Quaternary System LiCl Research Articles

Solid-liquid phase equilibria of quaternary systems LiCl+KCl+NaCl+H2O and LiCl+KCl+MgCl2+H2O at 308.2K

The phase equilibria of quaternary systems LiCl+KCl+NaCl+H2O and LiCl+KCl+MgCl2+H2O at 308.2 K were investigated by isothermal dissolution equilibrium method. The results reveal that the phase diagram of the quaternary system LiCl+KCl+NaCl+H2O consists of one invariant point, three univariable curves and three equilibrium solid crystallization fields (LiCl·H2O, NaCl and KCl). Two double salts appear in the quaternary system LiCl+KCl+MgCl2+H2O, namely KCl·MgCl2·6H2O and LiCl·MgCl2·7H2O, and the phase diagram is composed of three invariant points, seven univariable curves and five crystallization fields (LiCl·MgCl2·7H2O, MgCl2·6H2O, LiCl·H2O, KCl and KCl·MgCl2·6H2O). Moreover, the solubilities of salts in two quaternary systems are predicted by applying the Pitzer model. The calculated phase diagrams were in good accordance with the experimental phase diagrams. The results clearly show that lithium chloride crystallizes as LiCl·2H2O at low temperatures; however, it is precipitated as LiCl·H2O at 308.2 K. Compared with KCl·MgCl2·6H2O, LiCl·MgCl2·7H2O has a smaller crystallization zone. The phase equilibria in invariant points of quaternary systems LiCl+KCl+NaCl+H2O and LiCl+KCl+MgCl2+H2O at 308.2 K have been explored for the first time.

Measurement and Prediction of Phase Equilibria of Quaternary System LiCl–KCl–SrCl2–H2O at 273.2 K and its Applications

Measurement and Prediction of Phase Equilibria of Quaternary System LiCl–KCl–SrCl2–H2O at 273.2 K and its Applications

Studies on Phase Equilibria in Ternary System LiCl–SrCl2–H2O at 288.15 K and Quaternary System LiCl–KCl–SrCl2–H2O at 288.15 and 323.15 K

Studies on Phase Equilibria in Ternary System LiCl–SrCl₂–H₂O at 288.15 K and Quaternary System LiCl–KCl–SrCl₂–H₂O at 288.15 and 323.15 K

Phase Equilibria in the Quaternary System LiCl–NaCl–SrCl2–H2O at 273 and 323 K

Phase Equilibria in the Quaternary System LiCl–NaCl–SrCl₂–H₂O at 273 and 323 K

Solubility measurement and prediction of phase equilibria in the quaternary system LiCl + NaCl + KCl + H2O and ternary subsystem LiCl + NaCl + H2O at 288.15 K

Using isothermal dissolution method, the phase equilibrium relationship in quaternary system LiCl + NaCl + KCl + H2O and the ternary subsystem LiCl + NaCl + H2O at 288.15 K were investigated. Each phase diagram of two systems was drawn. The phase diagram of LiCl + NaCl + H2O system contains two solid phase regions of crystallization LiCl·2H2O and NaCl. In the phase diagram of LiCl + NaCl + KCl + H2O system, there are three crystallization regions: LiCl·2H2O, NaCl and KCl respectively. In this paper, the solubilities of phase equilibria in two systems were calculated by Pitzer's model at 288.15 K. The predicted phase diagrams generally agree with the experimental phase diagrams.

Phase Equilibria in the Ternary System NaCl–SrCl2–H2O (273 and 308 K) and Quaternary System LiCl–NaCl–SrCl2–H2O (308 K)

The phase equilibria of the ternary system NaCl–SrCl2–H2O at 273 and 308 K and quaternary system LiCl–NaCl–SrCl2–H2O at 308 K were measured by the isothermal dissolution equilibrium method. The pha...

Measurements and calculations of solid-liquid equilibria in two quaternary systems: LiCl–NaCl–SrCl2–H2O and LiCl–KCl–SrCl2–H2O at 298 K

Using the method of isothermal dissolution equilibrium, stable phase equilibria of unreported strontium-containing systems LiCl–NaCl–SrCl2–H2O and LiCl–KCl–SrCl2–H2O at 298 K have been studied in accordance with the compositions of the underground brine in western Sichuan Basin. The experimental results show that there are no solid solution and complex salt in two quaternary systems. The phase diagram of quaternary system LiCl–NaCl–SrCl2–H2O consists of two invariant points, five isothermal dissolution curves and four crystallization regions. The quaternary system LiCl–KCl–SrCl2–H2O belongs to a simple type and the phase diagram consists of two invariant points, five isothermal dissolution curves and four crystallization regions. The solubilities of salts in the above systems were accurately calculated with Pitzer electrolyte solution theory. It was found that the calculated phase diagrams coincided basically with the experimental phase diagrams by evaluated the accuracy through the experimental results. Meanwhile, the applicability of Pitzer parameters selected in this paper was validated.

Measurement and Prediction of Solid + Liquid Equilibria in the Quaternary System LiCl–KCl–Li2SO4–K2SO4–H2O at 288.15 K

The phase equilibria relationship between the quaternary system LiCl–KCl–Li2SO4–K2SO4–H2O and its subsystems LiCl–KCl–H2O and LiCl–Li2SO4–H2O was studied by the isothermal dissolution equilibrium method at 288.15 K, and the corresponding phase diagrams were drawn. At 288.15 K, ternary systems LiCl–KCl–H2O and LiCl–Li2SO4–H2O all belong to the simple type. In the phase diagram of the quaternary system LiCl–KCl–Li2SO4–K2SO4–H2O, there are five equilibrium solid phase crystallization fields: LiCl·2H2O, KCl, Li2SO4·H2O, K2SO4, and Li2SO4·K2SO4. Compared with the multitemperature phase diagrams of this system at 288.15–348.15 K, it was found that the basic configuration of the phase diagrams is the same. As the temperature increased, the phase region of double salt Li2SO4·K2SO4 clearly increased, whereas the phase region of single salt KCl and K2SO4 clearly decreased. On the basis of the experiment, the extended Harvie–Weare model of the Pitzer model was used to predict the solubility data of the quaternary system. The simulated and measured values were basically in good agreement.

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Using the method of isothermal dissolution equilibrium, stable phase equilibria of unreported strontium-containing systems LiCl–NaCl–SrCl2–H2O and LiCl–KCl–SrCl2–H2O at 298 K have been studied in accordance with the compositions of the underground brine in western Sichuan Basin. The experimental results show that there are no solid solution and complex salt in two quaternary systems. The phase diagram of quaternary system LiCl–NaCl–SrCl2–H2O consists of two invariant points, five isothermal dissolution curves and four crystallization regions. The quaternary system LiCl–KCl–SrCl2–H2O belongs to a simple type and the phase diagram consists of two invariant points, five isothermal dissolution curves and four crystallization regions. The solubilities of salts in the above systems were accurately calculated with Pitzer electrolyte solution theory. It was found that the calculated phase diagrams coincided basically with the experimental phase diagrams by evaluated the accuracy through the experimental results. Meanwhile, the applicability of Pitzer parameters selected in this paper was validated.

Prediction of Solubilities in the System Li++Na++K++Cl–+H2O at 25 °C and Industrial Process of Refining Muriate of Potash

A modified Pitzer model at very high ionic strengths is developed in this work for quaternary systems consisting of three uniunivalent salts with a common ion and water. The proposed model is a combination of the extended Debye–Huckel model and the Pitzer model. This model satisfactorily describes the solubilities for the ternary LiCl+NaCl+H2O, LiCl+KCl+H2O, and NaCl+KCl+H2O systems at 25 °C, and it predicts reasonably acceptably the solubilities of the quaternary system LiCl+NaCl+KCl+H2O at 25 °C, when comparing with the experimental results of the literature and those obtained by the original Pitzer model with modified parameters high concentrations. In addition, the proposed model was applied to the process of refining muriate of potash on an industrial plant of a Chilean mining and chemical company.

Mineral solubilities of salts in the three quaternary systems: LiCl–NaCl–MgCl2–H2O, LiCl–KCl–MgCl2–H2O and Li2SO4–K2SO4–MgSO4–H2O at 288.15 K

In this paper, the stable phase equilibria of the quaternary systems LiCl–NaCl–MgCl2–H2O, LiCl–KCl–MgCl2–H2O and Li2SO4–K2SO4–MgSO4–H2O were studied at 288.15 K using an isothermal dissolution equilibrium method and the solubility of each system was measured. Based on experimental solubility data, the dry salt diagrams and the diagrams of water-content vs composition of three quaternary systems were plotted. In addition to the single salts, there is a double salt LiCl·MgCl2·7H2O formation at 288.15 K in quaternary system LiCl–NaCl–MgCl2–H2O. In quaternary system LiCl–KCl–MgCl2–H2O, there are two kinds of double salt LiCl·MgCl2·7H2O and KCl·MgCl2·6H2O. It has been found that LiCl has a strong salting-out effect on both NaCl and KCl, which result in NaCl and KCl having larger crystallization regions in each phase diagram. At 288.15 K, the phase diagram of quaternary system Li2SO4–K2SO4–MgSO4–H2O has phase fields of single salt Li2SO4·H2O, K2SO4 and MgSO4·7H2O, and that of double salts K2SO4·MgSO4·6H2O and Li2SO4·K2SO4. The solubilities of the three quaternary systems at 288.15 K were calculated by using the Pitzer electrolyte solution theory model. The parameters involved but not previously reported were obtained by using the solubility data of ternary subsystems and the method of multivariate linear regression. The results show that the calculated results are in good agreement with the experimental results.

Phase diagram of the quaternary system LiCl+MgCl2+KCl+H2O at 323.15 K

ABSTRAT Solubility isotherms as well as the corresponding solid phases of the quaternary system LiCl+MgCl 2 +KCl+H 2 O and the eutectic points for the ternary systems LiCl+MgCl 2 +H 2 O, LiCl+KCl+H 2 O and MgCl 2 +KCl+H 2 O at 323.15 K have been elaborately determined by an isothermal equilibrium method. Five crystallization fields including two double salts (LiCl·MgCl 2 ·7H 2 O(s) and KCl·MgCl 2 ·6H 2 O(s)), two hydrate salts (MgCl 2 ·6H 2 O(s) and LiCl·H 2 O(s)) and one single salt (KCl(s)) were detected in the quaternary system. The reliability of the experimental results were verified both by testing the phase diagram rule and comparing with the literature data. It was found that all of the results were accordance with the phase diagram rule, and moreover, the excellent agreement between the experimental data and the literature data was also obtained, which indicate that the solubility data obtained in this work are reliable. Based on the quaternary phase diagram, the example was provided for industrial application. The measured phase diagram reported in this work are the essential tool to guide industrial process of extracting Li from the salt lake brine containing MgCl 2 and LiCl using KCl reagent.

Revisiting the thermodynamic properties of the LiCl–NaCl–KCl–H2O quaternary and its sub-ternary systems at 298.15 K

The phase diagram of the quaternary system LiCl–NaCl–KCl–H2O have been predicted with a Pitzer–Simonson–Clegg thermodynamic model by combining the binary and ternary model parameters, which were determined by simulating reliable experimental data. The predicted phase diagram shows a good agreement with the available experiment data from the literature. The other thermodynamic properties (e.g. water activity) of the quaternary and its sub-ternary systems have been investigated by the model and compared with the experimental data in literature. Significant improvements have been made in comparison with assessments.

Solid–liquid equilibrium in the aqueous system containing the chlorides of lithium, rubidium and magnesium at 323 K

The densities, refractive indices and compositions of solutions of electrolyte mixtures in quaternary system LiCl+RbCl+MgCl2+H2O at 323K were determined by isothermal evaporation method. The stereo phase diagram, the metastable phase diagram, the water content diagram, and the diagrams of the physicochemical properties depending on the composition were obtained using the measured data. The metastable phase diagram of this quaternary system contains three invariant points (H1, H2, and H3), seven univariant curves, and five crystallization fields corresponding to single salts lithium chloride monohydrate (LiCl·H2O), rubidium chloride (RbCl), magnesium chloride hexahydrate (MgCl2·6H2O), and two double salts: lithium carnallite (LiCl·MgCl2·7H2O) and rubidium carnallite (RbCl·MgCl2·6H2O). The scope of areas of crystallization of salts is such that RbCl·MgCl2·6H2O>RbCl>LiCl·H2O>MgCl2·6H2O>LiCl·MgCl2·7H2O. The physicochemical properties of the solutions, at equilibrium, change regularly with the change of the concentration of MgCl2.

Metastable Phase Equilibrium in the Quaternary System LiCl + KCl + RbCl + H2O at 348.15 K

The metastable phase equilibrium of the quaternary system LiCl + KCl + RbCl + H2O at 348.15 K was done by using an isothermal evaporation method. The solubilities, densities, and refractive indices of the equilibrated solution were determined experimentally. On the basis of the measured data, the stereo phase diagram, the metastable phase diagram, the water content diagram, and the physicochemical properties versus composition diagrams were constructed. Results show that the quaternary system is of a complex type with the solid solution of potassium chloride and rubidium chloride [(K, Rb)Cl] formed at 348.15 K. The metastable phase diagram consists of two invariant points, five univariant curves, and four crystallization fields corresponding to single salts potassium chloride (KCl), rubidium chloride (RbCl), lithium chloride monohydrate (LiCl·H2O), and a solid solution of potassium and rubidium chloride [(K, Rb)Cl]. Salt RbCl has the largest solubility among the coexisting salts and presents the smallest crystallization field in the phase diagram. The crystallization region of [(K, Rb)Cl] almost occupies the entire phase region, which shows that it is difficult to separate potassium from rubidium in chloride solution by only using evaporation and crystallization methods. This is compared with the metastable phase diagram of the quaternary system at 298.15 K that shows that the crystallization forms have not changed, while the crystallization fields have slightly change. The refractive index of the solution has been calculated using an empirical equation. The maximum absolute deviation between the calculated and experimental data of the refractive index is less than 0.007.

Thermodynamics metastable phase equilibria of aqueous quaternary system LiCl + KCl + RbCl + H2O at 323.15 K

The solubilities and physicochemical properties (densities and refractive indices) in the aqueous quaternary system LiCl+KCl+RbCl+H2O were investigated at 323.15K using an isothermal evaporation method. The stereo phase diagram, the projected diagram, the water content diagram and the physicochemical properties versus composition diagrams were plotted based on the measured data. There are two invariant points, five univariant curves and four crystallization fields corresponding to single salts potassium chloride (KCl), rubidium chloride (RbCl), lithium chloride monohydrate (LiCl·H2O) and a solid solution of potassium and rubidium chloride [(K, Rb)Cl] in the projected diagram. No double salt was formed. Comparisons between the metastable phase diagrams at 298.15K and 323.15K show that the crystallization zones of solid solution [(K, Rb)Cl] decreased at 323.15K, while the crystallization zones of single salts KCl, RbCl, and LiCl·H2O enlarged at 323.15K. The calculated refractive indices using empirical equations have a maximum relative error less than 0.008.

Solid–Liquid Isothermal Evaporation Metastable Phase Equilibria in the Aqueous Quaternary System LiCl + KCl + RbCl + H2O at 298.15 K

The metastable phase equilibria in the aqueous quaternary system LiCl + KCl + RbCl + H2O were investigated at 298.15 K using an isothermal evaporation method. The solubilities and physicochemical properties such as the density and refractive index of the equilibrated solution were determined. On the basis of the experimental results, the stereo phase diagram, the projected phase diagram, the water content diagram, and the physicochemical properties versus composition diagrams were constructed. The projected phase diagram consists of two invariant points, five isothermal univariant curves, and four crystallization fields corresponding to single salts potassium chloride (KCl), rubidium chloride (RbCl), lithium chloride monohydrate (LiCl·H2O), and a solid solution of potassium and rubidium chloride [(K, Rb)Cl]. The two invariant points are cosaturated with three salts, which are LiCl·H2O + RbCl + (K, Rb)Cl and LiCl·H2O + KCl + (K, Rb)Cl, respectively. No double salt was formed. The crystallization region of ...

Metastable Phase Equilibrium of the Reciprocal Quaternary System LiCl + KCl + Li2SO4 + K2SO4 + H2O at 308.15 K

The solubilities and the physicochemical properties including the density, viscosity, refractive index, conductivity, and pH value of the aqueous quaternary system LiCl + KCl + Li2SO4 + K2SO4 + H2O at 308.15 K were determined with the isothermal evaporation method. On the basis of the Jänecke indices, the dry-salt phase diagram, the water-phase diagram, and the diagrams of physicochemical properties were plotted. The dry-salt phase diagram of the system includes three three-salt cosaturation invariant points, seven univariant solubility curves, and five crystallization zones corresponding to potassium sulfate, potassium chloride, the double salt lithium potassium sulfate, lithium sulfate monohydrate, and lithium chloride monohydrate. Single-salt parameters β(0), β(1), and C(φ) for lithium sulfate, potassium sulfate, and potassium chloride, mixed electrolyte parameters θCl,SO4 and ΨK,Cl,SO4, and the Debye−Hükel limiting slope AΦ at 308.15 K were calculated according to the temperature-dependent equations presented in the literature. On the basis of Pitzer's semiempirical equations for a mixed aqueous electrolytic solution, the extended chemical equilibrium model of Harvie was used to fit the single-salt parameters β(0), β(1), and C(φ) for lithium chloride, the mixing two-ion pair parameter of θLi,K, and the mixing triplet-ion parameters of ΨLi,K,Cl and ΨLi,K,SO4 in this system at 308.15 K, which are not reported in the literature. The prediction solubilities for the quaternary system agree well with the experimental values.

Metastable Phase Equilibrium in the Aqueous Quaternary System LiCl + Li2SO4 + Li2B4O7 + H2O at 273 K

The metastable phase equilibrium in the quaternary system LiCl + Li2SO4 + Li2B4O7 + H2O was studied at T = 273 K using an isothermal evaporation method. The solubilities, densities, and pH values were determined experimentally. The crystalloid forms of the solid phase were determined using chemical analysis and an X-ray diffraction method. On the basis of the experimental data, the metastable phase diagram, water diagram, pH value diagram, and density diagram were plotted. The experimental results show that this system is of a simple eutectic type; no double salt or solid solution formed at the investigated temperature. The phase diagram consists of one invariant point, three univariant curves, and three crystallization regions. The three crystallization regions correspond to salts LiCl·H2O, Li2SO4·H2O, and LiBO2·8H2O. The salt LiBO2·8H2O has the largest crystallization field, whereas the salt LiCl·H2O has the smallest crystallization field. The salt LiCl has a strong salting-out effect on the salt Li2SO4·H2O. Comparisons between the metastable and stable phase diagrams at different temperatures show that the crystallization form of lithium borate has changed. In the stable phase diagrams at T = (298 and 288) K, the crystallization form of lithium borate is Li2B4O7·3H2O, while in the metastable phase diagram at T = 273 K, the crystallization form of lithium borate is LiBO2·8H2O.

Phase relationships of lithium, manganese, and chromium (III) chlorides - new lithium ion conducting materials

The phase diagram of the quaternary system LiCl 1b MnCl 2 1b CrCl 3 has been established by high-temperature X-ray diffraction and differential scanning calorimetry (DSC). The mutual solid solubility of the ternary compounds Li 2MnCl 4 and the novel Li 5CrCl 8 is relatively small despite the closely related crystal structures. Li 5CrCl 8 oC 28 undergoes a phase transition to a cubic high-temperature polymorph cF 56 at 750 K and it melts incongruently at 835 K. The electric conductivity of Li 5CrCl 8 measured by impedance spectroscopy methods is 2 × 10 −5 Ω −1 cm −1 at 470 K. That of Li 2MnCl 4 decreases with the increase in chromium content.