Solubilities, Densities, and Refractive Indices in the Salt-Water Ternary

Aug 11, 2015 - Solubilities, densities, and refractive indices for the salt-water ternary system (LiCl + LiBO2 + H2O) at T = 288.15 K and 298.15 K and...
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Solubilities, Densities, and Refractive Indices in the Salt-Water Ternary System (LiCl + LiBO2 + H2O) at T = 288.15 K and 298.15 K and p = 0.1 MPa Daolin Gao,†,‡ Yafei Guo,†,‡,¶ Xiaoping Yu,‡ Shiqiang Wang,‡ and Tianlong Deng*,‡ †

Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, P.R. China Tianjin Key Laboratory of Marine Resources and Chemistry, College of Chemical Engineering and Material Sciences, Tianjin University of Science and Technology, Tianjin 300457, P.R. China ¶ College of Chemistry and Material Sciences, Northwest University, Xi’an 710069, P.R. China ‡

ABSTRACT: Solubilities, densities, and refractive indices for the salt-water ternary system (LiCl + LiBO2 + H2O) at T = 288.15 K and 298.15 K and p = 0.1 MPa were determined using the isothermal dissolution equilibrium method. According to the experimental data at two temperatures, the phase diagrams and the diagrams of densities and refractive indices versus lithium chloride composition in the solution were plotted, respectively. In the phase diagrams at 288.15 K and 298.15 K, in all there are three crystallizing regions corresponding to lithium metaborate octahydrate (LiBO2·8H2O, Lb8), lithium metaborate dihydrate (LiBO2·2H2O, Lb2), and lithium chloride monohydrate (LiCl·H2O, Lc1), three univariant curves and two invariant points corresponding to (Lb8 + Lb2) and (Lb2 + Lc1). It was found that there are two kinds of hydrates for lithium metaborates (Lb8 and Lb2) formed at both termperatures, and the hydrate for lithium metaborate belongs to hydrate type II. Neither double salts nor solid solutions were found. A comparison of the phase diagrams at two temperatures shows that the areas of the crystalline regions of Lb8 and Lc1 are decreased and that of Lb2 is increased with increasing temperature. The density and refractive index in the ternary system at two temperatures change regularly with the increasing LiCl mass fraction in the solution to reach the maximum values in the ternary-invariant-point. The correlation equations of density and refractive index were used, and the calculated results agree well with the experimental data.

1. INTRODUCTION Lithium and its metal compounds are extensively used in ceramic, glass, coolant, lubricant, atomic energy, metallurgy, pharmacy, aerospace, military industry, lithium-ion battery, and so on.1−3 The demand of lithium resource has increased gradually with the development of the modern industry. Because of the high cost for lithium recovery from solid ores such as triphane, lepidolite, petalite, amblygonite, and zinn waldite, it is essential to exploit the lithium resources from salt lake brines in the world.4 In China’s western region, there are abundant salt lakes with high concentrations of lithium and boron.5,6 The composition of those salt lake brines belongs to the complex sevencomponent salt-water system (Na+ + K+ + Li+ + Mg2+ + Cl− + SO42− + borate + H2O).7,8 For those valuable brine resources, a comprehensive development and utilization has not been reported because of a lack of guidance of relative brine system phase diagrams.9 To effectively separate lithium-containing mixed salts, some lithium-containing systems (Li+ + Na+ + K+ + Cl− + B4O72− + H2O), (Li+ + K+ + Cl− + B4O72− + H2O), (Li+ + Na+ + K+ + B4O72− + H2O), (Li+ + Na+ + Mg2+ + B4O72− + H2O), (Li+ + K+ + Mg2+ + B4O72− + H2O), (Li+ + SO42− + BO2− + H2O), (Li+ + Na+ + SO42− + H2O), (Li+ + Mg2+ + SO42− + H2O) at © XXXX American Chemical Society

the temperature range from 273.15 K to 323.15 K have been investigated.10−16 However, the solubilities of the salt-water system (LiCl + LiBO2 + H2O) at 288.15 K and 298.15 K are not reported in the literature, and it is essential for the mixed salts containing lithium and boron. In this paper, the solubilities, densities, and refractive indices of the salt-water system (LiCl + LiBO2 + H2O) at 288.15 K and 298.15 K were presented, and the densities and refractive indices were also predicted with the empirical equations.

2. EXPERIMENTAL SECTION 2.1. Reagents and Apparatus. The chemicals recrystallized before use are shown in Table 1. Doubly deionized water (DDW, pH = 6.60 and κ = 1·10−4 S·m−1 at 298.15 K) was used. Magnetically stirred thermostatic water bath (HXC-500−6A, Beijing Fortune Joy Science Technology Co. Ltd., China) was used, and the temperature precision was controlled within ± 0.1 K. Density was measured using a DMA 4500 M high precision vibrating-tube densimeter (Anton Paar, Austria), and Received: February 8, 2015 Accepted: August 3, 2015

A

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Table 1. Chemicals Used code

grade

initial puritya

purified method

final puritya

Lb8b

A.R.d

0.99

recrystallization

0.995

Lcc

A.R.d

0.99

recrystallization

0.998

Table 2. Solubility of LiCl for the Binary System (LiCl + H2O) at T = 298.15 and p = 0.1 MPaa analytical method gravimetric method for BO2− titration for Cl−

salt LiCl LiCl LiCl LiCl

a

Purity in mass fraction. bLb8, lithium metaborate octahydrate, LiBO2·8H2O. cLc, lithium chloride anhydrous, LiCl. dA.R., either from the Sinopharm Chemical Reagent Co. Ltd. or Tianjin Chemical Reagent Manufactory.

the uncertainty is less than ± 0.00001 g·cm−3. Refractive index was measured by an Abbe refractometer (WAY-2S, Shanghai Yuguang Instrument Co. Ltd., China) with an uncertainty of ± 0.0001 connected with a thermostatic water-circulator bath (high precision thermoregulation, cc-k12, German Huber Company, Germany) to control the measured temperature. All physicochemical parameters of the aqueous solution in this study were measured in triplicate. 2.2. Experimental Method. The method of isothermal dissolution equilibrium was adopted, which was described by Deng et al.9 Generally, the synthetic series brines for the ternary system were mixed by adding different ratios of the crystallized solid salts of lithium sulfate and lithium metaborate octahydrate in series-sealed hard polyethylene bottles, and then the bottles were put into the magnetically stirred thermostatic water bath at a stationary temperature of either (288.15 ± 0.1) K or (298.15 ± 0.1) K with 120 r/min stirring speed to accelerate the solubility equilibrium. After about a week, the supernatants of the liquid phases in each bottle were taken out at intervals for chemical analysis. When the content of each component in the liquid phase did not change, those results demonstrated that the phase equilibrium in each bottle was achieved. After the synthetic brines reached equilibria, a series of liquid phase and solid phase samples were taken out for chemical analysis, and each solid phase sample was identified immediately with the BX51-type polarizing microscope (Olympus, Japan) combined with the X-ray diffractometer (MSAL XD-3, Beijing Purkinje General Instrument Co. Ltd., China). 2.3. Analytical Method. The Cl− concentration in the liquid and solid phases was determined by titration with a standard uncertainty u(Cl−) = 0.003 in mass fraction as described previously.15 The BO2− concentration was analyzed using a gravimetric method with sodium hydroxide standard solution in the presence of a mixture of indicators of methyl red plus phenolphthalein and the excessive mannitol conditions, and the standard uncertainty u(BO2−) was 0.0005 in mass fraction.17 The lithium ion concentration was calculated by difference and evaluated occasionally using inductively coupled plasma optical emission spectrometry (Prodigy, Leman Corporation, America). The compositions of LiCl and LiBO2 in mass fraction were then calculated corresponding to the analytical results of the Cl− and BO2− concentrations in the liquid phase, and the standard uncertainties u(w) for LiCl and LiBO2 are 0.0036 and 0.0025, respectively.

solubility in water 100 wB (from lit.) 44.89 45.77 45.85 45.50 45.65 45.72 45.80 45.80 45.87 45.87 45.90

ref 18 19 20 21

solubility in water 100 wB (expt, this work)b 45.81

equilibrium solid phasec Lc1 Lc1 Lc1 Lc1

a Standard uncertainties for u(T) = 0.1 K and u(p) = 0.005 MPa. bu(w) for LiCl, 0.0035. cLc1, LiCl·H2O.

system (LiCl + H2O) from literature, which was either from the ThermoLit18,19 or from handbooks20,21 is shown in Table 2. When we evaluted those data, the single-salt solubility of LiCl (100 wB) at 298.15 K equaled 45.78 ± 0.10 with a 95 % level confidence. This result indicates our experimental procedure and analysis are reliable. 3.1. Solubilities of the System (LiCl + LiBO2 + H2O) at 288.15 K and 298.15 K. Solubilities of the ternary system (LiCl + LiBO2 + H2O) at two temperatures are shown in Table 3. On the basis of the solubility data in Table 3, the phase diagram of this system (LiCl + LiBO2 + H2O) at both temperatures are drawn in Figure 1. For the ternary system (LiCl + LiBO2 + H2O) at 288.15 K in Figure 1a, there are three crystalline zones corresponding to lithium metaborate octahydrate (LiBO2·8H2O, Lb8), lithium metaborate dihydrate (LiBO2·2H2O, Lb2), and lithium chloride monohydrate (LiCl·H2O, Lc1), three univariant solubility curves of AE1, E1E2, and E2B, and two invariant points corresponding to E1 (Lb8 + Lb2) and E2 (Lb2 + Lc1). Points A and B stand for the boundary binary salt-water systems (LiBO2 + H2O) and (LiCl + H2O), and the solubilities of LiBO2 and LiCl with mass percentage are 1.87 and 44.24, respectively. The compositions of LiCl, LiBO2 at the invariant point E1 and E2 for the ternary system are 16.00, 1.48, and 43.80, 4.10 in mass percentage, respectively. It was found for the first time that two different kinds of hydrates of lithium metaborates, that is, LiBO2·8H2O and LiBO2·2H2O were formed, which is not reported in the literature. The identified results of X-ray diffraction analysis for the coexisting minerals in the invariant points E1 and E2 at 288.15 K are presented in Figure 2. Figure 2 panels a and b show that the invariant points E1 and E2 are (Lb8 + Lb2, i.e., LiB(OH)4 + LiB(OH)4·6H2O) and (Lb2 + Lc1, i.e., LiB(OH)4 + LiCl·H2O), respectively, where, LiB(OH)4 and LiB(OH)4·6H2O express the structural formula of LiBO2·2H2O and LiBO2·8H2O, respectively. It is worth noting that a small amount of LiBO2 coexisted in the invariant points E1 (Lb2 + Lb8) in Figure 2a and E2 (Lb2 + Lc1) in Figure 2b may be formed due to the hydrolysis of LiBO2·2H2O in the process of transfer or grinding for sample preparation of XRD analysis. Therefore, the coexisted minerals in the invariant points E1 and E2 were confirmed combined with an immersion observation of a polarizing microscope. As to the phase diagram of this system at 298.15 K in Figure 1b, there are also three crystalline areas corresponding to lithium metaborate octahydrate (Lb8), lithium metaborate dihydrate (Lb2), and lithium chloride monohydrate (Lc1), two invariant points corresponding to E1′ (Lb8 + Lb2) and E2′ (Lb2 + Lc1), and three univariant solubility curves of A′E1′, E1′E2′ and E2′B′.

3. RESULTS AND DISCUSSION Although there are no data reported for the binary system LiBO2 + H2O at both temperatures, the solubility data for the binary system LiCl + H2O at 298.15 K numbered almost a dozen and these are shown in Table 2. To verify the accuracy of the experimental data, a comparsion between our experimental solubility LiCl in water and the solubility of LiCl in the binary B

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Table 3. Solubilities, Densities, and Refractive Indices for the Ternary System (LiCl + LiBO2 + H2O) at T = 288.15 and 298.15 K and p = 0.1 MPaa liquid phase composition 100 wBb no.

LiCl

1, A 2 3 4 5 6, E1 7 8 9 10 11 12 13 14 15 16 17 18, E2 19 20, B

0.00 3.41 6.65 10.35 13.41 16.00 16.05 19.93 21.81 23.62 26.72 29.25 32.46 35.67 38.44 40.11 41.71 43.80 44.02 44.24

21, 22 23 24 25, 26 27 28 29 30 31 32 33 34 35 36 37 38 39, 40 41,

0.00 3.86 6.81 9.77 12.08 13.03 15.51 18.10 20.75 22.53 24.36 26.62 28.59 29.95 31.64 33.56 36.19 38.44 44.06 45.33 45.81

A′

E1′

E2′ B′

LiBO2

H2O

ρ g·cm−3c

nD

T = 288.15 K; p = 0.1 MPae 1. 87 98.13 1.02317 1.3410 1.09 95.50 1.02903 1.3441 0.96 92.39 1.05025 1.3512 1.02 88.63 1.06400 1.3572 1.00 85.59 1.08479 1.3641 1.48 82.52 1.10701 1.3714 1.11 82.84 1.10533 1.3711 1.09 78.74 1.12258 1.3772 1.26 76.93 1.13777 1.3828 1.19 75.19 1.14702 1.3862 1.09 72.19 1.16361 1.3893 1.20 69.55 1.17585 1.3953 1.16 66.38 1.18839 1.4018 1.34 62.99 1.19636 1.4063 1.40 60.47 1.22530 1.4118 1.55 58.34 1.25632 1.4171 1.38 56.91 1.26011 1.4240 4.10 52.10 1.32584 1.4337 0.28 55.70 1.28642 1.4326 0.00 55.76 1.28522 1.4324 T = 298.15 K; p = 0.1 MPa 3.36 96.64 1.03563 1.3452 2.16 93.97 1.04056 1.3474 1.85 91.33 1.05175 1.3536 1.91 88.32 1.07221 1.3606 2.51 85.41 1.09705 1.3672 1.87 85.10 1.09111 1.3669 1.87 82.62 1.10568 1.3719 1.58 80.32 1.12242 1.3778 1.53 77.72 1.14120 1.3848 1.59 75.89 1.15709 1.3905 1.61 74.03 1.16087 1.3918 1.57 71.81 1.17416 1.3960 1.66 69.75 1.18822 1.4010 1.62 68.43 1.19616 1.4040 1.68 66.68 1.21295 1.4090 1.84 64.60 1.22362 1.4121 3.02 60.79 1.25280 1.4209 3.13 58.43 1.29089 1.4419 5.31 51.10 1.35353 1.4479 1.14 53.53 1.30791 1.4379 0.00 54.19 1.29795 1.4367

equilibrium solid phased Lb8 Lb8 Lb8 Lb8 Lb8 Lb8 + Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 + Lc1 Lc1 Lc1 Lb8 Lb8 Lb8 Lb8 Lb8 + Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 Lb2 + Lc1 Lc1 Lc1

Figure 1. Phase diagram of the ternary system (LiCl + LiBO2 + H2O). ●, experimental points at 288.15 K; ○, experimental points at 298.15 K; Lb8, LiBO2·8H2O; Lb2, LiBO2·2H2O; Lc1, LiCl·H2O.

coexisting at 298.15 K, and similar identified results for the coexisting minerals in the invariant points E1′ and E2′ by X-ray diffraction analysis were also obtained (data not shown). Figure 3 is an area chart between 288.15 K and 298.15 K. It shows that the area of the crystalline regions of Lb8 and Lc1 decreases while the area of Lb2 increases obviously with increasing temperature. The solubilities of the two binary subsystems of LiBO2 and LiCl at 288.15 K and 298.15 K with mass percentage are 1.87 vs 3.36 for LiBO2 and 44.24 vs 45.81 for LiCl, respectively, while the compositions of LiCl, LiBO2 at the invariant points of the ternary system are E1 (16.00, 1.48) vs E1′ (12.08, 2.51) and E2 (43.80, 4.10) vs E2′(44.06, 5.31). This new information on phase change and phase transformation can be adapted for separating and purifying lithium chloride from the concentrated brines. 3.2. Density and Refractive Index at Two Temperatures. On the basis of density and refractive index data at 288.15 K and 298.15 K in Table 3, the diagrams of the density (refractive index) versus lithium chloride concentration in the solution were plotted in Figure 4. Figure 4a is the diagram of density versus lithium chloride concentration in solution at 288.15 K and 298.15 K. Figure 4a shows that densities in the crystalline regions of Lb8 and Lb2 (curve AE1E2 and A′E1′E2′) in the ternary system increase significantly with the increasing of LiCl concentration to reach

a

Standard uncertainties u(w) for LiCl and LiBO2 are 0.0036 and 0.0025 in mass fraction, respectively. u(x) for ρ and nD are 0.5 mg·cm−3 and 0.001, respectively. bwB, mass fraction. cρ and nD stand for density and refractive index. dLb8, LiBO2·8H2O; Lb2, LiBO2·2H2O; Lc1; LiCl·H2O. eu(T) = 0.1 K and u(p) = 0.005 MPa.

The solubilities of the binary single-salt systems (LiBO2 + H2O) and (LiCl + H2O) at 298.15 K in points A′ and B′ are 3.36 and 45.81 in mass percentage, respectively. The compositions of LiCl, LiBO2 at the invariant point E1′ and E2′ for the ternary system are 12.08, 2.51 and 44.06, 5.31 in mass percentage, respectively. Two kinds of lithium metaborate salts solid phases (Lb8 and Lb2) were also discovered C

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Figure 2. X-ray diffractive diagram for the coexisting minerals in the invariant points. (a) coexisting solid phases of LiBO2·2H2O and LiBO2·8H2O in the invariant point E1; (b) coexisting solid phases of LiBO2·2H2O and LiCl·H2O in the invariant point E2.

288.15 K and 298.15 K decrease sharply with increasing LiCl concentration. Generally, density in the ternary system at 288.15 K is relatively lower than that at 298.15 K at the same concentration of LiCl in Figure 4a. Figure 4b presents the relationship between refractive index versus LiCl concentration, and it was found that the solution refractive index from point A to point E2 at 288.15 K and point A′ to point E2′ at 298.15 K in the solubility curves of Lb8 and Lb2 in the ternary system increases obviously with increasing LiCl concentration, and the solution refractive index from point E2 to point B at 288.15 K and from point E2′ to point B′ at 298.15 K in the solubility curves of Lc1 decreases slowly with the increasing LiCl concentration. Also Figure 4b shows that the refractive index at 288.15 K is totally lower than that at 298.15 K at the same concentration of LiCl in the ternary system. 3.3. Calculated Density and Refractive Index. The following correlation equations between density (refractive index) and the composition of electrolyte solution were used.22

Figure 3. Comparison of the phase diagram for the system (LiCl + LiBO2 + H2O) at two temperatures: ●, at 288.15 K; ○, at 298.15 K; Lb8, LiBO2·8H2O; Lb2, LiBO2·2H2O; Lc1, LiCl·H2O.

the maximum values of 1.32584 and 1.35353 g·cm−3 at the invariant points E2 and E2′ at 288.15 K and 298.15 K, respectively, and densities in the crystalline regions of Lc1 both at D

ln

d = d0

ln

nD = n D0

∑ Ai ·wi ∑ Bi ·wi

(1)

(2) DOI: 10.1021/acs.jced.5b00121 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 4. Comparison between the Calculated (calcd) and Experimental (expt) Results for Densities and Refractive Indices in the Ternary System (LiCl + LiBO2 + H2O)a ρ/(g·cm−3)

Figure 4. Comparison of density and refractive index versus LiCl concentration in the system (LiCl + LiBO2 + H2O) at two temperatures: (a) density vs LiCl concentration; (b) refractive index vs LiCl concentration.

where d and d0 express the density values of the solution and the pure water at the same temperature, respectively. Accordingly, nD and nD0 present the refractive index values in the electrolyte solution and the pure water at the same temperature, respectively. The d0 and nD0 of pure water are 0.99909 g·cm−3 and 1.33339 at 288.15 K, and 0.99704 g·cm−3 and 1.33250 at 298.15 K, respectively.23 wi is the ith component in the electrolyte solution, which also is expressed in mass fraction. Ai and Bi are the constants of density and refractive index for the Ith component in the electrolyte solution, respectively. Ai and Bi at each temperature can be obtained from the density or refractive index versus composition of the two binary subsystems, that is, LiBO2 + H2O and LiCl + H2O at the same temperature, respectively. The uncertainties of these coefficients were controlled within ± 0.3 %. Density constants Ai of LiCl and LiBO2 are 0.0055992 and 0.0048961 at 288.15 K, and 0.0053130 and 0.014105 at 298.15 K, respectively. Refractive index constants Bi of LiCl and LiBO2 are 0.0013401 and 0.0051556 at 288.15 K, and 0.0016436 and 0.0028232 at 298.15 K, respectively. The calculated and experimental values for density and refractive index in this system (LiCl + LiBO2 + H2O) at two temperatures are shown in Table 4, and the results indicated that the calculated values are in good agreement with the experimental results.

no.

expt value

1, A 2 3 4 5 6, E1 7 8 9 10 11 12 13 14 15 16 17 18, E2 19 20, B

1.02317 1.02903 1.05025 1.06400 1.08479 1.10701 1.10533 1.12258 1.13777 1.14702 1.16361 1.17585 1.18839 1.19636 1.22530 1.25632 1.26011 1.32584 1.28642 1.28522

1, A′ 2 3 4 5, E1′ 6 7 8 9 10 11 12 13 14 15 16 17 18 19, E2′ 20 21, B′

1.03563 1.04056 1.05175 1.07221 1.09705 1.09111 1.10568 1.12242 1.14120 1.15709 1.16087 1.17416 1.18822 1.19616 1.21295 1.22362 1.25280 1.29089 1.35353 1.30791 1.29795

calcd value

nD relative error

expt value

T = 288.15 K; p = 0.1 MPab 1.00828 −0.014 1.3410 1.02380 −0.0051 1.3441 1.04188 −0.0080 1.3512 1.06400 0.0000 1.3572 1.08228 −0.0023 1.3641 1.10067 −0.0057 1.3714 1.09899 −0.0057 1.3711 1.12302 0.00039 1.3772 1.13585 −0.0017 1.3828 1.14702 0.0000 1.3862 1.16653 0.0025 1.3893 1.18381 0.0068 1.3953 1.20505 0.014 1.4018 1.22798 0.026 1.4063 1.24754 0.018 1.4118 1.26019 0.0031 1.4171 1.27047 0.0082 1.4240 1.30266 −0.018 1.4337 1.28010 −0.0049 1.4326 1.27992 −0.0041 1.4324 T = 298.15 K; p = 0.1 MPa 1.04543 0.0095 1.3452 1.04464 0.0039 1.3474 1.05882 0.0067 1.3536 1.07775 0.0052 1.3606 1.09961 0.0023 1.3672 1.09767 0.0060 1.3669 1.11346 0.0070 1.3719 1.12649 0.0036 1.3778 1.14316 0.0017 1.3848 1.15572 −0.0012 1.3905 1.16822 0.0063 1.3918 1.18299 0.0075 1.3960 1.19770 0.0080 1.4010 1.20657 0.0087 1.4040 1.21919 0.0051 1.4090 1.23498 0.0093 1.4121 1.27065 0.0062 1.4209 1.28882 −0.0016 1.4419 1.36441 0.0080 1.4479 1.31115 0.0025 1.4379 1.29795 0.0000 1.4367

calcd value

relative error

1.34631 1.34705 1.35200 1.35914 1.36459 1.37272 1.37020 1.37720 1.38188 1.38474 1.38979 1.39530 1.40103 1.40837 1.41405 1.41831 1.42011 1.44420 1.41646 1.41483

0.0040 0.0022 0.00059 0.0014 0.00036 0.0010 −0.00066 0.0000 −0.00066 −0.0011 0.00035 0.0000 −0.00055 0.0015 0.0016 0.00085 −0.0027 0.0073 −0.011 −0.012

1.34520 1.34918 1.35455 1.36139 1.36889 1.36855 1.37414 1.37887 1.38470 1.38899 1.39325 1.39828 1.40317 1.40615 1.41030 1.41540 1.42627 1.43200 1.45421 1.44019 1.43670

0.0000 0.0013 0.00070 0.00058 0.0012 0.0012 0.0016 0.00078 −0.000080 −0.0011 0.0010 0.0016 0.0015 0.0015 0.00092 0.0023 0.0038 −0.0069 0.0044 0.0016 0.0000

ρ and nD stand for density and refractive index, and standard uncertainties u(x) for ρ and nD are 0.5 mg·cm−3 and 0.001, respectively. bu(T) = 0.1 K and u(p) = 0.005 MPa. a

equilibrium method. The phase diagram and the diagram of density (refractive index) versus LiCl concentration in the solution at two temperatures are drawn. In all there are two invariant points for (LiBO2·8H2O + LiBO2·2H2O) and (LiBO2· 2H2O + LiCl·H2O), three univariant curves of (AE1 + E1E2 + E2B) at 288.15 K and (A′E1′ + E1′E2′ + E2′B′) at 298.15 K, three crystallizing zones corresponding to LiBO2·8H2O, LiBO2· 2H2O and LiCl·H2O, respectively. For the ternary system at both temperatures, two kinds of lithium metaborate hydrates (LiBO2·8H2O and LiBO2·2H2O) are found for the first time. A comparison shows that the area of crystallization regions of

4. CONCLUSION The solubilities, densities and refractive indices of the ternary system (LiCl + LiBO2 + H2O) at 288.15 K and 298.15 K were studied experimentally using the isothermal dissolution E

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LiBO2·8H2O and LiCl·H2O decrease and that of LiBO2·2H2O increases with increasing temperature. Density and refractive index in the ternary system at two temperatures show regular changes with increasing LiCl concentration. The calculated values of densities and refractive indices by the relative correlation equations for this system at two temperatures are in good agreement with the experimental results.

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(15) Guo, Y. F.; Gao, D. L.; Yin, H. J.; Shen, D. L.; Wang, S. Q.; Deng, T. L. Metastable phase equilibria in the ternary system (Na2SO4 + Li2SO4 + H2O) at 308.15 and 348.15 K. Fluid Phase Equilib. 2013, 358, 56−59. (16) Li, D. C.; Wang, S. Q. Metastable equilibria of ternary system (Li2SO4 + MgSO4 + H2O) at 273.15 K. Chin. Chem. Eng. 2014, 42, 37−44. (17) Qinghai Institute of Salt Lakes of CAS, Analytical Methods of Brines and Salts, 2nd ed.; Chinese Science Press: Beijing, 1988. (18) Al-Sahhaf, T. A.; Kapetanovic, E. Salt Effects of Lithium Chloride, Sodium Bromide, or Potassium Iodide on Liquid-Liquid Equilibrium in the System Water + 1-Butanol at 298 K and 101.33 kPa. J. Chem. Eng. Data 1997, 42 (1), 74−77. (19) Farelo, F.; Fernandes, C.; Avelino, A. Solubilities for Six Ternary Systems: NaCl + NH4Cl + H2O, KCl + NH4Cl + H2O, NaCl + LiCl + H2O, KCl+ LiCl + H2O, NaCl + AlCl3 + H2O, and KCl + AlCl3 + H2O at T = (298 to 333) K and 101 kPa. J. Chem. Eng. Data 2005, 50, 1470−1477. (20) Seidell, A. Solubilities of Inorganic and Metal Organic Compounds; Van Nostrand Co., Inc.: New York, 1940. (21) Silcock, H. L. Solubilities of Inorganic and Organic Compounds; Pergamon Press: Oxford, 1979; pp 732−779. (22) Deng, T. L.; Meng, L. Z.; Sun, B. Metastable phase equilibria of the reciprocal quaternary system containing sodium, potassium, chloride, and borate ions at 308.15 K. J. Chem. Eng. Data 2008, 53, 704−709. (23) Speight, J. M. Lange’s Handbook of Chemistry, 16th ed.; McGraw-Hill: New York, 2005.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel/Fax: 86-22-60602963. Funding

Financial support from the National Natural Science Foundation of China (21276194, 21306136 and U1407113), the Training Program for Yangtze Scholars and Innovative Research Team in University of China (2013−373), the Innovative Research Team of Tianjin Municipal Education Commission (TD12−5004), and the Fund of KLSLRC (KLSLRC-KF-13-HX-2) is acknowledged. Notes

The authors declare no competing financial interest.

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DOI: 10.1021/acs.jced.5b00121 J. Chem. Eng. Data XXXX, XXX, XXX−XXX