Ind. Eng. Chem. Res.

2008, 47, 1283-1287 1283

Boiling Point Rise Calculations in Sodium Salt Solutions

Marta Bialik,* Peter Sedin, and Hans Theliander
Forest Products and Chemical Engineering, Chalmers UniVersity of Technology, SE-412 96 Göteborg, Sweden

The boiling point rise (elevation) of aqueous industrial solutions is often regarded as an important property
with respect to chemical process design. This work shows an application of the Pitzer method for calculating
the activity coefficients to the estimation of the boiling point rise of single-component and multicomponent
electrolyte solutions. Good agreement between experimental and predicted values of the boiling point elevations
of solutions of several salts (NaOH, Na2CO3, Na2SO4, NaCl, Na2S2O3, Na2S, mixed NaOH-Na2CO3, and
mixed Na2CO3-Na2SO4) was obtained. A method for using the boiling point rise data to obtain ionic interaction
parameters for the Pitzer method is also shown.

Introduction Theory

Boiling point rise, also called boiling point elevation, has long
been recognized as an important property of numerous industrial
solutions. Boiling point rise is defined as the difference in
boiling temperatures of a given solution and its pure solvent
when measured at the same pressure.
The estimation of a true boiling temperature is an important
step in the design of boiling, evaporation, and heat-exchange
processes such as black liquor evaporation for pulp and paper
production, industrial crystallization, liquid waste handling, etc.
For this reason, many attempts have been made to develop a
reliable method for estimating the boiling point from measurable
solution properties.1 In the case of multicomponent industrial
solutions, especially those containing various organic com-
pounds (e.g., black liquor from the pulp and paper industry),
empirical or semi-empirical methods relating density or solid
content to boiling point elevation have frequently been used.2
Dühring’s rule, which involves plotting the boiling temperature
of a solution versus the temperature of the pure solvent at
different pressures, has also been applied.3
Estimating the boiling point elevation for multicomponent
industrial solutions is usually a challenging task. Both rigorous
thermodynamic methods and empirical methods based on easily
measurable solution properties have been used for this purpose.
For the rigorous thermodynamic methods, the calculation
procedure is often very complicated because of the large number
of chemical compounds present in the solution. Moreover, the
exact composition of many industrial solutions (e.g., black
liquor) is often difficult to determine with sufficient accuracy,
and the appropriate thermodynamic parameters for less typical
compounds are frequently not available. The empirical methods,
Many properties of solutions, including boiling point eleva-
tion, freezing point depression, and osmotic pressure, can be
related to the vapor pressure of the solvent and hence to its
activity. These properties are often called “colligative” properties
of a solution. In the rational system, the chemical potential,
µl, of a liquid solvent in a solution is expressed in terms
of the chemical potential of the pure liquid, µ0l , and its activity,
al, as7
µl(T,p) ) gl(T,p) + RT ln ai ) µ0i (T,p) + RT ln ai (1)
where al might be a function of temperature, pressure, and
composition. If the liquid solvent is in equilibrium with its vapor,
the equilibrium conditions can be written as an equality in
chemical potential7
µ0i (T,p) + RT ln ai ) µvap(T,p) (2)
Because the difference between the chemical potential of
vapor, µvap, and the chemical potential of pure liquid, µ0l , at
temperature T corresponds to the free energy of vaporization,
∆G0vap, of the pure liquid at this temperature, eq 2 can be
rearranged to7
-∆G0vap
ln a ) (3)
RT
Differentiating eq 3 with respect to activity and applying the
Gibbs-Helmholtz equation gives7

( )
on the other hand, usually have no support in solution theory 0
∆Hvap ∂T
1
and thus have very limited applications, modeling only one type )- (4)
of solution with acceptable precision. al RT2 ∂al p

The purpose of this work is to present a comprehensive set

of boiling point rise data from single-component and multi-
component salt solutions and to suggest a computational method
for predicting boiling point rise values for industrial salt systems
of great interest. For this application, the Pitzer method for
calculating the activity coefficients4,5 with interaction coef-
ficients from Pitzer5 and Weber6 was chosen, and the boiling
point elevation was calculated using Pitzer’s osmotic coefficient.
where ∆H0vap is the heat of vaporization. This expression can
then be integrated with the lower integration limit corresponding
to pure liquid, boiling at temperature T0, and the upper limit to
a solution with solvent activity a, boiling at temperature T. For
simplicity, the heat of vaporization is often assumed to be
independent of temperature within the small temperature range
between T0 and T. Thus, the final equation takes the form7

( ) [ ]
∆H0vap 1 1 ∆H0vap 1 1
* To whom correspondence should be addressed. E-mail: bialik@ ln a ) - ) - (5)
chalmers.se. Fax: +46-31-772-2995. R T T0 R (T0 + θ) T0

10.1021/ie070564c CCC: $40.75 © 2008 American Chemical Society

Published on Web 01/23/2008
1284 Ind. Eng. Chem. Res., Vol. 47, No. 4, 2008
where “0” refers to the properties of the pure solvent (water)
and θ is the boiling point elevation. If the activity of the solvent
is known, it is theoretically possible to use the eq 5 to predict
the boiling point rise of the solution.
There are numerous methods for calculating water activity
in aqueous solutions; however, only a few of them can be
applied to high-temperature, concentrated, multicomponent
systems. In this work, the semi-empirical Pitzer activity coef-
ficient method4,5 was chosen. This method has been widely used
for estimating activity coefficients in applications ranging from
the simple characterization of salt solutions to multifunctional
commercial simulation packages. The method, combining the
virial equation of state with the equation for potential energy
between ions, utilizes empirical interaction parameters of the
species present in the system. Consequently, the method requires
a set of well-established interaction parameters valid for the
desired temperature, pressure, and concentration conditions. The
basic interaction parameters from Pitzer5 and Weber,6 presented
in the Supporting Information, were used in this work (see
below).
For electrolyte solutions, the water activity calculation is
based on the definition of the practical osmotic coefficient, φ8
-1000 ln a
φ≡ (6)
Mw ∑
i)1
νimi
where Mw is the molecular mass of the solvent (water), mi is
the molality of the ith solute, and νi is the number of ions into
which the solute dissociates. Pitzer5 proposed the following
equation for the simplified calculation of the osmotic coefficient
[
-AφI3/2
(φ - 1) ) (2/ ∑i mi) + ∑c ∑a Intca +
1 + 1.2I1/2
]
∑ ∑ Intcc′(a) + ∑
c< c′
∑ Intaa′(c)
a< a′
(7)
where AΦ is the Debye-Hückel constant describing solvent
properties and I is the total ionic strength. The first summa-
tion term inside the square brackets represents the ionic
interactions in terms of Debye-Hückel theory. The second term
summarizes double-interaction terms, involving ions of different
signs (c, cation; a, anion). In analogy, the third and fourth terms
inside the square brackets summarize interactions of ions of
the same sign and also involve triple interaction terms (c-c′-a
or a-a′-c). The equations for the subsequent interaction terms
are given in the Supporting Information, and a detailed
description of the calculation procedure can be found else-
where.4,5
Ionic activities in a typical electrolyte system are highly
temperature-dependent; the activity coefficients in an ambient-
temperature solution can be as much as an order of magnitude
higher than those in a concentrated salt system boiling at
atmospheric pressure or higher. It is thus crucial that the activity
coefficient calculation method account for this temperature
dependence correctly. The Pitzer method addresses this problem
in two ways:5 by introducing the temperature dependence into
the solvent properties used in the calculation of the Debye-
Hückel constant and by also adjusting the empirical parameters
responsible for the interaction of two oppositely charged ions.
(The parameters are usually defined as temperature-dependent
polynomials.) The Debye-Hückel constant is defined as
( )x
2πd0NA
1 e 3
Aφ ) (8)
3 xDkT 1000
where D is the dielectric constant of the solvent, d0 is the solvent
density, T is the temperature, k is the Boltzmann constant, NA
is Avogadro’s number, and e is the unit charge. In addition to
its direct temperature dependence, AΦ includes two other
temperature-dependent quantities: D and d0. It is thus fairly
easy to calculate AΦ for a desired temperature. The temperature-
dependent polynomials for the interaction coefficients in eq 7
are often tabulated for common salt systems. This work uses
the temperature-dependence coefficients for the Pitzer param-
eters tabulated by Weber;6 for the systems whose coefficients
were not available, only the Debye-Hückel constant modifica-
tion was applied. For the sake of simplicity, Chen’s formula,4
which approximates the temperature dependence of Debye-
Hückel constants excellently, was used in this work
AΦ ) -61.44534 exp (T -273.15
273.15
)+
T - 273.15 2
2.864468[exp(
273.15 )]
+
T
183.5379 ln - 0.6820223(T - 273.15) +
273.15
0.0007875695(T2 - 273.152) + 58.95788
273.15
(9)
T
Because the entire calculation procedure is thoroughly explained
by Pitzer,5 it is relatively simple to program it for easy use
with a desktop computer or as part of more complex simula-
tion software. This work used a simple program written for
MATLAB (Mathworks, Inc., Natick, MA) software.
Estimation of Pitzer Parameters. The boiling point rise
calculation procedure presented above is very interesting.
Because eq 5 shows a mutual relationship between the boiling
point elevation and the corresponding solvent activity, it is
possible to use this procedure to calculate water activity in a
given aqueous solution if the value of a corresponding boiling
point rise is known. Once the water activity is known, it is
possible to calculate the osmotic coefficient in the Pitzer
equation according to eq 6. Consequently, reversing the Pitzer
equation for the osmotic coefficient (eq 7) makes it possible to
convert a set of well-established boiling point rise data into a
set of Pitzer empirical interaction parameters for a given salt
solution. This procedure could be applied for estimating the
Pitzer interaction parameters of complex solutions, especially
those involving atypical salts for which the original Pitzer
parameters are unknown (e.g., black liquor) and multicomponent
mixtures for which the higher-order interaction parameters have
not been identified.
Literature Data
In this work, two literature sources of experimental data for
boiling point elevations were used: the work of Makarov and
Krasnikov,9 containing a set of Na2CO3-Na2SO4 solubility data
for systems boiling at atmospheric pressure, and that of
Theliander,10 which includes the experimental boiling point rise
results from research on the physicochemical data of model
solutions for white liquor. The data include boiling point
elevation values for NaOH, Na2CO3, Na2SO4, NaCl, Na2S2O3,
Na2S, mixed NaOH-Na2CO3, and mixed Na2CO3-Na2SO4
solutions. The values of the experimental and modeled boiling
point rise values are summarized in the Supporting Information.

Figure 1. Boiling point rise as a function of molality: NaOH solution.
Figure 2. Boiling point rise as a function of molality: Na2CO3 solution.
Figure 3. Boiling point rise as a function of molality: Na2SO4 solution.
Figure 4. Boiling point rise as a function of molality: NaCl solution.
Figure 5. Boiling point rise as a function of molality: Na2S2O3 solution.
Results and Discussion
Single-Salt Solutions. Figures 1-5 show comparisons be-
tween the modeled and calculated boiling point rise values and
Ind. Eng. Chem. Res., Vol. 47, No. 4, 2008 1285
the experimental data obtained for single-salt systems. The
modeling was done in two steps: First, the temperature
extension was applied only for the Debye-Hückel constant
(with temperature-independent interaction parameters from
Pitzer5), and then, the temperature-dependent interaction coef-
ficients from Weber6 were introduced. (For the systems not
tabulated by Weber,6 only the first step was performed). The
results from both steps are shown for comparison. As can be
seen, for both approaches, the overall fit is remarkably good,
especially for moderate concentration levels (2-3 molal): the
difference between the experimental and predicted values for
moderately concentrated NaOH, Na2CO3 and Na2SO4 solutions
is approximately equal to 0.2 °C, which can be compared to
the experimental error estimated to be 0.1 °C.
At higher concentrations, the predictions deteriorate some-
what, especially in the case of the NaOH solution modeled
without including the temperature dependency in Pitzer param-
eters, for which a significant discrepancy between the experi-
mental and predicted values can be observed at m ) 9. This is,
however, not surprising given that it is very difficult to make a
proper thermodynamic description of concentrated salt solutions
at elevated temperatures. Moreover, the application of the
temperature-independent Pitzer interaction parameters for the
NaOH-H2O system is actually limited to 6 molal solutions.5
The model version that uses temperature-dependent interaction
parameters performs significantly better at higher NaOH
concentrations, which can be expected based on the fact that
the temperature behavior of highly concentrated NaOH solutions
has long been studied and evaluated.
The accuracy of the prediction of boiling point elevation
increased significantly with the introduction of the temperature
dependency into the interaction parameters for only two of the
four examined single-salt systems for which the temperature
extensions were available: NaOH and Na2SO4. For the NaCl
solution, no major improvement was observed within the
examined composition range, whereas for the Na2CO3 solution,
the prediction was somewhat worse. Several possible reasons
for such behavior can be mentioned: First, both NaOH and
Na2SO4 are well-known and thoroughly examined salt systems
with well-tested parameters, whereas studies of Na2CO3 solu-
tions are less common. Second, the parameters provided by
Weber6 seem to pertain mostly to saturated solutions, so the
advantage of using them might not appear clearly at lower
concentration levels, as in the case of the examined NaCl
solution.
As can be seen in Figures 1-5, the accuracy of the predictions
of boiling point rises differs between the univalent and divalent
salt systems examined: The predictions for NaOH and NaCl
tend to be slightly more exact for the same molality level than
are those for Na2CO3, Na2SO4, and Na2S2O3. This trend can be
explained by the fact that the two univalent salts are among the
most comprehensively examined systems within the scope of
solution chemistry: their interaction parameters are thoroughly
verified. Moreover, the solutions of salts with divalent anions
have ionic strengths that are 3 times higher than those of
univalent-anion systems. Thus, relating the magnitude of error
in their boiling point rise prediction to molality alone might
not be a truly fair measure of the efficiency of the prediction.
Multicomponent Solutions. The model was also used to
predict the boiling point rises in multicomponent electrolyte
solutions, resulting in a remarkably good fit, especially for
moderate concentrations. Figures 6 and 7 show the experimental
and predicted values for boiling point elevation plotted versus
ionic strength, adopted as a total concentration measure. The
1286 Ind. Eng. Chem. Res., Vol. 47, No. 4, 2008
Figure 6. Boiling point rise as a function of ionic strength: NaOH-Na2-
CO3 solution.
Figure 7. Boiling point rise as a function of ionic strength: Na2CO3-
Na2SO4 solution.
NaOH-Na2CO3 system shows an excellent fit, especially when
the temperature-dependent Pitzer parameters were used. Up to
an ionic strength of 3, the differences between the experimental
values and predictions from both versions of the model are still
smaller than the estimated experimental error. However, such
a good fit might possibly be due to the canceling of errors in
the individual parameters of the two single salts.
For the Na2CO3-Na2SO4 solution data from Makarov and
Krasnikov,9 the total concentration of salt was always kept at
the saturation level; only the proportion between the two salts
was varied. Given the fact that the solubility of sodium carb-
onate in boiling water is slightly higher than that of sodium
sulfate, the increasing ionic strength in Figure 7 roughly
reflects the increasing proportions of carbonate ions. Also, the
model predictions for this system compare favorably with the
experimental data. The greatest discrepancies can be observed
at both ends of the plot, which correspond to pure-salt solutions
at saturation. It is worth noting that, whereas use of the
temperature-independent Pitzer parameters tends to underesti-
mate the boiling point rises for solutions with higher Na2SO4-
to-Na2CO3 ratios, calculations including the temperature-
modified parameters overestimates them. For solutions rich in
sodium carbonate, the model predictions behave in exactly the
opposite way.
Na2S Solution. Aqueous solutions of sodium sulfide merit
special attention. When dissolved in water at 25 °C, Na2S
dissociates according to the following reaction scheme11
Na2S S Na+ + NaS- (pK1 ) 7.05)
NaS- S Na+ + S2- (pK2 ) 19)
Because of the high pK value of the second dissociation step,
the free S2- ion is virtually never present in a solution within
the operationally practical pH range. A hydrolysis reaction takes
place instead, which can be summarized as
Na2S + H2O S 2Na+ + HS- + OH-
Figure 8. Boiling point rise as a function of molality: Na2S solution.
Thus, the single-salt solution is actually a multicomponent
system under practical conditions and needs to be modeled as
such, which involves a need for higher-order interaction
parameters. The total salt concentration also changes slightly
by the amount of water molecules involved in the hydrolysis
reaction, so the first step in modeling a Na2S-H2O solution is
to recalculate the ionic concentrations.
Three different approaches to modeling of the Na2S-H2O
system were used in this work. The first approach involved
modeling the solution as if it did not contain any hydrosulfide
ions (i.e., only Na+ and OH- from water dissociation were
assumed to be present). The purpose of this approach was to
assess the magnitude of the influence of the hydrosulfide ions
on the system’s behavior. As can be seen in Figure 8, ignoring
the presence of SH- ions in the solution leads to an underes-
timation of the boiling point rise by roughly one-half of its value;
this suggests that these ions play a significant role in the
behavior of the system.
The second approach involved modeling the multicomponent
system in the usual manner, but ignoring the higher-order terms
for interactions between the two like-charged ions and for triple-
ion interactions (empirical parameters for these interactions were
not known). Because no temperature-dependence coefficients
for Na+-HS- Pitzer interaction parameters were available, the
behavior of OH- anions was, for consistency, also modeled
using only a simple temperature dependence in the form of a
modification of the Debye-Hückel constant. As can be seen
in Figure 8, this modeling approach offers a remarkably good
fit, with the absolute difference between the experimental and
calculated values never exceeding the experimental error. Such
good agreement suggests that higher-order interactions do not
play any significant role in the system behavior at these
temperature and concentration levels.
The third, and final, approach consisted of modeling the
behavior of all of the system anions as though they were
hydroxide ions. In other words, the presence of SH- ions was
ignored, and the amount of OH- ions was doubled (cf. the
stoichiometry of the hydrolysis reaction). Surprisingly good
agreement was obtained; again, the differences between the
experimental and calculated values were almost negligible and
never exceeded the level of the experimental error. Such an
excellent fit can probably be explained by similarities in the
behavior of OH- and SH- ions.
Conclusions
A technique for the calculation of boiling point elevation in
single-salt and multicomponent aqueous solutions was developed
in this work. This routine is based on the Pitzer ionic activity
coefficient method for the calculation of water activity and on
an osmotic coefficient calculation.
Predictions obtained using the method were compared with
the experimental boiling point elevation values for NaOH,

Na2CO3, Na2SO4, Na2S, mixed NaOH-Na2CO3, and mixed
Na2CO3-Na2SO4 solutions. Excellent predictions were observed
for moderate concentrations in both single-component and
multicomponent salt solutions. At significantly higher concen-
trations (solutions close to the saturation point), the predictions
deteriorate somewhat; nevertheless, the results can still be
recommended as a good first approximation in complex boiling
point rise calculations. It was also noticed that the predictions
for mixed systems were relatively better than those for pure
salts; this fact was especially true for the saturated Na2CO3-
Na2SO4 solution.
The modeling results for the complex solution of hydrolyzed
Na2S salt suggest a very weak influence of higher-order ionic
interactions on the solvent activity and the boiling point rise at
the concentration levels analyzed, as well as a strong similarity
between hydroxide and hydrosulfide ions. The technique
presented for estimating boiling point rises also offers a method
for calculating the empirical interaction parameters for the Pitzer
method for systems for which the original parameters are
unknown.
Nomenclature
a ) water activity
AΦ ) Debye-Hückel constant
d0 ) solvent density, kg/m3
D ) dielectric constant of water
e ) unit charge; e ) 1.6022 × 10-19 C
g ) free energy term in the definition of chemical potential
∆Gvap ) free energy change of vaporization, J/mol
∆Hvap ) enthalpy change of vaporization, J/mol
I ) ionic strength
Int ) ionic interaction term for the Pitzer method
k ) Boltzmann constant; k ) 1.3807 × 10-23 J/K
m ) salt molality, mol/(kg of solvent)
Mw ) molecular mass of water; Mw ) 18.02 kg/kmol
NA ) Avogadro’s number; NA ) 6.022 × 1023
p ) pressure
R ) gas constant; R ) 8.314 J/(mol K)
T ) temperature, K
Greek Letters
θ ) boiling point elevation, K (°C)
µ ) chemical potential
φ ) osmotic coefficient
ν ) stoichiometric number of ions from dissociation
Subscripts
c ) cation
Ind. Eng. Chem. Res., Vol. 47, No. 4, 2008 1287
a ) anion
i ) ith solute (ion)
l ) liquid (solvent)
vap ) vaporization
Superscript
0 ) properties of the pure solvent
Supporting Information Available: Tables showing the
Pitzer parameters for ionic interactions used in this work;
comparison of experimental and calculated boiling point rise
values for single-salt systems; comparison of the experimental
and calculated boiling point rise values for multicomponent salt
systems; and summary of the Pitzer method for calculation of
the osmotic coefficient (PDFs). This material is available free
of charge via the Internet at http://pubs.acs.org.
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(4), 151.
(3) Bujanovic, B.; Cameron, J. H. Effect of Sodium Metaborate on the
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(8) Tester, J. W; Modell, M. Thermodynamics and Its Applications, 3rd
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ReceiVed for reView April 23, 2007
ReVised manuscript receiVed October 23, 2007
Accepted November 27, 2007
IE070564C