International Journal of Thermodynamics (IJoT)

ISSN 1301-9724 / e-ISSN 2146-1511

www.ijoticat.com

Vol. 19 (No. 4), pp. 244-250, 2016

doi: 10.5541/ijot.5000200071
Published online: December 1, 2016

Volumetric and Acoustic Study of a Short Protic Ionic Liquids Binary Mixture: 2Hydroxy Ethyl Ammonium Formate (2-HEAF) + 2-Hydroxy Diethyl Ammonium
Acetate (2-HDEAA)
C. Ravazzano1, K. Lima1, R. S. Andrade1,2 and M. Iglesias*,1
1
Departamento de Engenharia Qumica, Universidade Federal da Bahia, Salvador, Brasil 41210-630
Departamento de Engenharia Qumica, Universidade Salvador - UNIFACS, Salvador, Brasil 41910-560
E-mail: *miguel.iglesias@ufba.br

Received 26 August 2016, Revised 27 November 2016, Accepted 30 November 2016

Abstract
Ionic liquids are being studied extensively in the last few years, due to their amazing properties and potential
industrial applications. Despite this effort, a considerable gap of knowledge is noted in terms of thermodynamic
information related to the temperature effect on mixing trend. In this work, a binary mixture of protic ionic liquids
comprising formate and acetate anions and 2-hydroxy ethyl ammonium and 2-hydroxy diethyl ammonium cations
have been studied in terms of volumetric and acoustic properties as a function of temperature. The measured
properties (density and ultrasonic velocity) were correlated to polynomial expansions. The corresponding derived
properties (excess molar volumes and change of isentropic compressibilities) have been computed from the
experimental data and fitted to a Redlich-Kister temperature dependent expression. The new experimental data were
used to test the prediction capability of different procedures for density (Mchaweh-Nasrifar-Moshfeghian (MNM)
model) and ultrasonic velocity (Collision Factor Theory (CFT)).
Keywords: Derived magnitudes; protic ionic liquid; theoretical models; temperature.
1. Introduction
Ionic liquids (ILs) are versatile new media for many
chemical synthesis and a wide spectrum of industrial
applications [1]. Typically, these compounds show
excellent chemical and thermal stability, high solvent power
and are described as environmentally friendly due to their
negligible vapor pressure which minimise potential risks of
atmospheric contamination and reduce/minimize associated
health concerns. In terms of purification processes, for
example, they allow an easy separation of organic
molecules by direct distillation without loss of the ionic
solvent. In what is referred to reaction media, ILs have been
the subject of enormous interest in the context of green
synthesis because of their wide acceptability as alternative
reaction media and have been found to act as selective
catalysts for different reactions.
Despite their potential advantages, there have been
reasonable doubts about the overall safety and
biodegradability of ionic liquids. Obviously, it is worth
mentioning that the only property of low vapour pressure
does not make automatically these new compounds, ionic
liquids, green [2-6].
The so-called protic ionic liquids have shown a minor
impact and almost negligible toxicity, retaining many of the
features previously observed in other analogous organic
salts [7-8]. Due to this fact, in the last few years, our
research work is focused on protic ionic liquids and their
potencial applications in different industrial areas [9-16].
In the last decade, a rising number of reseach papers is
being published on ILs, but only a reduced quantity is
devoted to analyse and understand their ion mixing
*Corresponding Author

mechanisms and thermodynamic properties of ionic liquid

into ionic media. This knowledge is necessary for design
and optimisation of equipments and processes where
mixing ionic liquids could be applied and for development
of new models for ionic liquids properties prediction and
processes simulation.
The present investigation deals with the thermodynamic
analysis of mixing interaction between two protic ionic
liquids recently developed and studied (2-Hydroxy Ethyl
Ammonium Formate (2-HEAF) and 2-Hydroxy Diethyl
Ammonium Acetate (2-HDEAA)) [9, 16], as a function of
temperature (288.15-323.15 K). The measured properties
(density and ultrasonic velocity) were correlated to
polynomial expansions which are dependent on
composition and temperature. The corresponding derived
properties (excess molar volumes and change of isentropic
compressibilities) have been computed from the
experimental data and fitted to temperature dependent
Redlich-Kister equation. The isobaric expansibility and
isothermal coefficient of pressure excess molar enthalpy
were computed due to their importance in the study of
specific molecular interactions.
Due to modern studies on chemical engineering process
involves the use of computer aided procedures for design,
disposable theoretical models comparison is necessary
when new systems or new compounds are studied. The new
experimental data gather in this work were used to test the
prediction capability of different models, for density
(Mchaweh-Nasrifar-Moshfeghian (MNM) model) and
ultrasonic velocity (Collision Factor Theory (CFT)).

Vol. 19 (No. 4) / 244

The obtained results indicate that protic ionic liquid

interactions into this mixture are stronger than in the ionic
pure components at any temperature. This trend is
reinforced for rising temperatures, due to molecular kinetics
and lower steric hindrance among aliphatic residues of
anions and cations.
2. Experimental
2.1 Preparation of the protic ionic liquids
The synthesis of the studied PILs, which is described
elsewhere [9] and [11], is a simple acidbase neutralization
reaction, creating the corresponding salt of ethanolamine.
Table 1 gathers the protic ionic liquid measured properties
and recent values from open literature.
Table 1. Comparison of experimental and open literature
densities and ultrasonic velocities for the pure protic ionic
liquids at 298.15 K and other relevant information.
/(gcm-3)

M/(gmol-1)(a)

u/(ms-1)

Exp.

Lit.

Exp.

Lit.

2-HEAF

107.110

1.1929

1.1765(b)

1782.87

1709.00(b)

2-HDEAA

165.190

1.1674

1.1702(c)

1863.35

na

(a)

Figure 1. FTIR spectra for 2-HDEAA protic ionic liquid.

[17], (b)[9], (c)[18], na: not available

2.2 Spectroscopic Test

FT-IR spectrum was taken by a Jasco FT/IR 680 plus
model IR spectrometer, using a NaCl disk. The broad band
in the 3500-2400 cm-1 range exhibits characteristic
ammonium structure for both neutralization products. The
OH stretching vibration is embedded in this band. The
broad band centered at 1600 cm-1 is a combined band of
the carbonyl stretching and N-H plane bending vibrations,
as well as two characteristic bands are showed 3500-2400
cm-1 for NH3+ + OH- and other wide band at 1600 cm-1
for COO- + N-H plane bend [9].
All the NMR experiments were performed at 298.15 K
in a 17.6 T Varian Inova-750 spectrometer (operating at
750 MHz proton frequency). The spectra were processed
with Mestre-C software. An external reference standard
capillary containing a deuterated 3-(trimethylsilil)propionic-D4 acid (TSP) 0.1 M in DMSO was introduced
coaxially in the tube. The external DMSO was used for
deuterium lock. The external TSP was used for chemical
shift referencing of the 1H and 13C NMR spectra (TSP
resonates at 0 ppm in these two types of spectra). The
external TSP proton signal was also used for the
determination of absolute concentrations with the 1H NMR
spectra. For this task, the integral of the 1H NMR signal of
TSP in the capillary was calibrated with respect to a sample
of 0.2 M of sucrose dissolved in D2O prepared in a 5 mm
NMR. The anomeric glucose proton appearing at 5.2 ppm
was chosen for the calibration. For each sample, a 1D-1H
NMR quantitative experiment was performed with a 33
pulse and a conveniently long interscan relaxation time (d1
10 s). These conditions were used to assure the exactness of
the signal integration.
For example, Figures 1 and 2 gather FTIR and 1H NMR
spectra corresponding to 2-HDEAA protic ionic liquid.

245 / Vol. 19 (No. 4)

Figure 2. 1H-NMR, 13C-NMR and HMBC spectra for 2HDEAA protic ionic liquid (Figure is in color in the on-line
version of the paper).
2.3 Physical properties equipment
During the course of the experiments, the purity of ionic
liquids was monitored by different physical properties
measurements. The pure ionic liquids were stored in sun
light protected form, constant humidity, nitrogen
atmosphere and ambient temperature. Usual manipulation
in our experimental work and a strong purification of water
pollution before use, due to the hygroscopic character of
these compounds, were applied [14, 15]. The molar mass
and experimental results at standard condition for the
studied protic ionic liquids are shown in Table 1, as well as,
disposable data into open literature [9, 16].
The densities and ultrasonic velocities of pure ionic
components were measured with an Anton Paar DSA-5000
vibrational tube densimeter and sound analyzer, with a
resolution of 10-5 gcm-3 and 1 ms-1. Apparatus calibration
was performed periodically in accordance with vendor
instructions using a double reference using Millipore
quality water and ambient air at each temperature, before
measurements (triple measurement at each composition).
Each mixture was prepared with a known mass of both
ionic liquids, by weighing with a precision (2 10-5 g)
device (GRAM-VXI Serie Analytical Balance). The
Int. Centre for Applied Thermodynamics (ICAT)

mixtures were sealed in the vials with an aluminum cap and

a rubber plug, the empty space in the vials being
minimized, in order to avoid atmospheric water pollution.
Accuracy in the temperature of measurement was better
than 10-2 K by a temperature control device that apply the
Peltier principle to maintain isothermal conditions during
the measurements into the density and ultrasonic velocity
cells.
2.4 Stability at room temperature
The potential exists for many of these protic ionic liquid
to undergo a condensation reaction to form an amide
compound. Therefore, an adequate control of temperature is
essential throughout the chemical reaction of salt formation,
as well as, their storage under stable conditions, otherwise
heat evolution may produce salt dehydration. As observed
in our laboratory during ionic liquid synthesis, dehydration
commences around 420 K, for those lighter ionic liquids in
this family (2-HEAF for example). The colour varies at
each case from transparent to slightly yellow when reaction
process and purification were finished (Supplementary
Figure SF-1). Strong agitation, low pressure and slight
heating for total vaporization of residual non-reacted acid
was applied at least for 72 h, this process let us obtain a
constant value of the physical properties of the pure salt.
These ionic compounds are strongly hygroscopic [14,15],
and in order to decrease the water content as much as
possible, they were dried for 48 h at room temperature and
under vacuum of 20 kPa while stirring, before sample
preparation and measurements. There was no detectable
decomposition for the ionic liquids studied here when left
for over 12 months at laboratory temperature. Less than 1%
amide was detected after this range of time. From these
results it appears evident that the probability of amide
formation is low for this kind of ionic compounds, if
storage recommendations are followed.

nDAT
zexp z pred
i 1

nDAT

Table 2. Fitting parameters (Eqs. (1) and (2)) for density,

ultrasonic velocity and isentropic compressibility at the
range 288.15323.15 K and root mean square deviations (
) (Eq. (3)) for (2-hydroxy ethyl ammonium formiate (2HEAF) + 2-hydroxy diethyl ammonium acetate (2HDEAA)) mixture.
Parameter

/(gcm-3)

u/(ms-1)

S/(TPa-1)

B00
B01
B02
B10
B11
B12

1.331
0.000
0.000
0.084
0.000
0.000

2753.176
-3.331
0.001
179.904
-3.294
0.008

160.443
-0.245
0.002
-356.971
2.795
-0.005

B20
B21
B22
B30
B31
B32
B40

-0.744
0.003
0.000
2.236
-0.009
0.000
-2.908

-9194.770
66.980
-0.118
30291.381
-217.615
0.377
-38212.826

4135.282
-28.295
0.047
-13046.938
88.563
-0.146
16335.391

B41
B42
B50
B51

0.011
0.000
1.379
-0.006

272.402
-0.469
16758.223
-118.816

-110.322
0.181
-7142.920
48.039

(1)

i 0

where Ai is a polynomial temperature dependence (Kelvin

degrees) function as follows:
Ai

BijT

(3)

The fitting parameters and the corresponding deviations

are gathered in Table 2. The measurements show the
progressive increment of density as a function of
composition of 2-HEAF protic ionic liquid until a
maximum at approximately 0.8 mole fraction. This
tendency is observed at each temperature.
In terms of ultrasonic velocity, a slight diminution of
this magnitude is observed for rising mole fraction of 2HEAF. The effect of temperature is similar to that observed
for density measurements, higher temperatures produce
lower values of ultrasonic velocity, showing an almost
linear decreasing trend with temperature. The increment of
isentropic compressibility (equation Newton-Laplace) for
decreasing concentrations of the heavier compound (2HDEAA) is observed, as well as, the progressive linear
diminution for decreasing temperatures.

3. Results and Discussion

3.1 Physical properties correlation
The density and ultrasonic velocity of the ionic mixtures
were correlated as a function of composition in accordance
to the Eq. (1):
P Ai xi

1/2

(2)

B52

0.000

0.204

-0.079

6.697E-7

30.627

3.105

j 0

and where P is density (gcm-3) or ultrasonic velocity (ms-1),

x is the molar fraction and Bij fitting parameters. N and M
stand for the extension of the mathematical series which
were optimised by means of the Bevington test. Densities
and ultrasonic velocity are given as Supplementary Material
(Table ST1) for this mixture. The fitting parameters were
obtained by the unweighted least squared method applying
a fitting Marquardt algorithm.
The root mean square deviations were computed using
Eq. (3), where z is the value of the property, and nDAT is
the number of experimental data.

3.2 Derived properties

The excess molar volumes and changes of isentropic
compressibilities on mixing (attending to Newton-Laplace
equation) are presented in Table ST1 and were computed
from the Eqs. (4) and (5):

V E xi M i 1 i1
i 1

1
u

i 1

xi
i ui2

(4)

(5)

In these equations, is the density, and S the

isentropic compressibility on mixing. The i, and Si
Int. J. of Thermodynamics (IJoT)

Vol. 19 (No. 4) / 246

C p (xi x j ) p

(6)

p 0

C p C piT i

(7)

i 0

where Qij is VE/(cm3mol1), or S/(TPa-1) of the

mixture, respectively. The degree of this equation (m
parameter) was optimized by applying the F-test. Each Cp
parameter was extended as quadratic polynomic dependent
function of temperature (Eq. (7)). The Cpi fitting parameters
are gathered into Table 3, with the corresponding root mean
square deviations (Eq. (3)). The Redlich-Kister parameters
present a thermodynamic significance once it can be used,
with some algebra, to calculate the partial molar quantities
of a component in a binary mixture.
No previously data of this mixture was found into open
literature. Figures 3 and 4 show the derived magnitudes as a
function of temperature. This mixture shows as a strong
contractive tendence in terms of excess molar volume
(Figure 3) and negative values for the change of isentropic
compressibility (Figure 4). Both derived properties show a
continuous decreasing trend for rising temperatures,
showing a minima at equimolar composition. Mobility ions
and a progressively higher kinetics when temperature rises,
make more probably ion-ion interaction and then, produce a
stronger contractive tendence into mixture.
Table 3. Fitting parameters of (Eqs. (6) and (7)) for the
derived magnitudes excess molar volumes and changes of
isentropic compressibilities at the range 288.15 338.15 K
and root mean square deviations () (Eq. (3)) for (2hydroxy ethyl ammonium formiate (2-HEAF) + 2-hydroxy
diethyl ammonium acetate (2-HDEAA)) mixture.
Parameter

VE/(cm3 mol-1)

S/(TPa-1)

C00
C01

10.614
-0.051

346.923
-2.264

C02
C10
C11

0.000
21.018
-0.123

0.003
398.278
-2.553

C12

0.000

0.004

C20
C21
C22
C30
C31
C32
C40

-25.625
0.153
0.000
-74.743
0.449
-0.001
62.126

-596.433
4.054
-0.007
-1655.784
10.645
-0.017
1886.671

C41

-0.339

-12.551

C42
C50
C51
C52

0.000
100.588
-0.565
0.001

0.020
3207.025
-20.964
0.034

0.003

2.391

247 / Vol. 19 (No. 4)

ln

T P, x

(8)

taking into account the temperature dependence of density.

These values are also enclosed into Table ST1. All the
thermal expansion coefficient for this mixture at the studied
temperature range were positive, showing a decreasing
tendence for rising 2-HEAF composition at the highest
studied temperatures.

0.0

VE /(cm3 mol-1 )

Qij xi x j

3.3 Calculation of the thermal expansion coefficient

A usual applied magnitude for industrial mixtures is the
temperature dependence of volume (isobaric expansibility
or thermal expansion coefficient). The open literature data
report normally, values of this coefficient for pure
compounds and their mixtures, assuming that the thermal
expansion coefficient remains constant in any thermal
range. As in the case of pure compounds, it can be
computed by the following expression:

-0.2

-0.4

-0.6

0.0
-0.8

0.2
0.4

300
0.6

310

T /(K

320

0.8
330

1.0

A
HE
X 2-

Figure 3. Curve of excess molar volumes (cm3mol-1) for 2HEAF + 2-HDEAA mixture at the range of temperatures
288.15 323.15 K (Figure is in color in the on-line version
of the paper).

0
-2

S /(TPa-1 )

symbols are the properties of pure chemicals at the same

temperature and n is the number of components in the
mixture. A modified Redlich-Kister type equation was used
to correlate the derived properties of the binary mixture, by
using the unweighted least squares method fitting
parameters were obtained by the unweighted least squared
method applying a fitting Marquardt algorithm, all
experimental points weighting equally. The fitting equation
can be expressed as:

-4
-6
-8
-10
-12
300
310

T/
(K
)

320
330
1.0

0.8

0.6

0.4

0.2

0.0

X 2 -HEAF

Figure 4. Curve of changes of isentropic compressibility

(TPa-1) for 2-HEAF + 2-HDEAA mixture at the range of
temperatures 288.15 323.15 K (Figure is in color in the
on-line version of the paper).
3.4 Calculation of the isothermal coefficient of pressure
excess molar enthalpy
The isothermal coefficient of pressure excess molar
enthalpy can be derived accurately from volumetric
measurements by application of the following expression:
Int. Centre for Applied Thermodynamics (ICAT)

 H E

E
V T
T , x

V E

P, x

(9)

TR

standing for the dependence of excess molar enthalpy of

mixing with pressure at fixed composition and temperature.
This magnitude shows positive values with slight
dependence of temperature (higher values for lower
temperatures). The computed isothermal coefficient of
pressure excess molar enthalpies gather a clear maximum at
equimolar composition. This magnitude is enclosed into
Table ST1, too.
3.5 Density estimation by Mchaweh-NasrifarMoshfeghian (MNM) model
Increasingly, modern process design involves the use of
computer aided procedures. Despite the success developing
several procedures of density estimation for pure
compounds or mixtures, only a few of them may be of real
application for chemicals of nonideal trend or high molar
mass [19]. In this case, a simplification for the Nasrifar
Moshfeghian liquid density correlation (NM correlation)
was applied, replacing the Mathias and Copeman
temperature-dependent term with the original Soave
RedlichKwong equation of state (SRK EOS) temperaturedependent term. This replacement has overcome the
limitations in use for the original model which were due to
the Mathias and Copeman vapor pressure dependent
parameters [20]. The NasrifarMoshfeghian model (NM)
[21] requires three parameters for each compound, that are
not readily available for all compounds. In the absence of
these three parameters, the NM correlation fails to predict
the density of pure compounds and their mixtures. The
modification of this model, MchawehNasrifar
Moshfeghian model (MNM), overcomes this barrier by
replacing the PSRK (Predictive Soave-Redlich-Kwong)
parameter with the original SRK term (SRK). The
parameter SRK is defined in terms of reduced temperature
(TR):
SRK

1 m 1 TR

equation of state, attending to Eq. (10). The reduced

temperature of the mixtures is defined as:

(14)

xiTCi
i 1

where T is the studied temperature and TC is the critical

temperature for each component into mixture.
The critical density ( C) of the mixture is calculated as
follows:
N
3/ 4
C xi Ci

i 1

-4/3

(15)

where xi is the molar fraction and Ci is the critical density

of each compound int mixture. The reference density of the
mixture (0) is computed using the following term:

0 1 1.1688 1 mix 3 1.8177 1 mix 3 ...

1

...2.6581 1 mix 3 2.1613 1 mix

3

(16)

The revised MNM model, after replacement, has the

following general formula for the solution density:

C 0

(17)

The critical properties and acentric factors required were

estimated by a group contribution method based on the
well-known concepts of Lydersen and of Joback and Reid,
proposed by Valderrama and Robles [22], due to these
parameters are not available for the protic ionic liquid
(Table 4).
Table 4. Estimated critical values for the compounds
enclosed into the binary mixture [22]
Compound

Pc(MPa)

Tc(K)

Zc

2-HEAF

54.049

683.2

0.377

0.898

2-HDEAA

31.830

829.3

0.291

1.404

(10)

is given by the following relation as a function of

where m
acentric factor ():
m 0.480 1.574-0.1762

0.09

(11)

0.08

xi i

(12)

i 1

The acentric factor is a parameter related to the

measurement of the complexity of the molecule as a
geometricl form in relation to a molecule with spherical
symmetry of a simple fluid for which the value of acentric
factor is zero.
The temperature dependent term mix is computed
using the following equation:

mix 1

TR
SRK

(13)

where TR is the reduced temperature of the mixture and SRK

is the term from the original Soave-Redlich-Kwong
Int. J. of Thermodynamics (IJoT)

0.07

exp -cal /(gcm-3 )

The acentric factor of the mixture is calculated as

follows:

0.06
0.05
0.04
0.03
0.02
0.01
0.00
-0.01
-0.02
-0.03
0.00

0.20

0.40

0.60

0.80

1.00

X2-HEAF

Figure 5. Comparison of experimental and estimated

density (gcm-3) by Mchaweh-NasrifarMoshfeghian (MNM)
model for 2-HEAF + 2-HDEAA mixture at () 288.15, ()
298.15, () 323.15 and () 338.15 K.
Vol. 19 (No. 4) / 248

technological processes and understanding the interactions

in such kind of compounds into mixture. A huge number of
reseach papers is being published on ILs, but only a
reduced quantity is devoted to analyse and understand their
ion mixing mechanisms and thermodynamic properties of
ionic liquid into ionic media. In the present paper, we have
presented new experimental data of densities and ultrasonic
velocity as a function of temperature of the binary mixture
3.6 Ultrasonic velocity estimation by Collision Factor (2-Hydroxy Ethyl Ammonium Formate (2-HEAF) + 2Theory (CFT)
Hydroxy Diethyl Ammonium Acetate (2-HDEAA)),
In the last few years an increasingly interest for the showing strong contractive behaviour at almost equimolar
application of low and high frequency ultrasound composition. No information on this mixture is gathered in
techniques for thermodynamic applications has occurred. In open literature as far as we know.
this work, experimental data for the ultrasonic velocity of
From these results, it was found:
the mixtures were compared with values determined by the
1. The theoretical procedures tested here were the
Collision Factor Theory (CFT) [23], which is dependent on Mchaweh-Nasrifar-Moshfeghian (MNM) model for density
the collision factors among molecules as a function of and the Collision Factor Theory (CFT) for ultrasonic
temperature into pure solvent or mixture:
velocity. Both methods were originally designed for
covalent
nature solvents.
This
model
gathers
underestimated values for the studied mixture, showing the
u xi Si xi Bi
(18) highest deviations at low compositions of 2-HEAF and at
u
V
high temperatures. The temperature is a secondary factor
and slightly affects the final prediction. In what is referred
u
where is 1600 m/s, S is the collision factor for each to the Collision Factor Theory (CFT), this model slightly
compound, B is the volume of molecule per mole for each underestimes the obtained experimental values but it shows
a notable accuracy (lower than 1,9% of deviation), despite
compound and V is molar volume of mixture.
the use of the group contribution method of Bondi for
estimation of the characteristic molar volumes of each
35
compound into mixture. Also, the highest deviations were
30
obtained for the highest temperatures at equimolar
compositions.
25
2. The obtained results indicate that protic ionic
20
liquid interactions into this mixture are stronger than in the
ionic pure components at any temperature. This trend is
15
reinforced for rising temperatures, due to molecular kinetics
10
and lower steric hindrance among aliphatic residues of
anions and cations.
5
3. Based on the reasons explained above - low cost,
0
simple synthesis, and biodegradation at environmental
-5
conditions [4-6] -, the potential interest of these protic ionic
0.00
0.20
0.40
0.60
0.80
1.00
liquids is amazing due to the possibility of a tailoredX 2-HEAF
designed ionic liquid or ionic liquid mixture for specific
Figure 6. Comparison of experimental and estimated processes. To this aim, the knowledge about
ultrasonic velocity (ms-1) by Collision Factor Theory (CFT) thermodynamic properties can be used for design and
for 2-HEAF + 2-HDEAA mixture at () 288.15, () optimisation of equipments and processes where mixing
298.15, () 323.15 and () 338.15 K
ionic liquids could be applied and for development of new
models for ionic liquids properties prediction for process
The pertinent relations for these calculations and its simulations.
theoretical basis were described in the literature indicated
above. The collision factors (S) of the pure solvents used in Acknowedgments:
the CFT calculations were estimated by using the
The authors would like to acknowledge FAPESB experimental ultrasonic velocities, and the molar volumes Fundao de Amparo Pesquisa do Estado da Bahia
enclosed in this paper. The characteristic molar volumes of (Projeto Ao Referncia, PET0071/2013), CAPES
each compound into mixture were calculated by the group Coordenao de Aperfeioamento de Pessoal de Nvel
contribution method of Bondi [24]. This model slightly Superior (scientific grant of R.S. Andrade), CNPq underestimes the obtained experimental values. The Conselho Nacional de Desenvolvimento Cientfico e
deviations of this procedure for the studied mixture are Tecnolgico, PIBIC - Programa Institucional de Bolsas de
gathered in Figure 6 using the pure parameters from Table 4 Iniciao Cientfica (scientific grants of K. Lima) and
and literature data. As observed, the highest deviations are Universidade Salvador UNIFACS, for their support in
obtained for the highest temperatures at equimolar developing this research.
compositions but always under lower than 1,9%.
Nomenclature
4. Conclusions
- isobaric expansibility or thermal expansion
The basic physicochemical data of protic ionic liquids coefficient, K-1
are important for both the design of new and greener
u exp -u calc /(m s -1 )

The deviation of this density estimation method with

respect to experimental data has been gathered into Figure
5. This model gathers underestimated values for the
mixture, showing the highest deviations at high
temperatures and low 2-HEAF compositions. The
temperature is a secondary factor and slightly affects the
final prediction.

249 / Vol. 19 (No. 4)

Int. Centre for Applied Thermodynamics (ICAT)

S changes of isentropic compressibility on mixing

(TPa-1)
S - isentropic compressibility, TPa-1
- density, Kg/m3
c critical density, Kg/m3
B - volume of molecule per mole, m3/mol
HE- excess molar enthalpy, J
nDAT - number of experimental data
S - collision factor
TC - critical temperature, K
TR - reduced temperature, K
u- ultrasonic velocity, m/s
V is molar volume of mixture
VE excess molar volumen, m3/mol
W acentric factor,
x molar fraction
Supplementary Information

Supplementary data related with this article can be

found in the online version.
References

[1] N. V. Plechkova, K. R. Seddon, Applications of ionic

liquids in the chemical industry, Chem. Soc. Rev., 37,
123-150, 2008.
[2] D. Zhao, Y. Liao, Z. D. Zhang, Toxicity of ionic
liquids, Clean-Soil Air Water, 35, 42-48, 2007.
[3] S. Zhu, R. Chen, Y. Wu, Q. Chen, X. Zhang, A minireview on greenness of ionic liquids, Chem. Biochem.
Eng. Q. 23, 207-211, 2009.
[4] B. Peric, E. Mart, J. Sierra, R. Cruaas, M. Iglesias, M.
A. Garau, Terrestrial ecotoxicity of short aliphatic
protic ionic liquids, Environ. Toxicol. Chem. 30, 28022809, 2011.
[5] B. Peric, J. Sierra, E. Mart, U. Bottin-Weber, S. Stolte,
(Eco)toxicity and biodegradability of selected protic
and aprotic ionic liquids, J. Hazard. Mater. 261, 99105, 2013.
[6] B. Peric, J. Sierra, E. Mart, R. Cruaas, M. A. Garau,
A comparative study of the terrestrial ecotoxicity of
selected protic and aprotic ionic liquids, Chemosphere.
108, 418-425, 2014.
[7] T. L. Greaves, C. J. Drummond, Protic ionic liquids:
Properties and applications, Chem. Rev. 108, 206-237,
2008.
[8] T. L. Greaves, C. J. Drummond, Protic ionic liquids:
Evolving structure-property relationships and expanding
applications, Chem. Rev., 115, 11379-11448, 2015.
[9] I. Cota, R. Gonzalez-Olmos, M. Iglesias, F. Medina,
New short aliphatic chain ionic liquids: synthesis,
physical properties, and catalytic activity in aldol
condensations, J. Phys. Chem. B, 111, 12468-12477,
2007.
[10] M. Iglesias, A. Torres, R. Gonzalez-Olmos, D.
Salvatierra, Effect of temperature on mixing
thermodynamics of a new ionic liquid: (2-hydroxy
ethylammonium formate (2-HEAF) + short hydroxylic
solvents), J. Chem. Thermodyn., 40, 119-133, 2008.

Int. J. of Thermodynamics (IJoT)

[11] M. Iglesias, R, Gonzalez-Olmos, I. Cota, F. Medina,

Brnsted ionic liquids: study of physico-chemical
properties and catalytic activity in aldol condensations,
Chem. Eng. J., 162, 802-808, 2010.
[12] I. Cota, F. Medina, R. Gonzalez-Olmos, M. Iglesias,
Alanine-supported protic ionic liquids as efficient
catalysts for aldol condensation reactions, C. R.
Chim., 17, 18-22, 2014.
[13] T. Espinosa, M. Jimenez, J. Sanes, A. E. Jimenez, M.
Iglesias, M. D. Bermudez, Low friction with a protic
ionic liquid boundary film at the water-lubricated
sapphirestainless steel interface, Tribol. Lett., 53, 1-9,
2014.
[14] J. Kulhavy, R. S. Andrade, S. M. Barros, J. S. Serra,
M. Iglesias, Influence of temperature on
thermodynamics of protic ionic liquid 2-hydroxy
diethylammonium dilactate (2-HDEAL) + short
hydroxylic solvents, J. Mol. Liq., 213, 92-106, 2016.
[15] D. Camargo, R. S. Andrade, G. Ferreira, H. Mazzer, L.
Cardozo-Filho, M. Iglesias, Investigation of the
rheological properties of protic ionic liquids, J. Phys.
Org. Chem., doi: 10.1002/poc.3553.
[16] M. Iglesias, R. S. Andrade, R. Garcia-Muoz, R.
Gonzalez-Olmos, New short aliphatic chain protic
ionic liquids: effect of temperature on thermodynamic
properties, Phys. Chem. Liq. (submitted for
publication), 2016.
[17] R. L. Rowley, W. V. Wilding, J. L. Oscarson, Y.
Yang, N. F. Giles, DIPPR Data Compilation of Pure
Chemical Properties, Design Institute for Physical
Properites, AIChE, New York, 2009.
[18] K. A. Kurnia, B. Ariwahjoedi, M. I. A. Mutalib, T.
Murugesan, Density and excess molar volume of the
protic ionic liquid bis(2-hydroxyethyl)ammonium
acetate with alcohols, J. Sol. Chem. 40, 470-480, 2011.
[19] B. E. Poling BE, J. M. Prausnitz, J. P. O`Connell,
The properties of gases and liquids, 5th ed McGrawHill, Internationals editions, New York, USA, 2001.
[20] N. Saha, B. Das, Apparent molar volumes of some
symmetrical
tetraalkylammonium
bromides
in
acetonitrile at (298.15, 308.15, and 318.15) K, J.
Chem. Eng Data, 42, 227-229, 1997.
[21] Kh. Nasrifar, Sh. Avatollahi, M. Moshfeghian, An
extended saturated liquid density equation, Fluid
Phase Equilib., 166, 163-181, 1999.
[22] J. O. Valderrama, P. A. Robles, Critical properties,
normal boiling temperatures, and acentric factors of
fifty ionic liquids, Ind. Eng. Chem. Res., 46, 13381344, 2007.
[23] W. Schaaffs, Problem of a theoretical calculation of
the velocity of sound for binary liquid mixtures,
Acustica, 33, 272-276, 1975.
[24] A. Bondi, Van der Waals volumes and radii, J. Phys.
Chem., 68, 3, 441451, 1964.

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