Accepted Manuscript

Title: Separation of the Ethanol/Water Azeotropic Mixture

using Ionic Liquids and Deep Eutectic Solvents
Author: Nansi Gjineci Elenitsa Boli Andromachi Tzani
Anastasia Detsi Epaminondas Voutsas
PII:
DOI:
Reference:

S0378-3812(15)30063-7
http://dx.doi.org/doi:10.1016/j.fluid.2015.07.048
FLUID 10700

To appear in:

Fluid Phase Equilibria

Received date:
Revised date:
Accepted date:

6-7-2015
25-7-2015
26-7-2015

Please cite this article as: Nansi Gjineci, Elenitsa Boli, Andromachi Tzani,
Anastasia Detsi, Epaminondas Voutsas, Separation of the Ethanol/Water Azeotropic
Mixture using Ionic Liquids and Deep Eutectic Solvents, Fluid Phase Equilibria
http://dx.doi.org/10.1016/j.fluid.2015.07.048
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Separation of the Ethanol/Water Azeotropic Mixture using Ionic Liquids and Deep Eutectic Solvents
Nansi Gjineci1, Elenitsa Boli1, Andromachi Tzani2, Anastasia Detsi2, Epaminondas Voutsas1,*
1

Laboratory of Thermodynamics and Transport Phenomena

2

Laboratory of Organic Chemistry

School of Chemical Engineering, National Technical University of Athens

9, Heroon Polytechniou Str., Zografou Campus, 15780 Athens, Greece

Abstract
Two ethanolamine-based ionic liquids (ILs) and two choline chloride-based deep eutectic solvents (DESs) were synthesized and evaluated as
entrainers for the separation of the ethanol/water azeotropic mixture. Isobaric vapor-liquid equilibrium data of the ternary system
ethanol/water/IL or DES were measured using an ebuliometer at 101.3 kPa. The ILs examined were 2-hydroxy ethylammonium acetate and 2hydroxy ethylammonium hexanoate, while the DESs were choline chloride:urea (1:2) and choline chloride:triethylene glycol (1:3). In all cases,
an increase of the relative volatility and, consequently, a displacement of the azeotropic point was observed. Depending on the entrainer,
concentrations of about 5.5 to 9 % w/w were adequate for the complete elimination of the azeotrope. Recoverability and biodegradation tests
were carried out for all ILs and DESs. DESs were found to be biodegradable, while ILs exhibited lower biodegradation capacity than DESs.
Furthermore, analysis with 1H NMR proved that all entrainers can be recycled and reused. Finally, thermodynamic modeling of the
ethanol/water/IL or DES mixtures was performed with the UNIQUAC and NRTL models. The results for both models were found to be in good
agreement with the experimental data.
Keywords: ethanol/water azeotrope, ionic liquids, deep eutectic solvents, vapor-liquid equilibrium, recoverability, biodegradability.
*

Corresponding author. Tel.: +302107723971; fax: +302107723155

E-mail address: evoutsas@chemeng.ntua.gr (E. Voutsas)

1. Introduction
Increasing concern about environmental issues, as well as the establishment of new regulations, has directed the attention of the scientific
community to novel processes based on greener technologies. In terms of biofuels, bioethanol is considered as the most promising alternative
on short and medium terms due to its excellent properties as alternative biofuel. An important problem for biofuel industrial processes is the
presence of azeotropic or close-boiling mixtures in their production, for example ethanol with water, since the separation is impossible by
ordinary distillation. Several potential processes for separating azeotropes have come to light with extractive distillation being the most widely
used process. The extractive distillation involves the addition in the system of a new heavy chemical compound (entrainer) which interacts with
the components by altering their relative volatilities [1-3].
Ionic liquids (ILs) and Deep Eutectic Solvents (DESs) have been evaluated as entrainers for extractive distillation [4-7], due to their unique
thermophysical properties. ILs are molten salts, consisting of large asymmetric organic cations and organic or inorganic anions. The low
symmetry, high vibrational freedom and charge delocalization of the ions composing an IL reduce the stability of the crystalline phases, and thus
their melting temperatures [8]. Many areas of application for ILs, except for use as entrainers, have been studied [9-11]. DESs are now widely
acknowledged as a new class of Ionic Liquid analogues because they share many characteristics and physico-chemical properties with ILs (low
vapor pressure, viscosity, density, conductivity, etc). They can be often found in literature as "Low Transition Temperatures Mixtures", (LTTMs)
[12] and are composed of two or three cheap, renewable and safe components, which are capable to self-associate through hydrogen bonding
interactions, to form a eutectic mixture with a melting point lower than that of each individual component [13]. The liquid state of the DES is
achieved through freezing point depression, whereby hydrogen-bonding interactions between an anion and a hydrogen bond donor (HBD) are
more energetically favored relative to the lattice energies of the pure constituents [14]. DESs were first reported in 2003 and since then, they have
been studied in different areas of applications such as: electrochemistry, organic synthesis, biodiesel processing and catalytic reactions [13-17].
Among the unique properties of ILs and DESs, such as negligible vapor pressure, wide liquid range, good thermal stability, non-flammability and
high dissolvability, the most important is that their physico-chemical properties can be tuned by proper selection of cation and anion in the case

of ILs or HBD in the case of DESs ("designer solvents"). Furthermore, their use as entrainers in extractive distillation can overcome the handling
problem associated with the use of solid salts due to the wide liquid range they exhibit. In addition, ionic liquids have been studied lately in
process simulations [18].
The objective of this study is the experimental evaluation of ILs and DESs as entrainers in the separation of the azeotropic ethanol/water mixture.
The ILs examined were 2-hydroxy ethylammonium acetate and 2-hydroxy ethylammonium hexanoate, while the DESs were choline
chloride:urea (1:2) and choline chloride:triethylene glycol (1:3). The chemical structure of ILs and DESs are illustrated in Figure 1.
Isobaric vapor-liquid equilibrium (VLE) measurements at 101.3 kPa and three different entrainer concentrations, 5%, 10% and 15% w/w, have
been performed. Furthermore, the VLE data were successfully modelled using the UNIQUAC and NRTL activity coefficient equations. The ILs
and DESs synthesized in this study were also investigated for their recoverability and biodegradability.
2. Materials and Methods
2.1 Materials
Ethanol (analytical reagent grade), water (HPLC gradient grade) as well as Aqualine Titrant 5 and solvent for the Karl Fischer titration were
purchased from Fischer Scientific. Ethanolamine analytical grade was purchased from SERVA. Choline chloride 98+% and hexanoic acid 98+%
were purchased from Alfa Aesar. From Alfa Aesar were also purchased acetic acid 98+% and triethylene glycol 99%. All reagents were used
without additional purification. The source and purities of the chemicals used are listed in Table 1. 1H NMR spectra (300 MHz) were recorded on
a Varian Gemini 2000 300 MHz spectrometer.

2.2 Synthesis and characterization of deep eutectic solvents and ionic liquids
2.2.1 Deep eutectic solvents
Choline chloride (ChCl), urea and triethylene glycol (TEG) were dried under vacuum for at least 3 hours before use.

ChCl:urea: ChCl (0.14 mol, 20 g) and urea (0.28 mol, 16.8 g) were mixed under continuous and vigorous stirring at 70 oC for 30 min, under an
inert atmosphere. The resulting colorless liquid was dried under reduced pressure for 5 h at 40 oC.
1

H NMR (300 MHz, DMSO-d6) (ppm): 5.44 (s, 8H, 2(-NH2)2, 3.78-3.85 (m, 2H, HO-CH2), 3.41 (t, 2H, J = 5.1 Hz, -N-CH2), 3.12 (s, 9H, (-

CH3)3).
ChCl:TEG: ChCl (0.06 mol, 8 g) and TEG (0.180 mol, 27.0 g) were mixed under continuous and vigorous stirring at 70 oC for 3.5 h, under an
inert atmosphere. The resulting colorless liquid was dried under reduced pressure for 5 h at 40 oC.
1

H NMR (300 MHz, DMSO-d6) (ppm): 4.59 (brs, 7H, -OH) 3.84-3.79 (m, 2H, OH-CH2), 3.50 (s, 12H, 3(OH-CH2)2), 3.47 (d, 12H, J = 6 Hz,

3(O-CH2)2), 3.41 (d, 12H, J = 6 Hz, 3(O-CH2)2), 3.38 (d, 2H, J = 3 Hz, CH2-N), 3.11 (s, 9H, (-CH3)3).
2.2.2 Ionic liquids
Hydroxyl ammonium ILs were prepared by neutralization of a carboxylic acid with ethanolamine as described in our previous work for
analogous compounds [19]. Ethanolamine (0.5 mol, 30.2 mL) was placed in a two necked round-bottomed flask equipped with a reflux
condenser and a dropping funnel. The flask was mounted in an ice bath due to the highly exothermic nature of the acid-base reaction. Increased
heat could lead to dehydration of the salt to the corresponding amide. 0.5 mol of the appropriate carboxylic acid was added drop wise to the flask
under nitrogen atmosphere and vigorous stirring using a magnetic stirrer. Stirring was continued for 24 hours at room temperature in order to
obtain a viscous clear liquid. All the newly synthesized ILs were dried for 4 h at 40 oC in vacuum before use.
2-hydroxyethylammonium acetate (IL1): Prepared following the General Procedure, using 0.5 mol (29.7mL) acetic acid. IL1 was obtained as a
light yellow liquid. 1H NMR (300 MHz, CDCl3) (pmm): 5.74 (4H, br s, -NH3+ and -OH), 3.45 (2H, t, J = 5.4 Hz, -OCH2-), 2.68 (2H, t, J = 5.4
Hz, -CH2-NH3+), 1.76 (3H, s, CH3).
2-hydroxyethylammonium hexanoate (IL2): Prepared following the General Procedure, using 0.5 mol (58.1 mL) hexanoic acid. IL2 was
obtained as an orange liquid. 1H NMR (300 MHz, CDCl3) (pmm): 6.62 (br s, 4H, NH3+, OH), 3.76 (t, J = 3.0 Hz, 2H, HO-CH2-), 2.99 (t, J =

3.0 Hz, 2H, -CH2-NH3+), 2.14 (t, J = 6 Hz, 2H, CH2COO-), 1.58 1.48 (q, J = 9 Hz, 2H, CH3CH2CH2CH2-), 1.37-1.21 (m, 4H, CH3CH2CH2CH2), 0.88 (t, J = 6.0 Hz, 3H, -CH3).

2.3 Apparatus and procedures

2.3.1 Vapor-liquid equilibrium (VLE) measurements
The apparatus used for the VLE measurements is FISCHER LABODEST VLE 602 (i-Fischer Engineering GmbH), which has been
previously described in Voutsas et al. [20]. Actually, it is an ebuliometer which is composed of a heating cell, an equilibrium cell and two watercooled condensers/coolers. A fixed value of pressure was set in each experiment and the corresponding equilibrium temperature was measured.
Pressure is measured with an uncertainty of 0.01 kPa, while temperature with an uncertainty of 0.01 K. After the equilibrium was attained (30-45
minutes approximately), liquid and condensed vapor samples were withdrawn from the apparatus. Their composition was determined at least
three times using a TitroLine Karl Fischer Titrator. The entrainers mass fraction of a sample was determined with gravimetric method, after
evaporating all the ethanol and water of the mixture. For high water mole fractions, the mass of the sample was quite small, ca. 0.05-0.08 gr.
Molar fractions were determined with an uncertainty of 0.001.

2.3.2 Recoverability test

In order to evaluate the recoverability of the ILs and DESs used in this study, an aqueous solution of about 5% w/w was made for each IL-DES
and underwent a boiling procedure, simulating the conditions of an extractive distillation column reboiler (1.5-2 hours at 110 C approximately).
After each run, the entrainer was recovered by evaporating the water in vacuo and reused for the subsequent run. The 1H NMR spectrum of the
recovered entrainer was then obtained.

2.3.3 Biodegradability test

Although ILs and DESs may help reduce the risk of air pollution, their release to aquatic environments could cause severe water contamination
because of their potential toxicity and inaccessible biodegradability. The determination of the biodegradability level of organic substances such
as ILs and DESs is essential in order to estimate their environmental print and possible negative impact to environment. During the process of
biodegradation, organic substances are decomposed by micro-organisms (mainly aerobic bacteria) into simpler substances such as carbon
dioxide, water and ammonia. In this work, VELP BOD manometric apparatus was used to measure the BOD of the IL-DES inoculated samples.
This method consists of filling each BOD flask with specific amount of IL or DES, 135 mL aqueous solution of nutrients and 15 mL
microorganisms. The seed source of microorganisms was mixed liquor which was taken from a secondary sedimentation tank of urban waste
water in Athens, Greece. The preparation of the solution of nutrients is described in our previous work [6]. The intent of this work is to measure
only the carbonaceous demand during the biodegradation, not the nitrogenous one. Inhibition of nitrogenous bacteria was achieved by a thiourea
solution (2 g thiourea to a final volume of 1 L with distilled water) which was also added to BOD samples (0.5 mL of the solution in each flask).
Thus, the BOD values will be reported as CBOD (organic carbon), since the oxygen required to oxidize nitrogen is not taken into account. A
blank solution was also prepared, containing only nutrients and mixed liquor.
The pH of all samples was maintained in a range from 6.5 to 7.5 which is suitable for bacterial growth and the Five-Day BOD (BOD5) incubation
was performed at 20 0C in the dark.

3. Results and discussion

3.1 Vapor-liquid equilibrium
VLE is calculated from the fugacity equality in both phases, as seen in Eq. (1). Using the - approach, we obtain the equilibrium Eq. (2).
Fugacity coefficients were calculated using the virial equation of state truncated at the second coefficient with Tsonopoulos correlations [21].
Vapor pressures and saturated liquid molar volumes required for the estimation of the Poynting effect (PE) were calculated from DIPPR
equations [22]. Finally, activity coefficients were calculated from Eq. (4).

fiV = fi L

(1)

yi p = xi i p PEi
V
i

s
i

s
i

(2)

vis ( p pis )

PEi = exp
RT

(3)

yiiV p
xi pisis PEi
The relative volatility of ethanol (1) with respect to water (2) is calculated by:

i =

12 =

y1 / x1
y2 / x2

(4)

(5)

3.2 Experimental data for the ethanol/water/IL ternary systems

VLE of the ethanol/water/entrainer ternary systems were measured for ethanol liquid phase concentration, on an entrainer-free basis, above 70%
molar for three initial entrainer concentrations in the feed solution, 5%, 10% and 15% w/w, except for ChCl:urea, which was used with initial
concentrations of 5% and 10% w/w. All the measurements were performed at a pressure of 1013.3 mbar. The experimental data are tabulated in
Tables 2, 3, 4 and 5.
As shown, the ethanol/water system equilibrium temperatures increase due to the addition of the non-volatile entainer; the more entrainer is
introduced in the system, the higher the equilibrium temperatures are. Relative volatility increases as the mass fraction of the entainer increases
and the azeotrope shifts to higher ethanol concentrations. All entrainers exhibit a salting-out effect which is substantially enhanced as the
entrainer concentration increases. Choline chloride:urea and 2-hydroxy ethylammonium acetate have similar and greater effect on the relative
volatility of the ethanol/water system than choline chloride:triethylene glycol and 2-hydroxy ethylammonium hexanoate that also have similar
behavior each other. Comparison with other entrainers presented in the literature [6, 23] indicate that ChCl;urea (1:2) and 2-hydroxy

ethylammonium acetate exhibit higher relative volatilities than other commonly used ILs, such as [BMIM][Br], [EMIM][Br], [EMIM][DEP] and
[BMIM][PF6] .
3.3 Thermodynamic modeling
The local composition activity coefficient models UNIQUAC [24] and NRTL [25] were used to calculate the activity coefficients of the ternary
systems using Eq. (2). The two binary interaction parameters for the ethanol/water system where obtained as mean values from the temperaturedependent parameters proposed by Voutsas et al. [20], for the temperature range examined in this work. The binary interaction parameters
between ethanol and entrainers as well as those between water and entrainers were determined by fitting the ternary VLE data, and they are
presented in Tables 6 and 7 for the two models. The objective function which was minimized is the following:
1
OF =
NP

{(T
NP

exp

calc
exp
calc

Ti calc ) + 100 ( y1,exp

i y1,i ) + 10 ( 12, i 12,i )
2

i =1

(6)

As demonstrated in Table 8, the calculated values of temperature (T), ethanol vapor phase molar fraction (y1) and relative volatility (12) are in
close agreements with the experimental data. For the UNIQUAC model the mean temperature deviations are equal to 0.37 K, the vapor phase
molar fractions are calculated with a mean deviation of c.a. 0.0012, while relative volatilities are predicted with a mean error of 1.35%. For
NRTL model, mean temperature deviations are at 0.20 K, vapor phase molar fractions are calculated with a mean deviation of c.a. 0.0013, while
relative volatilities are predicted with a mean error of 1.48%.
Figures 2 to 5 present the experimental relative volatility data along with the models predictions. It should be noted that the calculated curves
have been obtained by setting a constant IL or DES mass fraction, i.e. 5, 10 and 15% w/w.
In Table 9 the calculated by both models minimum entrainer concentrations for the complete elimination of the azeotrope are presented. These
values have been calculated by setting the relative volatility equal to one at the limit of unity ethanol molar fraction. For choline chloride:urea
and 2-hydroxy ethylammonium acetate this concentration is about 5.5.% w/w, while for choline chloride:triethylene glycol and 2-hydroxy

ethylammonium hexanoate about 9% w/w. In all cases, the two models give similar results except from 2-hydroxy ethylammonium hexanoate,
where UNIQUAC fits better the experimental data than NRTL.

3.4 Recoverability assessment

The 1H NMR spectra of the entrainers obtained at the end of the first and the fifth boiling cycles (Supplementary data) indicate that all four
entrainers are fully recoverable and do not undergo any changes in their chemical structure during the performed experimental procedure for five
cycles.

3.5 Biodegradability assessment

Since the oxygen required to oxidize nitrogen is not taken into account and the activity of nitrogenous bacteria was inhibited, is not included in
the calculation of biodegradation level of ILs and DESs studied. The terms that will be used for the calculations are the following:
CBOD5: Oxygen demand by microorganisms for degradation of the organic compound within five days (only carbonaceous stage).
UCBOD: Oxygen demand by microorganisms for the ultimate degradation of the organic compound referring only to the conversion of organic
carbon to carbon dioxide, water, and new microbial cellular constituents (ultimate carbonaceous demand).
CBOD5 is the indication of the apparatus after the subtraction of the endogenous respiration of the microorganisms (blank solution) and UCBOD
is the theoretically demanded oxygen for a complete oxidation of the IL after the subtraction of the amount that corresponds to nitrogen
oxidation. The biodegradation level of the organic substance is calculated and expressed by the ratio CBOD5/UCBOD [18]. The amount of ILs
and DESs required was calculated from the general reaction that describes the biodegradation process.
Taking into consideration the measured CBOD5 and the quantities of ILs and DESs used in CBOD5 tests, the values of CBOD5, UCBOD and the
CBOD5/UCBOD ratio were calculated and are presented in Table 10. From the experimental results, it can be stated that the DESs and ILs under

examination present remarkable biodegradability potential since the percentage of organic carbon biodegraded was higher than 80% in case of
ChCl:urea and varies from 42.8% to 51.7% for all the other substances.

4. Conclusions
The isobaric VLE data for the ternary systems ethanol/water/IL or DES show that the introduction of the entrainer leads to an increase of relative
volatility and the displacement of the azeotropic point of the ethanol/water system. The azeotropic point completely disappears for concentrations
of about 5.5% w/w for ChCl:urea (1:2) and 2-hydroxyethylammonium acetate, and about 9% w/w for 2-hydroxy ethylammonium hexanoate and
ChCl:triethylene glycol (1:3). This indicates that they are promising entrainers for extractive distillation. The recoverability of the entrainers
examined was proved after recovering the entrainer without change of its initial chemical structure after five boiling cycles. As far as
biodegradation is concerned, the percentage of organic carbon biodegraded was higher than 80% in case of ChCl:urea (1:2) and varies from
42.8% to 51.7% for the other entrainers. Finally, the thermodynamic modeling of the ternary systems with UNIQUAC and NRTL resulted to
satisfactory agreement with the experimental data.
List of symbols
<xps:span class=deft>p</xps:span> <xps:span class=defd> pressure</xps:span>
<xps:span class=deft>T</xps:span> <xps:span class=defd> temperature</xps:span>
<xps:span class=deft> fiV , fi L </xps:span> <xps:span class=defd>fugacity of component i in the vapor and liquid phase </xps:span>
<xps:span class=deft>yi, xi</xps:span> <xps:span class=defd>

molar composition of component i in the vapor and liquid phase</xps:span>

<xps:span class=deft> iV </xps:span> <xps:span class=defd>

fugacity coefficient of component i in the vapor phase</xps:span>

<xps:span class=deft> is </xps:span> <xps:span class=defd>

fugacity coefficient of component i in its saturation state</xps:span>

<xps:span class=deft> pis </xps:span> <xps:span class=defd>

vapor pressure of component i</xps:span>

<xps:span class=deft>PEi</xps:span> <xps:span class=defd>

Poynting effect of component i</xps:span>

<xps:span class=deft> vis </xps:span> <xps:span class=defd>

saturated molar volume of component i</xps:span>

<xps:span class=deft>i</xps:span> <xps:span class=defd> activity coefficient of component i</xps:span>

<xps:span class=deft>12</xps:span> <xps:span class=defd>
<xps:span class=deft>

<xps:span class=deft>

uij
R
gij
R

relative volatility of component 1 with respect to component 2</xps:span>

</xps:span> <xps:span class=defd>

binary interaction parameter of the UNIQUAC model</xps:span>

</xps:span> <xps:span class=defd>

binary interaction parameter of the NRTL model</xps:span>

Acronyms
IL(s)

ionic liquid(s)

DES(s)

deep eutectic solvent(s)

HBD

hydrogen bond donor

VLE

vapor-liquid equilibrium

NMR

nuclear magnetic resonance

BOD

biochemical oxygen demand

CBOD

carbonaceous BOD

UCBOD

ultimate carbonaceous BOD

NP

number of experimental data points

Superscript
<xps:span class=deft>exp</xps:span> <xps:span class=defd>

experimental value</xps:span>

<xps:span class=deft>calc</xps:span> <xps:span class=defd>

calculated value</xps:span>

Subscript
<xps:span class=deft>IL-free</xps:span> <xps:span class=defd>
DES-free

ethanol/water pseudo-binary mixture</xps:span>

ethanol/water pseudo-binary mixture

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Figure captions
Figure 1. Structures of the ionic liquids and deep eutectic solvents examined in this study.
Figure 2. Experimental relative volatility of the ethanol/water/ChCl:urea (1:2) system using: ( ) 5%, ( ) 10% w/w DES; solid curves
correspond to UNIQUAC and dotted curves to NRTL model predictions.
Figure 3. Experimental relative volatility of the ethanol/water/ChCl:triethylene glycol (1:3) system using: ( ) 5%, ( ) 10% and ( ) 15% w/w
DES; solid curves correspond to UNIQUAC and dotted curves to NRTL model predictions.

Figure 4. Experimental relative volatility of the ethanol/water/2-hydroxy ethylammonium acetate system using: ( ) 5%, ( ) 10% and ( ) 15%
w/w IL; solid curves correspond to UNIQUAC and dotted curves to NRTL model predictions.
Figure 5. Experimental relative volatility of the ethanol/water/2-hydroxy ethylammonium hexanoate system using: ( ) 5%, ( ) 10% and ( )
15% w/w IL; solid curves correspond to UNIQUAC and dotted curves to NRTL model predictions.

H 3N

OH

HO

O
O

NH3

2-hydroxy ethylammonium acetate 2-hydroxy ethylammonium hexanoate

N+
HO

C l-

HO

choline chloride:triethylene glycol

Figure 1

OH

HO

N+
Cl -

H2 N

NH 2

choline chloride:urea

Figure 2

Figure 3

Figure 4

Figure 5
Table 1. Materials description.
Chemical name

Source

Ethanol

Fisher Scientific

Water

Fisher Scientific

Fisher Scientific

Initial mole fraction

purity
Analytical reagent

Purification method

Final mole fraction

purity

Analysis method

None

HPLC gradient grade

None

None

grade

Aqualine Titrant 5
and solvent for Karl
Fischer titration

Choline Chloride

Alfa Aesar

Urea

98+%

None

Pure

None

Triethylene glycol

Alfa Aesar

99%

None

acetic acid

Alfa Aesar

98+%

None

hexanoic acid

Alfa Aesar

98+%

None

ethanolamine

SERVA

Analytical grade

None

ChCl:urea

synthesis

In vacuo evaporation

Choline
chloride:triethylene

ethylammonium acetate

synthesis

In vacuo evaporation

synthesis

In vacuo evaporation

spectroscopy
H/13C NMRa

spectroscopy
1

synthesis

In vacuo evaporation

hexanoate

H/13C NMRa

2-hydroxy
ethylammonium

spectroscopy
1

glycol
2-hydroxy

H/13C NMRa

Nuclear Magnetic Resonance

Table 2. Isobaric VLE data for ethanol (1)/water (2)/Choline chloride:urea (3)

H/13C NMRa

spectroscopy

w3,initial

5%

10%

w3
5.03%

T (K)
351.6

x1,DES-free
y1
1
2
12
0.815
0.843 1.037 1.899 1.223

5.57%

351.76

0.819

0.848 1.032 1.878 1.230

4.31%

351.69

0.848

0.865 1.018 1.983 1.149

5.73%

351.68

0.860

0.877 1.023 1.965 1.165

5.18%

351.58

0.916

0.923 1.012 2.065 1.096

5.02%

351.75

0.943

0.947 1.002 2.092 1.070

5.33%

351.83

0.956

0.957 0.996 2.153 1.034

5.16%

351.88

0.967

0.968 0.994 2.132 1.042

10.92% 352.02

0.714

0.793 1.107 1.614 1.536

11.08% 351.83

0.788

0.842 1.074 1.676 1.434

10.67% 351.47

0.846

0.881 1.061 1.763 1.347

10.01% 351.98

0.922

0.935 1.013 1.849 1.224

10.37% 351.62

0.973

0.978 1.017 1.879 1.191

10.02% 352.03

0.980

0.981 1.000 2.076 1.129

Table 3. Isobaric VLE data for ethanol (1)/water (2)/Choline chloride:triethylene glycol (3)
w3,initial
5%

w3
T (K) x1,IL-free
y1
1
2
12
4.98% 351.88
0.722 0.785 1.074 1.710 1.406
4.99% 351.83

0.763 0.807 1.047 1.805 1.295

4.99% 351.80

0.815 0.839 1.021 1.933 1.187

4.96% 351.76

0.862 0.873 1.005

2.05 1.097

10%

15%

4.99% 351.73

0.905

0.91 1.000 2.097 1.056

4.87% 351.78

0.956 0.957 0.993 2.158 1.027

4.93% 351.86

0.974 0.974 0.988 2.285 1.004

12.20% 352.22

0.732 0.797 1.068 1.659 1.438

10.60% 352.07

0.787 0.827 1.035 1.792 1.293

11.00% 352.03

0.836 0.862 1.018 1.864 1.225

9.00% 351.90

0.882 0.897 1.007 1.936 1.167

11.10% 352.03

0.910 0.918 0.996 2.015 1.116

8.50% 351.86

0.949 0.952 0.995 2.071 1.071

10.40% 351.80

0.943 0.946 1.000 2.090 1.071

10.46% 352.13

0.949 0.966 0.986 2.056 1.064

16.07% 352.28

0.794 0.841 1.041 1.689 1.379

14.25% 351.90

0.801 0.844 1.048 1.742 1.345

15.74% 352.28

0.833 0.866 1.020 1.770 1.296

15.37% 352.13

0.880

15.94% 352.18

0.934 0.944 0.997 1.872 1.191

15.10% 352.25

0.951 0.957 0.989 1.941 1.141

15.14% 352.20

0.971 0.975 0.990 1.871 1.159

0.9 1.011 1.831 1.227

Table 4. Isobaric VLE data for ethanol (1)/water (2)/2-hydroxy ethylammonium acetate (3)
w3,initial
5%

w3
T (K) x1,IL-free
y1
1
2
12
5.77% 351.71
0.775 0.814 1.061 1.875 1.264
3.85% 351.73

0.828 0.852 1.032

1.94 1.188

10%

15%

4.90% 351.65

0.879 0.892 1.025 2.016 1.129

3.65% 351.79

0.935

0.94 1.007 2.069 1.086

4.50% 351.70

0.968

0.97

10.34% 351.75

0.786

0.84 1.097 1.719 1.430

10.75% 352.13

0.825 0.865 1.063 1.751 1.362

10.15% 352.01

0.866 0.894 1.051 1.799 1.300

10.87% 352.11

0.891 0.913 1.043 1.806 1.279

10.71% 351.89

0.940

10.55% 351.90

0.974 0.977

15.43% 352.13

0.818 0.872 1.104 1.622 1.514

15.72% 351.96

0.887 0.916

14.72% 352.26

0.917 0.938 1.053 1.722 1.362

14.85% 352.16

0.943 0.957 1.051 1.764 1.347

1.01 2.143 1.047

0.95 1.039 1.895 1.229

1.03 2.021 1.144

1.08 1.738 1.393

Table 5. Isobaric VLE data for ethanol (1)/water (2)/2-hydroxy ethylammonium hexanoate (3)
w3,initial

5%

10%

w3
T (K) x1,IL-free
5.69% 351.82
0.803

y1
1
2
12
0.83 1.034 1.934 1.198

5.28% 351.70

0.847 0.863 1.018 2.002 1.138

5.26% 351.72

0.897 0.902 1.009 2.128 1.061

4.60% 351.81

0.946 0.947 0.995 2.205 1.024

4.89% 351.70

0.983 0.983 1.004 2.214 1.015

8.16% 351.97

0.805 0.837

8.36% 351.87

0.847 0.865 1.027 1.982

1.04 1.872 1.246

1.16

8.88% 351.79
10.58% 351.86
9.74% 351.96

15%

0.867 0.885 1.032 1.954 1.177

0.882 0.896

1.03 1.992 1.155

0.938 0.941 1.011 2.121

1.05

10.13% 351.91

0.981 0.983 1.013 2.074 1.061

15.79% 352.13

0.803 0.842 1.066 1.822

15.96% 352.20

0.846 0.874

15.36% 352.25

0.893 0.909 1.031 1.934 1.194

15.24% 352.20

0.943 0.951 1.024 1.970 1.152

14.77% 352.06

0.971 0.975 1.025 1.949 1.148

1.31

1.05 1.850 1.267

Table 6. Temperature-independent energy interaction parameters for the UNIQUACa model

Component i

Ethanol

Ethanol

Water

Ethanol

Water

Ethanol

Component j

Water

uij/R (K)
uji/R (K)

-39.14
216.27

ChCl:urea

-4700.32
2000.00

-4954.79
168.28

ChCl:triethylene glycol

124.57
-274.96

148.10
-350.08

Water

Ethanol

Water

2-hydroxy

2-hydroxy

ethylammonium

ethylammonium

acetate

hexanoate

165.22
-57.20

-43.31
-207.64

297.76
-281.81

760.39
-432.97

van der Waals volume (r) and van der Waals area (q) parameters: rEthanol=2.1055, rWater=0.9200, rChCl:urea=9.9224, rChCl:triethylene glycol=22.4412

qEthanol=1.9720, qWater=1.4000, qChCl:urea=9.12, qChCl:triethylene glycol=19.688, r2-hydroxy ethylammonium acetate =4.776, r2-hydroxy ethylammonium hexanoate =7.4736, q 2-hydroxy ethylammonium acetate =4.432,
q 2-hydroxy ethylammonium hexanoate =6.5920

Table 7. Temperature-independent energy interaction parameters for the NRTLa model.

Component

Ethanol

Ethanol

Water

Ethanol

Water

Ethanol

Water

Ethanol

Water

i
Component
j
gij/R (K)
gji/R (K)

ChCl:triethylene glycol

ChCl:urea

Water
-34.59
621.73

125.72
-1397.11

-265.87
-1598.04
a

-794.24
-2063.20

-548.74
-2110.81

2-hydroxy
ethylammonium acetate
1868.84
1364.04
-903.17
-1014.43

2-hydroxy ethylammonium
hexanoate
1173.30
138.53
2996.02
3150.43

The non-randomness parameter of the NRTL model was set equal to 0.3.

Table 8. Mean prediction errors of experimental data using UNIQUAC and NRTL.
UNIQUAC
y1,av
av ()
%12,av
1000
0.19
0.84
1.18
0.28
1.97
1.68
0.43
1.13
1.22
0.57
0.98
1.33

Entrainer
ChCl:urea
ChCl:triethylene glycol
2-hydroxy ethylammonium acetate
2-hydroxy ethylammonium hexanoate

%12,av

100
=
NP

NP

i =1

exp
calc
12,
i 12,i
exp
12,
i

1
yav =
NP

NP

i =1

NRTL
y1,av
av ()
%12,av
1000
0.25
0.80
1.03
0.18
1.97
1.89
0.26
1.30
1.50
0.10
1.16
1.49

yiexp yicalc
yiexp

Table 9. Minimum concentration % w/w of entrainer required for breaking the azeotrope of ethanol/water.
2-hydroxy ethylammonium hexanoate
2-hydroxy ethylammonium
ChCl:urea
ChCl:triethylene glycol
acetate
UNIQUAC

NRTL

UNIQUAC

NRTL

UNIQUAC

NRTL

UNIQUAC

NRTL

5.5

5.5

8.6

8.7

5.3

5.1

8.6

7.7

Table 10. Biodegradability assessment of the entrainers

ChCl:urea

ChCl:triethylene
glycol

2-hydroxy
ethylammonium

2-hydroxy
ethylammonium

CBOD5
(mgO2/L)
UCBOD
(mgO2/L)
CBOD5/
UCBOD

acetate

hexanoate

220.1

216.7

143.3

166.3

256.8

426.1

333.4

321.7

85.6%

50.9%

42.8%

51.7%