J Solution Chem (2009) 38: 1097–1117

DOI 10.1007/s10953-009-9433-0

Calculations of Freezing Point Depression, Boiling Point

Elevation, Vapor Pressure and Enthalpies
of Vaporization of Electrolyte Solutions by a Modified
Three-Characteristic Parameter Correlation Model

Xinlei Ge · Xidong Wang

Received: 26 January 2009 / Accepted: 18 February 2009 / Published online: 9 July 2009
© Springer Science+Business Media, LLC 2009

Abstract A method was proposed for calculating the thermodynamic properties, freezing
point depression, boiling point elevation, vapor pressure and enthalpy of vaporization for
single solute electrolyte solutions, including aqueous and nonaqueous solutions, based on a
modified three-characteristic-parameter correlation model. When compared with the cor-
responding literature values, the calculated results show that this method gives a very good
approximation, especially for 1-1 electrolytes. Although the method is not very suitable for
some solutions with very high ionic strength, it is still a very useful technique when experi-
mental data is scarce.

Keywords Electrolyte solutions · Freezing point · Boiling point · Enthalpy of vaporization

1 Introduction

Electrolyte solutions are of central importance in a variety of scientific fields and engineer-
ing. Accurate models that describe the non-ideal behavior of real solutions are therefore
necessary for designing processes related to ionic solutions for many industrial applications
such as desalination, phase separation, etc. Thus, in the past century, many models such as
those of Bromley [26], Pitzer [58], the NRTL model [28, 29], etc., have been developed. On
the other hand, many theories have been put forward, based on statistical mechanics aided by
the rapid development of computer technology, that focus on three aspects: molecular sim-
ulation (Monte Carlo and molecular dynamics simulation), integral equation theory (Mean
Spherical Approximation based theories [46, 64], etc.) and perturbation theory (SAFT [38],
etc.). However, these models often yield complex formulas and still involve adjustable pa-
rameters, which restricts their applications.

X. Ge ( )
Department of Materials Science and Engineering, Royal Institute of Technology, 10044 Stockholm,
Sweden
e-mail: xinleige@yahoo.com.cn

X. Wang
College of Engineering, Peking University, Beijing 100871, China
1098 J Solution Chem (2009) 38: 1097–1117

Recently, the present authors proposed a new three-particle-interaction model [33] with
the consideration of ion-ion and ion-molecule interactions based on the solvation concept
proposed by Lin et al. [44]. The Pitzer-Debye-Hückel term was used to account for ion- ion
interactions [32]. This modified model has two or three adjustable parameters, namely, the
distance of closest approach parameter, a solvation parameter and a distance parameter. This
model was extended for predicting the mean activity coefficient, osmotic coefficient and
solvent activity for many strong [32] and complex [35] aqueous solutions, as well as
nonaqueous solutions [34], over a wide range of concentration and temperature. However,
some of the other thermodynamic properties, including freezing point depression, boiling
point elevation, vapor pressure and enthalpies of vaporization, etc., are also recognized as
being very important physicochemical parameters for many chemical processes. Thus, in
this work, the aim is to demonstrate a new method to calculate these properties for electrolyte
solutions, including both aqueous and nonaqueous solutions, based on this model without
introducing any additional parameters.

2 Theoretical Modeling

2.1 Derivation of Freezing Point Depression and Boiling Point Elevation

The freezing point (melting point) of a pure solvent can always be lowered by adding a
solute. This lowering is called the freezing point depression (FPD). In this phenomenon,
solute molecules in a solution cannot dissolve in the solid phase, and only the liquid sol-
vent molecules can transform to the solid phase, such as ice, during the phase transition.
Generally, the FPD increases with increasing solute concentration.
When the solution reaches the freezing point at solid-liquid equilibrium, the chemical
potential of the solvent is equal in both the liquid and solid phase:

μliq(T , p) = μsol(T , p) (1)

where μliq(T , p) and μsol(T , p) represent the chemical potentials of the liquid solvent and
the corresponding solid solvent phase at the same temperature and pressure, respectively,
and T is the freezing point of the solution expressed with the absolute temperature in K.
Furthermore, the chemical potential of the liquid and solid solvent can be expressed as:

μliq(T , p) = μoliq(T , p) + RT ln aliq(T, p, m), (2a)

μsol(T , p) = μ sol(T , p) + RT ln asol(T , p)
o
(2b)
where μo (T , p) and μo (T , p) are the chemical potentials of the pure liquid and solid
liq sol
solvent at the same temperature and pressure, respectively, R = 8.314472 J ·mol−1 K · −1 is
the gas constant, aliq is the activity of the solvent in the electrolyte solution that is related
to the solute concentration, and asol = 1 is the activity of the solid solvent. The difference
between the chemical potential of the pure liquid and solid solvent at the same temperature
is the Gibbs energy of fusion, OGofus . With Eq. 1 and Eq. 2, it can be expressed as

OGofus = μoliq − μosol = −RT ln aliq (3)

According to the Gibbs-Helmholtz equation [41]

J Solution Chem (2009) 38: 1097–1117
. Σ OH
OG
d =− dT (4)
T T2
1100 J Solution Chem (2009) 38: 1097–1117

Combining Eq. 3 and Eq. 4, one obtains

d ln aliq OH Tfus
= (5)
dT RT 2

Equation 5 can be integrated as

∫ aliq ∫T
d ln aliq = ln aliq = OH fus dT (6)
T
1 TF RT 2

= TF, the
in going from the pure solvent (aliq 1,T = normal freezing point), to the solution (a liq,T
, the lowered freezing temperature). Here, OH fus is the
T enthalpy change upon fusion at the
lowered freezing point, T . It can be expressed as a function of temperature by
∫ T
fus fus fus

OHT = OH0,TF + TF
OCp dT (7)

where OH 0,T fus

F
is the enthalpy change of fusion of the pure solvent at TF. If the temperature
range [T, TF] is very narrow, OH Tfus can be assumed to be equal to OH fus 0,TF
. However, for
some electrolyte solutions with high concentration, the FPD, θF TF=T , can − be large. Under
this condition the second term of Eq. 7 should be considered. If OCfus is assumed p to be equal
to the difference of heat capacities between the
−1 liquid
−1 and solid phases at the normal
freezing point of solvent, then OC /J·mol ·K = C − OC becomes a constant and
fus liq sol
p p p
Eq. 7 can be rewritten as

OH Tfus = OH0,T
fus
F
+ OCfus(T − TF) (8)
p

Integrating Eq. 6 with Eq. 8, one can obtain

. Σ Σ . Σ Σ
1 − 1 TF − θF θF
RT ln a = OH fus + OC fus
ln − (9)

liq 0,TF
TF TF − θ F p TF TF − θ F

Equation 9 can be employed directly with the help of some computing tools to calculate
the freezing point depression. Moreover, the logarithmic function can be approximated using
a Taylor series expansion
. Σ . Σ . Σ3
x− 1 1 x−1 2 1 x− 1
ln x = +
x 2 x x
+ + ··· (10)
3

If we only retain the first two terms, Eq. 9 can be rearranged as

. Σ . Σ2
1 1 OCfus θ
OH +
 TF − θ F
J Solution Chem (2009) 38: 1097–1117 1099
− − RT ln aliq = 0 (11)
fus
0,TF TF 2p TF −Fθ F

Then, the solution for the freezing point depression is given by

,
OH fus − 2RTF ln aliq − 2OC fus T ln aliq + (OH )2
2 fus

0,TF p F 0,TF
θF = (12)
fus
2(OH0,T F
/T F + 0.5OCfus
p − R ln a liq )

A preliminary investigation with using Eq. 9 and Eq. 12 showed that the calculated results
from Eq. 12 are as good as ones from Eq. 9. However, the use of Eq. 12 greatly simplifies
1100 J Solution Chem (2009) 38: 1097–1117

the calculation procedures. Thus, if the activity of the solvent in the solution is known, the
FPD of an electrolyte solution can be estimated theoretically with Eq. 12.
In a binary solution, the activity of the solvent is related with the osmotic coefficient, φ,
by:
νmMsφ
ln ai =− (13)
1000
Here, ν =ν+ ν−+, ν+ and ν− are the stoichiometric ionization coefficients of the cation and
anion, respectively, m is the molality (in mol· kg−1) and Ms is the molecular weight of the
solvent (in g·mol−1). In the modified three-characteristic-parameter correlation model [32],
the following equation was proposed for the calculation of the osmotic coefficient:
. Σ . Σ
I 1/2 S 2n 2n
φ = 1 − |z+z−| Aφ +
1 + bI 1/2 T (ν+ + ν− ) 2n − 1 I , (14)
. Σ3/2
(2πLds)1/2 e2
Aφ = (15)
3 DkT

In the above equations, z+ and z− are the electronic charge numbers of the cation and
anion, respectively; Aφ is the Debye-Hückel parameter for the osmotic coefficient; L is
Avogadro’s number (6.023 ×1023 mol−1) e; is the unit electrical charge (1.6021 10×−19 C);
k
is Boltzmann’s constant (1.3805 10−23×J K−1 · ); d and areD
s the density and static
.
dielectric constant of the solvent which are functions of temperature; and I = 1/2 i mi zi 2
−1
is the ionic strength (in mol·kg ).
In Eq. 14, (b, S, n) are the three characteristic parameters. Herein, b is the distance of
closest approach parameter that represents the closest distance between ions, S is a solvation
parameter that can describe the interactions between ions and solvent molecules including
solvation effect or some kind of association effect of ions, and n is the distance parameter
related to the distance between the ion and solvent molecules. The parameters for single
salts in water and other solvents can be found in our previous work [32, 34, 35], and the
ones used in this work are listed in Table 1.
On the other hand, the boiling point elevation (BPE) is the difference in boiling temper-
ature of a given solution and the pure solvent at the same pressure. This factor is always a
consequence of the presence of solute particles. A procedure similar to that used for freezing
temperatures can be employed . to derive theΣequation forΣ boiling
. point
Σ elevation, yielding:
Σ
1 1 T + θ θB
= − + −
B B
−RT ln a OH vap
OC vap
ln (16)

liq 0,TB
TB TB + θ B p TB TB + θ B

−1 −1
p /J·mol ·K
where TB is the normal boiling point, θB is the boiling point elevation, OCvap =
C p − C p is the difference of heat capacities between vapor and liquid phase at the normal
vap liq

boiling point of the solvent, and OH 0,T

vap
B
is the enthalpy of vaporization of the pure solvent
at temperature TB.
A similar Taylor series expansion was performed and one obtains the significant solution
as
,
OH 0,T
vap
− 2RT B ln a + (OH vap )2 − 2OC vap T 2 ln a
B
vap
 liq 0,TB p B liq
B=
J Solution Chem θ
(2009) 38: 1097–1117 1099
2(OH0,T /T B + 0.5OCp − R ln aliq )
vap (17)
B

Thus, the BPD can be calculated from Eq. 16 or Eq. 17 with the activity of the solvent
estimated from Eqs. 13–15.
1100 J Solution Chem (2009) 38: 1097–1117
Table 1 The characteristic parameters for electrolyte solutions at T = 298.15 K

J Solution Chem (2009) 38: 1097–1117

Electrolytes mmax/mol·kg−1 b S n Electrolytes mmax/mol·kg−1 b S n

Water Water
HCl 16.0000 2.6630 202.0039 0.4758 CsI 3.000 19.4726 −280.1542 0.1881
HBr 11.0000 3.7544 179.6788 0.5691 CsNO3 1.500 20.3969 −432.7524 0.2621
LiCl 19.2190 1.9304 232.1466 0.4458 NH4Cl 7.405 2.8347 2.0781 0.9652
LiBr 20.0000 2.0933 228.3532 0.5000 NH4Br 7.500 2.6425 19.0497 0.5051
373.15 K 5.0000 3.9116 120.7532 1.2900 NH4I 7.500 2.9810 13.5922 0.5904
LiI 3.0000 6.3035 121.0137 0.6816 NH4NO3 25.954 20.3806 −329.8858 0.1867
LiOH 5.0000 7.7432 -198.2412 0.1427 AgNO3 15.000 21.7555 −436.6749 0.2214
NaOH 29.0000 1.3407 229.9241 0.3942 (CH3)4NCl 19.000 1.4426 63.6810 0.4822
CH3COONa 3.5000 4.6723 51.0027 0.7267 Citric acid 8.000 28.8874 129.8666 0.4047
NaCl 6.0000 3.5425 14.0326 0.8998 Li2SO4 3.000 2.5841 2.7436 1.0765
273.15 K 6.0000 2.8881 31.5739 1.2900 Na2SO4 4.445 8.1535 −514.8889 0.1700
273.15 K
373.15 K 6.0000 4.2989 41.0540 1.2900 1.500 1.9984 −45.8561 1.2900
Na2S2O3
NaBr 9.0000 3.4595 49.9861 0.6341 4.052 5.3497 −298.9463 0.1526
Na2S2O8
283.15 K 9.0000 4.5869 43.3435 1.2900 0.098 20.1298 −830.7216 0.2371
Na2HPO4
373.15 K 5.0000 3.7005 67.6177 1.2900 2.121 19.6318 −758.3691 0.1974
K2SO4
NaI 12.0000 3.5752 84.7943 0.5759 0.800 5.9898 −498.1185 0.2086
K2HPO4
NaNO3 6.0000 14.5232 -254.7813 0.1755 0.873 20.8050 −740.2638 0.1954
K2CrO4
NaNO2 12.3400 3.0859 1.6076 0.8414 3.372 6.8058 −395.3916 0.1704
K2Cr2O7
NaClO4 6.0000 3.2748 2.9747 1.0930
Cs2SO4 0.507 22.8902 −358.0912 0.4390
NaClO3 3.0000 17.6971 -215.6566 0.1776 3.105 1.9850 0.6311 1.3103
MgCl2
KCl 5.0000 2.7650 1.2015 1.3535 273.15 K 5.919 3.3156 127.0174 0.6224
273.15 K 4.0000 2.6809 2.5679 1.2900 373.15 K 4.000 3.5408 109.7150 1.2900
KBr 5.5000 3.0352 2.2813 1.1739 Mg(NO3)2 4.000 3.2694 107.4684 1.2900
273.15 K 5.0000 2.0759 22.6038 1.2900 MnCl2 5.123 3.3844 120.5300 0.5720
373.15 K 5.0000 3.2810 29.2771 1.2900 CuCl2 7.699 3.4896 159.9827 0.4237

1101
KI 4.5000 3.4704 5.4343 1.0340 5.750 3.7431 47.5279 0.5129
Table 1 (Continued)

1102
Electrolytes mmax/mol·kg−1 b S n Electrolytes mmax/mol·kg−1 b S n

Water Water
KNO3 3.5000 25.2117 −412.6326 0.2446 CaCl2 10.000 2.6803 260.0920 0.4476
KClO3 0.7000 17.5757 −369.8812 0.2691 273.15 K 7.000 4.3060 81.2196 1.2900
KH2PO4 1.8000 23.3901 −438.2261 0.2530 CaBr2 9.210 3.4120 170.0119 0.5763
KOH 20.0000 2.2214 175.0002 0.4752 CaI2 1.915 4.7918 99.9750 0.7208
273.15 K 5.0000 3.3361 79.8015 1.2900 Ca(NO3)2 20.000 2.5459 125.8526 0.3788
373.15 K 5.0000 3.0680 61.1378 1.2900 373.15 20.000 10.9057 7.6940 1.2900
KSCN 5.0000 2.7650 1.2015 1.3535 SrCl2 4.083 3.7759 49.9957 0.7078
RbCl 7.8000 2.5461 1.6154 1.0766 373.15 4.000 3.2699 72.1904 1.2900
CsCl 11.0000 2.0087 1.1615 1.0601 SrBr2 2.123 4.5517 40.0479 0.8496
343.15 K 8.5900 5.9827 9.3979 1.2900 SrI2 1.970 4.9576 79.9973 0.7521
CsBr 5.0000 11.6601 −223.3121 0.1563 BaCl2 2.000 3.0577 51.5110 0.6319
Water Methanol
BaCl2 273.15 4.0000 3.2272 27.4805 1.2900 Am4NBr 1.4000 5.1571 −194.8582 0.19950
373.15 K 4.0000 3.2694 107.4684 1.2900 Bu4NBr 1.6000 5.3380 −169.1235 0.19150
BaBr2 2.3210 4.0805 31.0113 0.8239 Bu4NClO4 2.4000 4.3052 −840.0172 0.18300
CoCl2 4.1180 4.1143 87.1268 0.6183 Bu4NI 0.9000 7.4185 −697.7628 0.21045

J Solution Chem (2009) 38: 1097–1117

CoBr2 5.6720 3.9643 199.9636 0.5292 CsI 0.1000 25.1079 −946.5040 0.23070
Cd(NO3)2 2.6380 4.0740 21.2660 0.7943 Et4NBr 1.8000 159.0368 −754.7582 0.16390
NiCl2 5.7140 3.7134 140.0036 0.5409 KBr 0.1000 14.7605 −587.5910 0.22305
ZnCl2 23.1930 2.5249 69.0252 0.4593 KI 0.7000 5.8683 −90.2423 0.18565
ZnBr2 20.1000 4.1120 109.0121 0.4215 NaCl 0.2000 9.2452 −295.2606 0.22025
UO2(NO3)2 5.5110 3.3233 330.0621 0.3649 NaClO4 1.2000 4.5797 55.0547 1.31915
Pb(NO3)2 1.9880 19.5633 −970.3734 0.1920 NaI 0.7000 5.0626 206.9776 1.03010
1.4000 1.8234 4.3885 0.9469 RbI 0.4000 8.8244 −395.7089 0.22555
CuSO4
CdSO4 3.5000 1.9075 2.3792 0.9978 NaBr 1.0000 5.2125 129.1934 1.1137
MgSO4 3.0000 2.1389 6.4328 0.8629 LiCl 4.4102 2.9755 219.1176 0.6179
 J Solution Chem (2009) 38: 1097–1117
Table 1 (Continued)
Electrolytes mmax/mol·kg−1 b S n Electrolytes mmax/mol·kg−1 b S n

Water Methanol
MnSO4 4.0000 1.9897 3.3404 0.9473 ZnCl2 6.2266 2.5859 0.0676 1.5327
ZnSO4 3.5000 2.0189 2.3298 1.0529 LiClO4 5.0585 7.3141 163.4196 0.71855
NiSO4 2.5000 1.9404 1.1474 1.1972 LiNO3 3.8049 4.0549 203.0365 0.46105
Al(NO3)3 3.1607 1.6008 246.0127 0.4948 NaSCN 3.4260 4.4505 265.0552 0.43230
La(NO3)3 6.4738 3.2498 71.9976 0.4974 CoCl2 2.0886 4.5980 0.1656 1.70915
MnCl2 4.5640 4.3152 41.3106 0.59195
NiCl2a 1.3352 4.7694 29.9712 0.74455
Ethanol
LiBr 2.8135 6.3721 107.9748 1.03835
LiCl 3.2979 4.7243 119.9855 0.9595
NaI 1.8000 5.9665 53.7595 1.46605
LiNO3 2.2155 6.0385 37.0773 1.39265
LiClO4 1.4560 6.9536 97.7842 1.30295
Ca(NO3)2 3.1852 5.6193 0.5900 1.25020
CaCl2 2.3717 6.1241 12.0000 0.86635
CoCl2 2.9453 4.9373 0.6182 1.40915
NiCl2 1.2101 10.1902 90.6512 0.88015
2-propanol
LiClO4 1.4884 2.9215 150.0250 0.87825
NaI 1.2000 2.4581 349.1303 0.49705
Acetonitrile
LiBr 0.8298 7.6241 −970.288 0.3935
NaI 1.4000 7.5426 −348.007 0.20295
aAll parameters are taken from [31, 32, 34, 35]

1103
1104 J Solution Chem (2009) 38: 1097–1117

Table 2 The thermodynamic properties of pure water and methanol at 1 atma

Boiling point, water 373.15 K
Specific heat capacity, Cps (T = 273.15 K), water(ice) 2.11 J·g−1·K−1
Specific heat capacity, Cpl (T = 273.15 K), liquid water 4.2176 J·g−1·K−1
Specific heat capacity, Cpl (T = 373.15 K), liquid water 4.2159 J·g−1·K−1
Specific heat capacity, Cpv (T = 273.15 K), water vapor 2.0784 J·g−1·K−1
vap
Enthalpy of vaporization, OH (TB = 273.15 K), water vapor
0,T B
40.657 kJ·mol−1

Enthalpy of fusion, OH fus (TF = 273.15 K), solid water (ice)

0,T 333.6 J·g−1
F

Boiling point, methanol 337.6 K

Specific heat capacity, Cpl (T = 298.15 K), liquid methanol 81.1 J·mol−1·K−1
Specific heat capacity, Cpv (T = 337.6 K), methanol vapor 44.1 J·mol−1·K−1
vap
Enthalpy of vaporization, OH (TB = 337.6 K), methanol vapor
0,T B
35.21 kJ·mol−1

aReference [43]

Table 3 The Antoine equation coefficients for different solvents

Solvents T /K A B C Refs.

Watera 273–303 5.40221 1838.675 −31.737 [25]

304–333 5.20389 1733.926 −39.485 [25]
334–363 5.07680 1659.793 −45.854 [25]
379–573 3.55959 643.748 −198.043 [45]
Methanola 288.0–356.83 5.20409 1581.341 −33.50 [2]
Ethanola 292.77–366.63 5.24677 1598.673 −33.50 [2]
Acetonitrileb 298.15–343.15 14.973 3410 −25.415 [51]
2-propanol 298.15 pos = 5777.4 Pa [18]
a log (p/bar) = A − {B/(T /K + C)}
10
b ln(p/kPa) = A − {B/(T /K + C)}

The calculations of FPD/BPE data also require the thermodynamic properties of the pure
solvent as indicated in Eq. 12 and Eq. 17. These constants can be found in handbooks and
they are listed in Table 2.

2.2 Derivation of Vapor Pressures and Enthalpies of Vaporization

At low pressure, the vapor pressure of the solvent in a solution is also related to the solvent
activity.
ps = aspso (18)

where as is the solvent activity in a solution (same as aliq), and ps and pso are the vapor
pressure of the electrolyte solution and pure solvent at the same temperature, respectively.
The values of pos can be calculated with the Antoine equation. For different solvents, the
vapor pressure is dependent only on temperature with solvent-specific empirical parameters.
J Solution Chem (2009) 38: 1097–1117 1105
The Antoine coefficients used in this work for calculating the vapor pressure of pure solvents
are listed in Table 3.
1106 J Solution Chem (2009) 38: 1097–1117

The enthalpy of vaporization, also known as the latent heat of vaporization or heat of
evaporation, is the energy required to transform a given quantity of a liquid substance into
its corresponding gas. In this work, for an electrolyte solution of specific concentration, the
Clausius-Clapeyron equation [47] can be used to describe the relationship between the
enthalpy of vaporization and the temperature-dependent vapor pressure,
d ln p OH vap
=− (19)
d(1/T ) R

Rearranging Eq. 19 and combining it with Eq. 18, one obtains

. d ln po Σ
s + d ln as
OH = RT
vap 2
(20)
dT dT

The first term on the right hand side of Eq. 20 can be calculated from the Antoine equa-
tion. For instance, the following equations are obtained for water:
d ln po 1838.675
s = (21a)
dT (T − 31.737)2

from T = 273 to 303 K and

d ln po 1733.926
s = (21b)
dT (T − 39.485)2
from T = 304 to 333 K.

The second term of Eq. 20 can be expressed by differentiating Eqs. 13–15, and the results
are:
. Σ
d ln as νmMs dφ
=− (22)
dT 1000 dT

. Σ. Σ . Σ
dφ dAφ I 1/2 S 2n 2n
= − |z+z−| − I (23)
dT dT 1 + bI 1/2 T 2(ν+ + ν− ) 2n + 1

Because the density of solvent, ds and the static dielectric constant, D, are both depen-
dent on the temperature, the form of dA φ /dT is very complicated. For aqueous solutions,
Bradley and Pitzer [24] recommended values of Aφ as a function of temperature from 0 to
350 °C at 1 bar and at 10 °C intervals. The following equations [49, 68] are used to fit these
values. For aqueous solutions above T = 298.15 K:

Aφ = 3.36901532 × 10−1 − 6.32100430 × 10−4T + 9.14252359/T

− 1.35143986 × 10−2 ln T + 2.26089488 × 10−3/(T − 263)
+ 1.92118597 × 10−6T 2 + 45.2586464/(680 − T ), (24a)
dAφ/dT = −6.32100430 × 10 −4
− 9.14252359/T − 1.35143986 × 10 /T
2 −2

− 2.26089488 × 10 /(T − 263)2 + 3.84237194 × 10−6T

−3
J Solution Chem (2009) 38: 1097–1117 1107
+ 45.2586464/(680 − T )2 (24b)

For aqueous solutions below T = 298.15 K:

Aφ = 86.6836498 + 8.48795942 × 10−2T − 8.88785150 × 10−5T 2

1108 J Solution Chem (2009) 38: 1097–1117

+ 4.88096393 × 10−8T 3 − 1.32731477 × 103/T − 17.6460172 ln T,

(25a)
dAφ/dT = 8.48795942 × 10−2 − 1.7775703 × 10−4T + 1.464289179 × 10−7T 2
+ 1.32731477 × 10 3/T 2 − 17.6460172/T (25b)

According to Eqs. 20–25, the enthalpies of vaporization of different electrolyte solutions

at a known concentration and temperature can be calculated. It should be pointed out that the
value estimated from this equation is only the value of enthalpy of vaporization at the begin-
ning of vaporization, without considering the variation of solution concentration occurring
during further vaporization.

3 Results and Discussion

In this work, the relative standard deviation between the calculated and literature data for an
electrolyte solution is defined as:

δ = (|V cal − V ref|/V ref)/np (26)

Here V stands for the values of θF, θB, ps and OH vap in this work, and np is the number
of data points taken from the literature. The superscript ‘cal’ and ‘ref’ refer to the calculated
results and reference data, respectively.
Calculations of the freezing point depression were carried out for many single electrolyte
solutions covering the 1-1, 1-2, 2-1, 2-2 and 3-1 charge types, by using Eqs. 12–15 and Eq.
17, with the parameters shown in Tables 1 and 2. These results along with the maximum
molality (mol ·kg−1), the temperature range, and the 102 δ values
× are shown in Table 4. From
this table, one can see that the calculated results are in good accordance with the literature
data for most of the systems, especially for 1-1 type electrolytes. However, the results are
less satisfactory for other types of electrolytes such as CaCl2, ZnCl2, ZnBr2, UO2(NO3)2,
MnSO4, etc. It should be noted that the integration of heat capacities assuming a linear
temperature dependence may give rise to some error.
However, the large deviations are more likely attributable to the following reasons:
(a) Deviation from the model assumptions. In the modified TCPC model, the electrolyte
molecules are assumed to dissociate completely, which is accurate for strong electrolyte so-
lutions or solutions with low molalities. Thus, good results are obtained for 1-1 electrolytes.
But for weak electrolytes or solutions with high ionic strength, it is less accurate due to in-
complete dissociation of electrolyte molecules or the association of ions. (b) The properties
of electrolytes. For asymmetric electrolytes, the size difference between anion and cation can
be very large, which cannot be fully described by the PDH term and solvation effect of this
model. Moreover, the hydrolysis of some salts, such as CaCl2, ZnCl2, ZnBr2, etc., can bring
about changes in the nature of the solute and formation of complex of ions in the solution
simultaneously, which also cannot be fully described by the present model. On the contrary,
the association effects of ions of some 2-2 type electrolytes, such as MnSO4, ZnSO4, etc.,
also cannot be neglected. These factors make the model perform less satisfactorily for these
electrolytes.
Tables 5 and 6 show the calculated boiling point elevation results compared with liter-
ature values for electrolytes in water and methanol, respectively. Similarly, a better perfor-
mance is observed for 1-1 electrolytes. However, poorer quality results are found in this
J Solution Chem (2009) 38: 1097–1117 1109

Table 4 Calculated results for the freezing point depression of single electrolyte aqueous solutions at 1 atm

Electrolytes mmax/mol·kg−1 Data points np 102 × δ Refs.

HCl 3.7400 12 2.17 [42]

HNO3 3.4840 15 4.79 [42]
LiCl 4.3827 17 2.79 [42, 72]
NaCl 5.2017 34 4.98/3.72a [36, 42, 72]
NaBr 1.8510 14 2.47/0.58b [42]
NaNO3 8.2200 22 4.94 [30, 42]
NaH2PO4 2.0840 20 4.12 [42]
CH3COONa 1.2060 10 1.03 [42]
KCl 3.2998 24 2.55/1.98a [1, 42, 72]
KBr 3.9540 29 3.75/4.17a [42, 72]
KI 4.0160 26 2.62 [42]
KOH 5.9412 12 5.79/4.35a [1, 42]
KNO3 1.0990 17 3.08 [36, 42]
KH2PO4 0.8160 12 0.73 [42]
CsCl 1.4850 16 4.65 [42]
NH4Cl 4.5802 23 1.42 [42, 72]
NH4NO3 8.7700 11 6.06 [30]
AgNO3 1.1210 14 1.66 [42]
Citric acid 2.2310 21 5.28 [42]
Na2HPO4 0.1070 3 2.22 [30, 42, 59]
Na2SO4 1.4100 24 5.32/2.46a [42]
Na2S2O3 1.5810 16 13.97 [42]
K2HPO4 0.4990 13 4.17 [37, 42]
K2SO4 0.3020 15 1.86 [42]
BaCl2 0.9150 20 0.85/1.63a [37, 42]
CaCl2 4.3254 33 8.69/4.87a [36, 42, 72]
MgCl2 2.9409 17 1.30/1.47a [42]
SrCl2 1.9920 18 2.94 [37]
CoCl2 0.4217 11 0.84 [36, 42, 72]
ZnCl2 3.1443 4 9.18 [36]
ZnBr2 3.6331 5 7.95 [36]
UO2(NO3)3 2.0700 42 20.33 [3]
CuSO4 1.0200 13 6.26 [42]
MgSO4 1.5820 22 4.52 [37, 42]
MnSO4 1.6560 15 13.89 [42]
ZnSO4 1.1800 14 8.27 [42]
La(NO3)3 0.1749 10 1.52 [37]

aCalculated with the parameters at 273.15 K

bCalculated with the parameters at 283.15 K

table, and the model failed to correctly calculate the BPE data for 2-2 electrolytes. Even
for some 1-1 electrolytes such as LiCl, LiBr, NaBr, etc., large deviations are obtained. The
1108 J Solution Chem (2009) 38: 1097–1117

Table 5 Calculated results for the boiling point elevation of single electrolyte aqueous solutions at 1 atm

Electrolytes mmax/mol·kg−1 Data points, np 102 × δ Refs.

LiCl 35.0000 9 80.39 [71]

5.0000 4 9.71 [71]
LiBr 17.0000 7 19.33/16.36a [71]
10.0000 5 5.72/5.49a [71]
NaCl 6.7800 19 2.15/1.58a [67, 71]
NaBr 10.0000 4 14.22/6.00a [71]
NaI 10.0000 6 4.52 [71]
NaNO3 24.8600 7 4.08 [71]
NaClO3 26.8600 4 2.02 [71]
KCl 7.8200 27 4.46 [66, 71]
KBr 5.0000 22 5.86/1.75 [40, 71]
KNO3 4.9500 16 4.72 [17]
KI 13.3000 7 14.85/11.12a [71]
2.0000 4 4.84/5.86a [71]
KClO3 5.0000 6 21.18 [71]
RbCl 12.1700 7 3.73 [71]
CsCl 17.2000 7 10.16/6.13b [71]
3.0000 4 6.13/3.77b [71]
CsNO3 1.0000 2 4.17 [71]
NH4Cl 16.3000 7 11.66 [71]
NH4Br 18.0000 7 13.11 [71]
5.0000 4 3.09 [71]
NH4I 11.5000 3 21.84 [71]
9.0000 6 3.82 [71]
AgNO3 8.0000 7 1.65 [71]
(CH3)4NCl 1.2000 5 3.72 [71]
Citric acid 70.0000 8 88.99 [71]
10.0000 5 6.08 [71]
BaCl2 2.5000 5 2.09/6.55a [71]
BaBr2 5.0000 5 22.57 [71]
3.0000 3 7.58 [71]
CuCl2 0.4000 4 2.66 [71]
CoCl2 0.7000 3 7.22 [71]
CoBr2 0.3000 3 6.88 [71]
NiCl2 0.7500 3 3.66 [71]
MnCl2 1.0000 3 2.31 [71]
MgCl2 6.0000 7 7.27/6.88a [71]
SrCl2 7.4100 7 36.56/32.38a [71]
3.0000 4 5.18/4.53a [71]
CaCl2 10.0000 7 15.07 [71]
5.0000 5 5.41 [71]

aCalculated with the parameters at 373.15 K

bCalculated with the parameters at 343.15 K

J Solution Chem (2009) 38: 1097–1117 1109

Table 5 (Continued)

Electrolytes mmax/mol·kg−1 Data points, np 102 × δ Refs.

Ca(NO3)2 22.9000 6 22.42/21.70a [71]

15.0000 4 7.85/8.80a [71]
Pb(NO3)2 3.5000 5 16.57 [71]
Li2SO4 4.0000 4 37.26 [71]
Na2SO4 2.9600 5 4.20 [71]
Na2S2O3 22.0000 6 20.17 [71]
3.0000 3 7.60 [71]
K2SO4 1.3900 4 8.34 [71]
K2CrO4 4.5700 5 7.44 [71]
K2Cr2O7 0.4000 3 2.75 [71]
ZnSO4 5.3000 6 26.91 [71]
CdSO4 2.6000 6 19.76 [71]
CuSO4 4.5000 6 21.38 [71]
MnSO4 4.5000 6 26.58 [71]
NiSO4 2.4000 6 35.36 [71]

aCalculated with the parameters at 373.15 K

Table 6 Calculated results for

boiling point elevation of some Electrolytes mmax/mol·kg−1 Data points np 102 × δ Refs.
single electrolytes in methanol at
1 atm LiCl 1.7000 8 2.47 [71]
NaI 0.8000 5 2.96 [71]
KI 0.8000 6 5.59 [71]
MnCl2 1.0000 4 7.24 [71]
CoCl2 0.3000 3 14.78 [71]
NiCl2 0.8000 5 5.56 [71]

main reason for this phenomenon is that the source data is taken at very high ionic strength,
such as 35 mol· kg−1 for LiCl, 30 mol· kg−1 for CaCl2 (also because of hydrolysis), etc.
Because of the reasons mentioned before, the model is of limited use in very highly concen-
trated solutions. Furthermore, incomplete dissociation due to the higher covalent character
of bonding in the solute, as in the case of LiCl, is also likely to add to the deviations.
Apart from these reasons, another reason is the applicability range of the parameters in
Table 1. These parameters have an applicable concentration range, and poor calculated re-
sults are obtained beyond this range. In Table 5, the maximum concentration listed for many
electrolytes are far beyond the applicable concentration range of the parameters. For in-
stance, they are 16.3 mol· kg−1 for NH4Cl (valid range < 7.405 mol· kg−1) and 5.0 mol· kg−1
for KClO3 (valid range < 0.7 mol· kg−1). Generally, a good calculated result is obtained
within the applicable molality range of the parameters. In Table 5, calculated results are also
listed for a decreased concentration range for these electrolytes, which show significant
improvements.
Moreover, it should be noted that the characteristic parameters given in Table 1 for calcu-
lating the solvent activity are regressed from literature data at T=298.15 K, but the activity
of solvent for FPD/BPE calculations should be either at a low temperature close to the freez-
1110 J Solution Chem (2009) 38: 1097–1117

Table 7 Calculated results of vapor pressure for single electrolyte aqueous solutions

Electrolytes mmax/mol·kg−1 T /K Data points np 102 × δ Refs.

LiOH 4.7722 298.15–363.15 220 0.26 [54]

LiCl 18.4560 303.15–343.15 40 5.02 [55]
LiBr 15.9710 303.15–343.15 40 4.67 [55]
LiI 10.1260 303.15–343.15 30 4.70 [55]
NaOH 3.7211 423.15–523.15 45 0.65 [27]
NaAc 6.4715 278.15–308.15 82 0.89 [22]
NaCl 5.8545 298.15 13 0.16 [57]
NaBr 7.9810 303.15–343.15 30 1.40 [56]
NaI 8.3980 303.15–343.15 40 1.46 [56]
KCl 4.2860 303.15–343.15 30 0.30 [56]
KBr 4.3490 303.15–343.15 30 0.86 [56]
KI 5.6480 303.15–343.15 40 0.62 [56]
RbCl 6.9490 303.15–343.15 30 1.26 [56]
CsCl 8.5900 303.15–343.15 30 2.20 [56]
CsBr 5.8880 303.15–343.15 30 0.41 [56]
CsI 2.5950 303.15–343.15 25 0.45 [56]
MgCl2 4.8010 303.15–343.15 40 0.89 [56]
CaCl2 7.8850 303.15–343.15 40 3.50 [56]
CaBr2 4.5960 303.15–343.15 40 1.02 [56]
CaI2 2.9150 303.15–343.15 25 3.70 [56]
SrCl2 3.2030 303.15–343.15 40 1.33 [56]
SrBr2 3.3400 303.15–343.15 40 0.99 [56]
SrI2 4.1560 303.15–343.15 40 3.01 [56]
BaCl2 1.3880 303.15–343.15 25 0.81 [56]
BaBr2 3.3980 303.15–343.15 40 1.18 [56]

ing point, or at a high temperature close to the boiling point. For these cases, the temperature
dependence of the model needs to be considered. Although in Eq. 14 the solvation parame-
ter is treated as being independent of temperature, which hopefully shows a positive effect
to overcome this problem, the activity coefficients in a solution at the freezing point or the
boiling point may be very different from the ones at T 298.15
= K. Thus, if the character- istic
parameters close to the freezing point or boiling point are known, then the calculated results
are expected to improve. These parameters for some salts have been obtained [31] and are
appended in Table 1. The calculated results with these coefficients are also listed in Tables 4
and 5. One can see that the 102 δ values× for most of those electrolytes (marked in Tables 4
×
and 5) are reduced, overall the 102 δ values decrease from 3.84 to 2.69 for freezing point
elevation, and from 6.02 to 5.32 for boiling point elevation.
The model is also used to calculate the vapor pressure of aqueous and nonaqueous so-
lutions with results presented in Tables 7 and 8, respectively. One can see that the cal- culated
results agree fairly well for most electrolytes, except only in the cases of ZnCl 2 (102 δ
14.8)×and=NaI (102 δ 8.99) in × methanol.
= The exception for ZnCl2 is due to the very high
ionic strength and a better result, 0.39, is obtained for concentrations below 2.06232
mol·kg−1. The large deviation for NaI is caused by the restricted validity range of
J Solution Chem (2009) 38: 1097–1117 1111

Table 8 Calculated results for the vapor pressure for single electrolyte nonaqueous solutions

Electrolytes Solvent mmax T /K Data points, 102 × δ Refs.

/mol·kg−1 np

Am4NBr Methanol 1.5563 298.15 29 0.15 [20]

Et4NBr Methanol 1.8735 298.15 30 0.19 [20]
Bu4NBr Methanol 1.6506 298.15 35 0.08 [20]
Bu4NClO4 Methanol 2.5034 298.15 23 0.25 [20]
Bu4NI Methanol 0.9073 298.15 43 0.03 [20]
LiCl Methanol 6.1762 298.05–323.15 126 1.31 [23, 60, 69]
LiClO4 Methanol 5.0586 298.15 73 0.49 [21, 52]
LiNO3 Methanol 3.8049 298.15 23 0.22 [52]
NaCl Methanol 0.2194 298.15 33 0.01 [19]
NaBr Methanol 1.5679 298.15 27 0.77 [23, 53]
NaI Methanol 4.5200 298.05–313.15 80 8.99 [19, 23, 69]
1.7030 298.05–313.15 55 0.49 [19, 23, 69]
NaSCN Methanol 3.4260 298.15–313.15 46 0.44 [53, 69]
NaClO4 Methanol 1.2940 298.15 22 0.07 [19]
KBr Methanol 0.1136 298.15 23 0.01 [19]
KI Methanol 1.1219 298.15 55 0.08 [19, 23]
RbI Methanol 0.4358 298.15 46 0.05 [19]
CsI Methanol 0.1311 29815 41 0.004 [19]
ZnCl2 Methanol 8.2553 298.15–323.15 84 14.8 [62]
2.0623 298.15–323.15 30 0.39 [62]
CaCl2 Methanol 2.6345 298.05–323.15 91 0.74 [23, 63]
MnCl2 Methanol 4.5640 298.15 27 0.31 [65]
CoCl2 Methanol 2.0886 298.15 29 0.16 [65]
NiCl2 Methanol 1.3352 298.15 30 0.13 [65]
LiCl Ethanol 3.2979 298.15–323.15 103 0.43 [48, 50, 61]
LiBr Ethanol 2.8135 298.15–323.15 108 0.27 [48, 50, 61]
LiNO3 Ethanol 2.2155 298.15–323.15 78 0.24 [48, 70]
LiClO4 Ethanol 1.4560 298.15 30 0.09 [21]
NaI Ethanol 1.9132 298.15 24 0.18 [18]
CaCl2 Ethanol 2.3717 298.15–323.15 79 0.25 [63, 73]
Ca(NO3)2 Ethanol 3.1852 298.15 17 0.29 [73]
NiCl2 Ethanol 1.2101 298.15 21 0.08 [65]
CoCl2 Ethanol 2.9453 298.15 33 0.31 [65]
NaI 2-propanol 1.4646 298.15 22 0.64 [18]
LiClO4 2-propanol 1.4884 298.15 15 0.44 [21]
NaI Acetonitrile 1.5423 298.15 26 0.22 [18]
LiBr Acetonitrile 0.8298 298.15–343.15 110 0.40 [51]

the parameters (valid range < 0.7 mol ·kg−1). A good agreement is obtained, 102 × δ= 0.49
for concentrations below 1.703 mol· kg−1.
On the other hand, the enthalpies of vaporization also can be calculated with Eqs. 20–25.
However, very limited experimental data for this property are found for electrolyte solu-
1112 J Solution Chem (2009) 38: 1097–1117

tions, except a series of works on saturated aqueous solutions by Apelblat et al. [4–16]. The
present method is employed to calculate values of the enthalpies of vaporization of differ-
ent saturated aqueous solutions at different temperatures, shown in Table 9. The saturated
vapor pressures are also estimated and listed in Table 9. Comparing the calculated results of
saturated vapor pressure in Tables 7 and 8, the deviations are larger. Good results for the
enthalpy of vaporization can be found for most 1-1 type electrolytes, but not so good for
some other electrolyte charge types. It should be noted that most of the experimental OH vap
values are those at the saturated solution points. The concentrations are very high, such as
36.229 mol·kg−1 for NH4NO3, or 10.421 mol ·kg−1 for Ca(NO3)2, which are well beyond
the valid range of the parameters in Table 1. As mentioned before, the agreement deterio-
rates at very high concentration. Accordingly, for a solution that is not saturated, such as
KSCN or CaCl2 in Table 9, good results can be obtained.
From the calculated results of FPD/BPE, whose vapor pressure and enthalpies of vapor-
ization are shown in Tables 4–9, large relative deviations are generally found in the high
ionic strength range that indicate that this method is not very suitable at very high concen-
trations. However, because the TCPC parameters of hundreds of salts have been generated
[32, 34, 35], this method still can be recommended as a very good approximation for calcu-
lation of these properties for electrolyte solutions, at least for strong electrolytes or solutions
in a concentration range within the applicable range of the parameters, which will be useful
when experimental data are scarce.

4 Conclusions

In this work, a new method for calculating the freezing point depression, boiling point el-
evation, vapor pressure and enthalpies of vaporization of aqueous and nonaqueous elec-
trolyte solutions is proposed, based on the modified three-characteristic-parameter correla-
tion model. The calculation only needs the thermodynamic constants for the pure solvent
and adjustable parameters reported in the literature. This method was used for calculation
of 37 freezing point depressions, 50 boiling point elevations (44 electrolytes in water and 6
electrolytes in methanol), 60 vapor pressures (25 electrolytes in aqueous solutions and 35
electrolytes in nonaqueous solutions), and 38 enthalpies of vaporization. The calculated re-
sults are acceptable, especially for 1-1 type electrolytes or solutions in a concentration range
that is not very high. A very good performance is found for vapor pressure calculations.
The present model is not suitable for solutions at very high concentrations, due to the
incomplete dissociation of electrolyte molecules or the association of ions. This model also
cannot fully describe some asymmetric electrolytes, and calculations for concentrations far
beyond the maximum applicable range of the characteristic parameters can easily result in
large deviations. Outside of this shortcoming, this method can be considered to provide a
good first approximation for the calculation of freezing point depression, boiling point
elevation, vapor pressure and enthalpies of vaporization, at least for the strong electrolytes
or solutions within the applicable concentration range of the characteristic parameters.

Acknowledgements This work was financially supported by the National Natural Science Foundation of
China (No. 50425415) and the National Basic Research Program of China (973 Program: 2007CB613608).
J Solution Chem (2009) 38: 1097–1117 1113

Table 9 Calculated results for the enthalpies of vaporization and saturated vapor pressure for saturated single
electrolyte aqueous solutions

Electrolytes mmax T /K Data points, np 102 × δ 102 × δ Refs.

/mol·kg−1 (Sat. V.P.) (OH vap)

LiCl 21.0390 283.15–313.15 7 28.44 10.71 [6]

NaCl 6.2220 278.15–323.15 10 0.68 1.51 [8]
NaBr 11.2700 278.15–323.15 10 6.52 1.42 [8]
NaNO3 13.3480 278.15–323.15 10 3.98 5.10 [8]
NaNO2 14.9150 278.15–323.15 10 8.29 3.13 [8]
CH3COONa 8.9700 278.15–318.15 9 9.25 6.52 [14]
NaClO4 21.0000 278.15–318.15 9 55.78 8.93 [14]
NaClO3 9.8300 288.15–303.15 4 5.25 6.38 [14]
KCl 5.5620 298.15–318.15 21 0.37 2.12 [7]
KBr 6.1570 283.15–308.15 6 3.15 3.32 [5]
KI 10.1500 278.15–323.15 10 19.67 3.58 [9]
KNO3 8.3070 278.15–323.15 10 2.84 4.65 [9, 39]
KClO3 2.4500 298.15–343.15 10 0.88 3.90 [14]
KSCN 15.4100 303.15 6 1.91 [39]
CsCl 13.0000 278.15–323.15 10 2.93 3.43 [12]
CsNO3 3.2820 278.15–323.15 10 1.49 1.98 [12]
CsI 3.6300 278.15–303.15 6 0.26 3.86 [12]
NH4NO3 36.2290 283.15–313.15 7 4.02 22.36 [6]
NH4Cl 8.5570 283.15–313.15 7 1.31 6.21 [6]
NH4Br 9.9300 278.15–323.15 10 7.10 0.69 [11]
NH4I 13.8930 278.15–323.15 10 14.54 5.12 [9]
Citric acid 12.9850 288.15–323.15 8 4.68 4.73 [15]
Na2S2O3 7.8370 278.15–318.15 9 4.26 12.96 [9]
Na2S2O8 3.5620 278.15–318.15 9 16.02 6.07 [16]
BaCl2 1.9580 283.15–313.15 7 4.33 9.75 [4]
SrCl2 4.6780 278.15–323.15 10 9.45 4.95 [9]
CaCl2 3.7760 303.15 11 0.69 [39]
MnCl2 6.7210 283.15–308.15 6 8.01 28.46 [5]
Ca(NO3)2 10.4210 283.15–308.15 6 5.84 40.04 [4]
Mg(NO3)2 5.7280 278.15–323.15 10 5.04 2.96 [9]
Cd(NO3)2 10.1800 278.15–323.15 10 34.75 10.88 [13]
UO2(NO3)2 5.3730 278.15–323.15 10 20.29 15.19 [9]
Li2SO4 3.2160 278.15–323.15 10 4.95 7.44 [9]
Cs2SO4 5.3900 278.15–323.15 10 8.33 7.12 [12]
CuSO4 1.6390 283.15–308.15 6 4.66 4.49 [5]
ZnSO4 4.1940 283.15–308.15 6 8.51 15.04 [4]
CdSO4 3.7800 278.15–323.15 10 4.37 6.11 [13]
Al(NO3)3 4.2100 278.15–323.15 10 10.16 19.27 [10]
1114 J Solution Chem (2009) 38: 1097–1117

References

1. Adams, L.H.: The measurement of the freezing-point depression of dilute solutions. J. Am. Chem. Soc.
37, 481–496 (1914). doi:10.1021/ja02168a005
2. Ambrose, D., Sprake, C.H.S.: Thermodynamic properties of organic oxygen compounds. XXV. Va- por
pressures and normal boiling temperatures of aliphatic alcohols. J. Chem. Thermodyn. 2, 631–645
(1970). doi:10.1016/0021-9614(70)90038-8
3. Apelblat, A.: Cryoscopy of uranyl nitrate solutions and activity coefficients. J. Inorg. Nucl. Chem. 39,
1852–1854 (1977). doi:10.1016/0022-1902(77)80220-0
4. Apelblat, A.: The vapour pressures of water over saturated aqueous solutions of barium chloride, mag-
nesium nitrate, calcium nitrate, potassium carbonate, and zinc sulfate, at temperatures from 283 K to 313
K. J. Chem. Thermodyn. 24, 619–626 (1992). doi:10.1016/S0021-9614(05)80033-3
5. Apelblat, A.: The vapour pressures of saturated aqueous solutions of potassium bromide, ammonium
sulfate, copper(II) sulfate, iron(II) sulfate, and manganese(II) dichloride, at temperatures from 283 K to
308 K. J. Chem. Thermodyn. 25, 1513–1520 (1993). doi:10.1006/jcht.1993.1151
6. Apelblat, A.: The vapour pressures of saturated aqueous lithium chloride, sodium bromide, sodium ni-
trate, ammonium nitrate, and ammonium chloride at temperatures from 283 K to 313 K. J. Chem. Ther-
modyn. 25, 63–71 (1993). doi:10.1006/jcht.1993.1008
7. Apelblat, A.: Vapour pressures of H216 O and H218 O, and saturated aqueous solutions of KCl from T
298= K to T 318= K by the isoteniscopic method. J. Chem. Thermodyn. 30, 1191–1198 (1998).
doi:10.1006/jcht.1998.0381
8. Apelblat, A., Korin, E.: The vapour pressures of saturated aqueous solutions of sodium chloride, sodium
bromide, sodium nitrate, sodium nitrite, potassium iodate, and rubidium chloride at temperatures from
277 K to 323 K. J. Chem. Thermodyn. 30, 59–71 (1998). doi:10.1006/jcht.1997.0275
9. Apelblat, A., Korin, E.: Vapour pressures of saturated aqueous solutions of ammonium iodide, potas-
sium iodide, potassium nitrate, strontium chloride, lithium sulphate, sodium thiosulphate, magnesium
nitrate, and uranyl nitrate from T =(278 to 323) K. J. Chem. Thermodyn. 30, 459–471 (1998).
doi:10.1006/jcht.1997.0311
10. Apelblat, A., Korin, E.: The molar enthalpies of solution and vapour pressures of saturated aqueous
solutions of aluminium chloride, aluminium nitrate and aluminium sulphate. J. Chem. Thermodyn. 34,
1919–1927 (2002). doi:10.1016/S0021-9614(02)00188-X
11. Apelblat, A., Korin, E.: The molar enthalpies of solution and vapour pressures of satu- rated
aqueous solutions of some ammonium salts. J. Chem. Thermodyn. 35, 699–709 (2003).
doi:10.1016/S0021-9614(02)00353-1
12. Apelblat, A., Korin, E.: The molar enthalpies of solution and vapour pressures of saturated aqueous
solutions of some cesium salts. J. Chem. Thermodyn. 38, 152–157 (2006). doi:10.1016/j.jct.2005.04.016
13. Apelblat, A., Korin, E.: The vapour pressures over saturated aqueous solutions of cadmium chloride,
cadmium bromide, cadmium iodide, cadmium nitrate, and cadmium sulphate. J. Chem. Thermodyn. 39,
1065–1070 (2007). doi:10.1016/j.jct.2006.12.010
14. Apelblat, A., Manzurola, E.: The vapour pressures over saturated aqueous solutions of sodium and
potassium acetates, chlorates, and perchlorates. J. Chem. Thermodyn. 39, 1176–1181 (2007).
doi:10.1016/j.jct.2006.12.006
15. Apelblat, A., Mariana, D., Jaime, W., Jacob, Z.: The vapour pressure of water over saturated aqueous
solutions of malic, tartaric, and citric acids, at temperatures from 288 K to 323 K. J. Chem. Thermodyn.
27, 35–41 (1995). doi:10.1006/jcht.1995.0004
16. Apelblat, A., Korin, E., Emanuel, M.: Solubilities and vapour pressures of saturated aqueous solu- tions
of sodium peroxydisulfate and potassium peroxydisulfate. J. Chem. Thermodyn. 33, 61–69 (2001).
doi:10.1006/jcht.2000.0780
17. Bancroft, W.D., Davis, H.L.: The boiling-points of aqueous solutions. J. Phys. Chem. 33, 591–604
(1929). doi:10.1021/j150298a008
18. Barthel, J., Lauermann, G.: Vapor pressure of non-aqueous electrolyte solutions. Part 3. Solutions of
sodium iodide in ethanol, 2-propanol, and acetonitrile. J. Solution Chem. 15, 869–877 (1986).
doi:10.1007/BF00646093
19. Barthel, J., Neueder, R., Lauermann, G.: Vapor pressure of non-aqueous electrolyte solutions. Part 1.
Alkali metal salts in methanol. J. Solution Chem. 14, 621–633 (1985). doi:10.1007/BF00646055
20. Barthel, J., Lauermann, G., Neueder, R.: Vapor pressure measurements on non-aqueous electrolyte so-
lutions. Part 2. Tetraalkylammonium salts in methanol, activity coefficients of various 1-1 electrolytes at
high concentrations. J. Solution Chem. 15, 851–867 (1986). doi:10.1007/BF00646092
J Solution Chem (2009) 38: 1097–1117 1115

21. Barthel, J., Neueder, R., Poepke, H., Wittmann, H.: Osmotic and activity coefficients of nonaqueous
electrolyte solutions. 1. Lithium perchlorate in the protic solvents methanol, ethanol, and 2-propanol. J.
Solution Chem. 27, 1055–1066 (1998). doi:10.1023/A:1022637316064
22. Beyer, R., Steiger, M.: Vapour pressure measurements and thermodynamic properties of aqueous solu-
tions of sodium acetate. J. Chem. Thermodyn. 34, 1057–1071 (2002). doi:10.1006/jcht.2002.0974
23. Bixon, E., Guerry, R., Tassios, D.: Salt effect on the vapor pressure of pure solvents: methanol with seven
salts; at 24.9 °C. J. Chem. Eng. Data 24, 9–11 (1979). doi:10.1021/je60080a005
24. Bradley, J.B., Pitzer, K.S.: Thermodynamics of electrolytes. 12. Dielectric properties of water and
Debye-Hückel parameters to 350 °C and 1 kbar. J. Phys. Chem. 83, 1599–1603 (1979).
doi:10.1021/j100475a009
25. Bridgeman, O.C., Aldrich, E.W.: Vapor pressure tables for water. J. Heat Transf. 86, 279–286 (1964)
26. Bromley, L.A.: Thermodynamic properties of strong electrolytes in aqueous solutions. AIChE J. 19,
313–320 (1973). doi:10.1002/aic.690190216
27. Campbell, A.N., Bhatnagar, O.N.: Osmotic and activity coefficients of sodium hydroxide in water from
150 to 250 °C. J. Chem. Eng. Data 29, 166–168 (1984). doi:10.1021/je00036a020
28. Chen, C.C., Evans, L.B.: A local composition model for excess Gibbs energy of electrolyte systems.
AIChE J. 32, 444–454 (1986). doi:10.1002/aic.690320311
29. Chen, C.C., Britt, H.I., Boston, J.F., Evans, L.B.: Local composition model for excess Gibbs energy of
electrolyte systems. AIChE J. 28, 588–596 (1982). doi:10.1002/aic.690280410
30. De Coppet, L.C.: On the molecular depression of the freezing-point of water produced by some very
concentrated saline solutions. J. Phys. Chem. 8, 531–538 (1904). doi:10.1021/j150062a001
31. Ge, X.L., Wang, X.D.: A simple two-parameter correlation model for aqueous electrolyte solutions
across a wide range of temperature. J. Chem. Eng. Data 54, 179–186 (2009)
32. Ge, X.L., Wang, X.D., Zhang, M., Seetharaman, S.: Correlation and prediction of activity and osmotic
coefficients of aqueous electrolytes at 298.15 K by the modified TCPC model. J. Chem. Eng. Data 52,
538–547 (2007). doi:10.1021/je060451k
33. Ge, X.L., Wang, X.D., Zhang, M., Seetharaman, S.: A new three-particle-interaction model to pre- dict
the thermodynamic properties of different electrolytes. J. Chem. Thermodyn. 39, 602–612 (2007).
doi:10.1016/j.jct.2006.09.002
34. Ge, X.L., Zhang, M., Guo, M., Wang, X.D.: Correlation and prediction of thermodynamic properties of
some complex aqueous electrolytes by the modified three-characteristic-parameter correlation model. J.
Chem. Eng. Data 53, 950–958 (2008). doi:10.1021/je7006499
35. Ge, X.L., Zhang, M., Guo, M., Wang, X.D.: Correlation and prediction of thermodynamic properties of
non-aqueous electrolytes by the modified TCPC model. J. Chem. Eng. Data 53, 149–159 (2008).
doi:10.1021/je700446q
36. Haghighi, H., Chapoy, A., Tohidi, B.: Freezing point depression of electrolyte solutions: experimental
measurements and modeling using the cubic-plus-association equation of state. Ind. Eng. Chem. Res.
47, 3983–3989 (2008). doi:10.1021/ie800017e
37. Hall, R.E., Harkins, W.D.: The free energy of dilution and the freezing-point lowering in solutions of
some salts of various types of ionization, and of salt mixtures. J. Am. Chem. Soc. 38, 2658–2676 (1916).
doi:10.1021/ja02269a009
38. Huang, S.H., Radosz, M.: Equation of state for small, large, poly disperse, and associating molecules.
Ind. Eng. Chem. Res. 29, 2284–2294 (1990). doi:10.1021/ie00107a014
39. Hunter, J.B., Harding, B.: Thermodynamic properties of aqueous salt solutions. Latent heats of va-
porization and other properties by the gas current method. Ind. Eng. Chem. 36, 945–953 (1944).
doi:10.1021/ie50418a019
40. Johnson, G.C., Smith, R.P.: The boiling point elevation. IV. Potassium bromide in water. J. Am. Chem.
Soc. 63, 1351–1353 (1941). doi:10.1021/ja01850a060
41. Li, W.C.: Physical Chemistry of Metallurgy and Materials. Metallurgy Press, Beijing (2001)
42. Lide, D.R. (ed.): CRC Handbook of Chemistry and Physics, 87th edn. CRC Press, Boca Raton (2006–
2007)
43. Lide, D.R. (ed.): CRC Handbook of Chemistry and Physics, 88th edn. CRC Press, Boca Raton (2007–
2008)
44. Lin, C.L., Tseng, H.C., Lee, L.S.: A three-characteristic-parameter correlation model for strong elec-
trolyte solutions. Fluid Phase Equil. 152, 169–185 (1998). doi:10.1016/S0378-3812(98)00393-8
45. Liu, C.T., Lindsay, W.T. Jr.: Vapor pressure of D2O from 106 to 300 °C. J. Chem. Eng. Data 15, 510–513
(1970). doi:10.1021/je60047a015
46. Lu, J.F., Yu, Y.X., Li, Y.G.: Modification and application of the mean spherical approximation method.
Fluid Phase Equil. 85, 81–100 (1996). doi:10.1016/0378-3812(93)80006-9
47. Modell, M., Reid, R.C.: Thermodynamics and Its Applications. Prentice Hall, Englewood Cliffs (1974)
1116 J Solution Chem (2009) 38: 1097–1117

48. Mohammed, T.Z.M., Jaber, J.S.: Isopiestic determination of osmotic coefficients and evaluation of vapor
pressures for electrolyte solutions of some lithium salts in ethanol. Fluid Phase Equil. 166, 207–223
(1999). doi:10.1016/S0378-3812(99)00293-9
49. Møller, N.: The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the
Na-Ca-Cl-SO4 − H2O system, to high temperature and concentration. Geochim. Cosmochim. Acta 52,
821–837 (1988). doi:10.1016/0016-7037(88)90354-7
50. Nasehzadeh, A., Noroozian, E., Omrani, H.: Experimental and theoretical studies of thermody- namics
of lithium halide solutions–ethanol mixtures. J. Chem. Thermodyn. 36, 245–252 (2004).
doi:10.1016/j.jct.2003.12.002
51. Nasirzadeh, K., Neueder, R., Kunz, W.: Vapor pressures, osmotic and activity coefficients for (LiBr
+
acetonitrile) between the temperatures (298.15 and 343.15) K. J. Chem. Thermodyn. 36, 511– 517
(2004). doi:10.1016/j.jct.2004.03.007
52. Nasirzadeh, K., Neueder, R.: Measurement and correlation of osmotic coefficients and evaluation of
vapor pressure for electrolyte solutions of LiClO4 and LiNO3 in methanol at 25 °C. J. Mol. Liq. 113, 13–
20 (2004). doi:10.1016/j.molliq.2004.02.028
53. Nasirzadeh, K., Salabat, A.: Isopiestic determination of osmotic coefficients and evaluation of vapor
pressures for solutions of sodium bromide and sodium thiocyanate in methanol at 25 °C. J. Mol. Liq.
106, 1–14 (2003). doi:10.1016/S0167-7322(03)00016-3
54. Nasirzadeh, K., Neueder, R., Kunz, W.: Vapor pressures and osmotic coefficients of aqueous LiOH
solutions at temperatures ranging from 298.15 to 363.15 K. Ind. Eng. Chem. Res. 44, 3807–3814 (2005).
doi:10.1021/ie0489148
55. Patil, K.R., Tripathi, A.D., Pathak, G., Katti, S.S.: Thermodynamic properties of aqueous electrolyte
solutions. 1. Vapor pressure of aqueous solutions of LiCl, LiBr, and LiI. J. Chem. Eng. Data 35, 166–
168 (1990). doi:10.1021/je00060a020
56. Patil, K.R., Tripathi, A.D., Pathak, G., Katti, S.S.: Thermodynamic properties of aqueous electrolyte
solutions. 2. Vapor pressure of aqueous solutions of NaBr, NaI, KCl, KBr, KI, RbCl, CsCl, CsBr, CsI,
MgCl2, CaCl2 , CaBr2 , CaI2, SrCl2 , SrBr2 , SrI2 , BaCl2 , and BaBr2 . J. Chem. Eng. Data 36, 225–230
(1991). doi:10.1021/je00002a021
57. Pepela, C.N., Dunlop, P.J.: A re-examination of the vapor pressure of aqueous sodium chloride solutions
at 25 °C. J. Chem. Thermodyn. 4, 255–258 (1972). doi:10.1016/0021-9614(72)90064-X
58. Pitzer, K.S., Mayogra, G.: Thermodynamics of electrolytes. I. Theoretical basis and general equations.
J. Phys. Chem. 77, 268–277 (1973). doi:10.1021/j100621a026
59. Randall, M., Scott, G.N.: The freezing point and activity coefficient of aqueous barium nitrate, sodium
sulfate and sulfuric acid. J. Am. Chem. Soc. 49, 647–656 (1927). doi:10.1021/ja01402a007
60. Safarov, J.T.: Study of thermodynamic properties of binary solutions of lithium bromide or lithium chlo-
ride with methanol. Fluid Phase Equil. 236, 87–95 (2005). doi:10.1016/j.fluid.2005.07.002
61. Safarov, J.T.: Vapor pressures of lithium bromide or lithium chloride and ethanol solutions. Fluid Phase
Equil. 243, 38–44 (2006). doi:10.1016/j.fluid.2006.02.012
62. Safarov, J.T.: Investigation of the vapor pressure p of zinc bromide or zinc chloride solutions with
methanol by static method. J. Chem. Thermodyn. 38, 304–311 (2006). doi:10.1016/j.jct.2005.05.017
63. Safarov, J.T.: Vapor pressure measurements of binary solutions of CaCl2 with methanol and ethanol
at (298.15 to 323.15) K using a static method. J. Chem. Eng. Data 51, 360–365 (2006).
doi:10.1021/je0502086
64. Salimi, H.R., Taghikhani, V., Ghotbi, C.: Application of the GV-MSA model to the electrolyte solutions
containing mixed salts and mixed solvents. Fluid Phase Equil. 231, 67–76 (2005).
doi:10.1016/j.fluid.2004.12.015
65. Sardroodi, J.J., Seyedahmadian, S.M., Sadr, M.H., Kazemi, Y.: Isopiestic study of the solutions of
MnCl2, CoCl2 and NiCl2 in methanol and ethanol at 298.15 K. Fluid Phase Equil. 240, 114–121 (2006).
doi:10.1016/j.fluid.2005.12.014
66. Saxton, B., Smith, R.P.: The activity coefficient of potassium chloride in aqueous solution from boiling
point data. J. Am. Chem. Soc. 54, 2626–2636 (1932). doi:10.1021/ja01346a005
67. Smith, R.P.: The boiling point elevation. II. Sodium chloride 0.05 to 1.0 M and 60 °C to 100 °C. J. Am.
Chem. Soc. 61, 500–503 (1939). doi:10.1021/ja01871a079
68. Spencer, R.J., Møller, N., Weare, J.H.: The prediction of mineral solubilities in natural waters: a chemical
equilibrium model for the Na-K-Ca-Mg-Cl-SO4−H2O system at temperatures below 25 °C. Geochim.
Cosmochim. Acta 54, 575–590 (1990). doi:10.1016/0016-7037(90)90354-N
69. Tomasula, P., Czerwienski, G.J., Tassios, D.: Vapor pressure and osmotic coefficients: electrolyte solu-
tions of methanol. Fluid Phase Equil. 38, 129–153 (1987). doi:10.1016/0378-3812(87)90008-2
70. Verevkin, S., Safarov, J.T., Bich, E., Hassel, E., Heintz, A.: Study of vapour pressure of lithium nitrate
solutions in ethanol. J. Chem. Thermodyn. 38, 611–616 (2006). doi:10.1016/j.jct.2005.07.015
J Solution Chem (2009) 38: 1097–1117 1117

71. Washburn, E.W.: International Critical Tables of Numerical Data, Physics, Chemistry and Technology,
1st electronic edn., pp. 1926–1930. Knovel, New York (2003)
72. Worth, H.R.: The Freezing points of concentrated solutions and the free energy of solution of salts. J.
Am. Chem. Soc. 40, 1204–1213 (1918). doi:10.1021/ja02241a008
73. Zafarani-Moattar, M.T., Jahanbin-Sardroodi, J.: Measurement and correlation of osmotic coefficients
and evaluation of vapor pressures for solutions of CaCl2 and Ca(NO3)2 in ethanol at 298 K. Fluid Phase
Equil. 172, 221–235 (2000). doi:10.1016/S0378-3812(00)00372-1