SPE 99848
Influence of Temperature on Wettability Alteration of Carbonate Reservoirs
A.A. Hamouda and K.A.R. Gomari, U. of Stavanger
Copyright 2006, Society of Petroleum Engineers
This paper was prepared for presentation at the 2006 SPE/DOE Symposium on Improved Oil
Recovery held in Tulsa, Oklahoma, U.S.A., 22–26 April 2006.
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Abstract
Carbonate reservoirs become more water-wet during thermal
recovery. The effect of temperature on wettability-altering
process is caused by contribution from several parameters
involving fluid/fluid and fluid/rock interactions. This paper
aims at describing the interrelationship between different
parameters of a simple oil/water/rock model over temperature
range of 25 to 130 degree centigrade.
Saturated and unsaturated fatty acids as well as
naphthenic acids with saturated and unsaturated rings are
selected for this work to alter the water-wet calcite surface.
The type of selected acids is based on the distribution of these
components in reservoirs in the Norwegian continental shelf.
Contact angle measurements on the treated calcite
surfaces are used as indication of wattability alteration. At
fluid/fluid interface the interfacial tension and distribution of
the solutions of n-decane /fatty acids /water systems are
measured at elevated temperature. A set of experiments is also
performed in order to understand the role of the temperature
on fluid/rock interface by zeta potential measurements.
As the temperature increases, calcite surface becomes
more water-wet. The obtained results at fluid/fluid interface
(IFT and distribution coefficients) and contact angle
measurements show that the trend of decrease in contact
angles with temperature follows the same trend as IFT and
distribution coefficients, specifically if one divides acids to
saturated and unsaturated separately. Electro-kinetic
measurements (zeta potential) of calcite surfaces with
temperature demonstrate that increasing temperature reduces
surface charge to less positive, which may enhance the
∗ Corresponding author : A.A. Hamouda
Email address: aly.hamouda@uis.no
Tel.: +47 518 322 71
repulsive forces between dissociated acids and calcite surface.
Due to this change in surface charge, the adsorption of acids
on the surface becomes less effective at high temperatures;
hence wettability of the calcite surface tends to be more water-
wet.
Keywords: Wettability alteration; Carbonate; Temperature;
IFT; distribution coefficients; surface charge
Introduction
The wettability of a hydrocarbon reservoir depends on how
and to what extent organic components are adsorbed to the
solid phase’s present1. For carbonate reservoirs naphthenic
acids and number of carboxylic acids are recognized to be the
most frequent acidic components that adsorbed on the surface
and altered the wettability2-5. The degree to which the
wettability is altered by these components is determined by
several parameters. Temperature is one of those controlling
parameter that has an effect on both oil/water and
water/mineral interfaces. Many authors have reported a shift in
wettability of mineral surfaces toward water-wet at elevated
temperatures6-9. Increasing the solubility of adsorbed materials
from surfaces and decreasing the IFT are two different effects
of temperature on wettability at elevated temperature2. Several
work have directed to the partition coefficients of carboxylic
acids between oil and water phase as a function of pH and
salinity and to perhaps a lesser extent on the effect of
temperature10-13. Hamouda et al.13 have performed an
extensive experimental work on wettability alteration of
calcite surfaces due to dissolved carboxylic acids in oil phase
at ambient temperature and different pHs. It was shown that
there is a possible implication between change in IFT and
partitioning with the wettability of the calcite surfaces. They
showed that the high soluble acids in water owing low
partitioning coefficients hence lesser effect on IFT has minor
change on wettability alteration of calcite surfaces. Increasing
pH decreased the IFT between water/n-decane /fatty acid
systems as well as partition coefficients of acids from oil to
the water phase. Consequence of those changes resulted in
decrease in contact angles on calcite surfaces. These behaviors
were explained by possible increase in the repulsive forces due
to dissociation of acids at water/n-decane interface hence
change in the surface charge of calcite surface.
Depending on the oil composition, both decreasing and in
some cases increasing in IFT with the temperature were
reported in literatures 6-7,14. In terms of partition coefficients it
has been shown insignificant effect by the temperature 11,15.
2 SPE 99848
In addition to the change in fluid properties at oil/water
interface with the temperature, it was also reported that the
electrokinetic properties of the solid surfaces might change
with the temperature9, 16. Combination of those effects,
temperature at oil/water interface (partitioning and IFT) and
water/calcite interface (potential surface charge), is
investigated in this paper.
Material and Methods
Materials: A simple model oil, n-decane, was selected here to
investigate the partitioning behavior, and interfacial activity of
dissolved fatty acids in n-decane in contact with aqueous
phase. This simple model was also used to check the wetting
state of calcite surface from those fatty acids. The n-decane
was supplied by Fluka in +99 % and +95 % purities. The
grade of +99 % purity of n-decane was used for treating
calcite and partitioning behavior, while +95 % grade was used
for IFT measurements. The structural formula as well as
suppliers for all acids is listed in Table 1.
The type of the calcite crystals, used in contact angle
measurements, is “Island-spar calcite”. Pieces of the chunk
were formed to the correct shape by filing (29 x 26.2 x 2 mm
and 39.6 x 14 x 2 mm). The surfaces were then cleaned
carefully and water-wetness was checked for each piece by
placing a drop of water on surface. The water spread on the
filed and cleaned calcite.
An outcrop chalk from Stevns Klint type near
Copenhagen, Denmark, was used as porous medium in
imbibition test. The core data are as follow:
Length=7 cm, Diameter=3.8 cm, Porosity=50.02 %, Oil in
place=26 ml, Pore Volume=39.71 ml, Swi (initial water
saturation) = 35.53%.
Methods:
Wettability Measurements: Organic components were
initially dissolved in the oil phase. The filed and cleaned
pieces of calcite were pre-wetted by dipping in aqueous phase.
In case of high temperature, both phases as well as calcite
surfaces were kept at the same temperature. The water pre-
wetted calcite was immediately inserted into oil phase and
aged for 1 day at the desired temperature. After this period of
time calcite was taken out and washed with distilled water, n-
heptane and dried with air. The air-dried surface was then
placed in the contact angle cell5 where pure n-decane was
introduced by a needle onto the calcite surface, which is
surrounded by distilled water. The advancing and receding
angles were measured by a microscope. In this work
advancing contact angles are reported since the variation of
the receding angles are insignificant.
Imbibition tests: Imbibition experiments at 70 and 90 o C
were carried out in a standard Amott test cell. Distilled water
was used as imbibing fluid. The recovered oil (n-decane) was
then recorded versus time.
It is important to note that the wettability of strongly
water-wet chalk before imbibintion was altered to oil-wet
using 0.001 M SA. The Swi for core sample was established
with distilled water. Afterwards the imbibition tests were
performed with the imbibing fluid.
Interfacial Tension Measurements: Interfacial tension
(IFT) measurements at elevated temperatures (25o±2o to
75o±2o C) were performed by the ring method, using a KRÜSS
tensiometer type 8451, having an accuracy of about ±
1.5mN/m. Due to technical problem (handling) using the ring
method at high temperature, the average of the high
temperature tests was about 75o±2o C.
Partition Coefficients Measurements: The measurements
were done using Perkin-Elmer spectrophotometer in the IR
region of the electromagnetic spectra, at a wave number17 of
1713 cm-1. The n-decane (containing 0.01 M of fatty acids)
and water ratio were kept at weight ratio of 1:1 (five grams of
the n-decane to five grams of aqueous phase in a glass bottle).
The bottles were then put in an agitator and shacked at the
desired temperature (25o, 50o and 70o C) for 1 day, afterwards
the bottles were placed at a stable position at the same
temperature for an equilibration period of 1 day. The n-decane
phase was then separated and the concentration of the
remained fatty acids in n-decane was measured. Due to
limitation of increasing temperature for the agitator higher
than 70o C, all partition coefficient measurements were
performed up to 70oC.
Partitioning coefficient of fatty acids in the equilibrated n-
decane+fatty acids (initial concentration of 0.01M)/water
system is estimated from the ratio of the distributed acids
between the n-decan and water from the measured fatty acids
in n-decane (after the equilibration process) and the difference
between the measured fatty acids and the initial concentration,
which is then assumed to be the concentration of the fatty acid
in the water.
Zeta Potential Measurements: Zeta potential of calcite
powder was measured using AcoustoSizer at the temperature
of 20o, 35o and 50o C. In these experiments solution of 2% by
weight of CaCO3 in distilled water was used. The mixer was
set at 360 rpm for all experiments done in this work. To
measure zeta potential at the desired temperature, first the
temperature of distilled water was set to the predetermined
temperature and then the powder was added to the water.
Results and Discussion
Wettability Measurement: It is in general agreement that
fatty acids are important polar components that may alter the
calcite surfaces to oil-wet3-5, 13, 18. The degree of alteration is
mainly dependent on the type and concentration of the acids,
oil /water composition, and temperature.
The wettability alteration is indicated by the contact angle
measurements at various temperatures. Fig.1 shows visual
pictures from squeezed and slipped n-decane droplet inside the
contact angle cell for three calcite surfaces pre-treated with
dissolved 0.01 M stearic acid in n-decane at elevated
temperature. As can be clearly seen from these pictures, the
pre-treated calcite at low temperature is strongly oil-wet, while
at high temperature, the pre-treated calcite is shown to be
more water-wet. The advancing contact angles for these
systems are 160, 131 and 90o ± 3o for the pre-treated surface at
25, 50 and 80 o C, respectively. The increasing water-wetness
for carbonates with increasing temperature was reported by
Anderson2, Wang and Gupta7, and Rao19. Enhancement of the
SPE 99848
desorption of surface active material from calcite surface due
to the increase in temperature was also reported by Tang and
Morrow 20, as well as Buckley and Liu 21. Thomas et al. 18
have tested the wettability alteration of calcite in present of
octanoic and palmetic acid at elevated temperature. Their
results showed a decrease in contact angle for both acids. They
suggested that this behavior may result from some desorption,
or more water penetration into the adsorbed layer due to the
higher vibrational activity of the chains at higher temperature.
Hjelmeland and Larrondo6 have investigated the
wettability alteration of carbonate reservoir at elevated
temperature using contact angle measurements. Their results
showed a significant decrease from strongly oil-wet with the
advancing angle of about 170o at 22o C to the strongly water-
wet with the advancing angle of about 18o at 60o C. They
suggested that the strong and rigid film formation at brine/oil
interface especially at low temperature results in strong oil-
wetting behavior at low temperature. They stated that the high
temperature favors desorption of adsorbed molecules,
consequently the formed film disappeared after a short period
of the time and more water-wet is expected.
In order to understand the temperature effect on the
alteration of the calcite surface, three approaches were
followed. In the first approach (test 1), a water pre-wetted
calcite surface was modified by aging for 24 hrs in a 0.01M
stearic acid dissolved in n-decane at different temperatures.
The second approach (test 2), the pr-wetted calcite surface was
modified by aging for 24 hrs in a 0.01M stearic acid dissolved
in n-decane at room temperature (25oC) and then immersed in
water having the pre-determined temperatures. In the third
approach, a water pre-wetted calcite surface was modified by
aging for 24 hrs in a 0.01 M stearic acid dissolved in n-decane
at different temperatures as test 1, then the modified calcite at
desired temperature immersed in water having the same pre-
determined temperature. In these three approaches the
modified calcite after treatment was dried in the air over night
and contact angle was measured inside the cell at 25oC. The
measured contact angles are shown in Fig.2. It is interesting
to observe that a steeper change in the contact angles for test 1
and 3 than that for test 2. When the temperature increased
from 25 to 130oC, the contact angle decreased from 160 to 68o
and 160 to 101o for test 1 and 2, respectively. In test 3, where
the contact angles were measured on the modified calcite at
the desired temperature followed by immersion in water at the
same temperature, lower values than that for test 1 were
observed. The lower contact angle observed in test 3
(decreased from 160 to 36o with temperature increase from 25
to 130oC, respectively) compared to test 1 may be explained to
be caused by possible re-establishing equilibrium between the
adsorbed SA / calcium stearate and water and/or desorption of
SA from the calcite surface. The lower contact angles in test 1
and 3 than measured in test 2, may in general, be explained
based on the available Ca2+ sites on the calcite surface. As the
temperature increases a lesser Ca2+ are available for
adsorption, the previously reported chemisorption of the SA,
on the calcite surface5. While in test 2, the strongly adsorbed
SA at low temperature, showed lesser degree of alteration of
the wettability to water-wet as the temperature increases. In
order to quantify this hypothesis, a simulation of solubility of
calcite in an open system (presence of CO2) was performed,
3
CO2 partial pressure of 10-3.5 atmosphere22 and pH of 7 using
PHRQPITZ Geochemical model of Plummer et al. 23, showed
a fractional reduction of calcium ion concentration [Ca2+], at
130oC relative to the [Ca2+] at 25oC, is estimated to be about
0.63. This corresponds to a fractional reduction of contact
angle of 0.6 and 0.58 for test 3 and 1, respectively. It is
interesting to observe that the fractional reduction of contact
angle in test 2 from 25 to 80oC is about 0.21, which may be
partially reflected by the approximated fractional reduction of
the surface excess of 0.13 when the temperature is increased
from 25 to about 75oC (the detail of this work is out of the
scope for this paper).
In order to further investigate the factors that affect the
wettability alteration at elevated temperatures, IFT
measurements of the interface between n-decane (without fatty
acid additives) and water at various temperatures that was
used in aging the modified calcite before contact angle
(referred to as equilibrium water here after) measurements was
done and is shown in Fig.3. The IFT measurements were done
at 25oC. It is interesting to see that the IFT of n-decane/water
systems decreases with the equilibrated water at high
temperature. However, no change is expected in IFT between
n-decane/water system interfaces as shown in our previous
work13. This may, suggest that there is re-distribution of the
stearic acid molecules between the water and the adsorbed
stearic acid on the calcite. The re-distribution of the fatty acids
may mainly be due to the solubility of the calcium stearate at
higher temperatures in the water, since the stearic acid
adsorption on the calcite is believed to be a chemisorption type
of reaction 5. In other words, the alteration of wettability of the
calcite surface to more water-wet is dominated by the reduced
Ca2+ sites at the calcite surface as the temperature increases.
This suggests explanation to the reduction of the contact angle
for test 1 and 3 since the calcite surface modification was done
at elevated temperatures. While for test 2, the dominated
process is perhaps the solubility of the calcium stearate and
desorption at high temperatures. The solubility of the long
chain fatty acids in the water is far much less than the calcite
solubility, hence the alteration of the wettablity is much lesser
in test 2 than for tests 1and 3 as shown in Fig.2. Different sets
of experiments were done to study the influence of
temperature on the recoverable oil in this system (n-
decane/water system) by studying the fluid imbibition. Fig.4
shows the recovered oil as a function of temperature. The
imbibition test was done first at 70oC. The recovered oil was
stabilized at about 53%. The test conditions were kept for 25
days with no additional increase. The temperature was then
raised to 90oC and an increased recovery up to about 61% was
reached in about 10 days. This once again confirmed the effect
of the temperature on the recovered oil (n-decane).
Wettability of mineral surfaces in reservoir is altered by
the attraction of the dissociated acid species at the oil/water
interface with the charged mineral surface 24. The interaction
between a positively charged calcite/water interface and a
negatively charged oil/water interface results in strong
chemisorption of dissociated acids at calcite surface 4-5, 14. The
change in zeta potential for silica surface over the temperature
range from 10o to 60o C in both water and 10 –3 M KCl
solution is reported by Dunstan 16. His experiments showed a
decrease in zeta potential with temperature in both solutions.
4 SPE 99848
An investigation of the calcite surface charge was done by
measuring zeta potential at elevated temperatures. Fig.5 shows
a decrease of the zeta potential from 2.95 mV at 20o C to 0.45
mV at 50o C. The reduction in the zeta potential from high
positive value to less positive value may indicate the
deficiency of the positive Ca2+ on the surface, which reduces
the adsorption sites for the carboxylate to adsorb on, hence the
surface, becomes less oil-wet. This agrees with the trend
obtained by the contact angle measurements in this work and
the work done by others. Schembre and Kovscek9 have
investigated the role of temperature on rock-fluid interactions
and rock properties. They found experimentally that fines
detachment for silica-silica system occurs at around 120oC.
They also reported that for low salinity and high pH, zeta
potential becomes more negative as the temperature increases
indicating stronger repulsive forces. In this work it is also
demonstrated a decrease in zeta potential charge (to a less
positive charge) with temperature indicating that the
temperature effect on zeta potential is also valid for calcite.
Effect of type of fatty acids on wettability at elevated
temperatures: Wettability in these tests was performed by
contact angle measurements. Two types of fatty acids were
investigated; saturated and unsaturated chain and fatty acids
with attached aromatic rings. The first type contains heptanoic
acid (HPA), stearic acid (SA) and oleic acid (OA) and the
second type contains 18-Phenoloctadecanoic acid (PODA) and
18-Cyclohexyloctadecanoic acid (CHOA). Three temperatures
were investigated; 25, 50 and 80oC. Fig.6 shows the behavior
of both types of fatty acids. The experiments were done at pH
6.5. SA, PODA, and CHOA have shown a tendency to convert
the calcite surface to a less oil-wet as the temperature
increases. While the calcite surface modified by OA and HPA
were not be affected by increase of the temperature. From our
previous investigation13 on effect of pH on interfacial tension,
it was shown that dissociation of OA occurred at pH>7.0.
When the pH was raised to about 7.8, the effect of the
temperature followed the same trend as for SA, PODA and
CHOA. The contact angle for HPA was taken to be zero (no
adhesion of n-decane droplet on the calcite surface surrounded
by water at the three measured temperatures). This explained
on the high solubility of HPA as a short chain fatty acid in the
water compared with the other tested long chain.
The effect of the temperature is less pronounced in case of
PODA and CHOA than that for SA and OA with SA being the
most affected component by the temperature. It is interesting
to observe that in presence of water film, the contact angle
measured for PODA is about 135o compared to the contact
angle for SA of about 160o. Our previous work25 has shown
that the adsorption of PODA on calcite surface is more
uniform compared to the SA. The obtained more oil-wet
(higher contact angle) behavior at low temperature for SA
compared to PODA in contrast to the results from water vapor
adsorption (without presenting of water film) where PODA
showed more oil-wet than that for SA is perhaps related to the
formation of rigid layer of calcium stearate on the surface due
to the stable water film on the surface at low temperature. At
high temperature the situation perhaps resemble the water
vapor adsorption experiments where the water film is unstable
(dry surface), hence more oil-wet behavior with PODA than
SA. A test has been conducted by modifying a humidified
calcite surface (no water film) with PODA showed a
calcite/air contact angle of 104o compared to 93o for SA. This
may be explained based on that the presence of aromatic in the
molecule enhances the negative inductive effect (-I) that
promotes the acid dissociation hence interaction with the
surface calcium ions, while in presence of water film the
carboxylate (+I) may counter acts this negative inductive
effect by the aromatic ring, hence reduces the degree of
dissociation resulting in a lesser contact angle. As the
temperature increases, all the fatty acids show a decreasing
trend of the contact angle, hence more water-wet. This was
explained earlier based on the solubility of calcite with the
temperature.
Young and Miller26 observed a phenomenon that deserves
some attention. They divided oleate adsorption isotherm into
two regions in a plot of adsorption density vs. oleate
concentration for two temperatures 20o and 60o C. Their
results showed an increase in adsorption for concentration
below 10-5 M with temperature (region I), however for higher
concentrations than 10-5 M, adsorption decreased with the
temperature (region II). They attributed this to chemisorption
in region I (<10-5M) while in region II, it was attributed to
formation of calcium dioleate precipitation. As the
temperature increases in region II, calcium dioleate solubility
increases. In this work, the effect of two concentrations of
oleic acid (10-4 and 10-2 M), were investigated on their effect
on contact angle. At the low concentration, it was difficult to
measure the contact angle in the cell; the measurement was
therefore done at air interface for the modified surface. A
slight increase with the temperature (from 31 to 42o at pH of
7.8 for temperatures of 25 and 80oC, respectively) was
recorded. A similar observation to Young and Miller26 at
higher concentration (10-2 M), although not directly
comparable since it was measured at water interface (Table 2),
is obtained.
Interfacial tension: The interfacial tension can be related to
the activity of fatty acids by the Gibbs adsorption energy 27:
1 dγ
Γ = − × …………………………………..(1)
RT d ln C
where Γ is the adsorption or surface excess of solute at unit
surface area, γ is the interfacial tension and R and T are gas
constant and temperature in Kelvin, respectively. The mean
area at surface (A) occupied by an adsorbed molecule can be
determined from surface excess as follow:
1
A= ………..……………………………....(2)
Γ × NA
where, NA is Avogadro number .
Fig.7 shows the effect of temperature on IFT. As expected
the IFT decreased with temperature except for OA and PODA.
Harley and Jennings28 have investigated the effect of
temperature on interfacial tension for pure n-decane/distilled
water. They showed that the decrease in interfacial tension
between pure n-decane and distilled water is due to the
decrease in density of the phases. The sensitivity of the IFT
SPE 99848
measurements at zero concentration of acid in n-decane was
compared with the available literatures. The measured IFT for
the n-decane/water system without fatty acid in this work is
46± 1 mN/m. This is in agreement with values reported in
literature where 45, 47 and 46± 1 mN/m, were reported by
Hamouda et al. 13, Morrow et al. 29, and Spildo et al. 30,
respectively.
The effect of concentration (0-0.01M) of SA at 25 and
75oC is shown in Fig.8. Fig.9 shows the effect of OA
concentration (from 0-0.01M) on IFT at two pHs (6.5 and 7.8)
and two temperatures (25 and 75oC). OA behaved similarly at
the two pHs but opposite to that for SA, where IFT increased
with temperature (in the case of OA). A decrease in IFT for
SA in temperature range from 25 to 75±2oC of about 15mN/m
was observed. This agrees reasonably well with the reported
results by McCaffery and Mungan14, where a decrease of
about 10mN/m for concentration ranges from 0 to 0.005 M for
temperature range from 25 to 75oC. It is worth mentioning that
at a concentration between 0.005 and 0.008 M, the IFT leveled
off, where the interface between the two phases has perhaps
reached a saturation point. This observation has been also
reported by Spildo et al.31 for interfacial tension between n-
decane/water as a function of the concentration of benzoic,
lauric and 4-heptylbezoic acids initially added to the n-decane.
Hjelmeland and Larrondo6 showed a significant decrease
in the interfacial tension of oil/brine with increasing
temperature and at atmospheric pressure. They suggested that
an oxidation process takes place that exceeds the contribution
from adsorption of surface-active material.
Wang and Gupta7 measured the interfacial tension for
mineral crude oil/distilled water and crude oil/brine systems at
elevated temperature and pressure. Their work showed that the
interfacial tension for the mineral/distilled water increased
with the temperature, however for the crude oil/brine systems,
it decreased as temperature increased. They suggested that this
contraversial behavior of interfacial tension is related to the
system composition.
For oleic acid the effect of pH, concentration and
temperature on IFT were investigated (Fig.9). The decrease in
interfacial tension is expected to be due to the ionization of
acid at interface32-34. Surface areas are calculated for the effect
of the pH using equations 1 and 2. The surface areas are
estimated to be about 63.7 and 57.2 Å 2 at 25oC for pH 6.5 and
pH 7.8, respectively. Although, the estimation used dependent
equations, it indicates the relative occupancy of the interfacial
area by the ionized acids compared to the partially ionized
acid, hence reflects the packing density at the interface.
Increasing OA concentration has decreased the IFT for each
individual pH and temperature. However, more pronounced
decrease in IFT with concentration is observed at pH of 7.8.
Similar calculation for surface area for the two temperatures,
showed an increase of the surface area from 63.7 to 77 Å 2, for
25 and 75oC, which corresponds to a decrease of surface
excess of OA per surface area from 2.6 µmol/m2 to 2.15
µmol/m2, respectively.
Partition coefficients: Equilibration experiments were
conducted with n-decane containing 0.01 M fatty acids and
5
distilled water at varying temperature (25-70o C). Partition
coefficients are calculated using equation 3:
[HA]o,eq C o ,eq
K = = ……………………………….(3)
[HA]w,eq C w ,eq
where Co, eq and Cw, eq are the concentration of fatty acids in
the n-decane and water at equilibrium, respectively. In this
work, n-decane containing fatty acids was aged for 1 day in
contact with water. After the equilibrium time, fatty acid
concentration was determined using IR adjusted to a wave
number of 1713 cm-1, which corresponds to C=O stretching
vibrations of the un-dissociated acid 17. The concentration of
fatty acid was then calculated by the following equation:
w
C w,eq = ⎡⎣Co ,i − C o ,eq ⎤⎦ o
……………………..(4)
w w
where Co,i is the initial concentration of fatty acids in n-decane,
wo and ww are the weight of n-decane and distilled water in the
system, respectively. For simplicity equal weights of the two
phases are used in this work, so eq. (4) is reduced to:
C = C o ,i − C o , eq …………………………………(5)
w,eq
Fig.10 shows the partitioning coefficients of PODA,
CHOA, SA, OA, and HPA between n-decane and distilled
water as a function of temperature. The long chain naphthenic
acid (PODA) shows the highest K among the other fatty acids;
while HPA (short chain) has the lowest partition coefficients.
The obtained results at 25oC for OA are comparable to the
results in our previous work13, where in this work log K is
0.86 comapred to 0.81.
Reinsel et al. 11 have investigated the effect of pH,
temperature and acid concentration on the partition
coefficients of fatty acids in the crude oil/ water systems.
Their work, which was limited to the short chain fatty acids,
showed that the pH of water has the major effect on
partitioning, while the concentration and temperature have
lesser effect. Standal et al. 12, Spildo et al. 35, and Havre et al.36
studied the partitioning of different acid and base components
in oil/water model system. They found that the distribution is
closely related to the dissociation of the components. In fact
the main objective of all those studies was effect of pH on
partitioning.
The change in log K (∆logK) with respect to the
temperature, in this work, shows an inverse trend to the
general trend of partitioning in n-decane-water systems (log
K). Fig.11 demonstrates this trend, presented as the ∆logK for
the tested fatty acids. For example heptanoic acid (HPA)
shows a ∆logK of about 0.216, while PODA, the long chain
naphthenic acid, ∆logK is only 0.043. In a review collection of
partition coefficients and their uses by Leo et al.37 it was
shown that a decrease in the partition coefficients of hexanoic
and octanoic fatty acids between octanol/water system at
elevated temperature depends on the hydrocarbon chain length
where hexanoic acid with shorter chain showed a difference of
about 1.7 x 10-2 log K/deg while octanoic acid having longer
6 SPE 99848
chain showed no difference over the temperature range
between 4 to 22o C. The trend is in line with our finding here.
Bennett and Larter15 reported a decrease in partitioning
coefficients of C0-C2 alkylphenols as a function of
temperature. They explained this behavior based on the
increase of the solvation of alkylphenols in water relative to
the oil.
Conclusions
Increasing temperature alters calcite to more water-wet. The
degree of wetting change is a complicated function of surface
charge, fluid/fluid and fluid/rock interactions, where the
combined effect of those functions determines the degree of
wettability alteration.
1. Modified calcite surface to oil-wet (SA) at low
temperatures shows a less degree of alteration to water-wet
when the temperature was raised compared to the modified
calcite with SA at elevated temperatures. This may be
explained based on passivation of the calcite surface by the
adsorbed SA and the slight change is only due to possible
re-establishment of equilibrium between the adsorbed SA
/calcium stearate and water and/or desorption of SA from
the calcite surface at the corresponding temperature.
Modified calcite by SA at elevated temperature, on the
other hand, is shown to be less oil-wet. This may in
general, be explained based on the less available Ca2+ ions
sites on the calcite surface for adsorption.
2. Investigated fatty acids in this work for long chain
saturated alkane (SA) or saturated aromatic rings (CHOA)
showed a decrease in IFT with temperature, however the
unsaturated alkane chains (OA) and alkane attached to
aromatic ring (PODA) showed the inverse behavior. This
is perhaps due to; in general, the more expanded film with
the unsaturated alkane than the corresponding saturated
acids. In addition, in case of OA has high affinity to water
compared to SA that increases with temperature as shown
by the partitioning coefficient trend. However, in case of
PODA more work is ongoing to address its behaviour.
Acknowledgments
The authors would like to thank University of Stavanger for
the financial support of this project.
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Table 1: Organic components

Organic component Supplier and Purity Structural formula

Heptanoic acid (HPA) Fluka >99 % CH3 (CH2) 5 COOH

Stearic acid (SA) Aldrich >98.5% CH3 (CH2) 16COOH

Oleic acid (OA) Fluka >98% C8H17CH=CH (CH2) 7COOH

( C H 2)1 7- C O O H
18-Phenoloctadecanoic acid
Chiron A/S >98%
(PODA)

(CH2)17-COOH
18-Cyclohexyloctadecanoic acid
Chiron A/S ------
(CHOA)

Table 2: Effect of temperature on contact angle on pre-treated calcite by 10-2 and 10-4 M
concentration of oleic acid.
-4 -2
C=10 M C=10 M
o o o o
T =25 C T =80 C T=25 C T =80 C
o o o o
θa=31 θa=42 θa=103 θa=54
8 SPE 99848

a: 25o C b: 50o C c: 80o C

Fig.1: A picture of n-decane droplet inside the cell. A squeezed and slipped drop of n-decane between two modified
o o
calcite surfaces by 0.01 M stearic acid at 25, 50 and 80 C. Contact angles in all cases are measured at 25 C.

170
160
150 Test 1
Advancing contact angle (degree)

140 Test 2
130
Test 3
120
110
100
90
80
70
60
50
40
30
20
0 20 40 60 80 100 120 140
o
Temperature ( C)

Fig.2: All tests are done on modified water pre-wetted calcite surface aged for 24 hrs in a 0.01M stearic acid in n-
o
decane. Test 1: modification at different temperatures. Test 2: Modification at room temperature (25 C), then
immersed in water at the corresponding temperature. Test 3: Modification at different temperatures then
immersed in water at the corresponding temperature. In all tests the modified calcite is dried in the air over
o
night and contact angle is measured inside the contact angle cell at 25 C.

45
43
41
39
IFT (mN/m)

37
35
33
31
29
27
25
0 20 40 60 80 100 120 140
o
Temperature ( C)

o
Fig. 3: IFT of pure n-decane/water system measured at 25 C. The water used is the equilibrated water with modified
calcite by 0.01 M SA at the different temperatures.
SPE 99848 9

65

60

55
oil recovery %

50
70o C 90o C
45

40

35

30
0 5 10 15 20 25 30 35
Time (Days)

o
Fig. 4: Influence of increased temperature from 70 to 90 C on oil recovery of oil-wet chalk, with 0.01 M SA in n-
decane, imbibed by distilled water.

3.5
Smoluchowski Zeta Potential (mV)

2.5

1.5

0.5

0
0 10 20 30 40 50 60
o
Temperature( C)

Fig. 5: Effect of temperature on zeta potential of pure calcite.

10 SPE 99848

SA
180 OA (in contact with pH 6.5 )
160 OA ( in contact with pH 7.8)
160
PODA
140 135
130 CHOA
120
θ adv. (degree)

103 110
100 96
85 90
80
67
60 53 51 54
47
40

20

0
25 50 80
Temperature (oC)

o
Fig. 6: Contact angle measured at ambient temperature on modified calcite at temperatures of 25, 50 and 80 C with
different fatty acids (SA, OA, PODA, and CHOA). Contact angle for HPA in all temperature tests was zero.

38
SA
36
HPA
34
OA
32 PODA
IFT( mN/m)

30 CHOA

28

26

24

22

20
15 25 35 45 55 65 75
o
Temperature ( C)

Fig. 7: Effect of temperature on interfacial tension of water/n-decane/fatty acids systems.

SPE 99848 11

50

45

T= 25o C
T= 75o C
IFT (mN/m)

40

35

30

25
0 0.002 0.004 0.006 0.008 0.01
Concentration (M)

Fig. 8: Effect of temperature and concentration on interfacial activity of stearic acid (SA).

50

pH=7.8 25oC
and T=23
45 pH=6.5 25oC
and T=23
pH=7.8 75oC
and T=70
40 pH=6.5 75oC
and T=70
IFT (mN/m)

35

30

25

20
0 0.002 0.004 0.006 0.008 0.01
Concentration (M)

Fig. 9: Effect of pH, temperature, and concentration on interfacial activity of oleic acid (OA) on the n-decane/
distilled water system.
12 SPE 99848

1.8

1.6
HP A
1.4 OA
SA
1.2 PODA
CHOA
1
Log K

0.8

0.6

0.4

0.2

0
15 25 35 45 55 65 75
Temperature (oC)

Fig.10: Partition coefficients of different fatty acids as a function of temperature.

0.25

0.20
∆ log K (70-25 C)
o

0.15

0.10

0.05

0.00
CHOA PODA SA OA HPA
Fatty acid

o o
Fig. 11:Calculated ∆Log K between 25 and 70 C for different fatty acids.