Fluid Phase Equilibria 451 (2017) 25e39

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Thermodynamic properties and corrosivity of a new absorption heat

pump working pair: Lithium nitrate þ 1-butyl-3- methylimidazolium
bromide þ water
Chunhuan Luo a, b, Yiqun Li a, Kang Chen a, Na Li a, Qingquan Su a, c, *
a
School of Energy and Environmental Engineering, University of Science and Technology Beijing, 30 Xueyuan Road, Haidian District, Beijing 100083, China
b
Beijing Key Laboratory of Energy Conservation and Emission Reduction for Metallurgical Industry, Beijing, 100083, China
c
Beijing Engineering Research Center for Energy Saving and Environmental Protection, University of Science and Technology Beijing, 30 Xueyuan Road,
Haidian District, Beijing 100083, China

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

Article history: LiNO3-[BMIM]Br/H2O ternary system has been proposed as a new absorption working pair to improve
Received 10 April 2017 the shortcomings of high crystallization temperature for LiNO3/H2O and high viscosity for [BMIM]Br/H2O
Received in revised form working pairs. The crystallization temperature, vapor pressure, density, viscosity, specific heat capacity,
26 July 2017
and dissolution enthalpy of this ternary system at a mass ratio of 2:1 (LiNO3 to [BMIM]Br) were
Accepted 31 July 2017
Available online 1 August 2017
measured. The specific enthalpy was calculated based on the measured specific heat capacity and
dissolution enthalpy. Regression equations for these thermodynamic properties were obtained by a least-
squares method. Results showed that LiNO3-[BMIM]Br/H2O had nearly identical vapor pressure with that
Keywords:
Working pair
for LiNO3/H2O at a 10% lower mass concentration. Meanwhile, under the same absorption ability, LiNO3-
Ionic liquids [BMIM]Br/H2O had much lower crystallization temperature than LiNO3/H2O, and much lower viscosity
LiNO3 than [BMIM]Br/H2O. At the temperature below 587.75 K, LiNO3-[BMIM]Br/H2O has a reliable thermal
Thermodynamic properties stability. The corrosivity of LiNO3-[BMIM]Br/H2O to carbon steel and copper was larger than that of
Corrosivity LiNO3/H2O, while obviously less than that of LiBr/H2O. As an alternative working pair, LiNO3-[BMIM]Br/
H2O shows a great potential in absorption heat pump, especially at high temperature.
© 2017 Published by Elsevier B.V.

1. Introduction
An absorption heat pump can be applied for refrigeration and
heating through utilizing renewable energy (such as solar energy
and geothermal energy) and industrial waste heat as driving force.
So, it has been paid much attention in energy saving field [1e3]. The
performance of an absorption heat pump greatly depends on the
thermodynamic properties of the working pair. So far, LiBr/H2O is
commonly used as the working pair in the absorption cycle.
However, the application of the absorption heat pump using LiBr/
H2O has been limited because of easy crystallization and strong
corrosivity to metallic materials.
To overcome the above problems of LiBr/H2O, lots of studies on
alternative working pairs including salt-water solutions and
* Corresponding author. School of Energy and Environmental Engineering, Uni-
versity of Science and Technology Beijing, 30 Xueyuan Road, Haidian District, Bei-
jing 100083, China.
E-mail address: suqingquan@ustb.edu.cn (Q. Su).
organic mixtures have been carried out in the past few years [4e6].
Generally, the salt-water solutions cannot simultaneously exhibit a
wide operating concentration range and good compatibility with
metallic materials. The organic mixtures showed a certain toxicity
and inflammability due to containing various alcohols. Recently,
ionic liquids (ILs) were focused on because of their tunable prop-
erties, almost zero vapor pressure, low melting points, high thermal
stability, and environmental safety [7]. In 2004, Kim et al. [8,9]
firstly proposed several new working pairs composed of imidazo-
lium ILs [BMIM]BF4 (1-butyl-3-methylimidazolium tetra-
fluoroborate), [BMIM]Br (1-butyl-3-methylimidazolium bromide),
[hydemin]BF4 (1-(2-hydroxyethyl)-3-methylimidazolium tetra-
fluoroborate) and refrigerants TFE (2,2,2-trifluoroethanol) and H2O.
The vapor pressures of the above working pairs were measured by
using the boiling-point method and correlated with an Antoine
equation. Zhao et al. [10,11] proposed [EMISE] (1-ethyl-3-
methylimidazolium ethyl sulfate)/H2O, [EMIM]DMP (1-ethyl-3-
methylimidazolium dimethylphosphate)/H2O, [EMIM]DMP/
CH3OH, and [EMIM]DMP/CH3CH2OH as alternative working pairs

http://dx.doi.org/10.1016/j.fluid.2017.07.024
0378-3812/© 2017 Published by Elsevier B.V.
26 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39
and studied their thermophysical properties including vapor
pressures, densities, specific heat capacities and excess enthalpies.
Zheng et al. [12e16] has carried out some theoretical and experi-
mental studies on imidazolium IL-based working pairs. The ther-
modynamic properties such as vapor pressures, densities, specific
heat capacities, and solubility were measured and correlated. The
effects for adding ionic liquids [DMIM]Cl (1,3-dimethylimidazolium
chloride) and [DMIM]BF4 (1,3-dimethylimidazo- lium tetra-
fluoroborate) to the working pairs of LiBr/H2O and LiCl/H2O were
investigated and the adding effect of [DMIM]Cl is superior to
[DMIM]BF4. The approach for selecting alternative working pairs
including water and short carbochain imidazolium ionic liquids
was also studied and halogen and phosphate anion ILs are suitable
for working pairs of absorption cycles.
Besides the above studies on thermodynamic properties, the
performance of IL-based working pairs in the absorption cycle has
also been investigated in recent years. Kim et al. [17,18] investigated
the feasibility of several refrigerant/IL working pairs for the ab-
sorption refrigeration system by a numerical method. Among the
refrigerants of H2O, R32 and R124, H2O combined with the absor-
bent of [EMIM][BF4] (1-ethyl-3-methylimidazolium tetra-
fluoroborate) gave the highest COP. Zhang et al. [19,20] simulated
the thermodynamic performance of the absorption chiller using
[EMIM]DMP/H2O based on the measured thermophysical proper-
ties, indicating that the performance coefficient and the generation
temperature for the [EMIM]DMP/H2O were lower than those based
on LiBr/H2O at the same condensing and absorbing temperature.
The performance simulation of a single-stage absorption heat
transformer using [EMIM]DMP/H2O was also conducted and
compared with those of LiBr/H2O and TFE/E181 (tetraethylenglycol
dimethylether). Results showed that the COP and exergy efficiency
based on [EMIM]DMP/H2O were less than those based on LiBr/H2O,
whereas larger than those based on TFE/E181. Abumandour et al.
[21] simulated the thermodynamic performance of an absorption
heat transformer using [DMIM]MeSO4 (1,3-dimethyl imidazolium
methylsulfate)/H2O and [EMIM]MeSO4 (1-ethyl-3-
methylimidazolium methylsufate)/H2O. Though the performances
based on the two new working pairs were slightly lowered in
comparison to LiBr/H2O, they still can be used for industrial ab-
sorption heat transformers. Based on the measured thermophysical
properties, Zheng et al. [22] predicted the performance of absorp-
tion heat pump using [DMIM]DMP (1,3-dimethylimidazolium
dimethylphosphate)/H2O as working pair, showing that the prob-
lems of crystallization and corrosion were relieved, although the
performance was slightly lower than that using LiBr/H2O as work-
ing pair. Zheng et al. [23] also reviewed the research about imida-
zolium ILs/H2O working pairs for absorption refrigeration cycle in
recent years, especially regarding the methods of evaluation and
selection, the measurement and modeling of thermophysical
properties, as well as the assessments of their future prospects. The
previous research showed that ILs/H2O had a wider operating
temperature range and less corrosivity to metals, thus being able to
avoid the problems of crystallization and corrosion for LiBr/H2O.
However, IL/H2O also has its own shortcoming, such as high vis-
cosity, which has a great influence on the heat and mass transfer in
the absorption cycle.
In our previous research, LiNO3/H2O was proposed as an alter-
native working pair, and its thermodynamic properties, corrosivity
and application in the absorption heat pump system were inves-
tigated [24e26]. Results showed that the absorption cycle based on
LiNO3/H2O had an obvious advantage in the temperature grade of
driving heat source. Moreover, its corrosivity to the structure ma-
terial and heat exchange material of absorption heat pump was
much less severe than that of LiBr/H2O. The coefficient of perfor-
mance (COP) for LiNO3/H2O was also higher than that for LiBr/H2O
under the same operation conditions. However, LiNO3/H2O still had
its own problem of easy crystallization.
In order to improve the performances of both LiNO3/H2O and
ILs/H2O, a ternary working pair of LiNO3-[BMIM]Br/H2O has been
proposed in this paper. The thermodynamic properties including
crystallization temperature, vapor pressure, density, viscosity,
specific heat capacity, specific enthalpy, and thermal stability for
this ternary system were measured. Moreover, the corrosions of
carbon steel and copper in this ternary system were also investi-
gated by weight loss method at a high temperature and compared
with those in LiNO3/H2O and LiBr/H2O solutions.
2. Experiments
2.1. Materials
[BMIM]Br reagent used in this work was obtained from
Shanghai Chengjie Chemical Co., Ltd. (China). LiNO3 and LiBr re-
agents were from Tianjin Jinke Institute of Fine Chemicals (China).
C7H6N2S (2-Mercapto benzimidazole) was supplied by Shandong
Xiya Chemical Co., Ltd. (China). AgNO3 was supplied by Tianjin
Fengchuan Chemical Co., Ltd. (China). K2CrO4 was supplied by
Tianjin Guangfu Chemical Co., Ltd. (China). NaCl and KCl were from
Sinopharm (China). There was no further purification with all the
reagents. The detailed information is listed in Table 1. Pure water
with an electric resistance of 18.2 MU$cm was produced by a super
pure water device (TTL-10B, Tongtailian Co. Beijing).
2.2. Procedures
The vapor pressure of the LiNO3-[BMIM]Br/H2O ternary system
was measured by the static method. The experimental apparatus
primarily consisted of a DKU-30 constant temperature oil bath
(Jinghong, Shanghai), a Pt-100 thermocouple, a solution autoclave
(700 ml), a vacuum valve, a vacuum pump and three precision
digital absolute pressure meters with ranges from 0 kPa to 6 kPa
(MIK-P300, Asmik, Hangzhou), 0 kPae20 kPa (MIK-P3000, Asmik,
Hangzhou), and 0 kPae110 kPa (AX-110, Aoxin, Xi'an). The pressure
meter with a minimum range was used when the vapor pressure
was less than 5 kPa. The pressure meter with an intermediate range
was used in a range from 5 kPa to 20 kPa. The detailed schematic
figure and procedure were reported in previous research [24]. For
each concentration and temperature, three repetitive runs were
carried out and the averages were adopted. The overall average
absolute relative deviation (AARD) of vapor pressure for all mea-
surements was determined to be 1.09% through the following
equation:
X
N
AARD ¼ 1=N jðp  pm Þ=pm j (1)
i¼1
where p (kPa) is the vapor pressure for each measurement, pm is the
mean value of the three repetitions, and N is the overall measure-
ment number. The largest relative deviation was 2.11%. In order to
verify the validity of the vapor pressure measurement, the vapor
pressure of water was measured from 274.15 K to 372.15 K, and
compared with the literature data [27]. The overall average abso-
lute relative deviation (AARD) between the measured values and
the literature data was 1.66%. It can be seen that the experimental
data are in good agreement with the literature data from the
comparison shown in Fig. 1.
The measurement apparatus for crystallization temperature
consisted of a precision thermostat (HX-3010, Bilang, Shanghai),
Erlenmeyer flasks and a precision balance (PL2002, Mettler Toledo,
 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39 27

Table 1
Provenance and mass fraction purity of the compounds used.

Compounds CAS Supplier Mass fraction purity Water content as mass fractionb Purity analysis methodc

[BMIM]Bra 85100-77-2 Chengjie >0.99 <0.003 Kjeldahl method

LiNO3 7790-69-4 Jinke >0.995 e e
LiBr 7550-35-8 Jinke >0.995 e e
C7H6N2S 583-39-1 Xiya >0.995 e e
AgNO3 7761-88-8 Fengchuan >0.998 e e
K2CrO4 7789-00-6 Guangfu >0.995 e e
NaCl 7647-14-5 Sinopharm >0.99 e e
KCl 7447-40-7 Sinopharm >0.99 e e
a
[BMIM]Br (1-butyl-3-methylimidazolium bromide): C8H15BrN2.
b
The mass fraction of water in [BMIM]Br are measured by using the Karl-Fischer Titrator.
c
The purity analysis method for [BMIM]Br was provided by supplier and all materials are used without further purification.

Fig. 1. Comparison of water vapor pressure between the experimental data and literature data.

Switzerland). A solution of LiNO3-[BMIM]Br/H2O with a certain
mass fraction was prepared in a ground 500 ml Erlenmeyer flask,
and then equally poured into three smaller Erlenmeyer flasks
(150 ml). The three parallel samples, sealed with rubber stoppers,
were then immersed in the precise thermostat at a certain tem-
perature for about 24 h. If the solution in any Erlenmeyer flask was
not crystallized, the setting temperature of the thermostat was
decreased and the solution was observed again for another 24 h.
Meanwhile, if crystallization took place in any Erlenmeyer flask, the
sample was dissolved firstly and observed for another 24 h at a
temperature 1 K higher than the last setting temperature. After
repeating the above operations, the last setting temperature at
which crystallization occurred was determined to be the crystalli-
zation temperature. For each mass fraction, three replicates were
carried out, and the average values were adopted. The overall
average absolute deviation (AAD) for all measurements was
determined to be 1.83 K through the following equation:
X
N precipitate with red-brick color suddenly appeared. It was indi-
AAD ¼ 1=N jTc  Tm j
i¼1
where Tc (K) is the crystallization temperature for each measure-
ment, Tm is the mean value of the three repetitions, and N is the
overall measurement number. The validity of the measurement
was verified through measuring the crystallization temperatures of
60 wt. % and 65 wt. % LiBr solutions. The differences between the
measurement values and the literature data were 1.2 K and 0.5 K,
respectively [28].
To investigate the equilibrium solid phases of the ternary system
with different mass ratios, the wet solid phase at the bottom of the
Erlenmeyer flask was filtered with glass cloth and dewatered with a
centrifuge (TGL-20B, Anke, Shanghai) lasting 3 min at 3000
r$min1. After the adhesive solution was removed, the equilibrium
solid phase was analyzed through TGA (Thermogravimetric Anal-
ysis) experiment by a differential scanning calorimeter (Labsys Evo,
Setaram, France) and baking experiment by a Muffle furnace at
523.15 K, respectively. The weight loss should be corresponding to
the crystal water. The amount of Cl ion in the solid phase was
determined by precipitating with AgNO3 solution at 0.1 mol$L1
using K2CrO4 solution (w ¼ 0.05) as an indicator. However, as one
drop of AgNO3 solution was added into the prepared solution,
(2) cated that there was no Cl ion in the solid phase. To further
determine the amount of nitrate in the solid phase, an atomic ab-
sorption spectrophotometer (TA990, Purkinje General Co. Beijing)
was used to measure the content of Liþ ion. The detailed procedures
28 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39
were reported in our previous research [24]. After knowing the
amounts of crystal water and Liþ, the amounts of other substances
were calculated. Then the composition of the equilibrium solid
phase was identified. The above measurements for each mass
fraction were also carried out three repetitions and had a good
reproducibility.
Densities were measured with a capillary pycnometer. The
experimental apparatus consisted of a SYP1003-H precision
viscometer oil bath, a capillary pycnometer (50 ml) with a capillary
diameter of around 1 mm and a BSA224S analytic balance (Sarto-
rius, Germany). The detailed procedure was reported in previous
research [24]. The measurements of density for each mass con-
centration and temperature were replicated three times, and the
averages were adopted. The AARD for all measurements was
determined to be 0.07%, and the largest relative deviation was
0.24%. The validity of the calibration was verified by measuring the
density of NaCl solution with a concentration of 10 wt. % in the
temperature range from 303.45 K to 351.65 K. The relative deviation
between the measured data and the literature data was 0.21% [27].
Viscosity measurements were accomplished by using Ubbe-
lohde capillary viscometers with several fine capillaries (0.36 mm,
0.46 mm, 0.58 mm, 0.73 mm, and 0.91 mm) and viscosity constants
which were already known. The detailed experimental schematic
and procedure were reported in previous research [24]. Three
repetitions were run to ensure the reproducibility for each absor-
bent concentration and temperature, and the results were aver-
aged. The viscosities were determined by the following equation:
n ¼ C$tm
where v (mm2$s) is the kinematic viscosity of LiNO3-[BMIM]Br/H2O
ternary system, and C (mm2$s2) is the viscosity constant, tm (s) is
the mean time of three repetitions. The AARD value of viscosity for
all measurements was determined to be 0.23%, and the largest
relative deviation was 0.47%. The capillary viscometers were also
validated using water in a range from 303.45 K to 351.65 K, and the
relative deviation between the measured data and the literature
data was 1.46% [27].
Measurements of specific heat capacities for LiNO3-[BMIM]Br/
H2O ternary system were done by a micro reaction calorimeter
(mRC, THT Co., UK). The apparatus is shown in Fig. 2. The mea-
surement was conducted by making a “step-change” in the tem-
perature. The experiments in this work utilized a temperature shift
of 1 K. For example, at a measurement temperature of 293.15 K, the
step-change corresponds to a shift from 292.65 K to 293.65 K, then
back to 292.65 K, where 293.15 K is the median temperature of the
total temperature step. A blank measurement, in which two empty
Fig. 2. Schematic of experimental apparatus for specific heat capacity.
vials (about 1.5 ml) were set in the sample and reference positions,
was conducted firstly. Then, an empty vial was left in the reference
position. The sample solution was prepared in the drying operation
cabinet filled with dry air due to the strong hygroscopicity of LiNO3
and [BMIM]Br. Then, suitable amount of solution (about half of the
vial volume) was added in another vial and weighed on a Sartorius
balance, and the vial was carefully set in the sample position. The
steps for the sample measurement were the same as the steps for
the blank measurement. The specific heat capacity was obtained
through subtracting the measured blank value from the measured
sample value by the mRC analysis software. Measurements of spe-
cific heat capacity were carried out for three repetitions for each
mass fraction and temperature, and the mean values were adopted.
The AARD for all measurements was determined to be 1.12%, and
the largest relative deviation was 1.68%. The pure water was used to
validate the method from 293.15 K to 353.15 K. The AARD between
the measured values and the literature data was 1.2% [27].
Specific enthalpy is important to simulate the performance of an
absorption heat pump. In this paper, the specific enthalpies of
LiNO3-[BMIM]Br/H2O were obtained from the following equation:
ZT
hðT; xÞ ¼ CpdT þ hðT0 ; xÞ (4)
T0
where Cp (J$g1$K1) is the specific heat capacity for LiNO3-[BMIM]
Br/H2O, h(T0,x) (kJ$kg1) is the specific enthalpy at a mass fraction
of x and temperature of T0 (K), which can be determined by the
(3)
following equations:
X
3
hðT0 ; xÞ ¼ xi hi ðT0 Þ þ Dhmix ðT0 Þ (5)
i¼1
ZT0
hi ðT0 Þ ¼ Cpi dT þ h0 (6)
273:15 k
where xi and hi(T0) are the mass fraction and the specific enthalpy
of the pure LiNO3, [BMIM]Br and H2O at the temperature of T0,
respectively. Dhmix(T0) is the dissolution enthalpy for the three
components at T0. Cpi is the specific heat capacity of the pure
component, and h0 is the specific enthalpy at 273.15 K. In ther-
modynamic calculation, it is usually only necessary to determine
the difference of the specific enthalpies at different state points.
Thus, a reference value should be specified. In order to agree with
 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39
the reference values of the specific enthalpies for LiBr/H2O in
literature [29,30] and for LiNO3/H2O in our previous study [25], the
specific enthalpies of pure water and absorbents are also defined to
be 418.6 kJ$kg1 at 273.15 K in this work.
Dissolution enthalpies of LiNO3 and [BMIM]Br into water were
also measured by the micro reaction calorimeter with a solid
addition accessory. The apparatus is shown in Fig. 3. For testing, a
certain amount of LiNO3 and [BMIM]Br with a mass ration of 2:1
were weighed in the drying operation cabinet and loaded into a
solid delivery tube. The tube base was sealed with a Teflon plug and
the top was sealed with a Teflon plunger. The delivery tube was
placed in a sample vial containing a certain amount of water, which
was inserted in the sample cell. Another vial with the same amount
of water was placed in the reference cell. Stirring was set to
150 rpm. After baseline stabilization at 313.15 K, LiNO3 and [BMIM]
Br with a mass ratio of 2:1 were in sequence released into the
sample cell using the plunger. Then, the heat output of LiNO3 and
[BMIM]Br in water was measured by lasting 30 min. The dissolution
enthalpy for the ternary system was calculated by the following
Fig. 3. Measurement of the dissolution enthalpy using a micro reaction calorimeter.
29
equation:
Qmix
Dhmix ¼ (7)
mLi þ mIL þ mH2 O
where, Qmix (kJ) was the heat output in the dissolution processes.
mLi (kg), mIL (kg), and mH2O (kg) were the mass of LiNO3, [BMIM]Br
and H2O, respectively. Dhmix(kJ$kg1) was the dissolution enthalpy
on the basis of the solution mass. Generally, an exothermic process
corresponds to a negative value. Repeating the above steps three
times, the average value was used. The validity of the measurement
was verified through measuring the dissolution enthalpy of KCl in
water at 298.15 K. To conveniently compare the measured data with
the literature data [31], the dissolution enthalpy was calculated
based on the mass of KCl, and the results are shown in Table 2. The
AARD between the measured values and the literature data was less
than 0.6%. The specific enthalpies for LiBr/H2O system at 50 wt. %
and 60 wt. % were calculated through Eq. (4) and compared with
the data in literature [30] to verify the specific enthalpy measure-
ment. The AARD between the calculated values and the literature
data was less than 1.20%. The comparison is shown in Fig. 4.
The corrosion rates of carbon steel and copper were measured
by the weight loss method. About 250 ml of LiNO3-[BMIM]Br/H2O
solution at a concentration of 70 wt. % using 0.4 wt. % Li2MoO4 and
0.1 wt. % C7H6N2S (2-Mercapto benzimidazole) as a complex in-
hibitor were prepared and poured into an autoclave made of duplex
stainless steel. Three burnished and cleaned metal samples were
suspended in the solution with Teflon tubes. After sealed and
vacuumed, the autoclave was held in a thermal container at
453.15 K for 200 h. Then, the test samples were taken out, rinsed,
cleaned and weighed again. The weight loss of three test samples
and their mean value were obtained. The corrosion rate was
calculated by the following equation:
m0  m1
v ¼ 8760  (8)
S$t$r
where v (mm$y1) is the corrosion rate, m0 (g) is the mass of test
sample before corrosion, m1 (g) is the mass of test sample after
cleaning corrosion product, S (m2) is the surface area of test sample,
t (h) is the corrosion time, and r (g$cm3) is the density of the metal
sample.
For the density and viscosity measurement, the temperatures
were obtained by the thermometer placed inside the precision
viscometer oil bath, and the standard uncertainty of the tempera-
ture measurement was ±0.05 K. The temperature in the crystalli-
zation temperature measurement was determined by the
thermometer in the precision thermostat, and the standard un-
certainty was ±0.2 K. The temperature in the vapor pressure
measurement was determined by a Pt-100 thermometer, and the
standard uncertainty was ±0.1 K. The temperatures in the specific
heat capacity and dissolution enthalpy measurements were
determined by the micro reaction calorimeter with an accuracy of
±0.001 K. The solutions prepared for crystallization temperature
and vapor pressure measurements were weighed on a Mettler
balance (PL2002) with a precision of ±0.01 g. The reagents for
density, viscosity, specific heat capacity, and specific enthalpy
measurements were weighed on a Sartorius balance (BSA224S)
with a precision of ±0.1 mg. The combined standard uncertainties
of vapor pressure, crystallization temperature, density, viscosity,
specific heat capacity and specific enthalpy were estimated to be
±0.02 p, ± 2.0 K, ± 0.002 g$cm3, ±0.02 n, ± 0.03 J$g1$K1 and
±0.02 h, respectively.
30 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39

Table 2
The dissolution enthalpy Dhmix for potassium chloride in water at 298.15 K and 0.1 MPa.a

Times KCl mass/g Water mass/g Output heat/J Dissolution enthalpy/kJ$kg1

NO. 1 0.0370 1.4657 8.35 225.68

No. 2 0.0483 1.4722 11.26 233.13
NO. 3 0.0527 1.4437 11.95 226.76
Literature value [31] e e e 231.0
a
Standard uncertainties u were u(T) ¼ ± 0.01 K, u(p) ¼ ± 3.0 kPa, and the relative standard uncertainty ur was ur (Dhmix) ¼ ± 0.02 Dhmix.

Fig. 4. Comparison of the measured specific enthalpy data for LiBr/H2O with the literature data.

3. Results and discussion 2:1 were measured from 298.15 K to 415.05 K and from 55 wt. % to
75 wt. %. The measured values are shown in Table 3. The vapor
3.1. Vapor pressure pressures over the absorbent mass fractions and temperatures
were fitted to Antoine Equation [33]:
Vapor pressures of LiNO3-[BMIM]Br/H2O ternary system at
70 wt. % with mass ratios of 1:1, 2:1 and 3:1 (LiNO3 to [BMIM]Br) X
4
were measured from 294.65 K to 410.95 K. As shown in Fig. 5, the logðp=kPaÞ ¼ ½Ai þ fBi=ðT  CiÞgð100wÞi (9)
vapor pressure of LiNO3-[BMIM]Br/H2O at 70 wt. % with the mass i¼0

ratio of 1:1 was nearly identical with that of LiNO3/H2O at 55 wt. %,

where p (kPa) is the vapor pressure, T (K) is the absolute temper-
while LiNO3-[BMIM]Br/H2O at the same concentration with the
ature, and w (wt. %) is the absorbent mass fraction. Ai, Bi and Ci are
mass ratios of 2:1 and 3:1 had almost the same absorption ability as
the regression parameters, which were determined by a least-
LiNO3/H2O at 60 wt. %. Here, the absorption ability is defined as the
squares method and are listed in Table 4. The overall AARD value
ability that one working pair with a certain concentration in the
between the measured values and the calculated results was
absorber of an absorption heat pump can absorb the refrigerant
determined to be 0.18%. The measured values (solid points) and the
vapor from the evaporator to achieve a certain refrigeration tem-
calculated results (solid lines) are plotted against temperature and
perature or utilize a certain grade low-temperature heat source.
compared with those (hollow points) for LiNO3/H2O [24] in Fig. 6 As
Results showed that the vapor pressure of this ternary system
shown in Fig. 6, the measured values were in good agreement with
increased with decreasing the mass ratio, meaning that raising the
the calculated results. The vapor pressure for LiNO3-[BMIM]Br/H2O
ratio of [BMIM]Br reduced the absorption ability of LiNO3-[BMIM]
was almost the same as that for LiNO3/H2O at a 10 wt. % lower mass
Br/H2O. However, on the other hand, more IL was helpful for
fraction. It is indicated that an absorption heat pump based on
decreasing the crystallization temperature [32]. For mass fraction
LiNO3-[BMIM]Br/H2O with a certain concentration can achieve the
of 70 wt. %, the crystallization temperature of LiNO3-[BMIM]Br/H2O
same refrigeration temperature or utilize the same low-
with the mass ratios of 3:1 and 2:1 were 287.15 K and 270.15 K,
temperature heat source in the evaporator, in comparison to that
respectively. The former was much higher than the latter. There-
based on LiNO3/H2O with a 10 wt. % lower concentration under the
fore, LiNO3-[BMIM]Br/H2O with the mass ratio of 2:1 was further
same absorption temperature. Thus, LiNO3-[BMIM]Br/H2O has a
studied.
nearly identical absorption ability with LiNO3/H2O at a 10 wt. %
Vapor pressures for LiNO3-[BMIM]Br/H2O with the mass ratio of
lower concentration.
 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39 31

Fig. 5. Vapor pressures of LiNO3-[BMIM]Br/H2O at 70 wt. % with different mass ratios.

Table 3
Vapor pressure p at temperature T and absorbent mass fraction w for the system of LiNO3 (1) þ 1-butyl-3-methylimidazolium bromide (2)þ H2O (3).a

T/K P/kPa T/K P/kPa T/K P/kPa T/K P/kPa T/K P/kPa

w1þ2 ¼ 0.55 w1þ2 ¼ 0.60 w1þ2 ¼ 0.65 w1þ2 ¼ 0.70 w1þ2 ¼ 0.75
298.25 1.775 298.45 1.479 298.15 1.106 298.65 0.823 353.35 10.399
303.35 2.437 303.15 1.982 303.15 1.536 303.15 1.101 358.85 13.188
308.25 3.211 308.65 2.716 308.55 2.109 308.85 1.551 363.65 16.121
313.15 4.187 313.25 3.499 313.45 2.777 313.65 2.046 368.35 19.492
323.15 6.983 323.35 5.916 323.15 4.651 323.25 3.454 373.25 23.626
332.75 11.023 333.15 9.492 333.35 7.689 333.75 5.876 378.75 29.113
343.35 17.606 343.25 14.927 342.95 11.938 343.45 9.269 383.55 34.734
353.65 26.852 353.45 22.828 353.35 18.597 352.65 13.887 389.05 42.253
363.25 38.750 363.65 33.889 363.15 27.437 363.45 21.620 393.85 49.872
368.45 46.797 368.65 40.720 368.95 34.121 369.05 26.862 398.65 58.592
373.35 55.564 373.45 48.286 373.65 40.461 373.75 32.032 403.75 69.195
378.15 65.386 378.25 56.943 378.35 47.724 378.65 38.264 408.25 79.815
383.65 78.291 383.25 67.239 383.75 57.331 383.25 44.987 415.05 98.370
390.35 96.649 388.65 79.965 388.25 66.471 388.55 53.894
395.25 98.023 393.35 78.198 393.95 64.389
400.95 98.660 398.35 74.112
407.75 98.851
a
The mass ratio of LiNO3 to1-butyl-3-methylimidazolium bromide was 2:1. Standard uncertainties u were u(T) ¼ ± 0.1 K and u(w1þ2) ¼ ± 0.002, and the relative standard
uncertainty ur were ur(p) ¼ ± 0.02 p.

Table 4 through the equation in our previous research [24]. As shown in

Values of Ai, Bi, Ci and AARD for least-squares representation by Eq. (9). Fig. 7, as the absorbent mass fraction was below 71 wt. %, the
i Ai Bi Ci AARD crystallization temperature for LiNO3-[BMIM]Br/H2O was about
0 15.045868 1.471436$103 71.676105 0.18%
30 K lower than that for LiNO3/H2O, indicating that the addition of
1 0.543627 6.792601 6.341188 [BMIM]Br was able to relieve the crystallization problem of LiNO3/
2 1.244513$102 1.089242$1017 16.447999 H2O. Crystallization temperatures for LiNO3-[BMIM]Br/H2O at
3 1.285728$104 6.431785$104 42.093146 70 wt. % with mass ratios of 1:1 and 3:1 were also shown in Fig. 7. It
4 5.555835$107 6.298872$105 6.586137$102
was confirmed that the crystallization temperature decreased with
decreasing the mass ratio. In this study, bulk hydrated crystals were
observed at mass fractions from 65 wt. % to 71 wt. %, and the
identified equilibrium solid phases was determined to be
3.2. Crystallization temperature LiNO3$3H2O. However, granular crystals were observed at the
higher mass fractions, and the identified equilibrium solid phases
Crystallization temperature for LiNO3-[BMIM]Br/H2O with the was determined to be anhydrous LiNO3 at mass fractions of 73 wt. %
mass ratio of 2:1 were systematically measured from 55 wt. % to and 75 wt. %. The detailed experimental data for crystallization
75 wt. %. Under the same absorption ability, the crystallization temperature are listed in Table 5.
temperature was compared with that of LiNO3/H2O obtained
32 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39

Fig. 6. Plot of vapor pressure for LiNO3-[BMIM]Br/H2O.

:, 55 wt. %; -, 60 wt. %; A, 65 wt. %; C, 70 wt. %; +, 75 wt. %; d, calculated results.
△, 45 wt. %; ,, 50 wt. %; >, 55 wt. %; B, 60 wt. %; *, 65 wt. % for LiNO3/H2O system [24].

Fig. 7. Plot of crystallization temperature for LiNO3-[BMIM]Br/H2O.

Table 5
Crystallization temperature Tc for the system of LiNO3 (1) þ 1-butyl-3-methylimidazolium bromide (2) þ H2O (3) at 0.1 MPa.a

Mass faction w1þ2 Tc/K Solid phase Mass faction w1þ2 Tc/K Solid phase

0.55 267.15 LiNO3$3H2O 0.67 273.15 LiNO3$3H2O

0.57 269.15 LiNO3$3H2O 0.69 271.15 LiNO3$3H2O
0.59 271.15 LiNO3$3H2O 0.70 270.15 LiNO3$3H2O
0.61 274.15 LiNO3$3H2O 0.71 273.15 LiNO3$3H2O
0.63 275.15 LiNO3$3H2O 0.73 303.15 LiNO3$H2O
0.65 275.15 LiNO3$3H2O 0.75 346.15 LiNO3$H2O
a
The mass ratio of LiNO3 to 1-butyl-3-methylimidazolium bromide was 2:1. Standard uncertainties u were u(p) ¼ ± 3.0 kPa, u(w1þ2) ¼ ± 0.002, and u(Tc) ¼ ± 2.0 K.
 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39 33

3.3. Density Table 7

Values of Ai, Bi, Ci and AARD for least-squares representation by Eq. (10).

Densities for LiNO3-[BMIM]Br/H2O were measured from i Ai Bi Ci AARD

293.15 K to 373.15 K and from 50 wt. % to 75 wt. %. The measured 0 1.876397 4.611518$103 6.762734$106 0.06%
values are given in Table 6. The polynomial Eq. (10) for density was 1 1.424048 1.139453$102 1.972696$105
obtained as a function of absolute temperature and absorbent mass 2 1.491830 7.880871$103 1.366279$105
fraction by a least-squares method from the measured values [34].

  2 h
X  i
r=g$cm3 ¼ Ai þ Bi T þ Ci T 2 wi
i¼0
3
where r (g$cm ) is the density, T (K) is the absolute temperature,
w (wt. %) is the absorbent mass fraction, and Ai, Bi, and Ci are the
regression parameters. The values of Ai, Bi, Ci and AARD are given in
Table 7. The measured values (solid points) and the calculated re-
sults (solid lines) were plotted against temperature in Fig. 8 and
compared with those (*) for LiNO3/H2O [24]. Results showed that
the measured values were in good agreement with the calculated
results. The density for LiNO3-[BMIM]Br/H2O at an absorbent mass
fraction of 70 wt. % was smaller than that for LiNO3/H2O at 60 wt. %,
indicating that the former had a lower density compared with the
latter with the same absorption ability.
3.4. Viscosity
Viscosities for LiNO3-[BMIM]Br/H2O were measured from
293.15 K to 373.15 K and from 50 wt. % to 75 wt. %. The measured
values shown in Table 8 were fitted to polynomial Eq. (11) as a
function of absolute temperature and absorbent mass fraction by a
least-squares method [35].
 .  X3 h .  i
log n mm2 $s1 ¼ Ai þ Bi =T þ Ci T 2 wi
i¼0
where v (mm2$s) is the kinematic viscosity, T (K) is the absolute
temperature, w (wt. %) is the absorbent mass fraction, Ai, Bi, and Ci
are the coefficients in Eq. (11). The values of Ai, Bi, Ci and AARD are
given in Table 9. The measured values (solid points) and the
calculated results (solid lines) were plotted against temperature in
Fig. 9, and compared with those for LiNO3/H2O (*) [24] and [BMIM]
Br/H2O (*) given in Table 10. Results showed that the measured
values agreed well with the calculated results. With the same ab-
sorption ability, The viscosity for LiNO3-[BMIM]Br/H2O at 70 wt. %
was larger than that for LiNO3/H2O at 60 wt. %, while much lower
than that for [BMIM]Br/H2O at 90 wt. %, whose absorption ability
was nearly equal to that of LiNO3-[BMIM]Br/H2O at 70 wt. % [9].
Thus, the shortcoming of high viscosity for [BMIM]Br/H2O was
improved.
3.5. Specific heat capacity
(10)
Specific heat capacities for LiNO3-[BMIM]Br/H2O were
measured from 293.15 K to 373.15 K and from 50 wt. % to 75 wt. %.
The measured values listed in Table 11 were fitted to the following
Eq. (12) [10].
   X2 h  i
Cp J$g1 $K 1 ¼ Ai þ Bi T þ Ci T 2 wi (12)
i¼0
where Cp (J$g1$K1) is the specific heat capacity, T (K) is the ab-
solute temperature, w (wt. %) is the absorbent mass fraction, Ai, Bi
and Ci are the regression parameters. The values of Ai, Bi, Ci and
AARD are given in Table 12. The measured values (solid points) and
the calculated results (solid lines) are plotted against temperature
in Fig. 10, and compared with those for LiNO3/H2O (*) [24]. Results
indicated that the measured values were in good agreement with
the calculated results. The specific heat capacity for LiNO3-[BMIM]
Br/H2O increased with increasing temperature and decreased with
increasing absorbent mass fraction. Compared to LiNO3/H2O with
the same absorption ability, LiNO3-[BMIM]Br/H2O had a lower
specific heat capacity. Working pair with lower specific heat ca-
pacity has advantages of consuming less heat in generator and
releasing less heat in absorber, so as to improve the performance of
(11) absorption refrigeration system.
3.6. Specific enthalpies
3.6.1. Specific heat capacity of LiNO3, [BMIM]Br and H2O
The specific heat capacity for [BMIM]Br was also determined by
the micro reaction calorimeter from 283.15 K to 373.15 K, and the
data are shown in Table 13. The specific heat capacity at 343.15 K
around the melting point was obviously larger than the values at
other temperatures. The specific heat capacity for LiNO3 and H2O
were obtained from our previous research [25] and the literature
[27], respectively.
3.6.2. Dissolution enthalpy
The dissolution enthalpies of LiNO3 and [BMIM]Br in water were
measured at the temperature of 313.15 K and the mass concen-
trations from 55 wt. % to 70 wt. %. The detailed experimental data

Table 6
Density r at absorbent mass fraction w for the system of LiNO3 (1) þ 1-butyl-3-methylimidazolium bromide (2) þ H2O (3) at 0.1 MPa.a

T/K r/g$cm3 T/K r/g$cm3 T/K r/g$cm3 T/K r/g$cm3 T/K r/g$cm3 T/K r/g$cm3
w1þ2 ¼ 0.50 w1þ2 ¼ 0.55 w1þ2 ¼ 0.60 w1þ2 ¼ 0.65 w1þ2 ¼ 0.70 w1þ2 ¼ 0.75
293.15 1.306 293.15 1.333 293.15 1.367 293.15 1.400 293.15 1.434 353.15 1.427
303.15 1.299 303.15 1.326 303.15 1.360 303.15 1.394 303.15 1.427 358.15 1.425
313.15 1.292 313.15 1.319 313.15 1.352 313.15 1.388 313.15 1.420 363.15 1.421
323.15 1.285 323.15 1.312 323.15 1.345 323.15 1.380 323.15 1.412 368.15 1.417
333.15 1.279 333.15 1.305 333.15 1.338 333.15 1.373 333.15 1.405 373.15 1.413
343.15 1.272 343.15 1.298 343.15 1.331 343.15 1.365 343.15 1.398
353.15 1.265 353.15 1.291 353.15 1.324 353.15 1.357 353.15 1.391
363.15 1.258 363.15 1.285 363.15 1.317 363.15 1.349 363.15 1.384
373.15 1.251 373.15 1.279 373.15 1.310 373.15 1.341 373.15 1.376
a
The mass ratio of LiNO3 to1-butyl-3-methylimidazolium bromide was 2:1. Standard uncertainties u were u(T) ¼ ± 0.05 K, u(w1þ2) ¼ ± 0.002 and u(p) ¼ ± 3.0 kPa, and the
combined standard uncertainty uc was uc(r) ¼ ± 0.002 g$cm3.
34 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39

Fig. 8. Plot of density for LiNO3-[BMIM]Br/H2O.

:, 50 wt. %; -, 55 wt. %; A, 60 wt. %; C, 65 wt. %; +, 70 wt. %; ;, 75 wt. %; d, calculated results.
*, 60 wt. % for LiNO3/H2O system [24].

Table 8
Viscosity v at absorbent mass fraction w for the system of LiNO3 (1) þ 1-butyl-3-methylimidazolium bromide (2) þ H2O (3) at 0.1 MPa.a

T/K n/mm2$s1 T/K n/mm2$s1 T/K n/mm2$s1 T/K n/mm2$s1 T/K n/mm2$s1 T/K n/mm2$s1
w1þ2 ¼ 0.50 w1þ2 ¼ 0.55 w1þ2 ¼ 0.60 w1þ2 ¼ 0.65 w1þ2 ¼ 0.70 w1þ2 ¼ 0.75
293.15 3.275 293.15 4.270 293.15 6.070 293.15 8.619 293.15 13.060 353.15 4.354
303.15 2.643 303.15 3.335 303.15 4.571 303.15 6.530 303.15 9.664 358.15 3.883
313.15 2.073 313.15 2.680 313.15 3.570 313.15 5.014 313.15 7.233 363.15 3.577
323.15 1.713 323.15 2.193 323.15 2.899 323.15 3.965 323.15 5.518 368.15 3.273
333.15 1.459 333.15 1.860 333.15 2.416 333.15 3.255 333.15 4.366 373.15 3.017
343.15 1.265 343.15 1.585 343.15 2.047 343.15 2.686 343.15 3.546
353.15 1.103 353.15 1.390 353.15 1.768 353.15 2.290 353.15 2.897
363.15 0.969 363.15 1.224 363.15 1.538 363.15 1.973 363.15 2.494
373.15 0.877 373.15 1.095 373.15 1.383 373.15 1.720 373.15 2.194
a
The mass ratio of LiNO3 to 1-butyl-3-methylimidazolium bromide was 2:1. Standard uncertainties u were u(T) ¼ ± 0.05 K, u(w1þ2) ¼ ± 0.002 and u(p) ¼ ± 3.0 kPa, and the
relative standard uncertainty ur was ur(v) ¼ ± 0.02 v.

Table 9 temperature according to Eq. (4). The detailed specific enthalpy

Values of Ai, Bi, Ci and AARD for Eq. (11). data are given in Table 15. The regression equation for specific
i Ai Bi Ci AARD enthalpy against the temperature and mass faction were obtained
as follows [36]:
0 31.072418 8.295421$103 5.031421$105 0.84%
1 1.350388$102 3.284854$104 3.290028$106
  X2 h  i
2 1.873043$102 3.320284$104 8.648450$106
3 82.613091 6.381501$103 6.301979$106
h=kJ$kg 1 ¼ Ai þ Bi w þ Ci w2 þ Di w3 T i (13)
i¼0

where h (kJ$kg1) is the specific enthalpy, T (K) is the absolute

are listed in Table 14. The dissolution enthalpies at different mass
concentrations were positive values, meaning that the dissolution
processes were endothermic. It is because that the endothermic
effect caused by breaking of the molecular lattice is larger than the
exothermic effect caused by hydration of the ion for both LiNO3 and
[BMIM]Br.
temperature, w (wt. %) is the absorbent mass fraction, Ai, Bi, Ci, and
Di are the regression parameters. The values of Ai, Bi, Ci, Di, and
AARD are given in Table 16. The measured values (solid points) and
the calculated results (solid lines) were plotted in Fig. 11. Results
showed that the measured values were in good agreement with the
calculated results.

3.6.3. Specific enthalpy 3.7. Thermal stability

Combining the measured dissolution enthalpies and specific
heat capacities, the specific enthalpies of the LiNO3-[BMIM]Br/H2O
system at 313.15 K for different mass concentrations were calcu-
lated by Eqs. (5) and (6). Then the specific enthalpies at other
temperatures were obtained through integral calculation to the
The thermal stability of the working pair is of significance for a
high-temperature absorption heat pump. Imidazolium-based ionic
liquid [BMIM]Br has a good thermal stability, and its onset tem-
perature for thermal decomposition is 546.15 K [37]. Meanwhile,
 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39 35

Fig. 9. Plot of viscosity for LiNO3-[BMIM]Br/H2O.

:, 50 wt. %; -, 55 wt. %; A, 60 wt. %; C, 65 wt. %; +, 70 wt. %; ;, 75 wt. %; d, calculated results.
*, 60 wt. % for LiNO3/H2O [24]; *, 90 wt. % for [BMIM]Br/H2O.

Table 10 Table 12
Viscosity v at absorbent mass fraction w1 ¼ 0.90 for the system of 1-butyl-3- Values of Ai, Bi, Ci and AARD for Eq. (12).
methylimidazolium bromide (1) þ H2O (2) at 0.1 MPa.a
i Ai Bi Ci AARD
n/mm2$s1 at T/K
0 7.051060 1.343831$102 2.062590$105 0.19%
T 313.15 323.15 333.15 343.15 353.15 363.15 373.15 1 13.137689 4.118574$102 5.236877$105
n 22.141 15.637 11.385 8.577 6.648 5.339 4.339 2 10.993908 4.423542$102 5.670538$105
a
Standard uncertainties u were u(T) ¼ ± 0.05 K, u(w1) ¼ ± 0.002 and u(p) ¼ ±
3.0 kPa, and the relative standard uncertainty ur was ur(n) ¼ ± 0.02 n.
As shown in Fig. 12, when the temperature increased, the
sample solution had an obvious weight loss and showed an endo-
LiNO3 also has a good thermal stability with a decomposition thermic effect before about 39 min corresponding to a temperature
temperature of 873.15 K [27]. To further investigate the thermal of 587.75 K. The weight loss rate at this temperature was around
stability of the mixture, a TGA (Thermogravimetric Analysis) 37.7 wt. % which nearly had a good agreement with the mass
experiment by a differential scanning calorimeter (Labsys Evo, fraction of water in the sample solution. It was confirmed that a
Setaram, France) was carried out. A solution of LiNO3-[BMIM]Br/ dehydration process occurred rather than thermal deposition at the
H2O at mass fraction of 60% was prepared. Approximately 106.5 mg temperature below 587.75 K. As the temperature further increased
of the sample solution was weighed in an open aluminum oxide to 640.95 K, the weight of the sample solution was sharply
crucible. TGA experiment was operated at a heating rate of decreased with a fierce exothermic effect, indicating that a certain
10 K min1 and from room temperature to 773.15 K in a flow of high chemical reaction occurred between the mixture of LiNO3 and
purity flow nitrogen atmosphere. [BMIM]Br, probably the oxidation of cation [BMIM]þ by the strong

Table 11
Specific heat capacities Cp at absorbent mass fraction w for the system of LiNO3 (1) þ 1-butyl-3-methylimidazolium bromide (2) þ H2O (3) at 0.1 MPa.a

T/K Cp/J$g1$K1 T/K Cp/J$g1$K1 T/K Cp/J$g1$K1 T/K Cp/J$g1$K1 T/K Cp/J$g1$K1 T/K Cp/J$g1$K1

w1þ2 ¼ 0.50 w1þ2 ¼ 0.55 w1þ2 ¼ 0.60 w1þ2 ¼ 0.65 w1þ2 ¼ 0.70 w1þ2 ¼ 0.75
293.15 2.82 293.15 2.70 293.15 2.59 293.15 2.48 293.15 2.41 348.15 2.40
303.15 2.84 303.15 2.72 303.15 2.61 303.15 2.49 303.15 2.42 353.15 2.41
313.15 2.85 313.15 2.73 313.15 2.62 313.15 2.51 313.15 2.44 358.15 2.42
323.15 2.87 323.15 2.75 323.15 2.63 323.15 2.52 323.15 2.44 363.15 2.42
333.15 2.89 333.15 2.76 333.15 2.65 333.15 2.53 333.15 2.46 368.15 2.44
343.15 2.90 343.15 2.78 343.15 2.66 343.15 2.55 343.15 2.47 373.15 2.46
353.15 2.92 353.15 2.80 353.15 2.68 353.15 2.57 353.15 2.49
363.15 2.94 363.15 2.83 363.15 2.70 363.15 2.60 363.15 2.52
373.15 2.98 373.15 2.85 373.15 2.73 373.15 2.63 373.15 2.53
a
The mass ratio of LiNO3 to 1-butyl-3-methylimidazolium bromide was 2:1. Standard uncertainties u were u(T) ¼ ± 0.01 K, u(w1þ2) ¼ ± 0.002 and u(p) ¼ ± 3.0 kPa, and the
combined standard uncertainty uc was uc(Cp) ¼ ± 0.03 J$g1$K1.
36 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39

Fig. 10. Plot of specific heat capacity for LiNO3-[BMIM]Br/H2O.

:, 50 wt. %; -, 55 wt. %; A, 60 wt. %; C, 65 wt. %; +, 70 wt. %; ;, 75 wt. %; d, calculated results.
*, 60 wt. % for LiNO3/H2O [24].

Table 13
Specific heat capacities Cp for 1-butyl-3-methylimidazolium bromide at 0.1 MPa.a

Cp/(J$g1$K1) at T/K

T 283.15 293.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15 373.15
Cp 1.21 1.23 1.26 1.32 1.41 1.65 3.22 1.61 1.64 1.66
Phase solid solid solid solid solid solid solid-liquid liquid liquid liquid
a
Standard uncertainties u were u(T) ¼ ± 0.01 K, u(p) ¼ ± 3.0 kPa, and the combined standard uncertainty uc was uc(Cp) ¼ ± 0.03 J$g1$K1.

Table 14 has a reliable thermal stability to meet the requirement for a high-
Dissolution enthalpies at absorbent mass fraction w for lithium nitrate (1) and 1- temperature absorption heat pump.
butyl-3-methylimidazolium bromide (2) into water (3) at 313.15 K and 0.1 MPa.a

w1þ2 0.55 0.60 0.65 0.70

3.8. Corrosivity
1
Dhmix/kJ$kg 15.95 21.44 25.38 28.45
a
Standard uncertainties u were u(T) ¼ ± 0.01 K, u(p) ¼ ± 3.0 kPa, and the relative The corrosivity of working pair to structural and heat
standard uncertainty ur was ur (Dhmix) ¼ ± 0.02 Dhmix. exchanging materials generally limited the application of the ab-
sorption heat pump systems, especially in the high temperature
fields. The corrosion behaviors of carbon steel and copper in LiNO3-
oxidizing NO3 . Generally, the operating temperature of a high-
[BMIM]Br/H2O solution with complex inhibitors of 0.4 wt. %
temperature absorption heat pump is below 513.15 K which can
Li2MoO4 and 0.1 wt. % 2-mercapto benzimidazole were investigated
almost completely cover the applications in different industrial
at 453.15 K and compared with those in LiNO3/H2O and LiBr/H2O
fields. Thus, as an alternative working pair, LiNO3-[BMIM]Br/H2O
solutions with the same absorption ability under the same

Table 15
Specific enthalpy h at absorbent mass fraction w for the system of LiNO3 (1) þ 1-butyl-3-methylimidazolium bromide (2) þ H2O (3) at 0.1 MPa.a

T/K h/kJ$kg1 T/K h/kJ$kg1 T/K h/kJ$kg1 T/K h/kJ$kg1

w1þ2 ¼ 0.55 w1þ2 ¼ 0.60 w1þ2 ¼ 0.65 w1þ2 ¼ 0.70

293.15 484.87 293.15 486.91 293.15 487.13 293.15 486.20
303.15 511.94 303.15 512.86 303.15 512.10 303.15 510.33
313.15 539.13 313.15 538.92 313.15 537.17 313.15 534.54
323.15 566.47 323.15 565.12 323.15 562.37 323.15 558.87
333.15 593.97 333.15 591.48 333.15 587.71 333.15 583.32
343.15 621.65 343.15 618.01 343.15 613.21 343.15 607.93
353.15 649.53 353.15 664.81 353.15 638.91 353.15 632.72
363.15 677.63 363.15 671.68 363.15 664.87 363.15 657.71
373.15 705.97 373.15 698.85 373.15 690.95 373.15 682.92
a
The mass ratio of LiNO3 to 1-butyl-3-methylimidazolium bromide was 2:1. Standard uncertainties u were u(T) ¼ ± 0.01 K, u(w1þ2) ¼ ± 0.002 and u(p) ¼ ± 3.0 kPa, and the
relative standard uncertainty ur was ur(h) ¼ ± 0.02 h.
 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39 37

Table 16
Values of Ai, Bi, Ci and AARD for Eq. (13).

i Ai Bi Ci Di AARD

0 8.699724$102 1.381671$103 62.498848 8.086976$102 0.01%

1 2.167977 5.459765 16.188265 11.325833
2 4.469642$103 1.810004$102 3.146440$102 1.878755$102

Fig. 11. Plot of specific enthalpy for LiNO3-[BMIM]Br/H2O.

þ, 293.15 K; , 303.15 K; ✳, 313.15 K; ;, 323.15 K; +, 333.15 K; A, 343.15 K; -, 353.15 K; :, 363.15 K; C, 373.15 K; d, calculated results.

Fig. 12. TG curves of LiNO3-[BMIM]Br/H2O ternary system at mass fraction of 60% and temperature up to 773.15 K.

condition. As shown in Fig. 13, the corrosion rate of carbon steel in
LiNO3-[BMIM]Br/H2O was about twice of that in LiNO3/H2O,
whereas it was obviously less than that in LiBr/H2O. With addition
of the complex inhibitor, carbon steel had a little corrosion in these
three solutions. As shown in Fig. 14, the corrosion rate of copper in
LiNO3-[BMIM]Br/H2O was also intermediate. Though copper had a
larger corrosion in comparison to carbon steel, the corrosion rate of
copper in LiNO3-[BMIM]Br/H2O and LiNO3/H2O can still meet the
standard of anti-corrosion [38]. Additionally, from Fig. 15, passive
compact films with grey color were formed on the copper surfaces
in both LiNO3-[BMIM]Br/H2O and LiNO3/H2O solutions. These tight
layers were helpful for further reducing the corrosion rate in a
longer corrosion time. On the contrary, the oxidation film on the
copper surface in LiBr/H2O was loos and easily exfoliation, which
was less protective against corrosion. Moreover, no pitting corro-
sion was observed for carbon steel and copper in LiNO3-[BMIM]Br/
38 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39

Fig. 13. Comparison of the corrosion rate of carbon steel in LiNO3-[BMIM]Br/H2O, LiNO3/H2O and LiBr/H2O solutions with complex inhibitor at 453.15 K.

Fig. 14. Comparison of the corrosion rate of copper in LiNO3-[BMIM]Br/H2O, LiNO3/H2O and LiBr/H2O solutions with complex inhibitor at 453.15 K.

H2O. So, it can be said that the corrosivity of LiNO3-[BMIM]Br/H2O
can meet the requirement of a high-temperature absorption heat
pump.
4. Conclusions
Crystallization temperatures, vapor pressure, density, viscosity,
specific heat capacity, and dissolution enthalpy for LiNO3-[BMIM]
Br/H2O with a mass ratio of 2:1 were measured. The specific
enthalpy was calculated based on the measured specific heat ca-
pacity and dissolution enthalpy. The regression equations for these
thermodynamic properties were obtained by a least-squares
method. The vapor pressure for LiNO3-[BMIM]Br/H2O was nearly
identical with that for LiNO3/H2O at a 10% lower mass concentra-
tion. Under the same absorption ability, when the absorbent con-
centration for LiNO3-[BMIM]Br/H2O was below 71 wt. %, its
crystallization temperature was about 30 K lower than that for
LiNO3/H2O. LiNO3-[BMIM]Br/H2O also had much lower viscosity
than that for [BMIM]Br/H2O. LiNO3-[BMIM]Br/H2O has a good
thermal stability at the temperature below 587.75 K. The corrosivity
of LiNO3-[BMIM]Br/H2O to carbon steel and copper can meet the
requirement of a high-temperature absorption heat pump. There-
fore, LiNO3-[BMIM]Br/H2O shows a great potential as an alternative
working pair.
 C. Luo et al. / Fluid Phase Equilibria 451 (2017) 25e39 39

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