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Department of Geoscience and Engineering, Delft University of Technology, Delft, 2628CN, 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.
2013 American Chemical Society 1015 dx.doi.org/10.1021/ef3017915 | Energy Fuels 2013, 27, 10151025
Energy & Fuels Article
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.
to keep the temperature constant. The gas supply system consists of a cell was lled with either distilled water or brine. Subsequently, the
gas bottle and a gas compressor that pumps CO2 into a buer cell system pressure was increased to the test pressure by injecting CO2
equipped with a pressure transmitter. The change in pressure gives into the cell from the gas buer cell with a low ow rate. Based on the
information about the number of moles of gas present in the modied decrease in pressure in the gas buer cylinder, the number of moles of
PDC, of which the dead volume and total volume are known. For CO2 added to the cell is calculated using the SpanWagner reference
mole calculations, the SpanWagner reference equation of state for equation of state.26 The compositional information is necessary to
CO2 has been used.26 In addition, a balance is used to determine the make sure that the aqueous phase has been fully saturated with CO2.
amount of water that is added to the system. The composition of the Moreover, a density meter inside the oven monitors the density of the
waterCO2 mixture is used to check whether the system is, at the mixture. A stable density value at constant pressure and temperature
given temperature and pressure, in the two-phase equilibrium region. shows that the system is in equilibrium. Once equilibrium had been
A density meter inside the oven determines the density of the water reached, a CO2 bubble was injected into the cell via the capillary tip,
CO2 mixture that is circulated through the system. The accuracy of the which is positioned at the bottom of the cell (see also Figure 2).
density meter is 0.1 kg/m3 in the temperature range between 273 and
Successive images of the bubble captured on the surface were taken
313 K. Gas is injected into the cell via a capillary tube connected to the
and then used as input of an in-house MATLAB image analysis routine
bottom of the cell an exchangeable tip with an inner diameter of 600
to determine the contact angle. For the image analysis, the prole of
m is mounted. The capillary is connected to a microneedle valve and
a high-pressure gas reservoir of known volume. The needle valve the bubble was split into two parts assuming an axis-symmetric shape
restricts the amount of gas transferred from the reservoir to the for the bubble. The YoungLaplace equation was then used to
injection tip. In the gas reservoir, the temperature and the pressure are describe both halves of the bubble proles separately. The details of
determined to facilitate the computation of the exact amount of gas the image processing and contact angle determination can be found
added to the pendant drop cell. A high resolution digital camera is elsewhere.21,27
connected to the cell using an endoscope. Digital images of the Having completed the test at the rst pressure level, more CO2 was
pendant drop are successively captured as sharp as possible on a injected into the cell to increase the system pressure to the next
vibration-free table. pressure level. The system was allowed to settle for at least 6 h to reach
2.3. Methodology. In this subsection, the experimental procedure the new equilibrium state. After equilibration, a CO2 bubble was
that is used to determine the wetting properties of the system rock, oil, injected into the cell, placed against the rock surface and the contact
brine, and CO2 is explained. Thereby, typical in situ conditions that angle determined with image analysis. This procedure was repeated in
might be encountered in CO2-injection processes are established. The pressure steps around 1.5 MPa, up to the maximum pressure of 16.0
main advantage of the proposed procedure is that the experiments can MPa, at a constant temperature of 318 K. This procedure was repeated
be conducted at realistic conditions of the most common CO2 for all six experiments conducted in this study (Table 2).
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 3. RESULT AND DISCUSSION
polished to mitigate the eect of surface roughness on the contact 3.1. Multiphase Contact Angle. Before we embark on an
angle determination. The characterization of the roughness of the explanation, we describe the expected wetting behavior of a
surface is based on the calculation of the so-called Pa factor.21 For an water-wet and an oil-wet sample after aging. We expect that the
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 Bentheimer sandstone samples that were only shortly
the surface is. Then, the rock slabs were dried in an oven at 333 K for exposed to crude A (i.e., SB-1SB-4) are no longer completely
48 h. Four substrates, viz., SB-1SB-4, were saturated with crude A water-wet but exhibit a nite contact angle in the waterCO2
without any treatment and ltration. The substrates were then aged at oil saturated substrate system. The substrate consists of patches
room temperature for at least six weeks. Crude B was used to saturate of oil and rock. This means that the substrate faces a larger part
the two other substrates, viz. SB-5 and SB-6. These two substrates the brine phase but a lesser part the carbon dioxide phase.
were aged with crude B for 22 months at 333 K (Table 2). This was
There is no water lm in between. The samples that were
done to allow investigating the eect of aging time and oil properties
on the wetting properties of the surface. 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
Table 2. Summary of the Experiments formed between the rock and CO2. For the shortly exposed
sample the interfacial tension s is between the rock/oil surface
crude aging aging temp. brine salinity s and for = brine or = CO2. For the samples exposed for
sample wettability oil time (K) (mg/L)
longer times the substrate s behaves as pure oil.
SB-1 water-wet A 6 weeks 298 distilled water Three interfacial and surface tensions can be identied for a
SB-2 water-wet A 6 weeks 298 5000
uiduidsolid substrate system such as depicted in Figure 3,
SB-3 water-wet A 6 weeks 298 20000
where the substrate is considered as a single phase. The
SB-4 water-wet A 6 weeks 298 35000
Youngs equation relates the contact angles to these three
SB-5 oil-wet B 22 333 distilled water
months interfacial tensions
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 Figure 3. Schematic of a captive bubble contact angle system.
sv sl
cos =
lv (1)
wet substrates before and after the experiments revealed that The contact angle data show that, even at low pressures, the
for the oil-wet substrates no oil liberated during the system is intermediate-wet. However, the wettability alters from
spontaneous imbibition test (see Figure 6). For the sake of 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
Figure 6. Bentheimer sandstone samples: (a) clear sample, (b) sample
similar for the system with 35 000 ppm brine and the system
saturated with oil before experiment, (c) partially water-wet sample
(saturated with crude A) after experiment, and (d) eectively oil-wet with distilled water, at all pressures investigated. Thus, it is
sample (saturated with crude B) after experiment. 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
comparison, two sets of contact angle data for two water-wet on the oil-wet and water-wet surfaces are compared. The
systems are also included in Figure 5. Three dierent regions images were taken at approximately the same pressure and
can be identied for the contact angle data of an oil-wet system. temperature and in presence of CO2-saturated aqueous liquid
(1) For pressures up to 4.0 MPa, the contact angle increases phase. It is obvious that, for the oil-wet surface, carbon dioxide
slightly from 95 to 100. This pressure range corresponds to
can wet the surface while for the water-wet sample CO2 is the
gaseous CO2 at 318 K. We call this region the subcritical region.
nonwetting phase even at high pressures. From a practical and
(2) In the pressure range between 4.0 and 9.0 MPa, that is, near
economical point of view, it is preferable to inject CO2 at lower
critical conditions of CO2 at 318 K, the contact angle increases
sharply from 100 to 140 and the substrate turns from pressures because of compression and injection costs. Based on
intermediate-wet to CO2-wet. This phenomenon could be the results of this study, if the wettability is the main concern, it
attributed to the formation of a layer of dense CO2 on the solid is expected that CO2 ooding of an oil-wet porous medium, in
and a large decrease in the lv.31 Because high-energy uids, for presence of water, results in higher recoveries when the CO2 is
example, water, tends not to spread on the low-energy surfaces, injected at near-critical conditions; at these conditions the rock
the presence of a low-energy CO2 layer on the surface will is CO2-wet and the contact angle hardly changes even if the
cause the CO2 contact angle value to increase in order to pressure increases further.
decrease contact between these two phases. In addition, the 3.3. Evaluation of the Contact Angles. The dependence
decrease in lv will cause to increase further above 90 to of the contact angle on the brine salinity and pressure can be
increase the interfacial area between water and CO2. (3) For explained by investigating the dependency of the three
pressures higher than 9.0 MPa, the contact angle slightly interfacial tensions in Youngs eq 1 (i.e., sv, sl, and lv) on
increases with pressure from 140 to 145. This region the brine salinity and pressure. In Youngs equation, lv and
corresponds to supercritical conditions of CO2 at 318 K. are parameters, which can be determined experimentally.
These results are in agreement with the experimental data from However, sv and sl remain unknown. In order to determine
Dickson et al.13 for a hydrophobic glass surface where the the unknowns, an additional correlation among lv, sl, and sv is
authors showed that the CO2 contact angle remains almost required. The most common method to derive such a
constant with pressure even if the system pressure increases to correlation is based on a surface free energy (SFE) analysis,
above 20.0 MPa. which is the subject of numerous studies, which are mostly
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.
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
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