1676 Energy & Fuels 2004, 18, 1676-1686

Morphology of Aggregated Asphaltene Structural Models

Ä lvarez-Ramı́rez, and J. M. Martı́nez-Magadán
J. H. Pacheco-Sánchez,* F. A
Programa de Ingenierı́a Molecular, Instituto Mexicano del Petróleo,
Eje Central Lázaro Cárdenas 152, México D.F. 07730, México

Received April 12, 2004. Revised Manuscript Received July 8, 2004

Aggregated asphaltene structural models have been generated through a molecular simulation
geometry optimization process, using periodic boundary conditions. This methodology has been
validated by first applying it to a pure aromatic system. Initially, a random distribution of 35
molecules was chosen and a geometry optimization process was performed, allowing the cell
dimensions to vary without restrictions. The structure factor (S(k)) of an optimized final cell was
obtained and compared with experimental results, and the agreement between theoretical and
experimental S(k) profiles was satisfactory. This methodology was next used in the analysis of
the morphology of 32 asphaltene model molecules and their aromatic cores; asphaltene model
molecules were taken from literature. It is remarkable that face-to-face stacking of asphaltene
aggregates was observed, as well as π-offset and T-shaped stacking geometries. Finally, the effect
of aliphatic chains on the aggregates was also analyzed.

1. Introduction whereas the RDF is related to the observed structure

Aggregated asphaltene structural models would be
useful in developing further understanding of important
problems in the petroleum industry, such as the ag-
gregation, flocculation, and precipitation of asphaltenes.
An operative definition of asphaltenes is that they are
insoluble in low-molecular-weight n-alkanes but soluble
in aromatic solvents. It is well-known that asphaltenes
self-associate in stacked aggregates, which form clus-
ters.1,2 However, the morphology of these clusters is not
yet clearly known. The most common morphology
considered until now is the face-to-face type. In the
literature, these interactions are usually only referenced
as aromatic-aromatic interactions, without going into
the fundamental molecular details. Some efforts in
determining the morphologies of asphaltene-aggregated
systems were performed by Yen et al.,3 Dickie and Yen,2
Wiehe and Liang,4 and Evdokimov et al.5,6
The morphology of these clusters is amorphous in
nature. Therefore, a possible way to characterize them
geometrically is either through the radial distribution
function (RDF) or through the structure factor S(k); this
is also called isotropic scattering. The RDF is defined
as the number of atoms lying at distances between r
and r + dr from the center of an arbitrary origin atom,7
* Author to whom correspondence should be addressed. E-mail
address: hpacheco@imp.mx.
(1) Sheu, E. Y. In Asphaltenes: Fundamentals and Applications;
Sheu, E. Y., Mullins, O. C., Eds.; Plenum Press: New York, 1995.
(2) Dickie, J. P.; Yen, T. F. Anal. Chem. 1967, 39, 1847-1852.
(3) Yen, T. F.; Erdman, J. G.; Pollack, S. S. Anal. Chem. 1961, 33,
1587-1594.
(4) Wiehe, I. A.; Liang, K. S. Fluid Phase Equilib. 1996, 117, 201-
210.
(5) Evdokimov, I. N.; Eliseev, N. Y.; Akhmetov, B. R. J. Pet. Sci.
Eng. 2003, 37, 135-143.
(6) Evdokimov, I. N.; Eliseev, N. Y.; Akhmetov, B. R. J. Pet. Sci.
Eng. 2003, 37, 143-152.
(7) ) Elliott, S. R. Physics of Amorphous Materials; Longman
Scientific and Technical: New York, 1990; Chapter 3.
factor S(k) by a Fourier transformation.7-12 In a pio-
neering work, Yen et al.3 performed X-ray diffraction
(XRD) measurements for asphaltenes in powdered solid
samples coming from Kuwait visbreaker tar oil. They
have compared their experimental S(k) profile for the
aromatic component of their asphaltenes to that com-
puted for a blend of five polynuclear aromatic com-
pounds of known structures.13 The S(k) profile and the
peak positions agree quite reasonably with that ob-
tained by Diamond.13 Based on these results, they have
proposed a model constituted by aromatic sheets that
are associated in a stacked cluster for an asphaltene
solid phase. A very similar morphology that has been
extended to aggregates of asphaltene particles was
experimentally obtained by Dickie and Yen.2 Asphalt-
enes appear as unitary stacking sheets that are com-
posed of a highly condensed polynuclear system of
aromatic rings bearing alkyl side chains. They proposed
that asphaltene association occurs via a stacking of 3-6
unitary sheets through π-π interactions. They define
these entities as unitary cells or particles, indicating
that the associations of such particles form micelles.
The morphology of polyaromatic compounds and
asphaltene aggregates have been studied theoretically
as induced aggregation in a vacuum,14,15 as spontaneous
(8) McQuarrie, D. A. Statistical Mechanics; Harper and Row: New
York, 1973.
(9) Hansen, J. P.; McDonald, I. R. Theory of Simple Liquids;
Academic Press: New York, 1986.
(10) Tildesley, M. P.; Allen, D. J. Computer Simulation of Liquids;
Clarendon Press: Oxford, U.K., 1987.
(11) Lee, L. L. Molecular Thermodynamics of Nonideal Fluids;
Butterworth: Boston, 1988.
(12) Evans, D. F.; Wennerström, H. The Colloidal Domain; VCH
Publishers: New York, 1994.
(13) Diamond, R. Acta Crystallogr. 1957, 10, 359-364.
(14) Brandt, H. C. A.; Hendriks, E. M.; Michels, M. A. J.; Visser, F.
J. Phys. Chem. 1995, 99, 10430-10432.
(15) Rogel, E. Colloids Surf. 1995, 104, 85-93.

10.1021/ef049911a CCC: $27.50 © 2004 American Chemical Society

Published on Web 08/19/2004
Aggregated Asphaltene Structural Models Energy & Fuels, Vol. 18, No. 6, 2004 1677

aggregation in a vacuum,16 and in the presence of

solvents15,17,18 by classical molecular dynamics (MD).19
An important result is that the structure of aggregates
could not be formed by considering only stacking
through π-π interactions. Two additional orientations,
such as those mentioned by Hunter and Saunders20 and
Leach,21 for aromatic-aromatic interactions seem to be
necessary. These authors summarized the results of
their investigations as follows: main orientations are
face-to-face geometry (π-π interactions), edge-on or
T-shaped geometry (π-σ interaction), and offset π-stacked
geometry (σ-σ interactions). Therefore, it was consid-
ered that these orientations can lead to different forms
of the asphaltene aggregates.2,16,22 These findings agree
with the results reported by Sheu,17 based on molecular
simulations for 64 asphaltene molecules, the structures
of which range in size from 3 aromatic rings to 11
aromatic rings, for simulations conducted in toluene. He
also found that asphaltene aggregates are formed not
only through face-to-face stacking but also through other
types of asphaltene clustering; such clustering is much
looser and rather irregular in appearance.
Generally, it is widely accepted that every designed
asphaltene molecule includes an aromatic component,
its own quantity of heteroatoms (such as N, S, and O),
and one or more aliphatic chains linked to the aromatic
region.23-26 Some asphaltene molecular models that
have the latter description have been proposed in the
literature. Four asphaltene structure model molecules
were selected from the following references: Groenzin
and Mullins,27 Speight and Moschopedis,28,29 Zajac et
al.,23 and Murgich et al.18 These molecules are repre-
Figure 1. Depiction of two asphaltene molecule structures:
sented in Figures 1 and 2. The corresponding asphalt- one designed by Groenzin and Mullins27 from Californian crude
enes of these references were extracted from Califor- oil, and the other was designed by Speight and Moschopedis28
nian, Venezuelan, Mayan, and Venezuelan crude oils, for Venezuelan crude oil.
respectively. Some physicochemical properties of these
molecules are given in Table 1. It is well-known that
petroleum fluids are comprised of asphaltene polydis-
perse systems. One of the main limits on the asphaltene
theoretical analysis lies in the diversity of structures
in which asphaltenes can exist. The difficulty associated
with the construction of molecular models of asphalt-

(16) Pacheco-Sánchez, J. H.; Zaragoza, P. I.; Martı́nez-Magadán, J.

M. Energy Fuels 2003, 17, 1346-1355.
(17) Sheu, E. Y. In Structures and Dynamics of Asphaltenes; Mullins,
O. C., Sheu, E. Y., Eds.; Plenum Press: New York, 1998; Chapter IV.
(18) Murgich, J.; Rodrı́guez, J.; Aray, Y. Energy Fuels 1996, 10, 68-
76.
(19) Cerius2 software, Molecular Simulations, Inc. (MSI) (now
Accelrys), San Diego, CA.
(20) Hunter, C. A.; Saunders, J. K. M. J. Am. Chem. Soc. 1990, 112,
2008-2010.
(21) Leach, A. R. Molecular Modeling; Addison-Wesley Longman,
Ltd.: Singapore, 1996.
(22) Takanohashi, T.; Sato, S.; Tanaka, R. Pet. Sci. Technol. 2003,
21, 491-505.
(23) Zajac, G. W.; Sethi, N. K.; Joseph, J. T. Scanning Microsc. 1994,
8, 463-470.
(24) Speight, J. G. The Chemistry and Technology of Petroleum;
Marcel Dekker: New York, 1999; Chapter X.
(25) Cimino, R.; Correra, S.; Del Bianco, A. In Asphaltenes: Fun-
damentals and Applications; Sheu, E. Y., Mullins, O. C., Eds.; Plenum
Press: New York, 1995; Chapter III.
(26) Pfeiffer, J. Ph.; Saal, R. N. J. Presented at the Sixteenth Colloid
Symposium, Stanford University, Palo Alto, CA, July 6-8, 1939; pp
139-165.
(27) Groenzin, H. G.; Mullins, O. C. Energy Fuels 2000, 14, 677-
684.
(28) Speight, J. G.; Moschopedis, S. E. Prepr.sAm. Chem. Soc., Div.
Pet. Chem. 1979, 24, 910-923. Figure 2. Depiction of two asphaltene molecule structures:
(29) Speight, J. G. The Chemistry and Technology of Petroleum; one designed by Zajac et al.23 from Mayan crude oil, and the
Marcel Dekker: New York, 1991. other exhibited by Murgich et al.18 for Venezuelan crude oil.
1678 Energy & Fuels, Vol. 18, No. 6, 2004
Table 1. Physicochemical Properties of Each of the Asphaltene Molecules Used in This Work
property Mullins
formula H98C72S1
molecular weight (amu) 995.64
molecular volume (Å3) 794.6
elemental analysis (%)
C 86.86
H 9.92
N 2.44
O 1.39
S 3.22
number of fused aromatic rings 7 14
CA 30
CS 42
HA 11
HS 87
enes is well-recognized, and the difficulty is even more
severe for a polydisperse system of a specific crude oil.
However, a reasonable starting guess is that the amor-
phous solid asphaltene phase is mainly comprised of an
average size molecule, as evidenced from experimental
work, which varies for each type of crude oil. Zajac et
al.23 proposed three asphaltene model molecules for
Mayan crude oil; they are built by rearrangement of
some aromatic rings or some aliphatic chains for the
asphaltene structures they proposed. As a consequence,
a polydisperse system can be constructed by a set of
monomer asphaltene molecular models in a vacuum,
which, as a first approach, should be a good model to
simulate asphaltene aggregates, as well as to investi-
gate how they agglomerate in an amorphous solid phase.
Self-association of covalent asphaltene model mol-
ecules was recently simulated through molecular simu-
lations by Pacheco et al.16,30 The stacked asphaltene
molecules were observed in the form of dimers, trimers,
tetramers, and pentamers. The morphologies of those
aggregates were proposed as a stacking of asphaltenes
not only assembled face to face but also in T-shaped and
offset orientations, in agreement with the results of
Hunter and Saunders20 and Leach.21 Furthermore,
using the same Groenzin and Mullins model utilized in
this work, the interaction energy between two asphalt-
ene models was calculated by minimizing the energy at
different distances, which, indeed, provided the energy
as a function of distance. Similar morphologies can be
observed in other systems,12 where it is also possible to
observe face-to-face (FF), edge-to-face (EF), and edge-
to-edge (EE) clay-particle associations.
In this work, a method to generate stable asphaltene
aggregates is presented; this methodology uses a peri-
odic cell ensemble of 32 asphaltene molecules. To find
a stable structure, an optimization process was per-
formed, using a force-field method. Our objective is
mainly (i) to find morphologies of asphaltene aggregates
that properly describe the experimentally reported S(k)
profile, (ii) to analyze the geometries through which the
aggregates are formed, and (iii) to study the effect of
the aliphatic chains, on the aggregated structure,
through the evolution of the structure factor. To this
end, a comparison between predicted and experimental
structure factors is examined for asphaltene aggregation
(30) Pacheco-Sánchez, J. H.; Alvarez-Ramı́rez, F.; Martı́nez-Ma-
gadán, J. M. Prepr.sAm. Chem. Soc., Div. Pet. Chem. 2003, 48, 71-
73.
Pacheco-Sánchez et al.
value
Speight Zajac Murgich
H79C80N2O1S2 H63C57N1S1 H159C138N3O2S2
1149.67 794.2 1955.95
892.7 637.3 1574.6
83.58 86.2 84.74
7.01 8 8.19
1.76 2.15
1.64
5.58 4.04 3.28
9 24
47 29 70
33 28 68
9 6 19
70 57 140
modeling, using molecular simulations for a set of one
type of asphaltene molecule.
2. Methodology
The methodology used is based on force-field concepts; it is
an analytical function that is mainly composed of two types
of terms. The first terms are associated with bond-interaction
energies, such as torsion, bending, and stretching. The second
terms are associated with nonbonded interactions, such as
Coulombic and van der Waals forces.31-34 Because of the force-
field features, this methodology is dependent on the molecular
characterization of the crude oil under study. One objective
behind MD is to find a stable molecular configuration where
that configuration is located in a local minimum of the
potential energy surface around the initial configuration.
However, as a consequence of the high molecular weight, the
asphaltene motion in a MD simulation is known to be very
slow. For this reason, finding the local minimum energy
requires hundreds of picoseconds.
First, a model system constituted by a blend of 35 molecules
composed of equal quantities of five different polynuclear
aromatic molecules was set up, as proposed by Diamond.13
These 35 molecules were randomly distributed in a simulation
cell using the Amorphous Cell program.35 The cell dimensions
(a, b, and c) are all equal to 63.25 Å, and the initial density in
the cell is equal to 0.1 g/cm3. Second, a complete cell geometry
optimization process was conducted, allowing free movement
of molecules, including internal lengths and angles, bringing
as a consequence, the effect of a comprised cell with a
representative density. The final density for the relaxed
structure was 1.39 g/cm3. This value is larger than the usual
experimental values.36 This behavior can be explained by the
lack of aliphatic chains pendant to the aromatic cores. The
COMPASS98_02 force field35 was chosen because it was
designed for organic and inorganic molecules, and it has been
extensively applied to these types of systems with successful
results. An internal stress of 1 × 10-4 GPa was selected as
the criterion of convergence.
Figure 3 shows the same final structure from two different
points of view, highlighting different molecules in each one.
The relaxed structure displays the presence of stacking, as
expected. Stacked polydisperse domain sheets were formed in
the cell; they can be seen in Figure 3a and b, where the
(31) Sun, H.; Rigby, D. Spectrochim. Acta A 1997, 53, 1301-1323.
(32) Rigby, D.; Sun, H.; Eichinger, B. E. Polym. Int. 1997, 44, 311-
330.
(33) Sun, H.; Ren, P.; Fried, J. R. Comput. Theor. Polym. Sci. 1998,
8 (1-2), 229-246.
(34) Sun, H. J. Phys. Chem. B 1998, 102, 7338-7364.
(35) Force Field-Based Simulations; MSI, Inc.: San Diego, CA, 1997;
pp 29, 265-268.
(36) Rogacheva, O. V.; Rimaev, R. N.; Gubaidullin, V. Z.; Khakimov,
D. K. Colloid J. USSR 1980, 490-493.
Aggregated Asphaltene Structural Models
Figure 3. Final structure of 35 aromatic molecules obtained
after geometry optimization process. Panels a and b show two
angles of different stacking structures of the same final relaxed
cell; the macrostructure of asphaltic material representing just
the aromatic portion is shown in panel b. Panel c shows a
planar representation of Figure 3b, which is a typical Dickie
and Yen2 model for aromatic components without considering
aliphatic chains.
domains are themselves constituted by different types of
molecules, which give the polydisperse character to the formed
aggregate. The generated aggregates are formed of dimer,
trimer, and tetramer domains. This description is consistent
with the results found by Dickie and Yen.2 One very important
detail, in the present study, is that the face-to-face stacking
geometrical orientation, as well as the offset π-stacked geom-
etry, was observed.
The positions of every molecule and atom can be determined
in the model, and then it is possible to get structural properties
as the spherically averaged distribution of interparticle vector
lengths (the radial distribution function, RDF) and its inverse
Fourier transformation (the structural factor, S(k)) within the
model. The structure factor was obtained for this model
system, and good agreement was observed between the
theoretical and experimental S(k) profile (Figure 4). In this
graph, we rescaled the abscissa axis (sin θ)/λ of Yen et al.3 by
a value of 4π, such that this axis now is denoted as k, where
k ) 4π(sin θ)/λ. The dotted curve in Figure 4 represents the
experimental curve of the amorphous blend of five aromatic
compounds of known structure, according to those results
computed by Diamond.13 He computed the intensity of X-rays
diffracted from randomly oriented, perfect aromatic molecules
of various sizes, using the Debye RDF. The dashed curve in
Figure 4 represents approximately the experimental XRD
pattern of the aromatic clusters in the asphaltene computed
by Yen et al.3 The solid curve in Figure 4 represents our own
simulation of the same amorphous blend of five aromatic
compounds of known structure. Therefore, the structural
model in Figure 3 can be considered to be a good approximation
of the real system. Because of these agreements, this meth-
odology will be extrapolated to different structure cases of the
Energy & Fuels, Vol. 18, No. 6, 2004 1679
Figure 4. Comparison between the structure factor S(k)
obtained in our simulation and those S(k) profiles reported by
Yen et al.3
asphaltene models, and the results will be compared against
at least one of those curves of the S(k) profile for several
asphaltenes reported by Yen et al.3
3. Asphaltene Aggregation Structures
Using the same methodology as before for aromatic
molecules proposed by Yen et al,3 four periodic cells with
32 asphaltene model molecules were built. The cells
were built using the four asphaltene molecular models
mentioned previously; for simplicity, let us call them
Mullins, Speight, Zajac, and Murgich. The minimization
of the energy was performed by allowing the relaxation
of the cell dimensions to obtain spontaneous self-
aggregation of the asphaltene molecules. Asphaltene
self-aggregation in crude oil is believed to occur as a
spontaneous aggregation, which can be investigated
using a geometry optimization process, such as that in
this work. An initial density of ∼0.1 g/cm3 was chosen
for all the cells. During the optimization process, the
equilibrium configuration of the system gradually de-
creases the cell length, leading to a squeezed cell. The
cells that have been built in this way have the following
final densities: 0.98 g/cm3 for the Mullins model mol-
ecules, 1.04 g/cm3 for the Speight model molecules, 1.02
g/cm3 for the Zajac model molecules, and 0.69 g/cm3 for
the Murgich model molecules.
3.1. Mullins Model Case. The final structure of the
cell that has been built using the Mullins asphaltene
model shows a very small number of stacking forma-
tions, compared to that of aromatic molecules. This is
attributed to the presence of aliphatic chains, which
hinder a close interaction between the aromatic cores
of the asphaltenes, as shown in Figure 5a.
In particular, both the aliphatic and aromatic regions
images were isolated. Figure 5b shows the aliphatic
region image, which displays a homogeneous distribu-
tion over the cell. The aromatic region image, in Figure
5c, shows two highlighted stacking formations: one in
an offset π-stacked geometry, and the other in a face-
to-face geometry. The stacking behavior can be ex-
plained by the repulsive steric effect of the aliphatic
chains, which decreases as the length of these chains
diminishes. Asphaltene face-to-face stacking has a more-
probable existence when short aliphatic chains overhang
from the aromatic rings.
1680 Energy & Fuels, Vol. 18, No. 6, 2004
Figure 5. (a) Cell showing the final asphaltene structure of
the Mullins model. (b) Isolated aliphatic region of the complete
final structure. (c) Isolated aromatic region, where some
stacking were highlighted.
For an optimized configuration, the following two
parameters of the simulation cell allow us to discuss
the diminishing of the stacking. The free-volume per-
centage in Figure 5a is 34.68%, which means that
asphaltene monomers are highly condensed in the cell.
The ratio of surface areas between the aromatic region
and the aliphatic region is ∼0.41, which means that the
aromatic portion is bigger than the aliphatic portion.
The small amount of stacking, in this case, is due to
the aliphatic chain size and number, with respect to the
aromatic core size, which does not allow a close interac-
tion between the aromatic components of the asphalt-
ene. These chains form walls between the asphaltene
nearest neighbors, which hinder the direct π-π interac-
tion. The increased separation generated by the pres-
ence of the chains is reflected directly in the S(k) profile.
This phenomenon can be observed when the S(k)
profiles for the aromatic and asphaltene cases are
compared. The presence of these chains produces a
discrepancy between the aromatic and asphaltene S(k)
profiles, which is reflected in the number of peaks and
their positions, for k < 2.5 Å-1. It was observed that
the first peak (the nearest to zero) for the aromatic case
is still present in the asphaltene S(k) profile; however,
it is shifted to a k value of <2 Å-1. A new peak, at k ≈
0.5 Å-1, is observed; this peak is not present in the
aromatic case, as shown in Figure 6. What we are
testing in Figure 6 generally is that the S(k) profile of
a complete asphaltene model has an important differ-
ence when is compared with the S(k) profile of aromatic
cores. We then must compare simulated S(k) profiles of
whole asphaltene aggregates against experimental S(k)
profiles of whole asphaltene aggregates. The other
comparison must be between theoretical and experi-
mental S(k) profiles of aromatic cores of the asphaltene
aggregates.
Pacheco-Sánchez et al.
Figure 6. Comparison between the asphaltene S(k) profile
of our relaxed cell and two aromatic S(k) profiles reported by
Yen et al.3
However, this structure shows an S(k) profile that is
in agreement with some experiments reported in the
literature. In particular, a direct comparison between
the S(k) profile associated with our structure and that
of the Ragusa crude oil asphaltene fraction experimen-
tally reported by Yen et al.3 is presented (Figure 7),
which corresponds to a more accurate comparison than
the other S(k) profile of the experimentally obtained
asphaltenes.
The fact that the model is able to reproduce the three
experimental S(k) peaks justifies that the methodology
developed here produces an adequate asphaltene ag-
gregate structure. Therefore, based on the morphology
of the model, it is possible to infer the existence of more
than one type of relative orientation between the
asphaltene molecules. These orientations are not re-
stricted to FF; some other orientations also are included.
To analyze the distance between different aromatic
regions in this aggregate, the RDF has been calculated,
using the same atom in each one of the asphaltene
molecules of this system, where this atom is located in
the aromatic region; the first peak on the RDF corre-
sponds to a minimum distance of 4.15 Å, which was
measured between the centers of the aromatic region.
The main reason this distance is deviated almost 15%
from the distance corresponding to the optimum binding
energy (3.55-3.7 Å) is because the distance between
centers of aromatic regions is not the shortest one in
each case, which reflects the effect of the aliphatic
chains that is due to the use of a complete asphaltene
model.
It is important to mention herein that Yen et al.3 also
measured a linear size distance of 16-20 Å for the
stacking of four-unit asphaltene sheets. From this
result, the following facts can be elucidated:
(1) The distance 3.55-3.7 Å is underestimated, in the
sense that corresponds only with the binding energy of
asphaltene molecules; however, the size of the well
potential includes a wider interaction range than this.16
(2) The distance 16-20 Å corresponds to asphaltenes
that are strongly influenced by aliphatic chains. Fur-
thermore, it is remarkable that Espinat et al.37 mea-
(37) Espinat, D.; Rosenberg, E.; Scarsella, M.; Barre, L.; Fenistein,
D.; Broseta, D. In Structures and Dynamics of Asphaltenes; Mullins,
O. C., Sheu, E. Y., Eds.; Plenum Press: New York, 1998; Chapter V.
Aggregated Asphaltene Structural Models Energy & Fuels, Vol. 18, No. 6, 2004 1681

Figure 7. S(k) profile for the Mullins aggregate model, compared with two experimental S(k) profiles, and the S(k) profile obtained
from a relaxed aggregation model built only with the aromatic cores (AC) of Mullins asphaltenes.

sured a linear size distance of four unit sheets of 14-

28 Å for the stacking of asphaltenes.
(3) Knowing that the distance between monomers in
a dimer is 3.55-3.7 Å, the linear size of a tetramer (16-
20 Å or 14-28 Å) probably indicates two dimers
interacting between themselves, with aliphatic chains
in the middle of them providing an interaction distance
of 8.9-12.9 Å or 6.9-20.9 Å, respectively.
In addition, Figure 7 shows a comparison between the
S(k) profile of the complete asphaltene aggregate model
and that obtained from an aggregate model that was
built using only the aromatic Mullins asphaltene core,
which will be analyzed in the next section.
3.2. Speight Model Case. The relaxed aggregate
structure of the cell built with the Speight model shows
an abundance of stacking. However, the largest amount
of stacking is in an offset π-stacked geometry. In this
particular geometry, at least one structure that con-
tains five members has been observed (Figure 8). It has
also highlighted two more stacking geometries: one is
T-shaped, and the other one is a face-to-face geometry.
It can be attributed to the increment of stacking in the
Speight aggregate, compared with the Mullins model
case, to the highest absolute area of the aromatic
section. This gives greater contact area than in the
Mullins model case. However, this contact is not so Figure 8. (a) Cell showing the final asphaltene structure of
great, because the aliphatic chains do not allow a close the Speight model. (b) Isolated aliphatic region of the complete
interaction. A ratio of 0.64 between the aromatic surface final structure. (c) Isolated aromatic region, where one offset
area and the aliphatic surface area was observed. The π-stacking with five members, one dimer in T-shaped stacking,
and one dimer in face-to-face stacking were highlighted.
molecules are less flexible, because of the rigidity of the
aromatic sheets and the fact that, in this case, they are molecules can self-aggregate: face to face, offset
larger than those in the Mullins model case. This effect π-stacked, and T-shaped. The irregular stacking is
produces an increase in the free-volume percentage, attributed to the concavity obtained by the aromatic
which, in this case, is 37.80%. For this aggregate, the cores at the end of the energy optimization of the
minimum distance between the aromatic cores is 3.65 molecular simulation.
Å and, it is the first peak on the RDF. The ratio between the aromatic and aliphatic surface
The comparison between the S(k) profile for the areas is 0.65, which is almost equal to that observed in
Speight aggregate and the experimental S(k) profile the Speight case. However, the absolute size of the
shows good agreement in the position of the peaks. The aromatic area is smaller for the Zajac molecule than the
best agreement is found with the Ragusa asphaltene Speight molecule and is larger than that for the Mullins
crude oil (Figure 9). molecule, bringing, as a consequence, a higher stacking
3.3. Zajac Model Case. The Zajac molecule is a formation than that observed in the Mullins model case
singular one, because it has only one long aliphatic but smaller than that in the Speight model case. The
chain. The relaxed final aggregate structure exhibits free volume of 36.96% indicates the role of the only one
molecules with a great curvature in the aromatic region aliphatic chain: that, despite the aromatic region, in
that generally move away from these regions, stopping this case, the free volume is bigger than that in the
a higher stacking formation. The aggregate shows an Mullins model case. Note that their free volumes have
irregular stacking structure. However, Figure 10 il- almost the same magnitude. The minimum distance
lustrates at least three geometries in which these between the aromatic cores, for this case, is 3.25 Å and,
1682 Energy & Fuels, Vol. 18, No. 6, 2004
Figure 9. S(k) profile for the Speight aggregate model, compared with two experimental S(k) profiles, and the S(k) profile obtained
from a relaxed aggregation model built only with the aromatic cores (AC) of Speight asphaltenes.
Figure 10. (a) Cell showing the final asphaltene structure of
Zajac model. (b) Isolated aliphatic region of the complete final
structure. (c) Isolated aromatic region exhibits highlighted
three geometries with two members at least: one offset
π-stacking, one edge-on or T-shaped, and one face to face. In
this case, the AC finished having a clear concavity.
it is the first peak on the RDF. This value is deviated
almost 9% from the distance corresponding to the
optimum binding energy (3.55 Å).
The aggregate S(k) profile, as in previous cases, shows
all the peaks in the positions reported experimentally.
The exception is the position of the second peak, where
there is good agreement for the Ragusa asphaltene
aggregates (Figure 11).
Figure 11. S(k) profile for the Zajac aggregate model, compared to both the two experimental S(k) profiles, and the S(k) profile
obtained from a relaxed aggregation model built only with the aromatic cores (AC) of Zajac asphaltenes.
Pacheco-Sánchez et al.
3.4. Murgich Model Case. The Murgich asphaltene
molecular model possesses the largest aromatic area
among all the asphaltene models analyzed here. The
rigidity of this area in the molecule does not allow it to
be folded to fill all the space. Therefore, the relaxed
aggregate structure obtained from the Murgich molecule
produces empty regions and jammed clusters of as-
phaltenes, instead of stacking configurations. The free
volume in this case is 57.30%, which is significantly
bigger than that observed in the other cases. Visualizing
carefully, however, these jammed clusters are formed
mainly by two of our three main stacking configura-
tions: offset π-stacked and edge-on or T-shaped con-
figurations. The most frequent configuration obtained
is the offset π-stacked orientation. The face-to-face
geometry configurations are not observed, which can be
attributed to a very extensive aromatic region in the
asphaltene model (Figure 12). A remarkable difference
with the other cases is the formation of two large
clusters in the simulation cell, meaning that the ali-
phatic regions are not uniformly distributed in the cell.
The ratio of aromatic and aliphatic surface areas was
determined to be 0.55, which is smaller than that
observed for the Speight and Zajac cases but larger than
the Mullins case. Nevertheless, as in the Speight case,
the absolute size of the aromatic area has an important
role in making the stacking formation more possible.
The minimum distance between the aromatic cores is
3.65 Å, which agrees with the known distance of
optimum binding energy for two asphaltenes. However,
the calculated peak between 1 Å-1 and 2 Å-1 is barely
described, considering that the first peak hides its own
shoulder peak in this region (Figure 13).
Aggregated Asphaltene Structural Models
Figure 12. (a) Cell showing the final asphaltene structure of
Murgich model. (b) Isolated aliphatic region of the complete
final structure. (c) Isolated aromatic region, where one is offset
π-stacked, one is edge-on, and one is face-to-face stacking with
two members was highlighted.
However, the comparison between the S(k) profile for
Murgich asphaltene aggregates and experimental re-
sults shows the closest agreement, in regard to the
position of its shoulder peak and the first peak of the
Gilsonite asphaltenes (see Figure 13).
4. Aromatic Cores
To explain the role of the aliphatic chains and the
aromatic core, all the aliphatic chains were cut from the
asphaltene models. After the aromatic cores were
obtained, our methodology was applied on all resulting
purely aromatic cores. The final densities of the aro-
matic asphaltene core cell (AACC) models without
aliphatic chains are higher than the whole asphaltene
model (WAM) (see Table 2).
Except for the Murgich case, the order of magnitude
of the WAM density values agree with those reported
by Speight24 for the specific gravity (density 60/60 °F38)
for various asphaltene samples obtained from different
bitumens.39 In all cases, the AACC model shows its
stacking presence, showing different geometries as a
mixture of the three geometries (face-to-face, edge-on
or T-shaped, offset π-stacked; see Figure 14).
Figure 13. S(k) profile for the Murgich aggregate model, compared to both the two experimental S(k) profiles available and the
S(k) profile obtained from a relaxed aggregation model built with the aromatic cores (AC) of Murgich asphaltenes.
Energy & Fuels, Vol. 18, No. 6, 2004 1683
Table 2. Final Densities of Asphaltene Molecules after
Energy Optimization for Both the Whole Asphaltene
Model (WAM) and the Aromatic Asphaltene Core Cell
(AACC) Cases
density (g/cm3)
model WAM AACC
Mullins 0.98 1.26
Speight 1.04 1.36
Zajac 1.02 1.28
Murgich 0.69 1.24
Table 3. Free Volumes of the Final Optimized Cells for
Both the Whole Asphaltene Model (WAM) and the
Aromatic Asphaltene Core Cell (AACC) Cases
free volume (%)
model WAM AACC
Mullins 34.68% 28.13%
Speight 37.80% 31.91%
Zajac 36.96% 31.81%
Murgich 57.30% 36.04%
As shown in Figure 14, there is a higher stacking
tendency of the aromatic sheets; for example, in the
Mullins case, one trimer and one pentamer are high-
lighted. However, the others are not selected, to pre-
serve clarity in the figure. As a comparison, only two
dimers are highlighted in the isolated aromatic region
shown in Figure 5, the Mullins asphaltene case. In the
Speight case, a trimer and a tetramer were chosen,
whereas, in the Zajac case, a dimer and a pentamer are
shown. Finally, in the Murgich aromatic model, just a
hexamer is highlighted. The geometric form chosen for
the Mullins and Murgich cases is offset π-stacked.
Correspondingly, the Speight and Zajac selected geo-
metric forms are offset π-stacked and T-shaped. A strict
face-to-face geometry can hardly be selected in any of
these cases. The free volumes of the AACC models are
smaller than those in the WAM, as shown in Table 3.
The difference between the free-volume percentages
of the WAM and AACC models is a clear evidence of
the role of aliphatic chains, because a great compression
of the sheets results when these are removed from the
systems. The aliphatic chains connected to the aromatic
cores then stop the attraction between aromatic cores
of asphaltenes, which produces a large amount of empty
space in the aggregation of asphaltenes.
When the structure factors of the AACC and WAM
models are compared, a second peak shift to a smaller
value of k for the WAM model, with respect to the AACC
model, is observed, as in the aromatic blend molecules
1684 Energy & Fuels, Vol. 18, No. 6, 2004
Figure 14. Different relaxed aromatic-core aggregated struc-
tures: (a) Mullins, (b) Speight, (c) Zajac, and (d) Murgich.
studied by Yen et al.3 These shifts are called the γ-band
and the (002)-band, respectively. Our results are due
to the fact that the WAM model has a stronger presence
of aliphatic chains than does the AACC model. This
effect was also very well-identified by Wiehe and Liang.4
They associated paraffins to the smallest 2θ value and
aromatics to the largest 2θ value on this peak of the
structure factor of asphaltenes that they obtained. This
shift behavior is independent of the asphaltene model
molecule used, as is shown in the sequence of Figures
7, 9, 11, and 13. When the aliphatic chains are removed
from the aromatic core in the Murgich case, the S(k)
profile recovers the characteristic peak at ∼1.2 Å-1; in
addition, the Murgich AACC density recovers typical
aromatic density values (see Table 2).
Given all these facts, aliphatic chains have a role in
inhibiting the stacking formation. Depending of the
asphaltene model, there are different inhibition mech-
anisms, such as intercalation of aliphatic chains be-
tween aromatic sheets or pulling the molecule in one
side and only allowing some degree of stacking in
another place. An example of the presence of the effect
of aliphatic chains is the Murgich case, where the
aliphatic chains cause a delay in the molecules forming
regions of empty space and clusters (see Figure 12). This
effect is not observed without aliphatic chains (see
Figure 14).
We have made the following three observations in our
graphs of the S(k) profile for k ) 0 to k > 0 in Figure
14. First, the first peak on the aromatic core (AC) of
Mullins asphaltenes is the smallest one, whereas the
first peak on the AC of Murgich asphaltenes is the
largest one, and its second peak is the smallest one
among all of the AC asphaltenes. Second, the S(k) profile
of Baxterville asphaltene3 includes the major component
(38) Relative density (60/60 °F), which was called density by Speight,
is the ratio of the mass of a given volume of liquid at 60 °F to the
mass of an equal volume of pure water at the same temperature.
(39) Speight, J. G. The Chemistry and Technology of Petroleum;
Marcel Dekker: New York, 1999; p 315.
Pacheco-Sánchez et al.
of both AC asphaltenes of Mullins, Speight, and Zajac
structure models, as shown in Figures 7, 9, and 11. This
agrees with the interpretation of Wiehe and Liang,4
meaning that the highest shoulder of the second peak
of the S(k) profile in Baxterville asphaltene is aromatic
and the other is paraffinic. The same figures also exhibit
Ragusa asphaltene,3 as it represents the best match
against asphaltenes of these types. Ragusa asphaltene
includes the major portion of the second peak of both
AC and asphaltenes of the Murgich average structure
model; however, Gilsonite asphaltene3 is the best match
against asphaltenes of the Murgich average structure
model. Third, in Figure 15, the height value on the S(k)
profile of AC compounds3 and AC Wafra A13 asphalt-
enes is observed to be larger than all the second peaks
of our asphaltene models. In addition to this point, the
k value of these experimental models is larger than that
of three of our models; only the second peak of the S(k)
profile on the AC of Speight asphaltene almost matches
the k value of the AC compounds.
5. Discussion
Our methodology for calculating the minimum dis-
tance between two asphaltenes in the stacking can give
us a reasonable prediction if the asphaltene molecule
has a compacted aromatic region that is well-designed,
which can be done using the methodology developed by
Ruiz-Morales.40 This is due to very good results that
have been obtained for the distance of binding energy
between two asphaltene molecules on the Speight and
Murgich cases; however, although the Zajac case is 9%
deviated from experimental values, the Mullins case has
a deviation of 15%. These deviations clearly indicate the
presence of aliphatic chains, which restrict both the
closest interaction distance between two asphaltene
molecules and its geometry of stacking. The following
comment of Ebert,41 that “only 36% of the aromatic
carbon was in stacks of two (‘dimers’) and 64% of the
aromatic carbon was not in a stack of any kind (‘amor-
phous’)” suggests agreement with our observations.
Another point is related to the number of aromatic
rings in the AC of one asphaltene molecule. Ruiz-
Morales40 suggests that asphaltenes present a polyaro-
matic core size of 1-2 aromatic systems with 4-10
fused rings in each one; according to the Mullins
experimental work.27 Rogacheva et al.36 reported as-
phaltenes with 4-10 fused aromatic rings. Rogel42 has
drawn polyaromatic rings with 9-14 fused rings to
represent the aromatic moieties of asphaltenes. We used
four different asphaltene molecules, with 7, 9, 14, and
24 aromatic rings, following previous models in the
literature. We believe that the use of molecular simula-
tions to calculate the structure factor S(k) is a good
starting point to improve this design.
By cutting aliphatic chains of asphaltenes, just ACs
were obtained. These ACs were also energetically
optimized, and their structure factors S(k) were ob-
tained, as shown in Figure 15. Figures 8c and 14a show
that an asphaltene molecule designed by Mullins with
seven fused aromatic rings exhibits at least one 5-aro-
matic-stack system. As we can also see in Figure 15,
(40) Ruiz-Morales, Y. J. Phys. Chem. A 2002, 106, 11238-11308.
(41) Ebert, L. B. Fuel Sci. Technol. Int. 1995, 13, 941-944.
(42) Rogel, E. Langmuir 2004, 20, 1003-1012.
Aggregated Asphaltene Structural Models
Figure 15. Comparison between structure factors of aromatic cores (AC) calculated by us (continuous line) and those proposed
by Yen et al.3 (dotted and dashed lines).
the AC of Speight asphaltenes with 14 fused aromatic
rings gave the best agreement between its second S(k)
peak and the first S(k) peak of AC compounds; however,
the AC of Mullins asphaltenes is deviated from match-
ing. Second, the S(k) peak of the AC of Zajac asphaltenes
with nine aromatic fused rings has a very similar
behavior to that of the AC of Mullins asphaltenes. In
the case of Murgich asphaltene, we found that the AC
of 24 fused aromatic rings has a behavior more similar
to asphaltenes than to ACs of asphaltenes (see Figure
13). After this analysis, it can be concluded that the
Murgich asphaltene case is only meaningful when
aliphatic chains are removed.
We must stress that minimization of the energy is
independent of the temperature, and a complete study
of the stability using entropy and thermodynamic
potentials is not possible within the present methodol-
ogy. At this time, we just want to show that we found a
very good matching between this theory and experiment
stabilizing asphaltenes by molecular simulations of
energy optimization.
It must be stated that, knowing the interaction
potential, the structure factor S(k) can be approximated
from the solution of the Ornstein-Zernicke (O-Z)
integral equation and an additional closure relation (PY,
MSA, RMSA, HNC, RY, etc.).43,44 The methodology of
Henderson-Barker-Abraham and of density functional
theory (DFT) can be used to obtain the solution of the
O-Z equation.9,45,46 However, these methods are de-
(43) D’Aguanno, B.; Klein, R. J. Chem. Soc., Faraday Trans. 1991,
87 (3), 379-390.
(44) Ortega-Rodrı́guez, A.; Cruz, S. A.; Gil-Villegas, A.; Guevara-
Rodrı́guez, F.; Lira-Galeana, C. Energy Fuels 2003, 17, 1100-1108.
(45) von Grünberg H. H.; Klein R. J. Chem. Phys. 1999, 110 (11),
5421-5431.
Energy & Fuels, Vol. 18, No. 6, 2004 1685
pendent on Euclidean geometric forms of the molecule,
because of the potential they use, as the hard-sphere
intermolecular potential of interaction. This is a gross
limitation, because the center of mass is translated,
which produces deviations from real systems as as-
phaltenes are. They usually compare their results
against MD simulations, Monte Carlo (MC) calculations,
and/or experiments.45 Yen et al.3 used a very clever
methodology to compare the XRD experimental pattern
for aromatic clusters in petroleum asphaltene with the
experimental pattern for a blend of five polynuclear
aromatic compounds of known structure by computing
the Debye RDF implemented by Diamond,13 which is
precisely the structure factor S(k). We calculated a very
good approximation of the S(k) profile by optimizing the
energy of a 35-membered aromatic system, using the
same five aromatic compounds mentioned previously in
groups with seven-membered rings.
Whether the approved SF profile is our guide to
validate generated morphologies, the effects of polydis-
persity on the SF profile are well-known, as shown in
some studies developed by D’Aguanno and Klein.43 In
that work, the effects of polydispersity in charged
colloidal dispersions are exhibited in a manner in which
the SF peaks are displaced, modifying its height and
width at different levels of polydispersity. Asphaltenes
are known to constitute a polydisperse system; however,
in the literature, it is usual procedure to characterize
crude oil systems by means of an asphaltene average
molecule.18,23,27,28 Because of this restriction on the
characterization of the entire polydispersity of the
asphaltenic system, as a first approach, we have taken
(46) Pacheco-Sánchez, J. H.; Rodrı́guez, A. G. Rev. Inst. Mex. Pet.
1993, 25 (2), 55-60.
1686 Energy & Fuels, Vol. 18, No. 6, 2004
a set of average molecules reported in the literature as
the starting point in this study.
Finally, our results here can help to improve the
experimental methodology for designing asphaltene
molecules, which can be useful, as many researchers
have shown.14-18,22,30,42,47
6. Conclusions
One possible way to determine the morphology of
asphaltene aggregates is through modeling and simu-
lating such aggregates. This is because (i) our simulated
structure factors (S(k)) of asphaltene aggregates agree
with those reported by Yen; (ii) the molecular models
of asphaltenes are experimentally designed from ex-
tracted crude oils; and (iii) experimentally, it is possible
to simply guess about the morphology of the aggregates.
We have proposed a procedure for generating as-
phaltene aggregated structures, based on a minimiza-
tion of the energy of the system in periodic cells. These
periodic cells were constructed using different asphalt-
ene models, such as those devised in the research of
Mullins, Speight, Zajac, and Murgich. Each cell was
built with one type of asphaltene model in an amor-
phous arrangement to optimize them. The developed
methodology is capable of reproducing the position of
the experimental S(k) profile. Important differences
were observed, with respect to the AC cases. The
presence of a shift in the peak located between 1 Å-1
(47) Rogel, E.; León, O. Energy Fuels 2001, 15, 1077-1086.
Pacheco-Sánchez et al.
and 2 Å-1 is associated with the stacking. We observed
stacking clusters when aromatic molecules are used.
Based on the similarity of the S(k) profiles, we can
conclude similarities in the asphaltene agglomeration
of the Zajac, Mullins, and Speight cases with Ragusa-
type asphaltene, and of the Murgich case with Gilsonite-
type asphaltene.
Generally, the positions of the main S(k) peaks were
correctly reproduced, showing a discrepancy on the
second peak region. Such a discrepancy can be at-
tributed to the tail presence in the aromatic sheets that
inhibits the π-π, π-σ, and σ-σ interactions, bringing,
as a consequence, an increase of the distance between
these sheets. The good correlation between the experi-
mental and predicted S(k) profiles would imply that the
asphaltene aggregate structure is an adequate model
for studying the asphaltene aggregation phenomenon.
Therefore, based on the present simulations, we
conclude that a nearest-neighbor stacking in face-to-face
geometry is not the only possible orientation. The
observed asphaltene aggregate structure represents just
one of the possible ensemble structures that could exist
in the system. The final cells are good models as a first
approach for representing asphaltene aggregates as well
as the way in which they agglomerate in an amorphous
solid phase. In addition, we applied our methodology to
the different asphaltene models used but without their
aliphatic chains, finding a similar stacking behavior for
each case.
EF049911A