Fluid Phase Equilibria 254 (2007) 158162

Solubility of sodium chloride in water under high pressure

Seiji Sawamura

, Nobuaki Egoshi, Yoshihiro Setoguchi, Hiroshi Matsuo

Department of Applied Chemistry, Faculty of Science and Engineering, Ritsumeikan University, Kusatsu, Shiga 525-8577, Japan
Received 21 October 2006; received in revised form 26 February 2007; accepted 1 March 2007
Available online 6 March 2007
Abstract
The solubility (m
sat
) of sodium chloride in water was measured in the pressure range 0.10300 MPa, and temperatures from 263 to 313 K.
In the region of high temperature and low pressure, the solubility values of NaCl anhydride obtained were tted to the equation ln[m
sat
(p,
T)/mol kg
1
] =2.86623 571.361/(T/K) +77,128/(T/K)
2
+4.0479 10
4
(p/MPa) 7.445 10
7
(p/MPa)
2
+6.209 10
10
(p/MPa)
3
with a stan-
dard deviation of 0.08%. In the low-temperature and high-pressure region, the values for NaCl2H
2
O were tted to ln[m
sat
(p,
T)/mol kg
1
] =5.35183 1366.040/(T/K) +108,664/(T/K)
2
+[0.010331 5.8869(T/K)
1
+831.7(T/K)
2
](p/MPa) with a standard deviation of
0.14%. The experimental values of the high-pressure solubilities were compared with thermodynamic estimates using density data of the solid and
aqueous solution of sodium chloride and the activity coefcient of the aqueous solution.
2007 Elsevier B.V. All rights reserved.
Keywords: Solubility; Sodium chloride; High pressure
1. Introduction
Sodium chloride and water constitute a prototypical solute
and solvent pair for solubility studies. The number of investiga-
tions measuring the solubility of this system amounts to more
than 100 [1]. Fig. 1 shows the domains where the measurements
were performed at pressures higher than 3 MPa. In this gure,
only four studies, namely #25, employed pressures exceed-
ing 50 MPa and these were executed about 100 years ago. Such
studies, where a high pressure of over 50 MPa is maintained in a
bomb for a long time in order to attain equilibrium was not easy.
Therefore, further direct measurements at such high pressures
have not been performed, although many measurements of the
solubility have continued at atmospheric pressure. As an alter-
native, thermodynamic estimates of the high-pressure solubility
have been attempted using the density of the solution and solid
solute [10,11].
We have measured the solubility of several compounds under
high pressures; not only inorganics [1215] but also organic
solids [1619], liquid hydrocarbons [2022], and a fullerene
[23,24]. Several improvements of pressure vessels and other
high-pressure equipment have been implemented in these stud-

Corresponding author. Tel.: +81 77 566 1111; fax: +81 77 561 2629.
E-mail address: sawamura@se.ritsumei.ac.jp (S. Sawamura).
ies in order to obtain more reliable solubility data. Since the
pioneering work of Adams et al. [6] and others [4,5] there have
also been improvements to commercially available pumps, pres-
sure gauges, and other high-pressure ttings; a exible tube used
in the present work is one of them. In the present work, we
applied these high-pressure techniques to the measurement of
the solubility of sodium chloride in water under high pressures.
We also measured the solubility of its hydrate, NaCl2H
2
O, at
low temperatures and high pressure.
2. Experimental
2.1. Materials
A special grade of sodium chloride (>99.5%) was purchased
from Nakarai Tesque Co. and used without further purication.
Water was deionized and distilled. The solid hydrate of sodium
chloride, NaCl2H
2
O, was prepared as follows. An excess quan-
tity of sodium chloride and water was mixed in a ask and
allowed to stand in a refrigerator at 273 K for 1 day. Then the
upper solution portion of the mixture was removed and further
cooled in a freezer at 258 K for one more day. We obtained a
plate-like precipitate which used as the solid hydrate. It was
stable up to a temperature of 281 K with hysteresis and was
dissociated into solid NaCl and water at higher temperatures.
0378-3812/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2007.03.003
S. Sawamura et al. / Fluid Phase Equilibria 254 (2007) 158162 159
Fig. 1. Diagram of solubility data of sodium chloride in water (p >3MPa): (1)
M oller (1862) [2]; (2) Von Stackelberg (1896) [3]; (3) Cohen and Sinnige (1910)
[4]; (4) Sill (1910) [5]; (5) Adams and Hall (1931) [6]; (6) Keevil (1942) [7]; (7)
Olander and Liander (1950) [8]; (8) Bischoff et al. (1986) [9]; (9) present work.
2.2. Apparatus and procedure
Fig. 2 shows the pressure vessel used for the preparation of
saturated solutions under high pressures. The outer diameter of
the main body is 70 mm and the inner bore is 1518 mm. It
is made of corrosion-resistant 17-4PH stainless steel and has
a valve (G) and an outlet tube (H). A jacket through which hot
water circulates is attached to the outlet tube and a similar mech-
anism is used to warm the valve. An inner cell (B) made of
uorinated plastic was connected to a plug (I). A glass lter was
attached to the tip of the inner cell to separate the solid solute
Fig. 2. Cylindrical pressure vessel with a valve and an inner cell: (A) cylinder;
(B) inner cell; (C) piston; (D) sample volume; (E) compression oil; (F) ball; (G)
valve with a heating device; (H) outlet tube with a heating jacket; (I) plug.
from sample solution. Water and an excess quantity of sodium
chloride was placed in the inner cell with a shaking ball (F) made
of uorinated plastic. In the case of NaCl2H
2
O, a mixture of the
solid solute (NaCl2H
2
O) and a solution prepared as above was
placed in the inner cell in the previously cooled pressure ves-
sel. The sample mixture was separated fromthe compression oil
(kerosine) in the inner cell by a uorinated plastic piston with
two uorinated o-rings. If we used the piston tted to the pres-
sure vessel directly to the cylinder without using the inner cell,
expansion of the cylinder, coupled with compression of the pis-
ton produces a slight opening between the piston and cylinder
of the pressure vessel at pressures higher than 200 MPa, and the
compression oil contaminated the sample solution. Details of
the inner cell are shown in Fig. 2. For the seal between the pres-
sure vessel and plug (I), a commercially available uorinated
o-ring and a back-up ring, which was made of annealed copper
and designed by us with an accuracy of 0.01 mm, were used;
these parts were exchanged for every measurement. The valve
cone and other metal-to-metal sealing parts were often cut and
polished and some parts were exchanged for new ones. Such
frequent high-pressure sealing maintenance allows us to easily
maintain the pressure constant at high values for a long time
without any trouble.
Fig. 3 shows the whole high-pressure system. The pressure
vessel (A) was xed on a seesaw(F) in a water bath (J) of 40 dm
3
volume and the seesaw was moved 23 times a minute in order
to stir the sample in the pressure vessel. At low temperatures,
the water in the bath was changed to aqueous ethylene glycol.
The compression oil was pushed into the pressure vessel from
a hydraulic pump (B) through a exible stainless tube (E) of
1.6 mm outer diameter. By using such a exible tube, the pres-
sure vessel connected to the tube can be shaken on the seesaw.
Fig. 3. Mixing equipment for the thermostatted cylindrical pressure vessel: (A)
pressure vessel; (B) hydraulic pump; (C) pressure gauge; (D) valve; (E) exible
tube; (F) seesaw; (G) thermoregulator; (H) stirrer; (I) motor with a reduction
gear; (J) water bath.
160 S. Sawamura et al. / Fluid Phase Equilibria 254 (2007) 158162
The whole system shown in Fig. 3 was placed in an air-
conditioned roomat 298 1 Kbecause the pressure in the closed
system depends on the room temperature. Further, the valve (D)
was closed during the shaking to reduce the part of the closed
system which is kept in an ambient condition. As the pressure
in this closed system decreased accompanying the dissolution
of the solute, we repeatedly adjusted the pressure in the vessel
several times until the system attained equilibrium. We used the
cessation of the need to adjust the pressure at equilibrium as a
convenient method to signal the achievement of equilibration.
After moving the seesawfor several tens of hours, it was then
stopped and the pressure vessel was allowed to stand for a while
to let particles of the solid solute in the inner cell sink; then the
sample solution was taken out drop by drop from the outlet by
slightly loosening the valve. Throughout this operation, the ves-
sel (A) was held at a constant pressure by pushing compression
oil into the vessel from the hydraulic pump. The initial portion
(23 cm
3
) of the solution was discarded and the subsequent part
(79 cm
3
) was collected. The sample was weighed before and
after drying in an electric oven at about 440 K to determine the
concentration. When the sample solution was taken out of the
pressure vessel, hot water was circulated around the valve (G)
and outlet tube (H) in Fig. 2 to avoid any precipitation of the
solute.
To measure the pressure in the system, a precise gauge (C in
Fig. 3) of the Bourdon-tube type with an accuracy of 1 MPa,
a Heise model (45 cm diameter, full scale is 700 MPa and the
smallest division is 0.5 MPa) produced by Dresser Industries,
was used. It was connected to the hydraulic pump (B) and the
pressure vessel (A) and calibrated by the same company with
a standard pressure gauge of free-piston type with an accuracy
of 0.01% of full scale based on American National Standards
Institute methods NCSL Z540-1 and ISO-10012. Because we
were conducting long-term measurements of the solubility, the
pressure gauge (C) was recalibrated by us with a new pressure
gauge of the same type purchased fromand calibrated by Dresser
Industries.
The temperature of water bath was regulated within 005 K
using an onoff type regulator designed by us with a sensitiv-
ity better than 1 mK. A suitable power level of the regulating
heater was selected or a cooler unit was used depending on the
environmental conditions. The temperature was measured with
a three-wire platinum-resistance thermometer.
3. Results and discussion
3.1. Equilibration time
The concentration of sodium chloride in the pressure vessel
is plotted against the equilibration time in Fig. 4. After 1 day,
the concentration becomes constant at each set of conditions
and this value was regarded as the solubility. For most cases, we
actually allowed more than 1 day for equilibration.
For the measurements close to the transition points between
the two solid phases of NaCl and NaCl2H
2
O, the equilibration
time often became much longer (sometimes too long to obtain
accurate estimates of the solubility) because of hysteresis. After
Fig. 4. Time course of the concentration of sodium chloride in the water phase
in the pressure vessel during mixing.
several trials, we selected the solute which should be placed in
the pressure vessel as follows. At all pressures and temperatures
between 283.15 and 313.15 Kand at 278.15 Kat pressures equal
to or lower than 100 MPa, we used anhydrous NaCl. For the other
conditions used in the present work, solid NaCl2H
2
O was used
as the sample solute. In all cases, the approach to equilibrium
near the phase-transition point was carefully checked.
3.2. High-pressure solubility
Values of the solubility obtained are listed in Table 1. Our val-
ues at atmospheric pressure coincide with the rounded values of
Cohen-Adad and Lorimer [1] within 0.15% though the propor-
tions of anhydrous NaCl in the former study are smaller than
those in the latter by 0.07% on average. We tted the data to the
following two equations. For the high-temperature/low-pressure
region (anhydrous NaCl):
ln[m
sat
(p, T)/mol kg
1
]
= 2.86623
571.361
(T/K)
+
77, 128
(T/K)
2
+4.0479
10
4
(p/MPa) 7.445
10
7
(p/MPa)
2
+6.209 10
10
(p/MPa)
3
(1)
and for the low-temperature/high-pressure region
(NaCl2H
2
O):
ln[m
sat
(p, T)/ mol kg
1
]
= 5.35183
1366.040
(T/K)
+
108, 664
(T/K)
2
+[0.010331
5.8869(T/K)
1
+831.7(T/K)
2
](p/MPa) (2)
The standard deviations of the logarithm of the solu-
bility, (ln m
sat
), listed in Table 1 were 0.08% for NaCl
S. Sawamura et al. / Fluid Phase Equilibria 254 (2007) 158162 161
Table 1
Solubility of sodium chloride in water (mol kg
1
)
p/MPa T/K
263.15 268.15 273.15 278.15 283.15 293.15 298.15 303.15 313.15
0.10
a
5.640 5.860 6.095 6.106 6.115 6.142 6.159 6.179 6.224
0.10 5.639 5.859 6.095 6.102 6.112 6.136 6.152 6.174 6.220
50.0 5.845 6.087 6.221 6.227 6.260 6.270 6.295 6.345
100.0 5.627 5.841 6.059 6.308 6.325 6.350 6.367 6.375 6.425
150.0 5.612 5.804 6.043 6.258 6.399 6.457
200.0 5.605 5.795 5.997 6.463 6.519 6.550 6.575
250.0 5.599 5.780 5.965 6.192 6.531 6.542 6.586
300.0 5.597 5.752 5.960 6.555 6.610
Solutes are NaCl for all pressures at 283.15313.15 and 0.10100 MPa at 278.15 K and NaCl2H
2
O for all pressures at 263.15273.15 K and 150300 MPa at
278.15 K.
a
Rounded values [1].
Fig. 5. Logarithmof relative solubility of sodiumchloride in water: (), present
work; () Cohen and Sinnige [4] at 297.2 K; () Sill [5] at 298.15 K; () Adams
and Hall [6] at 303.08 K; () Von Stackelberg [3] at 291.7 K.
and 0.14% for NaCl2H
2
O, respectively, where (ln m
sat
) =
_
_
(ln m
sat
)
2
/(N 1)
_
and N is the number of data. The
boundary line of the two NaCl and NaCl2H
2
O phases obtained
from these two equations goes through temperatures of 273.2 K
at 0.10 MPa and 288.6 K at 300 MPa. These are close to the
rounded values of 273.2 K at 0.10 MPa by Cohen-Adad and
Lorimer [1] and 288.4 K at 300 MPa which was estimated from
the gure provided by Adams and Gibson [25].
The logarithmof the solubilityof anhydrous NaCl normalized
to that at atmospheric pressure is plotted in Fig. 5 and compared
with literature data. The solid line corresponds to Eq. (1). It does
not depend on temperature. The values by Cohen and Sinnige
[4] and by Adams and Hall [6] t our line at pressures up to
50 MPa. At higher pressures, the latter values seem to lie below
our data for reasons that are not clear. The solubility data listed in
Table 1 are stereographically plotted in Fig. 6, allowing a birds-
eye viewof the solubility of NaCl and NaCl2H
2
Oin water over
the whole set of conditions.
3.3. Thermodynamic analysis
The pressure coefcient of the logarithm of the solubility of
sodium chloride in water,
p
[( ln m
sat
/p)
T
], can be thermo-
dynamically derived as Eq. (3) [13]:

p
=
_
V
2RTf

_ _
A
A nm
sat
_
(3)
where A is the amount of 1 kg water (55.51 mol) and n is the
number of molecules of hydration water for each molecule of
hydrated crystal (n =2 for NaCl2H
2
O).
f

1 +
_
ln

m
_
T
(4)
where

is the mean activity coefcient of the ions, and V

is the volume change accompanying dissolution, which cor-
responds to the difference between the partial molar volume,
V

sat
, of the solute (including that of 2 mol of water per mole of
NaCl2H
2
O) at saturated concentration and molar volume, V
C
,
of the solid solute, as shown in Eq. (5):
V = V

sat
V
C
(5)
Fig. 6. Solubility of sodium chloride in water.
162 S. Sawamura et al. / Fluid Phase Equilibria 254 (2007) 158162
As V

sat
is estimated as 23.67 0.2 cm
3
mol
1
from the den-
sity of aqueous sodium chloride at 0.10 MPa and 298.2 K [26],
the V
C
of NaCl is 27.00 0.02 cm
3
mol
1
from X-ray data
[27,28], and ( ln

/m)
T,p
=0.759 [29],
p
can be estimated as
(3.82 0.25) 10
4
MPa
1
using Eqs. (3)(5). Using a similar
method,
p
for NaCl2H
2
Oat 0.10 MPa and 273.2 Kis estimated
to be (0.94 0.47) 10
4
MPa
1
using V

sat
= 58.6 0.2
(=(23.30 0.2) +2 (17.65 0.02)) cm
3
mol
1
[26] including
2 mol of hydration water, V
C
=58.00 0.05 cm
3
mol
1
[25],
and ( ln

/m)
T,p
=0.797 [29]. We can compare these cal-
culated values with the experimental values of
p
for NaCl
and NaCl2H
2
O estimated from the curves of Eqs. (1) and
(2) are (4.05 0.04) 10
4
MPa
1
at 0.10 MPa and 298.2 K
and (0.74 0.05) 10
4
MPa
1
at 0.10 MPa and 273.2 K,
respectively. Our experimental values for
p
coincide with the
thermodynamic estimates and conrms the reliability of our
high-pressure measurements, although we should be aware that
the errors in the thermodynamic estimation are large.
4. Conclusions
The solubility of sodium chloride in water, a prototypical
solute and solvent pair for solubility investigations, was mea-
sured as a function of pressure and temperature with high
accuracy. The results of the present work nally provide a global
view of the solubility after a 100-year gap since the rst mea-
surements of high-pressure solubility of this pair were made.
List of symbols
A amount of 1 kg water (=55.51 mol)
f

concentration coefcient of mean activity coefcient

of ions, Eq. (4)
m concentration (mol kg
1
)
m
sat
solubility (mol kg
1
)
m
0
solubility (mol kg
1
) at 0.10 MPa
n number of hydration water molecule per hydrated
molecule
p pressure (MPa)
R gas constant (J K
1
mol
1
)
T temperature (K)
V volume change accompanying dissolution
(cm
3
mol
1
)
V
C
molar volume of solid (cm
3
mol
1
)
V

sat
partial molar volume at saturated concentration
(cm
3
mol
1
)
Greek letters

mean activity coefcient of ions in morality.

p
pressure coefcients of the solubility dened as
( ln m
sat
/p)
T
(MPa
1
)
(ln m
sat
) standard deviation of the logarithm of solubility
dened as
_
_
(m
sat
)
2
/(N 1)

, where N is the
number of data points
Acknowledgements
This work was partially supported by The Salt Science
Research Foundation, the 120th Anniversary of Ritsumeikan
Academy and the 19th Anniversary of Ritsumeikan Universitys
Fund for the Promotion of Research, and the Academic Fron-
tier Project from MEXT of Japanese Government, 20032007.
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