J. Chem.

Thermodynamics 138 (2019) 127–139

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

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
Rui-Zhi Cui a, Wu Li a,b,⇑, Ya-Ping Dong a,c, Zhen Nie d
a
Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, PR China
b
Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province, Xining 810008, PR China
c
Qinghai Engineering and Technology Research Center of Comprehensive Utilization of Salt Lake Resources, Xining 810008, PR China
d
Institute of Mineral Resources, CAGS, MLR Key Laboratory of Saline Lake Resources and Environments, Beijing 100037, China

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, the stable phase equilibria of the quaternary systems LiCl–NaCl–MgCl2–H2O, LiCl–KCl–
Received 14 June 2018 MgCl2–H2O and Li2SO4–K2SO4–MgSO4–H2O were studied at 288.15 K using an isothermal dissolution
Received in revised form 4 December 2018 equilibrium method and the solubility of each system was measured. Based on experimental solubility
Accepted 6 December 2018
data, the dry salt diagrams and the diagrams of water-content vs composition of three quaternary sys-
Available online 7 December 2018
tems 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
Keywords:
are two kinds of double salt LiCl
MgCl2
7H2O and KCl
MgCl2
6H2O. It has been found that LiCl has a strong
Brine
Phase diagram
salting-out effect on both NaCl and KCl, which result in NaCl and KCl having larger crystallization regions
Solubility in each phase diagram. At 288.15 K, the phase diagram of quaternary system Li2SO4–K2SO4–MgSO4–H2O
Lithium salt has phase fields of single salt Li2SO4
H2O, K2SO4 and MgSO4
7H2O, and that of double salts
Pitzer’s electrolyte solution theory 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 previ-
ously reported were obtained by using the solubility data of ternary subsystems and the method of mul-
tivariate linear regression. The results show that the calculated results are in good agreement with the
experimental results.
Ó 2018 Published by Elsevier Ltd.

1. Introduction lithium resources has been gaining popularity. According to some

estimates, approximately 59% of lithium occurs in the brine of salt
Salt lake brine is a complex system of natural water and salts. lakes; extracting lithium from brine is attractive as the process fea-
Research into phase equilibria can help predict the crystallization tures accompanying low energy consumption and costs. The devel-
and precipitation of salt minerals and the law of mineral symbiosis, opment of lithium resources in the brine of salt lakes has become
so as to reveal the evolution of brine and the formation of salt min- a primary focus in the development and utilization of lithium
erals which reflect the geochemical equilibrium behaviour of ele- resources. The Qinghai-Tibet Plateau in China and the Andean Pla-
ments in brine and minerals in salt beds. Furthermore, it is also teau in South America are the two regions with the highest concen-
the comprehensive application foundation of salt lake brine. trations of lithium-rich salt lakes and the largest lithium reserves [1].
Lithium is the lightest metal element and its electrochemical In China, for the brine of calcium-rich chloride type oil-gas
activity is very strong. Lithium metal and its compounds are widely fields in the Nanyi Mountain area of Qaidam Basin, Qinghai Pro-
used in battery, new energy, smelting, medicine, glass, ceramics vince, a series of metastable and stable phase equilibria studies
and other fields. With the increasingly prominent global resources of a Li–Na–K–Ca–Sr–Cl–B4O7–H2O system were carried out [2,3].
and environmental issues, the development and utilization of For the sulphate salt lake brine in Lop Nur, Xinjiang, the phase
equilibrium of a Na–K–Mg–Cl–SO4–NO3–H2O six-component sys-
tem at 298 K was studied [4,5]. For the carbonate type and borate
⇑ Corresponding author at: Key Laboratory of Comprehensive and Highly Efficient
Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy
type salt lake brine in Zabuye, Tibet, the metastable and stable
of Sciences, Xining 810008, PR China. phase equilibrium of the sub-systems of a Li–Na–K–Cl–CO3–SO4–
E-mail address: liwu@isl.ac.cn (W. Li). B4O7–H2O system at 273 K, 288.15 K and 298 K were investigated

https://doi.org/10.1016/j.jct.2018.12.011
0021-9614/Ó 2018 Published by Elsevier Ltd.
128 R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139

[6,7]. For the underground brine of the Sichuan Basin in China, the constructed; the single salt parameters, mixing parameters and
metastable and stable phase equilibria of Li–K–Rb–Mg–Cl–B4O7– the Gibbs standard formation energy of lithium salts in this six-
H2O multicomponent system at 298 K, 323 K and 348 K were stud- component system were also obtained [12,13].
ied with a primary focus on Pingluo underground brine enriched Considering the composition of salt lake brine in Qinghai-Tibet
with potassium, rubidium and borate [8,9]. For the underground Plateau and the local average temperature of approximately
brine in Western Sichuan enriched with borate, potassium and 288.15 K during the summer, the phase equilibria of three quater-
bromine, the stable phase equilibrium relationships of a series of nary systems at 288.15 K has been studied in this paper. It is signif-
sub-systems of Na–K–Cl–Br–SO4–B4O7–H2O system at icant for the utilization of this type of salt lake resources, the
298 K398 K were studied [10,11]. The salt lake area of the formulation of comprehensive utilization scheme of brine, and
Qinghai-Tibet Plateau has an average elevation of more than the revelation of the geochemical behaviour of salt lake brine.
3000 m. The salt lakes are abundant in quantity, type and mineral
resources. For the sulphate-type salt lake brine of Qaidam Basin,
Qinghai province, the brine is mainly composed of Li+, Na+, Mg2+, 2. Experimental
K+, Cl–, SO2–4 , and borate. Since the exploitation of salt-lake
resources cannot be separated from the study of multi- Both the water used for chemical analysis and experimental
temperature phase equilibrium, a series of phase equilibrium preparation was ultra-pure (resistivity greater than 18 MX
cm).
studies of water and salt systems at 298 K have been completed The reagents used in the preparation of the samples were given
focusing on the multi-component brine system. Based on the Pitzer in Table 1. They were analytical reagents (AR) and were used with-
ion interaction theory and thermodynamic data (solubility, activity out further purification. The purities were provided by suppliers
coefficient and permeability coefficient), the thermodynamic and were checked by chemical titration.
model of a Li–Na–K–Mg–Cl–SO4–H2O system at 298.15 K was All the systems studied in this paper were quaternary systems.
The isothermal dissolution equilibrium method was used to study
the stable phase equilibrium. From the invariant point of the ternary
Table 1
Example Sample Table. subsystems of the quaternion system, every new salt was added in
each rigid grinding glass bottle at a proportional interval of the first
Chemical Name Source Initial Purification
dense and then sparse. The glass bottles were sealed, placed in a con-
Mole Method
Fraction stant temperature shaking water bath and shaken until the samples
Purity had reached equilibrium. The equilibrium liquid phase was analysed
Lithium chloride Shanghai Macklin 0.99 a
None by chemical analysis. Among them, Li+ was analysed by ICP-OES
Biochemical Co., Ltd method; K+ by back titration with sodium tetraphenylborate; Mg2+
by EDTA volumetric method (masking Li+ with 1:9n-butanol and
a
Sodium chloride Shanghai Macklin 0.995 None
Biochemical Co., Ltd
a
anhydrous ethanol if Li+ exists); Cl was analysed by the Hg(NO3)2
Potassium chloride Shanghai Macklin 0.995 None
Biochemical Co., Ltd
volumetric method; SO2 4 was analysed using a gravimetric method;

Magnesium chloride Shanghai Macklin 0.99 a

None Na+ was determined by subtraction.
hexahydrate Biochemical Co., Ltd
a
Lithium sulfate Shanghai Macklin 0.995 None
monohydrate Biochemical Co., Ltd 3. Results and discussion
a
Potassium sulfate Shanghai Macklin 0.995 None
Biochemical Co., Ltd
a 3.1. Quaternary system LiCl–NaCl–MgCl2–H2O
Magnesium sulfate Shanghai Macklin 0.995 None
Biochemical Co., Ltd
a
The results of determination of the solubility of the quaternary
Provided by suppliers.
system LiCl–NaCl–MgCl2–H2O at 288.15 K are shown in Table 2; w

Table 2
Solubilities of solution in the quaternary system LiCl–NaCl–MgCl2–H2O at T = 288.15 K and p = 0.096 MPa.a

No. Composition of liquid phase Jӓnecke index J/(g per 100 g) Equilibrium solids
100
w(B) J(LiCl) + J(NaCl) + J(MgCl2) = 100
LiCl NaCl MgCl2 LiCl NaCl MgCl2 H2O
1, A 0.00 0.44 34.53 0.00 1.26 98.74 185.98 NC + MC6
2 1.27 0.41 33.85 3.58 1.15 95.27 181.48 NC + MC6
3 3.83 0.40 31.75 10.65 1.10 88.24 177.97 NC + MC6
4 6.68 0.37 28.94 18.55 1.02 80.43 177.90 NC + MC6
5 12.99 0.34 22.80 35.96 0.93 63.11 176.85 NC + MC6
6 15.13 0.33 19.98 42.69 0.92 56.39 182.16 NC + MC6
7 19.80 0.31 17.58 52.53 0.83 46.64 165.34 NC + MC6
8 25.08 0.32 14.12 63.48 0.80 35.73 153.08 NC + MC6
9 28.78 0.30 11.32 71.23 0.74 28.02 147.47 NC + LMC7
10 34.25 0.30 7.20 82.04 0.72 17.24 139.52 NC + LMC7
11 36.31 0.31 5.96 85.27 0.72 14.01 134.86 NC + LMC7
12, B 43.09 0.37 0.00 99.15 0.85 0.00 130.10 NC + LC2
13 42.25 0.33 0.69 97.63 0.77 1.60 131.10 NC + LC2
14 42.04 0.33 1.34 96.19 0.74 3.07 128.79 NC + LC2
15 41.24 0.31 4.46 89.64 0.66 9.70 117.35 NC + LC2
16, C 27.41 0.00 14.06 66.10 0.00 33.90 141.14 MC6 + LMC7
17, F1 27.75 0.30 13.68 66.51 0.71 32.78 139.67 MC6 + LMC7 + NC
18, D 39.90 0.00 5.29 88.29 0.00 11.71 121.29 LC2 + LMC7
19 39.70 0.16 5.09 88.32 0.35 11.33 122.47 LC2 + LMC7
20, F2 39.95 0.31 4.92 88.43 0.69 10.88 121.33 LC2 + LMC7 + NC
a
w(B) means mass fraction of component B in saturated solution. Standard uncertainties u are u(T) = 0.02 K, ur(p) = 0.05, ur[w(LiCl)] = 0.005, ur[w(NaCl)] = 0.005, ur[w
(MgCl2)] = 0.003. Abbreviations: LC2 = LiCl
2H2O, NC = NaCl, MC6 = MgCl2
6H2O, LMC7 = LiCl
MgCl2
7H2O.
 R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139 129

(B) indicates the mass fraction of the component B; J(B) indicates 230
the Jänecke index of the component B (calculated on the basis of
100 g total dry salt). The calculation method of J(B) is as follows:

wðSÞ ¼ wðLiClÞ þ wðNaClÞ þ wðMgCl2 Þ 200

wðBÞ A
JðBÞ ¼  100
wðsÞ
170
B = LiCl, NaCl, MgCl2 or H2O

J(H2O)
As shown in Table 2, the dry salt diagram and local magnifica-
tion diagram of the system were drawn with J(LiCl) as the abscissa
and J(NaCl) as the ordinate (Fig. 1). At the same time, in order to 140 C
F1 B
illustrate the water content change as a function of the system
composition, the corresponding diagram of water-content vs com-
D
position was shown in Fig. 2. As can be seen in Fig. 1, the three 110 F2

NaCl
100
80
0 20 40 60 80 100
J(LiCl)
80
Fig. 2. The diagram of water-content vs composition of quaternary system LiCl–
NaCl–MgCl2–H2O at T = 288.15 K.

60
J(NaCl)

sides of the triangle are the three three-subsystems of the quater-

NaCl nary system, namely: LiCl–NaCl–H2O, LiCl–MgCl2–H2O, NaCl–
40
MgCl2–H2O. The stable phase diagram of the quaternary system
at 288.15 K consists of two invariant points, five isothermal disso-
lution equilibrium curves and four crystalline fields (anhydrous
20 salt NaCl, hydrated salts LiCl
2H2O and MgCl2
6H2O, and double
MgCl2·6H2O LiCl·MgCl2·7H2O LiCl·2H2O salt LiCl
MgCl2
7H2O). The crystallization field decreases in order
A of NaCl > MgCl2
6H2O > LiCl
MgCl2
7H2O > LiCl
2H2O, and the solu-
F1 F2 B bility of the corresponding salt increases sequentially. The five
0 LiCl
MgCl2 0 isothermal dissolution equilibrium curves correspond to AF1,
20 40 60 C 80 D 100
F1F2, F2B, CF1 and DF2, respectively. The invariant point F1 is com-
J(LiCl)
posed of NaCl + MgCl2
6H2O + LiCl
MgCl2
7H2O, with w(LiCl)
(a) = 0.2775, w(NaCl) = 0.0030, w(MgCl2) = 0.1368; and the invariant
point F2 is composed of NaCl + LiCl
2H2O + LiCl
MgCl2
7H2O, with
w(LiCl) = 0.3995, w(NaCl) = 0.0031, w(MgCl2) = 0.0492.
10
In combination with Table 2 and Fig. 2, it can be seen that the
water content of quaternary system LiCl–NaCl–MgCl2–H2O
changes regularly with the change of LiCl concentration at
8 288.15 K. Regarding isothermal dissolution equilibrium curves
AF1 and F1F2, the value of J(H2O) decreases from 185.98 to
121.33 with the increase of J(LiCl), and increases gradually on the
curve F2B, while on the other two curves, CF1 and DF2, the water
6
content remains basically unchanged.
J(NaCl)

NaCl
3.2. Quaternary system LiCl–KCl–MgCl2–H2O
4
Table 3 shows the solubility of each component in the quater-
nary system LiCl–KCl–MgCl2–H2O at 288.15 K. According to the
2 LiCl·MgCl2·7H2O LiCl·2H2O data in Table 3, the corresponding phase diagram and local magni-
A fication diagram were drawn in Fig. 3. Fig. 3 and Table 3 both show
F1 F2 B that at 288.15 K the quaternary system contains double salts
MgCl2·6H2O (KCl
MgCl2
6H2O and LiCl
MgCl2
7H2O) and three invariant points
0 LiCl
MgCl2 0 20 40 60 C 80 D 100
(F3, F4 and F5). Among them, the liquid phase of invariant point
F3 is composed of w(LiCl) = 0.2739, w(KCl) = 0.0022, w(MgCl2)
J(LiCl)
= 0.1390, and the corresponding equilibrium solid phases are
MgCl2
6H2O, LiCl
MgCl2
7H2O and KCl
MgCl2
6H2O; the liquid
(b)
phase of invariant point F4 is composed of w(LiCl) = 0.3989, w
Fig. 1. (a) Stable phase diagram of the quaternary system LiCl–NaCl–MgCl2–H2O at (KCl) = 0.0050, w(MgCl2) = 0.0366, and the corresponding equilib-
T = 288.15 K; (b) Partially enlarged diagram of (a). rium solid phases are LiCl
2H2O, LiCl
MgCl2
7H2O and KCl
MgCl2-
130 R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139

Table 3
a.
Solubilities of solution in the quaternary system LiCl–KCl–MgCl2–H2O at T = 288.15 K and p = 0.096 MPa

No. Composition of liquid phase Jӓnecke index J/(g per 100 g) Equilibrium solids
100
w(B) J(LiCl) + J(NaCl) + J(MgCl2) = 100
LiCl KCl MgCl2 LiCl KCl MgCl2 H2O
1, G 0.00 2.85 26.68 0.00 9.65 90.35 238.60 KC + KMC6
2 1.85 2.77 25.63 6.13 9.15 84.72 230.54 KC + KMC6
3 5.07 2.65 22.89 16.56 8.65 74.79 226.75 KC + KMC6
4 9.66 2.54 18.95 31.02 8.16 60.82 220.99 KC + KMC6
5 17.78 2.34 12.26 54.92 7.22 37.86 208.92 KC + KMC6
6 25.89 2.16 6.91 74.06 6.19 19.76 186.07 KC + KMC6
7 33.87 1.99 3.28 86.53 5.08 8.38 155.47 KC + KMC6
8 39.77 1.92 2.11 90.80 4.38 4.82 128.29 KC + KMC6
9, E 0.00 0.17 35.22 0.00 0.49 99.51 182.50 MC6 + KMC6
10 3.52 0.19 33.20 9.53 0.51 89.96 171.01 MC6 + KMC6
11 6.66 0.20 30.17 17.99 0.53 81.48 170.12 MC6 + KMC6
12 12.44 0.24 24.24 33.70 0.65 65.65 170.85 MC6 + KMC6
13 20.23 0.20 18.78 51.60 0.52 47.88 154.99 MC6 + KMC6
14 29.02 0.28 12.22 69.90 0.67 29.43 140.85 MC6 + KMC6
15 34.96 0.49 8.06 80.35 1.12 18.53 129.87 MC6 + KMC6
16, C 27.41 0.00 14.06 66.10 0.00 33.90 141.14 MC6 + LMC7
17, F3 27.39 0.22 13.90 66.00 0.52 33.48 140.94 MC6 + LMC7 + KMC6
18, D 39.90 0.00 5.29 88.29 0.00 11.71 121.29 LMC7 + LC2
19, F4 39.89 0.50 3.66 90.55 1.14 8.31 126.98 LMC7 + LC2 + KMC6
20, H 43.39 1.98 0.00 95.64 4.36 0.00 120.40 KC + LC2
21 43.14 1.91 0.43 94.84 4.20 0.95 119.86 KC + LC2
22 42.93 1.89 0.87 93.98 4.13 1.90 118.88 KC + LC2
23, F5 42.03 1.80 1.39 92.94 3.99 3.07 121.15 KC + LC2 + KMC6
a
w(B) means mass fraction of component B in saturated solution. Standard uncertainties u are u(T) = 0.02 K, ur(p) = 0.05, ur[w(LiCl)] = 0.005, ur[w(KCl)] = 0.005, ur[w
(MgCl2)] = 0.003. Abbreviations: LC2 = LiCl
2H2O, KC = KCl, MC6 = MgCl2
6H2O, LMC7 = LiCl
MgCl2
7H2O, KMC6 = KCl
MgCl2
6H2O.

6H2O; the liquid phase of invariant point F5 is composed of w polarity of the solution, decreases the dielectric coefficient of the
(LiCl) = 0.4203, w(KCl) = 0.0180, w(MgCl2) = 0.0139, and the corre- solvent, increases the ionic electric field intensity and enhances
sponding equilibrium solid phases are KCl, LiCl
MgCl2
7H2O and the interaction between the ions and the solvent water molecules.
KCl
MgCl2
6H2O. More solvent water molecules are attracted to reduce the amount
Seven isothermal dissolution equilibrium curves are EF3, CF3, of water that can dissolve other substances, resulting in a salting
DF4, F3F4, F4F5, F5H, GF5, respectively. The five crystallization out. In addition, there is a great similarity between LiCl and H2O.
fields are KCl, LiCl
2H2O, MgCl2
6H2O, LiCl
MgCl2
7H2O and According to the similarity-intermiscibility theory, LiCl has a high
KCl
MgCl2
6H2O, respectively. The crystallization field of KCl is solubility in water, which leads to an increase in the polarity of
the largest, which accounts for more than 90% of the total area of the solution and is conducive to salting out [15,16].
the phase diagram of the system, indicating that the solubility of
KCl is the smallest while the solubility of LiCl
2H2O is the largest 3.3. Quaternary system Li2SO4–K2SO4–MgSO4–H2O
and has the smallest crystallization field.
In order to fully reflect the existence of a certain point in the The solubility of the simple quaternary system Li2SO4–K2SO4–
system, the diagram of the water-content vs composition was MgSO4–H2O at 288.15 K is shown in Table 4. The corresponding
drawn according to its dry salt composition (Fig. 4). It can be seen phase diagram (Fig. 6) and the corresponding diagram of water-
from this diagram that the water content maximizes at point G. At content vs composition (Fig. 7) were drawn according to their liq-
the isothermal dissolution equilibrium curves GF5, EF3 and F3F4, uid composition.
the water content in the solution clearly decreases with an Figure 6 shows that there is no solid solution formation at
increase of the concentration of LiCl. 288.15 K though double salts Li2SO4
K2SO4 and K2SO4
MgSO4
6H2O
Comparing the stable phase diagrams at 288.15 K and 298.15 K are formed. The stable phase diagram is composed of five phase
[14] (Fig. 5), we can see that the phase diagrams are similar in regions, seven isothermal dissolution equilibrium curves and three
shape and contain the same number of invariant points, isothermal quaternary invariant points. The equilibrium liquid phase and
dissolution equilibrium curves and equilibrium phase fields. The three equilibrium solid phases corresponding to the invariant
phase field of single salt KCl decreases slightly with an increase points (F6, F7 and F8) are described below:
in temperature while the size of the other phase fields remains F6: K2SO4 + Li2SO4
K2SO4 + K2SO4
MgSO4
6H2O, with w(Li2SO4)
unchanged. Lithium chloride hydrate contains two crystal water = 0.1013, w(K2SO4) = 0.1109 and w(MgSO4) = 0.0925; F7: MgSO4-
molecules (LiCl
2H2O) at 288.15 K, which is dehydrated to LiCl
H2-
6H2O + Li2SO4
K2SO4 + K2SO4
MgSO4
6H2O, with w(Li2SO4)
O at 298.15 K. = 0.1105, w(K2SO4) = 0.0409 and w(MgSO4) = 0.1770; F8: Li2SO4-
The experimental results show that LiCl has a strong salting-out
H2O + Li2SO4
K2SO4 + MgSO4
6H2O, with w(Li2SO4) = 0.1616, w
effect on NaCl and KCl in the LiCl–NaCl–MgCl2–H2O and LiCl–KCl– (K2SO4) = 0.0247 and w(MgSO4) = 0.1524.
MgCl2–H2O quaternary systems. The solvent water molecules in Figure 7 and Table 3 show that an increase of J(Li2SO4) gradually
the aqueous solution do not change and the strength of the inter- decreases the water content of the system on the isothermal disso-
action depends on the electric field intensity of ions while the elec- lution equilibrium curves JF7, IF6, F6, F7 and F7F8, minimizing at
tric field intensity depends on the potential value of the ions. As 195.26 K at the invariant point F8, and it increases gradually on
the larger ionic potential increases, so does the electric field inten- curves F6L, F8M and F8K.
sity of the ions. The ionic potential of Li+ surpasses that of most The stability of the quaternary system Li2SO4–K2SO4–MgSO4–
cations. The introduction of Li+ into the solution increases the H2O at 273.15 [17] and 298.15 K [18] has been reported.
 R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139 131

KCl 300
100

260
80
G

220
60

J(H2O)
J(KCl)

E
180
40
KCl

20 140 C
F3
D F5
G LiCl·2H2O H
F5 F4
E KCl·MgCl2·6H2O F3 H
F4 100
0
MgCl2 0 20 40 60 C 80 D 100LiCl 0 20 40 60 80 100
MgCl2·6H2O J(LiCl) LiCl·MgCl2·7H 2O J(LiCl)

(a) Fig. 4. The diagram of water-content vs composition of quaternary system LiCl–

KCl–MgCl2–H2O at T = 288.15 K.

10
G
the system (Fig. 9), it can be seen that at 288.15 K, the distribution
KCl of each crystallization region is similar. The phase region of single
8
salt K2SO4 is the largest, while the phase region of single salt Li2-
SO4
H2O is the smallest.
The three quaternary systems studied in this paper include
6 eight ternary subsystems, which are NaCl–MgCl2–H2O, KCl–
J(KCl)

MgCl2–H2O, LiCl–NaCl–H2O, LiCl–KCl–H2O, LiCl–MgCl2–H2O, Li2-

SO4–MgSO4–H2O and K2SO4–MgSO4–H2O [20–33]. A series of stud-
KCl·MgCl2·6H2O H
4 ies have been carried out on the stable phase equilibrium of these
F5
eight ternary subsystems at different temperatures and relevant
experimental data and phase diagrams have been obtained. Among
them, the ternary system NaCl–MgCl2–H2O showed an equilibrium
LiCl·2H2O

2 solid phase NaCl
2H2O at 253 K and 263 K, and the phase diagram
LiCl·MgCl2·7H2O F4
contained three crystallization regions (NaCl
2H2O, NaCl and
F3 MgCl2
6H2O). At 273 K, 288 K and 298 K, the system became a sim-
E MgCl2·6H2O
0 ple one, and only two crystallization regions (NaCl and MgCl2
6H2-
MgCl2 0 20 40 60 C 80 D 100LiCl O) were present in the phase diagram. The ternary system KCl–
J(LiCl) MgCl2–H2O had a double salt KCl
MgCl2
6H2O formation in the
(273–373) K range, while the shape of each phase diagram was
(b) similar and only the size of the phase fields changed. Both LiCl–
Fig. 3. (a) Stable phase diagram of the quaternary system LiCl–KCl–MgCl2–H2O at
NaCl–H2O system (273–363 K) and LiCl–KCl–H2O system (273–
T = 288.15 K; (b) Partially enlarged diagram of (a). 348) K are of the type I hydrate, which means that the phase dia-
grams all contained two univariant curves, an invariant point and
two crystallization regions and only the size of the phase region
changed. With the temperature range from 273 K to 348 K, the
For comparison purposes, it is shown in Fig. 8 along with data mea- double salt LiCl
MgCl2
7H2O was found in ternary system LiCl–
sured at 288.15 K. The diagrams show that the phase diagrams at MgCl2–H2O. In the three systems, lithium chloride contained two
three temperatures are all composed of single salts Li2SO4
H2O, crystalline waters at 273 K and 288 K. As the temperature
K2SO4, MgSO4
6H2O, and double salts Li2SO4
K2SO4, K2SO4
MgSO4
increased, the structure lost one molecule of crystalline water to
6H2O. It can be seen that as the temperature increases, the crystal- form a LiCl
H2O phase field within the 298–363 K range. At
lization regions of K2SO4, MgSO4
6H2O and K2SO4
MgSO4
6H2O 288 K, the ternary system Li2SO4–MgSO4–H2O is of the type I
obviously decrease; while that of Li2SO4
H2O and Li2SO4
K2SO4 hydrate, which means that the phase diagram contain two univari-
clearly increase, indicating that K2SO4, MgSO4
6H2O and ant curves, an invariant point and two crystallization regions
K2SO4
MgSO4
6H2O are easily crystallized with the increase of (Li2SO4
H2O and MgSO4
6H2O). At 288 K and 298 K, the phase dia-
temperature. gram of the K2SO4–MgSO4–H2O system contains three phase
Compared with the metastable phase diagram at the same tem- regions. They are corresponding to K2SO4, K2SO4
MgSO4
6H2O
perature (288.15 K) [19], the crystallization fields of each salt do and MgSO4
6H2O, respectively. Table 5 is the comparison between
not change. From the stable and metastable phase diagrams of the experimental data on the invariant points of the ternary sub-
132 R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139

KCl 4. Prediction of solubility

100
A large number of electrolyte solutions exist in chemical indus-
try, hydrometallurgy, environmental biochemistry, salt lake
80 exploitation and geochemistry. Thermodynamic properties such
as density, activity, osmotic coefficient and partial molar volume
are necessary for product development and design. Since then,
many physical chemists have derived various models based on sta-
60
tistical mechanics, classical theory and established semi-empirical
J(KCl)

models. Among the many models, the Pitzer electrolyte solution

model equation is widely used because of its simple form and com-
40 pact structure; in addition, it can be applied to high concentration
solutions [35]. The Pitzer model has been successfully applied in
KCl
the solubility calculations of multicomponent systems, such as
the solubility in stable and metastable phase equilibria, and the
20
calculation of material reaction ratios in chemical processes. A ser-
G LiCl·2H2O ies of calculations of brine evaporation can also be carried out to
F5
E KCl·MgCl2·6H2O F3 H predict the changing trend of brine evaporation.
F4
0 LiCl
MgCl2 0 20 40 60 C 80 D 100
4.1. Parameterizations
MgCl2·6H2O J(LiCl) LiCl·MgCl2·7H2O

For the four quaternary systems LiCl–NaCl–MgCl2–H2O, LiCl–

(a)
KCl–MgCl2–H2O and Li2SO4–K2SO4–MgSO4–H2O at 288.15 K in this
paper, the interaction parameter WK,Mg,SO4 of ternary mixed ions at
10
G 288.15 K has been reported [36], but their corresponding binary
mixed ion interaction parameter hK,Mg is inconsistent with those
calculated in this paper. Therefore, in this paper, hK,Mg = 0 [37],
KCl
8 and the solubility data of ternary subsystems are used to fit these
two parameters. In addition, WLi,K,Cl and WLi,Na,Cl, two parameters
which have not been reported at 288.15 K are fitted. The other bin-
6 ary mixed ions interaction parameters h, ternary mixed ions inter-
action parameters W, the single salt parameters b(0), b(1), b(2) and
J(KCl)

C/, and the solubility equilibrium constants (lnK) required for the
F5
KCl·MgCl2·6H2O H calculation are all found in the literature[25,32,38–43]. Tables 6,
4 7 and 8 listed the involved single salt parameters, mixed ion inter-
action parameters and dissolution equilibrium constants,
respectively.
LiCl·2H2O

2
LiCl·MgCl2·7H2O F4 4.2. Calculated solubility
F3
E MgCl2·6H2O Based on the parameters in Tables 6-8, the solubility in four
0
MgCl2 0 20 40 60 C 80 D 100LiCl quaternary systems at 288.15 K were predicted by using the Pitzer
J(LiCl) electrolyte solution theoretical model. By comparing the predicted
results with the experimental results, the corresponding compar-
(b) ison phase diagrams were drawn and shown in Figs. 10–12 (where
the real line is the experimental phase diagram and the dashed line
Fig. 5. (a) Comparison of stable phase diagram of the quaternary system LiCl–KCl– is the calculated phase diagram). In order to compare the predicted
MgCl2–H2O at T = (288.15 and 298.15) K; (b) Partially enlarged diagram of (a); ——, equilibrium solubility data with the experimental data, a contrast
288.15 K;




, 298.15 K.
was made between the experimental and calculated values of the
invariant points (shown in Table 9 and expressed uniformly by
mass fraction). As can be seen from Table 9 and Figs. 10–12, the
systems reported in previous studies and our experimental data. calculated results of equilibrium liquid composition corresponding
Our experimental results at 288 K are consistent with those previ- to each boundary point and invariant point agree with experimen-
ously reported within the allowed error range. And our experimen- tal results, and the positions of each boundary point and invariant
tal data is consistent with the tendency comparing with the point in the calculated phase diagrams are similar to those of the
literature data. experimental phase diagrams. Furthermore, the size of the
Li+ has strong hydration ability and can form multiple hydrates. phase regions is basically same, which indicates that the predicted
The dehydration of LiCl2
5H2O initially takes place at 205.95 K to solubility values are in good agreement with the experimental
form LiCl2
3H2O while additional single water molecule losses values.
takes place at 253.65 K and 293.05 K to form LiCl2
2H2O and LiCl2- A thermodynamic model has been used to simulate and calcu-

H2O, respectively. At 369 K, dehydration is complete and anhy- late the phase equilibrium of water and salt system theoretically;
drous LiCl forms [34]. The results of the current study show that this not only verifies experimental data, but also complements
the crystalline form of LiCl is LiCl2
2H2O at 288.15 K, so the number and perfects experimental data. It can also be used to calculate
of the crystalline water molecules is consistent with previous and simulate the production process. Therefore, the theoretical
studies. simulation and calculation of the phase equilibria of the brine sys-
Table 4
Solubilities of solution in the quaternary system Li2SO4–K2SO4–MgSO4–H2O at T = 288.15 K and p = 0.096 MPa.a

No. Composition of liquid phase Jӓnecke index J/(g per 100 g) Equilibrium solids
100
w(B) J(Li2SO4) + J(K2SO4) + J(MgSO4) = 100
Li2SO4 K2SO4 MgSO4 Li2SO4 K2SO4 MgSO4 H2O

R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139

1, I 0.00 10.81 11.20 0.00 49.12 50.88 354.46 KS + KMS6
2 1.25 10.90 10.91 5.40 47.26 47.34 333.73 KS + KMS6
3 2.54 10.94 10.53 10.60 45.56 43.84 316.54 KS + KMS6
4 3.84 10.79 9.91 15.65 43.96 40.39 307.46 KS + KMS6
5 6.76 11.01 9.59 24.72 40.23 35.05 265.37 KS + KMS6
6, J 0.00 4.93 23.48 0.00 17.35 82.65 252.08 KMS6 + MS7
7 2.99 4.79 21.44 10.23 16.39 73.38 242.31 KMS6 + MS7
8 5.16 4.64 20.19 17.19 15.47 67.33 233.48 KMS6 + MS7
9 6.68 4.58 19.02 22.06 15.12 62.82 230.23 KMS6 + MS7
10, F7 11.05 4.09 17.70 33.65 12.46 53.90 204.48 KMS6 + MS7 + LKS
11 13.61 2.97 15.52 42.39 9.25 48.36 211.49 LKS + MS7
12, M 16.37 0.00 15.14 51.96 0.00 48.04 217.35 LS1 + MS7
13 16.25 1.58 15.41 48.88 4.76 46.36 200.82 LS1 + MS7
14, F8 16.16 2.47 15.24 47.71 7.28 45.01 195.26 LKS + LS1 + MS7
15, K 26.03 2.38 0.00 91.62 8.38 0.00 252.05 LKS + LS1
16 24.41 2.40 2.72 82.67 8.13 9.21 238.60 LKS + LS1
17 21.58 2.37 7.25 69.17 7.60 23.23 220.50 LKS + LS1
18 18.98 2.32 11.09 58.58 7.17 34.25 208.72 LKS + LS1
19, L 12.12 8.76 0.00 58.03 41.97 0.00 378.90 LKS + KS
20 11.60 9.76 2.60 48.41 40.73 10.86 317.17 LKS + KS
21 11.52 10.60 5.06 42.38 39.01 18.61 267.87 LKS + KS
22, F6 10.13 11.09 9.25 33.24 36.40 30.35 228.28 KMS6 + LKS + KS
23 10.54 6.11 14.45 33.88 19.65 46.47 221.59 KMS6 + LKS
a
w(B) means mass fraction of component B in saturated solution. Standard uncertainties u are u(T) = 0.02 K, ur(p) = 0.05, ur[w(Li2SO4)] = 0.005, ur[w(K2SO4)] = 0.005, ur[w(MgSO4)] = 0.003. Abbreviations: LS1 = Li2SO4
H2O,
KS = K2SO4, MS7 = MgSO4
7H2O, KMS6 = K2SO4
MgSO4
6H2O, LKS: Li2SO4
K2SO4.

133
134 R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139

K2SO4 K2SO4
100 100

80 80

60 K2SO4 60 K2SO4
J(K2SO4)

J(K2SO4)
I I
L L
40 F6 40
F6
Li2SO4·K2SO4
20 20 Li2SO4·K2SO4
J J F7
F7 F8 F8
K K
MgSO4·7H2O Li2SO4·H2O MgSO4·7H2O Li2SO4·H2O
0 Li SO 0
MgSO4 0 M 60 MgSO4 0 M 60 Li SO
20 40 80 100 2 4 20 40 80 100 2 4
J(Li2SO4) J(Li2SO4)

Fig. 6. Stable phase diagram of the quaternary system Li2SO4–K2SO4–MgSO4–H2O Fig. 8. Comparison of stable phase diagram of the quaternary system Li2SO4–
at T = 288.15 K. K2SO4–MgSO4–H2O at T = (273.15, 288.15 and 298.15) K; —
—, 273.15 K; ——,
288.15 K;




, 298.15 K.

400 K2SO4
100
L

I
350
80

300
60 K2SO4
J(K2SO4)
J(H2O)

I
J K
250 L
40 F6
F6
M
200 Li2SO4·K2SO4
F7 20
F8 J
F7 F8
K
MgSO4·7H2O Li2SO4·H2O
150 0
0 20 40 60 80 100 MgSO4 0 M 60 Li SO
20 40 80 100 2 4
J(Li2SO4) J(Li2SO4)

Fig. 7. The diagram of water-content vs composition of quaternary system Li2SO4– Fig. 9. Comparison of stable and metastable phase diagram of the quaternary
K2SO4–MgSO4–H2O at T = 288.15 K. system Li2SO4–K2SO4–MgSO4–H2O at T = 288.15 K; =
=, metastable phase diagram;
——, stable phase diagram.

tems are of practical significance for the development of under- paper as well as the calculation program. It also lays a foundation
ground brine resources and the formulation of technological routes for further theoretical simulations and calculations for multi-
and processes. The study of thermodynamic properties of lithium- temperature phase equilibria in salt lake brine systems and
containing water salt systems is of great significance not only to reduces the need for tedious (and possibly expensive) measure-
the theory of electrolyte aqueous solution, but also to the develop- ments of experimental phase equilibria.
ment and utilization of lithium resources in salt lakes. In this
paper, the simulation and calculation of the phase equilibrium of 5. Conclusions
the Li-rich salt lake brine systems in the Qinghai-Tibet Plateau
have been carried out. These results show that the calculated phase Phase diagrams are important tools used to study and solve
diagrams are in good agreement with the experimental phase dia- phase equilibria problems. It can understand the order of salt
grams and show the reliability of the parameters utilized in this dissolution or precipitation, the composition change of the solu-
Table 5
The comparison data of invariant points for the ternary subsystems between this work and literature at different temperatures.

Ternary system NaCl–MgCl2–H2O Ternary system LiCl–NaCl–H2O

T Composition of liquid phase Equilibrium solids T Composition of liquid phase Equilibrium solids
100w(NaCl) 100w(MgCl2) 100w(LiCl) 100w(NaCl)
253 K [20] 3.30 23.30 NC2 + NC 273 K [22] 41.30 0.20 LC2 + NC
1.80 26.10 NC + MC12 288 Ka 43.09 0.37
263 K [20] 7.80 17.50 NC2 + NC 298 K [23] 45.54 0.19 LC1 + NC
0.30 32.90 NC + MC12 298 K [22] 45.58 0.11
273 K [20] 0.30 34.40 NC + MC6 313 K [23] 47.13 0.18
288 Ka 0.44 34.53 323 K [23] 48.14 0.24
298 K [21] 0.48 35.68 323 K [22] 48.41 0.33

R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139

Ternary system LiCl–MgCl2–H2O 333 K [23] 49.96 0.32
T Composition of liquid phase Equilibriumsolids 363 K [22] 54.67 0.75
100w(LiCl) 100w(MgCl2) Ternary system LiCl–KCl–H2O
273 K [24] 32.91 8.13 LC2 + LMC7 T Composition of liquid phase Equilibrium solids
30.06 10.43 LMC7 + MC6 100w(LiCl) 100w(KCl)
288 K[25] 39.82 5.29 LC2 + LMC7 273 K [22] 40.23 1.73 LC2 + KC
27.14 14.34 LMC7 + MC6 273 K [24] 43.87 2.12
288 Ka 39.90 5.29 LC2 + LMC7 288 Ka 43.39 1.98
27.41 14.06 LMC7 + MC6 298 K [22] 44.69 3.50 LC1 + KC
298 K [26] 40.11 5.73 LC1 + LMC7 298 K [23] 43.95 3.40
28.27 14.31 LMC7 + MC6 303 K [23] 44.26 3.80
298 K [27] 39.1 6.43 LC1 + LMC7 313 K [23] 44.93 4.59
28.34 14.18 LMC7 + MC6 323 K[22] 46.59 5.61
323 K [28] 39.98 8.75 LC1 + LMC7 323 K [23] 45.64 5.20
23.76 20.11 LMC7 + MC6 333 K [23] 46.57 6.07
Ternary system KCl–MgCl2–H2O 348 K [22] 48.38 8.61
T Composition of liquid phase Equilibrium solids 348 K [29] 42.30 6.16
100w(KCl) 100w(MgCl2) Ternary system Li2SO4–K2SO4–H2O
273 K [24] 2.40 26.74 KC + KNC6 T Composition of liquid phase Equilibrium solids
0.10 34.62 KMC6 + MC6 100w(Li2SO4) 100w(K2SO4)
288 Ka 2.85 26.68 KC + KNC6 288 K [32] 25.98 2.31 LKS + LS1
0.17 35.22 KMC6 + MC6 12.42 8.96 LKS + KS
333 K [30] 4.43 28.74 KC + KNC6 288 Ka 26.03 2.38 LKS + LS1
0.62 36.88 KMC6 + MC6 12.12 8.76 LKS + KS
373 K [31] 6.42 31.30 KC + KNC6 Ternary system K2SO4–MgSO4–H2O
0.50 42.04 KMC6 + MC6 T Composition of liquid phase Equilibrium solids
Ternary system Li2SO4–Mg2SO4–H2O 100w(K2SO4) 100w(MgSO4)
T Composition of liquid phase Equilibrium solids 288 Ka 10.81 11.20 KS + KMS6
100w(Li2SO4) 100w(MgSO4) 4.93 23.48 KMS6 + MS7
288 K [25] 16.64 14.93 LS1 + MS7 298 K [33] 10.70 12.68 KS + KMS6
a
288 K 16.37 15.14 4.03 26.39 KMS6 + MS7
a
Experimental Data in this work. Abbreviations: LC1 = LiCl
H2O, LC2 = LiCl
2H2O, NC = NaCl, NC2 = NaCl
2H2O, KC = KCl, MC6 = MgCl2
6H2O, MC12 = MgCl2
12H2O, LMC7 = LiCl
MgCl2
7H2O, KMC6 = KCl
MgCl2
6H2O, LS1 = Li2-
SO4
H2O, KS = K2SO4, MS7 = MgSO4
7H2O, KMS6 = K2SO4
MgSO4
6H2O, LKS: Li2SO4
K2SO4.

135
 136
Table 6
Single–salt parameters in the solution of the systems at 288.15 K.

Salt b(0) b(1) b(2) C/ Reference

LiCl 0.1500 0.3006 – 0.004211 [38]
NaCl 0.06698 0.2671 – 0.002636 [39]
KCl 0.04167 0.2022 – –0.00009683 [39]
MgCl2 0.3560 1.6502 – 0.007589 [40]
Li2SO4 0.1306 1.1550 – –0.001547 [41]
Na2SO4 0.008776 1.0329 – 0.01242 [38]
K2SO4 0.03793 0.8012 – –0.01880 [38]
MgSO4 0.1095 3.0049 0.7250 0.06742 [40]

R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139

Table 7
Debye-Hückel constant (A/) and mixing ion-interaction parameters in the solution of the systems at 288.15 K.

Parameter hLi,Na hLi,K hLi,Mg hNa,Mg hK,Mg WLi,K,SO4 WK,Mg,Cl

Value 0.05515 –0.008914 –0.03493 0.07000 0 –0.02079 –0.02360
Reference [42] [32] [25] [43] [37] [32] [37]
Parameter WNa,Mg,Cl WLi,Mg,SO4 WLi,Mg,Cl WLi,K,Cl WK,Mg,SO4 WLi,Na,Cl A/
Value –0.01310 0.01315 0.002329 –0.02060 –0.03547 –0.02657 0.3851
Reference [37] [25] [25] This work This work This work [39]
 R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139 137

Table 8
Solubility equilibrium constants of salts of the systems at 288.15 K.

Parameter lnK(LiCl
2H2O) lnK(LiCl
MgCl2
7H2O) lnK(KCl) lnK(MgCl2
6H2O) lnK(Li2SO4
K2SO4)

Value 12.1433 24.3589 1.8511 10.8098 –5.9385
Reference [25] [25] [39] [43] [32]
Parameter lnK(Li2SO4
H2O) lnK(KCl
MgCl2
6H2O) lnK(NaCl) lnK(K2SO4) lnK(Na2SO4
3K2SO4)
Value 1.2168 9.5826 3.6010 –4.4243 –7.9891
Reference [25] [43] [39] [39] [39]

KCl
NaCl 100
100

80
80

60
60

J(KCl)
J(NaCl)

NaCl 40
40
KCl

20
20
MgCl2·6H2O LiCl·MgCl2·7H2O LiCl·2H2O G LiCl·2H2O
F5
E KCl·MgCl2·6H2O F3 H
F1 F2 F4
A B 0
0 MgCl2 0 20 40 60 C 80 D 100LiCl
MgCl2 0 20 40 60 C 80 D 100LiCl
MgCl2·6H2O J(LiCl) LiCl·MgCl2·7H2O
J(LiCl)

(a) (a)

10 10
G
KCl
8 8

6 6
J(NaCl)

J(KCl)

NaCl H
4 4 KCl·MgCl2·6H2O
F5

LiCl·2H2O

2 2 LiCl·MgCl2·7H2O
LiCl·MgCl2·7H2O LiCl·2H2O
A MgCl2·6H2O F4
F1 F3
E
MgCl2·6H2O F2 B
0 0 LiCl
MgCl2 0 20 40 60 C 80 D 100LiCl MgCl2 0 20 40 60 C 80 D 100
J(LiCl) J(LiCl)

(b) (b)
Fig.10. (a) The experimental and calculated phase diagram of the quaternary Fig. 11. (a) The experimental and calculated phase diagram of the quaternary
system LiCl–NaCl–MgCl2–H2O at T = 288.15 K; (b) Partially enlarged diagram of (a); system LiCl–KCl–MgCl2–H2O at T = 288.15 K; (b) Partially enlarged diagram of (a);
—d—, experimental phase diagram; - - -s- - -, calculated phase diagram. —d—, experimental phase diagram; - - -s- - -, calculated phase diagram.

of the four quaternary systems that have not yet been reported.
tion, and provide a basis for the formulation of technological pro- The main conclusions are as follows:
cesses and proper determination of technological conditions. In The solubility data of equilibrium liquid phase of quaternary
this article, we have carried out studies on the phase equilibria systems LiCl–NaCl–MgCl2–H2O, LiCl–KCl–MgCl2–H2O and Li2SO4–
138 R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139

K2SO4 Using the Pitzer electrolyte solution theoretical model and the
100 experimental solubility data of ternary systems, the parameters
WLi,K,Cl, WK,Mg,SO4 and WLi,Na,Cl, of mixed ion interaction at 288.15 K
were determined. The solubility data of each component at the
80 equilibrium of the three quaternary systems mentioned above at
288.15 K were calculated and the corresponding calculated phase
diagrams and experimental phase diagrams were drawn based
K2SO4 on those calculated results. The calculated values are in good
60 agreement with the experimental values.
J(K2SO4)

I
L Acknowledgment
40
F6 The project was supported by the National Natural Science
Foundation of China (Grant No. 41473061, 41472078 and
Li2SO4·K2SO4
20 41273032).
J
F7 F8 K
References
MgSO4·7H2O Li2SO4·H2O
0 Li SO
MgSO4 0 20 40 M 60 80 100 2 4
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8311–8318.
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[3] T.L. Deng, Phase equilibrium for the aqueous system containing lithium,
- - -s- - -, calculated phase diagram.
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4 , NO3–H2O saturated with NaCl at 298.16 K (in
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[7] Y. Zeng, X.F. Lin, Solubility and density measurements of concentrated Li2B4O7
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Table 9
Experimental and calculated compositions of invariant points for the systems at 288.15 K.

System Composition of liquid phase 100
w(B) Equilibrium solids

LiCl–NaCl–MgCl2–H2O w(LiCl) w(NaCl) w(MgCl2)
Point F1 Experimental 27.75 0.30 13.68 MC6 + LMC7 + NC
Calculated 29.26 0.24 12.82
Point F2 Experimental 39.95 0.31 4.92 LC2 + LMC7 + NC
Calculated 41.00 0.52 3.34
LiCl–KCl–MgCl2–H2O w(LiCl) w(KCl) w(MgCl2)
Point F3 Experimental 27.39 0.22 13.90 MC6 + LMC7 + KMC6
Calculated 29.12 0.04 13.08
Point F4 Experimental 39.89 0.50 3.66 LMC7 + LC2 + KMC6
Calculated 40.79 0.34 3.66
Point F5 Experimental 42.03 1.80 1.39 KC + LC2 + KMC6
Calculated 42.29 1.79 1.30
Li2SO4–K2SO4–MgSO4–H2O w(Li2SO4) w(K2SO4) w(MgSO4)
Point F6 Experimental 10.13 11.09 9.25 KMS6 + LKS + KS
Calculated 10.23 14.58 9.02
Point F7 Experimental 11.05 4.09 17.70 KMS6 + MS7 + LKS
Calculated 11.35 5.25 17.16
Point F8 Experimental 16.16 2.47 15.24 LKS + LS1 + MS7
Calculated 16.14 2.75 15.09

Abbreviations: LC2 = LiCl
2H2O, NC = NaCl, KC = KCl, MC6 = MgCl2
6H2O, LMC7 = LiCl
MgCl2
7H2O, KMC6 = KCl
MgCl2
6H2O, LS1 = Li2SO4
H2O, KS = K2SO4, MS7 = MgSO4
7H2O,
KMS6 = K2SO4
MgSO4
6H2O, LKS = Li2SO4
K2SO4.
 R.-Z. Cui et al. / J. Chem. Thermodynamics 138 (2019) 127–139 139

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