Thermochimica Acta 551 (2013) 92–98

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Thermodynamic properties of LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 system

Tao Wang, Divakar Mantha, Ramana G. Reddy ∗
Department of Metallurgical and Materials Engineering, The University of Alabama, Tuscaloosa, AL 35487-0202, USA

a r t i c l e i n f o a b s t r a c t

Article history: A novel low melting eutectic salt was predicted in the LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 quater-
Received 29 April 2012 nary system using thermodynamic modeling. The melting point of the eutectic salt was predicted to
Received in revised form 8 August 2012 be 374.90 K. Differential scanning calorimetry (DSC) was used to experimentally determine the melting
Accepted 12 September 2012
point and specific heat capacity of the quaternary system. The mixture was measured to be completely
Available online 3 October 2012
melted at 373.90 ± 0.78 K which is in an excellent agreement with the predicted value. The measured
heat capacity data as function of temperature are fit to polynomial function. Subsequently, the thermo-
Keywords:
dynamic properties such as enthalpy, entropy and Gibbs energies of this novel quaternary eutectic salt
DSC
LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2
were deduced as function of temperature.
quaternary system © 2012 Published by Elsevier B.V.
Melting point
Heat capacity
Thermodynamic properties

1. Introduction melting point of 397.15 K [21]. Similarly, the eutectic composition

Parabolic trough is often used as a method for the solar power
conversion and constructed by silver coated parabolic mirror. The
upper limit temperature for the parabolic trough application is
773.15 K. In the working temperature range of 573.15–873.15 K,
molten salts are being used as media for the thermal energy storage
and heat transfer because of the low melting point, low unit cost,
high heat capacity, high thermal stability, negligible vapor pressure
and high energy storage capacity [1]. Three major groups of molten
salt mixtures (nitrate/nitrite group, carbonate group and chlo-
ride/fluoride group) are mostly studied. Generally, nitrate/nitrite
salts have much lower melting points compared to the other two
groups [2–11], which indicates larger working temperature range
of nitrate/nitrite salts. The heat capacities of nitrate/nitrite salts
[12,13] are similar to that of carbonate salts [7,8] which are rela-
tively higher than chloride/fluoride group salts [8]. All the three
salts groups present similar densities in liquid state, although
carbonate salts may have slightly higher values than the other
two groups [14–20]. On comparison, the nitrate/nitrite salts pro-
vide higher energy storage capacities than the other groups of
salts.
Several novel nitrate/nitrite salt systems were developed
in our research group. A new eutectic salt mixture in the
NaNO3 –NaNO2 –KNO3 ternary system was calculated using ther-
modynamic modeling and was experimentally verified to have a
∗ Corresponding author. Tel.: +1 205 348 4246; fax: +1 205 348 2164.
E-mail address: rreddy@eng.ua.edu (R.G. Reddy).
in the LiNO3 –NaNO3 –KNO3 ternary system was also developed and
the melting point was determined to be 391.15 K [22]. There is a
congruently melting compound, 2KNO3 ·Mg(NO3 )2 , which we refer
to as MgKN, in the Mg(NO3 )2 –KNO3 binary system. The melting
point of the MgKN compound was experimentally determined to
be 468.83 K [23]. This compound was studied as an additive in the
molten salt systems for the solar thermal energy storage applica-
tions.
From the previous results obtained for the eutectic composi-
tion in the LiNO3 –NaNO3 –KNO3 ternary system [22] and that of the
congruent melting compound MgKN [23], a new eutectic compo-
sition in the LiNO3 –NaNO3 –KNO3 –MgKN quaternary system was
identified by thermodynamic modeling. The melting point of the
novel eutectic system was determined from the Gibbs energies of
fusion of the individual salt components and the Gibbs energies
of mixing of constituent binary systems. The methodology used
in developing the thermodynamic model to predict eutectic point
(composition and temperature) in novel salt mixtures is described
elsewhere [22]. Similar approach was utilized in predicting eutec-
tic points in multi-component salt mixtures as well. In the present
work, a four-component salt mixture, the Gibbs energy of fusion of
each salt component is expressed in terms of partial excess Gibbs
energies of individual salt components. The partial excess Gibbs
energies of individual salt components are obtained from the inte-
gral excess Gibbs energy of mixing in the system. In this study,
integral molar excess Gibbs energy is obtained by the summation
of Gibbs energies of six constituent binary systems. Ternary and
higher order interactions are neglected. The Gibbs energies of con-
stituent binary systems that are available are directly taken from

0040-6031/$ – see front matter © 2012 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.tca.2012.09.035
 T. Wang et al. / Thermochimica Acta 551 (2013) 92–98
literature [22–26]. Gibbs energy of fusion of each component salt
in the multi-component salt mixture can be expressed as:
xs
Gio = −RT ln(Xi ) − Gi
xs
where Gio is the Gibbs energy of fusion of the salt ‘i’, Gi is the molar
excess Gibbs energy and Xi is the molefraction of the salt ‘i’. Newton-
Raphson method was used to solve these four non-linear equations
of Gibbs energies of fusion to obtain the four variables (three com-
position variables and temperature) by linearizing the non-linear
equations using the Taylor series and truncating the series to first
order derivatives. The convergence of solution vector (composi-
tion and temperature) is checked by subjecting to very small error
(10−12 ). Furthermore, the convergent solution (eutectic composi-
tion and temperature) is checked for thermodynamic stability by
means of classical stability expression for multi-component solu-
tion.
The melting point of the eutectic composition was calculated
as 374.90 K and the eutectic composition as 17.77 wt% LiNO3 ,
15.28 wt% NaNO3 , 35.97 wt% KNO3 and 30.98 wt% MgKN. In this
paper, we report the experimentally determined melting point and
heat capacity data. Subsequently, the thermodynamic parameters
such as entropy, enthalpy and Gibbs energy of the eutectic com-
position in the quaternary salt system as function of temperature
were deduced from the heat capacity data.
2. Experimental
2.1. Materials and salt preparation
The LiNO3 –NaNO3 –KNO3 –MgKN quaternary system was syn-
thesized by mixing corresponding amounts of lithium nitrate
(>98% pure), sodium nitrate (>99% pure), potassium nitrate (purity
99.0% min) and magnesium nitrate hexahydrate (98%) obtained
from Alfa Aesar® . No further purifications were applied to lithium
nitrate, sodium nitrate and potassium nitrate. However, the mag-
nesium nitrate hexahydrate was dehydrated before synthesizing
the 2KNO3 ·Mg(NO3 )2 compound using the dehydration process,
which were discussed previously [23]. The eutectic composition in
the LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 quaternary system is
17.77 wt% LiNO3 , 15.28 wt% NaNO3 , 35.97 wt% KNO3 and 30.98 wt%
2KNO3 ·Mg(NO3 )2 . Weighed amounts of the four constituent salts
were measured by the balance to an accuracy of 0.1 mg and mixed
mechanically in a stainless steel crucible. The mixture was then
heated up to a certain temperature which was about 50 K more than
the predicted melting temperature of the salt mixture and held for
about 30 min. The salt mixture was cooled to ambient temperature
after complete mixing. This procedure was repeated 3–4 times to
get a homogeneous eutectic mixture. The entire preparation was
conducted inside glove box covered by high purity argon gas to
prevent the absorption of moisture from the atmosphere.
2.2. Apparatus and calibration
The melting point and heat capacity of the newly developed
eutectic quaternary system was measured using PerkinElmer dia-
mond differential scanning calorimeter (DSC). The accuracies of
heat flow and temperature collections in the instrument are
0.0001 mW and 0.01 K, respectively. Before the actual measure-
ments, calibration of DSC temperature, the heat flow curve as
well as the blank experiment slope were performed by using pure
indium, zinc metal and solar salt based on the GEFTA calibration
procedure [27,28]. The measurements were conducted under high
purity argon atmosphere with a flow rate of 20 cc/min and at a
heating rate of 5 K/min.
93
2.3. Experimental procedure
The synthesized eutectic salt mixture was placed inside the
standard aluminum pan crimped with lid used for DSC measure-
ments. The empty pan and lid were weighed before the experiment.
The actual weight of the sample is determined by removing the
weight of the pan and lid. The crimped sample pan was immedi-
ately put inside the sample chamber of the DSC apparatus and held
at 523.15 K for 10 h under argon atmosphere to remove any trace
amounts of moisture that might have possibly caught in the process
of loading the salt mixture. In the melting point determination pro-
cess, a temperature range from 298.15 K to 523.15 K was set with
a heating rate of 5 K/min followed by a cooling cycle at the same
rate. The heating–cooling cycle was repeated for 6 times to ensure
homogeneous mixing of the salt mixture and reproducibility of the
results.
For heat capacity measurement, the sample heating tem-
perature was from 298.15 K to 623.15 K with the addition of
“iso–scan–iso” steps to the heating process. The “iso–scan–iso”
steps with a step width of 25 K were added into the program after
six heating–cooling cycles. The temperature was held for 5 min
before and after each scanning step. The small temperature scan
range was chosen to decrease the thermal resistance between the
device and the salt mixture and to increase the temperature detec-
tion accuracy. To get the value of molar heat capacity of the eutectic
mixture, the heat absorbed by the empty sample pan in the heat-
ing process was obtained. The slope of the blank experiment was
maintained to be zero after calibration to ensure the accuracy of the
heat capacity measurement. After the experiment, the sample was
collected from the chamber and weighed again to compare with the
weight measured before putting inside the DSC. Only when the dif-
ference is less than 0.2 mg, the measurements are considered to be
valid to ensure the accuracies of the enthalpy of fusion and specific
heat capacity.
3. Results and discussion
3.1. Melting point determination
The melting point of the eutectic composition in the
LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 quaternary system was
determined using differential scanning calorimetry (DSC). In the
measurement, a series of scanning rates ranges from 0.1–20 K/min
were employed to record the heat flow as function of temperature
in the studied temperature range. It is found that only at the lower
scanning rate less than 5 K/min, the accuracy of measurement can
be ensured by increasing the sensitivity of the instrument to the
heat flow variation within short time, which helps to detect any
small endothermic peaks. Fig. 1 shows the DSC plot of the heat-
ing process in the sixth cycle under scanning rate of 5 K/min. To
ensure the reproducibility of the results, the same eutectic com-
position was freshly prepared for at least three times and the
measurements were carried out with identical procedure. In all
the experimental runs, only one endothermic peak was observed
in the heating process which can be considered as the melt-
ing peak for the eutectic mixture in the quaternary system. The
onset of melting process is considered to be 356.37 ± 0.13 K based
on the slope of endothermic peak. Before and after the melting
peak, the heat flow curves were stable. There were no other solid
state phase transitions observed below the melting temperature in
Fig. 1.
For metallic samples with high thermal conductivities, the
experimental melting temperatures normally should be taken as
the onset points of the phase transformation peaks because of
the homogenous temperature distribution inside the sample upon
94 T. Wang et al. / Thermochimica Acta 551 (2013) 92–98
Fig. 1. Endothermic peak showing the melting point of the eutectic composition
in the LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 quaternary system determined by
Diamond DSC.
melting. However, because of the low thermal conductivities [29],
the salts cannot be completely melted at the onset temperature
of the transition process. The non-homogeneous temperature dis-
tribution inside the salt results in the internal heat flow which
can enhance the mixing and melting of the sample. Hence, the
complete transition can only be ensured at the peak transition
temperature. Thus, the peak temperature of melting is empha-
sized in nitrate salt mixture at which point every portion of salt
mixture had transitioned to liquid state and can be applied to the
energy storage. The peak melting temperatures of the eutectic mix-
ture in the quaternary system detected using DSC at scan rates of
0.1 K/min, 0.5 K/min, 1 K/min and 5 K/min are listed in Table 1. It
was observed that the detected temperature decreased with low-
ering scan rates. When the scanning rate is lower than 5 K/min,
the deviation was less than 1.60 K. Also, the deviation between
the experimentally determined melting temperature and the pre-
dicted value obtained from thermodynamic modeling was less than
1.78 K. The enthalpy of fusion of the eutectic composition was
6.0 kJ/mol determined from the area under the endothermic tran-
sition peak.
By using the 2KNO3 ·Mg(NO3 )2 compound as an additive to
the LiNO3 –NaNO3 –KNO3 ternary system, a new eutectic com-
position was identified in the quaternary system. The peak
melting point of the eutectic composition in the quaternary
system was lower by approximately 17 K than that of the eutec-
tic mixture in the LiNO3 –NaNO3 –KNO3 ternary system. This is
a significant improvement in the development of low melting
point salt mixtures. The peak melting point of 2KNO3 ·Mg(NO3 )2
compound, the eutectic composition in the LiNO3 –NaNO3 –KNO3
ternary system and the newly developed eutectic composition in
the LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 quaternary system are
listed in Table 2.
Table 1
Peak melting temperatures LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 systems under
different scanning rate.
Scanning rate (K/min) Melting point (K)
0.1 373.19 ± 0.07
0.5 373.46 ± 0.08
1.0 373.73 ± 0.10
5.0 374.53 ± 0.15
Table 2
Peak melting temperatures of MgKN compound, and eutectic compositions in the
LiNO3 –NaNO3 –KNO3 and LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 systems.
System/Compound Temperature (K)
2KNO3 ·Mg(NO3 )2 468.8
LiNO3 –NaNO3 –KNO3 391.5
LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 373.9
3.2. Heat capacity determination
From the thermodynamic definition, the heat capacity is the
amount of heat required to change a body’s temperature by a given
amount. In the measurement of heat capacity using DSC equipment,
the heat absorbed by the tested sample is recorded as a function of
temperature. In the heating process, the temperature profile can be
expressed as:
Tt = To + ˇt (1)
where To is the initial temperature in K, ˇ is the set heating rate
(K/min) and Tt is the temperature in K at a certain time t (min). On
the basis of the temperature variation trend, the heat capacity can
be expressed as follows [30]:
 dH     P 
1 1 dH/dt 1
Cp = = = (2)
m dT m dT/dt m ˇ
where the P is the actual DSC heat flow signal which has the unit
as mW, m is the mass for the sample of interest. This way the heat
capacity with the DSC heat flow data is calculated.
The heat capacity of the eutectic composition in the quaternary
system was measured by recording the heat flow as function of
temperature in “iso–scan–iso” steps at intervals of 25 K. This is a
standard procedure for the heat capacity measurement using the
DSC equipment which has two advantages; (i) any heat fluctuations
during every 25 K temperature scanning range can be avoided by
the isothermal steps and (ii) phase transition can be highlighted
by the choice of temperature range. Fig. 2 shows the heat capacity
of the eutectic composition in the quaternary system measured as
function of temperature in the range 298.15–623.15 K. Since the
heat capacity measurement corresponds to the process of collecting
heat flow with the identical procedure to that in the melting point
measurement, the heat capacity plot demonstrates the same shape
as that observed in the melting point determination. The melting
peak temperature is also observed at 374.53 K in the heat capacity
Fig. 2. Heat capacity of eutectic composition in the LiNO3 –NaNO3 –KNO3 –
2KNO3 ·Mg(NO3 )2 quaternary system as function of temperature determined by
Diamond DSC.
 T. Wang et al. / Thermochimica Acta 551 (2013) 92–98 95

Table 3
Heat capacities of the eutectic composition in the LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 quaternary system at different temperatures (298.15–623.15 K).

T (K) Cp (J/K mol) T (K) Cp (J/K mol) T (K) Cp (J/K mol) T (K) Cp (J/K mol)

298.15 133.05 365.01 413.52 385.15 177.52 515.15 181.54

305.15 133.25 366.09 439.37 390.15 177.68 520.15 181.69
310.15 133.85 367.09 470.55 395.15 177.83 525.15 181.85
315.15 134.82 368.09 500.14 400.15 177.98 530.15 182.00
320.15 136.17 369.08 530.52 405.15 178.14 535.15 182.16
325.15 137.89 370.08 563.74 410.15 178.29 540.15 182.31
330.15 139.99 371.07 597.87 415.15 178.45 545.15 182.47
335.15 142.46 372.07 633.59 420.15 178.60 550.15 182.62
340.15 145.31 373.15 667.26 425.15 178.76 555.15 182.77
345.15 148.53 374.38 723.10 430.15 178.91 560.15 182.93
348.15 150.64 374.65 673.95 435.15 179.07 565.15 183.08
350.10 156.32 375.10 644.12 440.15 179.22 570.15 183.24
351.10 168.17 375.46 614.76 445.15 179.38 575.15 183.39
352.09 182.38 376.05 566.27 450.15 179.53 580.15 183.55
353.09 198.84 376.54 521.00 455.15 179.68 585.15 183.70
354.09 214.27 376.89 460.62 460.15 179.84 590.15 183.86
355.09 229.66 377.19 403.76 465.15 179.99 595.15 184.01
356.09 245.67 377.52 356.80 470.15 180.15 600.15 184.16
357.10 262.61 378.03 313.06 475.15 180.30 605.15 184.32
358.10 277.50 378.52 275.56 480.15 180.46 610.15 184.47
359.10 293.70 379.06 241.38 485.15 180.61 615.15 184.63
360.10 309.25 380.07 204.28 490.15 180.77 620.15 184.78
361.10 325.97 381.07 186.51 495.15 180.92 623.15 184.88
362.10 343.97 382.08 182.64 500.15 181.07
363.10 363.06 383.09 180.03 505.15 181.23
364.10 386.87 384.10 178.33 510.15 181.38

plot. Moreover, the heat capacity after the phase transition peak is
very stable and increase linearly as function of temperature with a
very small slope.
The heat capacity data can be divided into two sections; (i)
solid state (298.15–348.15) K (ii) liquid state (385.15–623.15) K.
Accordingly, the heat capacity data are fit to two separate polyno-
mial equations corresponding to the different phases of the eutectic
composition.
3.2.1. Heat capacity of solid state: (298.15–348.15) K
In the temperature range of 298.15–348.15 K, the heat capacity
of the eutectic composition in solid state is given in Table 3 and
the data is fit to a second order polynomial equation. Eq. (3) gives
the polynomial equation along with the least square fit parameter
(R2 ) in the temperature range for the solid state of the eutectic
composition.
 J

Cp (solid state ˛) = 7.50 × 10−3 T 2 − 4.50T + 806.56
mol K
(3)
(298.15 − 348.15) K
R2 = 0.982
3.2.2. Heat capacity of liquid state: (385.15–623.15) K
In the temperature range of 385.15–623.15 K, the heat capacity
of the eutectic composition in liquid state is also given in Table 3
and the data is fit to a linear equation. Eq. (4) gives the equation
along with the least square fit parameter (R2 ) in the temperature
range for the liquid state of the eutectic composition.
3.2.3. Specific heat capacity at 773.15 K
The specific heat capacity of the molten salt at the upper
limit temperature of the thermal energy storage application is a
crucial parameter which determines the efficiency and potential
of energy storage ability. As discussed above, the heat capac-
ity of the eutectic composition shows linear increasing trend
in the liquid state, which is consistent with the observations
found in the eutectic composition of the LiNO3 –NaNO3 –KNO3
ternary system and the 2KNO3 ·Mg(NO3 )2 compound. As a result
of that, the massive specific heat capacity of the studied eutectic
composition in the quaternary system at 773.15 K was extrap-
olated and compared with that of the eutectic composition in
the LiNO3 –NaNO3 –KNO3 ternary system and 2KNO3 ·Mg(NO3 )2
compound in Table 4. It can be seen that the addition of
2KNO3 ·Mg(NO3 )2 to the LiNO3 –NaNO3 –KNO3 ternary system
results in a new eutectic composition with higher massive spe-
cific heat capacity than that of the LiNO3 –NaNO3 –KNO3 ternary
system. The volume specific heat capacities which are more perti-
nent for the heat storage application were also extrapolated and
Table 4
Massive specific heat capacities of MgKN compound, and eutectic compositions
in the LiNO3 –NaNO3 –KNO3 and LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 systems at
773.15 K.
System/Compound Massive heat
capacity (J/g K)
2KNO3 ·Mg(NO3 )2 1.88
LiNO3 –NaNO3 –KNO3 1.63
LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 1.67

 J

Cp (liquid) = 3.09 × 10−2 T + 165.62 Table 5
mol K
(4) Volume specific heat capacities of MgKN compound, and eutectic compositions
(385.15 − 623.15) K in the LiNO3 –NaNO3 –KNO3 and LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 systems at
773.15 K.
R2 = 0.993
System/Compound Density Volume heat
Heat capacity data of the LiNO3 -NaNO3 -KNO3 -2KNO3 ·Mg(NO3 )2 (g/cm3 ) capacity (J/cm3 K)
compound in the solid state follows a second order polynomial 2KNO3 ·Mg(NO3 )2 1.767 3.32
curve whereas the heat capacity follows a linear equation in the LiNO3 –NaNO3 –KNO3 1.741 2.84
liquid state. LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 1.748 2.92
96 T. Wang et al. / Thermochimica Acta 551 (2013) 92–98

Table 6 Table 7
Experimental and calculated molar heat capacities of MgKN compound, and Thermodynamic properties of the eutectic composition in the
eutectic compositions in the LiNO3 –NaNO3 –KNO3 and LiNO3 –NaNO3 –KNO3 – LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 quaternary system in solid state
2KNO3 ·Mg(NO3 )2 systems at 773.15 K. (298.15–348.15 K).

System Molar heat T (K) Cp So Ho Go

capacity (J/mol K) (J/mol K) (J/mol K) (kJ/mol) (kJ/mol)

2KNO3 ·Mg(NO3 )2 658.0 298.15 133.05 0.00 0.00 0.00

LiNO3 –NaNO3 –KNO3 142.7 300.15 133.03 0.88 0.26 0.00
LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 189.4 302.15 133.07 1.75 0.53 0.00
LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 (Calc.) 193.6 304.15 133.18 2.62 0.79 −0.01
306.15 133.34 3.49 1.05 −0.01
308.15 133.57 4.35 1.32 −0.02
310.15 133.85 5.20 1.58 −0.03
compared in Table 5 along with the density values at 773.15 K
312.15 134.19 6.05 1.85 −0.04
measured by the densitometer as well as Archimedes method 314.15 134.60 6.90 2.11 −0.06
described in the literature [16,31,32]. It can be seen that the heat 316.15 135.06 7.75 2.38 −0.07
capacity per unit volume of the present quaternary system is higher 318.15 135.59 8.59 2.65 −0.09
320.15 136.17 9.43 2.92 −0.10
than that of LiNO3 –NaNO3 –KNO3 ternary system.
322.15 136.81 10.27 3.19 −0.12
In thermodynamics, the heat capacity is a quantity related to the 324.15 137.52 11.11 3.46 −0.15
mobility of molecules within the system. The degree of freedom of 326.15 138.28 11.95 3.73 −0.17
a system is a significant factor in determining the heat capacity. 328.15 139.11 12.79 4.00 −0.19
The more mobile systems have higher heat capacities. On the basis 330.15 139.99 13.63 4.28 −0.22
332.15 140.93 14.47 4.56 −0.25
of that, the molar heat capacities of LiNO3 –NaNO3 –KNO3 ternary
334.15 141.94 15.31 4.84 −0.28
system, 2KNO3 ·Mg(NO3 )2 and quaternary system were listed in 336.15 143.00 16.15 5.12 −0.31
Table 6 along with the theoretically calculated molar heat capacity 338.15 144.12 16.99 5.40 −0.34
using the additivity law. The comparison between the experimen- 340.15 145.31 17.83 5.69 −0.38
342.15 146.55 18.68 5.98 −0.41
tal and calculated molar heat capacities of the quaternary system
344.15 147.86 19.53 6.27 −0.45
reveals negative excess heat capacity, which indicates a more rigid 346.15 149.22 20.38 6.56 −0.49
structure was formed by adding 2KNO3 ·Mg(NO3 )2 into the ternary 348.15 150.64 21.23 6.86 −0.53
system thereby decreasing the mobility in the salt system.

3.3. Thermodynamic properties

From the experimental measurements of heat capacity, 3.3.1. Solid state (298.15–348.15) K
the standard thermodynamic properties such as entropy, Standard entropy as a function of temperature of the eutectic
enthalpy, and Gibbs energy of the eutectic composition in the composition in the quaternary system in the solid state is given by:
LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 quaternary system can be
determined and expressed in terms of heat capacity as function
 T  
of temperature for the solid and liquid phases of the eutectic Cp
composition in the quaternary system. The results are expressed STo − S298.15
o
= dT
T (8)
298.15
in the following two sections: (i) solid state (298.15–348.15 K) (ii)
−3 −2
liquid state (385.15–623.15 K). = 3.75 × 10 T − 4.50T + 806.59lnT − 3587.30 J/K mol

Table 8
Thermodynamic properties of the eutectic composition in the LiNO3 –NaNO3 –KNO3 –2KNO3 ·Mg(NO3 )2 quaternary system in liquid state (385.15–623.15 K).

T (K) Cp (J/mol K) So (J/mol K) Ho (kJ/mol) Go (kJ/mol) T (K) Cp (J/mol K) So (J/mol K) Ho (kJ/mol) Go (kJ/mol)

385.15 177.52 53.90 18.97 −1.79 510.15 181.38 104.32 41.41 −11.81
390.15 177.68 56.19 19.86 −2.06 515.15 181.54 106.09 42.31 −12.34
395.15 177.83 58.46 20.75 −2.35 520.15 181.69 107.84 43.22 −12.87
400.15 177.98 60.69 21.64 −2.65 525.15 181.85 109.58 44.13 −13.42
405.15 178.14 62.90 22.53 −2.96 530.15 182.00 111.30 45.04 −13.97
410.15 178.29 65.09 23.42 −3.28 535.15 182.16 113.01 45.95 −14.53
415.15 178.45 67.25 24.31 −3.61 540.15 182.31 114.71 46.86 −15.10
420.15 178.60 69.39 25.21 −3.95 545.15 182.47 116.39 47.77 −15.68
425.15 178.76 71.50 26.10 −4.30 550.15 182.62 118.05 48.69 −16.26
430.15 178.91 73.59 26.99 −4.66 555.15 182.77 119.71 49.60 −16.86
435.15 179.07 75.66 27.89 −5.04 560.15 182.93 121.35 50.51 −17.46
440.15 179.22 77.71 28.78 −5.42 565.15 183.08 122.97 51.43 −18.07
445.15 179.38 79.73 29.68 −5.81 570.15 183.24 124.59 52.34 −18.69
450.15 179.53 81.74 30.58 −6.22 575.15 183.39 126.19 53.26 −19.32
455.15 179.68 83.72 31.48 −6.63 580.15 183.55 127.77 54.18 −19.95
460.15 179.84 85.69 32.37 −7.05 585.15 183.70 129.35 55.10 −20.59
465.15 179.99 87.63 33.27 −7.49 590.15 183.86 130.91 56.01 −21.24
470.15 180.15 89.56 34.17 −7.93 595.15 184.01 132.47 56.93 −21.90
475.15 180.30 91.46 35.08 −8.38 600.15 184.16 134.01 57.85 −22.57
480.15 180.46 93.35 35.98 −8.84 605.15 184.32 135.53 58.78 −23.24
485.15 180.61 95.22 36.88 −9.32 610.15 184.47 137.05 59.70 −23.92
490.15 180.77 97.07 37.78 −9.80 615.15 184.63 138.56 60.62 −24.61
495.15 180.92 98.91 38.69 −10.29 620.15 184.78 140.05 61.54 −25.31
500.15 181.07 100.73 39.59 −10.79 623.15 184.88 140.94 62.10 −25.73
505.15 181.23 102.53 40.50 −11.29
 T. Wang et al. / Thermochimica Acta 551 (2013) 92–98 97

Standard enthalpy as a function of temperature of the eutectic com- We also thank The University of Alabama for providing the exper-
position in the quaternary system in the solid state is given by: imental facilities to conduct this research project.
 T

HTo − H298.15
o
= Cp dT
(9) References
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−3 −3
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