ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING

Asia-Pac. J. Chem. Eng. (2017)

Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI: 10.1002/apj.2074

Research article
Ethaline and Glyceline binary eutectic mixtures:
characteristics and intermolecular interactions
F.S. Mjalli* and O.U. Ahmed
Petroleum and Chemical Engineering Department, Sultan Qaboos University, Muscat, Oman

Received 7 August 2016; Revised 11 January 2017; Accepted 24 January 2017

ABSTRACT: Deep eutectic solvents (DESs) are ionic liquids analogs that have been the subject of a growing interest in the
scientific community. Governed by their favorable chemical and physical properties, they were utilized in a wide variety of
fields. DESs possessing both desirable and undesirable properties for a specific application are not uncommon. As such,
investigation into the variation of their properties upon mixing, in order to understand and improve their properties for a
specific application, seems promising. In this study, the measurement of the physical and selected excess thermodynamic
properties of Ethaline upon addition of Glyceline was carried out. The deviation of excess molar volume as a function of
Glyceline molar fraction was observed to be alternating between negative and positive. This implies that the predominant
interactions is due to either the difference in the sizes and shapes of the constituent molecules or to the effect dispersion
forces. The highest deviations of the excess molar volume were observed at 30 and 90 mol% Glyceline. Density, viscosity,
pH, RI and conductivity of the pure and DES mixtures were measured at different Glyceline molar fractions within the
temperature range of 20 to 80 °C. © 2017 Curtin University of Technology and John Wiley & Sons, Ltd.

KEYWORDS: Ethaline; Glyceline; DES; eutectic; molecular interaction; physical properties

INTRODUCTION Although the large number of hydrogen bond donors

Because of their ease of synthesis, availability of
starting material and environmental friendliness, deep
eutectic solvents (DESs) have shown potential in
substituting both ionic liquids (ILs) and conventional
organic solvents for application in the chemical process
industries.[1] As a matter of fact, the potential of using
DES as solvent for applications in electrochemical,
fuel and drug processing have been studied and
reported.[2–5] To aid in the systematic studies of DESs,
Abbott and co-workers categorized DES into four
groups.[6] These include type I, which is prepared by
mixing a quaternary ammonium/phosphonium salt
with a metal halide. Type II can be generated by mixing
a quaternary ammonium/phosphonium salt with a
hydrated metal halide. Type III can be formed from
the mixture of quaternary ammonium/phosphonium
salt and a hydrogen bond donor while type IV is
synthesized by mixing a metal halide and a hydrogen
bond donor. Among the different types of DESs
aforementioned, the potential applications and physical
properties of the type III DES is the most extensively
studied. This could possibly be due to the large amount
of species that can act as hydrogen bond donors.
*Correspondence to: Farouq S. Mjalli, Petroleum and Chemical
Engineering Department, Sultan Qaboos University, Muscat,
Oman. E-mail: farouqsm@yahoo.com
© 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Curtin University is a trademark of Curtin University of Technology
gives added flexibility in terms of the design and
synthesis of task specific solvents (TSSs), it also makes
the problem more complicated because a large number
of DESs have to be generated and studied individually.
An alternative to this dilemma is to study mixtures of
DESs as this is expected to provide scientists and
engineers with the opportunity of rapidly designing
and synthesizing TSS. This can be performed by
studying the variation in properties of DES mixtures
formed from well-studied DESs and thereby
eliminating the need to keep synthesizing different
DESs and their associated difficulties.
Studying the variation in properties of DES mixtures
does not only allow researchers to rapidly design TSS,
it also presents them with the opportunity of
understanding the intermolecular interactions in the
respective DESs and their mixtures. This includes the
relative strength and extensiveness of hydrogen bond
networks and the relative abundance of H+/OH

among others available in the respective solvents.
Studies of this nature have been carried out using
binary mixtures of ionic liquids,[7,8] and mixtures of
water and ionic liquids and mixtures of molecular
solvent and ionic liquid.[9–11] The properties of whose
variations are frequently studied upon mixing include
density, viscosity and conductivity among others.
Using the excess thermodynamic properties, the
2 F. S. MJALLI AND O. U. AHMED
variation in density/molar volume can be used to gain
an understanding of the extent of bond breakage
and/or formation. Factors such as the difference in the
geometries of the unlike molecules can induce
intermolecular forces as well as the reorientation of
the molecular species.[12,13] Similar studies on the
mixture of ChCl : Urea (1 : 2) and ChCl : Glycerol
(1 : 2) have been carried out.[14] A positive deviation
of excess molar volume was observed upon addition
of ChCl : Glycerol (1 : 2) DES. The two respective
deviations indicate disruption of the more ordered
structure of ChCl : Urea (1 : 2). The consequences of
these disruptions led to a favorable decrease in
viscosity of pure ChCl : Urea (1 : 2) from about
1300 cP at 20 °C to 500 cP upon addition of
ChCl : Glycerol (1 : 2) to make up 30 mol%.
Subjecting the mixture of ChCl : Urea (1:2) and
ChCl : Ethylene glycol (1 : 2) to the same studies
resulted in negative deviation of both excess molar
volume and viscosity, which indicates interactions via
structural contribution because of the differences in
sizes and shapes of the component molecules present
in the mixture.[15]
Overall, it is this variation in properties upon mixing
that can be used to adjust the properties of a particular
solvent while not completely compromising its
efficiency especially in cases where the DES
constituents directly affect the process.[1] For example,
the choline chloride (ChCl) : glycerol system has been
used as a catalytic solvent for the mono-N-alkylation of
aromatic amines, as a biocatalytic solvent for the
conversion of ethyl valerate to butyl valerate[16] and
as an electrolyte for dye-sensitized solar cell.[1]
However, a typical ChCl : Glycerol (1 : 2) DES has a
viscosity of about 376 cP at 20 °C, which is relatively
on the high side. It is expected that upon mixing these
DES with a less viscous DES such as ChCl : Ethylene
glycol (1 : 2), the rupturing of the hydrogen bond
network may lead to a less viscous solvent. Although
a reduction in viscosity is desired, only limited amount
of viscosity breaking DES should be added so as to not
compromise the efficiency of the primary DES. This in
turn depends on the extent of the reduction of the
viscosity upon mixing, which has to be studied.
Therefore, in an effort to reduce the rigor associated
with the design and synthesis of TSS, DES mixtures
are presented as alternatives in this work. The work
particularly focuses on the variation of physical
properties of DES mixture made from Glyceline
(ChCl : Glycerol, 1 : 2 molar ratio) and Ethaline
(ChCl : EG, 1 : 2 molar ratio).
CHEMICALS
Choline chloride (ChCl), glycerol and ethylene glycol
(EG) (>98%) were supplied by Merck Chemicals
© 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
(Darmstadt, Germany). The chemical structures of the
DES constituents used in this work are as shown in
Scheme 1. Prior to DES synthesis, ChCl was dried in
an oven for at least 4 h to ensure very low moisture
content. The Karl Fisher titration analysis of the used
samples indicated water mass fraction of less than
0.0001
EXPERIMENTAL METHODS
DES preparation
Glyceline was synthesized by mixing choline chloride
(ChCl) with glycerol at a molar ratio of 1 : 2 in an
incubator shaker (Brunswick Scientific Model
INNOVA 40R) for 2 h at a mixing rate of 400 rpm
and temperature of 80 °C to yield a homogenous
transparent liquid. The standard uncertainty in molar
composition estimated to be 2.0 × 10
4. The incubator
shaker was operated at atmospheric pressure under
tight control of moisture. Ethaline was synthesized by
mixing choline chloride (ChCl) with glycerol at a
molar ratio of 1 : 2 using the same conditions as
mentioned previously. DES mixtures were prepared
by mixing Glyceline and Ethaline to make up the
following: 0, 10, 30, 50, 70 and 100 mol%
Glyceline/Ethaline. Air-tight vials were used to store
the prepared mixtures prior to physical property
measurements.
Physical property measurement
Density, viscosity, conductivity, pH and refractive
indices of the mixtures were determined using the
instruments indicated in Table 1. Table 1 also presents
the average estimated uncertainty for each measured
property. Table 2 lists the measured physical properties
of pure Ethaline and Glyceline as a function of
temperature.
RESULTS AND DISCUSSION
Melting point
The melting points of the DES mixtures were measured
as 270.73, 258.88, 268.05, 276.5 and 252.86 K for 10,
Scheme 1. Chemical structure of the deep eutectic solvent
component.
Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering ETHALINE–GLYCELINE 3
Table 1. Physical property measurement.

Physical property Measurement device Standard uncertainty

Melting point TA-Q20 Differential Scanning Calorimeter (DSC) Cooling system: u(Tm) = 0.01 °C
Liquid nitrogen quench system
Density Anton Paar DMA4500M Temp. control: Techne-Tempette TE-8A u(ρ) = 0.0001 g/cm3
(external water circulator)
Viscosity Anton Paar RheolabQc Temp. control: Techne-Tempette TE-8A u(μ) = 0.1 cP
(external water circulator)
Conductivity Jenway conductivity meter (model 4520) u(κ) = 5 μS/cm
pH Thermo Scientific 3 star pH Bench top meter Calibration: Standard pH u(pH) = 0.05
buffers Temp. control: JulaboLabortechnik (external water circulator)
Refractive index Bellingham and Stanley Abbe Refractometer(model 60/ED) with a u(nD) = 0.001
sodium D1 line Calibration: Deionized water

Table 2. Pure physical properties of Ethaline (eth) and Glyceline (gly) at different temperatures.

Density (g.Cm
3) Viscosity (cP) Refractive index Conductivity

Temperature (°C) Ethaline Glyceline Ethaline Glyceline Ethaline Glyceline Ethaline Glyceline
20 1.142 1.1932 52.1 376.0 1.471 1.486 6.17 2.03
30 1.136 1.1878 32.1 188.0 1.468 1.484 7.38 2.63
40 1.131 1.1822 21.3 104.0 1.466 1.482 9.62 3.77
50 1.125 1.1767 16.2 64.0 1.463 1.479 13.33 4.58
60 1.119 1.1712 12.1 42.0 1.460 1.477 16.21 6.45
70 1.113 1.1657 9.1 29.0 1.458 1.475 18.48 8.14
80 1.107 1.1603 7.1 20.0 1.455 1.472 20.82 9.51

30, 50, 70 and 90 mol% Glyceline, respectively. It can
be seen that the melting point of the mixture increased
from 207.15 K of pure Ethaline[1] to 270.73 K for
10 mol% Glyceline. A maximum freezing point of
276.5 K was attained at a molar composition of 70%
Glyceline. At this mixture composition, and
considering the freezing point depression as compared
with the melting point of choline chloride (575.15 K),
a minimum depression of 299.0 K is attained.
Compared with the previously reported DES mixtures
of Reline : Glyceline[14] and Reline : Ethaline,[5] the
depression achieved by these two mixtures were
291.9 K (at a mixture composition of 10% Glyceline)
and 320.9 K (at a mixture composition of 20%
Ethaline), respectively. The effect of adding more
Glyceline resulted in mixtures with melting points
larger that of the constituting pure DESs. This can be
attributed to the formation of new intermolecular
interactions between the two DES molecular structures,
resulting in a distortion to the original H-bonding
between the pure DES components (salt and HBD).
As a result, the degree of freezing point depression of
the two DES is reduced.
Molar volume
The variation of molar volume upon addition of
Glyceline was studied at different temperatures. The
molar volume of pure Ethaline was found to be
© 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
76.97 cm3/mol while that of Glyceline was determined
as 90.45 cm3/mol. The higher molar volume of
Glyceline can be attributed to the fact that Glyceline
contains glycerol as the H-bond donor, which has
larger number of atoms and OH groups as compared
with ethylene glycol in Ethaline. The molar volume
of the Ethaline decreased slightly from 76.97 to
73.75 cm3/mol (20 °C) upon addition of Glyceline to
make up 10 mol% Glyceline. Adding more Glyceline
to make up 30 mol% Glyceline resulted in an increase
in the molar volume to 77.28 cm3/mol. A continuous
increase in molar volume was observed as more
Glyceline was added to reach a maximum of
92.75 cm3/mol at 90 mol% Glyceline. The result
suggests that adding small amounts of Glyceline to
Ethaline leads to a slightly stronger interaction between
the constituent molecules. However, this stronger
interaction will be disrupted upon addition of more
Glyceline. This was assumed to be due to the rupturing
of the ChCl: ethylene glycol H-bonds and the
replacement of the more compact ethylene glycol
molecules with the bulkier glycerol molecules to form
the ChCl : glycerol H-bonds. On the other hand, adding
a small amount of Ethaline to Glyceline will result in
disruption of the existing interaction between the ChCl
and glycerol molecules and the formation of weaker
interaction with a consequent longer bond length and
larger molar volume. This trend was observed for all
the temperature range considered.
Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
4 F. S. MJALLI AND O. U. AHMED
Figure 1. Variation of deep eutectic solvent mixture molar
volume as a function of Glyceline molar fraction and
temperature.
The molar volume was observed to increase with the
increase in temperature. Because molar volume is the
volume occupied by a mole of substance, it gives an
indication of the length of the bonds between the atoms
of the molecules. The bond of interest here is hydrogen
bonding (H-bond), the network of which is believed to
be the reason behind the formation of DESs in the first
place. It is therefore safe to assume that the highly
extensive H-bond between the DES components will
lead to smaller H-bond length and consequently
smaller molar volume. The observed increase in the
molar volume with temperature can then be attributed
to the weakening and consequent increase in bond
length and molar volume. However, the increase in
molar volume with temperature was observed to be
only marginal (2.49 cm3/mol ± 0.06) for all the
mixtures (Fig. 1).
Viscosity
The variation in Ethaline degree of fluidity (as
indicated by viscosity) as a function of Glyceline
mol% and temperature was studied at different
temperatures. The viscosity of pure Ethaline was
measured as 52.1 cP. Upon addition of Glyceline to
make up 10 mol% Glyceline, only a slight increase in
viscosity (60.4 cP) was observed. The viscosity was
observed to oscillate around this value up to 50 mol%
Glyceline. Adding more Glyceline resulted in a more
pronounced increase to 93.1, 249.0 and 376.0 cP at
70, 90 and 100 mol% Glyceline, respectively, as shown
in Fig. 2. Hydrogen bonding, electrostatic and Van der
Waals interactions are said to govern the viscosity of
DESs. Therefore as Glyceline was added to Ethaline,
glycerol is expected to alter the interactions that exist
between the choline chloride and ethylene glycol
molecules, which could be accompanied by a change
© 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
Figure 2. Variation of deep eutectic solvent mixture viscosity
as a function of Glyceline molar fraction and temperature.
in the viscosity of the mixture. However, it was found
that the effect of the addition of Glyceline was not
pronounced up to 50 mol% Glyceline possibly because
both glycerol and ethylene glycol have similar
hydrogen bonding capability as can be seen from their
respective Hildebrand and Hansen solubility
parameters.[17] It can be assumed, then, that the
quantity of the glycerol present was not enough to
significantly alter the interactions in terms of bond
length and mobility between the Ethaline constituent’s
molecules. This trend was observed to be the same for
all the temperatures measured. In comparison with the
results obtained in our previous work, the viscosity
reduction from 188 cP of pure Glyceline to 149 cP of
10 mol% Ethaline (90 mol% Glyceline) at 30 °C is
similar to the reduction obtained by the 10 mol%
Glyceline of Reline : Glyceline mixture.[14] However,
this is less than the reduction obtained by adding
Ethaline to make up 10 mol% Ethaline of the
Reline : Ethaline mixture.[15] Addition of Ethaline
resulted in geometric decrease in viscosity as in the
case of the Reline : Glyceline[14] and the
Reline : Ethaline[15] mixtures at low temperature.
The viscosities of the pure DESs and their mixtures
decrease with the increase in temperature. This was as
a result of the corresponding increase in vibration of
the constituent’s molecules because of the increase in
kinetic energy with temperature. This results in the
weakening of bond strength and increasing bond length
with a consequent increase in mobility of the
constituents and thereby reduction in viscosity.
Fig. 3 shows how the ratio of the viscosity of a
mixture at a given shear rate to the viscosity of the
mixture at the lowest shear rate (μ/μo) varies with
increasing shear rate. All the mixtures showed minimal
changes in relative viscosity with variation in shear
rate. Therefore, these mixtures can be regarded to
possess Newtonian behavior. This behavior is different
than that attained by the Reline : Glyceline[14] and the
Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering
Figure 3. Variation of relative viscosity of deep eutectic
solvent mixtures as a function shear rate.
Reline : Ethaline[15] DES mixtures where a clear shear
thinning was identified. It can be realized that the
existence of Reline in the reported mixtures has a
pronounced influence on the variation of fluidity with
respect to shear rate.
Intermolecular interactions
Using Equation [1], the excess molar volumes V Em of the
mixtures were calculated, and the results were plotted
in Fig. 4.
2 The negative deviation in VEm was also observed to
V Em ¼ V m
∑ xi V m;i (1)
i¼1
where Vm is the molar volume of the mixture, xi is the
mole fraction, and Vm , i is the molar volume of
component i, respectively.
Figure 4. Plot of excess molar volume as a function of
Glyceline mole fraction and temperature.
© 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
ETHALINE–GLYCELINE 5
Three types of interactions have been identified as
existing between molecules in a mixture and
responsible for the variation in excess molar
volumes.[18] These are (1) structural contribution due
to the difference in size and shape of the component
molecules present in the mixture, (2) chemical or
specific interactions and (3) weak dipole–dipole
interactions. While interactions mentioned in (1) and
(2) previously lead to a negative contribution to the
VEm, the interaction mentioned in (3) previously leads
to a positive contribution to the molar volume.
Therefore, upon the addition of Glyceline to Ethaline,
a series of H-bond breakage and formation led to a
more favorable packing effect, where the molecules
fit with each other’s structure. Furthermore, the
negative contribution indicates a stronger interaction
upon the addition of Glyceline, possibly because of
formation of stronger H-bond and a more extensive
H-bond network. The variation of VEm with Glyceline
mole percent reached a minimum at 10 mol%
Glyceline. Upon addition of Glyceline, the deviation
in excess molar volume approached zero and
subsequently reached a maximum positive deviation
at 90 mol% Glyceline. Similar alternating behavior
has been observed in studies using ionic liquids
mixtures.[19–22] The result suggests that the addition
of small amount of Glyceline to Ethaline leads to
interactions similar to those mentioned in (1) and/or
(2) while addition of Ethaline to Glyceline result in
weak dipole–dipole interactions of type (3).
increase with the increase in temperature at 10 mol%
Glyceline indicating an increase in the interactions
mentioned in (1) and/or (2). However, the reverse
was observed at 90 mol% Glyceline, which indicates
weakening in the interaction mentioned in (3) and a
consequent expansion of the mixture. For modeling
the variation of excess molar volume, the Redlich–
Kister model (Equation [2]) was used.
m
V Em;RK ¼ xE xG ∑ ai ð1
xG Þi (2)
i¼0
where xE and xG stand for Ethaline and Glyceline
molar fractions, and ai’s are the model parameters.
Table 3 shows the parameters for all the studied
temperatures. The regression was carried out using an
optimization based on genetic algorithms technique
with an objective function shown in Equation [3]:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
n  2
E;i
σ ¼ ∑ V E;i m; exp
V m;RK =ðn
mÞ (3)
i¼1
Very small values of average relative deviation were
obtained after optimization, which indicates high
Asia-Pac. J. Chem. Eng. (2017)
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6 F. S. MJALLI AND O. U. AHMED Asia-Pacific Journal of Chemical Engineering
Table 3. Redlich-Kister model parameters for the excess volume (V Em ) of Ethaline + Glyceline mixtures.

Temperature (°C) a0 a1 a2 a3 a4 ARD SD

20
11.401 2.785 7.440 84.801 0.044 0.306 0.176
30
11.560 3.815 7.772 85.171 0.039 0.268 0.155
40
11.631 3.364 8.832 85.820 0.046 0.315 0.182
50
11.759 3.967 9.080 86.164 0.050 0.344 0.198
60
11.918 4.308 10.146 88.541 0.043 0.300 0.173
70
11.931 4.256 9.951 90.656 0.042 0.293 0.169
80
12.017 3.609 9.729 93.807 0.045 0.313 0.181

ARD, average relative deviation; SD, standard deviation.

model accuracy. Furthermore, the standard deviation is
less than 0.2 for all measured temperatures, which
indicates the close distribution of the experimental
values to the model predicted ones. The experimental
and fitted excess volume profiles are shown in Fig. 4.
Refractive index (RI)
The refractive indices of the mixtures were measured
and presented in Fig. 5. It can be seen that the variation
of the RI with Glyceline mole fraction is not
monotonic. The RI of pure Ethaline (1.4707 at 20 °C)
is lower than that of pure Glyceline (1.4864 at
20 °C). Upon addition of Glyceline to produce
10 mol% Glyceline mixture, a slight increase was
observed from 1.4707 to 1.4725. Adding more
Glyceline to reach 30 mol% led to a decrease in RI
(1.4699). Subsequent additions of Glyceline resulted
in a continuous increase in RI until it approached that
of pure Glyceline. This was observed to be the same
for all temperatures considered. While the RI of
Reline-based mixtures was observed to decrease
linearly by 0.0201 and 0.0358 upon the addition
Glyceline and Ethaline, respectively, the Ethaline RI
increased nonlinearly by 0.0157 upon addition of
Glyceline. It can be seen that the plot of density against
Glyceline molar fraction is not monotonic, which was
also the case in molar volume measurements.
The RI for the individual mixtures was observed to
decrease with increase in temperature. This was
expected because the RI is related to the density of
the mixture. The average reduction in the RI of the
mixtures upon decrease in temperature from 20 to
80 °C was determined as 0.01497 ± 0.00054.
Conductivity
The conductivity of the mixtures was also observed to
be non-monotonically changing as more Glyceline is
added to the mixture. This is depicted in Fig. 6. Partly
because of their respective viscosities, pure Ethaline
(6.17 mS/cm, 20 °C) is more conductive than pure
Glyceline (2.03 mS/cm, 20 °C). The conductivity value
increased to 9.64 mS/cm as Glyceline was added to
form the 10 mol% Glyceline mixture. This increase is
more pronounced at lower temperatures. More addition
of Glyceline (30 mol%) resulted in conductivity value
of 5.21 mS/cm, which is lower than that obtained for
pure Ethaline for all temperatures. Subsequent
additions of Glyceline resulted in a steady decrease in
conductivity to approach the value of pure Glyceline.
The decrease in conductivity with increase in mole

Figure 5. Plot of variation of refractive index as a function of Figure 6. Plot of variation of conductivity as a function of
Glyceline mole fraction and temperature. Glyceline mole fraction and temperature.
© 2017 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2017)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering
fraction of Glyceline is expected as the increase in the
mole fraction of Glyceline led to the increase in
viscosity of the mixture. Similar observations were
made in our previous works.[14,15] This can be
attributed to the fact that the more the viscosity of a
fluid, the less the motion of the ionic species, which
leads to lower conductivity of the fluid.[23]
Increasing temperature led to increase in the
conductivity of all the mixtures studied partly because
of the accompanied decrease in viscosity. Upon the
increase in temperature (20 to 80 °C), the
conductivities of pure Ethaline and Glyceline increased
by 14.65 and 7.48 mS/cm, respectively. The average
increase in conductivities of the mixtures is
11.05 mS/cm ± 0.67.
pH
Figure 7 shows the pH values of the various mixtures
of Ethaline and Glyceline. Pure Ethaline with a pH of
4.676 is acidic as compared with pure Glyceline with
a pH of 7.543. It can be seen that upon addition of
Glyceline to generate the 10 mol% Glyceline, the pH
increased to about 7.983, which is slightly basic.
Addition of more Glyceline did not have much effect
on the pH of the mixture. In fact the pH stabilized at
an average of 7.735 ± 0.186 at 20 °C and
7.098 ± 0.227 at 80 °C for all studied mixtures.
A slight decrease in pH with increasing temperature
was observed. The pH decreased by 0.655, 0.532,
0.663, 0.700, 0.593, 0.616 and 0.715 for 0, 10, 30,
50, 70, 90 and 100 mol% Glyceline, respectively, when
temperature was increased from 20 to 80 °C. This is an
interesting behavior of this mixture, as a little addition
of Glyceline results in a considerable change of the
mixture acidity. This behavior is similar to the reported
pH data for the addition of Reline to Ethaline.[14]
Figure 7. Plot of variation of pH as a function of Glyceline
mole fraction and temperature.
© 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
ETHALINE–GLYCELINE 7
CONCLUSION
Investigation into the variation of excess molar volume
and physical properties of Ethaline: Glyceline mixture
were carried out in this work. The investigation was
conducted by varying the molar fraction of Glyceline
(0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) and temperature within
the range of 20–80 °C.
While the melting point of the mixture was observed
to be generally low (<276.5 K), no specific pattern can
be inferred. The molar volume of the mixture decreased
slightly when small amount of Glyceline (10 mol%)
was present. However, further addition of Glyceline
resulted in an increase in molar volume to a value
greater than that of pure Glyceline at 90 mol%
Glyceline. It was concluded that adding a small amount
of either Glyceline to Ethaline or vice versa leads to an
unexpected behavior, where more or less interaction
than usual was observed. However, the effect of the
addition of Glyceline to Ethaline was expected as
similar behavior was observed in our previous studies
on other similar DES mixtures. The calculated excess
molar volume as function of Glyceline molar fraction
attained a sinusoidal trend, where at small Glyceline
molar percentage (10 mol%), the negative deviation
suggests strong interactions such as those because of
H-bonding or to difference in sizes and shapes of the
constituent molecules. At higher Glyceline molar
percentage (90 mol%), the positive excess molar
volume is a sign of weak interactions because of the
predominant dispersion forces. Only slight changes in
RI and conductivity were observed with the change in
the molar content of Glyceline. However, Glyceline
seems to have more influence on the pH of the mixture.
It can be concluded that mixing the two considered
DESs resulted in varying the properties of the resultant
mixture, which can further be used in understanding
the predominant interactions between the chemical
species present in the mixture. This can be utilized to
customize the properties of the individual DESs by
mixing carefully measured quantities of each DES.
Acknowledgement
The authors appreciate the support of College of
Engineering, Sultan Qaboos University, Muscat,
Oman.
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