9080 Langmuir 2002, 18, 9080-9086

Molecular Mechanics and Microcalorimetric Investigations

of the Effects of Molecular Water on the Aggregation of
Asphaltenes in Solutions
Juan Murgich*
Centro de Quı́mica, Instituto Venezolano de Investigaciones Cientı́ficas,
Apartado 21827, Caracas 1020A, Venezuela

Daniel Merino-Garcia and Simon Ivar Andersen

Department of Chemical Engineering, Building 229, Technical University of Denmark,
DK-2800 Lyngby, Denmark

José Manuel del Rı́o and Carlos Lira Galeana

Programa de Ingenierı́a Molecular, Instituto Mexicano del Petróleo,
Avda. Lázaro Cárdenas No. 152, Colonia San Bartolo Atepehuacan,
CP 07730, México DF, México

Received April 30, 2002. In Final Form: July 2, 2002

The interaction of two model asphaltene molecules from the Athabasca sand oil with a water molecule
in a toluene solution was studied by means of molecular mechanics calculations. It was found that water
forms bridging H bonds between the heteroatoms of asphaltenes with a considerable span in energies. The
stronger H bond found has energies higher than those corresponding to the stacking of the aromatic areas
of the same asphaltene molecules. This shows that the water molecule may generate additional mechanisms
of aggregation of asphaltenes in toluene solution, as found experimentally. The H bond mechanism depends
on the heteroatoms involved, the extension of the aromatic regions, and the steric interference present
in the asphaltene molecules. The simulation results have been compared with experimental values of
enthalpy of association of two different petroleum asphaltenes obtained by titration calorimetry. A simple
dimer dissociation model was used to derive the information about the heat and the constant of dissociation
from asphaltenes of Mexico and Alaska obtained from the calorimetric data. The association enthalpies
calculated were found to be in excellent agreement with those measured, although the simulation only
employed the interaction between averaged molecular structures.

Introduction asphaltenes and aggregate asphaltenes in solution. To

The effects of traces of water on the aggregation of
asphaltenes of several crude oils in solutions of toluene
have been recently studied by means of calorimetric
titration and other techniques.1 It was found that the
presence of even minute amounts of water in the solvent
(<0.015%) had significant effects on the aggregation
behavior of the asphaltenes studied.1 As small amounts
of water are present in most if not all crude oils,2 it is of
interest to study the effects of molecular water in the
aggregation process of asphaltenes occurring in solutions
of toluene. In this work, the study of the interaction of two
model asphaltene molecules from the Athabasca sand oil3
with a water molecule in a toluene solution was under-
taken using molecular mechanics calculations. It was
found that water molecules form bridging H bonds between
some of the heteroatoms of the asphaltenes that have
energies lower or higher than those corresponding to the
stacking of the asphaltene molecules.4 The existence of
rather strong H bonds shows that water molecules may
provide an additional aggregation mechanism for similar
* E-mail: jmurgich@qumica.ivic.ve and dmg@kt.dtu.dk.
(1) Andersen, S. I.; del Rio, J. M.; Khvostitchenko, D.; Shakir, S.;
Lira Galeana, C. Langmuir, 2001, 17, 307 and references therein.
(2) Speight, J. G. The Chemistry and Technology of Petroleum, 3rd
ed.; Marcel Dekker: New York, 1999.
(3) Strausz, O. P. Private communication, 1999.
(4) Murgich, J. Pet. Sci. Technol. 2002, 20, 1029.
check the values of the heats of interaction calculated
with molecular mechanics, a number of calorimetric
measurements have been carried out. The experimental
technique chosen was isothermal titration calorimetry5,6
(ITC), which allows the measurement of the heat developed
in the titration of a solution of known concentration of
asphaltenes when dissolved in a solvent with known water
concentration contained in the calorimeter. The experi-
mental data were interpreted by means of a model that,
for simplicity, only contemplated the dimer-monomer
dissociation process. It was found that the heats of
dissociation derived from ITC measurements using this
model were in agreement with the lowest values found by
the molecular mechanics calculations. Therefore, the
calculated heats of dissociation from the model asphaltenes
from Athabasca seem to also be representative of the
interaction between other types of asphaltenes and
between these asphaltenes and water molecules. However,
this result should be used with caution, as the simple
dimer model contains approximations, plus the fact that
the number of model asphaltene molecules used in the
calculation is rather limited and that these models may
not be the best representation of the molecules of the
specific fraction under study.
(5) Andersen, S. I.; Birdi, K. S. J. Colloid Interface Sci. 1991, 142,
497-502.
(6) Andersen, S. I.; Christensen. Energy Fuels 2000, 14, 38.

10.1021/la025882p CCC: $22.00 © 2002 American Chemical Society

Published on Web 10/19/2002
Aggregation of Asphaltenes in Solutions
Figure 1. Model asphaltene T4 molecule from the Athabasca
sand oil.3
Figure 2. Model asphaltene T5 molecule from the Athabasca
sand oil.3
Molecular Mechanics Methodology
Molecular mechanics determines the most stable con-
formation of molecules and their aggregates both in a
vacuum and in solution.7 This method makes use of
analytical functions to represent bond stretching, bending,
and torsional as well as nonbonded (electrostatic interac-
tions, dispersion attraction, and exchange repulsion)
energies of molecules. In molecular mechanics, an initial
configuration is specified and the interatomic distances
and bond angles are adjusted, using an iterative compu-
tational method, until the minimum energy configuration
is obtained.7 The algorithm used in this work was part of
the InsightII and Discover set of programs.8 Molecular
mechanics can only guarantee to locate the nearest local
minimum of the energy surface to the starting point of
the calculation. For this reason, several different starting
configurations were used in each case in order to see if the
same minima were obtained for each of them. If this is the
case, then one can assume that the minima reached are
representative of the conformations of interest.7
A box containing two different model asphaltene
molecules (T4 and T5 shown in Figures 1 and 2), 100
molecules of toluene, and a molecule of water was built
with the Amorphous Cell program.8 The average density
was fixed at 0.871 g/cm3, and the temperature during the
runs was kept at 298 K. The calorimetric experiments
have been carried out at 303 K. This small temperature
difference is expected to have only a very small or negligible
(7) Leach, A. R. Molecular Modelling, 2nd ed.; Prentice Hall: London,
2001.
(8) Accelrys Inc., San Diego, CA, 2001.
Langmuir, Vol. 18, No. 23, 2002 9081
Figure 3. Distances in angstroms between the water molecule
and the asphaltene molecules corresponding to the set of free
molecules.
Figure 4. Simulation box containing two asphaltenes bridged
by a water molecule. In this box, the water and asphaltene
molecules are shown as space filling objects while the toluene
molecules are drawn with lines only for simplicity.
influence on the values of the heats of interaction. The
dielectric constant used in the calculations was equal to
3.09. Periodic boundary conditions were employed in the
calculations so that an unbound liquid medium could be
modeled around the asphaltenes and water molecule.7
The diffusion of large molecules such as the model
asphaltenes in a liquid is a very slow process in terms of
the usual molecular times (10-12 s). So, instead of following
their diffusion, which will require the use of prohibitively
long computer times, four different boxes were employed
to simulate the different molecular arrangements of
interest. Each of these configurations is expected to occur
during the diffusion process present in solutions of
asphaltenes in toluene with traces of water. One of the
boxes contained the asphaltene and water molecules
separated by relatively large distances (see Figure 3). This
box represents the conformation of a set of free and
independent asphaltene and water molecules in a toluene
solution. Two more boxes were built where a water
molecule bridged the asphaltene molecules with H bonds
between different heteroatoms (see Figure 4). A fourth
box was built where the asphaltene molecules were allowed
to form a dimer while the water molecule was away from
them (Figure 5). Five initial configurations for each box
9082 Langmuir, Vol. 18, No. 23, 2002
Figure 5. Simulation box containing an asphaltene dimer and
a free water molecule. The water molecule can be seen in the
upper right corner of the box. All the molecules were drawn as
in Figure 4.
were chosen with noticeably different starting points, and
each of them was minimized until the gradient was less
than 0.1 kcal/mol‚Å. The resulting energy values in each
set agreed within 4%, and only the lowest ones are
reported.
The cell multipole summation method was used in the
calculation together with a summation cutoff distance of
14 Å. The well-proven CVFF interatomic force field8 has
been employed in this work to describe the intra- and
intermolecular interactions. The box containing the free
asphaltene and water molecules was taken as our refer-
ence conformation (see Figure 3) and was set as the zero
of energy. The first H bond involved one of the O atoms
of the asphaltene T4 and an N atom (N1) in T5, as seen
in Figures 1 and 2. The second one involved the N from
the asphaltene T4 and the N1 atom from T5.
Molecular Mechanics Results
The concentration dependence of several properties of
the asphaltenes in toluene has been used to determine an
apparent critical micellar concentration (cmc) of this
fraction.1,5,6 However, the cmc is obviously more opera-
tional than indicative of real monomer-molecular ag-
gregate equilibrium. Experimental results showed both
herein and in other papers1,5,6 indicate that there is no
critical concentration at which micelles are formed within
the concentration range examined (0.05-9 g/L toluene).
The molecular characteristics of the asphaltenes are very
different from those of the typical surfactants that form
micelles,9 as seen in Figures 1 and 2. Even if only the
average molecular structure of the asphaltenes is known,
none of the available models contain the well-defined polar
heads and the long hydrocarbon tails that characterize
the surfactant molecules. Instead, the average model
asphaltenes have saturated rings and rather short alkane
chains attached to their aromatic cores (see Figures 1 and
2). Some of the chains act as bridges between the aromatic
regions, so that the molecules have quite complex spatial
conformations. In general, several heteroatoms (S, N, O)
are also present in these molecules. The anisotropy of the
molecular polarity of the model asphaltenes is markedly
different from that of the typical surfactants.4 In the case
of the model asphaltene molecules, the presence of a small
(9) Evans, D. F.; Wennestrom, H. The Colloidal Domain, 2nd ed.;
Wiley-VCH: New York, 1999.
Murgich et al.
amount of heteroatoms and of asymmetric C-C bonds
generates a charge distribution with a finite dipole
moment. This polarity is, in general, rather weak because
the amount of highly electronegative atoms such as O
and N is low (<2-3%) in most asphaltenes. Moreover, the
intrinsic polarity of model asphaltenes is also low because
the molecular volume is, in general, large and the
estimated dipole moment is small.4 Consequently, the
driving mechanism responsible for the formation of the
asphaltene aggregates is likely to involve a different
balance of the intermolecular forces that are present in
the micelle formation.4 The existence of aromatic regions
provides the anisotropy that drives the formation of the
many asphaltene aggregates. Molecular mechanics cal-
culations showed that this contribution together with that
generated by the molecular net charges is responsible for
the formation of the asphaltene aggregates when no water
was present.10 The existence of atomic groups containing
basic N and O atoms implies not only that the asphaltene
molecules will be polar but also that they may interact
with molecules capable of H bonding such as water and
acidic asphaltenes and resins. The H bond is a strong
interaction that contains contributions from all the
intermolecular forces.11 It involves the interaction of a H
atom, attached to a highly electronegative one (i.e., O, N),
with an electronically rich atom of a neighboring molecule
or molecular fragment. This type of interaction between
fragments and molecules with closed electronic shells is
mostly determined by the local atomic charges of both of
them (electrostatic interaction). Little or no charge transfer
in the H bond is found, although noticeable charge
rearrangements may occur in both molecules, through
polarization and induction effects.4 H bonding may
contribute to the aggregate generation through its forma-
tion in different sites of the asphaltene molecules. These
sites must be free of steric hindrances in such a way that
proper interatomic contact is possible between the ap-
proaching water (or other acidic) molecule and the
accepting groups. Moreover, the strength of H bonding is
orientation dependent, so the approach of the molecules
involved should be at proper angles to generate a strong
interaction.12 Otherwise, the H bond will be weak and
contribute little to the aggregation process. As the
asphaltene molecules may contain several kinds of basic
sites, it is expected that H bonding will contribute to the
aggregate formation if they are available for interaction.
As in other compounds, the extension of the H bonding
depends on the chemical composition of the asphaltene
molecules and on their shapes. The great chemical
complexity of the heavy fractions2 suggests that a wide
distribution of H bonds is likely to exist in the molecular
aggregates formed by the different asphaltenes. The
existence of H bonding does not mean that the other parts
of the asphaltene molecules are not important in the
formation of the aggregates.4 Depending on the strength
of the interactions present in the aggregates, in some of
them the interaction between the aromatic regions will
be the governing factor while in others the H bonds will
be the dominant ones. A mixed aggregate may also be
envisioned. The complex 3D shapes of most of the model
asphaltene molecules are such that their aggregates
formed by, for example, stacking may leave some empty
intermolecular spaces, thus reducing the number of the
possible favorable atomic interactions. Small molecules
such as water or methane could fill these empty spaces
(10) Murgich, J.; Rodriguez, J.; Aray, Y. Energy Fuels 1996, 10, 68.
(11) Israelachvili, J. Intermolecular and Surface Forces, 2nd ed.;
Academic: New York, 1991.
(12) Muller-Dethlefs, K.; Hobza, P. Chem. Rev. 2000, 100, 143.
Aggregation of Asphaltenes in Solutions
Table 1. Changes in Enthalpy of the Different
Configurations of the Model System
changes in
enthalpy
configurationa (kcal/mol) distance (Å)
(T4-O- - -HOH- - -N1-T5) -21.5 T4-O- - -H-O 2.89
T5-N1- - -H-O 3.09
(T4-N2- - -HOH- - -N1-T5) -2.1 T4-N2- - -H-O 4.22
T5-N1- - -H-O 2.92
T4- - -T5 dimer and -6.3
free water
a T4-O- - -HOH- - -N1-T5 corresponds to the bridging of the
asphaltene T4-O and T5-N atoms by water while T4-N2- - -HOH- - -
N1-T5 indicates the same between the N atoms. The right column
shows the distance between the N or O atoms of the asphaltenes
and the O atom of the water molecule.
and act as an adhesive by contributing with further
attractive interactions to the system.13 This type of
behavior is found in many crystals of complex molecules
such as proteins and other complex macromolecules where
the inclusion of water (or other similar solvent) molecules
strongly stabilizes the resulting structures.13 In this
regard, it was recently shown14 that water plays an
important role in stabilizing the entire system of ligand
and duplex DNA by means of H bonds and that the water
molecule bridges play an important role in the recognition
of DNA by a bonding protein15 (trp-repressor). If the small
molecules have strong intrinsic polarity, as water does,
then H bonding will compete with the van der Waals
interaction when the empty inter-asphaltene spaces are
filled with them and receptor sites are available for
bonding. If the asphaltene molecular 3D shapes are such
that the basic O and N atoms are available for H bonding,
then a water molecule may act as a bridge between two
such asphaltenes. At high concentrations, these asphalt-
enes may also form trimers, tetramers, and so forth, if
additional water molecules are available for H bonding.
The dissociation model used in the fit of the experimental
values only considers dimers and monomers. Some of these
molecular arrangements have been studied in this work
using two molecular models of asphaltenes from Atha-
basca. In Table 1 are shown the changes in enthalpy
obtained for the different configurations of the model box
calculated in this work.
The H bonds between different heteroatoms of the
asphaltene molecules may have quite different energies,
as seen in Table 1. This reflects the fact that these bonds
are quite sensitive to the heteroatoms intervening in them,
the intermolecular orientation, and the interatomic dis-
tances.11 The last point can be seen in Table 1, where the
strongest H bonds are those with the shortest interatomic
distances.
It is reasonable to assume that the molecular complexity
of the asphaltene fraction will generate a distribution in
the H bond strength with water molecules. If the molecular
structure of the asphaltenes is such that it is able to
produce strong H bonds, as in the T4-O- - -HOH- - -N1-T
case or similar cases, this interaction could compete with
or even easily overcome the stacking process and generate
aggregates linked by water molecules acting as H bond
bridges. This mechanism will be particularly important
in asphaltene molecules with relatively small aromatic
regions and strong basic sites. Then, it is not surprising
that the presence of traces of water in toluene has an
(13) Kitaigorodsky, A. I. Molecular Crystals and Molecules; Aca-
demic: New York, 1973.
(14) Yang, L.; Feng, X.; Lee, I.; Bai, C. J. Mol. Struct. 1998, 444, 13.
(15) Suenaga, A.; Yatsu, C.; Komeiji, Y.; Uebayasi, M.; Meguro, T.;
Yamato, I. J. Mol. Struct. 2000 526, 209.
Langmuir, Vol. 18, No. 23, 2002 9083
important role in the formation of the aggregates of the
asphaltenes in solution. The large values of the changes
in enthalpy involved in some of the conformations may
explain the generation of asphaltene aggregates observed
when the amount of water is increased in the toluene
solution. At low water content, the asphaltene stacks are
more likely to occur than the formation of aggregates with
water bridges. At higher water concentration, the bridges
become more likely to occur and will then generate an
additional mechanism for the formation of the aggregates
of asphaltenes. It is also possible to visualize the formation
of water bridges between different aggregates if the
concentrations of both of them are high enough.
The water molecules are not the only ones that may
contribute to the formation of aggregates of asphaltenes
through the formation of intermolecular H bonds. In the
asphaltenes there are generally a basic, an acidic, an
amphoteric, and a neutral fraction.2 The water molecules
will then have to compete with the acidic asphaltenes in
order to form the intermolecular H bonds. Thus, asphalt-
enes with a large basic fraction but with a small acidic
fraction will be more prone to be affected by the H bonds
formed by the water molecules than the others where the
acidic one is the larger fraction. Further work is under-
way in order to study the influence of the different frac-
tions on the aggregation behavior of the asphaltene in
solution.
Calorimetric Measurements
Asphaltenes have been obtained following a modified
version of the IP143 standard.16 The solutions have been
prepared at least 24 h before the experiments and stored
in sealed vials in a dark place. To remove dissolved gases,
the samples have been placed in an ultrasonic bath for 1
h. Toluene has been dried with molecular sieves, and the
solutions with the different water contents have been
prepared by mixing dried and saturated toluene. Experi-
ments have been performed in a VP-ITC Microcal calo-
rimeter17 with asphaltenes from two different sources:
Alaska 95 and KU (Mexico). The experiments consist of
the injection of known volumes (10 µL) of asphaltene
solutions into a cell that contains toluene with the same
water content as that of the asphaltene solution. The
calorimeter was placed in a glovebox that had silica gel
in its interior to ensure low humidity. The syringe
contained concentrated solutions of asphaltenes (5, 30, or
50 g/L) to ensure that they are mainly in the associated
state. When these solutions were injected into the toluene,
the degree of association decreases until the equilibrium
is reached and the heat developed is counteracted by the
control system of the calorimeter, to keep the isothermal
conditions (303 K). This heat is recorded and displayed in
the computer, and the integration of the peaks gives the
heat developed in each injection (see Figure 6). The first
injection point is not used in the treatment of the data,
because the tip of the syringe has been in contact with the
solution in the cell during the equilibration time, prior to
the injections, and it is possible that some asphaltenes
have diffused into the cell.
The optimization of the calorimeter has allowed us to
work at very low concentrations and heats measured (<5
µcal/injection), yet keep a good noise level and peak
definition, as seen in Figure 6.
(16) IP 143/90 (or ASTM D3279-90), Institute of Petroleum, London,
U.K., 1985.
(17) Microcal Inc., Northampton, MA 01060-2327, 1995.
9084 Langmuir, Vol. 18, No. 23, 2002
Figure 6. Titration of a solution of KU asphaltenes in dried
toluene into dried toluene. The asphaltene concentration in
the measurement shown was 30 g/L.
Dissociation Model
Some investigators5,18,19 have suggested that asphalt-
enes in solution have, as the surfactants, a well-defined
cmc. If there was a cmc in the concentration range studied
(0.2-9 g/L), then the first injections (when Ccell < cmc)
should give a constant heat signal, as all the micelles would
break and asphaltenes would exist in the cell only in the
monomeric state (Figure 6). However, in the experiments
presented here, the heat developed decreased as the
concentration was increased, which means that the
aggregates break less and less as the solution gets more
and more concentrated. This rules out the possibility of
having a cmc in this range of concentrations1,6 and gives
support to the idea that the asphaltenes studied form
simple molecular aggregates even at very low concentra-
tions. It is, however, possible to argue that the cmc is at
even lower concentrations than the values usually found
in the literature. Nevertheless, according to the calori-
metric experiments, the association goes on at higher
concentrations than the “cmc”, following a stepwise
mechanism contrary to the behavior found for micelles.9
In this particular type of molecular aggregates formed
only by surfactants, an increase in concentration above
the cmc increases the number rather than the size of the
micelles. These results lead to the development of a
different model than that of micelles to fit the experimental
data for the dissociation of the aggregates of asphaltenes.
As a first approach, a simple dimer-monomer dissociation
model has been chosen. It has to be taken into account
that asphaltenes are a very complex fraction with a wide
distribution of molecular weights, aromaticity, and hetero-
atoms content,2 so the application of a more complex model
that will include the formation of higher aggregates is not
warranted at this stage. The simple model considers that
(18) Rogacheva, O. V.; Rimaev, R. N.; Gubaidullin, V. Z.; Khakimov,
D. K. Colloid J. USSR 1980, 42, 586 (Translated version).
(19) Sheu, E. Y.; De Tar, M. M.; Strom, D. A.; Decanio, S. J. Fuel
1992, 71, 99.
Murgich et al.
Figure 7.
asphaltenes present only equilibrium between the mono-
meric species A and the dimers A2, so that
A2 T 2A w Kd ) [A]2/[A2] (1)
where Kd is the dissociation constant. In this model, all
the asphaltenes interact with the same equilibrium
constant Kd. The starting solution is one of high concen-
tration, so the asphaltene molecules will mainly be in the
aggregated state. When this solution is injected into the
cell, it is no longer in equilibrium, and therefore the
aggregates dissociate until the equilibrium conditions are
reached again. The heat developed is then calculated as
hcalc ) moles of aggregates that dissociate × ∆Hd. Then,
∆Hd is the heat of dissociation in kilocalories per mole.
Consequently, the heat of interaction between asphaltene
molecules will be -∆Hd. The parameters of the dissociation
model are ∆Hd and Kd, and their values are optimized to
fit the model to the experimental data. In Figure 7 are
shown some examples of the fit of the simple dissociation
model. Table 2 contains the results for the three concen-
trations and the two water contents used in the experi-
ments. The measurements have been performed at three
different water concentrations: dried toluene, saturated
toluene, and 75% water saturated toluene (31SD Toluene).
The fitting of the simple dissociation model shown in
Figure 7 is surprisingly good considering the approxima-
tions employed in its derivation. Figure 8 shows the
Aggregation of Asphaltenes in Solutions
Figure 8. Squares represent KU asphaltenes, and circles
represent those of Alaska 95. The solid markers represent tests
with 75% water saturated toluene, and the open ones represent
tests with dried toluene. The dashed line represents the
calculated heat of interaction with water as a bridge between
the N atoms (N- - -HOH- - -N) (see Table 1).
Table 2. Dissociation Constants and Heats of
Dissociation Obtained from the ITC Measurements
dried toluene 75% water saturated toluene
conc ∆Hd 103Kd ∆Hd 103Kd
(g/L) (kJ/mol) (mol/L) (kJ/mol) (mol/L)
KUAsphaltene
5 0.9 0.83 1.0 0.69
30 1.3 3.25 1.2 1.80
Alaska 95 Asphaltene
5 1.7 0.12 1.4 0.79
30 2.1 5.04 1.8 3.86
50 1.6 9.11 1.4 5.19
comparison of the experimental heats of interaction with
the ones obtained in the molecular mechanics calculations.
There is excellent agreement among the experimental
results obtained for the different concentrations, which
suggests that the mechanism of interaction that prevails
is the same in the whole concentration interval studied.
The KU asphaltenes appear to have slightly lower heats
of interaction than those of the Alaska 95 crude oil.
The heats of dissociation measured in the experiments
for both types of asphaltenes are similar to the lower one
obtained in the molecular mechanics calculations for water
bridges between N atoms. This seems to suggest that the
H bonds present in these asphaltene aggregates are mostly
of medium strength. It is interesting to mention that the
heat of interaction obtained in the simulations shown in
Figure 4 (O- - -HOH- - -N type) seems to be much higher
than the experimental values of the calorimetric experi-
ments, so the occurrence of this type of strong H bond in
these asphaltenes is expected to be negligible in the KU
and Alaska 95. Also, the water content, in the case of KU
asphaltenes, does not seem to have any influence on the
heat of dissociation. In the case of asphaltenes from the
Alaska 95 crude oil, the decrease in water content leads
to an increase in the heat of interaction. This can be
explained as follows: when the concentration of water
decreases, the capacity of the system to form H bonds
decreases and therefore the heat of stacking becomes more
and more predominant. As seen in Table 1, the calculated
heat of stacking may be higher than the heat of interaction
by H bonds between N atoms of the model asphaltenes.
This result may explain the small rise in heat of dis-
Langmuir, Vol. 18, No. 23, 2002 9085
sociation observed in the experiments. It is important,
however, to take into consideration that the drying process
of the toluene is not complete and it has not been possible
to dry it below 10% saturation. The solubility of water in
toluene at 25 °C is approximately 0.055%, and the drier
solutions contain an average of 0.007% water, measured
by Karl Fischer titration. In the most unfavorable case
(the highest concentration of asphaltenes in the cell is 8
g/L), the ratio water/asphaltene in moles in the cell is 0.4
(one molecule of water for approximately every two of
asphaltene). This experimental problem must be taken
into account in the analysis of the influence of the water
content, as it is present in all tests. With this in mind, we
may say that the results obtained by ITC showed then
that a decrease in the water content reduces the degree
of H bonding and increases the contribution of the heat
of stacking for the asphaltenes studied. This is in
agreement with the conclusions drawn from the molecular
mechanics calculation, where one can see that the stacking
aggregation mechanism may have a larger energy, at least
for the model asphaltenes of Athabasca. The dissociation
constants obtained from the simple model are observed
to increase with asphaltene concentration and to decrease
with decreasing water content at fixed concentration. Both
effects can be explained by the same mechanism: as the
concentration of asphaltenes increases, the relative water
content on a molecular level decreases, hence favoring
the dissociation. When more water is present at fixed
asphaltene concentration, we observe that the dissociation
constant decreases as the water bridges keep asphaltene
molecules together. No transition from one mechanism to
another can be determined, as the heat of dissociation is
almost independent of concentration.
It is important to mention that all these results must
be used with some caution because of the approximations
employed in the dissociation model and in the molecular
mechanics calculations. First, the molecules of the Atha-
basca asphaltenes (Figures 1 and 2) do not necessarily
contain the heteroatoms in the same positions as those in
the asphaltenes of the KU and Alaska 95 crude oils used
in the experiments. Molecular variations are expected to
occur in the asphaltene fractions,2 so differences in the
number and character of the H bond acceptor sites are
expected to be present in the asphaltenes.
Second, the average molecular weight for these other
asphaltenes might be quite different than the average
one assumed (1200 g/mol‚g) for the asphaltenes from the
Athabasca sand oil. Moreover, the use of just a single
value to characterize a complex MW distribution such as
that found in asphaltene fractions is still open to discus-
sion. Third, the heats of dissociation measured by ITC
contain contributions of the dissolution of aggregates
containing all (or most of) the molecules that form the
asphaltene fraction. Each measured value is actually a
weighted average over the many different types of
aggregates formed by the great variety of molecules of the
asphaltene fraction. It is known that, in asphaltenes, the
MW distribution is complex, sometimes is multimodal,
and covers a wide range of values.20,21 Similar distributions
are expected to occur in other asphaltenes,2 thus showing
that this fraction encompasses a large variety of different
molecules. Therefore, the values of the heats of dissociation
measured contain contributions from different types of
molecular aggregates. On the other hand, the values
calculated by molecular mechanics only reflect the in-
(20) Selucky, M.; Kim, S. S.; Skinner, F.; Strausz, O. P. In Chemistry
of Asphaltenes; Bunger, J. W., Li, N. C., Eds.; Advances in Chemistry
Series 195; American Chemical Society: Washington, DC, 1981; p 83.
(21) Andersen, S. I. J. Liq. Chromatogr. 1994, 17, 4065.
9086 Langmuir, Vol. 18, No. 23, 2002
teraction between a specific pair of asphaltene molecules
that may or may not be the most representative of the
fraction of the crude oil under study. Therefore, the heats
of interaction displayed in Table 1 only provide an estimate
of its order of magnitude and should then be used with
care. The results obtained are then more of a qualitative
than quantitative nature, and further studies are required
to evaluate their general validity.
Conclusions
Molecular simulation of association of petroleum as-
phaltenes including association with water has been
performed and compared with experimental results of
heats of association obtained from titration calorimetry.
Murgich et al.
The results fall within the same order of magnitude,
verifying that H bonding indeed may be an important
factor in the association of asphaltenes. In this, water
may act as a promoter of the association because of its
small size and high intrinsic polarity.
Acknowledgment. The authors appreciate the valu-
able technical help provided by José A. Abanero, and they
thank Prof. O. P. Strausz for providing the molecular
structure of the asphaltenes from Athabasca prior to
publication. D.M.-G. and S.I.A. thank the Danish Techni-
cal Research Council for financial support under the Talent
program.
LA025882P