Fluid Phase Equilibria 344 (2013) 13–18
Contents lists available at SciVerse ScienceDirect
Fluid Phase Equilibria
journal homepage: www.elsevier.com/locate/fluid
Study of the solubility in Na–Ba–Cl–H2 O, Na–Ba–H2 PO2 –H2 O, Na–Cl–H2 PO2 –H2 O,
and Ba–Cl–H2 PO2 –H2 O ternaries, and in Na+ , Ba2+ /Cl− , (H2 PO2 )− //H2 O reciprocal
quaternary system at 0 ◦ C
Hasan Erge a , Vedat Adiguzel c,∗ , Vahit Alisoglu b
a
Department of Chemistry, Yuzuncu yıl University, Van 65080, Turkey
Department of Chemistry, Kafkas University, Kars 36100, Turkey
c
Department of Chemical Engineering, Kafkas University, Kars 36100, Turkey
b
a r t i c l e
i n f o
Article history:
Received 20 June 2012
Received in revised form
20 December 2012
Accepted 28 December 2012
Available online 24 January 2013
Keywords:
Phase diagram
Solid phase synthesis
Solvent effect
Phase transition
Hypophosphite
a b s t r a c t
The solubility and the physicochemical properties (density and conductivity) in the Na–Ba–Cl–H2 O,
Na–Ba–H2 PO2 –H2 O, Na–Cl–H2 PO2 –H2 O, and Ba–Cl–H2 PO2 –H2 O ternaries, and in Na+ , Ba2+ /Cl− ,
(H2 PO2 )− //H2 O reciprocal quaternary systems at 0 ◦ C were investigated using the isothermal method.
Two invariant point were determined in Na+ , Ba2+ /Cl− , (H2 PO2 )− //H2 O reciprocal quaternary system.
The composition of invariant point of the first (as a weight) was determined as fallowing; 15.03% mass
NaCl, 12.36% mass BaCl2 , 2.86% mass Ba(H2 PO2 )2 , and 69.75% mass H2 O. It was plotted that the liquid
phase and the following three solid phases were in equilibrium at the invariant point at 0 ◦ C. These are
NaCl, BaCl2 ·H2 O, Ba(H2 PO2 )2 ·H2 O.
As for the composition of the second invariant point (as a weight) was determined as follows: 1.06%
mass NaCl, 43.98% mass NaH2 PO2 , 0.51% mass Ba(H2 PO2 )2 , 54.45% mass H2 O. It was determined that the
liquid phase and the following three solid phases were in equilibrium at the invariant point at 0 ◦ C. These
are NaCl, NaH2 PO2 ·H2 O, Ba(H2 PO2 )2 ·H2 O.
According to results, the least soluble salt was Ba(H2 PO2 )2 . The crystallization field of this salt, being
the largest in comparison with those of other salts, occupied 82% of the general crystallization field.
© 2013 Elsevier B.V. All rights reserved.
1. Introduction
It is well known that phase diagrams and phase equilibria play
an important role in exploiting brine resources. Regarding thermodynamic equilibrium studies Van’t Hoff was the first to report a
stable phase diagram at T = 293.15 K using the isothermal dissolution method [1].
Metal phosphides, a class of materials with unique physical and
chemical properties, have attracted considerable attention for their
wide applications in many fields [2].
Hypophosphites are obtained from white phosphor with the
reaction of hot solutions of alkali metals.
4P + 3KOH + 3H2 O = 3KH2 PO2 + PH3
This method can be applicable for all the elements hydroxides of
which are soluble in the water like NH4 H2 PO2 , Ca(H2 PO2 )2 , etc. [3].
The synthesis of hypophospites obtained from hydroxides of
insoluble elements in the water are generally synthesized both
∗ Corresponding author. Tel.: +90 5325893035.
E-mail address: [email protected] (V. Adiguzel).
0378-3812/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fluid.2012.12.033
multi-step reactions and expensively. Such as Mn(H2 PO2 )2 synthesis is as follows:
8P + 3NaOH + 6H2 O = 3NaH2 PO2 + 2PH3
NaH2 PO2 + H2 SO4 = Na2 SO4 + 2H3 PO2
2H3 PO2 + MnCO3 = Mn(H2 PO2 )2 + CO2 + H2 O
As it is seen from the example, NaH2 PO2 is obtained from NaOH
soluted in the water. H3 PO2 is, then, obtained from the reaction of
100% H2 SO4 and NaH2 PO2 . Finally, Mn(H2 PO2 )2 is obtained from
H3 PO2 and MnCO3 or MnO2 [4]. To develop a more economic and
suitable method of synthesis A+ , Ba2+ /X− , (H2 PO2 )− //H2 O (A = Na,
K, NH4 ; X = NO3 , Cl, Br) systems can be established In this system,
Ba(H2 PO2 )2 can easily be obtained by using substitution reaction
of anions and cations.
It has not been encountered any article which contains both
ions; Ba2+ and H2 PO2 − in the literature yet. However, there are
some articles including H2 PO2 − ion systems at different temperatures [5–11].
14
H. Erge et al. / Fluid Phase Equilibria 344 (2013) 13–18
Table 1
Physical properties of the chemicals used in this work.
Chemical
CAS No
Source
NaCl
NaH2 PO2 ·H2 O
BaCl2
H3 PO2
CuCl2 ·2H2 O
C10 H14 N2 Na2 O8 ·2H2 O
HCl
K2 Cr2 O7
K2 CrO4
7647-14-5
10039-56-2
10361-37-2
6303-21-5
10125-13-0
6381-92-6
7647-01-0
7778-50-9
7789-00-6
Merck
Merck
Merck
Rİedel-de Haen
Merck
Rİedel-de Haen
Rİedel-de Haen
Merck
Merck
Aliev et al. [5] studied Na2 Cl2 –Mn(H2 PO2 )2 –H2 O system at 20 ◦ C
and they determined that NaCl and Mn(H2 PO2 )2 ·H2 O crystals are
in the solid phase.
Aliev et al. [6] studied Na2 (H2 PO2 )2 –Mn(H2 PO2 )2 –
(NH4 )2 (H2 PO2 )2 –Mn(H2 PO2 )2 –H2 O,
H2 O,
Ca(H2 PO2 )2 –Mn(H2 PO2 )2 –H2 O, systems at 20 ◦ C and they found
that NH4 H2 PO2 , Mn(H2 PO2 )2 ·H2 O and Ca(H2 PO2 )2 ·H2 O crystals
are in the solid phase.
Alisoglu [7] studied Na+ , Mn2+ /Cl− , (H2 PO2 )− //H2 O system
at 25 ◦ C and it was determined that NaCl, MnCl2 ·4H2 O and
Mn(H2 PO2 )2 ·H2 O crystals are in the solid phase.
Alisoglu [8] studied K2 Br2 –MnBr2 –Mn(H2 PO2 )2 –H2 O system
at 25 ◦ C and it was determined that KBr, MnBr2 ·4H2 O and
Mn(H2 PO2 )2 ·H2 O crystals are in the solid phase.
Alisoglu
and
Necefoglu
[9]
studied
that
Na2 (NO3 )2 –Na2 (H2 PO2 )2 –Mn(H2 PO2 )2 –H2 O system at 0 ◦ C and
they determined that NaNO3 , Mn(H2 PO2 )2 ·H2 O and NaH2 PO2 ·H2 O
crystals are in the solid phase.
Alisoglu [10] studied Na+ , Mn2+ /Br− , (H2 PO2 )− //H2 O system
at 25 ◦ C and it was determined that NaBr·2H2 O, MnBr2 ·4H2 O,
NaH2 PO2 ·H2 O and Mn(H2 PO2 )2 ·H2 O crystal hydrates are in the
solid phase.
Alisoglu and Adiguzel [11] studied K+ , Mn2+ /Br− , (H2 PO2 )− //H2 O
system at 25 ◦ C and they found that KBr, MnBr2 ·4H2 O, KH2 PO2 and
Mn(H2 PO2 )2 ·H2 O crystals are in the solid phase
Similarly, by establishing ternary, quaternary, and quinary systems the synthesis of many salts, purifying, and recycling can be
provided with the conclusion of substitution reaction of anions and
cat ions [12,13].
In this study; density, electrical conductivity, phases equilibrium, and solubility of Na+ , Ba2+ /Cl− , (H2 PO2 )− //H2 O system are
applied at 0 ◦ C. A proper method is prepared in order to synthesize
Ba(H2 PO2 )2 .
Purity (in mass fraction)
99%
99%
98%
30%
98%
98%
37%
98%
98%
d (kg m−3 )
–
–
–
1.13
–
–
1.19
–
–
2.2. Experimental method
2. Experimental
Reciprocal Na+ , Ba2+ /Cl− , (H2 PO2 )− //H2 O system at 0 ◦ C,
NaCl/NaH2 PO2 /H2 O, NaCl/BaCl2 /H2 O, NaH2 PO2 /Ba(H2 PO2 )2 /H2 O,
BaCl2 /Ba(H2 PO2 )2 /H2 O ternary and NaCl/Ba(H2 PO2 )2 /H2 O quaternary systems were studied in order to analyze the characteristics
of solubility and phase equilibrium at 0 ◦ C. For example, in order to
establish NaCl/BaCl2 /H2 O ternary system the saturated NaCl solution was prepared in the distilled 60 ml water, into waterproof
and sealed glass bottle at 0 ◦ C (until NaCl crystals appear in solid
phase). Then, a little amount of BaCl2 crystals was added into the
prepared NaCl solution which is stirred for one day and stabilized
along the day. After that, by obtaining some sample from the liquid phase the density, conductivity, and the composition of liquid
phase were measured by using classical analytical methods. This
operation was repeated until finding the invariant point. All these
operations were applied to the whole ternary systems. Then a solid
addition of another 3rd salt, added for the quaternary system, was
convenient for the prepared invariant point, and the solution was
stirred for one day. By obtaining some samples from the stabilized solution; the % composition of liquid phase, conductivity,
and density were analyzed. This operation was maintained until
these three salts came to the saturated invariant point. In this way
NaCl/Ba(H2 PO2 )2 /BaCl2 /H2 O and NaCl/NaH2 PO2 /Ba(H2 PO2 )2 /H2 O
systems were analyzed as well. By converting data to tables, 100
mole mixtures of salt and H2 O volumes which equal to 100 mole
mixture of salt were calculated. Figures were drawn by using calculated data. Interaction of these three salts and their solubility
were calculated by the % composition using drawn graphics. The
analyses of the liquid phase and residues were used to determine
the compositions of solid phases using the Schreinemakers graphic
method (Figs. 1–4, Tables 2–5). According to these results, the characteristics of the separation of Ba(H2 PO2 )2 from the other salts were
reported.
All test were performed in triplicate. Results were expressed as
mean value ± standard deviation.
2.1. Apparatus and reagents
2.3. Analytical methods [14,15]
The chemicals used in this work are described in Table 1. These
chemicals were used without further purification. For preparing solutions, double-distilled deionized water was used. Distilled
water with conductivity less than 10−4 S m−1 and pH 6.6 was used
to prepare the solid–liquid phases equilibrium experiments and for
chemical analysis. Barium hypophosphite was synthesized in our
lab with this classical reaction;
The concentration of Ba2+ ion was analyzed by complexometric titration method by means of EDTA. The concentrations of Cl−
ion was analyzed by Mohr titration method by means of K2 CrO4 .
The concentration of H2 PO2 − ion was analyzed by titrated with
CuCl in the acidic condition. Then, the concentration of Na+ ion was
calculated by ion equilibrium.
2H3 PO2 + BaCO3 → Ba(H2 PO2 )2 + H2 O + CO2
3. Results and discussion
For the analysis of the density of liquid phase, picnometer in
5 ml volume is used and then conductivity is done by using ‘Jenway’
conductometer.
The salt solubilities of binary systems which are constructed
to study ternary systems that belongs to phase equilibrium and
solubility of reciprocal quaternary Na+ , Ba2+ /Cl− , (H2 PO2 )− //H2 O
systems are measured as 24.12% mass BaCl2 , 15.03% mass
H. Erge et al. / Fluid Phase Equilibria 344 (2013) 13–18
15
Table 2
Solubility diagram for the ternary BaCl2 –Ba(H2 PO2 )2 –H2 O system at 0 ◦ C.
No
1
2
3
4
5
6
7
8
9
10
11
12
13
Liquid phase (% mass)
Wet solid phase (% mass)
Solid phase
BaCl2
Ba(H2 PO2 )2
H2 O
BaCl2
Ba(H2 PO2 )2
0.00
3.51
5.64
7.94
11.37
16.19
20.35
21.23
22.53
22.53
22.93
23.52
24.12
15.03
12.98
12.93
12.39
10.85
10.09
9.06
8.93
7.85
7.85
5.27
2.63
0.00
84.97
83.51
81.43
79.67
77.78
73.72
70.59
69.84
69.62
69.62
71.80
73.85
75.88
0.00
0.85
1.12
1.95
2.78
3.95
4.86
5.12
23.65
47.13
68.13
72.02
83.12
92.38
87.15
83.14
78.05
75.14
73.02
71.23
68.75
57.95
18.56
1.55
0.85
0.00
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O + BaCl2 ·2H2 O
Ba(H2 PO2 )2 ·H2 O + BaCl2 ·2H2 O
BaCl2 ·2H2 O
BaCl2 ·2H2 O
BaCl2 ·2H2 O
Standard uncertainties for mass fraction and temperature are ±0.0001 and ±0.2, respectively.
Table 3
Solubility diagram for the ternary NaCl–BaCl2 –H2 O system at 0 ◦ C.
No
1
2
3
4
5
6
7
8
9
10
11
12
13
Liquid phase (% mass)
Wet solid phase (% mass)
Solid phase
NaCl
BaCl2
H2 O
NaCl
BaCl2
0.00
2.15
3.95
5.25
7.80
8.52
11.18
13.00
15.17
15.17
17.64
20.83
26.25
24.12
21.25
19.50
18.14
16.08
15.01
13.35
13.05
12.43
12.43
7.35
4.08
0.00
75.88
76.60
76.55
76.61
76.12
76.47
75.47
73.95
72.40
72.40
75.01
75.09
73.75
0.00
1.30
2.07
2.23
2.66
5.33
6.08
8.45
35.03
55.05
83.27
85.11
88.02
83.25
73.15
68.93
66.81
64.28
63.33
62.05
58.87
35.14
17.33
1.10
0.45
0.00
BaCl2 ·2H2 O
BaCl2 ·2H2 O
BaCl2 ·2H2 O
BaCl2 ·2H2 O
BaCl2 ·2H2 O
BaCl2 ·2H2 O
BaCl2 ·2H2 O
BaCl2 ·2H2 O
BaCl2 ·2H2 O + NaCl
BaCl2 ·2H2 O + NaCl
NaCl
NaCl
NaCl
Standard uncertainties for mass fraction and temperature are ±0.0001 and ±0.2, respectively.
Ba(H2 PO2 )2 , 26.25% mass NaCl, 47.80% mass NaH2 PO2 at 0 ◦ C
(Table 6).
The density, conductivity, and % compositions data of ternary
and quaternary systems of invariant points belonging to solubility and phase equilibrium of reciprocal quaternary Na+ , Ba2+ /Cl− ,
(H2 PO2 )− //H2 O systems are shown below.
The invariant point of BaCl2 /Ba(H2 PO2 )2 /H2 O ternary
system is analyzed as 22.53% mass BaCl2 , 7.85% mass
Ba(H2 PO2 )2 , 69.62% mass H2 O. It is determined that
BaCl2 ·2H2 O and Ba(H2 PO2 )2 ·H2 O crystal hydrates are in
equilibrium with liquid phase, the density of invariant
point is 1399 kg m−3 and electrical conductivity of it is
3900 mS cm−1 .
The invariant point of NaCl/BaCl2 /H2 O ternary system is analyzed as 15.17% mass NaCl, 12.43% mass BaCl2 , 72.40% mass H2 O.
It is determined that BaCl2 ·2H2 O and NaCl crystal hydrates are
in equilibrium with liquid phase, the density of invariant point is
1238 kg m−3 and electrical conductivity of it is 7100 mS cm−1 .
Table 4
Solubility diagram for the ternary NaCl–NaH2 PO2 –H2 O system at 0 ◦ C.
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Liquid phase (% mass)
Wet Solid phase (% mass)
NaCl
NaH2 PO2
H2 O
NaCl
NaH2 PO2
26.25
24.18
22.37
20.36
17.81
14.46
12.28
10.19
8.07
5.86
4.12
1.80
1.12
1.12
0.78
0.00
0.00
2.97
5.68
9.22
12.85
19.62
23.51
27.16
31.12
35.90
38.54
42.60
44.02
44.02
45.90
47.80
73.75
72.85
71.95
70.42
69.34
65.92
64.21
62.65
60.81
58.24
57.34
55.60
54.86
54.86
53.32
52.20
92.95
91.22
89.63
87.21
84.83
82.53
80.28
77.79
75.40
72.98
70.56
68.12
54.53
8.54
0.18
0.00
0.00
0.85
1.12
2.73
4.41
6.13
7.81
9.52
11.33
12.74
13.83
14.52
31.10
64.34
72.13
75.20
Standard uncertainties for mass fraction and temperature are ±0.0001 and ±0.2, respectively.
Solid phase
NaCl
NaCl
NaCl
NaCl
NaCl
NaCl
NaCl
NaCl
NaCl
NaCl
NaCl
NaCl
NaCl + NaH2 PO2 .H2 O
NaCl + NaH2 PO2 ·H2 O
NaH2 PO2 ·H2 O
NaH2 PO2 ·H2 O
16
H. Erge et al. / Fluid Phase Equilibria 344 (2013) 13–18
Table 5
Solubility diagram for the ternary NaH2 PO2 –Ba(H2 PO2 )2 –H2 O system at 0 ◦ C.
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Liquid phase (% mass)
Wet solid phase (% mass)
Solid phase
NaH2 PO2
Ba(H2 PO2 )2
H2 O
NaH2 PO2
Ba(H2 PO2 )2
47.80
46.60
45.27
45.27
45.02
42.29
39.60
36.15
30.80
24.85
21.90
17.67
13.80
9.28
4.66
0.00
0.00
0.30
0.55
0.55
0.55
0.56
0.62
0.75
0.90
1.15
1.25
1.96
3.30
5.79
10.39
15.03
52.20
53.10
54.18
54.18
54.43
57.15
59.78
63.10
68.30
74.00
74.85
80.37
82.90
84.93
84.95
84.97
81.25
76.85
65.15
32.95
15.25
13.80
11.27
10.50
7.65
5.80
4.75
3.29
2.68
1.78
1.03
0.00
0.00
0.35
16.17
50.11
62.30
64.90
67.20
68.25
70.01
72.50
78.08
79.85
79.13
81.22
82.70
92.15
NaH2 PO2 ·H2 O
NaH2 PO2 ·H2 O
NaH2 PO2 ·H2 O + Ba(H2 PO2 )2 ·H2 O
NaH2 PO2 ·H2 O + Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Standard uncertainties for mass fraction and temperature are ±0.0001 and ±0.2, respectively.
Table 6
Solubility diagram for the quaternary NaCl–Ba(H2 PO2 )2 –H2 O system at 0 ◦ C.
No
Liquid phase (% mass)
Wet solid phase (% mass)
NaCl
Ba(H2 PO2 )2
H2 O
NaCl
Ba(H2 PO2 )2
1
2
3
4
5
6
7
8
9
10
11
26.25
24.89
23.33
22.80
22.80
20.85
15.47
10.95
6.33
3.34
0.00
0.00
2.66
6.07
8.33
8.33
9.12
10.58
11.92
13.33
14.20
15.03
73.75
72.44
70.60
68.87
68.87
70.03
73.95
77.13
80.34
82.46
84.97
100
95.55
89.78
66.85
23.95
83.53
76.97
67.72
52.02
34.93
0.00
0.00
4.45
10.22
13.80
49.12
16.47
23.03
32.28
47.98
65.07
100
Solid phase
NaCl
NaCl
NaCl
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 .H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Ba(H2 PO2 )2 ·H2 O
Standard uncertainties for mass fraction and temperature are ±0.0001 and ±0.2, respectively.
The invariant point of NaCl/Ba(H2 PO2 )2 /H2 O quaternary system
is analyzed as 22.80% mass NaCl, 8.33% mass Ba(H2 PO2 )2 , 68.87%
mass H2 O. It is determined that Ba(H2 PO2 )2 ·H2 O and NaCl crystal hydrates are in equilibrium with liquid phase, the density of
invariant point is 1243 kg m−3 and electrical conductivity of it is
6500 mS cm−1 .
The invariant point of NaCl/NaH2 PO2 /H2 O ternary system is analyzed as 1.12% mass NaCl, 44.02% mass NaH2 PO2 , 54.86% mass H2 O.
Fig. 1. Solubility diagram for the ternary BaCl2 –Ba(H2 PO2 )2 –H2 O system at 0 ◦ C by
using Schreinemakers method.
Fig. 2. Solubility diagram for the ternary NaCl–BaCl2 –H2 O system at 0 ◦ C by using
Schreinemakers method.
H. Erge et al. / Fluid Phase Equilibria 344 (2013) 13–18
17
Fig. 5. Solubility diagram for the quaternary NaCl–Ba(H2 PO2 )2 –H2 O system at 0 ◦ C
by using Schreinemakers method.
Fig. 3. Solubility diagram for the ternary NaCl–NaH2 PO2 –H2 O system at 0 ◦ C by
using Schreinemakers method.
It is determined that NaH2 PO2 ·H2 O and NaCl crystal hydrates are
in equilibrium with liquid phase, the density of invariant point is
1370 kg m−3 and electrical conductivity of it is 6650 mS cm−1 .
The invariant point of NaH2 PO2 /Ba(H2 PO2 )2 /H2 O ternary system is analyzed as 45.27% mass NaH2 PO2 , 0.55% mass Ba(H2 PO2 )2 ,
54.18% mass H2 O. It is determined that Ba(H2 PO2 )2 ·H2 O and
NaH2 PO2 ·H2 O crystal hydrates are in equilibrium with liquid phase,
the density of invariant point is 1282 kg m−3 and electrical conductivity of it is 7800 mS cm−1 .
The invariant point of NaCl/BaCl2 /Ba(H2 PO2 )2 /H2 O quaternary
system is analyzed as 15.03% mass NaCl, 12.36% mass BaCl2 , 2.86%
mass Ba(H2 PO2 )2 , 69.75% mass H2 O. It is determined that NaCl,
Ba(H2 PO2 )2 ·H2 O, and BaCl2 2H2 O crystal hydrates are in equilibrium with liquid phase (Figs. 5 and 6).
The invariant point of NaCl/NaH2 PO2 /Ba(H2 PO2 )2 /H2 O quaternary system is analyzed as 1.06% mass NaCl, 43.98% mass NaH2 PO2 ,
Fig. 4. Solubility diagram for the ternary NaH2 PO2 –Ba(H2 PO2 )2 –H2 O system at 0 ◦ C
by using Schreinemakers method.
0.51% mass Ba(H2 PO2 )2 , 54.45% mass H2 O. It is determined that
NaCl, Ba(H2 PO2 )2 ·H2 O, and NaH2 PO2 ·H2 O crystal hydrates are in
equilibrium with liquid phase.
By using the analysis results of quaternary systems, H2 O masses
which are equal to 100 mole salt compositions and 100 mole salt
compositions are calculated and formed in Table 7. Fig. 4 was drawn
by using data of Table 7 with Yeneke Method.
As it is seen in experimental data and figures the crystallization
of Ba(H2 PO2 )2 , being the largest in comparison with those other
Fig. 6. Reciprocal quaternary Na+ , Ba2+ /Cl− , (H2 PO2 )− //H2 O water–salt system’s in
solubility and phase equilibrium by using Yeneke method at 0 ◦ C.
18
H. Erge et al. / Fluid Phase Equilibria 344 (2013) 13–18
Table 7
Reciprocal quaternary Na+ , Ba2+ /Cl− , (H2 PO2 )− //H2 O water–salt system’s solubility, % mass liquid phase, % mole salt composition of liquid phase, and salt content of solid
phase at 0 ◦ C.
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Liquid phase (% mass)
Liquid phase (% mole composition of salt)
NaCl
BaCl2
NaH2 PO2
Ba(H2 PO2 )2
NaCl
BaCl2
NaH2 PO2
Ba(H2 PO2 )2
0.00
22.80
15.17
2.53
5.05
7.58
10.11
12.64
13.88
15.03
19.40
21.10
1.12
22.80
0.00
21.03
18.02
15.01
12.00
8.98
5.51
3.00
1.06
0.68
22.53
0.00
12.43
21.52
20.50
19.49
18.48
17.27
16.68
12.36
10.30
5.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
44.02
0.00
45.27
6.01
11.96
18.00
23.59
29.56
35.00
39.80
43.98
42.86
7.88
8.33
0.00
7.06
6.25
5.44
4.63
3.82
3.28
2.86
4.29
6.31
0.00
8.33
0.55
7.18
6.16
5.14
4.12
3.08
2.03
1.01
0.51
0.46
0.00
86.20
68.44
14.26
26.15
36.22
44.87
52.61
56.18
64.70
71.65
77.88
3.70
86.14
0.00
74.66
62.83
51.39
40.71
29.96
18.49
10.02
3.49
2.30
78.60
0.00
31.56
68.32
59.66
52.38
46.13
40.43
37.99
29.91
21.40
11.92
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
96.30
0.00
99.23
14.18
27.74
40.95
53.17
65.55
78.52
88.49
95.79
97.01
21.40
13.80
0.00
17.42
14.19
11.40
9.00
6.96
5.83
5.39
6.95
10.20
0.00
13.86
0.77
11.16
9.43
7.66
6.12
4.49
2.99
1.49
0.72
0.69
Solid phase
BaCl2 .2H2 O + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + BaCl2 ·2H2 O
BaCl2 ·2H2 O + Ba(H2 PO2 )2 ·H2 O
BaCl2 .2H2 O + Ba(H2 PO2 )2 .H2 O
BaCl2 ·2H2 O + Ba(H2 PO2 )2 ·H2 O
BaCl2 ·2H2 O + Ba(H2 PO2 )2 ·H2 O
BaCl2 .2H2 O + Ba(H2 PO2 )2 ·H2 O
BaCl2 ·2H2 O + Ba(H2 PO2 )2 ·H2 O
NaCl + BaCl2 ·2H2 O + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + NaH2 PO2 ·H2 O
NaH2 PO2 .H2 O + Ba(H2 PO2 )2 ·H2 O
NaH2 PO2 .H2 O + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + Ba(H2 PO2 )2 ·H2 O
NaCl + NaH2 PO2 ·H2 O + Ba(H2 PO2 )2 ·H2 O
NaH2 PO2 .H2 O + Ba(H2 PO2 )2 ·H2 O
Standard uncertainties for mass fraction and temperature are ±0.0001 and ±0.2, respectively.
salts, has occupied 82% of the general crystallization field. Therefore, Ba(H2 PO2 )2 has the largest crystallization field. Therefore;
BaCl2 ·2H2 O and NaH2 PO2 ·H2 O. It is found that Ba(H2 PO2 )2 salt
contains 82% of the general crystallization field.
2NaH2 PO2 + BaCl2
References
2NaCl + Ba(H2 PO2 )2
In the substitution reaction above, it is expressed that equilibrium is
towards Ba(H2 PO2 )2 . Experimental results and figures can be used
in the salt industry and recycling units. These Ba(H2 PO2 )2 , NaCl,
BaCl2 and NaH2 PO2 salts, which may contain industrial waste and
natural salt composition, are thought to be used as a separation
method from each other.
4. Conclusion
The physicochemical characteristics of reciprocal quaternary
Na+ , Ba2+ /Cl− , (H2 PO2 )− //H2 O water–salt system’s solubility and
phase equilibrium were studied by using isothermal method at 0 ◦ C.
A quaternary and 4 ternary systems’ solubilities, phase equilibrium,
conductivities, and densities were determined experimentally. The
solid phase of all systems were found as NaCl, Ba(H2 PO2 )2 ·H2 O,
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
Z. Li, T. Deng, M. Liao, Fluid Phase Equilibr. 293 (2010) 42–46.
Q. Guan, W. Li, M. Zhang, K. Tao, J. Catal. 263 (2009) 1–3.
R. Paris, P.C.R Tardy, Acad. Sci. (1946) 223–242.
J.R. Van Vazer, Encyclopedia of Chemical Technology, vol. 10, Interscience Publishers, New York, 1953.
V.A. Aliev, S.M. Velieva, Zr. Neorg. Khim. 30 (1985) 798–801.
R.M. Dolinina, V.A. Aliev, I.N. Lepeschkov, Zr. Neorg. Khim. 34 (1990)
1324–1327.
V. Alisoglu, C.R. Chim 5 (2002) 547–549.
V.C.R. Alisoglu, Acad. Sci. Paris, Ser. IIc 1 (1998) 781–784.
V. Alisoglu, H. Necefoglu, C.R. Acad. 324 (1997) 139–142.
V. Alisoglu, C.R. Chim. 8 (2005) 1684–1687.
V. Alisoglu, V. Adıguzel, C.R. Chim. 11 (2008) 938–941.
S. Sang, J. Peng, Calphad 34 (2010) 64–67.
C. Christov, Calphad 25 (1) (2001) 11–17.
T. Gündüz, Kantitatif Analiz Laboratuar Kitabi, Gazi Kitabevi, Ankara-Turkey,
1999.
J.R. Van Vazer, Phosphorus and its Compounds, Interscience Publishers, New
York, 1958.