Colloids and Surfaces A: Physicochem. Eng.

Aspects 216 (2003) 243
/259

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Wettability alteration in carbonates

Interaction between cationic surfactant and carboxylates as a
key factor in wettability alteration from oil-wet to water-wet
conditions
Dag C. Standnes *, Tor Austad
Stavanger University College, P.O. Box 8002, Ullandhaug, N-4068 Stavanger, Norway

Received 2 May 2002; accepted 6 December 2002

Abstract

The chemical interaction between cationic surfactants of the type R-N(CH3)3Br, termed Cn TAB, and carboxylates is
the key factor in changing the wettability from oil-wet chalk to more water-wet conditions. Oil can then be displaced
from the chalk by spontaneous imbibition of water. Carboxylates from the crude oil are the most strongly adsorbed
material onto the chalk surface, and they may act as ‘‘anchor’’ molecules for other surface-active components present in
the crude oil. This paper focuses on the ion-pair interaction between the cationic surfactant and the carboxylates
present in crude oil and model oil systems made by dissolving fatty acids (octanoic, lauric and stearic) in heptane and
crude oil. Partitioning of the cationic surfactant between the oil and the water phase was studied as a function of the
type and amount of acid present, pH, and composition of the brine. By means of static contact angle measurements, it is
verified that the concentration of surfactant is very important in desorbing carboxylates from the calcite surface. The
process nearly stops at surfactant concentrations below the critical micelle concentration, indicating that the desorbed
carboxylates must be stored in micelles or extracted into the oil phase in order to maintain a dynamic wettability
alteration process in a porous medium. Dynamic experiments, using model oil systems, containing different types of
fatty acids and C12TAB dissolved in brine, showed that the surfactant solution imbibed spontaneously into the oil-wet
material in a counter-current flow regime governed by mainly capillary forces, indicating that a wettability alteration
process had taken place.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Imbibition; Chalk; Wettability; Oil recovery

1. Introduction

The objective for this research program on

wettability alteration in chalk is to be able to
* Corresponding author.
E-mail addresses: dag.standnes@tn.his.no (D.C. Standnes),
imbibe water spontaneously into oil-wet carbonate
tor.austad@tn.his.no (T. Austad). rock in order to improve the oil recovery. Thomas
0927-7757/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0927-7757(02)00580-0
244 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
/259

Nomenclature
AN acid number (mg KOH per g oil)
ASTM American Society for Testing and Materials
CMC critical micelle concentration (wt.%, M)
Cn TAB cationic surfactants where n /10, 12, 14, 16
IFT interfacial tension (mN m1)
k permeability (mD)
K partitioning coefficient
M molar (mol dm 3)
Mw mol weight (g mol 1)
(ns)o number of moles of surfactant in the oil phase (mol)
(ns)w number of moles of surfactant in the water phase (mol)
OOIP original oil in place (cm3)
PA pro-analysis
PV pore volume (cm3)
Swi initial water saturation (%)
TDS total dissolved solid (g l1)
vol.% volume%
wt.% weight%
Greeks
f porosity (%)
u static contact angle measured through the water phase (8)

et al. [1] have verified that among the compounds
encountered in oil reservoir diagnosis and petro-
leum production, fatty acids and carboxylated
polymers adsorb most strongly onto carbonate
minerals. They observed that fatty acids made the
carbonate surface oil-wet, similar to polymers if
they were sufficiently hydrophobic. The adsorp-
tion of fatty acids onto the carbonate surface was
suggested to be nearly irreversible. They observed,
however, that 40% isopropanol in water or water-
saturated toluene cleaned the calcite surface for
fatty acids. Among the functional groups tested (
/
OH,
/OSO3,
/SO3,
/NH2), the carboxylates (
/
COO ) adsorbed, by far, most strongly onto the
carbonates. It is also verified that the potential for
the oil to increase the oil-wetting nature of the
chalk is directly related to the acid number (AN),
i.e., the higher the number of carboxylic groups
present in the oil, the more oil-wet state of the
chalk surface was achieved [2].
The brine in carbonate reservoirs is normally
buffered to a slightly basic pH, say about 8. At this
pH, the carboxylic groups present in the oil
become negatively charged in contact with the
brine, and they will adsorb strongly onto the rock
surface. Knowing that the carboxylic materials are
mainly located in the heavy end fraction of crude
oil, i.e., resins and asphaltenes, they are character-
ized as highly surface-active compounds. Owing to
the co-operational effects of surface-active mole-
cules present in the crude oil, a reasonable picture
of the adsorbed material onto the carbonate sur-
face may be as follows. First, the molecules
containing carboxylic groups will adsorb strongly
onto the surface. These molecules may act as
‘‘anchors’’ for other polar molecules adsorbing
onto the surface mostly by hydrophobic and
dipole
/dipole interaction in a co-operative pro-
cess. Provided that the reservoir fluid contains
enough surface-active materials, an organic layer
will cover the whole carbonate surface, and the
rock is described as completely oil-wet. No spon-
taneous imbibition of water takes place under
these conditions owing to a negative capillary
pressure, unless the water contains surface-active
wettability-modifying chemicals.
 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
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It has been observed that spontaneous imbibi-
tion of water took place in the presence of water-
soluble cationic surfactants, and it was verified
that a wettability alteration took place [3]. It was
suggested that the cationic surfactant was able to
desorb some of the negatively charged ‘‘anchor’’
molecules, and make the surface more water-wet
so that capillary forced imbibition can take place.
The decrease in the interfacial tension between the
oil and the aqueous surfactant solution must be
moderate in order to maintain a capillary forced
imbibition. The driving force for the desorption
process was suggested to involve an ion-pair
formation between the negatively charged car-
boxylic group and the cationic surfactant at the
rock
/oil
/water interface. The ion pairs complex
may then dissolve in the oil phase or be part of the
cationic micellar system, i.e., formation of mixed
micelles. A recent Ph.D. thesis by Karlsson [4]
reviews the chemistry of cationic
/anionic surfac-
tants formed through complexation between alka-
noic acids and alkylamines, confirming a very
strong 1:1 association.
In this paper, we will add more experimental
data to confirm the proposed mechanism using
both model oils and crude oil by focusing on [3]:
1) The effect of carboxylates on the partitioning
of cationic surfactants between the brine and
the oil phase as a function of pH.
2) The effect of brine composition on the parti-
tioning of cationic surfactant between the oil
and the water phase in the presence of
carboxylic acids.
3) The effect of the presence of surfactant
micelles in order to achieve more water-wet
conditions at the carbonate surface.
4) Spontaneous imbibition of aqueous solutions
of C12TAB into oil-wet low-permeable chalk
containing model oil spiked with fatty acids.
Table 1
Properties of crude oils used
Oil Acid number (mg KOH per g oil) Density at 20 8C (g cm 3)
Crude 1 0.12 0.835
Crude 2 0.52 0.815
Crude 3 1.73 0.816
245
2. Experimental
2.1. Material
2.1.1. Oils
The model oil used in the partitioning experi-
ments was a mixture of 20 vol.% toluene and 80
vol.% heptane (density/0.723 g cm 3), while
pure heptane was used as model oil in the
imbibition experiments. Both chemicals were PA-
graded. Three different crude oil samples from the
North Sea/Norwegian Sea of different ANs were
used in the crude oil partitioning experiments,
termed Crudes 1, 2, and 3. The acid number was
also increased in an artificial way by spiking Crude
1 with different amounts of octanoic acid. Proper-
ties of the crude oils are given in Table 1.
2.1.2. Porous medium
Outcrop chalk from Stevns Klint near Copenha-
gen, Denmark, was used as the porous medium [5].
Relevant data for the cores used in the imbibition
experiments regarding porosity, permeability, core
size, initial water saturation, etc. are presented in
Table 2.
2.1.3. Brine
Four different brines were used in this work.
Brine 1 was synthetic formation/injection water
while Brines 2 and 3 had the same ionic strength as
Brine 1, but lower content of Ca2. The pH,
viscosity, and density for Brine 1 were 8.0, 0.8 cP,
and 1.02 g cm 3, respectively. Brine 4 was a 0.1 M
solution of sodium chloride in distilled water. The
brine compositions are given in Table 3.
2.1.4. Acids
Octanoic acid (C7H15COOH, Mw /144.22 g
mol1, grade ]/98%) and lauric acid
(C11H23COOH, Mw /200.32 g mol1, grade ]/
Asphaltenes (wt.%) IFT Brine 1 at 20 8C (mN m 1)
0.90 19.8
0.33 20.3
0.23 15.4
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Table 2
Core data for imbibition experiments

Test k f Swi PV Oil phase Surfactant/concentration Core size length/diameter

(mD) (%) (%) (cm3) (wt.%) (cm)

1 :/3 44.7 30.1 25.75 Heptane with 0.5 wt.% lauric No surfactant; Brine 1 5.19; 3.76
acid
2 :/3 44.1 29.9 27.54 Heptane with 0.5 wt.% lauric C12TAB; 1.0 wt.% 5.62; 3.76
acid
3 :/3 44.9 0 35.10 Heptane with 0.25 wt.% stearic C12TAB; 1.0 wt.% 7.08; 3.75
acid
4 :/3 44.8 0 31.02 Heptane with 0.25 wt.% stearic No surfactant; Brine 1 6.27; 3.75
acid
5 :/3 45.3 0 33.11 Heptane with 1.0 wt.% octanoic C12TAB; 1.0 wt.% 6.66; 3.74
acid

Oil: heptane with different carboxylic acids dissolved; Brine 1; temperature: 40 8C.

Table 3
Brine compositions

Component Brine 1 (g l 1) Brine 2 (g l 1) Brine 3 (g l 1) Brine 4 (g l 1)

Na 12.14 15.07 18.02 2.33

K 0.25 0.25 0.25
/
Ca2 3.43 1.72
/
/
Mg2 0.93 0.93 0.93
/
Cl  26.54 28.05 29.57 3.55
SO2
4 1.56 1.56 1.56
/
HCO3 0.09 0.09 0.09
/
Total dissolved solid 44.94 47.67 50.42 5.88

99%) were purchased from Fluka, while stearic 2.2. Analysis

acid (C17H25COOH, Mw /284.5 g mol 1,
grade :/99%) was purchased from Sigma. All acids 2.2.1. Asphaltenes
were used as received without further purification. The amount of asphaltene in the crude oil
samples was determined by the following proce-
dure: 10 ml of oil was mixed with 400 ml of
2.1.5. Surfactants
heptane in a closed beaker. The mixture was stored
Four cationic surfactants termed C10TAB,
C12TAB, C14TAB and C16TAB were purchased
Table 4
from Fluka and Sigma. The chemical formula for CMC data for the different surfactants in distilled water at
the surfactants are: n -C10H21N(CH3)3Br 25 8C
(C10TAB), n -C12H25N(CH3)3Br (C12TAB), n-
Surfactant Producer Grade (%) CMCa at 25 8C (wt.%; M)
C14H29N(CH3)3Br (C14TAB) and n-
C16H33N(CH3)3Br (C16TAB). Literature data for C10TAB Fluka /98 1.9; 6.8/10 2
critical micelle concentration (CMC) values in C12TAB Sigma :/99 0.43; 1.4/10 2
distilled water are given in Table 4. Sodium C14TAB Sigma :/99 0.12; 3.5/10 3b
C16TAB Sigma :/99 0.03; 8/10 4
dodecylsulfate (SDS) with grade /99%, used for
two-phase titration of the cationic surfactants, was a
Ref. [15].
b
purchased from Sigma and used as received. Measured at 30 8C.
 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
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overnight at 5 8C, and then filtered through a 0.45
mm filter. The filter was dried at 50 8C and
weighed. The wt.% of asphaltenes could then be
calculated from the mass of the precipitate.
2.2.2. Acid numbers
The acid number for the crude oils was deter-
mined according to the ASTM D-664 standard
and reported as mg KOH per g of oil.
2.2.3. Two-phase titration of cationic surfactants
The concentration of cationic surfactant in the
water phase was determined by two-phase titration
using SDS [6]. It was confirmed that fatty acids
present in the aqueous phase did not affect the
titration analysis of the cationic surfactant. Owing
to the high concentration of sulfuric acid added,
carboxylic acid was extracted into the organic
phase prior to the titration.
2.2.4. Contact angles on calcite crystals
Static contact angles were measured through the
aqueous phase after exposing calcite crystals for
oils and thereafter surfactant solutions. For model
oils containing fatty acids, the following procedure
was used:
. Calcite crystals were cleaved and the pieces were
put in a closed container filled with 0.25 M
solution of lauric acid or 0.018 M stearic acid in
the model oil. The solution was stored for 30
min at room temperature.
. The samples were removed from the oil and
allowed to dry in air at room temperature.
Table 5
Static contact angles measured on water drops on calcite surfaces treated with Crude 3, stearic and lauric acid dissolved in the model oil
Calcite crystals exposed to u for crude oil 3 (8)
Brine 1 82
2.5 wt.% C10TAB in Brine 1 39
0.25 wt.% C10TAB in Brine 1 63
1.0 wt.% C12TAB in Brine 1 13
0.1 wt.% C12TAB in Brine 1 46
0.01 wt.% C16TAB in Brine 1 33
1/10 4 wt.% C16TAB in Brine 1 42
247
. Then they were soaked into solutions of pure
Brine 1, and C12TAB and C16TAB dissolved in
Brine 1 for 15 min at room temperature. After-
wards, they were washed in distilled water and
dried.
. The crystal pieces were then placed in a
horizontal position and a droplet of distilled
water was carefully transferred to the surface.
The pictures of the droplets were taken im-
mediately using a video camera.
. An estimated static contact angle was deter-
mined manually from the pictures of the water
droplets. The repeatability was about 9/48.
In the case of Crude 3, the contact angles were
determined in the following way:
. Calcite crystals were cleaved and the pieces were
put in a closed container filled with Crude 3.
The solution was stored for 12 h at room
temperature.
. The crystals were removed from the oil, washed
quickly with toluene and heptane to remove the
bulk oil, and then allowed to dry in air at room
temperature.
. The crystal pieces were then soaked in solutions
of pure Brine 1, and C12TAB and C16TAB
dissolved in Brine 1 for 15 min at room
temperature. They were then washed with
distilled water and dried. The advancing contact
angles, measured through the aqueous phase,
were then determined as described above.
The values of the estimated static contact angles
u after treatment with different surfactant systems
are given in Table 5.
u for stearic acid (8) u for lauric acid (8)
90 73
51 28
52 55
29 29
65 59
29 18
77 57
248 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
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2.3. Surfactant partition studies
2.3.1. Model oil system
Partitioning of C12TAB, C14TAB and C16TAB
into model oil, 20 vol.% toluene and 80 vol.%
heptane, containing octanoic acid was investigated
as a function of pH. Twenty-five milliliters of
model oil containing octanoic acid with a concen-
tration of 0.00835 M (AN /0.64 mg KOH per g
oil) was mixed with 25 ml of 0.00835 M surfactant
solution using Brine 4 and stored at 40 8C for at
least 1 day. The pH was measured at 20 8C and
adjusted with sodium hydroxide or hydrochloric
acid if necessary. The mixture was allowed to
equilibrate again at 40 8C, and the procedure was
repeated until pH in the water phase maintained at
the desired value. Samples of the water phase were
then analyzed for the amount of cationic surfac-
tant by two-phase titration using SDS. The parti-
tion coefficient was calculated as the number of
moles of the surfactant in the oil phase divided by
the number of moles of surfactant in the water
phase.
2.3.2. Crude oils
The partitioning of C12TAB (0.3 wt.%) between
the oil and the water phase for the three crude oils
of different ANs was studied in a similar manner
as described above using Brine 1.
2.3.3. Crude 1 spiked with octanoic acid
Different amounts of octanoic acid were added
to Crude 1 in the concentration range 0
/0.0334 M.
The partition studies of C12TAB were then
performed as described above.
2.3.4. Effects of Ca2
The effects of Ca2 on the partitioning of
C12TAB between Crude 1 and brine were studied
by changing the Ca2 concentration in the brine
(Brines 1, 2, and 3). The ionic strength was kept
constant by adding NaCl. Otherwise, the experi-
ments were performed as described above.
2.4. Imbibition studies using model systems
Imbibition tests were performed with and with-
out initial water present in the core. The cores were
prepared according to the method described pre-
viously to obtain homogeneously wetted material
[2]. In the presence of water, two cores were first
saturated with Brine 1 under vacuum, and porosity
was calculated from weight difference. They were
then flooded with 2 pore volumes (PV) of heptane
containing 0.5 wt.% of lauric acid in each direc-
tion. The cores were placed in standard Amott
cells in a vertical position, and the spontaneous
production of oil was determined as a function of
time. Pure Brine 1 and Brine 1 containing 1.0 wt.%
C12TAB were used as imbibition fluids in Tests 1
and 2, respectively. The cores without initial water
were saturated with oil under vacuum, and poros-
ity was calculated from weight difference. They
were then flooded with 2 PV of heptane containing
carboxylic acids (1.0 wt.% octanoic or 0.25 wt.%
stearic acid) in each direction to ensure homo-
geneous saturation. No further aging of the cores
after preparation was performed. Relevant data
related to the imbibition tests are listed in Table 2.
The core without initial water containing stearic
acid was cleaved vertically in order to picture the
saturation profiles inside the core. The cleaved
surfaces were sprayed with an indicator giving a
light blue (dark) color on the water-flooded zone.
3. Results and discussion
As a general notice in the discussion below, the
CMC values listed in Table 4 for the different
surfactants in distilled water are mainly used to
visualize the relative values. In the practical
experiments presented, the absolute CMC values
for the different surfactants will surely vary
according to brine composition and possible co-
surfactants (fatty acids, etc.) present in the oil
phase.
3.1. Partition coefficient
The partition coefficient, K , of the surfactant is
defined as the ratio between the concentration
(mol l 1) of the surfactant in the oil phase and in
the brine. It is important to note that the
concentration of surfactant in the aqueous phase
includes surfactants as part of micelles and mono-
 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
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mers. In all the experiments, the volume of the two
phases were equal, and in that case, the K value is
given by the mol ratio of the surfactant in the two
phases, i.e.,
(ns )o
K : (1)
(ns )w
3.1.1. Model oil system (20 vol.% toluene and 80
vol.% heptane)
The partition of C12TAB, C14TAB and
C16TAB between brine containing only NaCl
(Brine 4) and model oil, with and without octanoic
acid present, was studied at 40 8C (Fig. 1).
Octanoic acid was initially dissolved in the oil
and the surfactant was dissolved in the brine at
similar molar concentration (0.00835 M). Even
without octanoic acid present, the cationic surfac-
tants partition somewhat into the organic phase.
The partitioning of C14TAB and C16TAB into the
oil phase is low and constant within the pH range
3
/10, K :/0.18. In the case of C12TAB, the
relative concentration in the oil phase is much
higher, but also in this case it is constant in the
same pH range, K :/0.7. In the presence of
octanoic acid, in all cases, the partition coefficient
increases as the pH of the aqueous phase increases.
Fig. 1. Partitioning of Cn TAB (n/12, 14 or 16) surfactants into model oil (20 vol.% toluene and 80 vol.% heptane) as a function of
pH in the water phase. Conditions: temperature, 40 8C; Brine 4; initial concentration of acid and surfactant, 0.00835 M.
249
As expected, the partition of surfactant into the
oil phase without acidic additives is independent of
the pH. At surfactant concentrations in the aqu-
eous phase above the CMC, it is reasonable to
believe that the partitioning of homologous series
of Cn TAB into the oil phase is balanced between
the monomeric concentration (CMC) and the
hydrophobic nature of the individual molecules,
which of course are related. The high partitioning
coefficient of C12TAB compared with C14TAB
and C16TAB may be explained by the high CMC
value (Table 4). Even though the brine contained
5.88 g l 1 with NaCl, the C12TAB concentration
is hardly above the CMC value. It is expected that
only monomers are able to cross the oil
/water
interface, and according to Table 4, the CMC
value for the individual surfactants decreases
relatively by a factor of about 5 as the length of
the carbon chain increases from 12 to 14 and 16 C-
atoms. The concentration of C14TAB and
C16TAB is well above the CMC, and the parti-
tioning coefficient of C16TAB is slightly lower
than for C14TAB.
If the oil contains octanoic acid (AN /0.64), in
all cases, the partition coefficient increases as the
pH of the aqueous phase increases. At pHB/4, the
acid is almost completely protonated and un-
charged. Most of the fatty acid will probably
250 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
/259
stay in the oil phase dissolved as clusters. As the
pH increases up to about 8, the acid becomes more
and more dissociated in contact with brine, and
the concentration of carboxylic anions in the
aqueous phase increases. Owing to the very high
dissolution of octanoic acid in water, at pH /8,
the concentration of undissociated acid becomes
very low, and the concentration of carboxylate
ions is constant. In that case, it is also expected
that the K value for the cationic surfactant
becomes nearly constant. The species present in
equilibrium between the two phases are schemati-
cally illustrated below:
[(RCOOH)r (RCOO )n (RN (CH3 )3 )m ]k (aq)
RCOO (aq)RCOOH (aq)
RN (CH3 )3 (aq)
U[(RCOO )(RN (CH3 )3 ]x (oil)
(RCOOH)y (oil)
In the aqueous phase, mixed micelles between
the cationic surfactant and the fatty acid, disso-
ciated and undissociated, will be in equilibrium
with monomers of the cationic surfactant, the
carboxylate and the undissociated acid. The dif-
ferent species in the aqueous phase are again in
equilibrium with aggregates of ion pairs between
the cationic surfactant and the carboxylate and
aggregates of undissociated fatty acids in the oil
phase. The partitioning of carboxylic acid between
the two phases is surely related to the pH of the
aqueous phase, and owing to the strong electro-
static and hydrophobic interaction between the
cationic surfactant and the carboxylate, also the
partitioning of the cationic surfactant between the
two phases is pH-related. The fact that the
solubility of the cationic surfactants in the oil
phase increases as the solubility of the acid in the
water phase increases (formation of carboxylates)
is a strong evidence that ion pairs between the
cationic surfactants and carboxylates are formed
and to some extent extracted into the oil phase.
Even though the species are well solvated into the
mixed micelles in the aqueous phase, enhanced
partitioning of the cationic surfactant into the oil
phase is observed.
It is well documented in the literature that
alkylammonium carboxylates are soluble in apolar
organic solvents such as benzene and even cyclo-
hexane [7]. In the absence of water, a general trend
in the published work is to model a progressive
association of the surfactants, i.e., the concept of
CMC used in aqueous solution does not apply in
this type of solvent [8]. In the presence of water,
however, reversed micelles are formed and water is
solubilized. Kitahara [7] has reviewed many stu-
dies on this subject prior to 1980. These systems
can be considered as water-in-oil microemulsions.
The formation of ion pairs between alkylammo-
nium ions and anionic surfactants has been used as
an analytical separation technique in reversed-
phase liquid chromatography [9,10]. The separa-
tion technique is based on different solubility of
the ion pairs in aqueous solution and organic
solution, and the solubility behaviour is very
sensitive to the anionic counter ion. Anionic
(2) ethoxylated sulfonates can be separated according
to the degree of ethoxylation using a cationic
mixed-mode reversed-phase column of the C8 type
[9].
Thus, even though octanoic acid is very soluble
in water, in the case of a carbonate reservoir with a
pH of 8, it is verified by Fig. 1 and the discussion
above that carboxylates from the crude oil will
enhance the partitioning of cationic surfactants
into the oil phase probably by means of ion-pair
formation. In the oil phase, larger aggregates may
be formed and water is probably solubilized into
the centre of the reverse micelles.
3.1.2. Crude oil systems
According to the results from the model oil
system described above, it is to be expected that
the partitioning of cationic surfactant into the oil
phase must be related to the acid number of real
crude oils. The partition coefficient of C12TAB,
with initial concentration of 0.3 wt.%, i.e., close to
CMC, for three crude oils at 40 8C, with different
natural acid numbers, is shown in Fig. 2. The high-
salinity Brine 1 was used, and it is noticed that the
natural pH of the different solutions was in the
range 6.89/0.4. As expected, the partition coeffi-
cient increases as AN increases. Crude 1 with
AN /0.12 mg KOH per g oil has a partition
 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
/259
coefficient of K /0.62. The corresponding values
for Crude 3 are AN /1.73 mg KOH per g oil and
K /6.94, respectively. At equilibrium, it was
observed that the water phase in the case of
Crudes 1 and 2 was slightly colored, indicating
that oil components were solubilized into the
surfactant micelles, i.e., the surfactant concentra-
tion in the aqueous phase was above CMC. For
Crude 3, however, the aqueous phase was not
colored, and the surfactant concentration was in
fact determined to be below the CMC. In this case,
the equilibrium between the different species in the
two phases will not contain mixed micelles in the
aqueous phase, and a drastic increase in the
partition coefficient will occur as discussed later.
Besides acid number, pH and surfactant concen-
tration, the K value is also expected to depend on
the properties of the molecules containing the
carboxylic groups and the salinity and composi-
tion of the brine.
Crude 1 was spiked with different amounts of
octanoic acid, and the partition coefficient of
Fig. 2. Partitioning of C12TAB (0.3 wt.%) into crude oils with
different acid numbers. Conditions: temperature, 40 8C; pH:/
6.89/0.4; Brine 1.
251
C12TAB (0.3 wt.%) was determined in Brine 4,
i.e., the low-salinity NaCl brine (Fig. 3). At these
conditions, the partitioning coefficient was ob-
served to be K /0.57 for the unspiked Crude 1.
This is quite comparable to the value obtained for
Brine 1. The partitioning coefficient of the surfac-
tant increased to 0.93 when a concentration of
0.033 mol l 1 of octanoic acid was added to the
crude oil, corresponding to a total AN /2.33 mg
KOH per g oil. In all cases, the pH of the aqueous
solution was 4.39/0.3. Thus, even at this rather
low pH, the acid is able to increase the oil
solubility of the cationic surfactant in the oil
phase.
Multivalent cations in solution, especially Ca2,
have high affinity towards the carboxylic groups.
They are efficient in screening electrostatic double-
layer repulsions, they adsorb strongly onto nega-
tively charged electron-donating surfaces, and
their capability to bridge colloidal particles in-
creases efficiency in flocculation and coagulation
[11]. It was, therefore, of interest to see how
sensitive the partitioning coefficient was for
Fig. 3. Partitioning of C12TAB dissolved in Brine 4 into Crude
1 spiked with octanoic acid. Conditions: temperature, 40 8C;
pH:/4.3; Brine 4.
252 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
/259
changes in the Ca2 concentration. Normally, the
concentration of Ca2 in carbonate brine in oil
reservoirs is very high. The concentration of Ca2
in Brine 1 was decreased from 3.43 to 1.42 and 0 g
l 1 while the ionic strength was kept constant by
adding NaCl. The partitioning data for C12TAB
(0.3 wt.%) between Crude 1 and the brine are
shown in Fig. 4. As expected, the Ca2 ions
probably compete with the cationic surfactants
for the anionic carboxylic groups by decreasing the
ion-pair formation between the surfactant and the
carboxylates. Corresponding experiments by de-
creasing the Mg2 concentration from 0.93 g l 1
in Brine 1 did not show any significant effects on
the partitioning of C12TAB. The difference in
behaviour can be related to the difference in
hydration of the cations. Since Mg2 is smaller
than Ca2, it is more strongly hydrated, and ion
hydration provides an energy barrier against
coordinating to carboxylic groups.
It is quite clear that the partitioning coefficient
of the cationic surfactant is not constant with
regard to the total surfactant concentration. At
Fig. 4. The effect of Ca2 concentration on the partitioning
coefficient of C12TAB (0.3 wt.%). Conditions: temperature,
40 8C; pH:/7.3 and Brine 1 with variable content of Ca2 .
specific brine conditions, i.e., brine composition
and pH, the partitioning coefficient should be
quite constant as long as the surfactant concentra-
tion in the aqueous phase is above CMC. In that
case, all the equilibrium species suggested above
are present. However, at surfactant concentrations
below CMC in the water phase, the micelles, which
solubilize the surfactants strongly into the water
phase, are absent. In that case, the partitioning of
the cationic surfactant into the oil phase is
expected to increase strongly. The partitioning
coefficient was determined as a function of the
initial concentration of C12TAB in the aqueous
phase using Brine 1 and Crude 3 (AN /1.73 mg
KOH per g oil; Fig. 5). It appears to be a slight
increase in the K value as the surfactant concen-
tration decreases towards the CMC value. Then,
the K value increases drastically from about 1.2
close to CMC (according to the figure, CMC :/0.4
wt.% in this case) to about 7 at an initial surfactant
concentration of 0.25 wt.% in the aqueous phase.
Thus, at surfactant concentrations well below
CMC, the cationic surfactant will dissolve nearly
completely into the oil phase, if AN is high. The
pH of the aqueous phase was about 6.4 during
Fig. 5. Effects of the surfactant, C12TAB, concentration on the
partitioning coefficient. Conditions: temperature, 40 8C; pH:/
6.4 and Brine 1. CMC /0.4 wt.%.
 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
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these experiments. It should be noted that Crude 3
has an AN /1.73 mg KOH per g oil, and it is
expected that the cationic surfactants form aggre-
gates between ion pairs with different carboxylates
present in the crude oil. This observation is
completely in line with the results from our
previous paper showing that the ability of
C12TAB to change the wettability of the chalk in
imbibition studies was drastically decreased at
surfactant concentrations below CMC [3]. This
again supports the suggested mechanism for wett-
ability alteration from oil-wet to water-wet condi-
tions.
3.2. Contact angles on calcite
The interaction between different cationic sur-
factants of the type Cn TAB and adsorbed carbox-
ylates from model oil and surface-active materials
from crude oil was also studied by determining
static contact angles on calcite, as explained in
Section 2. The objectives were to determine the
relative desorption potential of different surfac-
tants; C10TAB, C12TAB, and C16TAB towards
different carboxylic acids; lauric and stearic acids
dissolved in model oil. Also, desorption of surface-
active materials from Crude 3 was tested. The
effect of the contact angle on the concentration of
surfactant, above and below CMC, was also
studied. Typical examples of the video pictures of
the water droplet on the calcite crystal are shown
in Fig. 6 and the data are given in Table 5.
3.2.1. Lauric acid
Lauric acid is an n -C12 carboxylic acid, and the
contact angles for the acid-brine-surfactant sys-
tems are shown in Fig. 7. It is evident from the
figure that lauric acid has the ability to modify the
calcite surface, and the static contact angle after
Fig. 6. Pictures from the contact angle measurements on calcite surfaces exposed to lauric acid dissolved in n -heptane followed by: (a)
Brine 1, (b) 0.1 wt.% C12TAB in Brine 1, and (c) 1/10 4 M C16TAB in Brine 1.
253
exposed to brine was about 708. The value of the
contact angle indicates that the surface is mixed-
wet to slightly water-wet. The advancing contact
angle, after being in contact with the different
surfactant solutions at concentrations well above
CMC, is quite similar for C10TAB (2.5 wt.%) and
C12TAB (1.0 wt.%), i.e., slightly below 308. For
the C16TAB (0.01 wt.%) system, the contact angle
was about 188, even though the concentration was
more than 100 times lower than for C10TAB and
C12TAB. At surfactant concentrations below
CMC, the contact angles were in the range 55
/
598 for the three surfactants (CMC values listed in
Table 4). Thus, the adsorbed carboxylate was far
less desorbed by the cationic surfactants, even
though the concentration of C10TAB (0.25 wt.%)
and C12TAB (0.1 wt.%) was more than 10 times
higher than the concentration of the C16TAB
(0.01 wt.%) which resulted in a contact angle
below 208. The present results indicate that:
. The concentration of the surfactant solution
must be above CMC in order to have the
greatest effect on improving the water-wet
nature of the calcite surface.
. The more hydrophobic surfactant appeared to
have the greatest potential to desorb the car-
boxylate in such a static process.
With regard to the lower aqueous phase contact
angles found above CMC, an alternative explana-
tion to the wettability alteration may be the
possibility of surfactant hemi-micelle or double-
layer formation. This was discussed in detail in a
previous paper, and it was suggested that some
ethoxylated sulfonates could behave in this way,
but desorption of organic materials appeared to be
in line with the experimental data for cationic
surfactants [3].
254 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
/259
Fig. 7. Contact angles measured on calcite surfaces treated with model oil containing 0.25 M lauric acid followed by different
surfactant solutions.
This appears reasonable, and it is in line with the
proposed mechanism that ion pairs between the
cationic surfactant and the carboxylate are formed
initially. Owing to the insoluble nature of the ion
pairs in water, the desorbed carboxylates must be
trapped in the surfactant micelles, and the so-
called mixed micelles are formed. In this static
experiment, the monomer concentration of the
actual surfactant appeared to be of less impor-
tance. It is interesting to note that C16TAB
appeared to interact more strongly with the
carboxylate ion of lauric acid compared with
C10TAB and C12TAB, probably owing to stron-
ger hydrophobic interaction in the desorption
process. Both the mutual interaction in the deso-
rption process and the trapping of the carboxylate
in the micelles seems to be important factors in
creating the most water-wet surface.
3.2.2. Stearic acid
Stearic acid is an n -C18 carboxylic acid. The
hydrophobic nature of stearic acid is therefore
higher than for lauric acid. This is also reflected in
the higher value of the static contact angle when
exposed to pure brine, u/908 for stearic acid
compared with u /708 for lauric acid (Table 5). As
indicated by the u values for surfactant concentra-
tions well above the respective CMC values, stearic
acid is also more difficult to displace from the
calcite surface compared with lauric acid. The u
values for C10TAB and C12TAB are close to 508,
and for C16TAB the value is slightly below 308
(Fig. 8). Also in this case, the C16TAB surfactant
is the best water-wetting agent. At surfactant
concentrations well below the respective CMC
values, the u values appear to decrease with
increasing concentration of the surfactant. It is
noticed that the u value for C10TAB is the same as
for surfactant concentration above and below
CMC. This is hard to explain, but may be the
surfactant concentration is not low enough to
prevent the formation of mixed micelles in the
low-surfactant concentration case owing to the
desorption of some stearic acid. It is well known
that the CMC value is drastically decreased in
mixed micelles of cationic and anionic surfactants
owing to strong negative deviation from ideality
for binary pairs of surfactants [13].
3.2.3. Crude oil 3
Crude 3 has a relative high acid number, AN /
1.73 mg KOH per g oil, and it is expected that
surface-active components containing carboxylic
groups will adsorb onto the surface of the calcite
crystals and make it less water-wet. This is also
confirmed by the high u value when exposed to the
pure brine solution, u /828 according to Fig. 9. At
surfactant concentrations above the respective
CMC values, it is interesting to note that
C12TAB is the best water-wetting agent, resulting
 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
/259 255

Fig. 8. Contact angles measured on calcite surfaces treated with model oil containing 0.018 M stearic acid followed by different
surfactant solutions.

in an static contact angle as low as 138. The u
values for C10TAB and C16TAB were 398 and
338, respectively. According to our previous study,
it should be noticed that C12TAB was also the
most efficient surfactant to change the wettability
in chalk cores using the same crude oil system [3].
At surfactant concentrations well below CMC, the
trend in the contact angles is opposite to what was
observed for the stearic acid system. The u values
decrease as the hydrophobic nature of the surfac-
tant increases.
The material adsorbed onto the calcite surface
from the crude oil is a complex mixture of surface-
active compounds. Molecules containing car-
boxylic groups are expected to adsorb most
strongly to the surface, and these molecules may
serve as ‘‘anchor’’ molecules for further adsorption
of surface-active material in a cooperative way.

Fig. 9. Contact angles measured on calcite surfaces treated with Crude oil 3 followed by different surfactant solutions.
256 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
/259
Fig. 10. Imbibition into chalk saturated with heptane containing 0.5 wt.% of lauric acid at 40 8C.
Similar to the carboxylic acid systems, the most
water-wet surface is obtained if the desorbed
material is trapped in the micelles of the surfac-
tant. In this way, the surfactant, besides being a
desorbing agent, also acts as a detergent in
solubilizing the desorbed material.
3.3. Imbibition studies
It is evident from Fig. 10 that a 0.5 wt.%
solution of lauric acid in heptane in combination
with Brine 1 is able to make the chalk cores with
an initial water saturation of about 30% to act oil-
wet from an imbibition point of view without any
further aging time. The small and fast imbibition
of brine at the start was related to some inhomo-
geneous saturation of oil close to the core surface,
and it is related to the core preparation procedure,
as discussed previously [2]. Afterwards, only traces
of water imbibed during a period of nearly 30
days. Thus, even though the static contact angle
for the same system on calcite showed a value of
only 708, indicating a slightly water-wet condition,
the porous chalk material appeared to act as oil-
wet, in terms of imbibition of water.
In the presence of 1.0 wt.% C12TAB in Brine 1,
water imbibes and about 23% of OOIP were
recovered within 30 days. It is noticed that the
plateau production was not reached at that time.
The imbibition and the ultimate oil recovery are
less than for the crude oil system with acid number
of 1.73 mg KOH per g oil [3]. A solution of 0.5
wt.% lauric acid in heptane corresponds to an acid
number of 1.41 mg KOH per g oil, and in that
case, the two oils are comparable. It must, how-
ever, be noticed that one of the cores were treated
with 0.5 wt.% lauric acid in heptane solution and
aged at 50 8C for about 4 days. The core was
handled, as described previously, by shaving off
about 2 mm of the outermost layer of the core
surface [2]. This core became so strongly oil-wet
that no imbibition of brine or surfactant solution
took place during a period of 14 days. Thus,
during the imbibition experiment, lauric acid
present in the oil-phase not contacted by the
surfactant solution, will probably continue to
adsorb onto the surface and make it even more
strongly oil-wet. This may explain the special
shape of the imbibition curve, which becomes
nearly linear after about 8 days. In the case of
crude oil, the imbibition profile was curved all the
way until the plateau was reached, which is typical
for a counter-current fluid flow governed by
capillary forces. Regarding crude oils, the func-
tional carboxylate groups are situated on organic
molecules of great variety regarding molecular size
and structure. Some of the smaller molecules may
easily be desorbed from the surface by C12TAB,
and in that way enhance the water-wetness of the
material compared with the model oil system
containing a large chain fatty acid.
 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
/259
In order to get some more information about
the imbibition mechanism using C12TAB and
model oil systems, imbibition studies were per-
formed at 100% oil saturated conditions using
octanoic and stearic acids (Fig. 11). Only traces of
pure Brine 1 was imbibed into the core containing
stearic acid, confirming that the core appeared oil-
wet from an imbibition point of view [12]. The
imbibition of C12TAB solution into the cores
containing octanoic and stearic acids was recorded
for more than 40 days at 40 8C. In the case of
octanoic acid, about 13% of the oil was expelled
within 20 days, which appeared to be close to the
plateau production, and only traces of oil was
recovered thereafter. It should be noticed that the
concentration of octanoic acid in heptane was as
high as 1.0 wt.%, and furthermore, octanoic acid is
quite soluble in the aqueous phase. It is, therefore,
suggested that during the experiment, some octa-
noic acid will move into the aqueous phase and
form mixed micelles with the cationic surfactant.
The C12TAB monomer concentration will then
decrease drastically because the CMC of the mixed
micellar system containing oppositely charged
surfactants is lowered. Thus, even though the total
concentration of C12TAB in the aqueous phase is
high, the imbibition rate is related to the monomer
concentration of the surfactant [3].
Fig. 11. Imbibition of Brine 1 and C12TAB solutions into chalk cores saturated with 100% heptane containing stearic or octanoic acid
at 40 8C.
257
The spontaneous oil expulsion from the core
containing stearic acid is fast at the start, but after
about 10 days it appeared to be a linear relation-
ship between oil production and time. Oil was still
produced from the core after 40 days, and no
production plateau was reached within the experi-
mental time frame. The solubility of stearic acid in
water is very low compared with octanoic acid,
and it is therefore not expected that the concentra-
tion of stearic acid in the mixed micelles is very
high. Besides, the acid concentration in heptane is
only 0.25 wt.% in this case. The shape of the
imbibition curve is very similar to what was
observed for imbibition of surfactant solution
into mixed-wet long-core chalk materials at low
IFT [14]. The break in the curve was related to a
change in the imbibition mechanism. Capillary
forces expelled the oil in the beginning while
gravity forces dominated the fluid flow later on,
i.e., oil was displaced mainly from the top surface.
In order to get some knowledge about the imbibi-
tion mechanism for the present stearic acid system,
the core was cleaved vertically. Difference in color
of the water-imbibed area and the non-contacted
area was obtained by spraying the cleaved surfaces
with an indicator (Fig. 12). The dark area is the
water-contacted zone, and the light area is the oil
area not contacted by the surfactant solution.
258 D.C. Standnes, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 216 (2003) 243
/259
Fig. 12. Picture of the cleaved core imbibed by aqueous
C12TAB solution. Oil phase: 0.25 wt.% stearic acid dissolved
in heptane. The dark area has been contacted by water, while
the imbibition fluid has still not contacted the light area.
Obviously, the fluid distribution is not in line with
an imbibition mechanism governed by gravity
forces. The vertical segregation of the oil is not
pronounced. It appears as water has imbibed most
strongly from the top and the bottom surfaces,
and oil is displaced mostly from the side surface of
the core. The figure indicates that channels of high
oil saturation from the non-contacted oil zone to
the side surface of the core were established as oil-
producing zones. The rock volume contacted close
to the side surface of the core is rather small
compared with the volume at the bottom and end
surfaces. The residual oil saturation profile ap-
peared a little bit strange for homogeneous rock
material where only capillary forces govern im-
bibition. More experiments are, however, needed
in order to be able to explain the exact mechanism
behind the oil expulsion in this case.
4. Conclusion
This work is a further confirmation of the
suggested mechanism for the spontaneous imbibi-
tion of water into oil-wet carbonate rock by means
of a wettability alteration using cationic surfactant
[3]. The following conclusions are drawn from this
work:
. The partitioning of cationic surfactants of the
type Cn TAB into the oil phase increases in the
presence of carboxylic acids. The cationic
surfactants are probably dissolved in the oil
phase as aggregates of ion pairs between the
surfactant and carboxylates.
. The partitioning of the surfactant into the oil
phase increases as the pH of the aqueous phase
increases, confirming the presence of a cation
/
anion surfactant complex.
. The partitioning coefficient is quite constant at
surfactant concentrations above CMC, but it
increases drastically below CMC.
. The partitioning coefficient appears to decrease
as the concentration of Ca2 in the brine
increases.
. For crude oils, the partitioning of cationic
surfactants into the oil phase increases as the
acid number increases.
. Contact angle measurements support that car-
boxylates adsorbed onto calcite surfaces are
desorbed by an interaction between cationic
surfactants and the negatively charged carbox-
ylate ion. The desorbed material is then trapped
in the surfactant micelles.
. From an imbibition point of view, u values in
the range 70
/908 on the calcite surface, will act
as an oil-wet system in porous chalk material
using fatty acids dissolved in heptane as the oil
phase. Aqueous solutions of C12TAB imbibe
spontaneously into these moderately aged chalk
cores.
Acknowledgements
The authors wish to thank Phillips Petroleum,
Statoil and Reslab for providing the oil samples
and Seniorforsker Dan Olsen at GEUS, Copenha-
gen, Denmark, for helping to provide the chalk
material used in the imbibition experiments.
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