Article

pubs.acs.org/jced

Estimation of Normal Boiling Temperatures, Critical Properties, and

Acentric Factors of Deep Eutectic Solvents
Nouman Raque Mirza, Nathan J. Nicholas, Yue Wu, Sandra Kentish, and Georey W. Stevens*
Department of Chemical and Biomolecular Engineering, The University of Melbourne, Parkville, Victoria 3010, Australia
ABSTRACT: Deep eutectic solvents (DESs) are novel solvents that have shown
the ability to capture carbon dioxide from ue gases. Thermodynamic modeling is
needed to validate the experimental vaporliquid equilibria (VLE) of the CO2
DES systems. To establish thermodynamic models of these solvents, their critical
properties must be estimated. In the present study, a combination of the modied
LydersenJobackReid (LJR) method and the LeeKesler mixing rules has been
applied to estimate the critical properties of 39 dierent DESs. Normal boiling
temperatures and acentric factors have also been determined. The accuracy of this
method has been tested by comparison of theoretical densities determined from
the estimated critical properties with experimental values. Absolute deviations
ranging from 0 % to 17.4 % were observed for the estimated density values. An
overall average absolute deviation of 4.9 % was observed for the studied DESs.
Absolute deviations for DESs consisting of aliphatic precursors ranged from 0 % to
9.5 %, whereas for DESs consisting of at least one aromatic precursor, these ranged from 5.8 % to 17.4 %. The accuracy fell as the
percentage of hydrogen-bond donors (HBD) increased. The method was also found to accurately take into account the variation
in density due to a temperature change.
intensive purication steps common in the synthesis of ILs.2 As
a result, DESs have found potential utilization in many dierent
areas such as innovative organic synthesis, 15 catalytic
processes,16 biodiesel purication,17 drug solubilization,18
electrodeposition,19 electropolishing of metals, and metal
oxide processing.20 DESs and aqueous mixtures of DESs have
also shown promising results for the absorption of acid
gases.2126
In order to develop processes based upon DESs, their
physical, physicochemical, and transport properties (i.e.,
density, viscosity, conductivity, pH, vapor pressure, critical
properties, normal boiling temperature, Gibbs free energy, etc.)
need to be determined. However, the focus of present-day
research has mainly been on the determination of only the
physicochemical and transport properties (mainly density,
viscosity, and conductivity) of these solvents.12,2729 In order
to develop thermodynamic models for these solvents, an
understanding of their phase equilibria is also needed. More
importantly, the development of a database for the critical
properties of these solvents is needed so that thermodynamic
models can be applied to validate the experimental data.
Because of their tendency to thermally decompose at high
temperatures,14 their critical properties are extremely dicult to
determine experimentally and thus have to be predicted
theoretically.
In this study, the critical temperatures (Tc), critical pressures
(Pc), critical molar volumes (Vc), normal boiling temperatures

1. INTRODUCTION
Deep eutectic solvents (DESs) have attracted much attention
from the scientic community in recent years, and a number of
studies have been published outlining various applications of
these solvents.1,2 A DES is a combination of a salt and a
hydrogen-bond donor (HBD), which when mixed in a certain
molar ratio and heated mildly at a moderate temperature form a
clear liquid.3 The liquid has a freezing point considerably lower
than that predicted from ideal solution theory using the fusion
enthalpies of the original precursors4 and thus is termed a
deep eutectic solvent. There are a large number of precursors
that can develop aliations with each other and hence
formulate deep eutectic solvents.5 These solvents share
properties similar to those of low-transition-temperature
mixtures (LTTMs)5 and have also been called natural deep
eutectic solvents (NADES)6,7and ionic liquid analogues8,9 in
the literature.
Deep eutectic solvents share many similarities with ionic
liquids (ILs)2 yet are regarded as dierent. This is due to the
fact that DESs are not always composed entirely of ionic
species, as the precursors for DESs can be neutral entities, e.g.,
a DES resulting from ZnCl2 and urea.10 Furthermore, as DESs
are formed from the mixing of neutral species, they are not
limited by a charge balance ratio, and therefore, the molar ratio
of its precursors can be varied to obtain the eutectic solvent.
Furthermore, unlike protic ionic liquids,11 a complete proton
transfer is not necessarily required to form a eutectic solvent.
Some major advantages of DESs over ILs are that they can be
biodegradable, nontoxic, and nonammable and can have
negligible vapor pressure.1214 Another major advantage is that
they can be manufactured cheaply and readily without requiring
2015 American Chemical Society

Received: January 13, 2015

Accepted: May 15, 2015
Published: June 2, 2015
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Table 1. Structures and Molar Ratios of Organic Salts and Hydrogen-Bond Donors for the Studied DESs

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Table 1. continued

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Table 1. continued

individual contributions to the critical properties are summated

to obtain the nal estimate for critical properties. The accuracy
of these methods varies, and the choice of method is based
upon the spectrum of its applicability, ease of use, and the
additional data required for estimating critical properties.35
The methods proposed by Lydersen,32 Ambrose and
Young,33 and Klincewicz and Reid34 require prior knowledge
of normal boiling temperatures to further estimate the critical
properties of the chemical compounds. Joback and Reid36
proposed a method that also included estimation of the normal
boiling points and is still used with slight modications to
estimate the properties. Constantinou et al.30 initially proposed
a complex contribution method in which the molecule, on the
basis of a rearrangement of the valence electrons, is considered
to be composed of its dominant and recessive conjugate forms.

(Tb), and acentric factors () of 39 dierent DESs have been

estimated. The accuracy of the estimation has been tested by
predicting the densities of the DESs using the estimated critical
properties and comparing the results with the values already
quoted in the literature. Table 1 presents the structures and
molar ratios of the precursors for the 39 deep eutectic solvents
studied in this work.

2. ESTIMATING CRITICAL PROPERTIES

Presently there exist a number of methods in the literature for
estimating critical properties. Group contribution methods have
been reported by Constantinou et al.,30 Constantinou and
Gani,31 Lydersen,32 Ambrose and Young,33 and Klincewicz and
Reid34 In group contribution methods, the type and frequency
of individual atoms or groups of atoms are considered and their
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The method provides good estimates of the properties;

however, its application can be tedious because of the various
conjugate forms of many organic molecules. Constantinou and
Gani31 later proposed another group contribution method in
which a molecule is divided into two dierent levels. The
primary level consists of the rst-order functional groups such
as those used in the Lydersen method.32 The secondary level
contains functional groups that are worked up by considering
the rst-order functional groups as building blocks and provide
more information about the molecular structure of the chemical
compound. Property estimation is done on the basis of the
primary level and then extended to the secondary level to make
it more accurate and applicable for isomers.
Lydersen32 dened 43 dierent structural groups and
proposed the following equations to estimate the critical
properties of organic compounds:
Tc =
Pc =

Pc =

Vc = 6.75 +

(1)

M
(0.34 + niPLi)2

(2)

Vc = 40 +

niVLi

(3)

In these equations, Tb is the normal boiling temperature (K), ni

is the frequency of appearance of the ith group of atoms in the
molecule, TL is their contribution to the critical temperature
(K), PL is their contribution to the critical pressure (bar),
VL is their contribution to the critical molar volume (cm3
mol1), and M is the molar mass of the entire molecule (g
mol1).
Later on, Joback and Reid36 dened 41 structural groups and,
on the basis of the elemental analysis of molecules, proposed
the following equations to estimate the critical properties:
Tc =
Pc =

TcD =

1
(0.113 + 0.0032N niPJi)2

niVMi

(10)

1
VcD0.25

yyi j Vcij 0.25Tcij

i

(11)

where

Tcij = (TciTcj)0.5 kij

Tb
0.584 + 0.965 niTJi ( niTJi)2

(9)

In these equations, ni is the frequency of appearance of the ith

group of atoms in the molecule, TbM is their contribution to
the normal boiling temperature (K), TM is their contribution
to the critical temperature (K), PM is their contribution to the
critical pressure (bar), VM is their contribution to the critical
molar volume (cm3mol1), and M is the molar mass of the
molecule (gmol1).
In this work, the modied LydersenJobackReid method
has been applied to estimate the critical properties of the
precursors constituting the 39 deep eutectic solvents under
study. This method was chosen because it gives an accurate
estimation of the critical properties of high-molecular-weight
organic molecules and is relatively simple to apply. A summary
of the functional groups used in the modied LJR method and
their contributions to the critical properties is presented in
Table 2.
Since DESs are mixtures of two or more precursors, the
method used to estimate the properties of the pure precursors
must be extended to estimate the properties of the nal
mixture. After the critical properties of the precursors were
determined, the LeeKesler mixing rules, as recommended by
Knapp et al.,39 were used to estimate the nal critical properties
of the DESs. These rules are given by the following equations:

Tb
0.567 + niTLi ( niTLi)2

M
(0.2573 + niPMi)2

(12)

(4)

VcD =

yyi j Vcij
i

(13)

(5)

where
Vc = 17.5 +

niVJi

(6)

Vcij =

In these equations, N is the number of atoms in the molecule,

Tb is the normal boiling temperature (K), ni is the frequency of
appearance of the ith group of atoms in the molecule, TJ is
their contribution to the critical temperature (K), PJ is their
contribution to the critical pressure (bar), and VJ is their
contribution to the critical molar volume (cm3mol1).
Alvarez and Valderrama37 combined the Lydersen32 and
JobackReid36 methods to give the modied Lydersen
JobackReid (LJR) method, which is specically applicable to
high-molecular-weight compounds. The method uses the same
equations for estimation of critical properties as were originally
proposed by Lydersen32 and JobackReid36 but with dierent
parameters. The equations proposed in the method are the
following:
Tb = 198.2 +

Tc =

niTbMi

PcD = (0.2905 0.085D)

(14)

RTcD
VcD

(15)

where

D =

yi i
i

(16)

In the above equations, the subscript D refers to the nal

properties of the mixture, i and j refer to the pure components,
yi and yj are the mole fractions of the pure components, and
TcD, PcD, VcD, kij , and D are the critical temperature (K),
critical pressure (bar), critical molar volume (cm3mol1),
binary interaction parameter, and acentric factor, respectively,
for the eutectic mixture. The acentric factors of the precursors
(i) were estimated using the correlation proposed by
Valderrama and Robles:38

(7)

Tb
0.5703 + 1.0121 niTMi ( niTMi)2

1
(Vci1/3 + Vcj1/3)3
8

(8)
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has successfully been used to predict the densities of ionic

liquids,38 is given by the following equation:

Table 2. Groups of Atoms and Their Contributions to the

Critical Properties for the Modied LJR Method38
TbMa
group

CH3
CH2
>CH
>C<
CH2
CHC<
C
CH
C
OH (alcohol)
O
>CO
CHO
COOH
COOHCOO
O (others)
NH2
>NH
>N
N
CN
NO2
F
Cl
Br
I
CH2
>CH
CH
>C<
C<
O
OH (phenol)
>CO
>NH
>N
N
B
P
SO2
a

TM

PM

Without Rings
23.58
0.0275
22.88
0.0159
21.74
0.0002
18.18
0.0206
24.96
0.017
18.25
0.0182
24.14
0.0003
26.15
0.0029
0.0078
0.0078
92.88
0.0723
22.42
0.0051
94.97
0.0247
72.24
0.0294
169.06
0.0853
81.1
0.0377
0.036
10.5
0.0273
73.23
0.0364
50.17
0.0119
11.74
0.0028
74.6
0.0172
125.66
0.0506
152.54
0.0448
0.03
0.0228
38.13
0.0188
66.86
0.0124
93.84
0.0148
With Rings
27.15
0.0116
21.78
0.0081
26.73
0.0114
21.32
0.018
31.01
0.0051
31.22
0.0138
76.34
0.0291
94.97
0.0343
52.82
0.0244
0.0063
57.55
0.0011
Other Groups
24.56
0.0352
34.86
0.0084
147.24
0.0563

bar

VM

L =

cm mol
3

0.3031
0.2165
0.114
0.0539
0.2493
0.1866
0.0832
0.0934
0.1429
0.1429
0.1343
0.13
0.2341
0.3128
0.4537
0.4139
0.4752
0.2042
0.1692
0.0322
0.0304
0.1541
0.3697
0.4529
0.2912
0.3738
0.5799
0.9174

66.81
57.11
45.7
21.78
60.37
49.92
34.9
33.85
43.97
43.97
30.4
15.61
69.76
77.46
88.6
84.76
97.77
44.03
49.1
78.96
26.7
45.54
89.32
123.62
31.47
62.08
76.6
100.79

0.1982
0.1773
0.1693
0.0139
0.0955
0.1371
0.0493
0.2751
0.0724
0.0538
0.0559

51.64
30.56
42.55
17.62
31.28
17.41
17.44
59.32
27.61
25.17
42.15

0.0348
0.1776
0.0606

22.45
67.01
112.19

1 + (1 T )2/7
R

=
1 + (1 TbR )2/7

P
P
(Tc 43 K)
log c + log c 1
(Tc Tb)
Pb
Pb

(19)

in which
TR =

T
Tc

(20)

and
TbR =

Tb
TC

(21)

In these equations, L is the density of the DES (gcm3), M is

the molar mass (gmol1), Pc is the critical pressure (bar), R is
the universal gas constant (8.314 Jmol1K1), Tc is the critical
temperature (K), Vc is the critical molar volume (cm3mol1),
TR is the reduced temperature, and TbR is the reduced normal
boiling point.
Binary interaction parameters (kij ) for DESs have not yet
been reported in the literature. Labinov and Sand40 studied 12
binary mixtures of other chemical species and reported that for
mixtures of nonpolar substances the value of kij should range
from 1.0 to 1.3, while for mixtures of polar substances the value
should range from 0.95 to 1.06. In the present study, because of
the unavailability of experimental data, a value of unity for kij
was assumed in all of the calculations. To ensure that this
assumption was reasonable, optimum kij values were estimated
for four dierent DESs, each chosen from one of the categories
dened in this study, by minimizing the error in the density
after the critical properties were estimated from the current
methodology. These kij values ranged from 0.81 to 1.56. A
sensitivity analysis was also carried out, and the results showed
that the absolute deviation of the density remained within 10 %
across this range of kij values. This qualies the assumption that
in the absence of experimental data a value of unity for kij yields
satisfactory results.

3. RESULTS AND DISCUSSION

The estimated critical properties (Tc, Pc, and Vc), normal
boiling temperatures (Tb), molar masses (M), acentric factors
(), and ratios of the normal boiling point to the critical
temperature (Tb/Tc) as well as the resultant estimated DES
densities (est), their values previously reported in the literature
(lit), and the deviations between the estimated and
experimental densities () are presented in Table 3. It should
be pointed out that the correlation used to estimate the density
values (eqs 18 to 21) is completely independent of the
modied LJR method and the LeeKesler mixing rules.
Therefore, it can be said that density estimation and
comparison with published values is a reliable, independent
test of the accuracy of the estimated properties. Table 3 shows
that the estimated densities are in good agreement with the
published values. The minimum absolute deviation is observed
for (ChCl:EG)1:3 (0 %), while the maximum deviation is 17 %
for (Me-tri-PBR:TEG)1:5. The overall average absolute

P
(Tb 43 K)(Tc 43 K)
log c
(Tc Tb)(0.7Tc 43 K)
Pb

(18)

where

Missing values were assumed to be equal to zero.

i =

MPcD 0.3445PcDVcD1.0135

RTcD
TcD

(17)

To estimate the density from these critical properties, a

correlation based upon the work of Spencer and Danner41 was
used. The correlation42 requires knowledge of the normal
boiling temperature, molecular weight, and critical properties to
estimate the density of the compound. The correlation, which
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Table 3. Estimated Critical Properties and Comparison of Densities (at 40 C) with Literature Values for 39 Dierent DESs
DES
(ChCl:U)1:2
(ChCl:EG)1:2
(ChCl:G)1:2
(ChCl:MA)1:2
(ChCl:B)1:3
(ChCl:TFA)1:2
(ChCl:LA)1:1.3
(ChCl:Ph)1:2
(AcChCl:U)1:2
(EtACl:U)1:1.5
(EtACl:AA)1:1.5
(EtACl:TFA)1:1.5
(di-EtACl:EG)1:2
(di-EtACl:G)1:2
(Me-tri-PBr:G)1:2
(Me-tri-PBr:EG)1:3
(Me-tri-PBr:TEG)1:5
(ChCl:G)1:1
(ChCl:G)1:3
(di-EtACl:TFA)1:2
(ChCl:EG)1:3
(ChCl:Ph)1:3
(ChCl:Ph)1:4
(ChCl:LA)1:1.5
(ChCl:LA)1:2
(ChCl:LA)1:2.5
(ChCl:LA)1:3
(ChCl:LA)1:3.5
(ChCl:LA)1:4
(ChCl:LA)1:5
(ChCl:LA)1:8
(ChCl:LA)1:10
(ChCl:LA)1:15
(Me-tri-PBr:G)1:1.75
(Me-tri-PBr:EG)1:4
(ChCl:F)2.5:1
(ChCl:F)2:1
(ChCl:F)1.5:1
(ChCl:F)1:1
a

Tb

Tc

Pc

Vc

gmol1

bar

cm3mol1

86.58
87.92
107.93
115.91
102.50
121.90
111.62
109.28
100.60
68.65
68.06
100.44
92.60
112.61
180.50
135.86
184.68
115.86
103.97
126.58
81.46
105.49
103.21
109.90
106.59
104.23
102.47
101.09
99.99
98.34
95.58
94.58
93.18
188.5
121.1
151.2
153.13
155.84
159.89

445.6
439.0
515.4
550.3
471.0
408.8
495.2
445.3
461.6
381.6
351.8
348.5
446.5
522.9
635.4
526.7
608.0
500.9
522.6
416.4
436.7
443.8
442.9
497.5
502.0
505.2
507.6
509.4
510.9
513.1
516.8
518.2
520.1
643.7
507.3
574.9
594.5
621.9
663.0

644.4
602.0
680.67
738.71
637.97
589.24
671.26
651.15
667.24
582.07
544.27
531.92
611.68
690.79
832.40
708.03
799.52
664.90
688.98
596.14
600.48
655.66
658.52
674.60
681.14
685.93
689.60
692.50
694.85
698.42
704.52
706.78
710.00
843.77
684.72
737.10
756.99
785.24
828.52

49.35
40.39
33.06
37.90
33.42
39.58
35.26
44.53
45.80
63.13
57.73
49.52
38.38
31.42
26.87
35.16
25.56
31.05
34.20
37.82
43.41
47.91
50.12
35.97
37.42
38.53
39.39
40.09
40.67
41.57
43.14
43.74
44.62
26.41
37.58
25.71
25.46
25.05
24.28

254.37
259.67
315.17
319.65
330.34
303.67
328.35
297.58
287.55
192.20
203.09
232.77
270.13
326.30
455.97
335.88
517.16
345.17
300.50
320.32
239.41
281.06
271.30
321.82
309.42
300.66
294.15
289.11
285.10
279.12
269.24
265.68
260.69
475.58
303.04
451.68
453.53
456.15
460.06

0.661
0.952
1.251
1.097
0.968
0.532
0.977
0.538
0.624
0.468
0.369
0.351
1.019
1.317
1.334
1.058
1.078
1.137
1.307
0.542
0.968
0.511
0.496
0.989
1.012
1.028
1.040
1.049
1.056
1.067
1.084
1.091
1.100
1.311
1.064
1.188
1.259
1.359
1.510

Tb/Tc
0.69
0.73
0.76
0.74
0.74
0.69
0.74
0.68
0.69
0.66
0.65
0.66
0.73
0.76
0.76
0.74
0.76
0.75
0.76
0.70
0.73
0.68
0.67
0.74
0.74
0.74
0.74
0.74
0.74
0.73
0.73
0.73
0.73
0.76
0.74
0.78
0.79
0.79
0.80

est

lit

gcm3

gcm3

1.076
1.097
1.211
1.284
1.057
1.248
1.152
1.150
1.131
1.055
0.974
1.250
1.120
1.248
1.511
1.409
1.323
1.182
1.235
1.239
1.117
1.170
1.183
1.160
1.175
1.185
1.193
1.199
1.204
1.212
1.224
1.229
1.235
1.514
1.395
1.260
1.296
1.347
1.425

44

1.189
1.10945
1.18346
1.18525
1.052a,47
1.342b,1
1.15748
1.08749
1.206b,1
1.140b,1
1.041b,1
1.273b,1
1.09027
1.173b,27
1.306b,27
1.24027
1.186b,28
1.156b,27
1.19527
1.29027
1.117b,27
1.08249
1.08049
1.16548
1.16948
1.17448
1.17948
1.18248
1.18248
1.18948
1.19648
1.19948
1.19948
1.290b,27
1.233b,27
1.259b,50
1.278b,50
1.304b,50
1.337b,50

9.5
1.1
2.4
8.4
0.5
7.0
0.4
5.8
6.2
7.5
6.4
1.8
2.8
6.4
15.7
13.6
11.6
2.3
3.4
4.0
0.0
8.1
9.5
0.4
0.5
0.9
1.2
1.4
1.9
1.9
2.3
2.5
3.0
17.4
13.1
0.1
1.4
3.3
6.6

At 293.15 K. bAt 298.15 K.

the presence of these stronger interactions aects the accuracy

of the LRJ and LeeKesler methods, both of which assume no
interactions within the chemical species.3941,44,47 DESs
containing a greater number of aromatic rings are observed
to show larger deviations. For example, (ChCl:Ph)1:3, which
contains only one ring, shows a deviation of 8.1 %, while (Metri-PBr:EG)1:3, which contains three rings, shows a deviation of
13.6 %. It is also observed that as the mass percentage of ringcontaining precursor is increased in a certain DES, the resulting
deviation is also increased. For example, the deviations for
(ChCl:Ph)1:2, (ChCl:Ph)1:3, and (ChCl:Ph)1:4 are 5.8 %, 8.1 %,
and 9.5 %, respectively.
There are only two DESs in the group containing carboxylic
acids. Deviations for these two DESs range from 0.4 % to 8.4
%. (ChCl:MA)1:2 shows a higher deviation than all of the DESs
involving (ChCl:LA). This could be attributed to an additional
carboxylic radical present in the (ChCl:MA)1:2 DES. An
increase in the number of functional groups means that there

deviation of the density is 4.9 %, showing good agreement with

the published data.
An attempt was made to classify the DESs on the basis of the
functional groups they contain, and this resulted in four distinct
groups (Table 1): amide-containing DESs, aromatic-containing
DESs, carboxylic acid-containing DESs, and alcohol-containing
DESs. It is clear that all of the DESs containing at least one
amide group result in a negative deviation in the predicted
density. The deviation ranges from 1.8 % to 9.5 %. DESs
containing two amide groups exhibit an absolute deviation of
more than 6 %. A maximum deviation of 9.5 % is observed for
(ChCl:U)1:2, which contains two amide groups, while the
minimum deviation is 1.8 % for (EtACl:TFA)1:1.5, which
contains only one amide group.
Greater deviations are exhibited by DESs containing one or
more aromatic rings. Aromatics are small molecules with
stronger interaction forces between them.51 In addition to the
hydrogen bonding that exists between the precursors of DESs,
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Table 4. Comparison of Absolute Deviations of Densities from the Present Work and a Previous Study29 (Obtained Using Same
Methods)
||/%

Salt

HBD

DES

this work

ref 29a

choline chloride
choline chloride
choline chloride
N,N-diethylethanolammonium chloride
N,N-diethylethanolammonium chloride
methyltriphenylphosphonium bromide
methyltriphenylphosphonium bromide

ethylene glycol
triuoroacetamide
glycerol
glycerol
triuoroacetamide
glycerol
ethylene glycol

(ChCl:EG)1:2
(ChCl:TFA)1:2
(ChCl:G)1:1
(di-EtACl:G)1:2
(di-EtACl:TFA)1:2
(Me-tri-PBr:G)1:2
(Me-tri-PBr:EG)1:4

1.1
7.0
2.3
6.4
4.0
15.7
13.1

23.4
28.9
17.4
12.3
22.6
21.8
0.30

Deviations for estimated densities at 35 and 45 C are given. Interpolation was done to obtain deviation values for 40 C.

Figure 1. Variation of the deviation in densities with dierent mole fractions of precursors in the DESs. Dotted lines represent linear ts to the
deviations.

exception of (Me-tri-PBr:EG)1:4] were observed in the present

work. It is to be noted that the authors of the previous study29
used a dierent correlation for the density to check the
accuracy of the estimated critical properties. This suggests that
the correlation described by Valderrama and co-workers38,42
(eqs 18 to 21) results in better estimates of the density values
of DESs.
Figure 1 shows the variation in density predictions with HBD
content for choline chloride:glycerol (ChCl:G)-based and
choline chloride:lactic acid (ChCl:LA)-based DESs. For both
type of DESs, the absolute deviation tends to increase with
increasing mole fraction of HBD in the deep eutectic solvent.
An increase in the amount of HBD results in the introduction
of more potential sites to develop weak bonding between
HBDs and anions of the organic salt. This more complex
bonding reduces the accuracy of the current method for
estimating the critical properties. Therefore, with an increase in
the amount of HBD, a larger deviation in the density estimate is
observed. In the case of ChCl:G-based DESs, the absolute
deviation ranges from 1.4 % to 3.4 %, while in the case of
ChCl:LA-based DESs it ranges from 0.4 % to 3.0 %.
In the literature it is a common practice to draw an analogy
between ionic liquids and DESs because of their similar
physicochemical properties.2,8,9 This analogy is not completely
valid with regard to the estimation of critical properties.

are more potential active sites and hence greater potential for
more inter- and intramolecular forces, resulting in more
complex bonding forces. Since the method does not take into
account the eect of bonding forces, their existence reduces the
accuracy of the method.
Alcohol-containing DESs are the largest group. The
minimum deviation within this group is 0 % for (ChCl:EG)1:3,
while the maximum deviation of 6.6 % is observed for
(ChCl:F)1:1. In all of the DESs, an increase in the mass
percentage of precursor containing a larger number of OH
groups results in higher deviations. For example, the mass
percentages of glycerol in (ChCl:G)1:1, (ChCl:G)1:2, and
(ChCl:G)1:3 are 39.74 %, 56.89 %, and 69.07 %, respectively,
and the deviations for these DESs are 2.2 %, 2.4 %, and 3.4 %,
respectively.
In a previous study, Shahbaz et al.29 compared dierent
methods of estimating the critical properties of DESs and
applied these to the same density evaluation test. One of the
methods they applied was the same as the one used in this
study. However, their results dier from those presented here.
Table 4 shows seven of the nine DESs studied by these authors
and compares their results with the ones obtained in the
current study.
It is clear from Table 4 that in comparison to the previous
study,29 signicantly lower absolute deviations [with the
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Figure 2. Variation of estimated and experimental densities with temperature for various DESs. Open symbols are estimated values, and solid
symbols are experimental values; dashed and solid lines are linear ts to the data points.

LeeKesler mixing rules were used to combined these

individual parameters to estimate the nal critical properties
and acentric factors of the DESs. After the nal critical
properties of DESs were obtained, a correlation proposed by
Valderrama and Abu-Sharkh42 was used to estimate the
densities of these DESs. These density estimates were then
compared with experimental values to check the accuracy of the
estimated boiling points, acentric factors, and critical properties.
The results showed that the amide-containing DESs showed
a negative deviation in the density estimation (in the range of
1.8 % to 9.5 %), aromatic-containing DESs a higher positive
deviation (in the range of 5.8 % to 17.4 %), carboxylic acidcontaining DESs a moderate deviation (in the range of 0.4 %
to 8.4 %), and alcohol-containing DESs a lower deviation (in
the range of 0 % to 6.6 %). In all of the DESs studied, an
increase in mass percentage of the HBD also increased the
deviation in the density estimation.

Therefore, certain aspects of the estimation methods for critical

properties applied to ILs cannot be assumed to work perfectly
well for DESs. Values of the ratio of the normal boiling point to
the critical temperature (Tb/Tc) are also given in Table 3. In a
previous study,43 a xed value of 0.60 was assumed for this ratio
to estimate the normal boiling points and critical temperatures
of ionic liquids. Table 3 shows that the values of the Tb/Tc ratio
range between 0.65 and 0.80 for dierent DESs, so a xed value
for the ratio cannot be assumed.
Finally, the density values for three dierent DESs
[(ChCl:EG)1:2, (ChCl:G)1:2, and (Me-tri-PBr:G)1:2] were
estimated over the temperature range from 298.15 K to
348.15 K. A comparison of these values with literature data is
shown in Figure 2. The experimental value for (ChCl:EG)1:2
drops suddenly at 318.15 K, which could be attributed to an
experimental error. Other than this, density values for both
(ChCl:EG)1:2 and (ChCl:G)1:2 agree well with the published
literature. The deviations in the densities for these two DESs
range from 0.0 % to 3.6 % over this temperature range.
However, the deviation for (Me-tri-PBr:G)1:2 ranges from 14.2
% to 15.7 %. This large deviation can be attributed to the
presence of aromatic species in the DES in the form of
methyltriphenylphosphonium bromide, which reduces the
accuracy of the method because of the additional interaction
forces.
In summary, on the basis of the functional groups present,
the DESs in this study have been classied into four dierent
categories: amide-containing DESs, carboxylic acid-containing
DESs, alcohol-containing DESs, and aromatic-containing DESs.
The critical properties of these DESs were estimated using a
combination of a modied LydersenJobackReid method
and the LeeKesler mixing rules via the following procedure.
First, by means of the group contribution method, individual
boiling points and the critical properties of the constituents of
the DESs were estimated using the modied LJR method.
From the boiling points and critical properties of the individual
constituents, individual acentric factors were estimated using a
correlation described by Valderrama and Robles.38 Then the

4. CONCLUSIONS
A combination of the LydersenJobackReid method and the
LeeKesler mixing rules was applied to estimate the critical
properties of 39 dierent deep eutectic solvents. Additionally,
the acentric factors and normal boiling temperatures were
determined. The consistency of the method was tested by
estimating the densities of these deep eutectic solvents using an
independent correlation and comparing the values with
experimental data in the literature. The correlation used for
density estimation was based upon the critical properties and
the molecular weight of the deep eutectic solvents and
therefore can safely be assumed to be a good test of the
applicability of the method to DESs. Comparison of the
estimated and published density values shows good agreement
for DESs consisting of aliphatic precursors. However, because
of the presence of stronger interaction forces, the method yields
higher deviations when at least one aromatic group is present in
the DES. The method gives satisfactory results when changes in
molar ratios and density variations with temperature are taken
into account.
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AUTHOR INFORMATION

Corresponding Author

*Tel.: +61 3 83446621. Fax: +61 3 83448824. E-mail:

gstevens@unimelb.edu.au.
Funding

This research was funded by the University of Melbourne and

used facilities from the Cooperative Research Centre for
Greenhouse Gas Remediation, Australia.
Notes

The authors declare no competing nancial interest.

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