Fluid Phase Equilibria 360 (2013) 139–145

Contents lists available at ScienceDirect

Fluid Phase Equilibria

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

Effect of different families (imidazolium and pyridinium) of ionic

liquids-based surfactants on interfacial tension of water/crude
oil system
Ali Zeinolabedini Hezave a , Samira Dorostkar b , Shahab Ayatollahi a,∗,1 ,
Moein Nabipour a , Bahram Hemmateenejad b
a
EOR Research Center, School of Chemical and Petroleum Engineering, Shiraz University, Mollasadra Avenue, Shiraz 71345, Iran
b
Chemistry Department, Shiraz University, Shiraz, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Interfacial tension between crude oil and water plays a significant role in enhanced oil recovery. Many
Received 30 April 2013 researchers seek surfactants to reduce the interfacial tension of crude oil and water that can be applicable
Received in revised form 7 September 2013 in reservoir conditions of high salinity and temperature. The current study introduces the results of
Accepted 11 September 2013
using two different families of ionic liquids (ILs) including imidazolium (1-dodecyl-3-methylimidazolium
Available online 20 September 2013
chloride ([C12 mim][Cl]) and 1-octyl-3-methylimidazolium chloride ([C8 mim][Cl])) and pyridinium (1-
dodecyl pyridinium chloride ([C12 Py][Cl]) and 1-octyl pyridinium chloride ([C8 Py][Cl])) for this purpose.
Keywords:
Measured IFT values between solutions of ILs and a southern Iranian crude oil reveal that these ILs are
Ionic liquids
Interfacial tension
successful in reducing the IFT. Unlike traditional surfactants, these ILs are more effective as the salinity
Crude oil increases. Also the measurements revealed that there is a correlation of the IFT of the solutions with
Spinning drop salinity and temperature.
Pendant drop © 2013 Elsevier B.V. All rights reserved.

1. Introduction surfactant injection processes in specific reservoirs for more oil

Ionic liquids (ILs) are liquids at ambient or even far below ambi-
ent temperature that have 1 unique feature to make them good
candidates for conventional solvents replacement [1–9].
One of the important industries that is a good candidate for the
application of ILs is oil industry. In the light of high oil prices because
of increasing demands followed by the limitation on recovery effi-
ciencies from the existed oil reservoirs petroleum companies are
looking for oil from unconventional oil reserves which imposes
high amount of expenses. However, as a way out it is possible
to seek for new technologies that can extract more oil from the
existed oil reservoirs called enhanced oil recovery (EOR) [10–23].
The main mechanisms during EOR to mobilize trapped oil in the
reservoirs are interfacial (IFT) reduction and wettability alteration.
Surfactant flooding utilizes these two main techniques to modify
capillary number in the oil reservoirs consequently increases the
oil recovery efficiency. Regarding to this potential, several inves-
tigations have been carried out to examine the effectiveness of
∗ Corresponding author at: EOR Research Center, School of Chemical and
Petroleum Engineering, Shiraz University, P.O. Box. 71345-1719, Shiraz, Iran.
E-mail address: Shahab@shirazu.ac.ir (S. Ayatollahi).
1
Now with Sharif University of Technology, Tehran, Iran.
recovery efficiency. As an example, Bansal et al. [15] reported that
the recovery of oil is mainly depends on miscibility and mobility
control of oil/water/rock interface.
Although, during the past decades, different types of surfactants
have been proposed and utilized by several researchers; how-
ever, still there is an ample space in the area of designing specific
surfactants which are to tolerate harsh conditions of salinity and
temperature. This is the main goal in surfactant industry to design
and formulate the best surface active agent to reduce the oil/water
IFT even at very high salinity (similar to the formation brine) and
high temperature. It is commonly accepted that most of the con-
ventional surfactants lose high portion of their functionality at
reservoir condition. In the present study the feasibility of ILs as an
IFT reducing agent which can tolerate harsh conditions of salinity
and temperature was examined.
There seem to be few systematic investigations on the effect of
ILs on the IFT reduction of crude oil + water system except those
reported by the authors [24,25]. For example, Gardas et al. [26] have
reported interfacial tensions of several 1,3-dialkyl imidazolium
based ionic liquids, including 1-alkyl-3methylimidazoliumbis
{(trifluoromethyl)sulfonyl}imide with alkyl change length of
C1 –C8 , 1-butyl-3-methylimidazolium trifluoromethylsulfonate
[C4 mim][CF3 SO3 ], and 1-butyl-3-methylimidazolium trifluoroac-
etate [C4 mim][CF3 COO], with water and with the n-alkanes,

0378-3812/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fluid.2013.09.025
140 A. Zeinolabedini Hezave et al. / Fluid Phase Equilibria 360 (2013) 139–145

Table 1
Crude oil composition.

Experiments Unit Standard Results

Acidity mg KOH/g sample ASTM D664 3.7

Saturates content Mass percent SARA 45%
Aromatic content Mass percent SARA 32%
Asphaltene Mass percent SARA 5%
Resin content Mass percent SARA 8%

n-hexane, n-octane and n-decane using the pendant drop method

as a function of temperature from 293 to 323 K [26].
The applicability of 1-dodecyl-3-methylimidazolium chloride
([C12 mim][Cl]) for EOR of light and heavy crude oil was investi-
gated by the coauthors [24,25] recognizing its desired behavior at
high salinity. The results showed high potential to utilize this kind
of surfactant in EOR processes to reduce the IFT hence increasing
oil recovery efficiency.
Based on these findings, in the present study two different meth-
ods of IFT measurement techniques (pendant drop and spinning Fig. 1. Schematic of the pendant drop geometry [32].

drop) were employed to measure the IFT of crude oil and four differ-
ent ILs solutions including [C12 mim][Cl], [C8 mim][Cl], [C12 Py][Cl]
and [C8 Py][Cl] from two different families (imidazolium and pyri-
dinium) at the presence and absence of salinity. The effects of NaCl
concentration, temperature and IL concentration on the IFT were
systematically studied.
2. Experimental procedure
2.1. Materials
1-Methylimidazole, 1-chlorododecyl, 1-chlorooctane, pyridine
and diethyl ether were purchased from Merck/Fluka and used with-
out any further purification. Using available procedures [27] the ILs
([C12 mim][Cl], [C8 mim][Cl], [C12 Py][Cl] and [C8 Py][Cl]) were syn-
thesized by reacting 1-methylimidazolium or pyridine with excess
amount of the 1-chlorododecane or 1-chlorooctane without any
additional solvent in a round-bottomed flask fitted with a reflux
condenser (heating and stirring at 70 ◦ C for 48–72 h). The resulting
viscous liquid was cooled to room temperature, and then washed
using diethyl ether. After drying overnight at 100 ◦ C, the purity of
the products was assessed by H-NMR spectroscopy. Crude oil was
obtained from one of the southern Iranian oilfields with the API◦ 30
(see Table 1). The composition of the used formation brine is given
in Table 2.
2.2. IFT measurement
The interfacial tension of IL solution and crude oil was measured
using spinning drop method (KRUSS, SITE-100; KRUSS, Germany).
A detailed description of the used spinning drop method has been
brought elsewhere [28,29]. The IL solution as outer-phase was
injected into the glass tube, and 3–4 ␮L crude oil as inner-phase
was put into the middle of the tube. Then, the interfacial tension
was measured applying a rotating velocity of 5000–6500 rpm in all
Table 2
The formation brine composition.
Ions Concentration (ppm)
cases as usual. The interfacial tension was obtained from Eq. (1)
below [28,29]:
ω2 D3
= (1)
32
where ω, D and  are the angular velocity, diameter of oil drop and
density difference between outer-phase and inner-phase (mg L−1 ).
The used IFT measurement apparatus was designed and calibrated
to measure the IFT in the range of 10−6 to 50 mN m−1 . In this study,
the IFT(s) below 6 mN m−1 were measured by spinning drop while
higher IFT values were measured by pendant drop method. The
applicability and accuracy of spinning drop for measuring low IFT(s)
were examined and validated by measuring the IFT of water (bulk
phase) + 1-octanol (drop phase). In the literature [30], the IFT of
water + 1-octanol has measured and reported to be 8.5 mN m−1
while the spinning drop used in the current study demonstrated
7.9 mN m−1 with the absolute relative deviation percent (AARD %)
of 7.3%. This AARD % rises from different parameters such as cali-
bration, purity of the samples and rotational speed of the spinning
drop. The IFT measurement close to 1 mN m−1 is more accurate
using the spinning drop apparatus. In addition, it must be men-
tioned that for the high IFT solutions, pendent drop instrument
(KRUSS, DSA 100, Germany) was employed.
Pendent drop technique is an important practical technique
since it permits continuous study of interfacial phenomena. The
technique involves the formation of a drop of oil on the tip of a cap-
illary tube immersed in the bulk of the continuous aqueous phase.
The pendant drop method involves the determination of the profile
of a drop of one liquid suspended in another liquid at mechanical
equilibrium. The profile of a drop of liquid suspended in another
liquid is determined by the balance between gravity and surface
forces. The equation of Bashforth and Adams [31] which is based
on Laplace’s equation correlates the drop profile to the interfacial
tension through a nonlinear differential equation which is given
below:
1 sin ϕ z
+ = −B + 2 (2)
R1 /a x/a a
where B defined as below:

Na+ /K+ 47,020 a2 g

B= (3)
Ca2+ 4000 
Mg2+ 1458
Cl− 81,650 where  is the difference between the densities of the two liquids
SO4 2− 2800 in contact, g is the gravitational constant,  is the interfacial tension,
HCO3 − 366
a is the radius of curvature at the apex of the drop, x, z, F are the
 A. Zeinolabedini Hezave et al. / Fluid Phase Equilibria 360 (2013) 139–145
Fig. 2. Schematic of the used pendant drop equipment.
coordinates (see Fig. 1) and R1 is the radius of curvature at the point
with coordinates (x, z).
R1 and ϕ can be defined geometrically by:
2 3/2
ds [1 + (dz/dx) ]
R1 = = (4)
dϕ d2 z/dx2
dz/dx
sin ϕ = (5)
2 1/2
[1 + (dz/dx) ]
A typical pendant drop apparatus consists of three parts: an exper-
imental cell, an illuminating and a viewing system to visualize the
drop and a data acquisition system to infer the interfacial tension
from the pendant drop profile (see Fig. 2).
3. Results and discussions
In the present work, effects of presence and absence of
ions, different ILs concentrations and temperature on the IFT of
binary systems containing crude oil and ILs namely [C12 mim][Cl],
[C8 mim][Cl], [C12 Py][Cl] and [C8 Py][Cl] were investigated.
3.1. Effect of ILs on IFT of crude oil and distilled water
In the first stage of this study, the effects of ILs on the reduction of
distilled water + crude oil IFT with no salinity were investigated. The
obtained results listed in Table 3 revealed very interesting behavior
for the two different families of ILs with two different tail lengths
(see Fig. 3). As it is shown in Fig. 3, ILs of pyridinium with eight car-
bon numbers is less effective than the IL with the same tail length
from imidazolium family, while for longer chain (twelve carbon
numbers) the trend was reversed. On the other hand, comparing the
IFT of ILs with eight carbon numbers ([C8 Py][Cl] and [C8 mim][Cl])
with the IFT of ILs with twelve carbon numbers ([C12 Py][Cl] and
[C12 mim][Cl]) revealed stronger effect of ILs with longer tail length
on IFT reduction. It means, as the length of the chain increases
the capability of the IL to reduce the IFT increases. This observed
trend can be related to two different possible reasons including the
effect of hydrophobic tail length and the CMC of ILs. In detail, Smit
and his coworkers [33] showed that as the hydrophobic tail length
increases higher IFT reduction is observed. In other words, longer
tails are more effective at low concentrations; that is, less surfac-
tant is needed to achieve the same IFT. Hence, more economical
and environmental friendly process is possible.
In more detail, the results revealed that the measured IFT of
[C8 Py][Cl] decreases slightly from 39.98 mN m−1 to 21.89 mN m−1
while the IFT for [C12 Py][Cl] experienced significant reduction
(from 39.98 mN m−1 to 5.63 mN m−1 ). Therefore, a sharp criti-
cal micelle concentration (CMC) can be observed for [C12 Py][Cl]
compared with [C8 Py][Cl]. Generally, the proportion of molecules
141
50
[C8Py][Cl]
[C Py][Cl]
40 12
Interfacial Tension (mN.m -1)
[C mim][Cl]
8
[C12mim][Cl]
30
20
10
0
0 2000 4000 6000 8000 10000
IL Concentration (ppm)
Fig. 3. Effect of IL concentration on IFT reduction using distilled water.
present at the surface or micelles in the bulk of the liquid depend
on the concentration of the amphiphile. As the surface becomes
crowded with surfactant more molecules will arrange into micelles.
At some concentrations the surface becomes completely loaded
with surfactant and any further addition of surfactant arrange as
micelles. This concentration is called the CMC [34,35]. Based on
this definition, it can be concluded that the CMC for [C12 Py][Cl] is
500 ppm while no sharp CMC can be observed for [C8 Py][Cl]. In
addition, comparing the results of [C8 mim][Cl] and [C12 mim][Cl]
demonstrated that similar trend can be observed for these two ILs
([C8 mim][Cl] and [C12 mim][Cl]) although the CMC for [C8 mim][Cl]
is sharper (1000 ppm) compared to [C8 Py][Cl].
A closer examination in Table 3 revealed that not only
[C12 Py][Cl] shows lower CMC (500 ppm) compared with CMC of
[C12 mim][Cl] (2000 ppm), but also the capability of [C12 Py][Cl]
is higher compared to [C12 mim][Cl] for IFT reduction. This
observed trend can be described in this way that hydrophobicity
(lipophilicity) of pyridinium (log P = 0.65) is more than imidazolium
(log P = −0.97) head group simulated by (HyperCube Inc., version
7.0). Thus, in the interface of water/oil, cationic pyridinium head
group immerse into oil better than imidazolium head group and
the repulsion effect between cationic head group decreases. On
the other hand, since more pyridinium-based ILs are available at
the interface, higher reduction in CMC and IFT will be observed
compared to imidazolium-based ILs.
Furthermore, a glance at Table 3 revealed that as the concen-
tration of [C8 mim][Cl] increases from 1000 ppm to 2000 ppm, IFT
decreases from 16.77 mN m−1 to 12.56 mN m−1 while an increase of
[C12 mim][Cl] concentration from 1000 ppm to 2000 ppm reduces
the IFT from 28.44 mN m−1 to 7.23 mN m−1 . The critical effect of
the concentration observed for [C12 mim][Cl] solution can be risen
from the longer hydrophobic tail of [C12 mim][Cl], which increases
the strength of surfactant and consequently more IFT reduction is
observed.
3.2. Effect of ILs on the IFT of crude oil and formation brine
The IFT between the crude oil and different solutions prepared
by formation brine and four different ILs was measured at this stage.
The obtained results listed in Table 4 interestingly revealed that
the presence of ions in the medium leads to a lower interfacial ten-
sion compared with the solutions prepared by distilled water. This
142 A. Zeinolabedini Hezave et al. / Fluid Phase Equilibria 360 (2013) 139–145

Table 3
Effect of imidazolium and pyridinium based ILs solution prepared by distilled water on the IFT (mN m−1 ) of crude oil (ı is standard deviation obtained using minimum three
dependent measurements for each data point).

Ionic liquid concentration (ppm) Interfacial tension (mN m−1 ) ± ı

[C8 Py][Cl] [C12 Py][Cl] [C8 mim][Cl] [C12 mim][Cl]

0 39.98 ± 1.02 39.98 ± 1.02 39.98 ± 1.02 39.98 ± 1.02a

100 38.49 ± 0.79 37.12 ± 1.05 38.77 ± 1.11 37.59 ± 0.78a
250 35.82 ± 0.82 33.5 ± 0.94 35.77 ± 0.95 34.21 ± 0.71
500 31.68 ± 0.75 8.72 ± 0.43 34.55 ± 0.81 32.36 ± 0.63
750 30.21 ± 0.70 7.42 ± 0.37 29.87 ± 0.44 29.12 ± 0.52
1000 29.53 ± 0.62 7.38 ± 0.31 16.77 ± 0.47 28.44 ± 0.38a
2000 26.62 ± 0.58 4.27 ± 0.15 12.56 ± 0.23 7.23 ± 0.20
5000 23.33 ± 0.55 2.68 ± 0.10 11.87 ± 0.40 6.84 ± 0.21a
10,000 21.89 ± 0.52 5.63 ± 0.21 10.87 ± 0.39 6.54 ± 0.18
a
These data are obtained from Ref. [26].

Table 4
Effect of imidazolium and pyridinium based ILs solution prepared by formation brine on the IFT (mN m−1 ) of crude oil (ı is standard deviation obtained using minimum three
dependent measurements for each data point).

Ionic liquid concentration (ppm) Interfacial tension (mN m−1 ) + ı

[C8 Py][Cl] [C12 Py][Cl] [C8 mim][Cl] [C12 mim][Cl]

0 38.02 ± 1.00 38.02 ± 1.00 38.02 ± 1.00 38.02 ± 1.00

100 33.10 ± 0.56 25.20 ± 0.57 31.32 ± 0.74 0.81 ± 0.03a
250 31.20 ± 0.55 7.10 ± 0.21 26.50 ± 0.56 0.85 ± 0.03
500 29.78 ± 0.48 6.30 ± 0.33 11.12 ± 0.42 0.83 ± 0.03
750 18.24 ± 0.42 5.10 ± 0.34 8.70 ± 0.48 0.83 ± 0.03
1000 17.78 ± 0.33 4.40 ± 0.20 6.47 ± 0.35 0.95 ± 0.03a
2000 17.07 ± 0.21 4.20 ± 0.11 5.97 ± 0.26 0.95 ± 0.03
5000 16.30 ± 0.25 4.10 ± 0.13 5.01 ± 0.28 0.96 ± 0.03a
10,000 15.30 ± 0.24 3.87 ± 0.14 4.57 ± 0.17 0.95 ± 0.03
a
These data are obtained from Ref. [26].

observed trend is in contrast to those observations reported for con- the solution reduces the repulsion between the Cl− ions of imidaz-
ventional surfactants. In other words, it has been usually believed olium based ILs, which leads to formation of micelles in the lower
that the presence of ions especially divalent cations can reduce the concentrations (see Fig. 4).
functionality of surfactants while in the case of using ILs, reverse As mentioned previously, the hydrophobicity of imidazolium
results were obtained. Based on these results, it is possible to con- head group is less than pyridinium head group. Thus, in the
sider the ILs as a new type of surfactants capable to reduce the water/oil interface, cationic imidazolium head group shows more
IFT between the crude oil and water even at harsh salinity con- tendencies to water compared to pyridinium head group, con-
dition. Similar results was previously obtained by authors [24,25] sequently more effective repulsion between cationic head group
examined the effect of 1-dodecyl-3-methylimidazolium chloride in imidazolium-based ILs will be occurred. However, if the dis-
([C12 mim][Cl]) on the IFT of heavy and light crude oil and saline tilled water is replaced by formation of brine (consisted of large
water. The possible mechanism can be related to this fact that amount of ions especially negative ions) the repulsion forces
these four ILs are cationic with positive charges. Therefore, in the replace with attraction forces between Cl− and IL positive surface
absence of any ions either positive or negative, the IL molecules charges at the molecular level. But, since pyridinium head group
cannot freely arrange at the oil–water interface, where the high
charge density leads to a molecular repulsion. However, when high
amount of ions especially negative ions are present in the solution,
the repulsion forces are replaced by the attraction between the Cl−
and IL positive surface charges at the molecular level which causes
slight decrease of repulsion which influences the cationic charges
of IL head groups. In other words, the negatively charged ions neu-
tralize the positive surface charges of cationic surfactant (IL). This
leads to easier accumulation of IL molecules at oil–brine interface,
which causes more IFT reduction (see Fig. 4).
In addition, detailed investigation in Table 4 illustrated that not
only the presence of ion can increase the strength of IL to reduce the
IFT but also are able to modify the CMC for all of the four used ILs.
For example, the obtained results demonstrated that the presence
of ions reduces the CMC of [C12 Py][Cl] from 500 ppm to 250 ppm,
and CMC of [C8 mim][Cl] from 1000 ppm to 500 ppm and CMC of
[C12 mim][Cl] from 2000 ppm to 100 ppm. It is completely obvious
that the presence of ions was more effective to reduce the CMC
for imidazolium based ILs compared to pyridinium based ILs with Fig. 4. Schematic representation of the effect of ions on the decreasing of IFT in the
more profound effect for [C12 mim][Cl]. The presence of cations in oil/water interface.
 A. Zeinolabedini Hezave et al. / Fluid Phase Equilibria 360 (2013) 139–145 143

Fig. 5. Schematic representation of the effect of head group of ionic liquids on the decreasing of IFT in the oil/water interface, (a) pyridinium and (b) imidazolium.

Table 5
Effect of NaCl concentration on the IFT (mN m−1 ) between crude oil and different ILs solutions (ı is standard deviation obtained using minimum three dependent measurements
for each data point).

NaCl concentration (ppm) [C12 Py][Cl] concentration (ppm)

100 250 500 750 1000

300,000 1.14 ± 0.09 0.98 ± 0.03 1.03 ± 0.06 0.95 ± 0.05 0.91 ± 0.04
250,000 1.59 ± 0.05 1.38 ± 0.08 1.39 ± 0.07 1.37 ± 0.03 1.47 ± 0.08
200,000 2.71 ± 0.11 2.13 ± 0.06 1.99 ± 0.05 1.96 ± 0.07 1.90 ± 0.07
150,000 2.99 ± 0.10 2.95 ± 0.05 2.65 ± 1.12 2.60 ± 0.08 2.57 ± 0.10

[C8 mim][Cl] concentration (ppm)

0 25 50 100 250 500 750 1000

300,000 32.60 ± 1.10 29.87 ± 0.91 25.60 ± 0.17 14.10 ± 0.34 12.23 ± 0.44 9.60 ± 0.33 1.51 ± 0.08 1.29 ± 0.06
250,000 30.80 ± 1.05 30.23 ± 0.83 27.20 ± 0.14 14.20 ± 0.68 11.87 ± 0.71 10.70 ± 0.31 1.63 ± 0.04 1.37 ± 0.06
200,000 35.70 ± 1.00 30.01 ± 0.98 26.35 ± 0.22 14.40 ± 0.25 11.45 ± 0.39 11.30 ± 0.35 1.82 ± 0.05 1.43 ± 0.07
150,000 32.60 ± 1.12 28.45 ± 0.72 26.54 ± 0.31 15.90 ± 0.41 13.54 ± 0.51 12.10 ± 0.15 2.01 ± 0.07 1.78 ± 0.06

[C8 Py][Cl] concentration (ppm)

0 25 50 100 250 500 750 1000

300,000 32.60 ± 1.10 31.23 ± 0.69 27.85 ± 0.54 16.54 ± 0.31 15.62 ± 0.20 14.32 ± 0.09 13.54 ± 0.41 12.01 ± 0.46
250,000 30.80 ± 1.05 30.62 ± 0.30 28.96 ± 0.21 16.00 ± 0.10 15.23 ± 0.09 14.05 ± 0.08 13.48 ± 0.10 11.98 ± 0.51
200,000 35.70 ± 1.00 30.20 ± 0.15 28.62 ± 0.16 15.64 ± 0.13 15.41 ± 0.11 13.91 ± 0.09 13.33 ± 0.34 11.86 ± 0.31
150,000 32.60 ± 1.12 29.89 ± 0.32 28.41 ± 0.17 14.75 ± 0.20 14.61 ± 0.29 13.90 ± 0.05 13.25 ± 0.13 11.23 ± 0.21

is more hydrophobic than imidazolium head group, they slightly
immerse into the oil and the repulsion effects between cationic
pyridinium head group in the interface will be less effective (see
Fig. 5).
3.3. Effect of NaCl concentration on the IFT of crude oil and ionic
liquid solutions
In this stage, the effect of NaCl concentration on the IFT of crude
oil and IL solution at different concentrations of ILs was examined.
The results given in Table 5 revealed that the NaCl concentration
at higher concentrations reduces the IFT significantly. As previ-
ously mentioned, this observed trend is in contrast with the results
obtained for other conventional surfactants. This makes the ILs
as effective alternatives to IFT reducing agents for EOR processes
dealing with harsh salinity conditions.
In addition, the results demonstrated critical effect of NaCl on
CMC of [C12 Py][Cl] from 500 ppm (prepared by distilled water) to
50 ppm (see Table 5 and Fig. 6), although a high concentration of
NaCl did not modify the CMC of [C8 mim][Cl] and [C8 Py][Cl] signif-
This trend was not observed for ionic liquids with shorter tail
length of [C8 mim][Cl] and [C8 Py][Cl].
3.4. Effect of temperature on the IFT of crude oil and ionic liquid
solutions
In the final stage of this study, the effect of temperature (293 K,
303 K, 313 K, 323 K and 333 K) on the IFT of crude oil and IL solution
(IL + formation brine) was examined. The obtained results given in
Table 6 revealed that temperature elevation leads to the increase
of IFT between the crude oil and ILs solutions (see Table 6). The
results revealed that temperature increase has greater effect on the
IFT of [C12 Py][Cl] compared to [C8 mim][Cl] and [C8 Py][Cl]. This is
because of the presence of nitrogen atoms in the imidazolium and
pyridinium based ILs.
Table 6
Effect of temperature on the IFT (mN m−1 ) between crude oil and aqueous solu-
tion (10,000 ppm IL + 300,000 ppm NaCl) (ı is standard deviation obtained using
minimum three dependent measurements for each data point).

icantly. Temperature (K) [C8 mim][Cl] [C12 Py][Cl] [C8 Py][Cl]

The point which is completely obvious in Fig. 6 is less time is 293 1.29 ± 0.07 0.91 ± 0.04 12.10 ± 0.15
required for the IFT to reach to equilibrium as the salinity increases. 303 1.74 ± 0.05 1.47 ± 0.05 13.12 ± 0.25
It is suggested that, as the salinity (concentration of NaCl) increases, 313 2.11 ± 0.08 2.09 ± 0.06 15.60 ± 0.18
the available counter-ions to neutralize the charge of surfaces for 323 2.42 ± 0.07 2.54 ± 0.05 16.01 ± 0.10
333 2.91 ± 0.05 2.76 ± 0.04 16.45 ± 0.12
rapid orientation of surfactant molecules increases.
144 A. Zeinolabedini Hezave et al. / Fluid Phase Equilibria 360 (2013) 139–145

10 boundary of two immiscible phases increases by increasing tem-

a) perature, which reduces the interfacial tension, thus, the interfacial
300000 ppm NaCl
9 tension decreases by increasing the temperature. While, when the
250000 ppm NaCl
solution temperature reaches PIT, the adsorption of surfactant onto
200000 ppm NaCl
Interfacial Tension (mN.m -1)

8 the interface achieves its maximum value, leads to the minimum

150000 ppm NaCl
interfacial tension. It is proved for the temperature higher than
7
PIT; the surfactant adsorbed onto the interface diffuses into the oil
6 phase, which may lead to the inversion of emulsion as the content
of surfactant in oil phase accumulated to some extent [36,37].
5
4. Conclusions
4
In the present study, the possibility of using four different ILs
3
including [C12 mim][Cl], [C8 mim][Cl], [C12 Py][Cl], and [C8 Py][Cl]
2 from two different families namely imidazolium and pyridinium
to reduce the interfacial tension of crude oil/water system were
1 investigated. For this purpose, different IFT measurements tech-
0 200 400 600 800 1000 1200 niques including pendant drop and spinning drop methods were
Time (s) employed and the effects of NaCl concentration, temperature and
absence and presence of ions were evaluated.
35
b) In general, the results revealed that contrary to the conventional
300000 ppm NaCl surfactants, all of the four examined ionic liquids were more effec-
30 250000 ppm NaCl tive at the presence of salinity to reduce the IFT. In addition, the
200000 ppm NaCl
Interfacial Tension (mN.m -1)

results demonstrated that the presence of ions in the water reduces

150000 ppm NaCl more the critical micelle concentrations of all of the examined ILs
25 compared to the ILs solutions prepared by distilled water. Also, the
measurements at different temperatures illustrated less function-
ality of the used ILs when the temperature increases. Furthermore,
20
possible mechanisms were discussed in details based on the simu-
lations performed by Hyperchem software (HyperCube Inc., version
15 7.0).
In general, due to an unusual but favorable characteristic of the
examined ILs, it seems that utilization of ILs is more applicable and
10 feasible for EOR purposes. However, before any reliable judgment
on the field application of these ILs, it is critically important to
design ILs based which are not only able to tolerate the harsh reser-
5
0 500 1000 1500 2000 voir salinity conditions but also to reduce more the IFT several order
Time (s) of magnitude. In addition, the adsorption of tailored ILs on the rock
surfaces must be examined since this parameter is vital if a sur-
Fig. 6. Effect of NaCl concentration on the dynamic interfacial tension at different factant is going to be used in the field scale. Regarding these facts,
concentrations of [C12 Py][Cl], (a) 50 ppm and (b) 25 ppm. it seems that this new function of ionic liquids is in the beginning
stage of its ever growing applications.

To check the temperature effect in more detail on the imid-
azolium based ILs; Hyperchem software (HyperCube Inc., version
7.0) was employed which revealed that the cationic head of
[C12 mim][Cl] is more lipophile than the cationic head of conven-
tional surfactants, e.g., DTAB (e.g., log P imidazolium = −0.97 and
log P ammonium = −1.3). This can be attributed to the fact that
in imidazolium, nitrogen atoms are in aromatic ring (with sp2
hybridization), and the positive charge is in resonance. Thus, as
the temperature increases, the diffusion of ILs into the oil phase
increases which results in emulsion inversion as the content of
ILs in oil phase accumulated to some extent. This would be con-
sidered as the most reliable reason behinds the IFT changes by
temperature. In addition, phase inversion temperature (PIT) might
be effective when the IFT(s) of the solutions prepared by these four
ILs and crude oil are altered by temperature. As described in our
previous work [26], these obtained results can be related to vari-
ation in surfactant distribution between oil and water as well as
the emulsions inverting from oil-in-water at low temperatures to
water-in-oil as the temperature increases. The temperature corre-
sponding to a minimum in interfacial tension is known as the phase
inversion temperature (PIT). It is described as when the tempera-
ture is below PIT, the adsorption of surfactant molecules onto the
References
[1] P. Wasserscheid, T. Welton, Ionic Liquids in Synthesis, 2nd ed., Wiley-VCH
Verlag GmbH & Co. KGaA, Darmstadt, Federal Republic of Germany, 2009.
[2] P. Nockemann, B. Thijs, S. Pittois, J. Thoen, C. Glorieux, K. Van Hecke, B. Van
Meervelt, L. Kirchner, K. Binnemans, J. Phys. Chem. B 110 (2006) 20978–20992.
[3] V.M. Egorov, D.I. Djigailo, D.S. Momotenko, D.V. Chernyshov, I.I. Torochesh-
nikova, S.V. Smirnova, I.V. Pletnev, Talanta 80 (2010) 1177–1182.
[4] E.D. Bates, R.D. Mayton, I. Ntai, J.H. Davis, J. Am. Chem. Soc. 124 (2002) 926–927.
[5] J. Gui, Y. Deng, Z. Hu, Z. Sun, Tetrahedron Lett. 45 (2004) 2681–2683.
[6] H. Xing, T. Wang, Z. Zhou, Y. Dai, Ind. Eng. Chem. Res. 44 (2005) 4147–4150.
[7] H. Luo, S. Dai, P.V. Bonnesen, A.C. Buchanan, J. Alloys Compd. 418 (2006)
195–199.
[8] X. Sun, Y. Ji, J. Chen, J. Ma, J. Rare Earths 27 (2009) 932–936.
[9] A.R. Katritzky, R. Jain, A. Lomaka, R. Petrukhin, M. Karelson, A.E. Visser, R.D.
Rogers, J. Chem. Inf. Comput. Sci. 42 (2002) 225–231.
[10] A.T. Gregory, Trans. IChemE 72 (1994) 137–143.
[11] M.K. Sharma, D.O. Shah, Use of surfactants in oil recovery, in: E.C. Donald-
son, G.V. Chilingarian, T.F. Yen (Eds.), Enhanced Oil Recovery: II. Processes and
Operations, Elsevier, New York, 1989.
[12] R.G. Larson, G. Hirasaki, Soc. Pet. Eng. J. 18 (1978, February) 42–58.
[13] H.J. Hill, H. Reisberg, G.L. Stegemeier, J. Pet. Technol. 25 (1973) 186–194.
[14] D.O. Shah, R.S. Schechter, Improved Oil Recovery by Surfactant and Polymer
Flooding, Academic Press Inc., New York, 1977.
[15] J.A. Davis Jr., S.C. Jones, J. Pet. Technol. 20 (1968, December) 1415–1428.
[16] W.B. Gogarty, J. Pet. Technol. 28 (1976, January) 93–102.
[17] S.M. Farouq Ali, C.D. Stahl, Paper SPE 3994. Presented at the 47th Annual Fall
Meeting, Texas, 1972.
[18] S.P. Gupta, S.P. Trushenski, Soc. Pet. Eng. J. (1978, February) 5–12.
 A. Zeinolabedini Hezave et al. / Fluid Phase Equilibria 360 (2013) 139–145
[19] M.H. Sayyouh, S.M. Farouq Ali, C.D. Stahl, Soc. Pet. Eng. J. 21 (1981, August)
469–479.
[20] S.P. Trushenski, D.L. Dauben, D.R. Parrish, Soc. Pet. Eng. J. 14 (1974, December)
633–642.
[21] W.R. Foster, Pet. Technol. 25 (1973) 205–210.
[22] R.N. Healy, R.L. Read, Soc. Pet. Eng. J. 14 (1974) 491–501.
[23] R.N. Healy, R.L. Reed, Soc. Pet. Eng. J. 39 (1977) 129–139.
[24] A. Zeinolabedini Hezave, S. Dorostkar, S. Ayatollahi, M. Nabipour, B. Hemma-
teenejad, Colloids Surf., A 421 (20) (2013) 63–71.
[25] A. Zeinolabedini Hezave, S. Dorostkar, S. Ayatollahi, M. Nabipour, B. Hemma-
teenejad, J. Mol. Liq. 187 (2013) 83–89.
[26] R. Gardas, R. Ge, N. Ab Manan, D. Rooney, C. Hardacre, Fluid Phase Equilib. 294
(2010) 139–147.
[27] P. Wasserscheid, T. Welton, Ionic Liquids in Synthesis, 1st ed., Wiley-VCH Verlag
GmbH & Co. KGaA, Mörlenbach, 2002.
[28] M. Aoudia, R.S. Al-Maamari, M. Nabipour, A.S. Al-Bemani, Sh. Ayatollahi, Energy
Fuels 24 (2010) 3655–3660.
145
[29] M.J. Rosen, H.Z. Wang, P.P. Shen, Y.Y. Zhu, Langmuir 21 (2005)
3749–3756.
[30] A. Taylor Florence, D. Attwood, Physicochemical Principles of Pharmacy, 4th
ed., Pharmaceutical Press, USA, 2006.
[31] S. Bashforth, J.C. Adams, An Attempt to Test the Theory of Capillary
Action, Cambridge University Press and Deighton, Bell and Co., London,
1882.
[32] E.Y. Arashiro, N.R. Demarquette, Mater. Res. 2 (1) (1999) 23–32.
[33] B. Smit, A.G. Schlijper, L.A.M. Rupert, N.M. Van Os, J. Phys. Chem. 94 (18) (1990)
6933–6935.
[34] A. Kopczynska, G.W. Ehreinstein, J. Mater. Educ. 29 (2007) 325–340.
[35] M.Y. Khan, A. Samanta, K. Ojha, A. Mandal, Asia Pac. J. Chem. Eng. 3 (2008)
579–585.
[36] Zh. Ye, F. Zhang, L. Han, P. Luo, J. Yang, H. Chen, Colloids Surf., A 322 (2008)
138–141.
[37] R. Aveyard, B.P. Binks, J. Chen, J. Esquena, P.D.I. Fletcher, Langmuir 14 (1998)
4699–4709.