Journal of Colloid and Interface Science 242, 230–238 (2001)
doi:10.1006/jcis.2001.7728, available online at http://www.idealibrary.com on
Bitumen-in-Water Emulsions Stabilized with Natural Surfactants
Socrates Acevedo,† Xiomara Gutierrez,∗ and Hercilio Rivas∗,1
∗ PDVSA-Intevep. P.O. Box 76343, Caracas 1070-A, Venezuela; and †Organic Chemistry Center, Science Faculty,
Central University of Venezuela, Caracas 47102, Venezuela
Received November 13, 2000; accepted May 25, 2001; published online August 16, 2001
The stability and rheological properties of bitumen-in-water
emulsions prepared in the presence of different concentrations of
sodium carbonate in the aqueous phase were investigated. When the
carboxylic acids present in the bitumen are contacted by an alkaline
aqueous solution, surface-active compounds or natural surfactants
are formed. These surfactants are responsible for the very low val-
ues of interfacial tensions observed and for the stabilization of the
bitumen-in-water emulsions formed. The mean droplet diameter of
the emulsions prepared decreased as the concentration of sodium
carbonate increased. The apparent viscosity of the emulsions also
increased with the sodium carbonate concentration. Eventually, a
sodium carbonate concentration was reached at which emulsions
were completely unstable. Results are explained by considering that,
at low electrolyte concentrations, emulsions are stabilized by elec-
trostatic repulsion forces between the electrical double layers, while
at high electrolyte concentrations, the short-range interaction forces
are predominant. ⃝C 2001 Academic Press
Key Words: bitumen; emulsions; natural surfactants; alkaly.
INTRODUCTION
Heavy crude oils and bitumen are known to contain signif-
icant quantities of native carboxylic acids and phenols (1, 2).
When such acidic crude oils are contacted by alkaline water
solutions, surface-active soaps are formed at the interface due
to the reaction between the carboxylic acids present in crude oil
and the alkaline species in the aqueous phase (3). Due to its im-
portance in several of the processes, normally carried out in the
petroleum industry, specially in crude oil production, treatment,
and transportation, these native tensoactive compounds, referred
to here as natural surfactants (NS), have been the subject of
many studies. Thus, Seifet and Howells (4) reported the isolation
of carboxylic acids from a light Californian crude oil by means
of a long extraction procedure. According to these authors,
such acids are responsible for the very low values of interfacial
tension found in the alkaline regions of crude oil/water systems.
Rather similar results were reported by Acevedo et al. (5, 6),
working with bitumen from the Orinoco Belt in Venezuela.
Others authors (7, 8) have emphasized the importance of the
1 To whom correspondence should be addressed.
0021-9797/01 $35.00
Copyright ⃝ C 2001 by Academic Press
All rights of reproduction in any form reserved.
so-called natural surfactants, in the stabilization of the water
in oil emulsions, formed during the processes of crude oil
production.
The importance of the very low values of interfacial tensions,
and their obtainment by means of alkaline flooding, have been
long recognized in enhanced oil recovery. Upon adsorption of
these natural surfactants at the crude oil/water interface, the
interfacial tension may fall by several orders of magnitude to
ultralow values (5, 9, 10). Under conditions of ultralow interfa-
cial tensions, capillary forces are substantially reduced and oil
displacement is facilitated (11). However, it is worth pointing
out that the interfacial tension arising from the crude oil/caustic
interactions is greatly affected by the nature of the crude oil, the
effective caustic concentration at the interface, the type of caus-
tic agent, the presence of electrolytes, the temperature, and so
forth (12, 13). The effectiveness of a synergetic effect between
natural surfactants and synthetic surfactants on the efficiency of
the enhanced oil recovery processes has also been studied (14).
Under appropriate conditions, natural surfactants can also be
utilized as emulsifying agents in the formation of bitumen-in-
water emulsions (15). The use of such emulsions for transporta-
tion purposes, since they have viscosity values which are sev-
eral order of magnitude lower than the viscosity of the bitumen
itself, is well known. The development of an adequate tech-
nology aimed at handling very viscous hydrocarbons through
their emulsification in water has been studied over the past two
decades by several authors (15, 16). However, not very much in-
formation on bitumen-in-water emulsions stabilized by natural
surfactants has been published so far.
In this paper, we will discuss several important issues related
to the behavior of natural surfactants as emulsifying agents. The
main properties of the bitumen-in-water emulsions stabilized by
those surfactants will also be discussed.
THEORETICAL BACKGROUND
The stability of an emulsion can be quantified as the time
elapsed between its formation and its total collapse. Ideally, very
concentrated emulsions (70% or more of the dispersed phase)
consist of an agglomeration of polyhedral droplets separated by
thin liquid films of the continuous phase (Fig. 1). Three adjacent
liquid films meet at the Plateau border channels. The curvature at
230
 BITUMEN IN WATER EMULSIONS
FIG. 1. Polyhedral structure of a concentrated oil in water emulsion.
the Plateau border walls generates a pressure difference between
the thin liquid film and the Plateau borders, causing flow out
of the films into the Plateau border channels. Thus, the liquid
films become thinner with time, and eventually they might col-
lapse, promoting the destabilization of the emulsion. So emul-
sion stability depends on the stability of the thin liquid films.
The stability of the thin liquid films was first discussed in
terms of a “disjoining pressure” by Derjaguin and Kussakov
(17). The disjoining pressure is the hydrostatic pressure in the
interior of the films, operating at right angles to the surface of
the films, which opposes the approach and coalescence of two
droplets in an emulsion. In other words, it is the force per unit
area that opposes film drainage.
London–van der Waals and electrostatic forces (DLVO forces)
(18, 19) and the so-called short-range interaction forces (20) are
the main interaction forces across the thin liquid films which
significantly contribute to the disjoining pressure (21). The effect
of these forces becomes significant when the film thickness is
on the order of 1000 Å, and their importance increases with
decreasing film thickness. The stability of the thin liquid films
in an emulsion is very much enhanced by the presence of a
surfactant adsorbed at the surface of the dispersed droplets. The
surfactant modifies the interaction forces between droplets and
prevents film drainage (22).
The total potential energy between two droplets, UT , is given
by
UT = UA + UR + USR ,
where UA represents the London–van der Waals attractive forces,
UR is the contribution due to electrostatic interactions, and USR
is the term that refers to the short-range forces.
The contribution of the London–van der Waal forces to the
disjoining pressure is always negative for the case where a
droplet is forced to approach its homophase. The attractive
energy UA rapidly increases as the droplets approach each
other, and its effect is to enhance the rate of thin liquid films
thinning. The electrostatic forces create a positive contribution
231
to the disjoining pressure, which tends to stabilize the films
and to oppose coalescence. The contribution of short-range
forces to the disjoining pressure may be positive or negative,
depending on the characteristics of the systems. Thus, the net
contribution of the two opposing effects determines whether
the thin films will reach a critical thickness at which they
become unstable and ruptures and coalescence occurs or will
attain an equilibrium thickness at which further drainage stops.
Film rupture can therefore only occur if the disjoining pressure
decreases when the film thickness decreases, i.e., when its
derivative with respect to film thickness is positive.
For concentrated bitumen-in-water emulsions, with a struc-
ture similar to the one in Fig. 1, in which the thin liquid film thick-
ness separating droplets is very small compared to droplet sizes,
it is reasonable to neglect the curvature effects and treat the liquid
films as planar films. In this article, we will discuss the proper-
ties of emulsions with mean droplet diameters ranging between
6 and 40 µm, separated by distances shorter than 100 Å. There-
fore, the expressions for planar liquid films can be applied here.
The London–van der Waals interaction energy per unit area
for two thick, flat blocks of material, α, interacting through
another material, medium, β, is given by the well-known
Hamaker equation (23),
UA = −Aαβα /12π H 2 , [2]
where Aαβα is the Hamaker constant and H the separation dis-
tance between the interacting surfaces (equal to the thickness of
the thin liquid film). Retardation effects (24, 25) were not taken
into account in our calculations and a value of 5.0 × 10−20 J
was used for the Hamaker constant (20).
Electrostatic forces in charged liquid films are due to interac-
tion between the electrical double layers associated with each
interface. As charged surfaces approach one another, the diffuse
parts of the electrical double layer interpenetrate, generating a
repulsive force (26). When the interacting surfaces (α and β)
separated by a given medium (γ ), have the same potential, ψs , the
electrical interaction energy is the repulsive energy, UR , given
by
UR = εκψs2 (1 −tanh κ H/2). [3]
In this equation, derived by Hogg et al. (27), ε is equal to the
[1] product of the permittivity of the free space and the dielectric
constant of the water; this is (8.85 × 10−12 )(78.54) C2 J−1 m−1 ,
and κ is the Debye parameter, which depends on the electrolyte
concentration in the medium. Equation [3], which assumes
that the double-layer potential remains constant during the
approach, provides a good estimate of the repulsive potential
energy. Overbeek (28) has shown that the linear approximation
assumed by Hogg et al. (27) is remarkably good, even at a
surface potential of 100 mV.
To compute the electrostatic repulsion energy using Eq. [3],
it is necessary to determine the electrostatic potential ψs
232 ACEVEDO, GUTIERREZ, AND RIVAS
and the Debye parameter κ. Several investigators (29, 30)
have suggested that the zeta potential (ζ ), determined by
electrophoretic measurements, is approximately equal to the
interfacial potential, ψs . Thus, the values of the zeta potential,
determined for our bitumen-in-water emulsions, were used in
place of ψs in Eq. [3]. The values of κ were calculated using
the expression
κ = (2n 0 v 2 e2 /εr ε0 kT )1/2 , [4]
where n 0 is the number of ions of each type per volume unit of
bulk phase, v is the magnitude of the valence of the ions, e is
the electron charge, εr is the relative permittivity of the solution
phase and ε0 of free space, k is the Boltzman constant, and T
is the absolute temperature.
In our analysis, the contribution of the short-range interaction
energies will be briefly mentioned during the discussion of the
experiments results.
EXPERIMENTAL
Materials. In this study, Cerro Negro bitumen, from the
Orinoco Basin in Venezuela, was used. This bitumen has an
API gravity of 8.5, a viscosity of 105 mPa s at 25◦ C, and an acid
number of 3.7 mg of KOH/g. Alkaline solutions were prepared
by dissolving in double-distilled water the required quantities
of lithium, sodium, or potassium carbonates (analytical-grade
reagents). The alkaline solutions of carbonate salts were chosen
because they produce a buffer solution, which is able to keep the
pH practically constant at around 11.3 ± 0.3 over a wide range
of carbonate concentrations (Fig. 2). If the pH remains constant,
the system can be better controlled. For interfacial tension exper-
iments, it was necessary to dilute the bitumen with 10% (w/w)
of analytical-grade xylem, since the density of bitumen was very
close to that of the water alkaline solutions.
FIG. 2. pH of an aqueous solution as a function of the sodium carbonate
concentration.
Interfacial tensions. Equilibrium dynamic interfacial ten-
sion measurements were made using the spinning drop ten-
siometer (University of Texas, Model 500) and the procedure
of Cayias et al. (31). Glass sample tubes with a length of 10 cm
and an internal diameter of 4 mm were used. The oil-drop volume
used was 3 µl, dispensed using a 50-µl Hamilton syringe into
the glass sample tube containing the aqueous solution. The tube
was placed in the instrument and accelerated at 6000 rpm. Mea-
surements were carried out at 25.0 ± 0.1◦ C. The oil drop was a
solution of 90% (w/w) bitumen in xylene. The aqueous phases
were solutions of lithium, sodium, or potassium carbonates in
water, at different concentrations. Using aqueous solutions of
lithium, sodium, or potassium carbonates, the effect of the ionic
radius of the cation on the interfacial tension can be determined.
The interfacial tension at the interface, pure xylem/water, did
not change with the carbonate concentration in the aqueous
phase. This indicates that the variations of interfacial tensions,
observed at the interface, bitumen solution in xylem/carbonate
aqueous solutions, should be attributed only to the presence of
natural surfactants (NS) in the bitumen.
Emulsions preparation. Emulsions of Cerro Negro bitu-
men in water, stabilized with natural surfactants, were prepared
at 60◦ C. At 30◦ C this bitumen has a viscosity in excess of
100 mPa s. Natural surfactants were activated by adding dif-
ferent concentrations (ranging between 1000 and 15,000 ppm)
of sodium carbonate to the aqueous phase of emulsions.
Emulsions were prepared following the “high internal phase
ratio” (HIPR) method developed by Chirinos et al. (32), which
requires initial dispersion to be carried out at packing fractions
greater than the critical. This facilitates the formation of highly
concentrated emulsions, with a very narrow droplet diameter dis-
tribution. According to this method, a mixture of bitumen and
an alkaline water solution (alkalinized with sodium carbonate),
containing a volume fraction of bitumen of 0.90, was stirred for
several minutes using a Rushton paddle-equipped mixer until
a constant mean droplet size was obtained. During the homog-
enization process, the mixing vessel was immersed in a 60◦ C
water bath. The modest shaft speed and high mixture viscosity
resulted in mixing conditions that posed no risk of air entrap-
ment. Furthermore, emulsions were diluted with the aqueous
phase to obtain final bitumen volume fractions of 0.70.
After preparation, emulsions were stored at 25◦ C in sealed
containers and analyzed for mean droplet diameter and distribu-
tions, using an instrument based on a light diffraction technique
(Malvern, Model Master Seizer). These measurements allow
monitoring of emulsion stability.
Emulsion viscosity. Viscosity (η) and shear stress (τ ), as
a function of shear rate (γ ), were obtained using a Haake–
Rotovisco rotational viscometer (RV-20) provided with concen-
tric cylinders type MV1.
Electrophoretic mobility. Electropheretic mobilities were
determined using a Rank Mark II microelectrophoresis appa-
ratus (Rank Brothers, Cambridge, England). One part of each
 BITUMEN IN WATER EMULSIONS 233

emulsion was diluted in 1000 parts of continuous phase. The

diluted emulsion was poured into a glass cell with flat sides.
Platinum-black-coated electrodes were inserted into each end of
the cell, taking care than no air bubbles were included. The cell
was immersed in a water bath at a temperature of 25.0 ± 0.2◦ C.
When a potential difference of 30 V dc was applied across the
electrodes, charged drops suspended within the medium inside
the cell migrated with a measurable velocity toward one of the
electrodes. The droplets were viewed through the calibrated eye-
piece of the microscope, and the rate of droplet movement was
measured over a known distance. A series of 20 readings were
taken at each stationary level to give a mean value of mobility.
The potential was reversed for each determination to minimize
polarization of the electrodes. The electrophoretic mobility and
the charge density were calculated using the equations given in FIG. 3. Interfacial tension, at 25◦ C for the bitumen/water system, as a func-
the literature (29, 30). tion of the sodium carbonate and sodium chloride concentrations in the aqueous
phase.
RESULTS AND DISCUSSION
cation was detected. A further increase in the Na2 CO3 concen-
Interfacial properties. The effect of pH on the equilibrium tration promoted an increase in interfacial tension.
interfacial tensions in systems formed by crude oil containing The presence of NaCl in the aqueous phase promoted an in-
organic acids or acid bitumen/aqueous solutions of NaOH was crease in the interfacial tensions at any of the sodium carbon-
discussed in previous papers (5, 33–36). The proposed mech- ate concentrations studied (Figs. 3 and 4). By the addition of
anism relies on the interfacial reaction between the carboxylic 5000 ppm NaCl into the aqueous phase, the zone of spontaneous
acids present in the oleic phase and the alkali in the aqueous emulsification, i.e., the region where ultralow interfacial tensions
phase. This reaction produces carboxylate ions, which are the were observed, disappeared. In all these experiments, the pH
ionized form of acids (soaps). The adsorption of these soaps at of the aqueous phase remained constant at around 11.3 ± 0.3,
the interface significantly lowers the interfacial tension (5). while the sodium (Na+ ) concentration increased progressively.
For these systems, the interfacial tension decreased very It is evident that, under conditions of constant pH, the effective-
rapidly at pH values above 9, reaching values lower than ness of the ionized carboxylic acids in reducing the interfacial
0.1 dyn/cm in the range of pH between 10.5 and 12. Ultra low tension depends very much on the Na+ concentration.
values of interfacial tension were achieved at a pH of 11.5. At This behavior can be explained by the adsorption–desorption
this point, an adsorbed monolayer of ionized and unionized acid mechanism proposed in Fig. 5. At a Na2 CO3 concentration of
molecules should be adsorbed at the interface (5). A further in- 500 ppm in the aqueous phase, the concentration of hydroxyl
crease in the pH to 13 or higher promotes an increase in the ions (OH−) is high enough to promote the ionization of the
interfacial tension, attributed to the complete ionization of the carboxylic acids (AH) present at the bitumen/water interface,
carboxylic acids, followed by the formation of insoluble salts of forming the carboxylate ions (A−), whose interfacial activity is
sodium carboxylate.
It is evident that pH is a very important parameter for con-
trolling the phase behavior of bitumen/alkaline aqueous solution
systems. However, we believe that the ionic strength should play
an important role too. Thus, experiments were carried out us-
ing Na2 CO3 as the alkaline agent. In fact, Na2 CO3 generates a
kind of buffer solution, whose pH remains practically constant
at around 11.3 ± 0.3 over a wide range of carbonate concentra-
tions (Fig. 2). The use of Na2 CO3 as an alkaline agent allows
also investigation of the effect of the Na+ concentration on the
interfacial tension in bitumen/water systems.
Figure 3 shows the effect of Na2 CO3 on the interfacial ten-
sion in the system Cerro Negro bitumen/aqueous solutions of
Na2 CO3 . As the Na2 CO3 concentration increases from 500 to
700 ppm, a sharp decrease in interfacial tension is observed. FIG. 4. Interfacial tension, at 25◦ C, for the bitumen/water system, contain-
In the range of concentrations between 700 and 2000 ppm, ul- ing 4000 ppm sodium carbonate, as a function of the sodium chloride concen-
tralow interfacial tension developed and spontaneous emulsifi- tration, in the aqueous phase.
234 ACEVEDO, GUTIERREZ, AND RIVAS

whose ionization constant is given by

K a = [A− −
w ][H3 O ]/[HAw ]. [8]

Adsorption of the carboxylate ions at the bitumen/water in-

terface, according to the equilibrium

A− −
w ⇔ As , [9]

with an adsorption constant, K s , defined by

K s = [A− −
s ]/[Aw ]. [10]

Precipitation of the carboxylate ions, as sodium carboxylate,

whose reaction is given by

A− +
w + Na ⇔ ANa, [11]

which is governed by the following constant (solubility product

FIG. 5. Adsorption–desorption mechanism for carboxylate ions.
constant):

well known (5, 10). Since the bitumen contains a mixture of K p = 1/[A− +
w ][Na ]. [12]
carboxylic acids, with different molecular structures and molec-
ular weights (6), a fraction of the carboxylate ions remain ad- All those equilibria are affected by the water ionization
sorbed at the interface, while the rest diffuse to the aqueous
phase. 2H2 O ⇔ H3 O+ + OH− [13]
As the concentration of Na2 CO3 increases, the pH of the aque-
ous phase tends to remain constant, but the concentration of Na+
and its constant K w , or the ionic product of water, given by
increases. This increase in Na+ concentration makes the car-
boxylate ions, dissolved in the aqueous phase, more and more
K w = [H3 O+ ][OH−]. [14]
hydrophobic, promoting its diffusion and adsorption at the in-
terface, with a consequent decrease in the interfacial tension. A
The total concentration of carboxylic acids in the system is given
point is reached (between 700 and 2000 ppm sodium carbonate)
by the following mass balance:
where ultralow interfacial tensions were detected. Further in-
creases in the Na2 CO3 concentration introduce into the system
[HAo ] = [HAw ] + [A− −
w ] + [As ] + [ANa]. [15]
the required Na+ concentration to promote the formation of in-
soluble sodium carboxylate salts (NaA). Under these conditions
Rearrangement of Eq. [15], with the use of the equilibrium re-
the interfacial tension increases.
lationships, yields the following equation:
The interfacial behavior discussed above could be better un-
derstood using a simple model, deducted from the system chem-
istry shown in Fig. 5. Thus, there are the following: [A− − −
s ] = [Aw ](K w /K a K d [OH ]) −[NaA]. [16]

Partitioning of the carboxylic acids (H A) between the bitumen If the pH of the aqueous phase remains constant, Eq. [16] can
and the aqueous sublayer, be rewritten as

HAo ⇔ HAw , [5] [A− −

s ] = K [Aw ] −[NaA]. [17]

with a partition coefficient, K p , defined as According to Eq. [17], the concentration of carboxylate ions ad-
sorbed at the interface decreases as the concentration of sodium
K p = [HAw ]/[HAo ]. [6] carboxylate (NaA) increases. There is a critical Na+ concen-
tration, given by Eq. [12], at which the precipitation of sodium
Dissociation of the carboxylic acid at the aqueous side of the carboxylate (NaA) starts. Once the NaA starts to precipitate, the
interface according to the reaction excess of Na+ added to the aqueous phase only contributes to
the removal of the carboxylate ions adsorbed at the interface
HAw + H2 O ⇔ A− −
w + H3 O , [7] by the formation of more and more ANa. Consequently, as was
 BITUMEN IN WATER EMULSIONS
FIG. 6. Interfacial tension for the bitumen/water system, as a function of
temperature, and sodium carbonate concentration.
observed experimentally, the interfacial tension increases with
the concentration of Na+ in the aqueous phase.
The effect of temperature on the interfacial tension of the
system Cerro Negro bitumen/aqueous solution of Na2 CO3 is
shown in Fig. 6. It can be observed that, for Na2 CO3 concen-
trations larger than that required to reach the minimum interfa-
cial tension in the system, the interfacial tension decreased with
the temperature. This effect should be attributed to changes in
the solubility of the sodium carboxylate (NaA). As the tempera-
ture increases, the sodium carboxylate becomes more water sol-
uble; thus, the term [NaA] in Eq. [17] decreases. Consequently,
the concentration of carboxylate ions adsorbed at the interface
tend to increase and the interfacial tension to decrease.
Figure 7 shows the interfacial tension as a function of the con-
centrations of lithium, sodium, and potassium carbonates for the
system Cerro Negro bitumen/alkaline water. The concentration
of the alkaline agent required to reach the minimum interfacial
tension varied in the following order:
[Li2 CO3 ] < [Na2 CO3 ] < [K2 CO3 ].
This effect is associated with the ionic radius of the respective
cation. The smaller the ionic radius of the cation, the lower
FIG. 7. Interfacial tension, at 25◦ C for the bitumen/water system, as a func-
tion of the lithium, sodium, and potassium carbonates concentrations, in the
aqueous phase.
235
FIG. 8. Mean droplet diameter as a function of the sodium carbonate
and sodium chloride concentrations, the aqueous phase, for bitumen in water
emulsions.
the solubility of the carboxylate salt formed for such cations.
Lithium, with the smallest ionic radius, forms the least soluble
carboxylate, followed by sodium and potassium. According to
Eq. [17], the more soluble the carboxylate salt, the larger the
concentration of carboxylate ions at the interface and the lower
the interfacial tension.
Emulsion formation. The natural surfactants present in the
Cerro Negro bitumen can be used, under appropriate conditions,
for stabilizing highly concentrated bitumen in water emulsions.
Heavy and extra-heavy crude oils and bitumen can be produced
and transported emulsified in water (15, 16, 32, 37–39) since
the viscosity of these concentrated emulsions, containing vol-
ume fractions (φ) of hydrocarbon on the order of 0.7, is several
orders of magnitude lower than the viscosity of the hydrocarbon
itself.
Figure 8 shows that the mean droplet diameter of Cerro Negro
bitumen in water emulsions, with φ = 0.7, decreases as the con-
centration of Na2 CO3 in the aqueous phase increases. All these
emulsions were prepared under the same conditions, namely,
stirring at 700 rpm for 4 min. Emulsions prepared in the pres-
ence of 5000 ppm NaCl, in excess of the Na2 CO3 concentration,
showed lower mean droplet diameter values than those formed
in the absence of sodium chloride.
The process of the formation of bitumen-in-water emulsions
stabilized by NS can be better understood if the chemical reac-
tions occurring in the solution and at the interface are taken into
account. Thus, when the sodium carbonate is dissolved in water,
ionization occurs according to
Na2 CO3 → 2Na+ + CO−2
3 , [18]
followed by the alkaline hydrolysis of carbonate ions and the
formation of a buffer solution, which maintains a constant pH
236 ACEVEDO, GUTIERREZ, AND RIVAS

of the aqueous phase,

CO−2 − −
3 + H2 O ⇔ CO3 H + OH ; [19]
subsequently, the formation of the carboxylate ions and its ad-
sorption at the interface occur:

HAw + OH− ⇔ A−
w + H2 O [20]
A−
w ⇔ A−
s [21]

When the concentration of Na2 CO3 is increased, maintaining

constant pH, more carboxylate ions are formed in the aqueous
phase (Eqs. [19] and [20]) and more carboxylate ions are avail-
able to adsorb at the interface bitumen/water (Eq. [21]). If the
concentration of surfactant increases in the aqueous phase, with
the bitumen fraction kept constant, a larger interfacial area can
be saturated by the surfactant and the mean droplet diameter of
the formed emulsions should decrease.
The presence of NaCl in the continuous phase of the emulsions
promotes a decrease in the mean droplet diameter of the emul-
sions prepared at Na2 CO3 concentrations lower than 6000 ppm
(Fig. 8). In fact, an increase in salt concentration causes compres-
sion of the electrical double layer and also results in increased
binding of the sodium ions to the adsorbed carboxylate ions. This
means that the carboxylate ion concentration at the interface in- FIG. 9. Mean droplet diameter as a function of the storage time for bitumen
in water emulsions containing different concentrations of sodium carbonate
creases, which in turn allows an increase in the interfacial area (a) in the absence of sodium chloride and (b) in the presence of 5000 ppm
or a decrease in the mean droplet diameter of the emulsions. An sodium chloride.
excess of sodium ions in the aqueous phase completely desta-
bilizes the emulsion due to the precipitation of the carboxylate The total energy of interaction (per unit area) as a function of
ions as sodium carboxylate. Thus, emulsions containing more the Na2 CO3 concentration for two bitumen droplets, calculated
than 10,000 ppm Na2 CO3 were completely unstable; the same from Eqs. [2] and [3], is presented in Table 2. There is a strong
behavior was observed in emulsions prepared in the presence of repulsion among droplets at the distance of separation at which
5000 ppm NaCl and more than 6000 ppm Na2 CO3 . the diffused parts of the electrical double layers start to inter-
act; that is, when droplets are separated by a distance equal to
Emulsion stability and electrophoretic behavior. Stable bi-
2(1/κ). If the distance of separation decreases to 1.5(1/κ), UT as
tumen in water emulsions was prepared in the range of Na2 CO3
expected increases. A clearer picture of the phenomena is shown
concentration between 2000 and 10,000 ppm. At concentrations
in Fig. 10 where the UT values for emulsions containing different
below or above this range, emulsions were completely unstable.
Na2 CO3 concentrations are plotted as a function of the distance
Stable emulsions did not present any indication of coalescence,
of separation between droplets. The shape of the curves sug-
since as Fig. 9 shows, no variation in the mean droplet diam-
gests that, in all those emulsions, the double-layer electrostatic
eter was observed when they were stored at 30◦ C, for 50 days
repulsion dominates over the London–van der Waals attractions.
or more. The mean droplet diameter distributions and the pH
values for these emulsions remained constant too.
The zeta potential values (ζ ) for the studied emulsions are TABLE 1
presented in Table 1. A decrease in ζ is observed when the con- Debye Parameter (κ), Electrical Double-Layer Thickness (1/κ),
centration of Na2 CO3 increases from 2000 to 4000 ppm due to and Zeta Potential (ζ) Values for the Different Emulsions Studied
the compression of the electrical double layer (see the calcu-
lated 1/κ values in Table 1). When the Na2 CO3 concentration Concentration of κ 1/κ ζ
was subsequently increased from 4000 to 6000 ppm, the charge Emulsion Na2 CO3 (ppm) (m−1 × 10−10 ) (m × 1010 ) (mv)
density on the emulsion droplets remained constant due to com- 1 2000 7.8 12.8 9.0
plete saturation of the interface by the carboxylate ions. A further 2 3000 9.6 10.4 8.0
increase in the Na2 CO3 concentration to 8000 ppm promoted a 3 4000 11.1 9.0 7.5
decrease in the zeta potential. This effect should be attributed 4 5000 12.3 8.1 7.6
5 6000 13.6 7.3 7.5
to the precipitation, as ANa, of some of the carboxylate ions
6 8000 15.6 6.4 6.2
adsorbed on the surface of the bitumen droplets.
 BITUMEN IN WATER EMULSIONS
TABLE 2
Total Interaction Energy (UT ) at Two Distances of Separation
(H) between Droplets as a Function of the Sodium Carbonate
Concentration in the Aqueous Phase
UT (J m−2 × 103 ) at
Concentration of
Emulsion Na2 CO3 (ppm) H = 1.5(1/κ) m H = 2(1/κ) m
1 2000 1.2 0.8
2 3000 0.9 0.7
3 4000 0.8 0.6
4 6000 0.7 0.5
5 8000 0.3 0.2
However, when the Na2 CO3 concentration increases, the energy
barrier decreases and the probability of droplet coalescence in
the primary minimum becomes evident. In fact, emulsions con-
taining more than 10,000 ppm of Na2 CO3 are unstable.
Thus, the stability of emulsions, which means droplet diame-
ters as a function of the storage time are shown in Fig. 9, should
be attributed to the positive contributions of the electrostatic re-
pulsion to the disjoining pressure. This contribution inhibits the
drainage of the interfacial liquid thin films, toward the Plateau
borders, avoiding drop coalescence and preventing emulsions
from collapsing.
An increase in the Na2 CO3 concentration causes a compres-
sion of the electrical double layer and also results in increased
binding of the sodium ions to the adsorbed carboxylate ions.
The accompanying decrease in the surface potential means that
the carboxylate ion concentration near the interface increases
and that the concentration of adsorbed carboxylate ions also
increases, which in turn raises the surface viscosity (Table 3).
The presence of 5000 ppm NaCl in the continuous phase of the
emulsions containing Na2 CO3 promoted an additional compres-
sion of the electrical double layer and the corresponding increase
in the interfacial viscosity (Table 3). The more compressed the
electrical double layer, the more compact the adsorbed surfac-
tant layer and the higher the interfacial viscosity.
In emulsions containing more than 6000 ppm Na2 CO3 and
5000 ppm NaCl, precipitation of sodium carboxylate salts (ANa)
occurred and the interfacial viscosity became lower (Table 3). It
FIG. 10. Total energy of interaction between droplets in bitumen in water
emulsions containing different concentrations of sodium carbonate.
237
TABLE 3
Interfacial Viscosity, at 25.0 ± 0.1◦ C, in Surface Poise (s.p), for
the Bitumen/Water system as a Function of the Sodium Carbonate
Concentration (a) in the Absence of NaCl and (b) in the Presence
of 5000 ppm NaCl
Interfacial viscosity (s.p)
Concentration of
Na2 CO3 (ppm) (a) (b)
3000 0.2 1.6
5000 0.4 2.0
6000 0.8 1.0
8000 1.0 0.7
10,000 0.8 0.4
is supposed that surface viscosity affects the drainage behavior
of the thin liquid films in emulsions. The higher the surface
viscosity, the lower the rate of film drainage. The very poor
stability of the bitumen in water emulsions, containing more
than 10,000 ppm Na2 CO3 in the absence of NaCl, or more than
6000 ppm of Na2 CO3 in the presence of 5000 ppm NaCl, should
be attributed to the very low values of surface viscosity observed.
Emulsion viscosity. Emulsions viscosity, at 30◦ C and 20 s−1 ,
increased slowly when the Na2 CO3 concentration, in the con-
tinuous phase, was increased from 2000 to 6000 ppm (Fig. 11).
This decrease in viscosity should be attributed to a decrease
in the mean droplet diameter and to a thinning of the thin liq-
uid films separating the bitumen droplets. In fact, as the mean
droplet diameter decreases, the interfacial area increases and the
number of interactions between droplets becomes larger.
Emulsions containing 8000 ppm Na2 CO3 showed a viscosity
which is at least 5 times higher than the viscosity of emulsions
having 6000 ppm Na2 CO3 . This difference in viscosity should
be attributed to a difference in the mean droplet diameter
(lower in the more viscous emulsion) but especially to the total
energy of interaction between droplets. In fact, emulsions with
6000 ppm Na2 CO3 show a repulsion energy barrier (Fig. 10)
high enough to avoid droplet flocculation in the primary mini-
mum; however, bitumen droplets in those emulsions containing
8000 ppm of Na2 CO3 , with a very low repulsive energy barrier,
FIG. 11. Viscosity at 30◦ C and 20 s−1 for bitumen in water emulsions, as
a function of sodium carbonate and sodium chloride concentration.
238 ACEVEDO, GUTIERREZ, AND RIVAS
can easily overcome this barrier and flocculate in the primary
minimum. The situation is even more clear in emulsions
stabilized with 10,000 ppm of Na2 CO3 ; the very high values
of viscosity observed in these emulsions indicate that definitely
bitumen droplets flocculated in the primary minimum. These
results suggest that emulsions containing more than 8000 ppm
Na2 CO3 are stabilized by short-range repulsive forces. A
similar situation was observed in the emulsions prepared in the
presence of NaCl; all of them showed higher viscosity values
than the emulsions formed in the absence of NaCl (Fig. 11).
CONCLUSIONS
We study in detail the interfacial properties of the natural
surfactants present in the Cerro Negro bitumen from the Orinoco
Belt in Venezuela. It was found that the interfacial tension of
the bitumen/water system is very much affected by the Na2 CO3
concentration in the aqueous phase. Thus, the interfacial
tension decreases with the Na2 CO3 concentration until ultra
low values are reached in the range of concentrations between
800 and 2000 ppm. Further increases in the sodium carbonate
concentration promoted an increase in the interfacial tension.
At any concentration of Na2 CO3 , the interfacial tension was
lower when 5000 ppm NaCl was added to the aqueous phase.
The properties of the bitumen-in-water emulsions stabilized
by natural surfactants were also studied. Stable emulsions were
prepared in the range of Na2 CO3 concentrations, in the aqueous
phase, between 2000 and 10,000 ppm. The mean droplet
diameter of the emulsions decreased as the sodium carbonate
concentration in the system increased. No variation in the mean
droplet diameter was observed during the experiment (more
than 30 days), which means that the emulsions were highly sta-
ble against coalescence. With the zeta potential values obtained
through electrophoretic experiments, the electrostatic repulsion
potentials among droplets were calculated. The results indicate
that emulsions containing up to 6000 ppm sodium carbonate
were stabilized by double-layer repulsion interactions; how-
ever, those emulsions containing 8000 and 10,000 ppm sodium
carbonate were probably stabilized by short-range interaction
forces, as deduced from the measured viscosity values.
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