Enthalpies of dissociation of clathrate hydrates of carbon dioxide,nitrogen, (carbon dioxide + nitrogen), and (carbon dioxide + nitrogen + tetrahydrofuran)

A calorimetric technique is described for measuring the enthalpy of dissociation liberated from solid hydrates. In this study, the enthalpies of dissociation were determined at T =  273.65 K andp =  0.1 MPa for simple and mixed hydrates of carbon dioxide, nitrogen, (carbon dioxide  +  nitrogen), and (carbon dioxide  +  nitrogen  +  tetrahydrofuran) using an isothermal microcalorimeter. The addition of tetrahydrofuran (THF) promoted hydrate stability and increased the number of guest molecules encaged in the small and large cavities of the hydrate lattice, resulting in lower enthalpy of dissociation, compared with structure II hydrate. The composition ratio of guest molecules did not affect the enthalpy of dissociation, which was found to be nearly constant for the same mixture.     

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.     

Ionic liquids as entrainers for water + ethanol,water + 2-propanol,and water + THF systems: A quantum chemical approach

Ionic liquids (ILs) are used as entrainers in azeotropic systems such as water + ethanol, water + 2-propanol, and water + tetrahydrofuran (THF). Ionic liquids consisting of a cation and an anion has limitless combinations, thereby making experimentation expensive and time taking. For the prediction of the liquid phase nonidealities resulting from molecular interactions, “COnductor-like Screening MOdel for Real Solvents” (COSMO-RS) approach is used in this work for the screening of potential ionic liquids. Initially benchmarking has been done on 12 reported isobaric IL based ternary systems with an absolute average deviation of 4.63% in vapor phase mole fraction and 1.07% in temperature. After successful benchmarking, ternary vapor + liquid equilibria for the azeotropic mixture of (a) ethanol + water, (b) 2-propanol + water, and (c) THF + water with combinations involving 10 cations (imidazolium, pyridinium, quinolium) and 24 anions were predicted. The VLE prediction, which gave the relative volatility, showed that the imidazolium based ionic liquid were the best entrainer for the separation of the three systems at their azeotropic point. ILs with [MMIM] cation in combination with acetate [OAc], chloride [Cl], and bromide [Br] anion gave the highest relative volatility.     

The partition coefficients of ethylene between vapor and hydrate phase for methane + ethylene + THF + water systems

The vapor-hydrate equilibria were studied experimentally in detail for CH₄ + C₂H₄ + tetrahydrofuran (THF) + water systems in the temperature range of 273.15–282.15 K, pressure range of 2.0–4.5 MPa, the initial gas–liquid volume ratio range of 45–170 standard volumes of gas per volume of liquid and THF concentration range of 4–12 mol%. The results demonstrated that, because of the presence of THF, ethylene was remarkably enriched in vapor phase instead of being enriched in hydrate phase for CH₄ + C₂H₄ + water system. This conclusion is of industrial significance; it implies that it is feasible to enrich ethylene from gas mixture, e.g., various kinds of refinery gases or cracking gases in ethylene plant, by forming hydrate.     

Hydrate phase equilibrium for the (hydrogen + tert-butylamine + water) system

The three-phase equilibrium conditions of ternary (hydrogen + tert-butylamine + water) system were first measured under high-pressure in a “full view” sapphire cell. The tert-butylamine–hydrogen binary hydrate phase transition points were obtained through determining the points of intersection of three phases (H–L_w–V) to two phases (L_w–V) experimentally. Measurements were made using an isochoric method. Firstly, (tetrahydrofuran + hydrogen) binary hydrate phase equilibrium data were determined with this method and compared with the corresponding experimental data reported in the literatures and the acceptable agreements demonstrated the reliability of the experimental method used in this work. The experimental investigation on (tert-butylamine + hydrogen) binary hydrate phase equilibrium was then carried out within the temperature range of (268.4 to 274.7) K and in the pressure range of (9.54 to 29.95) MPa at (0.0556, 0.0886, 0.0975, and 0.13) mole fraction of tert-butylamine. The three-phase equilibrium curve (H + L_w + V) was found to be dependent on the concentration of tert-butylamine solution. Dissociation experimental results showed that tert-butylamine as a hydrate former shifted hydrate stability region to lower pressure and higher temperature.     

Dissociation behaviour of (tetra-n-butylammonium bromide + tetra-n-butylammonium chloride) mixed semiclathrate hydrate systems

The thermal properties of {tetra-n-butylammonium bromide + tetra-n-butylammonium chloride (TBAB + TBAC)} mixed semiclathrate hydrates prepared from aqueous solutions were investigated by dissociation temperature measurements and differential scanning calorimetry (DSC). The maximum dissociation temperature of the mixed hydrate crystals at 0.1 MPa is 288.5 K for x_TBAB = 0.2 {mole fraction of TBAB to (TBAB + TBAC)}, which is higher than that of the pure hydrates {T = (285.5 and 288.2) K for TBAB and TBAC hydrates, respectively}. In addition, the dissociation enthalpies of the mixed hydrates are higher than those of the pure hydrates {(5.55 ± 0.06) kJ ⋅ mol⁻¹ H₂O for pure TBAB hydrate and (5.30 ± 0.05) kJ ⋅ mol⁻¹ H₂O for pure TBAC hydrate}, with a maximum of (5.95 ± 0.12) kJ ⋅ mol⁻¹ H₂O recorded at approximately x_TBAB = 0.4. It was therefore suggested that the crystal distortion in (TBAB + TBAC) mixed hydrates, caused by replacing water molecules by both bromide and chloride anions, was smaller than that observed for each pure hydrate. Consequently, the hydration numbers in the mixed hydrates were hypothesized to be slightly higher than those of the pure hydrates.     

Hydrate structural transition depending on the composition of methane + cyclopropane mixed gas hydrate

The methane + cyclopropane mixed gas hydrate system has been investigated at 291.1 K by means of gas chromatography and Raman spectroscopy. Both of pure guest species generate the structure-I hydrate in the present conditions. Isothermal phase equilibria exhibit discontinuity around the equilibrium cyclopropane composition (water-free) in the gas phase of 0.20. The Raman shifts have changed bordering at the point. These results reveal that the methane + cyclopropane mixed gas hydrate generates the structure-II crystal in the methane rich region, while the structure-I crystal is generated in the cyclopropane rich region.     

Isothermal phase equilibria for the (HFC-32 + HFC-134a) mixed-gas hydrate system

Isothermal phase equilibria (pressure-composition relations in hydrate, gas, and aqueous phases) in the {difluoromethane (HFC-32) + 1,1,1,2-tetrafluoroethane (HFC-134a)} mixed-gas hydrate system were measured at the temperatures 274.15 K, 279.15 K, and 283.15 K. The heterogeneous azeotropic-like behaviour derived from the structural phase transition of (HFC-32 + HFC-134a) mixed-gas hydrates appears over the whole temperature range of the present study. In addition to the heterogeneous azeotropic-like behaviour, the isothermal phase equilibrium curves of the (HFC-32 + HFC-134a) mixed-gas hydrate system exhibit the negative homogeneous azeotropic-like behaviour at temperatures 279.15 K and 283.15 K. The negative azeotropic-like behaviour, which becomes more remarkable at higher temperatures, results in the lower equilibrium pressure of (HFC-32 + HFC-134a) mixed-gas hydrates than those of both simple HFC-32 and HFC-134a hydrates. Although the HFC-134a molecule forms the simple structure-II hydrate at the temperatures, the present findings reveal that HFC-134a molecules occupy a part of the large cages of the structure-I mixed-gas hydrate.     

Phase transitions on (liquid + liquid) equilibria for (water + 1-methylnaphthalene + light aromatic hydrocarbon) ternary systems at T = (563, 573, and 583) K

Phase transitions for (water + 1-methylnaphthalene + light aromatic hydrocarbon) ternary systems are observed at their (liquid + liquid) equilibria at T = (563, 573, and 583) K and (8.6 to 25.0) MPa. The phase transition pressures at T = (563, 573, and 583) K were measured for the five species of light aromatic hydrocarbons, o-, m-, p-xylenes, ethylbenzene, and mesitylene. The measurements of the phase transition pressures were carried out by changing the feed mole fraction of water and 1-methylnaphthalene in water free, respectively. Effects of the feed mole fraction of water on the phase transition pressures are very small. Increasing the feed mole fraction of 1-methylnaphthalene results in decreasing the phase transition pressures at constant temperature. The slopes depending on the feed mole fraction for 1-methylnaphthalene at the phase transition pressures are decreased with increasing temperature for (water + 1-methylnaphthalene + p-xylene), (water + 1-methylnaphthalene + o-xylene), and (water + 1-methylnaphthalene + mesitylene) systems. For xylene isomers, the highest and lowest of the phase transition pressures are obtained in the case of p- and o-xylenes, respectively. The phase transition pressures for ethylbenzene are lower than those in the case of p-xylene. The similar phase transition pressures are given for p-xylene and mesitylene.     

(Solid + liquid) equilibria of (naphthalene + isomeric dichlorobenzenes)

(Solid + liquid) equilibria (SLE) have been measured for naphthalene + o-dichlorobenzene, + m-dichlorobenzene, and + p-dichlorobenzene using differential scanning calorimetry (DSC) over the whole concentration range. It was found that the phase diagram of (naphthalene + m-dichlorobenzene) is of a simple eutectic type with the eutectic point at 244.85 K and 0.058 mole fraction of naphthalene, the phase diagram of (naphthalene + p-dichlorobenzene) is of a simple eutectic type with the eutectic point at 302.85 K and 0.390 mole fraction of naphthalene and in the system of (naphthalene + o-dichlorobenzene), a 1:1 incongruently melting compound is formed and that the phase diagram show a eutectic and a peritectic, the eutectic point is at 232.55 K and 0.130 mole fraction of naphthalene, the peritectic point at 250.15 K and 0.077 mole fraction of naphthalene. Furthermore, the activity coefficients of components in mixtures of (naphthalene + m-dichlorobenzene) and (naphthalene + p-dichlorobenzene) have been correlated by the Scatchard–Hildebrand solubility parameter expression. This approach offers a useful procedure for estimating with good accuracy.     

Hydrate phase equilibrium in the system of (carbon dioxide + 2,2-dimethylbutane + water) at temperatures below freezing point of water

The four-phase equilibrium conditions of (vapor + liquid + hydrate + ice) were measured in the system of (CO₂ + 2,2-dimethylbutane + water). The measurements were performed within the temperature range (254.2 to 270.2) K and pressure range (0.490 to 0.847) MPa using an isochoric method. Phase equilibrium conditions of hydrate formed in this study were measured to be at higher temperatures and lower pressures than those of structure I CO₂ simple hydrate. The largest difference in the equilibrium pressures of structure I CO₂ hydrate and the hydrate formed in the present study was 0.057 MPa at T = 258.3 K. On the basis of the four-phase equilibrium data obtained, the quintuple point for the (ice + structure I hydrate + structure H hydrate + liquid + vapor) was also determined to be T = 266.4 K and 0.864 MPa. The results indicate that structure H hydrate formed with CO₂ and 2,2-dimethylbutane is stable exclusively at the temperatures below the quintuple temperature.     

Equilibrium solubility of sodium 3-sulfobenzoate in binary (sodium chloride + water), (sodium sulfate + water), and (ethanol + water) solvent mixtures at temperatures from (278.15 to 323.15) K

The solubility of sodium 3-sulfobenzoate in binary (sodium chloride + water), (sodium sulfate + water), and (ethanol + water) solvent mixtures was measured at elevated temperatures from (278.15 to 323.15) K by a steady-state method. The results of these experiments were correlated by a modified Apelblat equation. The dissolution enthalpy and entropy of sodium 3-sulfobenzoate in aqueous solutions of different mole fraction were obtained.     

A thermodynamic study of the (difluoromethane + water) system

A study of the (difluoromethane + water) system was conducted at temperatures between (255 and 298) K, and pressures from (0.06 to 1.30) MPa. The solubility of difluoromethane in liquid water was measured from (280 to 298) K, at pressures up to the hydrate formation pressure. The (p, T) behavior of the (liquid + hydrate + vapor) three-phase equilibrium was measured from (274 to 292) K. The (p, T) behavior of the (ice + hydrate + vapor) three-phase equilibrium was measured from (257 to 273) K. Solubility-corrected enthalpies of dissociation were determined at the lower quadruple point (Q1) using the Clapeyron equation. The de Forcrand method was used to determine the hydration number of the hydrate at Q1. The results show that not all of the cages in the SI hydrate structure are filled.     

Isothermal phase equilibria for the (xenon + cyclopropane) mixed-gas hydrate system

Isothermal three-phase equilibria of gas, aqueous, and hydrate phases for the {xenon (Xe) + cyclopropane (c-C₃H₆)} mixed-gas hydrate system were measured at two different temperatures (279.15 and 289.15) K. The structural phase transitions from structure-I to structure-II and back to structure-I, depending on the mole fraction of guest mixtures, occur in the (Xe + c-C₃H₆) mixed-gas hydrate system. The isothermal pressure–composition relations have two local pressure minima. The most important characteristic in the (Xe + c-C₃H₆) mixed-gas hydrate system is that the equilibrium pressure–composition relations exhibit the complex phase behavior involving two structural phase transitions and two homogeneous negative azeotropes. One of two structural phase transitions exhibits the heterogeneous azeotropic-like behavior.     

Effect of ionic liquids on (vapor + liquid) equilibrium behavior of (water + 2-methyl-2-propanol)

Isobaric T, x, y data were reported for ternary systems of {water + 2-methyl-2-propanol (tert-butyl alcohol, TBA) + ionic liquid (IL)} at p = 100 kPa. When the mole fraction of TBA on IL-free basis was fixed at 0.95, measurements were performed at IL mass fractions from 0.6 down to 0.05, in a way of repeated synthesis. The vapor-phase compositions were obtained by analytical methods and the liquid-phase compositions were calculated with the aid of mass balances. Activity coefficients of water and TBA were obtained without the need of a thermodynamic model of the liquid-phase. Six ILs, composed of an anion chosen from [OAc]^? or [Cl]^?, and a cation from [emim]⁺, or [bmim]⁺, or [hmim]⁺, were studied. Relative volatility and activity coefficients were presented in relation with the IL mole fraction, showing the effect of the ILs on a molar basis. The effect of the ILs on relative volatility of TBA to water was depicted by the effect of anions and cations on, respectively, the activity coefficients of water and TBA. The results indicated that, among the six ILs studied, [emim][Cl] has the most significant effect on enhancement of the relative volatility, which reaches a value of 7.2 at an IL mass fraction of 0.58. Another IL, [emim][OAc], has also significant effect, with an appreciable value of 5.2 for the relative volatility when the IL mass fraction is 0.6. Considering the relatively low viscosity and melting point of [emim][OAc], it might be a favorable candidate as solvent for the separation of water and TBA by extractive distillation. Simultaneous correlation by the NRTL model was presented for both systems of (water + ethanol + IL) and (water + TBA + IL), using consistent binary parameters for water and IL.     

Thermodynamic evaluation and optimization of the (NaCl + KCl + MgCl2 + CaCl2 + MnCl2 + FeCl2 + CoCl2 + NiCl2) system

A complete critical evaluation of all available phase diagram and thermodynamic data has been performed for all condensed phases of the (NaCl + KCl + MgCl₂ + CaCl₂ + MnCl₂ + FeCl₂ + CoCl₂ + NiCl₂) system, and optimized model parameters have been found. The (MgCl₂ + CaCl₂ + MnCl₂ + FeCl₂ + CoCl₂ + NiCl₂) subsystem has been critically evaluated in a previous article. The model parameters obtained for the binary subsystems can be used to predict thermodynamic properties and phase equilibria for the multicomponent system. The Modified Quasichemical Model was used for the molten salt phase, and the (MgCl₂ + MnCl₂ + FeCl₂ + CoCl₂ + NiCl₂) solid solution was modeled using a cationic substitutional model with an ideal entropy and an excess Gibbs free energy expressed as a polynomial in the component mole fractions. Finally, the (Na,K)(Mg,Ca,Mn,Fe,Co,Ni)Cl₃ and the (Na,K)₂(Mg,Mn,Fe,Co,Ni)Cl₄ solid solutions were modeled using the Compound Energy Formalism.     

Phase equilibria in ternary (carbon dioxide + tetrahydrofuran + water) system in hydrate-forming region: Effects of carbon dioxide concentration and the occurrence of pseudo-retrograde hydrate phenomenon

In the present work, the three- and four-phase hydrate equilibria of (carbon dioxide (CO₂) + tetrahydrofuran (THF) + water) system are measured by using Cailletet equipment in the temperature and pressure range of (272 to 292) K and (1.0 to 7.5) MPa, respectively, at different CO₂ concentration. Throughout the study, the concentration of THF is kept constant at 5 mol% in the aqueous solution. In addition, the fluid phase transitions of L_W–L_V–V → L_W–L_V (bubble point) and L_W–L_V–V → L_W–V (dew point) are determined when they are present in the ternary system. For comparison, the three-phase hydrate equilibria of binary (CO₂ + H₂O) are also measured. Experimental measurements show that the addition of THF as a hydrate promoter extends hydrate stability region by elevating the hydrate equilibrium temperature at a specified pressure. The three-phase equilibrium line H–L_W–V is found to be independent of the overall concentration of CO₂. Contradictory, at higher pressure, the phase equilibria of the systems are significantly influenced by the overall concentration of CO₂ in the systems. A liquid–liquid phase split is observed at overall concentration of CO₂ as low as 3 mol% at elevated pressure. The region is bounded by the bubble-points line (L_W–L_V–V → L_W–L_V), dew points line (L_W–L_V–V → L_W + V) and the four-phase equilibrium line (H + L_W + L_V + V). At higher overall concentration of CO₂ in the ternary system, experimental measurements show that pseudo-retrograde behaviour exists at pressure between (2.5 and 5) MPa at temperature of 290.8 K.     

Isobaric vapor–liquid and vapor–liquid–liquid equilibrium data for the system water + ethanol + cyclohexane

Isobaric vapor–liquid (VLE) and vapor–liquid–liquid equilibria (VLLE) were measured for the ternary system water + ethanol + cyclohexane at 101.3 kPa. The experimental determination was carried out in a dynamic equilibrium still with circulation of both the vapor and liquid phases, equipped with an ultrasonic homogenizer. The experimental data demonstrated the existence of a ternary heterogeneous azeotrope at 335.6 K with a composition of 0.188, 0.292, 0.520 mole fraction of water, ethanol and cyclohexane, respectively. The experimental data were compared with those obtained using UNIFAC and NRTL models with parameters taken from literature.     

Thermodynamic evaluation and optimization of the (LiF + NaF + KF + MgF2 + CaF2 + SrF2) system

A complete critical evaluation of all available phase diagram and thermodynamic data has been performed for all condensed phases of the (LiF + NaF + KF + MgF₂ + CaF₂ + SrF₂) system, and optimized model parameters have been found. The (LiF + NaF + KF + MgF₂ + CaF₂) subsystem has been critically evaluated in a previous article. The model parameters obtained for the binary and ternary subsystems can be used to predict thermodynamic properties and phase equilibria for the multicomponent system. The Modified Quasichemical Model for short-range ordering was used for the molten salt phase, and the low-temperature and high-temperature (CaF₂ + SrF₂) solid solutions were modelled using a cationic substitutional model with an ideal entropy and an excess Gibbs free energy expressed as a polynomial in the component mole fractions. Finally, the (Li, Na, K)(Mg, Ca, Sr)F₃ perovskite phase was modelled using the Compound Energy Formalism.     

(Vapor + liquid) equilibrium properties of (ethane + ethanol) system at (295, 303, and 313) K

The (vapor + liquid) equilibrium data for binary system of (ethane + ethanol) at three temperatures (295, 303, and 313) K were measured using a designed pressure–volume–temperature (PVT) apparatus. A wide range of pressures, (1 to 5) MPa, were considered for the measurements. The phase composition, saturated density, and viscosity of liquid phase were measured for each pressure and temperature. The experimental (vapor + liquid) equilibrium data were compared with the modeling results obtained using the Peng–Robinson and Soave–Redlich–Kwong equations of state.