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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
DOI: 10.1021/acs.jced.5b00046
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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
DOI: 10.1021/acs.jced.5b00046
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Article
Pc =
Vc = 6.75 +
(1)
M
(0.34 + niPLi)2
(2)
Vc = 40 +
niVLi
(3)
TcD =
1
(0.113 + 0.0032N niPJi)2
niVMi
(10)
1
VcD0.25
(11)
where
Tb
0.584 + 0.965 niTJi ( niTJi)2
(9)
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 =
Tc =
niTbMi
(14)
RTcD
VcD
(15)
where
D =
yi i
i
(16)
(7)
Tb
0.5703 + 1.0121 niTMi ( niTMi)2
1
(Vci1/3 + Vcj1/3)3
8
(8)
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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)
P
(Tb 43 K)(Tc 43 K)
log c
(Tc Tb)(0.7Tc 43 K)
Pb
(18)
where
i =
MPcD 0.3445PcDVcD1.0135
RTcD
TcD
(17)
DOI: 10.1021/acs.jced.5b00046
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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
DOI: 10.1021/acs.jced.5b00046
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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.
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
1851
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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.
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
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