You are on page 1of 19

Accepted Manuscript

(Solid + liquid) phase equilibrium for the ternary system (K2CO3-Na2CO3-H2O)


at T = (323.15, 343.15, and 363.15) K

Congcong Yin, Meitang Liu, Jing Yang, Hongwen Ma, Zheng Luo

PII: S0021-9614(17)30001-0
DOI: http://dx.doi.org/10.1016/j.jct.2017.01.001
Reference: YJCHT 4949

To appear in: J. Chem. Thermodynamics

Received Date: 25 September 2016


Revised Date: 31 December 2016
Accepted Date: 2 January 2017

Please cite this article as: C. Yin, M. Liu, J. Yang, H. Ma, Z. Luo, (Solid + liquid) phase equilibrium for the ternary
system (K2CO3-Na2CO3-H2O) at T = (323.15, 343.15, and 363.15) K, J. Chem. Thermodynamics (2017), doi: http://
dx.doi.org/10.1016/j.jct.2017.01.001

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
(Solid + liquid) phase equilibrium for the ternary system
(K2CO3-Na2CO3-H2O) at T = (323.15, 343.15, and 363.15) K
Congcong Yina,c, Meitang Liua,*, Jing Yang a,b, Hongwen Maa,b, Zheng Luoa,c

a
School of Materials Science and Technology, China University of Geosciences, Beijing 100083,
China
b
Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Wastes, China
University of Geosciences, Beijing 100083, China
c
Bluesky Technology Corporation, Beijing 100083, China
Abstract: In order to provide a theoretical basis and fundamental data for industrial
utilization of insoluble potassium rocks to produce potassium salts, the phase
equilibrium of the ternary system K2CO3-Na2CO3-H2O at 323.15 K, 343.15 K and
363.15 K was determined using the isothermal dissolution equilibrium method.
According to the experimental results of salt solubility, the phase diagrams were
constructed and the crystallization zones are discussed in detail. All of the solubility
isotherms at 323.15 K, 343.15 K and 363.15 K consist of two invariant points, three
univariant curves and three crystallization fields corresponding to Na2CO3·H2O,
K2CO3·Na2CO3 and K2CO3·1.5H2O, respectively. The densities of the liquid phase of
the ternary systems were investigated as well.
Keywords: Phase diagram, Solubility, Potassium carbonate, Sodium carbonate,
Thermodynamic properties
1. Introduction
Potassium is an inorganic chemical raw material. The soluble potassium resource
is the main source of potassium salts [1]. However, the distribution of soluble
potassium resources is in serious imbalance all over the world, a few countries of the
northern hemisphere (Canada, Russia, Belarus, and Germany) account for 93% of the
world’s total reserves [1, 2].
China depends more than 50% on import for potassium salts due to the lack of
soluble potassium resources. However, the potassium containing rocks with the
principal mineral of K-feldspar exist throughout the country and by using these
valuable rocks to produce potassium salts, one can alleviate severe shortages of
potash resources in China. We have done a series of investigations about
comprehensive utilization of potassic rocks [3-8]. K-feldspar can be decomposed in
the media of sodium hydroxide via hydrothermal treatment. The filtered liquors are
treated by a causticizing reaction, and then carbonated by contact with CO2 so that the
mixed solution of potassium carbonate and sodium carbonate is obtained [3], that is,
the ternary system K2CO3-Na2CO3-H2O.
Experimental research about the phase equilibria of the system K2CO3-Na2CO3-
H2O is carried out at intermediate temperatures ranging from 273.15 K to 423.15 K
[9-14] and it is found that the phase diagrams usually consist of multiple invariant
curves and invariant points due to the formation of new double salts. Therefore, one
cannot separate the components through a simple isothermal evaporation process in
the mixture solution. It is essential to apply also polythermal evaporation
crystallization steps for the purpose. The phase equilibria of the system over a wide
temperature range can optimize the separation process of potassium carbonate and
prepare high quality potassium carbonate. Therefore, we expanded the dimensions of
the three solubility curves at 323.15 K. The phase equilibria of the system at 343.15 K
and 363.15 K which have not been reported are also studied in this work.

2. Experimental
2.1. Reagent and instruments
The chemicals used are of analytical grade and summarized in Table 1. The
materials were kept continuously in an electric oven at 473.15 K before being used to
ensure the potassium bicarbonate and sodium bicarbonate were removed. Deionized
water, with an electrical conductivity less than 1.2×10 -4 S·m-1 and pH = 6.60 at 298.15
K, was used for the phase equilibrium experiments and chemical analysis of the
samples.
A thermostatic vibrator with a precision of 0.1 K (HZS-HA, Harbin Donglian
Electronic and Technology Development Co. Ltd., China) was employed for the
phase equilibria measurements.
TABLE 1
Chemical samples used in this study.
Initial mass Final mass
Chemical CAS
Sourcea faction Purification method faction Analysis methodc
name number
purityb purity
Dried in an oven at
K2 CO3 584-08-7 A.R. ≥0.990 0.993 Gravimetric method for K+
473.15 K
Dried in an oven at
Na2CO3 497-19-8 A.R. ≥0.998 0.999 Titration method for CO32-
473.15 K
a
from Beijing Chemical Reagent Co., Ltd., China.
b
stated by the suppler.
c
for the purified chemical samples.
2.2. Experimental methods
The solid-liquid phase equilibrium experiments were studied by the classical
isothermal solubility equilibrium method [15-19]. For each experiment, the dry
carbonates K2CO3 and Na2CO3 in a selected quantity were weighed, mixed with
deionized water and placed into hard sealed plastic bottles, and then placed in the
thermostatic vibrator until equilibrium was attained. The temperature of the vibrator
was set at (323.15 ± 0.1) K, (343.15 ± 0.1) K and (363.15 ± 0.1) K, respectively. The
vibrational frequency was set to 120 rpm in order to accelerate the establishment of
equilibrium states. The system could be considered to reach thermodynamic
equilibrium if the composition of the solution remains constant [20, 21]. Before
sampling, the temperature was kept constant more than 24 h for the establishment of
an aqueous solution. An amount of supernatant liquid was drawn up in a warmed
pipettete and transferred into a volumetric flask after being weighed, and then diluted
with deionized water for analysis of salts solubility according to the analytical
methods. The solid phase were separated from the liquid phase by isothermal
filtration, and then, the wet solid samples were studied by chemical analysis and
further determined after drying with filter paper by X-ray diffraction [15, 22, 23].
2.3. Analytical method
The concentration of K+ was analysed by a gravimetric method using sodium
tetraphenylborate [24, 25], with a relative uncertainty less than 2%. The total amount
of CO32- was titrated with hydrochloric acid standard solution [26], using methyl red-
bromocresol green as an indicator, the results were the average value of triple titration
determinations, and the relative uncertainty of the determination was less than 2% by
this method. The composition of Na+ was calculated by the subtraction method [27].
When the weight ratio of potassium carbonate to sodium carbonate exceeded 10:1,
another analysis method similar to Ref. [10] was employed [10]. An appropriate
amount of sample was put into a crucible which had been dried to a constant weight.
The weighed sample was covered and evaporated to dryness in an oven at 373.15 K.
The residue was heated to a constant weight in a muffle furnace at 673.15 K, and from
the total loss in weight the water content of the sample and the total weight of the
mixed carbonates became known, respectively. The same residue was then dissolved
in deionized water and titrated with hydrochloric acid, the total moles of the mixed
carbonates became known. Therefore, the percent of each salt in the mixture could be
calculated and hence in the weighed sample, and the relative uncertainty of the
determination was within 2%.
The density was determined by a 5 mL pycnometer and the volume of the
pycnometer at the experimental temperature was recalibrated by deionized water, and
the absolute uncertainties were estimated to be within 0.01 g·cm-3. A Siemens D500
X-ray diffractometer with Ni-filtered Cu Kα radiation was used to identify the solid
phases.

3. Results and discussion


In Table 2, the experimental results for the ternary system K2CO3-Na2CO3-H2O at
(323.15, 343.15 and 363.15) K are compared to literature data [10, 28-31]. Some
deviations for densities are evident. The deviations for ternary systems at 323.15 K
might be caused by the different analytical method from Ref. [10], as stated by the
authors “liquid was drawn up in a 5 cm3 pipette (warmed when necessary), run into a
platinum dish and weighed, and values for a rough density determination were
obtained” [10]. The deviations at 363.15 K might be caused by a slight change of
temperature and by evaporation of an extremely small amount of water from the
equilibrium liquid in the process of weighing the pycnometer. The interference of
these factors was minimized by carrying out the test in an incubator as far as possible
and conducting a multiple parallel test. On the whole, the agreement of the
experimental results with those of the literature is fairly close, which demonstrates
that the experimental methods and analytical methods are feasible in this study.

TABLE 2
Comparison of experimental and literature values for the liquid phase at (323.15, 343.15 and
363.15) K and pressure p = 0.1 MPa.a
Experimental results Literature values
Equilibrium
system ρ/ ρ/
b b
100w (Na2CO3) 100w (K2CO3) b b
100w (Na2CO3) 100w (K2CO3) solid phasec
(g·cm-3) (g·cm-3)

T = 323.15 K

Na2CO3+H2O 32.30 0.00 1.3235 32.2d 0.0d 1.331f Na1

Na2CO3+K2CO3+H2O 8.19 43.00 1.5416 8.0d 44.5d 1.530d Na1+ K·Na

Na2CO3+K2CO3+H2O 3.28 52.13 1.5976 3.3d 52.3d 1.574d K·Na +K3/2


K2CO3+H2O 0.00 54.95 1.5832 0.0d 54.8d 1.5782g K3/2

T = 343.15 K

Na2CO3+H2O 31.41 0.00 1.3102 31.01e 0.00 1.3195k Na1

Na2CO3+K2CO3+H2O 10.03 39.45 1.5218 -n - 1.5185m Na1+ K·Na

Na2CO3+K2CO3+H2O 2.37 55.79 1.6156 - - 1.6254m K·Na +K3/2

K2CO3+H2O 0.00 57.53 1.5943 0.00 57.17e 1.6009g K3/2

T = 363.15 K

Na2CO3+H2O 30.71 0.00 1.2687 30.51e 0.00 1.2987k Na1

Na2CO3+K2CO3+H2O 9.27 40.45 1.5032 - - 1.5010m Na1+ K·Na

Na2CO3+K2CO3+H2O 2.25 59.10 1.6595 - - 1.6493m K·Na +K3/2

K2CO3+H2O 0.00 59.61 1.6265 0.00 59.68e 1.6213g K3/2


a
Standard uncertainties u are u (T) = 0.1 K, u (p) = 0.005 MPa, ur (w) = u (w)/w = 0.02, u (ρ) =
0.01 g·cm-3.
b
w, mass fraction.
c
Na1: Na2CO3·H2O; K·Na: K2CO3· Na2 CO3; K3/2: K2CO3·3/2H2O.
d
from E.H. Arthur and W.M. Frederick (ref. [10]).
e
from Lange's handbook of chemistry (ref. [28]).
f
from A.E. Hill, L.R. Bacon (ref. [29]).
g, k
calculated by using the equations for densities of sodium carbonate solution and potassium
carbonate solution at (323.15, 343.15 and 363.15) K respectively, in the paper of D.M. Ginzburg,
N.S. Pinkulina and V.P. Litvin (ref. [30], ref. [31]).
m
calculated by using the equation (5) for density of ternary system H2O-Na2 CO3-K2CO3 in the
paper of E. E. Yaskelyainen, et al.(ref. [32]).
n
not detected.
3.1. Phase diagrams at T = (323.15, 343.15 and 363.15) K
The experimental results obtained for the mutual solubility of salts in the ternary
system are tabulated in Table 3, including the densities for the system. The ion
concentration values are measured in mass fraction (100w). On the basis of the
solubility values, the phase diagrams of the ternary system are constructed as shown
in Figure 1, Figure 2 and Figure 3, respectively.

TABLE 3
The phase equilibrium results for the ternary system K2 CO3-Na2CO3-H2O at T = (323.15, 343.15
and 363.15) K and pressure p = 0.1 MPa.a
Composition of Composition of wet
Densities, ρ /(g·cm-3)
liquid phase, 100wb residue phase, 100wb
NO. Equilibrium
solid phasec relative
K2 CO3 Na2CO3 K2CO3 Na2CO3 exp value calcd value
errord

T = 323.15 K

1,C 0 32.30 NDe ND Na1 1.3235 1.3235 0

2 5.58 28.45 ND ND Na1 1.3513 1.3409 -0.0078

3 12.35 25.49 ND ND Na1 1.3862 1.3835 -0.0020

4 18.26 22.00 2.56 77.98 Na1 ND ND ND

5 26.29 16.52 ND ND Na1 1.4480 1.4377 -0.0072

6 42.24 8.84 13.97 56.63 Na1 ND ND ND

7,E1 43.00 8.19 47.80 34.91 Na1+K·Na 1.5416 1.5388 -0.0018

8 44.16 7.82 ND ND K·Na 1.5553 1.5490 -0.0040

9 45.63 7.10 ND ND K·Na 1.5653 1.5585 -0.0044

10 45.98 6.85 52.34 24.84 K·Na ND ND ND

11 47.63 6.41 ND ND K·Na 1.5636 1.5756 0.0076

12 51.50 3.71 ND ND K·Na 1.5939 1.5895 -0.0028

13,E2 52.13 3.28 ND ND K·Na+K3/2 1.5976 1.5919 -0.0036

14 52.86 2.38 76.55 1.09 K3/2 ND ND ND

15 53.87 1.8 ND ND K3/2 1.5889 1.5944 0.0034

16,D 54.95 0 ND ND K3/2 1.5832 1.5832 0

T = 343.15 K

1,F 0 31.41 NDe ND Na1 1.3102 1.3102 0.0000

2 15.57 22.46 ND ND Na1 1.3597 1.3759 0.0118

3 25.01 16.98 11.21 52.68 Na1 ND ND ND

4 29.9 13.60 13.46 56.21 Na1 1.4454 1.4310 -0.0101

5,E3 39.45 10.03 29.56 42.30 Na1 + K·Na 1.5218 1.5012 -0.0138

6 39.62 9.92 ND ND K·Na 1.5243 1.5018 -0.0149

7 41.73 8.37 ND ND K·Na 1.5268 1.5070 -0.0131


8 43.93 8.03 50.69 24.77 K·Na ND ND ND

9 50.60 3.60 ND ND K·Na 1.5528 1.5544 0.0010

10 52.84 3.45 ND ND K·Na 1.5804 1.5821 0.0010

11 53.23 2.63 ND ND K·Na 1.5826 1.5752 -0.0047

12,E4 55.79 2.37 59.02 14.45 K·Na + K3/2 1.6156 1.6060 -0.0060

13 55.95 1.18 ND ND K3/2 1.5986 1.5904 -0.0051

14 56.23 1.02 ND ND K3/2 ND ND ND

15 56.78 0.87 ND ND K3/2 1.5921 1.5971 0.0031

16,G 57.53 0 ND ND K3/2 1.5943 1.5943 0

T = 363.15 K

1,H 0 30.71 NDe ND Na1 1.2687 1.2687 0

2 13.48 23.56 ND ND Na1 1.3387 1.3396 0.0006

3 18.39 20.60 ND ND Na1 1.3461 1.3620 0.0117

4 20.96 19.66 12.98 44.87 Na1 ND ND ND

5 25.67 15.45 ND ND Na1 1.3832 1.3866 0.0025

6 34.85 12.03 12.36 58.32 Na1 ND ND ND

7 35.74 11.24 ND ND Na1 1.4796 1.4587 -0.0143

8,E5 40.45 9.27 32.63 43.39 Na1+ K·Na 1.5032 1.4937 -0.0064

9 47.21 4.72 52.23 27.10 K· Na ND ND ND

10 51.66 3.81 ND ND K· Na 1.5616 1.5695 0.0050

11 54.16 3.14 ND ND K· Na 1.5885 1.5947 0.0039

12,E6 59.10 2.25 59.97 24.88 K·Na + K3/2 1.6595 1.6520 -0.0045

13 59.43 1.45 ND ND K3/2 1.6356 1.6450 0.0057

14,K 59.61 0 ND ND K3/2 1.6265 1.6265 0


a
Standard uncertainties u are u (T) = 0.1 K, u (p) = 0.005 MPa, ur (w) = u (w)/w = 0.02, u (ρ) =
0.01 g·cm-3.
b
w, mass fraction.
c
Na1: Na2CO3·H2O; K·Na: K2CO3 ·Na2CO3; K3/2: K2CO3·3/2H2O.
d
Relative error = (calcd value – exp value) / calcd value.
e
ND, not determined.
FIGURE 1. Phase diagram of the ternary system K2CO3-Na2CO3-H2O at 323.15 K.

FIGURE 2. Phase diagram of the ternary system K2CO3-Na2CO3-H2O at 343.15 K.


FIGURE 3. Phase diagram of the ternary system K2CO3-Na2CO3-H2O at 363.15K.
As shown in Figure 1, Figure 2 and Figure 3, Points A, B and W represent pure
solid of Na2CO3, pure solid of K2CO3 and H2O, respectively. Point C (F, H)
represents the solubility of Na2CO3 in water at 323.15 K (343.15 K, 363.15 K). Point
D (G, K) represents the single salt mass fraction of K2CO3 that saturated in water at
323.15 K (343.15 K, 363.15 K). Point E1 (E3, E5) is an invariant point at 323.15 K
(343.15 K, 363.15 K), which represents the co-saturated of Na2CO3·H2O and
anhydrous double salt K2CO3·Na2CO3. Point E2 (E4, E6) belongs to commensurate
eutectic point, which represents the co-saturated of K2CO3·3/2H2O and anhydrous
double salt K2CO3·Na2CO3. The solubility curve at 323.15 K has three branches. The
curve between points C and E1 indicates that sodium carbonate has been saturated in
the water, whereas sodium carbonate has been precipitated in the form of
Na2CO3·H2O. The curve between points E1 and E2 indicates that anhydrous double
salt K2CO3·Na2CO3 has been saturated in the water. The curve between points E2 and
D presents the saturation process of potassium carbonate as well as the precipitation
of K2CO3·3/2H2O. It can be found that the solubility curve of the system at 343.15 K
and 363.15 K are similar to that of 323.15 K.
As shown in Figure 1, Figure 2 and Figure 3, alongside the solubility curve CE1
(FE3 or HE5), we connected the composition points of wet residue phase with the
saturated liquid phase points and then extended it to the X axis, the point of
intersection is approximately the solid phase component for Na2CO3·H2O. In the
same way, along the solubility curve E2D (E4G or E6K), linking the component points
of the liquid phase and wet residue phase and extending it to Y axis, the point of
intersection is approximately the solid phase component for K2CO3·3/2H2O. The
same method is applied to determine the equilibrium solid phase component of E1E2
(E3E4 or E5E6), and the result turns out to be K2CO3·Na2CO3. As shown in Figure 4,
with the characterization of XRD analysis, the solid phase components of E2 (323.15
K), E4 (343.15 K) and E6 (363.15 K) are certified to be K2CO3·3/2H2O and
K2CO3·Na2CO3, respectively. This system belongs to a complex type due to the
incongruent double salt formed at the investigation temperature.
It can be seen from Figure 1, Figure 2 and Figure 3 that the area of WCD, WFG
and WHK represent unsaturated regions at (323.15, 343.15 and 363.15) K,
respectively; CE1L, FE3P and HE5R are crystalline regions of Na2CO3· H2O, E1NE2,
E3OE4 and E5TE6 stand for crystallization regions of K2CO3·Na2CO3, E2DM, E4GQ
and E6KS represent crystallization regions of K2CO3·3/2H2O. It is found that, the
crystallization area of Na2CO3·H2O is much larger than that of K2CO3·3/2H2O. These
results show that the potassium carbonate has a greater solubility than sodium
carbonate. In addition, the concentration of sodium carbonate decreases with the
increasing concentration of the potassium carbonate, which is most likely caused by
the strong salting-out effect of potassium carbonate on sodium carbonate.
FIGURE 4. X-ray diffraction pattern of the invariant point. (a) E2 at 323.15 K; (b) E4 at 343.15 K;
(c) E6 at 363.15 K
A comparison of diagrams at (323.15, 343.15 and 363.15) K is shown in Figure 5,
it further illustrate that the temperature can influence the equilibrium of the ternary
system. Increasing the temperature from (323.15 to 363.15) K, the unsaturated region
and the crystallization zones of K2CO3·3/2H2O become slightly smaller, whereas the
crystallization zones of Na2CO3·H2O become slightly larger in reverse. These changes
indicate that the solubility of potassium carbonate is positively correlated with
temperature whereas the solubility of sodium carbonate is negatively correlated with
temperature. Differences between the solubility of Na2CO3 at invariant points
corresponding to K2CO3·Na2CO3 + K2CO3·3/2H2O are (3.28, 2.37 and 2.25) wt. % at
(323.15, 343.15 and 363.15) K, respectively, which confirms the salting-out effect of
potassium carbonate on sodium carbonate. Therefore, the mixture of potassium
carbonate and sodium carbonate can be separated and purified by using the
temperature variation effects.
FIGURE 5. Comparison of phase diagram of the system K2CO3-Na2CO3-H2O at (323.15,
343.15 and 363.15) K. ▲, at T = 323.15 K; ●, at T = 343.15 K; ■, at T = 363.15 K;
3.2. Solution density in the system K2CO3-Na2CO3-H2O
The experimental density of solution versus the mass concentration of potassium
carbonate is plotted in Figure 6. It is seen that the density curves of the equilibrium
liquid phase in this system at (323.15, 343.15 and 363.15) K show an upward
tendency with the increase percentage of potassium carbonate in the solution and

reaches the maximum value of 1.5976 g·cm-3 at the eutectic point E2 at 323.15 K,

1.6156 g·cm-3 at the eutectic point E4 at 343.15 K and 1.6595 g·cm-3 at the eutectic

point E6 at 363.15 K. The reason for this phenomenon is that potassium carbonate has
a strong salting-out effect on sodium carbonate. In addition, at the same potassium
carbonate concentration, the solution density at 363.15 K is lower than that at (343.15
and 323.15) K.
FIGURE 6. Comparison of the experimental density data versus K2CO3 concentration in the
system K2CO3 -Na2CO3-H2 O at (323.15, 343.15 and 363.15) K. ▲, at T = 323.15 K; ●, at T =
343.15 K; ■, at T = 363.15 K.
The density indices of the ternary system (K2CO3-Na2CO3-H2O) at 323.15 K,
343.15 K and 363.15 K were calculated according to the following empirical equation,
which was developed in the previous study [33,34].

ln (d/d0) = ∑ Ai×wi

where, d and d0 refer to the density values of the solution and the pure water at
the same temperature. The d0 values of the density of the pure water are 0.98804

g·cm-3 at 323.15 K, 0.97777 g·cm-3 at 343.15 K and 0.9653 g·cm-3 at 363.15 K,

respectively. The wi is the mass fraction of salt i in the equilibrium aqueous solutions
of the system; Ai is the constant of each possible component i in the solution, and can
be obtained from the densities versus composition of the two boundary values in the
ternary system with mass fraction (i.e., the saturated solubility of the two binary
systems) at 323.15 K, 343.15 K and 363.15 K. The calculated constants Ai for K2CO3
and Na2CO3 are 0.858017, 0.904990 at 323.15 K, 0.849845, 0.931743 at 343.15 K
and 0.875267, 0.889968 at 363.15 K. A comparison between the calculated density
and the experimental results are shown in Table 3, the maximum relative error is
0.0149. The calculated values agree well with the experimental findings, confirming
that the coefficients Ai for K2CO3 and Na2CO3 obtained in this work are reliable for a
more complicated system containing both of them.
4. Conclusions
The phase equilibrium of the ternary system K2CO3-Na2CO3-H2O at 323.15 K,
343.15 K and 363.15 K was measured using the isothermal dissolution equilibrium
method. On the basis of the experimental results, the phase diagrams of the system
were constructed. All of the phase diagrams at (323.15, 343.15 and 363.15) K consist
of two invariant points, three univariant curves and three crystallization zones. The
crystallization zone of Na2CO3·H2O is much larger than that of K2CO3·3/2H2O, which
indicates that the potassium carbonate has a strong salting-out effect on sodium
carbonate. It was also found that the salting-out effect was enhanced with increasing
temperature, therefore both can be effectively separated by the method of polythermal
evaporation crystallization steps, which provide a strong foundation for the industrial
utilization of insoluble potassium rocks to produce potassium salts.
Acknowledgments
The authors gratefully acknowledge the support of Fundamental Research Funds
for the Central Universities (2652015422, 2652014017, 53200859555), China
Geological Survey Project (12120113087700), and the National Key Technology
R&D Program in the 11th five-year plan of China (2006BAD10B04).

References
[1] H.W. Ma, Potassic rock in China: resource and clean utilization techniques, Chemical Industry
Press, 2010, pp. 1-5.
[2] D A. C. Manning. Mineral sources of potassium for plant nutrition. a review, Agron. Sustain.
Dev 30 (2) (2010) 281-294.
[3] S.Q. Su, H.W. Ma, X.Y. Chuan, Hydrothermal decomposition of K-feldspar in KOH – NaOH -
H2O medium, Hydrometallurgy 156 (2015) 47-52.
[4] S.Q. Su, J. Yang,. H.W. Ma, P. Zhang, The technology evaluation of preparation of potassium
salt by using insoluble potassium resources, Techno. Chem. Ind. Miner. 2 (2014) 46-51.
[5] X. Ma, J. Yang, H.W. Ma, C.J. Liu, Hydrothermal extraction of potassium from potassic
quartz syenite and preparation of aluminum hydroxide, Int. J. Miner. Process. 147 (2016) 10-
17.
[6] H.W. Ma, J. Yang, S.Q. Su, M.T. Liu, H. Zheng, et al., 20 years advances in preparation of
potassium salts from potassic rocks: a review, Acta Geol. Sin. 89 (2015) 2058-2071.
[7] Z. Luo, J. Yang, H.W. Ma, M.T. Liu, X. Ma, Recovery of magnesium and potassium from
biotite by sulfuric acid leaching and alkali precipitation with ammonia, Hydrometallurgy 157
(2015) 188-193.
[8] J.Y. Yuan, J. Yang, H.W. Ma, C.J. Liu, Crystal structural transformation and kinetics of
NH4+/Na+ ion-exchange in analcime, Micropor. Mesopor. Mat. 222 (2016) 202-208.
[9] Z.Y. Zheng, Y. Zeng, X.F. Lin, Experimental study on the phase equilibrium of the ternary
system K2CO3-Na2CO3-H2O at 273K, J. Salt Chem. Ind. 36 (2006) 7-9.
[10] E.H. Arthur, W.M. Frederick, Ternary systems. IV. potassium carbonate, sodium carbonate
and water, J. Am. Chem. Soc. 49 (1927) 669-685.
[11] S.H. Sang, H.A. Yin, M.L. Tang, Experimental study on the phase equilibrium of the ternary
system K2CO3-Na2CO3-H2O at 288K, Inorg. Chem. Ind. 35 (2003) 22-25.
[12] Y. Zeng, H.A. Yin, M.L. Tang, L.S. Wang, Experimental study on the phase equilibrium and
physicochemical properties of the ternary system Na2CO3-K2CO3-H2O at 298K, J. Sichuan
Univ.: Eng. Sci. Ed, 3 (1999) 135-139.
[13] X.T. Liu, M.T. Liu, H.W. Ma, Equilibrium phase diagram and solution properties of Na2CO3-
K2CO3-H2O Ternary System at 333 K, J. Sal. Chem. Ind. 40 (2011) 3-5.
[14] Jr. G. Ervin, A. L. Giorgi, C. E. McCarthy, The system potassium carbonate-sodium
carbonate-water at 100 and 150℃, J. Am. Chem. Soc. 66 (3) (1944) 384-387.
[15] H.Y. Cao, H. Zhou, X.Q. Bai, R.X. Ma, L.N. Tan, J.M. Wang, (Solid + liquid) phase
equilibria of (Ca(H2PO2)2 + NaH2PO2 + H2O) ternary systems at T = 323.15 K, J. Chem.
Thermodynamics 93 (2016) 255-260.
[16] X.R. Zhang, Y.S. Ren, W.J. Ma, H.J. Ma, (Solid + liquid) phase equilibrium for the ternary
system (NaCl + NaH2PO4 + H2 O) at T = (298.15 and 33.15) K and atmospheric pressure, J.
Chem. Thermodynamics 77 (2014) 107-111.
[17] D.C. Li, J.S. Yuan, F. Li, Solid-liquid stable equilibrium of the quaternary system NaCl-KCl-
CaCl2-H2O at 303.15 K, J. Chem. Eng. Data. 60 (2015) 1886-1891.
[18] E. Özduğan, B. Andak, N. Bulutçu, et al., Ternary phase diagrams of CdSO4 –NiSO4–H2O at
40℃ and 80℃, Fluid Phase Equilibr. 381 (2014) 67-70.
[19] H.F. Guo, J.L. Gao, J.J. Wang, Phase diagrams of Na2SO4-MgSO4-(NH4)2SO4-H2O system at
25℃ and their application, Fluid Phase Equilibr. 367 (2014) 79-84.
[20] W. Shen,; Y.L. Wang, T.T. He, X.R. Zhang, Study on the phase equilibrium of the quaternary
systems Na+ (K+) // H2PO4-, Cl-, SO42--H2O at 313.15 K, Fluid Phase Equilibr. 403 (2015) 85-
94.
[21] D.L. Gao, Y.F. Guo, X.P. Yu, 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, J. Chem.
Eng. Data. 60 (2015) 2594-2599.
[22] S.Y. Qin, B.W. Yin, Y.F. Zhang, Phase equilibria of the NaOH-NaBO2 -Na2CO3-H2O system
at 30℃, 60 ℃, and 100 ℃, J. Chem. Eng. Data. 60 (2015) 3018-3023.
[23] X.L. Huang, P.S. Song, L.J. Chen, Liquid-solid equilibria in quinary system Na+, Mg2+/Cl-
,SO42-, NO3- - H2O at 298.15 K, CALPHAD 32 (2008) 188-194.
[24] J.X. Hu, S.H. Sang, M.F. Zhou, W.Y. Huang, Phase equilibria in the ternary systems KBr-
MgBr2 - H2O and NaBr - MgBr2 - H2O at 348.15 K, Fluid Phase Equilibr. 392 (2015) 127-131.
[25] P. Wang, J. Li, J.H. Luo, Y. Jin, Z.P. Yang, Solid-liquid phase equilibrium for the ternary
system K2 SO4 + KH2PO4 + H2O at (298.15 and 333.15) K, J. Chem. Eng. Data 57 (2012) 836-
839.
[26] S.H. Sang, H.A. Yin, M.L. Tang, Y. Zeng, (Liquid + solid) phase equilibria in the quaternary
system Na2CO3 + K2B4O7 + K2CO3 + Na2B4O7 + H2O at 288 K, J. Chem. Eng. Data 49 (2004)
1775-1777.
[27] F.P. Yan, X.D. Yu, Q.H. Yin, The solubilities and physicochemical properties of the aqueous
quaternary system Li+, K+, Rb+ // Borate - H2O at 348 K, J. Chem. Eng. Data 59 (2014) 110-
115.
[28] J.G. Speight, Lange's handbook of chemistry, New York: McGraw-Hill, 2005.
[29] A.E. Hill, L.R. Bacon, Ternary systems. VI. Sodium carbonate, sodium bicarbonate and water,
J. Am. Chem. Soc. 49 (1927) 2487-2495.
[30] D.M. Ginzburg, N.S. Pinkulina, V.P. Litvin, Density of sodium carbonate solutions, Zh. Prikl.
Khim., 1964, 37, 2749-2750.
[31] D.M. Ginzburg, N.S. Pinkulina, V.P. Litvin, Density of aqueous potassium carbonate
solutions, Zh. Prikl. Khim., 1964, 37, 2353-2357.
[32] E.E. Yaskelyainen, L.A. Kanunnikov, G.I. Shvachko, O.A. Dubovikov, A.N. Naumchik,
Density of ternary system H2O-Na2CO3-K2CO3,Zh. Prikl. Khim., 1990, 63, 1118-1120.
[33] W. Liu, Y. Xiao, Y.S. Liu, F.X. Zhang, J.F. Qu, Phase equilibrium for the ternary system
K2SO4 + KCl + H2O in aqueous solution at 303.15 K, J. Chem. Eng. Data 60 (2015) 1202-
1205.
[34] B.H. Bu, L. Li, N. Zhang, et al, Solid-liquid metastable phase equilibria for the ternary
system (Li2 SO4 + K2SO4 + H2O) at 288.15 and 323.15 K, p = 0.1 MPa, Fluid Phase Equilibr.
402 (2015) 78-82.
Highlights

 The phase equilibrium of the ternary system K2CO3-Na2CO3-H2O at


(323.15, 343.15 and 363.15) K which have not been reported were
determined using the isothermal dissolution equilibrium method.

 The solubility isotherms at (323.15, 343.15 and 363.15) K consist of


two invariant points, three univariant curves and three crystallization
fields.

 The salting-out effect of potassium carbonate on sodium carbonate


was enhanced with the increasing of temperature, therefore, the both
can be effectively separated by the method of polythermal evaporation
crystallization steps.

 The densities of the liquid phase of the ternary systems were


investigated and compared with the caculated value.

You might also like