CHEM. RES.

CHINESE UNIVERSITIES 2010, 26(1), 114—117

Solid-liquid Metastable Equilibria in Quaternary System

(NaCl+Na2CO3+Na2SO4+H2O) at 273.15 K

WANG Rui-lin and ZENG Ying*

Department of Chemical Engineering, Chengdu University of Technology, Chengdu 610059, P. R. China

Abstract The metastable phase equilibria of the quaternary system NaCl+Na2CO3+Na2SO4+H2O were studied at
273.15 K. The salts’ solubilities, densities and pH values of the equilibrated solution in this system were determined.
According to the experimental data, the metastable equilibrium phase diagram, the diagram of density vs. composi-
tion and pH vs. composition diagram were plotted. The phase diagram consists of five univariant curves, four crystal-
lization fields and two invariant points. The four crystallization fields correspond to sodium carbonate decahydrate
(Na2CO3·10H2O), sodium sulfate decahydrate(Na 2SO4·10H2O), sodium chloride(NaCl) and burkeite(2Na2SO4·
Na2CO3), respectively. The crystallization field of sodium sulfate decahydrate(Na2SO4·10H2O) is the largest, which
indicates that sodium sulfate is easy to saturate and crystallize from solution at 273.15 K.
Keywords Quaternary system; Metastable phase equilibrium; Sulfate
Article ID 1005-9040(2010)-01-114-04

1 Introduction 25 °C have also been completed[6,7]. Although all the

mentioned researches have played an important role in
The Zabuye Salt Lake, Tibet, located in the west
exploiting the salt lake brine resources, they are al-
of China, is famous for its high concentrations of li-
most concentrated on the metastable equilibria of
thium, boron, and potassium in the world. The main
temperature above 15 °C, while the climate conditions
components of its brine are Li+, K+, Na+, B4O72–,
in the region of Zabuye Salt Lake are generally windy,
CO32–, Cl–, SO42– and H2O, including rare elements
arid, little rainfall and has great evaporating capacity,
such as Rb+ and Cs+[1,2]. Metastable phase equilibrium
its average temperature is about 273.15 K[8]. Aiming
and phase diagram play an important role in exploi-
at the characteristics of the clime and the composition
ting the brine resources. To economically exploit salt
of Zabuye Salt Lake, the researches focused on the
lake brine resources, it is important to adopt the local
metastable equilibrium at 273.15 K will have an im-
natural energy such as the sun and the wind, thus the
portant guiding significance[9].
technique like the solar pond is widely used. The
The quaternary system NaCl+Na2CO3+Na2SO4+
comprehensive utilization of brines is strongly depen-
H2O is a subsystem of the Zabuye Salt Lake brines. So
dent on mutual metastable equilibrium solubilities of
far, no report has been found about the metastable
salts, and therefore, the investigation of metastable
phase equilibria of this quaternary system. The present
equilibrium is of important theoretical and practical
paper covers the metastable equilibria of the quater-
significance.
nary system(NaCl+Na2CO3+Na2SO4+H2O) at T=
The metastable equilibrium phase diagram, also
273.15 K. The solubilities and the physicochemical
called the “solar phase diagram”, was begun to be stu-
properties such as density and pH value of the equili-
died in the early 1920s. Metastable equilibrium stu-
brated solution were measured.
dies aiming at the sea water system Na++K++Mg2++
Cl– +SO42–+H2O at 15, 25, and 35 °C[3―5] have been 2 Experiments
reported, respectively. Metastable equilibria in the
quinary system Na++K++Cl– +CO32– +SO42– +H2O and 2.1 Reagents and Instruments
the quaternary system Li++Mg2++Cl–+SO42–+H2O at All the chemicals used were of analytical purity
———————————
*Corresponding author. E-mail: zengy@cdut.edu.cn
Received February 2, 2009; accepted April 8, 2009.
Supported by the National Natural Science Foundation of China(No.40673050), the Research Fund for the Doctoral Program
of Higher Education from the Ministry of Education of China(No.20070616008) and the Scholarship Leaders Training Fund from
Sichuan Province, China(No.2008-140).
No.1 WANG Rui-lin et al.
grade and obtained from Chengdu Kelong Chemical
Reagent Manufactory, China. They were sodium chlo-
ride(NaCl, 99.5%, mass fraction), sodium carbonate
(Na2CO3, 99.5%, mass fraction), sodium sulfate
(Na2SO4, 99.5%, mass fraction). Doubly deionized
water was obtained from a Millipore water system
with an electrical conductivity less than 1×10–4 S/m
and pH=6.6.
An SHH-250 type thermostatic evaporator made
by the Chongqing INBORN Instrument Corporation,
China, was used for the metastable phase equilibrium
experiments. There were temperature-controlling ap-
paratus and blower accessory equipment in it to con-
trol the temperature and the evaporation quantity of
the evaporated system. The temperature controlling
precision was ±0.1 K. A PHS-25 precision pH meter
supplied by the Shanghai Leici Instrument Factory
was used to measure the pH value, with a precision of
±0.01. A SIMENS D500 X-ray diffractometer with
Ni-filtered Cu Kα radiation was used to analyze the
crystalloid form of the solid phase. An Optima 5300V
type ICP-OES made by PE Corporation, USA, was
used for the determination of the sodium ion concen-
tration.
2.2 Experimental Methods
The isothermal evaporation method was em-
ployed in this study. According to the phase equili-
brium composition, an appropriate quantity of salts
and distilled water were mixed together as a series of
artificial synthesized brines and loaded into clean po-
lyethylene containers(15 cm long, 10 cm wide and 7
cm high) and then the containers were put into the
SHH-250 type thermostatic evaporator for the iso-
thermal evaporation at (273±0.1) K. The crystal beha-
viors of the solid phases were observed periodically.
When enough new solids appeared, the solids were
separated from the solutions, dried at 273.15 K and
waited to identify. Meanwhile, 5.0 mL of the sample
of the clarified solution was taken from the liquid
phase and diluted to a final volume of 100 mL in a
volumetric flask filled with the deionized water to
analyze the liquid phase components. Another 5.0 mL
of sample was taken to measure the density. The re-
mainder of the solution continued to be evaporated to
reach the next metastable equilibrium point.
The densities(ρ) of the equilibria solution were
measured by means of a density bottle method with a
115
3
precision of ±0.0002 g/cm . The pH value was
measured with a PHS-25 precision pH meter, with a
precision of ±0.01. The pH meter was calibrated with
standard buffer solutions prepared by either the
mixing agents of sodium dihydrogen phosphate and
dipotassium hydrogen phosphate(pH 6.86) or borax
(pH 9.18).
2.3 Identification of Solid Phases
When sufficient new solid phases appeared, the
solids were separated from the solutions. The obtained
wet crystals of the solid phase were separated from
each other according to the crystal shapes as much as
possible. The solids were then analyzed by chemical
methods to obtain the composition, and further identi-
fied by X-ray diffraction to ascertain the crystalloid
form.
2.4 Analytical Methods
According to the method reported in ref. [10], the
chlorine ion(Cl–) concentration was measured by
silver nitrate titration(uncertainty of 0.5%, mass frac-
tion). The sulfate ion concentration(SO42–) was deter-
mined by a method of mixing barium chloride and
magnesium chloride-EDTA titration(uncertainty of
0.5%). The carbonate ion concentration(CO32–) was
determined by means of a method of acid-base titra-
tion. The sodium ion concentration(Na+) was eva-
luated on an ion balance, and assisted by ICP-OES
(uncertainty less than 0.5%, mass fraction).
3 Results and Discussion
The experimental results of solubilities and
physicochemical properties such as density and pH
value of the metastable equilibria of the quaternary
system NaCl+Na2CO3+Na2SO4+H2O at 273.15 K are
listed in Table 1. In Table 1, the salts’ solubilities of
the equilibrated solution are expressed as mass
fraction, and the composition of the solid phases are
calculated with 100 g of dry salt as benchmark, that is,
J(NaCl)+ J(Na2CO3)+J(Na2SO4)=100 g. According to
the composition of dry salt, the metastable phase dia-
gram of this system at 273.15 K was plotted, as shown
in Fig.1(A). Fig.1(B) is the partial enlarged diagram of
Fig.1(A). In Fig.1, there are four crystallization fields
corresponding to sodium carbonate decahydrate
(Na2CO3·10H2O, G1EBG1), sodium sulfate decahy-
drate(Na 2 SO 4 ·10H 2 O, G 2 FAG 2 ), sodium chloride
116 CHEM. RES. CHINESE UNIVERSITIES Vol.26

(NaCl, BEFAB) and burkeite(2Na 2 SO 4 ·Na 2 CO 3 , regions indicate that Na2SO4 is of a low solubility;
G1EFG2G1). The crystallization field of NaCl is the therefore, most sodium sulfate salt can be easily crys-
smallest, while the crystallization field of Na2SO4· tallized from the solution.
10H2O is larger than the rest. The large crystallization
Table 1 Determined values of salts’ solubility, density and pH value of equilibrated solution in the quaternary
system NaCl +Na2CO3 +Na2SO4 +H2O at 273.15 K*
Composition of solution, w(B)(%) Composition of solid phase Jb/(g·100 g–1 dry salt) Density,
No. Solid phase pH
w(NaCl) w(Na2CO3) w(Na2SO4) w(H2O) J(NaCl) J(Na2CO3) J(Na2SO4) ρ/(g·cm–3)
1,A 25.23 0.00 1.55 73.23 94.22 0.00 5.78 ncl+ns 1.2109 9.31
2 25.23 0.50 1.53 72.74 92.54 1.84 5.63 ncl+ns 1.2145 9.60
3 25.01 0.64 1.55 72.80 91.95 2.35 5.69 ncl+ns 1.2165 9.41
4 24.31 1.16 1.50 73.03 90.14 4.29 5.57 ncl+ns 1.2219 9.21
5 23.83 1.85 1.59 72.74 87.40 6.77 5.83 ncl+ns 1.2261 9.42
6 23.36 2.63 1.38 72.64 85.37 9.60 5.03 ncl+ns 1.2289 9.43
7,B 24.19 6.13 0.00 69.68 78.15 21.85 0.00 nc+ncl 1.2268 11.08
8 23.73 3.29 0.31 72.68 86.85 12.02 1.12 nc+ncl 1.2226 10.52
9 23.76 3.28 0.31 72.65 86.86 12.00 1.14 nc+ncl 1.2259 10.24
10 23.65 3.33 0.32 72.70 86.64 12.21 1.16 nc+ncl 1.2276 9.81
11 22.80 3.98 0.89 72.33 82.40 14.38 3.22 nc+ncl 1.2364 9.41
12,G1 0.00 6.90 2.22 90.88 0.00 75.69 24.31 nc+nsc 1.0961 11.47
13 0.47 6.03 1.91 91.60 5.58 71.72 22.69 nc+nsc 1.0921 11.26
14 5.38 8.77 2.35 83.50 32.61 53.13 14.27 nc+nsc 1.1628 10.61
15,E 21.85 5.69 1.01 71.45 76.52 19.93 3.55 nc+nsc+ncl 1.2440 10.41
16,G2 0.00 5.15 2.25 92.60 0.00 69.56 30.44 ns+nsc 1.0794 11.84
17 0.45 5.31 2.07 92.17 5.69 67.82 26.49 ns+nsc 1.0842 11.50
18 1.25 5.71 2.43 90.62 13.30 60.83 25.87 ns+nsc 1.1014 10.78
19 5.46 7.90 2.87 83.77 33.63 48.65 17.71 ns+nsc 1.1556 10.21
20,F 22.46 4.33 1.08 72.13 80.60 15.54 3.86 ns+nsc+ncl 1.2377 10.18
21 22.14 5.23 1.03 71.59 77.95 18.41 3.64 nsc+ncl 1.2426 10.36
22 22.35 4.73 1.06 71.85 79.40 16.82 3.78 nsc+ncl 1.2392 10.38
* ns: Na2SO4·10H2O; ncl: NaCl; nc: Na2CO3·10H2O; nsc: 2Na2SO4·Na2CO3.

Fig.1 Metastable phase diagram of quaternary system NaCl +Na2CO3 +Na2SO4 +H2O at 273.15 K(A) and
part enlargement diagram of Fig.1(A)(B)
The phase diagram has five univariant curves
(B→E, A→F, F→E, E→G1 and F→G2), and two iso-
thermal invariant points E and F. The invariant point E
is saturated with three salts Na2CO3·10H2O, NaCl and
2Na2SO4·Na2CO3, and the invariant point F is satu-
rated with three salts Na2SO4·10H2O, NaCl and
2Na2SO4·Na2CO3. Burkeite 2Na2SO4·Na2CO3 is found
in this quaternary system. The sodium sulfate(Na2SO4)
causes a weak salting-out effect on the salt sodium
carbonate(Na2CO3).
On the basis of data collected in Table 1, the rela-
tionship between the physicochemical properties of
solution(density and pH value) and the mass fraction
of sodium chloride w(NaCl) are shown in Figs.2 and
3, respectively. Fig.2 shows that in the process of wa-
ter evaporation, the density of the equilibrated solu-
tion increases regularly with the increasing of sodium
chloride concentration in a w(NaCl) range of 0―22%,
and reaches the maximum values at the co-saturation
point E(1.2440 g/cm3) and point F (1.2377 g/cm3). In
No.1 WANG Rui-lin et al. 117

Fig.3, the pH value of the metastable equilibrium of

aqueous solution decreases gradually with the in-
creasing of sodium chloride concentration.
Fig.2 Phase diagram of density-content of quaternary
system NaCl+Na2CO3+Na2SO4+H2O at 273.15 K
4 Conclusions
Metastable equilibria of the quaternary system
NaCl+Na2CO3+Na2SO4+H2O at 273.15 K were stu-
died. Solubility of the salts and properties such as
density and pH value of the equilibrated solution were
determined experimentally. According to the experi-
mental data, the phase diagram and corresponding
diagrams of properties vs. composition were plotted.
The experimental results show that there are two
invariant points, five univariant curves, and four crys-
tallization fields in this system. Burkeite 2Na2SO4·
Na2CO3 is formed in this quaternary system. The
crystallization form of sodium sulfate is Na2SO4·
10H2O at 273.15 K. The salt sodium sulfate has the
smallest solubility and it can be easily crystallized
from the solution.

References
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[2]
[3]
Fig.3 Diagram of pH value vs. composition of quaternary
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[4]
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[14]
crystallization form of sodium sulfate is Na2SO4·
10H2O at 273.15 K.
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