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Accepted Manuscript

Title: Molar heat capacities of choline chloride-based deep


eutectic solvents and their binary mixtures with water
Authors: Rhoda B. Leron, Meng-Hui Li
PII:
DOI:
Reference:

S0040-6031(11)00579-X
doi:10.1016/j.tca.2011.11.036
TCA 75896

To appear in:

Thermochimica Acta

Received date:
Revised date:
Accepted date:

5-10-2011
26-11-2011
29-11-2011

Please cite this article as: R.B. Leron, M.-H. Li, Molar heat capacities of
choline chloride-based deep eutectic solvents and their binary mixtures with water,
Thermochimica Acta (2010), doi:10.1016/j.tca.2011.11.036
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*Highlights

Highlights
> The molar heat capacities for choline chloride-based deep eutectic solvents and their
binary mixtures with water were measured. > The measured data were reported as

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functions of temperature and composition. > A RedlichKister type equation was used
to correlate the data. > The applied correlation satisfactorily represented the data.

Page 1 of 24

*Manuscript

Molar heat capacities of choline chloride-based deep

Rhoda B. Leron, Meng-Hui Li *

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eutectic solvents and their binary mixtures with water

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R&D Center for Membrane Technology and Department of Chemical Engineering,

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Chung Yuan Christian University, Chung Li, 32023, Taiwan, R.O.C.

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*Corresponding author. Tel: + 886 3 265 4109; fax: + 886 3 265 4199; E-mail address:

mhli@cycu.edu.tw (M.-H. Li)

ABSTRACT

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In this study, the molar heat capacities, CP, of three choline chloride-based deep eutectic solvents
(DESs); Reline, Ethaline and Glyceline, and their binary mixtures with water were determined. Using

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a heat flow differential scanning calorimeter, the heat capacities were measured at standard pressure
from (303.2 to 353.2) K and over the complete range of composition. Results showed that the molar
heat capacity increased with increasing temperature and, for the binary systems, with increasing DES

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concentration. The temperature-dependence of the pure DESs were successfully represented by a


second-order empirical correlation with an AAD% of 0.05. The excess molar heat capacities, CPE, of
the binary mixtures also determined and found generally negative over the whole composition range
while exhibiting negative temperature dependence. The CPE values were fitted to a Redlich-Kister type
equation to correlate them to the temperature and DES mole fraction and the molar heat capacities of
the binary mixtures were predicted. The applied models successfully correlated the experimental CP
data as functions of both temperature and composition.
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KEYWORDS: Choline chloride, Deep eutectic solvents, Excess molar heat capacity, Molar heat
capacity, RedlichKister equation
1. Introduction
Room-temperature ionic liquids (RTILs) have attracted much attention over the past decades. Due
to their unique properties such as negligible vapor pressure, wide liquid range, high thermal stability,

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high solvation capacity and non-flammability [1-7], their potential use in a variety of chemical and
industrial applications has been greatly explored. However, RTILs are too expensive to be used in bulk

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applications. Some of them even have very low moisture tolerance and their toxicology remains

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unclear [8-10].

Low-cost alternatives to RTILs are deep eutectic solvents (DESs). They belong to another class of

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ionic liquids made by mixing a quaternary ammonium salt with a metal salt [11], a hydrated salt [12]
or a simple hydrogen bond donor (HDB) such as alcohol, amide and carboxylic acid [13, 14] as

complexing agent. This result in the formation of a eutectic mixture with a melting point that is

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considerably lower than its original precursors; hence, it is called DES. DESs were found to have
similar characteristics with RTILs [15, 16]. They posses unusual solvent properties and have the

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potential as tunable solvents due to the great number of possible complexing agents available [17, 18].
Furthermore, DESs overcome some disadvantages inherent to conventional RTILs. They are easy to
prepare in the pure state at relatively low cost, non reactive with water, with biodegradable

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constituents and their toxicology is known [14, 19]. Because of these unusual characteristics, DESs
have become the interest of many recent undertakings. They were used as solvents in the
electrodeposition and electropolishing of metals, metal oxide processing and other synthetic processes
[20-23]. They are also considered as potential green solvents for biodiesel purification [24, 25],
polymer synthesis [26-28], drug solubilization [19] and gas (i.e. CO2) absorption [29, 30].
The evaluation of DESs as solvents for specific applications requires knowledge of their physical
and thermodynamic properties. The heat capacity, for instance, is one of the properties necessary to
assess the suitability of DESs as solvents for heat transfer applications. To date, however, there is
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practically no data available on the heat capacity of most deep eutectic solvents as well as for their
binary mixtures with water. Thus, in this work, the molar heat capacities, CP, of three DESs namely:
Reline, Ethaline and Glyceline and their aqueous mixtures were determined. All of which are based on
choline chloride as the quaternary ammonium salt being the most commonly used precursor for
eutectic based ionic liquids due to its biodegradability and low cost [31]. The measurements were done

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over the temperature range (303.15 to 353.15) K and for the entire range of composition (DES mole
fraction, x1 = 0.1 0.9). For the pure DESs, the temperature-dependence of the CP was represented by

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a second-order empirical equation. Also the excess molar heat capacity, CPE, for the binary systems

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correlated to the systems temperature and composition.

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were determined. Using a RedlichKister type equation, the experimental CPE and the CP data were

2. Experimental Section

2.1 Chemicals

The pure deep eutectic solvents Reline, Ethaline and Glyceline (purity > 98%) were obtained

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from Scionix Ltd. Their specific compositions, molar masses and freezing points are given in Table 1.
All pure samples were used without further purification except for drying. Each pure sample was

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vacuum dried at 343 K for at least 48h, in an evacuated oven, to remove any volatile impurities and
reduce the water content to minimum. The water contents of the samples after drying were measured
using a Mettler Toledo Karl-Fischer (model DL31) titrator and were 1.5 10-3 (mass fraction).

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Distilled deionized water (Type I reagent-grade; resistivity = 183 Mcm; total organic carbon
content (TOC) < 15 ppb), processed in a Barnstead Thermolyne (model Easy Pure 1052) water system,
was used in all the experiments. All weight measurements were done using a Mettler Toledo (model
AL204) digital balance with an accuracy of 1 10-4 g.
2.2 Measurement of molar heat capacity
The heat capacity, CP, measurements were performed in a differential scanning calorimeter (DSC)
from TA Instruments (model DSC-2010) that was equipped with a thermal analysis controller. The
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repeatability of the temperature measurements is 0.1C. The DSC has a calorimetric sensitivity of 1
W (rms) and a calorimetric precision of 1% based on measurements of metal samples. The
apparatus and the experimental procedures were described in detail in the previous work of Chiu et al.
[32] and only pertinent details are discussed here.
For each measurement, a sample of mass (10 15) mg encapsulated in an aluminum hermetic

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sample pan was used. The CP of the sample was measured by comparing the differential heat flow
curve of the sample with that of standard sapphire. Both curves were blank corrected. For each run, the

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method used consisted a 5-min isothermal period at 20C, followed by a temperature ramp from (20C

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to 90C) at a heating rate of 5 K/min, and then an isothermal stage at 90C for the final 5 min. The
purge gas used was nitrogen at a flow rate of 40 mL/min. For each sample, measurements were done in

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three to five replicate runs. The method used was validated by measuring the CP of water of which the
details were discussed in our previous works [33, 34]. Based on tests performed with water and taking

into account the uncertainties in the weighing involved, the overall uncertainty in our CP measurements
was estimated to be 2%. In addition, periodic calibration (using indium as calibrant) of the DSC was

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conducted to ensure the accuracy of the measurements.

3. Results and Discussion

The experimental molar heat capacities, CP, of the pure DESs Reline, Ethaline and Glyceline at
different temperatures are summarized in Table 2. Results show that the CP of the pure DESs increase

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with temperature. It can also be noted that, at the same temperature, the CP values are in the order:
Reline < Ethaline < Glyceline, indicating that the CP increases with increasing DES molar mass. Such
results may be expected since CP is associated with the number of translational, vibrational, and
rotational energy storage modes in the molecule [35, 36]. It is also apparent that, at the same
temperature, the CP of each pure DES is greater than that of water, which can be attributed to the
higher molar mass of the DES compared to water. To our knowledge, there is no data on the heat
capacity of the pure DESs studied here except for a single data reported for the CP of Glyceline at
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298 K (cP = 1.71 0.03 Jg1K1) [37] which appears to be lower than our reported measurements.
The difference in the purity and water content of the purchased DES may have contributed to such
deviation.
The experimental CP values for the pure DESs were correlated to the temperature using a
second-order empirical polynomial equation of the form
2

(1)

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CP / J mol-1 K -1 a0 a1 T / K a2 T / K

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where T is the absolute temperature and a0, a1 and a2 are fitting parameters determined by the
least-squares method. The determined parameters and the AAD% of the fit are tabulated in Table 3.

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The absolute average deviation (AAD) between the experimental and calculated data were determined

AAD / %

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using the following equation

100
n
i=1 cal exp / exp
i
n

(2)

where cal and exp are the experimental and calculated values, respectively. Based on the overall AAD

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of 0.05 % for a total of 33 data points, it can be said that the proposed equation provides good
correlation of the experimental data. This is also shown by the excellent fit between the experimental

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and calculated CP values given in Figure 1.

The molar heat capacities of the binary solutions of Reline, Ethaline and Glyceline with water at
different temperatures and DES mole fractions, x1 are presented in Tables 4, 5 and 6, respectively. To

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clearly show the temperature- and composition-dependences of the obtained CP data, a representative
plot for the CP of the binary solutions of Reline (1) + H2O (2) as a function of temperature is presented
in Figure 2. Results show that for the aqueous binary systems, CP values slightly increase with
increasing temperature. This effect, however, decreases as the mole fraction of the DES decreases. It is
also clear that CP of the binary solutions increases as the concentration of the DES increases. Such
results are expected since the CP of the pure DESs are higher than that of water. Similar behaviors
were also observed for the binary solutions of the other DES systems (Ethaline and Glyceline)
investigated in this study. These trends have also been observed for many ionic liquids reported in
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literature [36, 38] and in our previous works [33, 34, 39-43]. Since DES is a class of ionic liquids, it is
not surprising that they exhibit behaviors similar to those of RTILs.
The excess molar heat capacity of a binary mixture, CPE, is generally defined as the difference
between the heat capacity of the real mixture and that of the ideal mixture. In this work, the CPE for the
aqueous DES solutions were calculated using the expression defined by Lide and Kehiaian [44] as

CP E CP xiCP, i

(3)

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where CP, i is the molar heat capacity of the pure component i. For liquid water, the CP data used in the

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calculations were those reported by Osborne et al. [45].

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The excess molar heat capacities, CPE, are shown as points on the curves in Figures 3 to 5. As
shown, for all three DES systems, the CPE for the binary solutions are generally negative over the

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whole composition range suggesting the presence of stronger interactions between DES and water than
those in the pure liquids. Negative temperature dependence was also observed. For Reline + H2O

mixtures (Figure 3), a minimum occurred in the low DES concentration region (x1~ 0.3) while for

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Ethaline + H2O (Figure 4) and Glyceline + H2O (Figure 5) systems the minima were virtually observed
at intermediate compositions. At high water concentrations and high temperature, a maximum was also

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observed for Glyceline + H2O system which may be due to partial dissociation of the DES as a result
of dilution [46] and the weakening of the hydrogen bonds in the DES at elevated temperature [47, 48].
It is also noticeable that the trends in the CPE are similar for Ethaline + H2O and Glyceline + H2O

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systems which may be attributed to the similarity in structure of the hydrogen bond donors comprising
the two DESs. The CPE values for these two systems were also relatively smaller than those of the
Reline + H2O solutions.

The excess molar heat capacity, CPE were correlated to the composition and temperature using a
RedlichKister type equation of the form
n

CP E / J mol-1 K -1 x1 x2 A i x1 x2

i 1

(4)

i 1

Ai was assumed to be temperature-dependent such that


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A i ai ,0 ai ,1 T / K

(5)

where ai,0 and ai,1 are the fitting parameters whose values are summarized in Table 7, along with their
corresponding AAD. The predicted values are shown as smooth curves in Figures 3 to 5. With the
good agreement between the experimental and predicted data and the low overall AAD values of 0.08
and 4.3 % for Cp and CPE, respectively, it can be said that applied empirical equation successfully

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correlated our experimental data to both temperature and composition.

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4. Conclusions

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The molar heat capacities of the deep eutectic solvents Reline, Ethaline and Glyceline and their
binary mixtures with water were measured in the temperature range (303.2 to 353.2) K and over a

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complete range of composition. The CP of the pure DES varied slightly with temperature. This
temperature-dependence was suitably represented by a second-order empirical equation with three

fitting parameters.

For the DES + H2O systems, the CP increased with increasing temperature and DES mole fraction

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in the solution. The excess molar heat capacities of the binary solutions were generally negative over

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the whole composition range while exhibiting negative temperature dependence. The CPE was
successfully correlated to the temperature and composition using a RedlichKister type equation with
low overall AAD values of 0.08% for CP and 4.3% for CPE. It can therefore be concluded that the data

accuracy.

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and correlations presented in this work can be used in engineering design calculations with sufficient

Acknowledgements

This research was supported by Grant, NSC 99-2221-E-033-044-MY3, of the National Science
Council of the Republic of China.

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Table 1
Choline chloride (ChCl)-based DESs studied, their compositions, molar masses and freezing points
a

DES trade name

Molar ratio

HBD

(ChCl:HBD)

Molar mass,
MDESb
-1

(gmol )

Freezing point
(oC)

Urea

1:2

86.58

12 [13]

Ethaline

Ethylene glycol

1:2

87.92

-66 [49]

Glyceline

Glycerol

1:2

107.94

-35 [24]

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t

Reline

Trade/commercial name given to the DES by the manufacturer (Scionix Ltd).

M DES x ChCl M ChCl x HBD M HBD where x and M are mole fraction and molecular weight, respectively.

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Table 2
Molar heat capacities of pure DESs
Molar heat capacity, CP (Jmol-1K-1)a
Ethaline

Glyceline

303.15

181.4 0.5

190.8 0.4

237.7 0.6

308.15

182.2 0.6

192.2 0.3

239.1 0.5

313.15

183.2 0.5

194.0 0.3

240.8 0.4

318.15

183.5 0.5

194.9 0.4

323.15

184.5 0.6

196.4 0.2

328.15

185.3 0.6

197.6 0.2

333.15

186.4 0.5

199.2 0.3

338.15

187.4 0.5

200.6 0.3

343.15

188.5 0.7

348.15

189.5 0.6

353.15

190.8 0.8

241.9 0.2

cr

us

an

243.5 0.4
244.9 0.1

246.9 0.1
248.4 0.4
250.3 0.3

203.9 0.2

252.1 0.3

205.6 0.2

254.3 0.4

202.1 0.1

ce
pt

ed

J/molK refers to J/molDESK.

ip
t

Reline

Ac

T (K)

12
Page 13 of 24

Table 3
Fitting parameters for Eq. (1)a for the CP of the pure DES
parameter
DES

a0

a1

a2

no. of data
points, n

Reline

247.4

-0.5633

1.141 10-3

11

0.05

Ethaline

181.9

-0.1936

7.371 10-4

11

0.06

Glyceline

302.8

-0.6783

1.531 10-3

11

0.04

33

0.05

CP / J mol-1 K -1 a0 a1 T / K a2 T / K .

AAD / %

cr

ip
t

overall

AADb (%)

Ac

ce
pt

ed

an

us

100
n
i=1 cald expt / expt .
i
n

13
Page 14 of 24

Table 4
Molar heat capacities of Reline (1) + H2O (2) solutions
Molar heat capacity, CP (Jmol-1K-1)a
x1 = 0.0998

x1 = 0.2995

x1 = 0.4981

x1 = 0.6975

x1 = 0.8926

303.15

81.51 0.1b

100.5 0.3

122.1 0.2

145.0 0.8

168.3 0.2

308.15

81.93 0.1

101.1 0.3

122.9 0.2

146.1 0.9

169.2 0.1

313.15

82.32 0.1

101.7 0.3

123.8 0.3

147.1 0. 8

170.1 0.2

318.15

82.44 0.2

102.1 0.4

124.3 0.2

147.6 1.0

170. 6 0.3

323.15

82.79 0.2

102.8 0.4

125.2 0.2

148.5 0.8

171.4 0.3

328.15

83.09 0.2

103.4 0.4

125.9 0.3

149.2 1.0

172.3 0.4

333.15

83.51 0.2

104.1 0.4

126.8 0.3

338.15

83.82 0.2

104.8 0.5

127.7 0.3

343.15

84.17 0.2

105.6 0.5

128.5 0.5

152.3 1.1

175.3 0.5

348.15

84.62 0.1

106.3 0.6

129.6 0.4

153.3 1.2

176.5 0.4

353.15

85.15 0.1

107.4 0.6

130.7 0.4

154.6 0.9

177.8 0.5

Mean standard deviation.

cr
151.1 1.0

174.2 0.4

us

an

173.4 0.6

J/molK refers to J/molsolnK.

150.3 1.0

Ac

ce
pt

ed

ip
t

T (K)

14
Page 15 of 24

Table 5
Molar heat capacities of Ethaline (1) + H2O (2) solutions
Molar heat capacity, CP (Jmol-1K-1)
x1 = 0.0997

x1 = 0.3005

x1 = 0.4965

x1 = 0.6937

x1 = 0.8893

303.15

84.33 0.6

104.7 0.4

126.8 0.2

151.0 0.3

175.9 0.3

308.15

84.93 0.5

105.8 0.4

128.1 0.4

152.5 0.3

177.3 0.2

313.15

85.45 0.5

106.8 0.4

129.4 0.4

153.7 0.2

178.9 0.3

318.15

85.68 0.5

107.5 0.4

130.2 0.4

154.6 0.3

179.8 0.2

323.15

86.10 0.5

108.5 0.4

131.3 0.5

155.9 0.3

181.2 0.4

328.15

86.37 0.4

109.3 0.3

132.3 0.6

157.1 0.3

182.4 0.3

333.15

86.89 0.4

110.2 0.3

133.6 0.6

338.15

87.21 0.3

111.1 0.3

134.7 0.7

343.15

87.56 0.3

112.0 0.3

135.9 0.7

161.0 0.3

186.6 0.3

348.15

87.95 0.1

112.9 0.4

137.1 0.7

162.3 0.1

188.2 0.1

353.15

88.34 0.1

114.0 0.2

138.4 0.7

163.9 0.3

189.8 0.5

cr

ip
t

T (K)

183.9 0.3

159.6 0.3

185.2 0.3

Ac

ce
pt

ed

an

us

158.4 0.3

15
Page 16 of 24

Table 6
Molar heat capacities of Glyceline (1) + H2O (2) solutions
Molar heat capacity, CP (Jmol-1K-1)
x1 = 0.1000

x1 = 0.2995

x1 = 0.4947

x1 = 0.6993

x1 = 0.8980

303.15

88.93 0.1

119.2 0.1

150.4 0.4

184.4 0.4

218.8 0.6

308.15

89.42 0.1

120.2 0.2

151.6 0.5

185.7 0.4

220.4 0.7

313.15

89.92 0.1

121.2 0.1

153.0 0.7

187.1 0.6

221.9 0.5

318.15

90.19 0.1

122.0 0.1

153.8 0.6

188.1 0.6

223.0 0.6

323.15

90.69 0.1

123.0 0.1

155.2 0.6

189.4 0.5

224.5 0.7

328.15

91.02 0.1

123.9 0.1

156.2 0.7

190.5 0.4

225.8 0.9

333.15

91.66 0.1

125.0 0.1

157.8 0.7

338.15

92.08 0.1

126.0 0.1

159.0 0.7

343.15

92.56 0.1

127.0 0.1

160.3 0.7

195.3 0.6

230.9 1.1

348.15

93.10 0.1

128.1 0.1

161.7 0.8

196.8 0.8

232.6 0.9

353.15

93.51 0.1

129.3 0.1

163.3 0.9

198.7 0.6

234.7 1.2

cr

ip
t

T (K)

227.6 0.9

193.8 0.5

229.1 0.9

Ac

ce
pt

ed

an

us

192.3 0.5

16
Page 17 of 24

Table 7
Fitting parameters for Eq. (4) a for the aqueous DES systems

ai,0

ai,1

Reline (1) + H2O (2)

-110.2

0.2855

63.55

-0.1542

-41.53

0.0919

-120.1

0.3219

74.78

-0.2344

8.112

-0.0269

-125.6

0.3502

83.75

-0.2695

-20.67

0.0471

Ethaline (1) + H2O (2)

Glyceline (1) + H2O (2)

overall

3.5

0.09

55

4.7

0.08

4.8

0.06

4.3

0.08

55

165

where A i ai ,0 ai ,1 T / K .

ce
pt

ed

i 1

i 1

55

an

CP E / J mol-1 K -1 x1 x2 A i x1 x2

CP

Ac

CPE

ip
t

us

System

AAD (%)

no. of data
points

cr

parameters

17
Page 18 of 24

Figure Captions

Figure 1. Molar heat capacity of the pure DES as a function of temperature: , Reline; , Ethaline;
, Ethaline, data from this work; and lines, calculated using Eq. (1)
Figure 2. Molar heat capacity for Reline (1) + H2O (2) solutions as a function of temperature, at

ip
t

different mole fractions: , x1 1.0; , x1 0.1; , x1 0.3; , x1 0.5; , x1 0.7; , x1 0.9,


data from this work; , liquid water, data from Osborne et al. [45]; and lines, calculated using Eqs. (3)

cr

and (4)

us

Figure 3. Excess molar heat capacity, for Reline (1) + H2O (2) solutions as a function of DES mole
fraction, at different temperatures: , 303.2 K; , 313.2 K; , 323.2 K; , 333.2 K; , 343.2 K; ,

an

353.2 K; and lines, calculated using Eq. (4)

Figure 4. Excess molar heat capacity, for Ethaline (1) + H2O (2) solutions as a function of DES mole
fraction, at different temperatures: , 303.2 K; , 313.2 K; , 323.2 K; , 333.2 K; , 343.2 K; ,

ed

353.2 K; and lines, calculated using Eq. (4)

ce
pt

Figure 5. Excess molar heat capacity, for Glyceline (1) + H2O (2) solutions as a function of DES mole
fraction, at different temperatures: , 303.2 K; , 313.2 K; , 323.2 K; , 333.2 K; , 343.2 K; ,

Ac

353.2 K; and lines, calculated using Eq. (4)

18
Page 19 of 24

Figure 1

ip
t

Leron et al., 2011

cr

280

an
M

200

ce
pt

120

ed

160

300

310

320

330

Ac

-1

CP/ Jmol K

-1

us

240

340

350

360

T/ K

19
Page 20 of 24

Figure 2
Leron et al., 2011

cr

ip
t

210

us
an

150

-1

CP/ Jmole K

-1

180

ed

120

300

Ac

60

ce
pt

90

310

320

330

340

350

360

T/ K

20
Page 21 of 24

Figure 3
Leron et al., 2011

ip
t

cr
us

-2

an
ed

-4

-8
0.0

ce
pt

-6

0.2

0.4

0.6

Ac

-1

CP / Jmol K

-1

0.8

1.0

x1

21
Page 22 of 24

Figure 4
Leron et al., 2011

ip
t

us
an

-2

-1

CP / Jmol K

-1

cr

ed

-4

0.2

0.4

0.6

0.8

1.0

x1

Ac

0.0

ce
pt

-6

22
Page 23 of 24

Figure 5

ip
t

Leron et al., 2011

us

cr

-1

CP / Jmol K

-1

an

-4

Ac

-6

ce
pt

ed

-2

0.0

0.2

0.4

0.6

0.8

1.0

x1

23
Page 24 of 24