Journal of Industrial and Engineering Chemistry 20 (2014) 3349–3355

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Physical properties of aqueous mixtures of N-methyldiethanolamine

(MDEA) and ionic liquids
R. Yusoff *, A. Shamiri, M.K. Aroua, A. Ahmady, M.S. Shafeeyan,
W.S. Lee, S.L. Lim, S.N.M. Burhanuddin
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

A R T I C L E I N F O A B S T R A C T

Article history: In the present study, experiments have been conducted to measure the surface tension and heat capacity
Received 14 July 2013 of aqueous mixtures of N-methyldiethanolamine (MDEA) and ionic liquids (ILs) at atmospheric pressure.
Received in revised form 25 November 2013 Two types of ILs, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4] and 1-butyl-3-methyl-
Accepted 8 December 2013
imidazolium dicyanamide [bmim][DCA]) were used in these experiments. The surface tension was found
Available online 17 December 2013
to decrease with increasing temperature and ionic liquid concentration. Furthermore, the heat capacity
of the mixtures increases with decreasing ionic-liquid concentration and increasing temperature. Linear
Keywords:
equations were used to correlate the measured surface tension values, quadratic equations were applied
Physical properties
Ionic liquids
to correlate the heat capacity at different compositions and temperatures.
Surface tension ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Heat capacity reserved.
Thermal conductivity

1. Introduction benefits are negligible volatility, thermal stability, and favorable

Carbon dioxide (CO2) is widely regarded as a primarily
greenhouse gas, which causes environmental problems especially
global warming and climate change [1]. This gas is emitted by
many crucial industries, particularly by natural gas processing,
coal gasification, synthetic and petroleum refinery industries [2].
Alkanolamines such as monoethanolamine (MEA), diethanolamine
(DEA), N-methyldiethanolamine (MDEA), diglycolamine (DGA), di-
isopropanolamine (DIPA) and 2-amino-2-methyl-1-propanol
(AMP) have been widely used in CO2 absorption applications for
years [3–6]. However, the alkanolamines solvent have a significant
number of drawbacks such as temperature and oxidative
degradation, high energy consumption, equipment corrosion, high
volatility, high operating cost with adverse environmental pollu-
tion.
Ionic liquids (ILs) have been proposed as an alternative solvent
platform to aqueous amine solvents for CO2 absorption applica-
tions such as CO2 removal from the flue gas in coal-fired power
plants to overcome the existing drawbacks with using of
conventional aqueous amine solvents [7–10].
Ionic liquid (IL) as absorbent, has attracted attention consider-
ing their demonstrated advantages in recent years [11]. The main
* Corresponding author. Tel.: +603 7967 6891; fax: +603 7967 5319.
E-mail addresses: ryusoff@um.edu.my, ryusoff67@yahoo.com (R. Yusoff).
solubility of CO2 gas [12]. CO2 loading in mixture of aqueous MDEA
and imidazolium based ionic liquids, 1-butyl-3-methyl-imidazo-
lium tetrafluoroborate ([bmim][BF4]), 1-butyl-3-methyl-imidazo-
lium acetate (bmim][Ac]) and 1-butyl-3-methyl-imidazolium
dicyanamide ([bmim][DCA]) at different temperatures and CO2
partial pressure were investigated by Ahmady et al. [13]. They
found that the CO2 loading in all IL + MDEA mixtures increases
with increasing CO2 partial pressure and decreases with increasing
temperature. Moreover, the mixtures of ILs with MDEA have been
suggested for application in CO2 absorption [2,12–15]. Therefore,
the determination of accurate physical properties over a wide
temperature range is important for reasonable and optimized
design of absorber, stripper and heat exchange equipment in the
CO2 absorption process [16–20].
Surface tension is crucial for the hydrodynamic study as well as
physical behavior of solvents in CO2 absorption [21,22]. The
surface tension value has a significant impact on the CO2
absorption rate when CO2 transfers into the aqueous solutions
of alkanolamines. Therefore, the influence of surface tension on the
bubble size of CO2 has been widely studied in the open literature
[23].
Heat capacity and thermal conductivity are key parameters in
the design of heat exchange equipment as well as energy balance
calculations. It can also be applied in the CO2 gas absorption
process to ensure that the process temperature is maintained. Still,
such information is lacking in the open literature [24].

1226-086X/$ – see front matter ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.12.019
3350 R. Yusoff et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 3349–3355

In this work, surface tension and heat capacity of two water
soluble ILs, [bmim][BF4] and [bmim][DCA] and aqueous MDEA
solutions as well as their mixtures have been determined
experimentally. The dependence of temperature and concentra-
tion of ILs and MDEA to these physical properties have been
correlated in polynomial functions based on the experimental
data.
the sample and crucible. Then, a blank curve correction was done by
subtracting the blank curve from the raw DSC heat flow signal.
A KD2 Pro Decagon Device Inc. thermal conductivity meter was
used to measure thermal conductivity of the solvents. All
experiments were done at room temperature.
3. Result and discussion

2. Experimental 3.1. Surface tension measurement

2.1. Materials 3.1.1. Validation of tensiometer

Ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate
[bmim][BF4], 1-butyl-3-methyl-imidazolium dicyanamide
[bmim][DCA] and N-methyl-diethanolamine (MDEA) were sup-
plied by Merck at >98% purity. Distilled water degassed by boiling
was used for making ILs + amine solutions. The mass of the liquid
mixtures was measured using an analytical balance (Mettler
Toledo model AS120S) with a precision of 0.0001 g.
2.2. Methods
To validate the tensiometer and the experimental measure-
ment, the surface tension of pure [bmim][BF4] was measured from
303.15 K to 323.15 K at every 10 K increment. The results were
compared to the values reported in the literature and presented in
Table 1. In this table the surface tension measurements for pure
[bmim][BF4] in this work are compared to Kim et al. [25] and Freire
et al. [26]. The average absolute deviations were 2.76% and 2.04%,
respectively. Thus, the surface tensions obtained in this study were
in good agreement with the data from Kim et al. [25] and Freire
et al. [26].

Surface tension was determined with a Krüss K-11 tensiometer
using the Du Noüy ring method. The ring employed was a
commercial platinum ring supplied by Krüss. The platinum ring
was cleaned with water and acetone and flame-dried before each
measurement. Surface tension measurements were carried out in
the temperature ranging from 303 K to 343 K with 10 K increment.
The uncertainty in the measurement of temperature was 0.1 K.
Each reported value was the average of three measurements. The
experimental uncertainty was estimated to be 0.12 mN m1.
Specific heat capacity was measured by the direct method using
a Mettler Toledo Differential Scanning Calorimeter (DSC). The heat
capacity of these aqueous mixtures was measured in the
temperature ranging from 303 to 353 K at atmospheric pressure.
Both the temperatures and the heat flow associated with the
transitions in materials can be rapidly measured with the system.
The DSC operates with a temperature repeatability of 0.1 K.
Calorimetric sensitivity is 1 mW (rms) with a precision of
0.01 kJ kg1 K1. Nitrogen was used as a purge gas with flow rate
of 4  105 m3 min1. The heating rate was set to 10 K min1. The
sample was prepared within hermetically-sealed sample pan with
the internal volume was approximately 10 mm3. Sample weight was
in the range of 15 mg to 20 mg. All measurements runs were
performed in triplicate.
For the direct method, the determination is derived from the
equation that defines the specific heat capacity. The numerator and
denominator of the specific heat capacity equation are differenti-
ated with respect to time to give the heat flow divided by the
heating rate of the sample. The rate of change of enthalpy, dH/dt, is
equal to the DSC heat flow, Ø. Meanwhile, the heating rate, d is the
rate of change of temperature, dT/dt. If no chemical reaction occurs,
the heating rate of the sample is equal to the heating rate of
temperature program. Below is the specific heat capacity equation:
3.1.2. Experimental results of [bmim][BF4] and MDEA (aq) mixtures
The measured surface tension of [bmim][BF4] and MDEA (2.0 M
and 4.0 M) solutions are presented in Fig. 1. Surface tensions of
mixtures were decreased with increasing temperature from
303.15 to 343.15 K. As temperature increases, the average kinetic
energy of the molecules of MDEA, water, and ions of ionic liquid,
[bmim][BF4] increases and higher kinetic energy enables the
molecules to overcome the intermolecular attractive forces (van
der Waals forces). Therefore, surface tension decreases with
increasing temperature.
The surface tension values of the mixtures also decreased
slightly with increasing the molarity of ionic liquids, [bmim][BF4],
in the mixtures. The surface tension of [bmim][BF4] is lower than
that of MDEA or aqueous MDEA. Hence, adding the ionic liquid to
the aqueous MDEA solution leads to a decrease in the surface
tension of the mixtures.
3.1.3. Experimental results of [bmim][DCA] and MDEA (aq) Mixtures
The measured surface tension of [bmim][DCA] and MDEA
(2.0 M and 4.0 M) solutions is presented in Fig. 2. This figure shows
that the surface tension of mixtures decreases with increasing
temperature of aqueous 2.0 M and 4.0 M MDEA solutions with
various concentration of [bmim][DCA].
Increasing the concentration of [bmim][DCA] in the aqueous
2.0 M MDEA solutions resulted in a decrease in the surface tension
of the solutions. Therefore, adding more ionic liquid leads to lower
surface tension of the solutions.
However, the measured surface tension for aqueous 4.0 M
MDEA solution mixed with a different amounts of [bmim][DCA]
was scattered and did not follow the predicted trend. These
negative results are probably a function of the degree of solubility
of [bmim][DCA] in the aqueous MDEA. During the preparation of

dH 1 dH=dt 1 ? 1
cp ¼  ¼  ¼  (1) Table 1
dT m dT=dt m bs m Comparison of the surface tension, s, of pure [bmim][BF4] in this work with the
literature.
This technique requires two measurements for each sample.
T (K) s (mN m1) Deviation (%)
The first one is to obtain blank cure with an empty crucible and the
second one with a sample. The two crucibles with lids were [25] [26] This work [25] [26]

selected with a difference of weight less than 50 mg for blank and 303.15 42.40 44.18 43.12 1.67 2.46
sample measurement to ensure identical runs for both measure- 313.15 41.40 43.58 42.55 2.70 2.42
323.15 40.40 42.90 42.05 3.92 2.02
ments. Then throughout the experiment, the reference crucible
333.15 42.27 41.47 1.93
cannot be moved and sample mass should be large enough to obtain a 343.15 41.64 41.07 1.39
signal of 5 to 10 mW in order to ensure good thermal contact between
 R. Yusoff et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 3349–3355 3351

50 50
MDEA 2.0 M
49 (a) MDEA 2.0 M 49 (a) MDEA 2.0 M+[bmim][DCA] 0.5 M
MDEA 2.0 M+[bmim][BF4] 0.5 M
48 48 MDEA 2.0 M+[bmim][DCA] 1.0 M
MDEA 2.0 M+[bmim][BF4] 1.0 M MDEA 2.0 M+[bmim][DCA] 1.5 M
47 MDEA 2.0 M+[bmim][BF4] 2.0 M 47 MDEA 2.0 M+[bmim][DCA] 2.0 M
Surface tension (mN/m)

Surface tension (mN/m)

MDEA 2.0 M+[bmim][BF4] 2.0 M
46 46
45
45
44
44
43
43
42
42
41
41
40
40
39
39
38
38
37
300 305 310 315 320 325 330 335 340 345 350
300 305 310 315 320 325 330 335 340 345 350
Temperature (K)
Temperature (K)
52
MDEA 4.0 M MDEA 4.0 M
51 (b) MDEA 4.0 M+[bmim][BF 4] 0.5 M 50 MDEA 4.0 M+[bmim][DCA] 0.5 M
(b)
MDEA 4.0 M+[bmim][DCA] 1.0 M
50 MDEA 4.0 M+[bmim][BF 4] 1.0 M
49 MDEA 4.0 M+[bmim][DCA] 1.5 M
MDEA 4.0 M+[bmim][BF4] 1.5 M MDEA 4.0 M+[bmim][DCA] 2.0 M
49
MDEA 4.0 M+[bmim][BF 4] 2.0 M
Surface tension (mN/m)

48
48

Surface tension (mN/m)

47
47
46 46

45 45
44 44
43
43
42
42
41
41
40
39 40
300 305 310 315 320 325 330 335 340 345 350
39
Temperature (K) 300 305 310 315 320 325 330 335 340 345 350

Temperature (K)
Fig. 1. Surface tension, s, for (a) 2.0 M MDEA, (b) 4.0 M MDEA; with various
[bmim][BF4] molarity (0.5 M, 1.0 M, 1.5 M, 2.0 M) from 303.15 to 343.15 K.
Fig. 2. Surface tension, s, for (a) 2.0 M MDEA (b) 4.0 M MDEA; with various
[bmim][DCA] molarity (0.5 M, 1.0 M, 1.5 M, 2.0 M) from 303.15 to 343.15 K.

the solution, the mixture turned cloudy. This means that the
solution is saturated with the solute. In fact that addition of the MDEA + [bmim][DCA] mixtures at temperatures from 303.15 to
second solvent results in a solvent mixture in which the solute is 343.15 K were expressed as follows [21,28,29]:
less soluble. Such formation, which mostly happened at 1.0 M and
2.0 M [bmim][DCA] with 4.0 M MDEA, might be caused by the high
concentration of the mixtures with presence of ionic liquids and
s ¼ L1  TðK  273:15Þ þ L0 (2)
consequently difficulty in dissolving in the solutions. High where parameters L1 and L0 are determined from the y-intercept
concentration of the mixtures with presence of ionic liquids and slope of the linear graph of the linear graph of surface tension
may lead to disturb the balance among electrostatic interactions, versus temperature at different concentrations using experimental
van der Waals interactions, and geometrical properties [27]. data, and represented by Eqs. (3) and (4) for aqueous mixture of
Therefore, the higher concentration may cause the interruption of MDEA and [bmim][BF4]:
the intermolecular interaction forces and unpredicted behavior of
mixtures. Behavior between ions–ions or molecules–molecules in
L1 ¼ ð0:0024  C MDEA þ 0:0066Þ  C ½bmim½BF 4  3
solutions may have been changed. In conclusion, the surface
interaction of ionic liquid is a complex matter and thus hard to þ ð0:0123  C MDEA  0:0223Þ  C ½bmim½BF 4  2
predict [26]. þ ð0:0197  C MDEA þ 0:0115Þ  C ½bmim½BF 4 
þ ð0:0121  C MDEA  0:0287Þ (3)
3.1.4. Surface tension correlation
Alvarez et al. [21] concluded that the relationship of surface L0 ¼ ð0:3812  C MDEA þ 2:2366Þ  C ½bmim½BF 4  2
tension of amine mixtures and temperature is linear. As stated, the þ ð1:3991  C MDEA  9:7188Þ  C ½bmim½BF 4 
relationship of measured surface tension values of aqueous 2.0 M þ ð1:885  C MDEA þ 55:344Þ (4)
and 4.0 M MDEA solutions with various concentrations of
[bmim][DCA] and temperatures were found to be linear. Therefore, and Eqs. (5) and (6) for aqueous mixture of MDEA and
a linear correlation for the different concentrations of aqueous [bmim][DCA]:
3352 R. Yusoff et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 3349–3355

L1 ¼ ð0:0095  C MDEA þ 0:0311Þ  C ½bmim½BF 4  3

þ ð0:0259  C MDEA  0:0943Þ  C ½bmim½BF 4  2
þ ð0:0086  C MDEA þ 0:0737Þ  C ½bmim½BF 4 
þ ð0:0112  C MDEA  0:031Þ (5)

L0 ¼ ð1:827  C MDEA þ 2:0807Þ  C ½bmim½BF 4  3

þ ð6:8622  C MDEA  6:7346Þ  C ½bmim½BF 4  2
þ ð6:8025  C MDEA þ 1:199Þ  C ½bmim½BF 4 
þ ð1:6745  C MDEA þ 44:935Þ (6)

3.1.5. Validation of correlation

Fig. 4. Comparisons of calculated surface tension with experimental surface tension
The measured and calculated surface tension data were
for various concentration of [bmim][DCA].
compared to validate the correlation. Fig. 3 shows the deviation
between calculated and measured data. The maximum deviations
of these correlations are at 2.0 M MDEA and 4.0 M MDEA mixture 3.2.2. Experimental results for the heat capacity of aqueous
solutions: 8.38% and 8.39%, respectively. These amounts of MDEA + [bmim][BF4] mixtures
deviation show that the correlations are applicable for the studied The measured heat capacity of pure [bmim][BF4], MDEA (2.0 M
range of [bmim][BF4] concentrations and temperatures. and 4.0 M) and their aqueous mixtures are shown in Table 5. These
As already mentioned, the measured surface tension data for data show that the heat capacity of mixtures increases with
[bmim][DCA] showed scattered experimental data. In this case, the increasing temperature from 303.15 to 353.15 K. On the other
proposed correlation cannot be used due to the existing hand, heat capacity of the mixtures decreases with increasing
unacceptable errors, especially for the concentrations of 1.5 M, [bmim][BF4] concentration at a fixed temperature and MDEA
2.0 M [bmim][DCA] in 2.0 M, 4.0 M MDEA solutions. This fact can concentration. Heat capacity values of [bmim][BF4] and 4.0 M
be seen clearly in Fig. 4. However, for other concentrations, such as MDEA mixtures are lower than those of [bmim][BF4] and 2.0 M
0.5 M and 1.0 M [bmim][DCA] in 2.0 M and 4.0 M MDEA solutions, MDEA mixtures. Water has the highest heat capacity among all the
the correlation is still applicable. For such combinations, the three components, followed by MDEA and [bmim][BF4]. Thus, as
maximum error in the correlation is 4.5%. Although in this work expected, the solutions with higher water content will tend to have
there are some reports of big deviations but the presented a larger heat capacity value.
empirical models for the surface tension achieved good precision
for most of cases. 3.2.3. Experimental results of aqueous MDEA + [bmim][DCA]
mixtures
3.2. Heat capacity measurement The experimental results of heat capacity of [bmim][DCA], MDEA
and their aqueous mixtures are presented in Table 6. Similarly, an
3.2.1. Validation of differential scanning calorimeter (DSC) increase in temperature resulted in the heat capacity increasing for
The heat capacity of binary mixture of [bmim][BF4] and water, the solutions at fixed composition. As illustrated in Table 6, the heat
pure [bmim][BF4] and pure MDEA were measured over the range capacity was decreased by increasing the [bmim][DCA] and MDEA
from 303.15 to 353.15 K at 5 K increments. To validate the concentrations. The values of heat capacity for aqueous mixture of
measurements of the DSC, the results were compared to the values MDEA and ionic liquids are in the following order: MDEA + [b-
reported in the available literature and presented in Tables 2–4. mim][DCA] > MDEA + [bmim][BF4]. The order of this heat capacity
The maximum deviations for the heat capacity measurements of for aqueous mixture of MDEA and ionic liquids generally follows the
binary mixture of [bmim][BF4] and water, pure [bmim][BF4] and order of heat capacity for pure ionic liquids. It is obvious that pure
pure MDEA were 4.25%, 0.41% and 2.21%, respectively. Thus, the [bmim][DCA] possesses higher heat capacity compared to
heat capacities obtained in this study were in good agreement with [bmim][BF4]. Basically, water has the highest heat capacity
the data from literature. compared to the other systems due to its degrees of freedom and

50.00 2.0M MDEA

2.0M MDEA + Table 2

Experimental Surface Tension (mN/m)

48.00 0.5M [Bmim][BF4] Heat capacity of MDEA + water binary system from this work and the comparison
2.0M MDEA +
1.0M [Bmim][BF4]
with literature.
46.00 2.0M MDEA +
1.5M [Bmim][BF4] Heat capacity (J g1 K1)
2.0M MDEA +
44.00 2.0M [Bmim][BF4] T (K) [31] This work (%) Deviation with [31]
4.0M MDEA
303.15 1.390 1.331 4.25
42.00 4.0M MDEA + 308.15 1.401 1.342 4.19
0.5M [Bmim][BF4] 313.15 1.410 1.357 3.73
4.0M MDEA + 318.15 1.420 1.369 3.57
40.00 1.0M [Bmim][BF4]
4.0M MDEA +
323.15 1.430 1.381 3.42
1.5M [Bmim][BF4] 328.15 1.439 1.394 3.11
38.00 4.0M MDEA + 333.15 1.447 1.399 3.30
38.00 40.00 42.00 44.00 46.00 48.00 50.00 2.0M [Bmim][BF4] 338.15 1.454 1.414 2.77
Calculated surface tension (mN/m) 343.15 1.466 1.428 2.57
348.15 1.475 1.430 3.05
Fig. 3. Comparisons of calculated surface tension with experimental data for various 353.15 1.485 1.435 3.38
concentration of [bmim][BF4].
 R. Yusoff et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 3349–3355 3353

Table 3 hydrogen bonding which increases intermolecular forces between

Heat capacity of pure [bmim][BF4] from this work and the comparison with
molecules. Thus, the solution which contains more water will tend to
literature.
have higher heat capacity value. It can be concluded that the heat
Heat capacity (J g1 K1) capacity increases with increasing ionic liquids as well as lower
T (K) [32] This work (%) Deviation with [32] MDEA concentration.
303.15 1.630 1.632 0.12
308.15 1.642 1.647 0.32 3.2.4. Heat capacity correlation
313.15 1.651 1.653 0.14 As mentioned before, the measured heat capacity for various
318.15 1.662 1.664 0.15 concentration of [bmim][DCA] in 2.0 M and 4.0 M MDEA increased
323.15 1.672 1.676 0.21
quadratically with increasing temperature. This finding is sup-
328.15 1.681 1.688 0.41
333.15 1.689 1.691 0.10 ported by Nieto de Castro et al. [30], who suggested the
338.15 1.697 1.701 0.22 experimental values of heat capacity can be expressed by a second
343.15 1.710 1.713 0.17 order polynomial as a function of temperature. Therefore, the
348.15 1.720 1.724 0.23 obtained heat capacity data for the aqueous solutions of MDEA and
353.15 1.729 1.735 0.33
ionic liquid at temperatures ranging from 303.15 to 353.15 K were
correlated using Eq. (7):

C p ¼ a þ b  T ðK  273:15Þ þ g  ½T ðK  273:15Þ2 (7)

Table 4
Heat capacity of pure MDEA from this work and the comparison with literature. The parameters a, b and g for the ternary studied were
1 1
determined by fitting the Cp data from this work using Eq. (7).
Heat capacity (J g K )
Further to this, these parameters were discovered from the graph
T (K) [33] This work (%) Deviation with [33] of heat capacity versus temperature at different concentrations by
303.15 2.283 2.232 2.21 determining the y-intercept and the slope of the graph. The results
308.15 2.308 2.274 1.45 are presented by Eq. (8) to Eq. (13).
313.15 2.333 2.299 1.44 For the aqueous mixture of MDEA and [bmim][BF4], the
318.15 2.358 2.341 0.71
equations are represented by
323.15 2.392 2.383 0.35
328.15 2.417 2.409 0.35
333.15 2.442 2.417 1.03 a ¼ ð628:15½MDEA þ 126:55Þð½bmim½BF 4 Þ3
338.15 2.476 2.450 1.02 2
þ ð335:79½MDEA  58:77Þð½bmim½BF 4 Þ
343.15 2.501 2.476 1.01
348.15 2.526 2.518 0.33 þ ð37:87½MDEA þ 0:73Þð½bmim½BF 4 Þ
353.15 2.551 2.534 0.66 þ 0:05½MDEA þ 4:57 (8)

Table 5
Experimental result of heat capacity for aqueous MDEA and [bmim][BF4].

Heat capacity (J g1 K1)

303.15 K 313.15 K 323.15 K 333.15 K 343.15 K 353.15 K

2M MDEA + 0.5 M [bmim][BF4] 4.121 4.172 4.218 4.251 4.287 4.291

2M MDEA + 1.0 M [bmim][BF4] 3.844 3.927 3.993 4.035 4.065 4.092
2M MDEA + 1.5 M [bmim][BF4] 3.604 3.679 3.780 3.805 3.842 3.914
2M MDEA + 2.0 M [bmim][BF4] 3.513 3.592 3.682 3.740 3.779 3.814
4M MDEA + 0.5 M [bmim][BF4] 3.820 3.865 3.896 3.930 3.975 4.001
4M MDEA + 1.0 M [bmim][BF4] 3.795 3.850 3.886 3.921 3.964 3.991
4M MDEA + 1.5 M [bmim][BF4] 3.779 3.840 3.873 3.915 3.950 3.986
4M MDEA + 2.0 M [bmim][BF4] 3.754 3.823 3.858 3.892 3.931 3.964

The uncertainty for molar concentration is 0.002 and the uncertainty of measured heat capacity at corresponding temperature was estimated to be as 0.05 J g1 K1 and
0.01 K, respectively.

Table 6
Experimental result of heat capacity for aqueous MDEA and [bmim][DCA].

Heat capacity (J g1 K1)

303.15 K 313.15 K 323.15 K 333.15 K 343.15 K 353.15 K

Pure [bmim][DCA] 2.140 2.218 2.333 2.546 2.665 2.869

2 M MDEA + 0.5 M [bmim][DCA] 4.188 4.207 4.231 4.247 4.271 4.290
2 M MDEA + 1.0 M [bmim][DCA] 4.122 4.147 4.185 4.203 4.218 4.233
2 M MDEA + 1.5 M [bmim][DCA] 4.075 4.115 4.153 4.178 4.192 4.227
2 M MDEA + 2.0 M [bmim][DCA] 4.008 4.064 4.096 4.142 4.163 4.181
4 M MDEA + 0.5 M [bmim][DCA] 4.040 4.077 4.113 4.143 4.152 4.175
4 M MDEA + 1.0 M [bmim][DCA] 3.983 4.040 4.081 4.115 4.141 4.152
4 M MDEA + 1.5 M [bmim][DCA] 3.934 3.978 4.010 4.050 4.090 4.117
4 M MDEA + 2.0 M [bmim][DCA] 3.885 3.973 3.999 4.015 4.053 4.097
3354 R. Yusoff et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 3349–3355

Table 7 b ¼ ð7:632½MDEA  0:390Þð½bmim½DCA3

Comparisons of calculated heat capacities and experimental data for aqueous 2 M 2
and 4 M MDEA with various concentration of [bmim][BF4] at 303.15 K. þ ð5:109½MDEA þ 0:112Þð½bmim½DCAÞ
þ ð0:929½MDEA þ 0:054Þð½bmim½DCAÞ
Heat capacity (J g1 K1)
 0:027½MDEA  0:01 (12)
Exp. Cal. (%) Deviation

2M MDEA + 0.5 M [bmim][BF4] 4.121 4.108 0.31 g ¼ ð0:026½MDEA  0:007Þð½bmim½DCAÞ3

2M MDEA + 1.0 M [bmim][BF4] 3.844 3.846 0.06
2
2M MDEA + 1.5 M [bmim][BF4] 3.604 3.715 2.98 þ ð0:019½MDEA þ 0:006Þð½bmim½DCAÞ
2M MDEA + 2.0 M [bmim][BF4] 3.513 3.466 1.35
þ ð0:003½MDEA þ 0:0018Þð½bmim½DCAÞ
4M MDEA + 0.5 M [bmim][BF4] 3.820 3.803 0.46
4M MDEA + 1.0 M [bmim][BF4] 3.795 3.859 1.66 þ 0:00001½MDEA þ 0:0002 (13)
4M MDEA + 1.5 M [bmim][BF4] 3.779 3.789 0.25
4M MDEA + 2.0 M [bmim][BF4] 3.754 3.781 0.72
3.2.5. Validation of correlation
To validate the proposed correlation, measured and calculated
heat capacities were compared. The comparisons of calculated
Table 8 heat capacities and experimental data for aqueous 2.0 M and 4.0 M
Comparisons of calculated heat capacities and experimental data for aqueous 2 M
MDEA with various concentrations of MDEA + [bmim][BF4] and
and 4 M MDEA with various concentration of [bmim][DCA] at 303.15 K.
[bmim][DCA] are shown in Tables 7 and 8. The calculated
Heat capacity (J g1 K1) deviations of the results from the experimental heat capacity data
Exp. Cal. (%) Deviation for these solutions were less than 3%. Among all the combinations,
the aqueous mixtures of 2.0 M MDEA +1.5 M [bmim][BF4] showed
2M MDEA + 0.5 M [bmim][DCA] 4.188 4.209 0.49
2M MDEA + 1.0 M [bmim][DCA] 4.122 4.101 0.51 the maximum deviation of the experimental data from calculated
2M MDEA + 1.5 M [bmim][DCA] 4.075 4.057 0.45 values. Thus, the equations successfully correlated the heat
2M MDEA + 2.0 M [bmim][DCA] 4.008 3.960 1.22 capacity at different compositions and temperatures.
4M MDEA + 0.5 M [bmim][DCA] 4.040 4.040 0.01
4M MDEA + 1.0 M [bmim][DCA] 3.983 3.945 0.96
4M MDEA + 1.5 M [bmim][DCA] 3.934 3.860 1.91 3.3. Thermal conductivity
4M MDEA + 2.0 M [bmim][DCA] 3.885 3.824 1.59
Table 9 shows the measured thermal conductivity for aqueous
MDEA + [bmim][BF4] solutions at room temperature.
As illustrated in Table 9, thermal conductivity decreases with
b ¼ ð4:124½MDEA  1:261Þð½bmim½BF 4 Þ3
increasing ionic liquid concentration in the solvent. This might be
2
þ ð2:003½MDEA  0:554Þð½bmim½BF 4 Þ due to adding ionic liquid to water causes the formation of ion-pairs
þ ð0:167½MDEA  0:005Þð½bmim½BF 4 Þ and dispersing centers and that restrict the reproduction of heat in
 0:02½MDEA þ 0:009 (9) the studied mixture. Consequently, the overall heat resistance of the
heat exchangers in industrial units can be increased as a result of
thermal conductivity reduction. Thus, in spite of many advantages of
existing ionic liquid in the aqueous MDEA, this issue can be
g ¼ ð0:053½MDEA þ 0:013Þð½bmim½BF 4 Þ3 considered as a drawback of ionic liquid with existing amine
þ 0:026½MDEA  0:005Þð½bmim½BF 4 Þ
2 solvents in industrial applications. More study is required to
evaluate the effect of this parameter on all design calculations.
þ ð0:003½MDEA þ 0:0001Þð½bmim½BF 4 Þ
þ 0:0003½MDEA  0:0001 (10)
4. Conclusions

The surface tension and heat capacity for aqueous mixtures of

For the aqueous mixture of MDEA and [bmim][DCA], the
MDEA mixed with two types of ionic liquids, [bmim][BF4] and
equations are represented by
[bmim][DCA], were measured under atmospheric pressure. The
results showed that surface tension decreases linearly with
increasing temperature. An increase in concentration of the
a ¼ ð639:76½MDEA þ 37:64Þð½bmim½DCAÞ3
[bmim][BF4] and [bmim][DCA] in the mixtures resulted in a
2
þ ð222:45½MDEA  14:46Þð½bmim½DCAÞ decrease in surface tension. Linear equations were used to
þ ð38:703½MDEA þ 0:841Þð½bmim½DCAÞ correlate the measured surface tension values, while quadratic
þ 0:738½MDEA þ 4:621 (11) equations were used for heat capacity at different compositions
and temperatures.
The calculated deviations for the suggested correlation for
surface tension of aqueous MDEA + [bmim][BF4] mixtures were
Table 9
Thermal conductivity (k) of aqueous MDEA + [bmim][BF4] solutions.
reported to be about 8.4%. The proposed correlation can be applied
for the aqueous MDEA + [bmim][DCA]with known amount of
Solvents T (K) k (W m1 K1) doubt and unreliability.
4M MDEA 298.70 0.363 The heat capacity of aqueous MDEA + [bmim][BF4] and
4M MDEA + 0.2 M [bmim][BF4] 298.01 0.345 MDEA + [bmim][DCA] solutions increased with increasing tem-
4M MDEA + 0.5 M [bmim][BF4] 298.62 0.316
perature. Increasing [bmim][BF4] and [bmim][DCA] concentra-
4M MDEA + 1.0 M [bmim][BF4] 298.60 0.272
4M MDEA + 1.5 M [bmim][BF4] 298.20 0.233 tions in the mixtures resulted in decreasing heat capacity as well.
4M MDEA + 2.0 M [bmim][BF4] 298.50 0.208 The maximum deviation between experimental and calculated
The uncertainty for molar concentration is 0.002 and the uncertainty of measured
data for aqueous MDEA + [bmim][BF4] and MDEA + [bmim][DCA]
thermal conductivity at corresponding temperature was estimated to be as mixtures heat capacity were 2.98% and 1.91%, respectively. The
0.05 W m1 K1 and  0.01 K, respectively. proposed correlation can be applied for calculation of heat capacity
 R. Yusoff et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 3349–3355
for aqueous MDEA + [bmim][BF4] and MDEA + [bmim][DCA] mix-
tures within the presented ranges of temperature, ILs and MDEA
concentrations.
The thermal conductivity of aqueous 4 mol/L MDEA + [b-
mim][BF4] was measured at 298 K. The results showed that
conductivity of solvents decreased with increasing ionic liquid
concentration in the solutions, this reduction exceeded 40% for
4 mol/L MDEA + 2 mol/L [bmim][BF4].
Acknowledgment
This work was carried out under University of Malaya Centre for
Separation Science & Technology (CSST) and was financed by
UMRG grant no. RP015/2012E.
References
[1] B.-H. Lu, J.-J. Jin, L. Zhang, W. Li, International Journal of Greenhouse Gas Control
11 (2012) 152.
[2] A. Ahmady, M.K. Aroua, M.A. Hashim, Journal of Chemical and Engineering Data
55 (2010) 5733.
[3] L.-F. Chiu, M.-H. Li, Journal of Chemical and Engineering Data 44 (1999) 1396.
[4] L.S. Tan, A.M. Shariff, K.K. Lau, M.A. Bustam, Journal of Industrial and Engineering
Chemistry 18 (2012) 1874.
[5] L.-F. Chiu, H.-F. Liu, M.-H. Li, Journal of Chemical & Engineering Data 44 (1999)
631–636.
[6] Y.E. Kim, J.H. Choi, S.C. Nam, Y.I. Yoon, Journal of Industrial and Engineering
Chemistry 18 (2012) 105.
[7] J.L. Anderson, J.K. Dixon, E.J. Maginn, J.F. Brennecke, Journal of Physical Chemistry
B 110 (2006) 15059.
[8] J.E. Bara, T.K. Carlisle, C.J. Gabriel, D. Camper, A. Finotello, D.L. Gin, R.D. Noble,
Industrial and Engineering Chemistry Research 48 (2009) 2739.
[9] M.B. Shiflett, D.W. Drew, R.A. Cantini, A. Yokozeki, Energy Fuels 24 (2010) 5781.
[10] Y.S. Sistla, A. Khanna, Journal of Industrial and Engineering Chemistry (2013).
[11] S.M. Hosseini, M.M. Alavianmehr, D. Mohammad-Aghaie, F. Fadaei-Nobandegani,
J. Moghadasi, Journal of Industrial and Engineering Chemistry 19 (2012) 769.
[12] Z. Feng, F. Cheng-Gang, W. You-Ting, W. Yuan-Tao, L. Ai-Min, Z. Zhi-Bing,
Chemical Engineering Journal 160 (2010) 691.
3355
[13] A. Ahmady, M.K. Aroua, M.A. Hashim, Fluid Phase Equilibria 309 (2011) 76.
[14] K.-S. Hwang, Y.-S. Son, S.-W. Park, D.-W. Park, K.J. Oh, Journal of Industrial and
Engineering Chemistry 15 (2009) 854.
[15] A. Ahmady, A. Shamiri, M.A. Hashim, M.K. Aroua, Journal of the Taiwan Institute of
Chemical Engineers (2013).
[16] E. Alvarez, J.M. Correa, C. Riverol, J.M. Navara, International Communications in
Heat and Mass Transfer 27 (2000) 93.
[17] E. Alvarez, D. Gomez-Diaz, M.D. La Rubia, J.M. Navaza, Journal of Chemical &
Engineering Data 51 (2006) 955.
[18] G.L.M. Sanchez, G.W. Meindersma, A.B. de Haan, Chemical Engineering Research
and Design 85 (2007) 31.
[19] G. Vazquez, M.A. Cancela, C. Riverol, E. Alvarez, J.M. Navara, ICheme Trans 78
(2000) 889.
[20] R. Yusoff, M.K. Aroua, A. Shamiri, A. Ahmady, N.S. Jusoh, N.F. Asmuni, L.C. Bong,
S.H. Thee, Journal of Chemical & Engineering Data 58 (2013) 240.
[21] E. Álvarez, D. Gómez-Dı́az, M.D. La Rubia, J.M. Navaza, Journal of Chemical &
Engineering Data 53 (2007) 318.
[22] E. Alvarez, D. Gomez-Diaz, J.M. Navaza, B. Sanjurjo, Chemical Engineering Journal
137 (2008) 251.
[23] A.H.G. Cents, D.J.W. Jansen, D.W.F. Brilman, G.F. Versteeg, Industrial & Engineer-
ing Chemistry Research 44 (2005) 4863.
[24] L.-F. Chiu, H.-F. Liu, M.-H. Li, Journal of Chemical & Engineering Data 44 (1999)
631.
[25] K.-S. Kim, D. Demberelnyamba, B.-K. Shin, S.-H. Yeon, S. Choi, J.-H. Cha, H. Lee, C.-S.
Lee, J.-J. Shim, Korean Journal of Chemical Engineering 23 (2006) 113.
[26] M.G. Freire, P.J. Carvalho, A.M. Fernandes, I.M. Marrucho, A.J. Queimada, J.A.P.
Coutinho, Journal of Colloid and Interface Science 314 (2007) 621.
[27] W. Zhao, F. Leroy, B. Heggen, S. Zahn, B. Kirchner, S. Balasubramanian, F. Muller-
Plathe, Journal of the American Chemical Society 131 (2009) 15825–15833.
[28] A. Muhammad, M.I.A. Mutalib, C.D. Wilfred, T. Murugesan, A. Shafeeq, Journal of
Chemical & Engineering Data 53 (2008) 2226.
[29] A. Venkat, G. Kumar, M. Kundu, Journal of Chemical & Engineering Data 55 (2010)
4580.
[30] C.A. Nieto de Castro, E. Langa, A.L. Morais, M.L.M. Lopes, M.J.V. Lourenco, F.J.V.
Santos, M.S.C.S. Santos, J.N.C. Lopes, H.I.M. Veiga, M. Macatrao, J.M.S.S. Esperança,
C.S. Marques, L.P.N. Rebelo, C.A.M. Afonso, Fluid Phase Equilibria 294 (2007) 157.
[31] Y.-H. Yu, A.N. Soriano, M.-H. Li, Journal of the Taiwan Institute of Chemical
Engineers 40 (2009) 205.
[32] Y.-H. Yu, A.N. Soriano, M.-H. Li, The Journal of Chemical Thermodynamics 41
(2009) 103.
[33] M. Mundhwa, A. Henni, Journal of Chemical & Engineering Data 52 (2007)
491.