J. Cent. South Univ.

(2012) 19: 27512754

DOI: 10.1007/s11771-012-1337-2

Thermodynamic equilibrium diagram of CaCl2-Ca(OH)2-H2O system

LIU Wei-ping(), XU Hui(), YANG Xi-yun(), SHI Xi-chang(), CHEN Ya()

School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China
Central South University Press and Springer-Verlag Berlin Heidelberg 2012

Abstract: The lg cpH diagram of the CaCl2-Ca(OH)2-H2O system and its two subsystems at 298.15 K are constructed according to
the theory of thermodynamic equilibrium. The interaction characteristics between the solubility of CaCl2 and Ca(OH)2 can be found
out from the diagrams. CaCl2.6H2O (s), Ca(OH)2(s) and solution coexist when the pH value of solution is about 10.8. CaCl2 with the
minimum solubility of 1 682.4 g/L is in equilibrium with solution when the pH value is lower than 9.4, and Ca(OH)2 with the
minimum solubility of 2.749 g/L is in equilibrium with solution at the pH value over 12.1, which provides a theoretical basis for the
treatment and reuse of calcium chloride mother liquor for collocating lime cream which is the precipitant in the process of
synthesizing magnesium hydroxide.

Key words: CaCl2-Ca(OH)2-H2O system; solubility; lg cpH diagram; thermodynamic equilibrium; magnesium hydroxide

have a bad influence on the quality of the product and the

1 Introduction
Magnesium hydroxide, a very popular,
environmental friendly and thermally stable flame-
retardant filler in composite materials [13], is also used
in catalysis, as an additive in paint, ceramics,
neutralizing acidic waste streams and gases rich in
sulfuric oxides [4], as antacid excipient in pharmaceutics
[5], in pulp and paper industry, as fertilizer additive, and
as the most important precursor for magnesium oxide.
For example, magnesium hydroxide can be used as
precursor for the synthesis of MgO with special
mechanic, catalytic and electronic properties. Most
importantly, it has lately been demonstrated that
magnesium hydroxide can play a key role in the mineral
sequestration of an important green house gas CO2 [6].
The wet route (mixing of MgCl2 and the alkaline
(NaOH, NH4OH or Ca(OH)2) solutions at room
temperature followed by the hydrothermal treatment) is
one of the main methods to synthesize functional
Mg(OH)2 powders [7].
With lower ammonia utilization efficiency and
higher production cost, the ammonium was used as a
precipitating agent to produce magnesium hydroxide
which will pollute the environment [8]. Colloidal
magnesium hydroxides will be produced by the sodium
hydroxide and magnesium salts if the parameters of
technology have not been controlled well [9], which will
ions Na+, Cl and other impurities are involved, and the
cost of precipitant sodium hydroxide is high. Compared
with the ammonia process and sodium hydroxide
process, the lime milk method has better properties
which are the richness of lime in natural resources, low
cost and a promising prospect in industry. ZHANG and
YUAN [10], ZHANG et al [11], HAN et al [12], and
GAO et al [13] have made many improvements to the
traditional lime milk method, the content of calcium is
lower and the purity of production is improved. However,
abundant of by-product calcium chloride mother liquor is
produced, which should be utilized circularly. If the
liquor is utilized properly, not only the cost of the
method is reduced but also the content of Ca2+ in solution
will increase which will cause lower oversaturation and
better sedimentation property [14]. However, most of the
previous studies mainly focus on the influence of process
parameter and area of the mechanism in detail is seldom
concerned.
In this work, aiming at promoting the reuse and
recycling of calcium chloride mother liquor for
collocating lime cream, the lg cpH diagram of the
CaCl2-Ca(OH)2-H2O system at 298.15 K, as a theoretical
guidance for the practical process, is constructed
according to the thermodynamic equilibrium principle.
This diagram reveals the interaction characteristics
between the solubility of CaCl2(s) and Ca(OH)2(s) which
can be the theoretical guidance for practical process.

Foundation item: Project(2008BAB35B04) supported by National High Technology Research and Development Program of China; Project(2010QZZD003)
supported by Advanced Research Program of Central South University, China
Received date: 20110930; Accepted date: 20111226
Corresponding author: XU Hui, Professor, PhD; Tel: +8613974800183; E-mail: lwp19860830@gmail.com
2752 J. Cent. South Univ. (2012) 19: 27512754

2 Drawing of thermodynamic equilibrium

diagram

2.1 Thermodynamic relationship between Ca(OH)2(s)

solubility and pH value
There are two kinds of calcium hydroxyl complex
ions in Ca(OH)2-H2O system such as CaOH+ and
Ca(OH)2. Accordingly, their equilibrium equations and
cumulative formation constants at 298.15 K are
expressed as follows [1519]:

c(CaOH )
Ca2++OH CaOH+, 1 101.4 (1)
c(Ca 2 )c(OH )
Ca2++2OH Ca(OH)2,
Fig. 1 Diagram of lg cpH of Ca(OH)2-H2O system at
c(Ca(OH) 2 ) 3.83
2 10 (2) 298.15 K
c(Ca 2 )c(OH ) 2
Knowing that: 2.2 Thermodynamic relationship between CaCl2(s)
Ca(OH)2(s) Ca2++2OH, solubility and pH value
KSP=c(Ca )c(OH)2=5.5106
2+
(3) There also exist two kinds of calcium hydroxyl
complex ions, CaOH+ and Ca(OH)2, in CaCl2-H2O
The following equation and constant could be
system. Correspondingly, their equilibrium equations and
obtained according to Eq. (1) and Eq. (3) [20]:
cumulative formation constants at 298.15 K are
Ca(OH)2(s) CaOH++OH, expressed as follows:
KS1=KSP1=c(CaOH+)c(OH)=103.86 (4)
H2O H++OH+, KSP=c(OH+)c(H+) (9)
Equally, the combination of Eq. (2) and Eq. (3)
From Eq. (1) and Eq. (9), Eq. (10) can be deduced:
generates the following equation and constant:
2+
Ca +H2O CaOH++H+,
Ca(OH)2(s) Ca(OH)2,
KS2=KSP2=c(Ca(OH)2)=101.43 (5) c(CaOH )c(H )
K1 K SP 1 10 12.6 (10)
c(Ca 2 )
Taking the logarithm of both sides of Eqs. (3)(5)
gives: From Eq. (2) and Eq. (9), Eq. (11) can be deduced:
2+
2+
lg c(Ca )=22.742pH (6) Ca +2H2O Ca(OH)2+2H+,
lg c(CaOH+)=10.14pH (7) c(Ca(OH)2 )c(H ) 2
K 2 K SP 2 2
10 24.17 (11)
c(Ca )
lg c(Ca(OH)2)=1.43 (8)
The concentrations of Ca(OH)2, Ca2+ and CaOH+ The mass balance for calcium in solution is [21]
could be calculated by Eqs. (6)(8) at a given pH value, cT(Ca)=c(Ca2+)+c(CaOH+)+c(Ca(OH)2) (12)
respectively. The lgcpH diagram of the Ca(OH)2-H2O
It should be noted that the cT(Ca), which represents
system at 298.15 K are shown in Fig. 1 [2123].
the total soluble concentration of calcium, is also termed
The lines in Fig. 1 demonstrate the lgc of different
as the solubility of calcium.
calcium-containing species related to the pH values when
From Eq. (10) and Eq. (11), the following equations
the relative ions are in equilibrium with Ca(OH)2(s). The
can be deduced:
stable zone of Ca(OH)2(s) is surrounded by small short
lines. The others are the unsaturated zones of K1
c(CaOH ) c(Ca 2 ) (13)
Ca(OH)2(s). Boundaries constituting this stable zone c(H )
could approximately represent the total solubility of
K 2
Ca(OH)2(s) at different pH values in this system. From c(Ca(OH) 2 ) 2
c(Ca 2 ) (14)
Fig.1, it can also be seen that the minimum solubility of c(H )
Ca(OH)2(s) is 2.749 g/L as the pH value varies from 12.1 Inserting Eq. (13) and Eq. (14) into Eq. (12) gives
to 14.0; As the pH value is lower than 12.1, the solubility
K1 K 2
of Ca(OH)2(s) will increase with the decline of the pH c(Ca 2 ) cT (Ca )(1
) (15)
value. c(H ) c( H ) 2
J. Cent. South Univ. (2012) 19: 27512754 2753
Hydrochloric acid is a monoprotic acid, which may
yield one proton. Correspondingly, its ionization
equations and equilibrium constants are expressed as
follows [21]:
c(Cl )c(H )
HCl H++Cl, K 106.1 (16)
c(HCl)
The mass balance for chlorine in solution is
cT(Cl)=c(Cl)+c(HCl) (17)
Similarly, cT(Cl) represents the total concentration
of chlorine. Inserting Eq. (16) into Eq. (17) gives

c(H + ) 1
c(Cl )=cT (Cl)(1+ ) (18)
K
Fig. 2 lg cpH diagram of CaCl2-H2O system at 298.15 K
The solubility of CaCl2 is 46.08% (mass fraction) at
298 K (the density of water is 0.997 07 g/mL), solid
when the solution is in equilibrium with CaCl26H2O(s).
phase crystallization is CaCl26H2O [2425]. The
equilibrium equation and the solubility-product constant The area above the curve is the stable zone of
are expressed as follows: CaCl26H2O(s), where CaCl26H2O(s) could exist stably,
and below the curve is the unsaturated zone. Boundary
CaCl26H2O Ca2++2Cl+6H2O, K=c(Ca2+)c(Cl)2 (19) constituting this stable zone can approximately illustrate
According to the total solubility of CaCl26H2O(s) at different pH
values in the CaCl2-H2O system. The minimum
K MN XN N 3H 2 O exp[( M N XN N 3H 2O N1 M
1 2 1 2 solubility of CaCl2(s) is 1 682.4 g/L at the pH value of

N2 M N 3 M ) /( RT )] (20) 09.4, and beyond this scope the solubility of CaCl2(s)
increases.
The standard chemical potential of CaCl26H2O:
2.3 Thermodynamic equilibrium diagram of CaCl2-
CaCl 2 6H 2 O
=RT ( 893.65) (21)
Ca(OH)2-H2O system
The standard chemical potential of Ca2+: The thermodynamic equilibrium diagram of the

Ca CaCl2-Ca(OH)2-H2O system (Fig. 3) is constructed by
2 RT ( 223.30) (22)
combination of Fig. 2 and Fig. 1 [2123]. From Fig. 3, it
The standard chemical potential of Cl: can be concluded that the stable zones of Ca(OH)2(s) and
CaCl2(s) overlap partially. The point a represents the
Cl RT ( 52.955) (23)
triple equilibrium point where CaCl26H2O(s) and
Inserting Eq. (21), Eq. (22) and Eq. (23) into Ca(OH)2(s) are in equilibrium with the solution
Eq. (20) gives simultaneously, and the dash line vertical to the pH axis
from point a (pH=10.8) represents that CaCl26H2O(s)
K CaCl2 6 H 2O exp[893.65 (223.30) 2 (52.955) and Ca(OH)2(s) coexist at this pH value. The area on the
6 ( 95.663 5)] 13 918.86 (24) left of the dash line is the stable zone of CaCl26H2O(s),
where the solubility of CaCl26H2O(s) is less than that of
Inserting Eq. (15), Eq. (18) and Eq. (24) into Eq. (19)
Ca(OH)2(s), and Ca(OH)2(s) dissolves into the solution
gives
and CaCl2.6H2O precipitates. The area on the right of the
K1 K 2 c(H + ) 2 dash line is the stable zone of Ca(OH)2(s), and
K =cT (Ca)(1+ + ) 1 cT (Cl) 2 (1+ ) CaCl26H2O dissolves and Ca(OH)2 precipitation occurs.
c (H + ) c(H + ) 2 K
The area above the solid line is the stable zone where the
(25) corresponding precipitates exist at different pH values,
The total concentration of chlorine is two times that while the area below the solid line is the unsaturated
of calcium in the system according to calcium chlorine zone where solution exists stably. And the solid line
ionization equation, and the lg cpH diagram of the represents the total equilibrium concentration of calcium
CaCl2-H2O system can be obtained according to Eq. (25) at different pH values. Figure 3 also shows that the
as shown in Fig. 2 [21]. minimum solubility of Ca(OH)2(s) is 2.749 g/L at the pH
The curve in Fig. 2 represents the total concentration value over point b (pH=12.1), and the concentration of
of calcium-containing species related to the pH value the Ca(OH)2(s) retains its maximum concentration as the
2754
solubility of CaCl2 keeps a constant at the pH value of
010.8. Figure 3 also indicates that Ca(OH)2(s) dissolves
into the solution and CaCl26H2O precipitates in the
ternary system located on the equilibrium line at the pH
value below the triple equilibrium point a. Reversely,
Ca(OH)2 is preponderant at the pH value over the triple
equilibrium point a.
Fig. 3 lg cpH diagram of CaCl2-Ca(OH)2-H2O system at
298.15 K
3 Conclusions
1) The lg cpH diagrams of CaCl2-Ca(OH)2-H2O
system and its subsystem at 298.15 K are constructed
according to the theory of thermodynamic equilibrium.
The interaction characteristics between the solubility of
CaCl2(s) and Ca(OH)2(s) can be found out from
diagrams.
2) CaCl26H2O(s), Ca(OH)2(s) and solution coexist
at the pH value of about 10.8. In the solution equilibrated
with CaCl26H2O(s), the minimum solubility of CaCl2 is
1 682.4 g/L at the pH value below 9.4, while the solution
is in equilibrium with Ca(OH)2(s) and its minimum
solubility is 2.749 g/L at the pH value over 12.1.
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