Cl–, Br–, SO42

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Solid−Liquid Equilibria in the Quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K Rui-Zhi Cui,†,‡ Shi-Hua Sang,*,†,‡ and Qian Liu†,‡ †

College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, People’s Republic of China ‡ Mineral Resources Chemistry Key Laboratory of Sichuan Higher Education Institutions, Chengdu 610059, People’s Republic of China ABSTRACT: Solid−liquid equilibria in the quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K were measured by the isothermal solution saturation method, and the equilibrium solid phases, solubilities and densities of saturated solutions were determined experimentally. Using the experimental results, the dry salt phase diagrams, water diagrams, and the densities versus composition diagrams were plotted (saturated with Na2SO4 and K2SO4, respectively). The experimental results show that there is solid solution formed in the quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K. The two projected phase diagrams of this system all consist of one univariant curve, two crystallization fields, and have no invariant point. Saturated with the salt Na 2 SO4 , the crystallization forms are the double salt Na2SO4·3K2SO4 (Gla) and the solid solution Na(Cl,Br); the two crystallization forms are Na2SO4·3K2SO4 (Gla) and the solid solution K(Cl,Br) saturated with the salt K2SO4.

1. INTRODUCTION With the mineral resource exhausting, the rational development and utilization of brine resources in China is very urgent. There are not only many salt lakes but also a lot of underground brines in China. Sichuan Basin has very abundant underground brine resources, which have excellent quality. These liquid mineral resources are rare and have good exploitation prospects. Especially in the West of Sichuan Basin, many useful components of brines exceed the demand of comprehensive utilization considerably.1 In addition to NaCl, the brine resources still have potassium, boron, bromine, iodine, and lithium and all of them are indispensable and important materials in the high-tech area.2 The study of multitemperature phase diagram is of practical significance for reasonable exploitation of liquid mineral resources. Aiming at the underground brine in the West of Sichuan Basin, our research group has carried out a series of works, such as the quinary systems Na+, K+//Cl−, SO42−, B4O72−−H2O at 298 and 323 K3,4 and KCl−KBr−K2SO4− K2B4O7−H2O at 323 and 348 K5 and the quaternary systems NaCl−NaBr−Na 2 SO 4 −H 2 O at 323 K, 6 NaCl−NaBr− Na2B4O7−H2O at 348 K,7 and KCl−KBr−K2SO4−H2O at 323, 348, and 373 K.8−10 The quinary system Na+, K+//Cl−, Br−, SO42−−H2O is an important subsystem of the underground brine in Western Sichuan Basin. So far, no report has been found to describe the phase equilibria of this system at 373 K. In this paper, the phase equilibria of quinary system Na+, K+//Cl−, Br−, SO42−−H2O © XXXX American Chemical Society

were studied at 373 K and the solubilities and densities in the system were measured, which will be useful in guiding the extraction of potassium salt and solid solution from the brines.

2. EXPERIMENTAL SECTION 2.1. Reagents and Instruments. Distilled water was obtained from a Millipore water system with an electrical conductivity less than 1 × 10−4 S·m−1 and pH = 6.6, and the water was used to produce the experimental solutions. All chemicals used in this work were of analytical grade. There were NaCl, NaBr, Na2SO4, KCl, KBr, and K2SO4 (Chengdu Kalong Chemical Reagent Factory). An SHA-GW type oil-bath thermostat vibrator made by Jintan Guowang instrument factory with a precision ±0.1 K by using precision thermometer calibration was used for equilibrium measurements. A standard analytical balance (AL104) of 110 g capacity made by the Mettler Toledo Instruments Co., Ltd. with 0.0001 g precision was employed for the determination of the solution densities. 2.2. Experimental Method. The experiments for the quinary system have been done by the method of isothermal solution saturation. According to the equilibrium composition, salts were prepared proportionally. The appropriate calculated quantity of salts was dissolved in distilled water but the salt Received: July 22, 2015 Accepted: December 22, 2015

A

DOI: 10.1021/acs.jced.5b00633 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Solubilities and Densities of Solution in the Quinary System Na+, K+//Cl−, Br−, SO42−−H2O at 373 K and 0.1 MPa (Saturated with Na2SO4)a,b Jänecke index J/mol·100 mol−1 (J(2K+) + J(2Cl−) + J(2Br−) = 100 mol)

composition of liquid phase 100·w(B) no.

w(K+)

w(Na+)

w(Br−)

w(Cl−)

w(SO42−)

J(2K+)

J(2Cl−)

J(2Br−)

J(2Na+)

J(H2O)

equilibrium solid

density ρ/g·cm−3

1A 2 3 4 5 6 7 8F 9 10 11 12 13 14 15

6.48 7.26 7.87 8.81 9.37 9.84 10.22 3.36 4.26 4.44 4.77 5.68 7.78 8.21 8.90

8.90 8.63 8.40 7.31 7.08 6.76 6.62 10.25 10.11 10.09 9.96 9.49 8.43 8.13 7.13

0.00 2.64 5.11 7.12 9.31 13.31 17.06 42.09 39.94 38.48 36.37 34.46 31.24 27.92 24.69

16.78 16.24 15.64 14.94 14.42 12.77 11.35 0.00 1.53 2.31 3.33 4.22 5.84 7.19 7.69

3.82 3.35 2.97 1.58 1.16 0.89 0.76 0.25 0.28 0.29 0.29 0.37 0.48 0.54 0.57

25.92 27.43 28.5 30.63 31.41 32.32 32.88 14.03 16.71 17.22 18.19 20.89 26.37 27.53 30.20

74.08 67.68 62.45 57.27 53.31 46.28 40.26 0.00 6.60 9.85 13.98 17.12 21.83 26.62 28.79

0.00 4.89 9.05 12.10 15.28 21.40 26.86 85.97 76.69 72.93 67.83 61.99 51.80 45.85 41.01

60.59 55.45 51.75 43.21 40.34 37.75 36.23 72.79 67.47 66.50 64.54 59.31 48.57 46.42 41.16

1112.41 1014.85 942.91 908.76 853.23 804.48 753.25 797.91 747.21 746.00 749.07 730.51 679.63 698.89 751.62

NC + NS + Gla Gla + NS + NCB Gla + NS + NCB Gla + NS + NCB Gla + NS + NCB Gla + NS + NCB Gla + NS + NCB Gla + NB + NS Gla + NS + NCB Gla + NS + NCB Gla + NS + NCB Gla + NS + NCB Gla + NS + NCB Gla + NS + NCB Gla + NS + NCB

1.2930 1.3089 1.3192 1.3380 1.3606 1.4000 1.4150 1.7371 1.7117 1.7005 1.6789 1.6385 1.5756 1.5221 1.4930

a Gla, Na2SO4·3K2SO4; NCB, solid solution Na(Cl,Br); NS, Na2SO4; NB, NaBr; NC, NaCl bStandard uncertainties u are u(T) = 0.1 K, u(Na+) = 0.005, u(K+) = 0.030, u(Cl−) = 0.005, u(Br−) = 0.003, u(SO42−) = 0.003, u(ρ) = 0.0002 g·cm−3.

respective ion concentration values are expressed in the mass fraction w(B), and the solution density (ρ) is expressed the equilibrium solution in grams per cubic centimeter. Jänecke index values are expressed the dry salt mole indexes with J(2K+) + J(2Cl−) + J(2Br−) = 100 mol. On the basis of Jänecke index values, the phase diagram saturated with salt Na2SO4 was constructed and were shown in Figure 1. Figure 2 is the X-ray diffraction photograph of the equilibrium solids Na(Cl,Br), Na2SO4, and double salt Na2SO4·3K2SO4 (Gla) in the quinary system (saturated with Na2SO4).

cannot be dissolved thoroughly. The mixtures were put into a sealed glass bottle for the solubility experiments. Then, sealed glass bottles were placed in the oil bath thermostat vibrator (SHA-GW), and the temperature was maintained at (373 ± 0.1) K. The solutions were taken out periodically to analyze the concentration of the solution. When the concentration was unchanged, the sign of equilibrium was reached. The solid−liquid systems in sealed tubes were stirred for 5 days. The purification of the equilibrated solutions needs about 3 days. After equilibrium, the liquid phases were taken out and diluted to volumetric flask for the quantitative analysis of the composition. The densities of the solutions were determined using a pycnometer with an uncertainty of 0.0002 g·cm−3. 2.3. Analytical Methods.11 The potassium ion concentration (K+) was determined using a sodium tetraphenylborate (STPB)−hexadecyl trimethylammonium bromide (CTAB) titration. The SO42− concentration was measured by a method of alizarin red S volumetry. Total quantities of the bromide ion concentration (Br−) and chloride ion concentration (Cl−) were analyzed by silver nitrate volumetry. The bromide ion concentration (Br−) was determined by iodometry, and from the total quantities minus the bromide ion concentration (Br−) we obtained the chloride ion concentration (Cl−). The sodium ion concentration (Na+) was evaluated according to the ion balance.

3. RESULTS AND DISCUSSION The quinary system Na+, K+//Cl−, Br−, SO42−−H2O has five quaternary subsystems but only Na+, K+//Cl−, SO42−−H2O and Na+, K+// Br−, SO42−−H2O systems have invariant points. So in this paper, the projected phase diagram saturated with the salt Na2SO4 and salt K2SO4 of the system were plotted using the experimental data, respectively. 3.1. The Na + , K + //Cl − , Br − , SO 4 2− −H 2 O System (Saturated with Na2SO4). The experimental results of solubilities, densities, and equilibrium solids of the equilibrated solution in the quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K (saturated with Na2SO4) are shown in Table 1. The

Figure 1. Equilibrium phase diagram of the quinary system Na+, K+// Cl−, Br−, SO42−−H2O at 373 K and 0.1 MPa (saturated with Na2SO4).

The quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K is a type of solid solution. There is only one univariant curve and two crystallization fields in this system (saturated with Na2SO4) at 373 K, which is solid solution Na(Cl,Br) and double salt Na2SO4·3K2SO4 (Gla). The double salt Na2SO4· 3K2SO4 (Gla) has the smaller solubility, it means that it can be easily separated from solution, whereas the solid solution B

DOI: 10.1021/acs.jced.5b00633 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Figure 2. X-ray diffraction photograph of a point of the quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K (saturated with Na2SO4) [solid solution Na(Cl,Br) + Na2SO4 + and double salt Na2SO4· 3K2SO4 (Gla)].

Figure 4. Water contents of saturated solutions in quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K and 0.1 MPa (saturated with Na2SO4).

Na(Cl,Br) has the larger solubility. It has only one univariant curve (AF) and has no invariant point. Point A is the invariant point of the quaternary subsystem Na+, K+//Cl−, SO42−−H2O of this quinary system at 373 K, which is saturated with NaCl, Na2SO4, and Gla (Na2SO4· 3K2SO4) [w(K+) = 0.0648, w(Na+) = 0.089, w(Cl−) = 0.1678, w(SO42−) = 0.0382]. Point F is the invariant point of the quaternary subsystem Na+, K+//Br−, SO42−−H2O of this quinary system at 373 K, which is saturated with NaBr, Na2SO4, and Gla (Na2SO4·3K2SO4) [w(K+) = 0.0336, w(Na+) = 0.1025, w(Br−) = 0.4209, w(SO42−) = 0.0025]. In order to reflect the state of each phase point fully, the Na+ content diagram (Figure 3), the water content diagram (Figure

Figure 5. Density-composition relations of the solutions in quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K and 0.1 MPa (saturated with Na2SO4).

3.2. The Na + , K + //Cl − , Br − , SO 4 2− −H 2 O system (saturated with K2SO4). The experimental solubilities of salts and densities of saturated solutions in the quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K (saturated with K2SO4) are presented in Table 2. Using the Jänecke index values (J(2Na+) + J(2Cl−) + J(2Br−) = 100 mol), the dry salt phase diagram (saturated with K2SO4) was plotted in Figure 6 and the X-ray diffraction photograph of a point of this system (saturated with K2SO4) is given in Figure 7. The projected phase diagram saturated with the salt K2SO4 of the system (Figure 6) also has two crystallization regions [solid solution K(Cl,Br) and double salt Na2SO4·3K2SO4 (Gla)], one univariant curve (CD), but no invariant point. Apparently, the areas of the two crystallization regions are very close to each other and the double salt Na2SO4·3K2SO4 (Gla) has the smaller solubility. Points C and D are the invariant points of the quaternary subsystems Na+, K+//Cl−, SO42−−H2O and Na+, K+// Br−, SO42−−H2O of this quinary system at 373 K. At point C

Figure 3. Na+ content diagram of the quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K and 0.1 MPa (saturated with Na2SO4).

4), and the density diagram (Figure 5) of the system were constructed, respectively. It shows that the Na+ content first decreases to a minimum in a J(2Br−) range of 0 up to 26.86 and then increases in a J(2Br−) range of 26.86 up to 85.97. The water contents decrease with the content increases of Br−, and the density values of the system increase with the content increases of Br−. C

DOI: 10.1021/acs.jced.5b00633 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 2. Solubilities and Densities of Solution in the Quinary System Na+, K+//Cl−, Br−, SO42−−H2O at 373 K and 0.1 MPa (Saturated with K2SO4)a,b Jänecke index J/mol·100 mol−1 (J(2Na+) + J(2Cl−) + J(2Br−) = 100 mol)

composition of liquid phase 100·w(B) no.

w(K+)

w(Na+)

w(Br−)

w(Cl−)

w(SO42−)

J(2K+)

J(2Cl−)

J(2Br−)

J(2Na+)

J(H2O)

equilibrium solid

density ρ/g·cm−3

1C 2 3 4 5 6 7 8 9D 10 11 12 13 14 15

16.03 14.81 14.54 12.96 12.02 11.42 10.93 10.74 13.88 13.32 13.15 12.59 11.90 11.07 10.37

2.30 3.38 3.65 4.56 5.05 5.61 5.60 5.49 1.73 2.50 3.04 3.66 3.82 4.56 5.01

0.00 2.64 3.73 7.40 10.54 11.95 15.76 19.42 33.88 31.55 30.52 29.18 26.82 25.66 23.41

17.25 16.72 16.50 14.91 13.50 13.25 11.13 9.24 0.00 1.69 2.82 3.85 4.52 5.40 6.46

1.14 1.01 0.90 0.79 0.68 0.61 0.56 0.47 0.30 0.32 0.35 0.36 0.37 0.37 0.38

69.90 58.12 55.44 46.60 41.95 38.07 37.04 37.01 71.10 61.81 56.63 50.87 48.35 42.16 38.25

82.92 72.37 69.37 59.12 51.99 48.72 41.62 35.10 0.00 8.64 13.39 17.16 20.24 22.69 26.27

0.00 5.08 6.95 13.02 18.01 19.49 26.14 32.74 84.91 71.66 64.31 57.69 53.33 47.81 42.28

17.08 22.55 23.68 27.86 29.99 31.80 32.25 32.16 15.09 19.70 22.29 25.15 26.43 29.50 31.45

1197.27 1046.33 1003.86 926.12 881.77 826.59 823.90 817.14 1115.59 1019.71 936.63 882.80 927.19 874.57 870.67

KC + KS + Gla KS + Gla + KCB KS + Gla + KCB KS + Gla + KCB KS + Gla + KCB KS + Gla + KCB KS + Gla + KCB KS + Gla + KCB KS + KB + Gla KS + Gla + KCB KS + Gla + KCB KS + Gla + KCB KS + Gla + KCB KS + Gla + KCB KS + Gla + KCB

1.3127 1.3221 1.3258 1.3540 1.3831 1.4028 1.4263 1.4545 1.6441 1.6300 1.5981 1.5700 1.5474 1.5455 1.5296

a Gla, Na2SO4·3K2SO4; KB, KBr; KCB, solid solution K(Cl,Br); KS, K2SO4; KC, KCl bStandard uncertainties u are u(T) = 0.1 K, u(Na+) = 0.005, u(K+) = 0.030, u(Cl−) = 0.005, u(Br−) = 0.003, u(SO42−) = 0.003, u(ρ) = 0.0002 g·cm−3.

Figure 7. X-ray diffraction photograph of a point of the quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K (saturated with K2SO4) [solid solution K(Cl,Br) + K2SO4 + and double salt Na2SO4·3K2SO4 (Gla)]. Figure 6. Equilibrium phase diagram of the quinary system Na+, K+// Cl−, Br−, SO42−−H2O at 373 K and 0.1 MPa (saturated with K2SO4).

NaBr−Na2SO4−H2O and KCl−KBr−K2SO4−H2O. This quinary system also consists of nine ternary subsystems: NaCl− KCl−H2O, NaBr−KBr−H2O, Na2SO4−K2SO4−H2O, NaCl− NaBr−H2 O, NaCl−Na 2 SO 4 −H 2 O, NaBr−Na 2 SO 4 −H 2 O, KCl−KBr−H2O, KCl−K2SO4−H2O, and KBr−K2SO4−H2O. The quaternary system Na+, K+//Cl−, SO42−−H2O is a classical salt-water system. Measurements of the phase equilibria in this quaternary system and its four subsystems have been reported at multitemperature and the experimental and calculated data is accurate and reliable through long-term validation. The data presented here in Tables 1 and 2 and the composistion of quaternary invariant solutions (point A and C) are similar to those predicted by the model of Greenberg and Møller.12 This also means that experimental results presented in Tables 1 and 2 are credible. The Br-bearing quaternary system Na+, K+//Br−, SO42−−H2O and its three ternary subsystems NaBr−KBr−H2O, NaBr−Na2SO4−H2O, and KBr− K2SO4−H2O at 373 K have been studied in our previously work.13,14

[w(K+) = 0.1603, w(Na+) = 0.023, w(Cl−) = 0.1725, w(SO42−) = 0.0114], the solution is saturated with KCl, K2SO4, and Gla (Na2SO4·3K2SO4). At point D [w(K+) = 0.1388, w(Na+) = 0.0173, w(Br−) = 0.3388, w(SO42−) = 0.003], the solution is saturated with KBr, K2SO4, and Gla (Na2SO4·3K2SO4). The K+ content diagram, the water content diagram, and the density-compoistion diagram of the quinary system are shown in Figures 8−10. According to the Table 2 and Figure 8, the K+ content of the system initially decreases but finally increases with the content change of J(2Br−). In Figures 9 and 10, the variation trends of J(H2O) and solution density with J(2Br−) have similar changes to the Figures 4 and 5. The quinary system Na+, K+//Cl−, Br−, SO42−−H2O consists of five quaternary subsystems: three reciprocal systems Na+, K+//Cl−, SO42−−H2O, Na+, K+//Br−, SO42−−H2O, and Na+, K+//Cl−, Br−−H2O and two common cation systems NaCl− D

DOI: 10.1021/acs.jced.5b00633 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Figure 8. K+ content diagram of the quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K and 0.1 MPa (saturated with K2SO4).

Figure 10. Density-composition relations of the solutions in quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K and 0.1 MPa (saturated with K2SO4).

solid phases. Solid phase of the salt-water system usually consists of pure salt, complex salt, or hydrated salt but not very often a solid solution. The solid solution can be formed when Cl− and Br− coexist. Radii of Cl− and Br− are close and chemical properties of them are similar, so solid solution can be formed extremely easily. With ternary systems such as NaCl− NaBr−H2O,15−17 KCl−KBr−H2O,15,18,19 and MgCl2−MgBr2− H2O,15,20 the compositions of solid solution all transit continuously from one kind of pure salt to another kind of pure salt, and the research results agree with this paper. However, we have not yet found any systems that can generate limited solid solution when chlorine ion and bromine ion coexist.

4. CONCLUSIONS The phase equilibrium of the quinary system Na+, K+//Cl−, Br−, SO42−−H2O was studied at 373 K by isothermal evaporation method. It was found that the quinary system contains the solid solution. The projected phase diagram saturated with the salt Na2SO4 of the system consists of two fields of crystallization but has one univariant curve and no invariant point. The crystallization forms are the double salt Na2SO4·3K2SO4 (Gla) and the solid solution Na(Cl,Br). The projected phase diagram saturated with the salt K2SO4 of the system also has no invariant point, a univariant curve, and two crystallization regions: double salt Na2SO4·3K2SO4 (Gla) and the solid solution K(Cl,Br).

Figure 9. Water contents of saturated solutions in quinary system Na+, K+//Cl−, Br−, SO42−−H2O at 373 K and 0.1 MPa (saturated with K2SO4).

In the phase diagrams of quaternary systems Na+, K+//Cl−, SO42−−H2O, Na+,K+//Br−,SO42−−H2O, and ternary subsystem Na2SO4−K2SO4−H2O at 373 K, the double salt Na2SO4· 3K2SO4 was found. It was found that quaternary systems Na+, K+//Cl−, Br−−H2O, NaCl−NaBr−Na2SO4−H2O, and KCl− KBr−K2SO4−H2O and ternary systems NaCl−NaBr−H2O and KCl−KBr−H2O contain the solid solution of Na(Cl,Br) or K(Cl,Br). Their solubility diagrams have no invariant point, and each has a univariant curve. The seven phase diagrams of ternary systems NaCl−KCl−H2O, NaBr−KBr−H2O, Na2SO4− K2SO4−H2O, NaCl−Na2SO4−H2O, NaBr−Na2SO4−H2O, KCl−K2SO4−H2O, and KBr−K2SO4−H2O at 373 K were simple cosaturation types, each having an invariant point, two univariant curves, and two crystallization regions. The equilibrium solid phases in the quaternary and ternary systems are all anhydrous solids. Solid solution is a homogeneous crystalline in which one or more kinds of atoms or molecules may be partly substituted for the original atoms and molecules without changing the structure, which means that it can form one or more available

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]; [email protected]. Tel: 13032845233. Funding

This project was supported by open the National Natural Science Foundation of China (Grant 41373062), the Specialized Research Fund (20125122110015) for the Doctoral Program of Higher Education of China, scientific research and innovation team in Universities of Sichuan Provincial Department of Education (15TD0009) and the youth science and E

DOI: 10.1021/acs.jced.5b00633 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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technology innovation team of Sichuan Province, China (2013TD0005). Notes

The authors declare no competing financial interest.

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REFERENCES

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DOI: 10.1021/acs.jced.5b00633 J. Chem. Eng. Data XXXX, XXX, XXX−XXX