Article

pubs.acs.org/EF

Investigation on Interfacial Interactions among Crude OilBrine

Sandstone RockCO2 by Contact Angle Measurements
A. Ameri,,* N. Shojai Kaveh, E. S. J. Rudolph, KH. Wolf, R. Farajzadeh,, and J. Bruining

Department of Geoscience and Engineering, Delft University of Technology, Delft, 2628CN, The Netherlands

Shell Global Solutions International, 2288GS Rijswijk, The Netherlands

ABSTRACT: Wettability plays a crucial role on the performance of enhancing oil recovery techniques because of its eect on
uid saturations and ow behavior in porous medium. This study is directed toward determining contact angles (i.e., wettability)
in systems with carbon dioxide, brine, and an oil-saturated rock system. Two situations are considered: Rock system I is partially
water-wet, whereas rock system II is eectively oil-wet. Contact angles have been determined experimentally as a function of
brine salinity and pressure using the pendant-drop shape analysis. The experiments were carried out at a constant temperature of
318 K and pressures varying between 0.1 up to 16.0 MPa in a pendant-drop cell. For rock system I, the partially water-wet
substrate, brine, and CO2 system, the dependence on the pressure at constant salinity is very small. For this system, at a constant
pressure, the contact angle decreases for increasing brine salinity. The results show that the carbon dioxide is the nonwetting
phase in the pressure and salinity range studied. This behavior can be quantitatively understood in terms of the expected
dependencies of the three interfacial tensions (IFTs) in Youngs equation on pressure and brine salinity. For rock system II, the
eectively oil-wet substrate, brine, and CO2 system, the dependency of contact angle on pressure is considerable. This study
proves that carbon dioxide becomes the wetting phase at pressures higher than 10.0 MPa. Beyond 10.0 MPa (i.e., in the
supercritical region), the contact angle remains practically constant. The eect of salinity on the contact angle of the oil-wet rock
system II is small. The behavior can again be quantitatively understood based on expected trends of the three IFTs that
determine the contact angle. It is also shown that use of the equation of state method makes it possible to approach the
experimental data quantitatively. We conclude that contact angle measurements form an essential ingredient to determine the
eciency of carbon dioxide ooding and storage.

1. INTRODUCTION of the rock wettability, which controls the transport properties,

Carbon dioxide injection, either miscible or immiscible, has
been recognized as an ecient method to enhance oil recovery
and to reduce CO2 emission.13 By performing an exergy
analysis, Eftekhari et al.4 showed that the cost of separation and
reinjection of CO2 is comparable to the recovery process gain.
Therefore, to make the CO2-based oil enhancement processes
economically more ecient, the recovery process should be
optimized to maximize the oil recovery and to minimize the
storage costs. CO2 injection is typically applied after water
ooding where a signicant volume of oil is left behind due to
capillarity. However, the unfavorable gas mobility ratio and the
rock heterogeneity contribute to ngering and channeling,
which results in poor volumetric sweep eciency. To improve
the mobility ratio between the injected uid and the oil, water
and CO2 are usually injected in alternating slugs.5,6 It has been
shown by dierent studies that the chemical composition of the
aqueous phase has signicant eect on the performance of such
a process.79 At the same time, this may lead to the trapping of
a signicant volume of oil in the form of ganglia surrounded by
thin water lms. Consequently, the injected gas may not
directly contact the trapped oil.10 For such a condition, the
interactions between oil, water, CO2, and the rock surface
determine the ow characteristics of the system. One practical
approach to analyze and understand the ow behavior of such a
complex system is through investigation of the dynamic
interfacial interactions between rock, brine, CO2, and oil at
reservoir conditions. In this study, we focus on the investigation
viz. the relative permeability, the capillarity, and the residual
saturations of brine, CO2, and oil in the reservoir rock. This is
crucial for the control of the performance of any CO2 injection
process.
The wettability is determined by the relative surface energy
of, for example, two uids to a solid surface.11 Contact angle
determination is the most widely accepted method for
determining the average wettability of a specic surface at
reservoir conditions.12 Although this method is strongly
inuenced by several parameters including surface roughness,
viscous eects, contact line uctuations, and vibrations, it is
relatively easy to conduct and can be applied at high pressures
and temperatures. By denition, the contact angle is
determined through the densest phase. A reservoir rock is
considered to be water-wet when the contact angle of a water
droplet on the rock surface is in a range between 0 and 70. If
the water droplet has a contact angle in the range between 75
and 105, the surface is considered to be intermediate-wet.
Finally, when the contact angle is in the range between 105 and
180, the rock is oil-wet.
In general, for a CO2liquidsolid system, CO2 is assumed
to be the nonwetting phase. For most practical conditions, the
injected CO2 is in its supercritical state. Therefore, disregarding
Received: November 4, 2012
Revised: January 24, 2013
Published: January 28, 2013

2013 American Chemical Society 1015 dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025
Energy & Fuels Article

Table 1. Physical Properties of the Oil Samples Used in the Experiments

oil MW (g/gmol) density (g/mL) acid no. (mg KOH/g oil) base no. (mg KOH/g oil) C7+ (wt %) C11+ (wt %)
A 223.04 0.8376 0.24 0.02 0.294 0.01 96.38 77.57
B 223.98 0.8532 3.52 0.05 1.46 0.05 95.42 78.44

the possibility of partial wetting of CO2 may lead to an water-wet sandstone rock slabs. The contact angle data are then
underestimation of the eciency for oil recovery and storage described using an equation of state approach, which is the
implementation. Recent experiments and observations for subject of numerous studies, being carried out mostly by
dierent uidsolid combinations reveal that CO2 can be Neumann et al.2325
considered as the wetting or partially wetting phase with partial
water saturation.1315 Yang et al.16,17 addressed the eect of 2. MATERIALS AND METHOD
temperature, pressure, and CO2 dissolution and diusion on 2.1. Materials. Synthetic reservoir brines were prepared by
the wetting properties of the reservoir crude, reservoir brine, dissolving NaCl in doubly distilled water. Three dierent brines
reservoir rock, and CO2 system. The authors showed that CO2 representing low (5000 mg/L), intermediate (20 000 mg/L), and high
injection can alter the wettability of a limestone rock slice and salinity (35 000 mg/L) were used in the experiments. Six rock slabs
were obtained from a Bentheimer sandstone block. Each slab has
thus will signicantly inuence the oil recovery and CO2 dimensions of 30 12 6.0 mm3. The Bentheimer sandstone is
storage eciency. Chalbaud et al.18,19 conducted interfacial composed of 95% quartz, 3% clay, and less than 2% feldspars and is
tension experiments for brineCO2 systems at dierent naturally water-wet. The average porosity is 21%, and the permeability
pressures, temperatures, and salinity conditions representing a is around 1.5 Darcy. Carbon dioxide (purity 99.7%) is obtained from
CO2 storage operation. The authors concluded that, for a Linde Gas Benelux. Two crude oil samples, crude A and crude B, with
strong hydrophilic porous medium, the CO2 does not wet the dierent physical properties (Table 1) were used.
solid surface whereas if the porous medium is less hydrophilic 2.2. Experimental Setup. The experiments were conducted in a
the CO2 signicantly wets the surface. Chiquet et al.20 pendant-drop cell (PDC) that was adapted to allow captive-bubble
contact-angle measurements on real rock surfaces. The determination
conducted a series of contact angle experiments with various
of the contact angle is based on visual observation. The schematic of
brine solutions and CO2 as the uid phases and with solid the experimental setup is shown in Figure 1. The PDC consists of an
substrates mica or quartz, which are water-wet in the presence
of hydrocarbons. The experimental data revealed that the
wetting properties of mica change from water-wet toward
intermediate-wet at pressures higher than 10.0 MPa. In
addition, the wettability alteration is a consequence of CO2
dissolution, which leads to a decrease in the pH of the brine
solution. Shojai Kaveh et al.21,22 proved that CO2 can change
the wetting properties of a medium rank high volatile
bituminous (hvBb) coal from intermediate-wet to gas-wet.
For the injection of a synthetic ue gas, 20 vol % CO2, and 80
vol % N2, a change from water-wet to intermediate-wet was
observed. For the high rank semianthracite coal, the wettability Figure 1. Schematic representation of the experimental setup
alteration from intermediate-wet to gas-wet with CO2 injection (modied pendant drop cell).
was observed at pressures above 5.7 MPa.
Despite its importance for improved oil recovery and CO2 Inconel steel cylinder, which is resistant to brine with a wall thickness
storage, there are limited experimental data in the literature of 3.5 cm and a volume of 160 cm3. Both sides of the cell contain high
concerning the wettability behavior of the system consisting of pressure resistant glass windows, which make visual observation
crude oil, rock, brine, and CO2 at reservoir conditions. Most of possible on one side and a light source on the other side. This light
the previous studies on this topic concerned the wetting makes it possible to take pictures of the contour of the captured
behavior of the system consisting of rock, brine, and CO2 as bubble inside the PDC. The rock sample is positioned inside the cell
with a holder (Figure 2). The whole cylinder is placed in an oven box
function of pressure, temperature, and salinity. However, even
though the system including crude oil, rock, brine, and CO2 is
more realistic for the industry, only limited experimental data
on these systems are available in the literature. To our
knowledge, the work conducted by Yang et al.17 is the only
published research that attempts to identify the interfacial
interactions between crude oil, rock, brine, and CO2.
The main purpose of this study is to extend the research of
the previous studies. To this end, dierent substrates with
dierent wetting properties and dierent brines with varying
salinity are studied experimentally. A modied experimental
procedure, which simulates the real conditions in the CO2
injection process, is applied to evaluate the wetting properties
of a system consisting of crude oil, brine, rock, and CO2. Figure 2. Digital photograph of the inside of the modied pendant
Equilibrium contact angle experiments were conducted using a drop cell with a Bentheimer sandstone sample mounted inside. At the
modied pendant drop cell (PDC) technique at high pressures, bottom, the injection tip with an outer diameter of 2 mm and an inner
elevated temperature, and dierent salinities using oil-wet and diameter of 600 m is observed.

1016 dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025

Energy & Fuels
to keep the temperature constant. The gas supply system consists of a
gas bottle and a gas compressor that pumps CO2 into a buer cell
equipped with a pressure transmitter. The change in pressure gives
information about the number of moles of gas present in the modied
PDC, of which the dead volume and total volume are known. For
mole calculations, the SpanWagner reference equation of state for
CO2 has been used.26 In addition, a balance is used to determine the
amount of water that is added to the system. The composition of the
waterCO2 mixture is used to check whether the system is, at the
given temperature and pressure, in the two-phase equilibrium region.
A density meter inside the oven determines the density of the water
CO2 mixture that is circulated through the system. The accuracy of the
density meter is 0.1 kg/m3 in the temperature range between 273 and
313 K. Gas is injected into the cell via a capillary tube connected to the
bottom of the cell an exchangeable tip with an inner diameter of 600
m is mounted. The capillary is connected to a microneedle valve and
a high-pressure gas reservoir of known volume. The needle valve
restricts the amount of gas transferred from the reservoir to the
injection tip. In the gas reservoir, the temperature and the pressure are
determined to facilitate the computation of the exact amount of gas
added to the pendant drop cell. A high resolution digital camera is
connected to the cell using an endoscope. Digital images of the
pendant drop are successively captured as sharp as possible on a
vibration-free table.
2.3. Methodology. In this subsection, the experimental procedure
that is used to determine the wetting properties of the system rock, oil,
brine, and CO2 is explained. Thereby, typical in situ conditions that
might be encountered in CO2-injection processes are established. The
main advantage of the proposed procedure is that the experiments can
be conducted at realistic conditions of the most common CO2
injection scenarios (i.e., tertiary gas injection after water ooding
and water-alternating-gas injection processes).
Prior to the experiments, one side of each of the six rock slabs was
polished to mitigate the eect of surface roughness on the contact
angle determination. The characterization of the roughness of the
surface is based on the calculation of the so-called Pa factor.21 For an
ideal surface with zero roughness, Pa is zero. For a real surface, the Pa
factor is always higher than zero. The higher the Pa value, the rougher
the surface is. Then, the rock slabs were dried in an oven at 333 K for
48 h. Four substrates, viz., SB-1SB-4, were saturated with crude A
without any treatment and ltration. The substrates were then aged at
room temperature for at least six weeks. Crude B was used to saturate
the two other substrates, viz. SB-5 and SB-6. These two substrates
were aged with crude B for 22 months at 333 K (Table 2). This was
done to allow investigating the eect of aging time and oil properties
on the wetting properties of the surface.
Table 2. Summary of the Experiments
crude aging aging temp. brine salinity
sample wettability oil time (K) (mg/L)
SB-1 water-wet A 6 weeks 298 distilled water
SB-2 water-wet A 6 weeks 298 5000
SB-3 water-wet A 6 weeks 298 20000
SB-4 water-wet A 6 weeks 298 35000
SB-5 oil-wet B 22 333 distilled water
months
SB-6 oil-wet B 22 333 35000
months
For each run, a saturated rock slab was placed inside the cell and
leveled horizontally (Figure 2) before the cylinder is closed and made
leak-free. Subsequently, the cell was placed in the oven and was aligned
with the camera, the endoscope, and the light source. Next, the cell
was vacuumed to remove air. Then, the gas buer cell was lled and
pressurized with CO2 to make sure that enough CO2 is available for a
complete experimental run. The whole set up was then preheated to
318 K. After reaching the desired temperature, the temperature in the
oven was kept constant at 318 K for all experiments. Thereafter, the
1017
Article
cell was lled with either distilled water or brine. Subsequently, the
system pressure was increased to the test pressure by injecting CO2
into the cell from the gas buer cell with a low ow rate. Based on the
decrease in pressure in the gas buer cylinder, the number of moles of
CO2 added to the cell is calculated using the SpanWagner reference
equation of state.26 The compositional information is necessary to
make sure that the aqueous phase has been fully saturated with CO2.
Moreover, a density meter inside the oven monitors the density of the
mixture. A stable density value at constant pressure and temperature
shows that the system is in equilibrium. Once equilibrium had been
reached, a CO2 bubble was injected into the cell via the capillary tip,
which is positioned at the bottom of the cell (see also Figure 2).
Successive images of the bubble captured on the surface were taken
and then used as input of an in-house MATLAB image analysis routine
to determine the contact angle. For the image analysis, the prole of
the bubble was split into two parts assuming an axis-symmetric shape
for the bubble. The YoungLaplace equation was then used to
describe both halves of the bubble proles separately. The details of
the image processing and contact angle determination can be found
elsewhere.21,27
Having completed the test at the rst pressure level, more CO2 was
injected into the cell to increase the system pressure to the next
pressure level. The system was allowed to settle for at least 6 h to reach
the new equilibrium state. After equilibration, a CO2 bubble was
injected into the cell, placed against the rock surface and the contact
angle determined with image analysis. This procedure was repeated in
pressure steps around 1.5 MPa, up to the maximum pressure of 16.0
MPa, at a constant temperature of 318 K. This procedure was repeated
for all six experiments conducted in this study (Table 2).
3. RESULT AND DISCUSSION
3.1. Multiphase Contact Angle. Before we embark on an
explanation, we describe the expected wetting behavior of a
water-wet and an oil-wet sample after aging. We expect that the
Bentheimer sandstone samples that were only shortly
exposed to crude A (i.e., SB-1SB-4) are no longer completely
water-wet but exhibit a nite contact angle in the waterCO2
oil saturated substrate system. The substrate consists of patches
of oil and rock. This means that the substrate faces a larger part
the brine phase but a lesser part the carbon dioxide phase.
There is no water lm in between. The samples that were
exposed to crude B for much longer times (i.e., SB-5 and SB-6)
are considered to be completely oil-wet, that is, an oil lm has
formed between the rock and CO2. For the shortly exposed
sample the interfacial tension s is between the rock/oil surface
s and for = brine or = CO2. For the samples exposed for
longer times the substrate s behaves as pure oil.
Three interfacial and surface tensions can be identied for a
uiduidsolid substrate system such as depicted in Figure 3,
where the substrate is considered as a single phase. The
Youngs equation relates the contact angles to these three
interfacial tensions
Figure 3. Schematic of a captive bubble contact angle system.
dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025
Energy & Fuels Article

sv sl
cos =
lv (1)

where, lv (mN/m) is the liquidvapor interfacial tension and

sv(mN/m) and sl(mN/m) are the solidvapor and solid
liquid interfacial tensions, respectively. According to eq 1, a
change of contact angle should depend on the variation of
one or more of these interfacial tensions.
Two dierent sets of contact angle data are normally
reported in the literature, viz., equilibrium (stable) and
transient contact angles. The transient contact angle gives
information on the change, increase or decrease, of the contact
angle in time while the stable contact angle refers to a constant
contact angle with the system in equilibrium.12,21,22,28 Even
though the transient contact angle is an eective method to
investigate the transient phenomena that occur at the interface,
care must be taken in interpreting these results regarding Figure 4. Stable contact angles for partially water-wet substrates SB-
wettability determination. For an unsaturated system, as found 1SB-4 (oil A saturated substratebrineCO2) as a function of
in other experiments,12,28 the transient contact angle provides pressure and brine salinity at a temperature of 318 K. The dashed lines
important information concerning the (interfacial) interactions give the best linear t through the respective data.
between dierent phases such as dissolution, diusion, and
convective mass transfer. Indeed, the change in contact angle only one substrate was used. Consequently, the substrate was
might be correlated with the contribution of the dierent exposed to dierent brine phases with dierent salinities for a
mechanisms involved rather than the wettability alteration. In long time. This caused the surface to become again strongly
contrast, for a fully saturated system, equilibrium has already hydrophilic. As a result, salinity increased the contact angle,
been established and no further mass transfer across the phases which is in agreement with the results from Espinoza et al.14 for
occurs; therefore, the stable contact angle determines the a strongly hydrophilic surface.
wetting properties of the system alone. For such a system, Oil-Wet System. The behavior of the contact angle (i.e.,
injection of a gas bubble into an equilibrated system, which wettability) of the oil-wet substrates (SB-5 and SB-6) is
consists of water and CO2, induces an initial uctuation of the depicted in Figure 5. The primary objective for this set of
determined contact angle values. However, due to the fact that
the overall composition is within the two-phase region, the
releasing of a new gas bubble only gives a small disturbance of
the equilibrium, which does not last long.21,29 Hence, after the
system attains equilibrium, the contact angle should not change
with time. In this study, all contact angle determinations were
performed using a fully CO2-saturated aqueous phase (water/
brine) so that the mass transfer involved in the process is
negligible and the contact angle determination is not aected
by such mechanisms.
3.2. Eect of Salinity, Pressure, Aging Time, and Oil
Properties. Partially Water-Wet System. Figure 4 shows the
stable contact angle data as a function of pressure at dierent
salinities for partially water-wet substrates (SB-1SB-4)
saturated with crude A. For each test, a dierent sample from
the same Bentheimer core was used. It can be observed from
Figure 4 that for a constant salinity the contact angle remains Figure 5. Stable contact angles for the eectively oil-wet (saturated
nearly constant and is less than 90 in the pressure range and aged with crude B, that is, SB-5 and SB-6) and partially water-wet
studied. The contact angle never exceeds 65, and the surface (saturated and aged with crude A, that is, SB-1 and SB-4) substrates vs
remains partially water-wet when the pressure increases from pressure for dierent salinities.
0.5 to 14.0 MPa. However, at constant pressure, the contact
angle decreases as the salinity increases. The system including experiments was to examine the eect of aging time on the
distilled water has a larger contact angle than at higher salinities. contact angle measurements. To this end, two substrates, viz.,
According to Figure 4, the wettability of the surface changes SB-5 and SB-6 (Table 2), were saturated with crude B and were
from strongly water-wet for a high saline brine to less water-wet aged for 22 months at a constant temperature of 333 K. As a
for distilled water. These results are not in agreement with the result of the aging procedure (aging with crude B for 22
data from the work of Espinoza et al.14 for a hydrophilic-quartz months at 333 K), the wettability of the substrates changed
surface. This disagreement is attributed to the presence of oil from strongly water-wet to eectively oil-wet. The change in
patches on the surface, which make the wetting properties of the initial wettability was examined by immersing the substrates
clear and untreated sandstone dierent than that of shortly in brine and distilled water to allow them to produce oil
aged substrate. However, in our previous study,30 we found that spontaneously. For both rock slabs (i.e., SB-5 and SB-6), no oil
salinity increases the contact angle, which means the surface production was observed even after one month. Besides, digital
becomes less brine wet. In our previous set of experiments30 images along with the mass balance of the oil-wet and water-
1018 dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025
Energy & Fuels
wet substrates before and after the experiments revealed that
for the oil-wet substrates no oil liberated during the
spontaneous imbibition test (see Figure 6). For the sake of
Figure 6. Bentheimer sandstone samples: (a) clear sample, (b) sample
saturated with oil before experiment, (c) partially water-wet sample
(saturated with crude A) after experiment, and (d) eectively oil-wet
sample (saturated with crude B) after experiment.
comparison, two sets of contact angle data for two water-wet
systems are also included in Figure 5. Three dierent regions
can be identied for the contact angle data of an oil-wet system.
(1) For pressures up to 4.0 MPa, the contact angle increases
slightly from 95 to 100. This pressure range corresponds to
gaseous CO2 at 318 K. We call this region the subcritical region.
(2) In the pressure range between 4.0 and 9.0 MPa, that is, near
critical conditions of CO2 at 318 K, the contact angle increases
sharply from 100 to 140 and the substrate turns from
intermediate-wet to CO2-wet. This phenomenon could be
attributed to the formation of a layer of dense CO2 on the solid
and a large decrease in the lv.31 Because high-energy uids, for
example, water, tends not to spread on the low-energy surfaces,
the presence of a low-energy CO2 layer on the surface will
cause the CO2 contact angle value to increase in order to
decrease contact between these two phases. In addition, the
decrease in lv will cause to increase further above 90 to
increase the interfacial area between water and CO2. (3) For
pressures higher than 9.0 MPa, the contact angle slightly
increases with pressure from 140 to 145. This region
corresponds to supercritical conditions of CO2 at 318 K.
These results are in agreement with the experimental data from
Dickson et al.13 for a hydrophobic glass surface where the
authors showed that the CO2 contact angle remains almost
constant with pressure even if the system pressure increases to
above 20.0 MPa.
Figure 7. Digital images of CO2 bubble on the oil saturated-Bentheimer surface in the presence of CO2-saturated aqueous liquid phase at 318 K; (a)
partially water-wet (saturated with crude A) sample at P = 8.62 MPa, = 63.02 and (b) eectively oil-wet (saturated with crude B) sample at P =
8.80 MPa, = 139.70.
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The contact angle data show that, even at low pressures, the
system is intermediate-wet. However, the wettability alters from
intermediate-wet to CO2-wet at pressures higher than 9.0 MPa.
This means that CO2 is able to enter the small pores, due to the
sign change of capillary pressure, and come into contact with
the oil that has been trapped by water after the initial water
ooding. The results for an oil-wet substrate are in agreement
with the results of Suicmez et al.32,33 for a three-dimensional
random network model where the authors showed that for an
oil-wet porous medium, the gas relative permeability is lower in
the presence of water than oil because the gas is no longer the
most nonwetting phase. For practical purposes this means that
an initial oil-wet substrate becomes carbon dioxide-wet at
pressures relevant for CO2-based oil recovery processes. As it
can be observed in Figure 5, the contact angles are almost
similar for the system with 35 000 ppm brine and the system
with distilled water, at all pressures investigated. Thus, it is
concluded that the contact angles of the investigated oil-wet
substrates are fairly independent of the brine salinity.
In Figure 7, the digital images of the captured CO2 bubbles
on the oil-wet and water-wet surfaces are compared. The
images were taken at approximately the same pressure and
temperature and in presence of CO2-saturated aqueous liquid
phase. It is obvious that, for the oil-wet surface, carbon dioxide
can wet the surface while for the water-wet sample CO2 is the
nonwetting phase even at high pressures. From a practical and
economical point of view, it is preferable to inject CO2 at lower
pressures because of compression and injection costs. Based on
the results of this study, if the wettability is the main concern, it
is expected that CO2 ooding of an oil-wet porous medium, in
presence of water, results in higher recoveries when the CO2 is
injected at near-critical conditions; at these conditions the rock
is CO2-wet and the contact angle hardly changes even if the
pressure increases further.
3.3. Evaluation of the Contact Angles. The dependence
of the contact angle on the brine salinity and pressure can be
explained by investigating the dependency of the three
interfacial tensions in Youngs eq 1 (i.e., sv, sl, and lv) on
the brine salinity and pressure. In Youngs equation, lv and
are parameters, which can be determined experimentally.
However, sv and sl remain unknown. In order to determine
the unknowns, an additional correlation among lv, sl, and sv is
required. The most common method to derive such a
correlation is based on a surface free energy (SFE) analysis,
which is the subject of numerous studies, which are mostly
dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025
Energy & Fuels Article

carried out by Neumann et al.2325 This relation is called an Table 3. Results of the contact Angle Prediction Using the
equation-of-state and is described by Equation of State Approach for the Oil-Wet Substrate SB-5
(Saturated with Crude B), CO2, and Distilled Water System
f (lv , sv , sl) = 0 (2)
pressure (MPa) lv (mN/m)a exp. CAb sv (mN/m)c model CAd
This idea was proposed for the rst time by Berthelot.34
0.18 68.12 96.90 26.29 89.31
Berthelot assumed that the interfacial adhesion work can be
0.30 67.56 100.10 25.60 89.90
considered as the geometric mean of the cohesion work of a
0.30 67.56 98.80 25.60 89.90
solid and the cohesion work of the relevant liquid phase. By
1.99 59.69 101.30 16.82 98.33
further modication of the Berthelot hypothesis, Neumann et
3.93 51.39 105.10 9.64 107.95
al.,2325 developed three dierent expressions of the equation
4.88 47.75 112.00 7.13 112.60
of state to determine sl. The basic assumption in this method is
6.20 43.20 116.70 4.53 119.01
that sl only depends on the properties of the solid surface and
6.20 43.20 117.90 4.53 119.01
the liquid phase used in the contact angle measurements and sv
7.07 40.56 123.80 3.29 123.17
remains practically unchanged. They showed that if the
7.59 39.11 124.60 2.70 125.63
measurements are done properly, the lv times cosine (adhesive
8.61 36.62 132.43 1.81 130.26
force) of the contact angle, lv cos , depends only on lv, and
8.81 36.19 139.70 1.67 131.12
sl. The authors then proposed:
8.81 36.19 140.10 1.67 131.12
sl = sv + lv 2 lvsv [1 1(lv sv)2 ] (3) 9.97 33.95 142.30 1.05 136.00
10.00 33.90 139.10 1.04 136.13
combining eq 3 with Youngs eq 1 yields 10.20 33.57 143.80 0.96 136.91
sv 11.60 31.71 142.10 0.57 141.76
cos = 1 + 2 [(1 1(lv sv )2 ] 12.25 31.10 140.90 0.47 143.54
lv (4) 14.30 30.60 142.50 0.39 145.08
15.50 30.20 144.50 0.33 146.38
where 1 is a constant. The constant 1 and sv are determined a
using eq 4 by a least-squares t of a given set of and lv data Experimental data from refs 13 and 35. bCA = contact angle.
c
Calculated using eq 5. dCalculated using eq 6.
measured on one and the same type of solid surface. Once sv
and 1 are determined, they can be used to determine the
contact angle for the same surface and dierent pairs of liquid comparison between predicted and experimental contact angles
vapors. Now, it is possible to estimate the theoretical contact for the substrate SB-5 is shown in Figure 8a and b. According to
angle and to provide a validation method of contact angle Figure 8, the model equation is able to reproduce the contact
measurements. angle data in the range of pressures studied. In other words, the
In this study, we follow the same approach to determine sv equation of state method can be used to evaluate the wetting
as that applied by Neumann et al.24 A key dierence between properties of a specic surface, if a number of reliable contact
this study and the Neumann groups approach is that instead of angle and interfacial tension data are available for the system
using multiple liquids to determine sv and 1, the lv and data under consideration.
at dierent pressures are used to determine sl and 2. It can be Having determined the sl and 2, eq 5 was used to calculate
shown (Appendix A) that eq 3 and eq 4 can be rewritten for sv, sv. The results are depicted in Figure 9 and show that sv
under the condition that the sl remains constant with pressure: decreases with pressure. The decrease in sv and a constant
value of sl makes the numerator of eq 1 more negative at
sv = sl + lv 2 lvsl [1 2(lv sl)2 ] (5) increasing pressures. The decrease in lv will also make cos
Replacing eq 5 in Youngs eq 1 gives more negative. Thus, both the numerator and denominator of
eq 1 contribute to negative values of cos (increase in ) as the
sl CO2 pressure increases. Figure 9 also shows that above 10.0
cos = 1 2 [1 2(lv sl)2 ]
lv MPa both lv and sv remain almost constant with increasing
(6)
pressure. This, with a constant sl, explains the nearly constant
In this study, a pair of experimental lv data points of the for oil-wet substrate SB-5 as the system pressure increases
oil-wet substrate SB-5 and distilled water at low (0.5 MPa) and above 10.0 MPa. In addition, a low value of sv at pressures
high (10.0 MPa) pressures were used to calculate the sl and the higher than 10.0 MPa indicates that the surface becomes gas-
constant 2 using eq 6. For the interfacial tension data between wet.
distilled water and CO2, literature data at relevant pressures and The same series of calculations were performed for the oil-
temperature were used.13,35 With these data and eq 6, the sl wet substrate SB-6. As eq 6 shows, lv data (i.e., interfacial
and parameter 2 for substrate SB-5 were calculated to be 25.48 tension between brine and CO2) at relevant pressures,
mN/m and 1.057 104 (m/mN)2, respectively. These values temperature, and brine salinity are needed to calculate the sl
were then used in eq 6 to compute the contact angles of the oil- and parameter . Even though literature experimental lv data
wet substrate SB-5, CO2, and distilled water at the experimental are available for a variety of pressure, temperature, and salinity
temperature of 318 K and experimental pressures. Table 3 conditions, they are not comparable to the conditions
summarizes the experimental and predicted contact angles for considered in this study. However, the results reported by Li
the oil-wet substrate SB-5, CO2, and distilled water. The et al.36,37 can be used to estimate the lv at pressure,
average deviation (error) and the standard deviation are 3.41% temperature, and salinity conditions relevant to the exper-
and 4.61%, respectively (Appendix B). It can be seen from imental conditions of the oil-wet substrate SB-6. To this end, an
Table 3 that eq 6 can reproduce the whole set of contact angle empirical correlation that was developed by Li et al.36,37 was
data within an acceptable range of accuracy (<5%). The used to estimate the interfacial tensions between brine (with
1020 dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025
Energy & Fuels Article

Figure 9. Calculated IFT-values versus pressure. lv from refs 3537

and sv from eq 5 vs pressure. sv was calculated for the oil-wet
substrates SB-5 and SB-6 (saturated with crude B) also using eq 5.

Table 4. Results of the Contact Angle Prediction Using the

Equation of State Approach for the Oil-Wet Substrate SB-6
(Saturated with Crude B), CO2, and Brine System
pressure (MPa) lv (mN/m)a exp. CAb sv (mN/m)c model CAd
0.43 63.87 93.08 29.74 87.73
2.15 59.04 91.97 22.05 95.01
2.20 58.85 96.50 21.78 95.29
4.35 50.46 98.76 11.43 108.22
4.40 50.27 100.98 11.24 108.52
6.40 43.79 108.05 5.69 119.44
7.86 40.58 120.32 3.66 125.49
8.62 39.00 134.62 2.83 128.69
9.50 37.20 145.24 2.02 132.63
10.80 36.20 144.63 1.63 134.97
12.00 34.80 146.00 1.16 138.48
Figure 8. (a) Contact angle as function of pressure for the system oil- 14.00 33.60 145.40 0.82 141.78
wet CO2distilled water (SB-5, saturated with crude B) at a a
Experimental data from ref 36. bCA = contact angle. cCalculated
temperature of 318 K. Symbols display the experimental data; the using eq 5. dCalculated using eq 6.
line shows the prediction using eq 6. (b) Point by point comparison.
The dashed lines show the 95% condence interval.
inconsistency between these data is of concern.38 Note that for
35 000 ppm NaCl) and CO2 at related pressures and the oil-wet substrate SB-6, CO2, brine system, correlated lv
temperature. This correlation gives the CO2brine interfacial values rather than experimental lv data were used which leads
tension as a function of pressure, temperature, and brine to higher errors. Nevertheless, the shape is well represented.
salinity. The results are shown in Figure 9. It can be observed Therefore, it can be concluded that the equation of state
that with increase of salt concentration lv increases slightly. approach can be used to describe the contact angle data if a set
Using eq 6 and a pair of experimental lv data points, the sl of reliable lv data set is available for the system under
and parameter 2 for substrate SB-6 were calculated to be 27.22 consideration. The comparison between predicted and
mN/m and 1.968 104 (m/mN)2, respectively. These values experimental contact angles for the oil-wet substrate SB-6,
were then used in eq 6 to calculate the contact angles of the oil- CO2, and brine with 35 000 ppm salinity is shown in Figure 10.
wet substrate SB-6, CO2, and brine at the experimental The mismatch between the observed and calculated contact
temperature of 318 K and experimental pressures. The angles can be attributed to the accuracy of the calculated lv
experimental and predicted contact angles are given in Table data using the Li et al.36 correlation, the surface roughness, and
4. The average deviation and the standard deviation are 5.54% the experimental error in contact angle measurements.
and 6.46% respectively, which are higher than the error values Having determined the sl and 2, the eect of pressure on sv
of the oil-wet substrate SB-5, CO2, and distilled water system. can be examined using eq 5 and is shown in Figure 9 as lled
Equation 6 shows that the applicability of the equation of state dots. As Figure 9 shows, increasing brine salinity has a small
method is highly aected by the accuracy and availability of eect on sv for an oil-wet substrate in the pressure and salinity
experimental lv data. Although numerous experimental data are range considered in this study. In fact, the dierence between
available in the literature for brineCO2 interfacial tension at two cases is within the experimental accuracy (see Figure 5).
various pressuretemperature conditions, the uncertainties and Therefore, similar to the oil-wet substrate SB-5, CO2, and
1021 dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025
Energy & Fuels
Figure 10. (a) Contact angle as function of pressure for the system oil-
wet substrateCO2brine with 35 000 salinity (SB-6, saturated with
crude B) at a temperature of 318 K. Symbols display the experimental
data; the line the prediction using eq 6. (b) Point by point comparison.
The dashed lines show the 95% condence interval.
distilled water system, the numerator and denominator in
Youngs eq 1 change in a way that the contact angle of an oil-
wet substrate, CO2, water/brine is hardly aected by the brine
salinity (Figure 5).
The evolution of the contact angle of the partially water-
wet surface can be explained in the same way. Equation 6 with a
pair of experimental lv data points of the partially water-wet
substrate SB-1 at low (2.0 MPa) and high (12.0 MPa) pressures
were used to calculate sl and the constant 2. The sl and
constant 2 for the substrate SB-1 were determined to be 2.88
(mN/m) and 2.371 105 (m/mN)2, respectively. For a
completely water-wet surface, sl is considered to be zero. The
low value of the sl reveals that the surface is partially water-wet.
Thereafter, the sv for SB-1 system was calculated using eq 5
and is shown in Figure 11 as triangles. It can be seen that sv for
the partially water-wet substrate SB-1 decreases from 22.05 to
14.03 mN/m, when the pressure increases from 1.0 to 15.0
MPa. The obtained data for sl and sv reveal that sl is negligible
when compared to sv. Consequently, the main controlling
interfacial tensions in Youngs eq 1 for the partially water-wet
system SB-1 are sv and lv.
1022
Article
Figure 11. Calculated IFT values vs pressure. lv from ref 36 and sv
from eq 5 vs pressure. sv was calculated for the partially water-wet
substrate SB-1 (saturated with crude A), CO2, and distilled water again
using eq 5.
The ratio between sv and lv (sv/lv) is also shown in Figure
11 as lled dots (2nd y-axis). It is obvious that in the pressure
range studied, sv/lv slowly increases from 0.0 to 10.0 MPa.
Consequently, the contact angle remains almost constant (eq
1). The experimental results reported in this study are in
agreement with the experimental and theoretical data from
Dickson et al.13 for a hydrophilic surface, CO2, and distilled
water system. The authors showed that even if both sv and lv
decrease with pressure, the ratio between sv and lv remains
approximately constant in the pressure range from 0.1 to 14.0
MPa, and hence, the contact angle remains nearly constant with
pressure.
The evolution of the contact angle with salinity for the
partially water-wet substrates SB-2SB4 can be understood by
examining the eect of salinity on the three interfacial tensions
in eq 1. As it is shown in Figure 9, the addition of salt has a
relatively small eect on sv while lv increases. To examine the
eect of salinity on sl for a partially water-wet substrate, sl was
calculated for substrate SB-4 (saturated with crude A), brine
with 35000 ppm salinity, and CO2, again using a pair of
experimental lv data points and eq 6. The sl and 2 for
substrate SB-4 were calculated having the values 0.015 mN/m
and 1.6 105 (m/mN)2, respectively. The results from
substrate SB-1, viz. distilled water, and substrate SB-4, that is,
brine with 35 000 ppm salinity, reveal that increasing brine
salinity from zero to 35000 ppm changes the anity of the
surface toward more water-wetness. Moreover, in Youngs
equation the numerator increases and the denominator also
increases but only by a small amount. In summary, the cosine of
the contact angle increases with increasing salt concentration
and the contact angle decreases. Table 5 summarizes the
parameters, viz. sl and , calculated for eectively oil-wet (SB-5
and SB-6) and partially water-wet (SB1 and SB4) substrates.
The wettability behavior of the oil-wet substrate, brine, and
CO2 might be related to the CO2 solubility in water, the CO2
density, and the interfacial tension between the CO2-rich gas
phase and the aqueous phase. Figure 12 shows the
dimensionless solubility, density, interfacial tension, and contact
angle of the oil-wet samplebrineCO2 system vs pressure.
These dimensionless parameters are obtained by dividing each
value by its respective maximum value within the given pressure
dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025
Energy & Fuels
Table 5. Summary of the Calculated sl and Parameters for
Oil-Wet and Water-Wet Systems
case sl (mN/m) (m/mN)2
SB-1 (water-wet saturated with crude A) 2.88 2.371
SB-4 (water-wet saturated with crude A) 0.015 1.601
SB-5 (oil-wet saturated with crude B) 25.48 1.057
SB-6 (oil-wet saturated with crude B) 27.22 1.968
Figure 12. Dimensionless density,26 CO2 solubility in water,39 IFT
between CO2 and distilled water, and the stable contact angle on oil-
wet Bentheimer sandstone at a constant temperature of 318 K as
function of pressure. The stability point is the point above which the
contact angle remains constant.
range. This maximum occurs at the highest pressure for all of
the quantities, except for the IFT for which the maximum
occurs at the lowest pressure. According to Figure 12, the
contact angle becomes constant in the same pressure range in
which the interfacial tension, the density, and the CO2 solubility
become nearly constant. Our present data do not allow
determining the degree of importance of each of the aecting
parameters.
3.4. Eect of Bubble Size. The eect of bubble size on the
contact angle measurements has been addressed by dierent
studies.40,41 However, the conclusions are not generally in
agreement. Drelich et al.40 derived advancing and receding
contact angles by analyzing the shapes of sessile-drops and
captive-bubbles. The authors showed that for a smooth and
homogeneous solid surface the contact angle does not change
with respect to the bubble size. In this study, the eect of
bubble size on the contact angle measurements is examined for
three dierent substrates with dierent degrees of roughness.
Figure 13 shows the contact angle vs bubble radius for a water-
wet and two oil-wet sandstone systems. The contact angle
measurements were all performed at a temperature of 318 K.
The contact angle data for the water-wet substrate with zero-oil
saturation was already obtained in ref 29. It can be seen from
Figure 13 that the contact angle is more dependent on the
bubble size for the surface with higher Pa (roughness) factor
(see section 2.3). This relation is highly pronounced for the
water-wet substrate with zero-oil saturation with roughness
factor of 0.32 mm. However, for oil-wet substrates with Pa
values of 0.16 mm and 0.21 mm, the contact angle does not
change much with the bubble radius. Our results conrm the
observations by Drelich et al.40 for a smooth and homogeneous
solid surface. Therefore, it can be concluded that the eect of
Article
105
105
104
104
Figure 13. Dependency of the stable contact angle as a function of
bubble radius for naturally water-wet29 and oil-wet sandstone systems
at a temperature of 318 K.
bubble radius on contact angle measurement becomes more
important as the surface becomes rougher. These consider-
ations are in agreement with the observations in Figure 13. The
eect surface roughness is only apparent for water-wet
Bentheimer sandstone in the absence of oil.
4. CONCLUSIONS
It is possible to prepare both water-wet and oil-wet
substrates by aging Bentheimer sandstone with appro-
priately chosen crude oils. The water-wet sample, which
was obtained after short exposure to the oil, is called rock
system I, and the oil-wet sample, obtained after long
exposure, is called rock-system II. Rock system I is
partially water-wet, whereas rock system II is eectively
oil-wet. The contact angles can be determined as a
function of brine salinity and pressure.
For rock system I, viz., partially water-wet surface, the
dependence of the contact angle with pressure is very
small. The carbon dioxide is the nonwetting phase. The
contact angle decreases for increasing brine salinity. This
behavior can be quantitatively understood in terms of the
expected dependencies of the interfacial tension on the
pressure and brine salinity (see Figure 9).
For rock system II, the eectively oil-wet surface, the
dependence on pressure is considerable. The carbon
dioxide becomes the wetting phase at high pressures as
proved with the experimental evidence. The contact
angle is initially 95 and increases only slightly in the
range 04.0 MPa. Between 4.0 and 10.0 MPa the contact
angle increases more or less linearly until it reaches a
value of 150 (Figure 6). Beyond 10 MPa, that is, in the
supercritical region, the contact angle remains constant.
The eect of salinity on the contact angle is small. The
behavior can again be quantitatively understood based on
expected trends of the three interfacial tensions that
determine the contact angle.
Use of the equation of state approach makes it possible
to predict the experimental data quantitatively provided
that a reliable set of lv data are available.
1023 dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025
Energy & Fuels Article

We conclude that contact angle measurements form an sl

essential ingredient to determine the eciency of carbon cos = 1 2 [1 2(lv sl)2 ]
lv (A.12)
dioxide ooding and storage.

APPENDICES
Appendix A: Derivation of the Equation of State
It is important to note that this approach can only be applied
for the same liquid phase and if the solid phase is not altered
due to swelling, chemical reaction, or mineral dissolution so
that the assumption of a constant sl is fullled. It is worth
Surface energy is usually dened as the amount of the required
noting that any deviation between the predicted contact angle
work to create a unit area of surface of the object in its
by eq A.12 and the experimental contact angle values can be
environment. In other words, surface energy indicates the work
caused by the non-ideality of the rock surface (i.e., roughness,
required to split a bulk sample to two surfaces42 in its
heterogeneity, and/or the small changes in the sl with
environment. In case the surfaces are not identical, the work of
pressure).
adhesion is considered as the energy of cleaving species 1 from
species 2 in a medium of species 3: Appendix B: Error Analysis
Average deviation and standard deviation in percentages are
W12 = 13 + 23 12 (A.1) calculated using eqs B.1 and B.2, respectively.
where 13 and 23 are the surface energies of the two new
species in medium 3 and 12 is the interfacial tension between Average Deviation (%)
n
species 1 and 2. Based on the denition of cleavage work, the 1 ABS(CA iexp CA icalc)
cleavage energy of a single species (W11 = W22),42 the surface = 100
energy of each surface can be written as n i = 1 CA iexp (B.1)
W11 = 213 (A.2)
Standard Deviation (%)
W22 = 223 (A.3)
n ABS(CA exp CA calc)
i i 2
1
i = 1 100
For a captive bubble system, free energy of adhesion per unit n CAexpi

area of a solidvapor pair Wsv is equal to the work required to =
n1 (B.2)
separate a unit area of the solidvapor interface (v = 1, s = 2, l
= 3)43
Nomenclature
Wsv = lv + sl sv (A.4) hvBb = high volatile bituminous
IFT = interfacial tension
The interfacial adhesion work can be approximated as the PDC = pendant drop cell
geometric mean of the cohesion work of a solid and the SFE = surface free energy
cohesion work of the relevant gas phase:34 s = solid
Wsv = WssWvv l = liquid
(A.5)
v = vapor
By using eqs A.2 and A.3: Wij = work of adhesion between species i and j per unit area
(mN/m)
Wss = 2sl (A.6) 1 = constant in eq A.9
1 = constant in eqs 3 and 4 (m/mN)2
Wvv = 2lv (A.7) 2 = constant in eqs 5 and 6 (m/mN)2
25
On the basis of this concept, Neumann et al. proposed an = constant in eq A.8
alternative formulation of this combination rule: lv = liquidvapor interfacial tension (mN/m)
sv = solidvapor interfacial tension (mN/m)
ij = (1 (ii jj)2 ) iijj (A.8) sl = solidliquid interfacial tension (mN/m)
= contact angle (degree)
where is the energy parameter 44,45
that is directly propor- ij = the potential energy parameter (well depth) of unlike-
tional to the free energy W and is a tting parameter. pair interactions

Consequently, the combining rule for the free energy of
adhesion for a solidvapor pair eq A.5 can be written as AUTHOR INFORMATION
2
Wsv = (1 2(Wvv Wss) ) WssWvv (A.9) Corresponding Author
*Tel.:+31152788307. E-mail:a.amerighasrodashti@tudelft.nl.
Replacing eqs A.6 and A.7 in eq A.9 gives
Notes
Wsv = 2[1 2(lv sl)2 ] lvsl The authors declare no competing nancial interest.

(A.10)
Using eq A.4 and A.10, an alternative equation of state can be ACKNOWLEDGMENTS
obtained to determine the solid-vapor interfacial tension sv:
This research was conducted in the laboratory of Geoscience
sv = lv + sl 2 lvsl [1 2(lv sl)2 ] (A.11)
and Engineering at Delft University of Technology. Our
grateful thanks to the technical sta of the laboratory,
Combining this equation with Youngs equation (eq 1) particularly J. Etienne, M. Friebel, and J. van Meel. We also
yields: thank the CATO2 project for its contribution.
1024 dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025
Energy & Fuels

Article

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1025 dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025