. However for the latter case, critical lines do not show the minimum in temperature observed in real systems. Comparison between theoretical and experimental results are given for HeNH₃ and ArH₂O mixtures.     

Phase equilibria in the binary system lead fluoride [PbF2]-calcium fluoride [CaF2]

The phase diagram of the binary system lead fluoride [PbF₂]-calcium fluoride [CaF₂] was determined over the whole composition range. The investigations were carried out by means of thermal microscopic, X-ray and dilatometric analyses. It was concluded that the components did not form chemical compounds.     

Equations for describing liquid-vapor phase equilibria in binary mixtures

Three forms of equations for describing experimental data on liquid and vapor pressures, depending on temperature and composition at phase equilibria in binary mixtures, are proposed and evaluated. It is determined that the form of equation depends on the relationship between the temperature of a mixture and the critical temperatures of the components of the mixture. Exact data on the phase equilibria in nitrogenoxygen, nitrogen-argon, and oxygen-argon mixtures [1] are approximated to assess the effectiveness of the equations’ forms. It is found that the equations also allow us to determine the phase composition at a given temperature and pressure and temperatures of phases at a given pressure and composition.     

Phase equilibria in binary mixtures of ethane + docosane and molar volumes of liquid docosane

Experimental results for various types of phase behaviour which can occur in the binary ethane + docosane system are presented. The experimental data cover various two-phase boundaries and the three-phase equilibria solid docosane + liquid + vapour and liquid + liquid + vapour. In addition, p,V,T measurements of liquid docosane are carried out. The experimental work is performed within a temperature range of ∼ 290–370 K and at pressures of up to 16 MPa.     

Multiphase equilibria for binary and ternary mixtures containing propionic acid,n-butanol,butyl propionate,and water

Isothermal vapor–liquid equilibrium (VLE) data were measured for propionic acid + butyl propionate at 373.15 and 393.15 K, and isothermal vapor–liquid–liquid equilibrium (VLLE) data were also measured for n-butanol + water, butyl propionate + water, and water + n-butanol + butyl propionate at temperatures ranging from 323.15 to 393.15 K. No azeotrope was found in propionic acid + butyl propionate. The mutual solubility data of the binary aqueous systems were correlated well with the NRTL model accompanying with temperature-dependent parameters. Improvement on the calculation of saturated vapor compositions has been made by using two-term virial equation with one adjustable binary interaction parameter to represent the non-ideality of the vapor phase. The model parameters determined from the binary VLLE data of n-butanol + water and butyl propionate + water and the binary VLE data of n-butanol + butyl propionate are capable of predicting satisfactorily the VLLE properties for the ternary system of water + n-butanol + butyl propionate.     

Phase equilibria on five binary systems containing 1-butanethiol and 3-methylthiophene in hydrocarbons

Isothermal vapor–liquid equilibrium (VLE) of the following systems was measured with a recirculation still: 1-butanethiol + methylcyclopentane at 343.15 K, 1-butanethiol + 2,2,4-trimethylpentane at 368.15 K, 3-methylthiophene + toluene at 383.15 K, 3-methylthiophene + o-xylene at 383.15 K, and 3-methylthiophene + 1,2,4-trimethylbenzene at 383.15 K. 1-Butanethiol + methylcyclopentane and 1-butanethiol + 2,2,4-trimethylpentane systems exhibit positive deviation from Raoult's law, whereas systems containing 3-methylthiophene in aromatic hydrocarbons exhibit only slight positive deviation from Raoult's law. A maximum pressure azeotrope was found in the system 1-butanethiol + 2,2,4-trimethylpentane (x₁ = 0.548, P = 100.65 kPa, T = 368.15 K). The experimental results were correlated with the Wilson model and compared with original UNIFAC and COSMO-SAC predictive models. Raoult's law can be used to describe the behavior of 3-methylthiophene in aromatic hydrocarbons at the experimental conditions in this work. Liquid and vapor-phase composition were determined with gas chromatography. All measured data sets passed the thermodynamic consistency tests applied. The activity coefficients at infinite dilution are also presented.     

Arsenic pentafluoride equilibria in anhydrous hydrogen fluoride

Earlier work has indicated that arsenic pentafluoride when dissolved in anhydrous HF is present largely as the anion As₂F₁₁^-, particularly temperatures much below ambient. Raman spectra and conductance measurements are used here to show that, at and near room temperature, there are significant concentrations of molecular AsF₅, AsF₆^- and As₂F₁₁^-in equilibrium and that on reduction of temperature, As₂F₁₁^- is formed at the expense of AsF₅ and AsF₆^-. The implications of the Lewis acid and oxidant strengths of AsF₅ are discussed as affecting synthetic procedures in anhydrous HF.     

Phase equilibria in the binary system PbO-PbCl2

The present paper forms part of a series of studies on the ternary system PbO-P₂O₅ -PbCl₂. The side binary system PbO-PbCl₂ has been investigated over the entire composition range and its phase diagram has been established. The components form three oxychlorides: Pb₅Cl₂O₄, Pb₃Cl₂O₂ and Pb₂Cl₂O. The examinations were carried out by means of thermal, microscopic, dilatometric, X-ray and IR absorption analyses. X-ray identification data for Pb₅Cl₂O₄ are presented.

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Zusammenfassung Vorliegende Arbeit ist Teil einer Untersuchungsreihe des ternÄren Systemes PbO-P₂O₅-PbCl₂. Dabei wurde das binÄre Untersystem PbO-PbCl₂ im gesamten Konzentrationsbereich untersucht und ein Phasendiagramm erstellt. Die Komponenten bilden die drei Oxidchloride Pb₅Cl₂O₄, Pb₃Cl₂O₂ und Pb₂Cl₂O. Die Untersuchungen wurden mittels mikroskopischer, dilatometrischer, röntgenographischer, IR- und Thermoanalyse durchgeführt. Die röntgenographischen Angaben für Pb₅Cl₂O₄ werden gegeben.

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The author is most grateful to Or. Janusz Matuszewski for bis help in the X-ray investigations.     

Small-angle X-ray scattering from binary liquid-crystalline mixtures of polar and non-polar compounds

The phase diagrams of several binary mixtures consisting of cyanobiphenyls and different terminally non-polar mesogenic compounds exhibit induced smectic A phases. The smectic A layer spacing, d, of these induced phases have been investigated by small-angle X-ray scattering as a function of the molar fraction x_i . Large deviations of the layer spacings from the additivity rule d _mix = σ x_id_i , have been observed in all mixed systems. Assuming a dimerization of the terminally polar compounds, the degree of association β(x) was calculated as a function of composition for different dimerization constants. The theoretical relations d _mix(x) obtained from the calculated β(x) values do not fit the experimental curves for d(x). This fact can be interpreted by the formation of weak complexes between the polar and the terminally non-polar molecules of the binary mixtures. This kind of complexing seems to be responsible for the formation of induced smectic phases of the S_Ad-type and might disturb the monomer-dimer equilibrium 2M _p D _p of the polar compounds.     

Thermodynamics of organic mixtures containing amines. X. Phase equilibria for binary systems formed by imidazoles and hydrocarbons: Experimental data and modelling using DISQUAC

(Solid + liquid) equilibrium (SLE) temperatures have been determined using a dynamic method for the systems (1H-imidazole, + benzene, + toluene, + hexane, or + cyclohexane; 1-methylimidazole + benzene, or + toluene, 2-methyl-1H-imidazole + benzene, + toluene, or + cyclohexane, and benzimidazole + benzene). In addition (liquid + liquid) equilibrium (LLE) temperatures have been obtained using a cloud point method for (1H-imidazole, + hexane, or + cyclohexane; 1-methylimidazole + toluene, and 2-methyl-1H-imidazole + cyclohexane). The measured systems show positive deviations from the Raoult’s law, due to strong dipolar interactions between amine molecules related to the high dipole moment of imidazoles. On the other hand, DISQUAC interaction parameters for the contacts present in these solutions and for the amine/hydroxyl contacts in (1H-imidazole + 1-alkanol) mixtures have been determined. The model correctly represents the available data for the examined systems. Deviations between experimental and calculated SLE temperatures are similar to those obtained using the Wilson or NRTL equations, or the UNIQUAC association solution model. The quasichemical interaction parameters are the same for mixtures containing 1H-imidazole, 1-methylimidazole, or 2-methyl-1H-imidazole and hydrocarbons. This may be interpreted assuming that they are members of a homologous series. Benzimidazole behaves differently.     

Phase equilibria in chemical reactive fluid mixtures

Downstream processing is a major part of nearly all processes in the chemical industries. Most separation processes in the chemical (and related) industries for fluid mixtures are based on phase equilibrium phenomena. The majority of separation processes can be modelled assuming that chemical reactions are of no (or very minor) importance, i.e., assuming that the overall speciation remains unchanged during a separation process. However, there are also a large number of industrially important processes where the thermodynamic properties are influenced by chemical reactions. The phase equilibrium of chemical reactive mixtures has been a major research area of the author’s group over nearly 40 years. In this contribution, three examples from that research are discussed. The first example deals with the vapour phase dimerisation of carboxylic acids and its consequences on phase equilibrium phenomena and phase equilibrium predictions. The second example deals with the solubility of sour gases (e.g., carbon dioxide and sulfur dioxide) in aqueous solutions of ammonia. That topic has been of interest for many years, e.g., in relation with the gasification and liquefaction of coal and, more recently, with the removal of carbon dioxide from flue gas in the “chilled ammonia process”. The third example deals with phase equilibrium phenomena in aqueous solutions of polyelectrolytes. It deals with the phenomenon of “counter ion condensation” and methods to model the Gibbs free energy of such solutions.