2474 Energy & Fuels 2005, 19, 2474-2479

Calorimetric Probing of n-Alkane-Petroleum Asphaltene

Interactions
R. Mahmoud,‡ P. Gierycz,§ R. Solimando,‡ and M. Rogalski*,†
Laboratoire de Thermodynamique des Milieux Polyphasés Université de Metz, 1, Boulevard
Arago, CP 87811, 57078 METZ Cedex 3 France, ENSIC-INPL, BP 451, 1, rue Grandville,
F-54001 Nancy Cedex, Radom Technical University, Faculty of Material Science and
Footwear, Technology, Chrobrego 27, 26-600 Radom, Poland, and Institute of Physical
Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa, Poland

Received May 30, 2005. Revised Manuscript Received July 26, 2005

In this work, we report results of calorimetric studies on interactions between petroleum

asphaltenes and n-alkanes. It was observed that mixing of n-alkanes with asphaltenes leads to
exothermic thermal effects. This effect is irrespective of the asphaltene state and occurs either
with precipitated asphaltenes or with solutions containing dissolved asphaltenes. This phenom-
enon is explained by a partial immobilization of n-alkanes in the protecting shell formed by
aliphatic lateral chains of asphaltenes. The proposed mechanism of interactions between n-alkanes
and lateral alkyl chains of asphaltenes contributes to understanding the role of n-alkanes in
nucleation of the wax deposition and of the asphaltene flocculation.

1. Introduction aromatic core is surrounded by alkyl side chains of an

average length of five to six carbon atoms.7 Such
Asphaltenes, the heaviest components of the crude molecular structures favor stacking of polyaromatic
oils, are defined as the solubility class and correspond moieties. Nevertheless, the balance between the stack-
to the oil fraction soluble in toluene and not soluble in ing tendencies of fused aromatics and the entropic
light n-alkanes.1 In the crude oil, asphaltenes form a penalty of this process lowers the aggregation number
colloidal dispersion composed of asphaltene aggregates
and leads to the formation of small aggregates built with
probably solvated by certain components of the oil.2 The
five to six monomeric moieties. Further clustering of
precipitation of asphaltenes occurs when aggregates
small aggregates is hindered by the lateral alkyl chains
start to cluster. While the asphaltene deposition is a
either of asphaltenes themselves or of molecules (resins,
very well-known process, the role that asphaltenes play
naphthenic acids) associated with asphaltene aggre-
in the wax deposition processes was less investigated.
gates. The stabilizing role played by lateral alkyl chains
The enhanced wax crystallization observed in this case
was extensively studied in the case of liquid-crystal
was explained by existence of nucleation sites on the
compounds. In this case, the alkyl moiety can be
surface of asphaltene flocs.3 Therefore, interactions
regarded as being an entropy reservoir tuning the
between asphaltanes and alkanes play an essential role
balance between two energetically close phases.8 It was
in the formation of all solid precipitates of petroleum
observed that successive melting of alkyl chains at-
fluids.
tached to a molecular core of liquid crystals increases
The stability of the crude oil in respect to the
disorder (entropy), which modulates the relative ther-
flocculation is mainly governed by the content and the
modynamic stability of the molecular ordering.8 The
polarity of asphaltenes and by the composition and
highly disordered chains can behave like a solvent
properties of dispersing media.3-6
capable to dissolve molecules present in the solution.
Asphaltene monomers consist of two to six poly-
We think that lateral alkyl chains play the similar role
nuclear aromatics and contain small amounts of sulfur,
in the process of asphaltene aggregation. Accordingly,
nitrogen, oxygen, and trace amounts of metals. The
n-alkanes may be dissolved in the “pseudosolvent” phase
* Author to whom correspondence should be addressed. E-mail:
formed with asphaltene lateral chains and increase the
rogalski@sciences.univ-metz.fr. disorder of the latter. In this way, the steric protection
† Université de Metz.
‡ ENSIC-INPL.
of aggregates is lost and the progressing aggregation
§ Radom Technical University. leads to flocculation.
| Polish Academy of Sciences.
The analysis of bottom sediments found in the storage
(1) Speight, J. G. Fuel Sci. Technol. 1996, 14, 1-12.
(2) Rogel, E.; Leon, O.; Torres G.; Espidel, J. Fuel 2000, 79, 1389- vessels showed the presence of molecular complexes
1394. formed by long-chain n-alkanes and asphaltenes.9,10 The
(3) Carbognani, L. Energy Fuels 2001, 15, 1013-1020.
(4) Savvidis, T.; Fenistein, D.; Barre, D.; Behar, E. AIChE J. 2001,
206-211. (7) Speight, J. G. J. Pet. Sci. Eng. 1999, 22, 3-12.
(5) Hammami, A.; Phelps, C. H.; Monger-McClure, T. Energy Fuels (8) Sorai, M.; Saito, K. Chem. Rec. 2003, 3, 29-39.
2000, 14, 14-18. (9) Garcia, A. Energy Fuels 2000, 14, 1043-1048.
(6) Mansouri, G. A. J. Pet. Sci. Eng. 1997, 17, 101-111. (10) Garcia, A.; Carbognani, D. Energy Fuels 2001, 15, 1021-1027.

10.1021/ef050161u CCC: $30.25 © 2005 American Chemical Society

Published on Web 09/01/2005
Calorimetric Probing of n-Alkane-Petroleum Interactions
mechanism of formation of these complexes depends on
asphaltene characteristic properties but is nearly inde-
pendent of the wax composition and formation pathway.
This finding confirms the idea that the wax crystalliza-
tion is induced by alkane dissolution in the alkyl
protecting shell and the subsequent loss of the chain
mobility. This process promotes the crystallization of the
long-chain alkanes.
Recent calorimetric studies showed that the mixing
of asphaltenic crude oils with n-alkanes produces a
strong exothermic heat effect.11 The molecular inter-
pretation of this heat effect is not straightforward. In
our opinion, the energy balance of asphaltenes-n-
alkanes interactions is an important issue in compre-
hension of the asphaltene flocculation mechanism. In
the present work, we report calorimetric results ob-
tained during the asphaltenes-n-alkanes mixing pro-
cess.
The present study is focused on measurements and
interpretation of enthalpic effects observed during mix-
ing of asphaltenes with n-alkanes.
At first, we studied the melting process of n-alkane
in the presence of petroleum asphaltenes. DSC experi-
ments allowed the determination of the enthalpy ab-
sorbed by the systems formed by asphaltenes and one
of three n-alkanes, n-eicosane (C20H42), n-octacosane
(C28H58), and n-hexatriacontane (C36H74). The change
of the melting enthalpy of n-alkanes was ascribed to the
asphaltene-n-alkane interactions.
Next, an adiabatic calorimeter was used to determine
the global enthalpy effect of mixing liquid n-alkanes
with asphaltenes.
Finally, the influence of asphaltenes on phase dia-
grams of {n-alkanes + polyaromatic hydrocarbon} was
studied using differential scanning calorimetry.
2. Experimental Section
2.1. Materials. Asphaltenes were obtained from the crude
oil of European origin furnished by the Petroleum Company
Total according to the protocol described previously.12 All
n-alkanes were purchased from Aldrich Chemie. The melting
and solid-solid transition temperatures as well as the en-
thalpy of fusion determined with differential scanning calo-
rimetry were in good agreement with the literature data.
2.2. Differential Scanning Calorimetry. Temperature
and enthalpy of fusion were measured using a differential
scanning calorimeter DSC 111 of SETARAM. Samples of about
50 mg of {asphaltenes + n-alkane} mixture were prepared by
weight, using Sartorius balance with precision of (0.00001 g.
Before experiment, samples were melted and then quenched
with the liquid air to obtain a homogeneous solid mixture. The
accuracy of the temperature measurements was of 0.1 K. The
temperature rise rate was 0.5° min-1 with all experiments
performed.
The same experimental procedure was used to determine
liquid-solid solubility diagrams with systems {asphaltenes +
n-eicosane + dibenzofuran} and {n-eicosane + dibenzofuran}.
The diagrams were established with calorimetric data using
the previously described procedure.13
(11) Stachowiak, C.; Viguié, J. P.; Grolier, J.-P. E.; Rogalski, M.
Langmuir 2005, 21, 4824-4829.
(12) Mutelet, F.; Ekulu, G.; Solimando, R.; Rogalski, M. Energy Fuels
2004, 18, 667-673.
(13) Mahmoud, R.; Solimando, R.; Bouroukba, M.; Rogalski, M. J.
Chem. Eng. Data. 2000, 45 (1), 433-236.
Energy & Fuels, Vol. 19, No. 6, 2005 2475
Figure 1. Image of asphaltenes-n-eicosane mixture at the
melting temperature of n-alkane obtained using an optical
microscope (magnification 100×).
2.3. Isothermal Calorimetry. Measurements of the heat
of mixing were performed using isothermal calorimeter C-80
of Setaram. This calorimeter built according to the Calvet
principle includes two calorimetric cells placed in the calori-
metric block and maintained at constant temperature to within
(0.02 K. Two components of the mixture are initially sepa-
rated by a membrane. When the thermal equilibrium of the
system is attained, the membrane is broken out and the
calorimetric cell is rotated that allows mixing two components.
When a difference of temperature between the measuring and
the reference cell is detected, the controlling system generates
an electrical signal proportional to the heat effect in the
measuring cell. All experiments were carried out at the
temperature T ) 408.25 ( 0.02 K higher than the melting
temperature of n-eicosane. At this temperature, the thermal
stability of the system was reached after 7 h.
3. Results and Discussions
3.1. Phase Transitions of n-Eicosane in the Pres-
ence of Asphaltenes, Optical Microscopy. Before
carrying on calorimetric experiments with {asphaltenes
+ n-eicosane} mixtures, we have realized visual obser-
vations of phase transitions occurring in this system.
We used an optical microscope (magnification 100× )
to observe phase behavior of the {asphaltenes + n-
eicosane} mixture at the melting temperature of the
n-alkane. The solid sample of the mixture was placed
on the thermoregulated optical table of the microscope.
The temperature was slowly increased up to the melting
point of n-alkane. As shown in Figure 2, the liquefaction
of n-alkane causes partial disintegration of asphaltene
particles. This process is probably due to the elution of
certain components of asphaltene aggregates and leads
to the formation of a fine dispersion of asphaltene
particles in the liquid n-alkane. Dramatic changes of
the asphaltene particle granulometry suggest that
eluted molecules were at least partly responsible for the
cohesion of solid asphaltenes. Figures 2 and 3 show
subsequent stages of n-alkane crystallization. When the
mixture is thoroughly solidified, small asphaltene par-
ticles are dispersed in the crystalline n-alkane, as can
be seen in Figure 3. Therefore, it may be thought that
the interfacial energy at the alkane-asphaltene inter-
face is low.
3.2. Asphaltenes + n-Alcanes, Heat of Mixing.
The exothermic heat effect observed upon mixing of
n-heptane with a crude oil11 was interpreted in terms
2476 Energy & Fuels, Vol. 19, No. 6, 2005
Figure 2. Image of asphaltenes-n-eicosane mixture after a
partly crystallization of n-alkane obtained using an optical
microscope (magnification 100×).
Figure 3. Image of asphaltenes-n-eicosane mixture com-
pletely solidified obtained using an optical microscope (mag-
nification 100×).
of the decrease of the mobility of n-alkane molecules
engaged in the interactions with the asphaltene alkyl
chains. This phenomenon was attributed to a “quasi-
crystallization” of n-alkanes in the asphaltene network.
According to the recent paper of Stachowiak and al.,11
these exothermic heat effects are due to the interactions
through induced conformational changes and molecular
orientation correlation between the n-alkanes and the
asphaltene aliphatic chains. This effect depends on the
solvation of the asphaltenes with the oil components and
is different for different oils. In the present study, we
probed asphaltenes-n-alkanes interactions carrying on
measurements of heat of mixing of n-alkanes with
precipitated asphaltenes. Figures 4 and 5 show results
obtained with mixtures containing 30% mole of asphalt-
enes and 70% mole of n-eicosane. Thermal curves
representing the process of mixing are very complex.
According to the mechanism of mixing revealed by
optical microscopy, a series of exothermic effects prob-
ably correspond to the gradual disintegration of par-
ticles. Figure 5 reveals that the mixing process gener-
ates partly canceling exothermic and endothermic heat
fluxes. The endothermic heat corresponds to a partial
dissolution by n-eicosane of molecules present in as-
phaltane precipitate and is smaller than the exothermic
effect that prevails at all temperatures. In agreement
with our previous results,11 we think that the exother-
mic heat is due to a partial immobilization of n-eicosane
Mahmoud et al.
Figure 4. Heat of mixing of the system {asphaltene (30 mol
%) + C20H42} at T ) 351.9 K.
Figure 5. Thermal curve observed during process of mixing
of asphaltenes (30 mol %) with C20H42 at T ) 421.4 K.
within the asphaltene matrix. Nevertheless, measure-
ments done with samples containing different asphalt-
enes/n-eicosane ratios did not lead to consistent results
usually obtained with binary systems of simple mol-
ecules. The heterogeneity of the asphaltene containing
system and the complexity of heat effects make it
impossible to get a quantitative determination of the
heat of mixing diagram. For this reason, we decided to
study the heat generated by mixing of n-eicosane with
solutions containing asphaltenes. A solution containing
5 wt % of asphaltenes dissolved in dibenzofuran was
used. Figure 6 shows enthalpy of mixing of the system
{(95%, dibenzofuran + 5 w/w %, asphaltenes) + n-
eicosane} determined at 406.6 K. The second curve
shown in the same figure corresponds to the enthalpy
of mixing of the system {dibenzofuran + n-eicosane}.
The presence of asphaltenes causes a dramatic change
of the heat flux. The positive enthalpy of mixing of the
binary {C20H22-DBF} is shifted toward negatives val-
ues. The shift is proportional to the n-alkane content.
Therefore, the contact of n-eicosane with asphaltenes
(precipitated or dissolved) generates an exothermic heat
flux.
According to these results, it might be thought that
n-alkane present in the {asphaltenes + n-alkanes} alloy
is partly bonded with asphaltenes and partly loses the
mobility characteristic for molecules in the liquid state.
3.3. Enthalpies of Fusion of n-Alkanes in the
Presence of Asphaltenes. With the view to confirm
previously described results, we used differential scan-
Calorimetric Probing of n-Alkane-Petroleum Interactions Energy & Fuels, Vol. 19, No. 6, 2005 2477

Figure 6. Heat of mixing at T ) 406.6 K of systems b

{dibenzofuran (1) + C20H42 (2)} and O {(dibenzofuran, 95 mol
% + asphaltenes) (1) + C20H42 (2)}. The negative value of the
heat of mixing at x ) 0 corresponds to the thermal effect of
mixing of {asphaltenes + dibenzofurane}; the value observed
at x ) 1 is the heat of mixing of the system {asphaltenes +
C20H42}. Figure 8. DSC thermal curve of (a) pure C36H74 and (b)
{asphaltene + C36H74, 70 mol %}.

Figure 7. DSC thermal curve of asphaltenes.

ning calorimetry to determine the enthalpy of fusion of

a series of long-chain n-alkanes at different ratios of
asphaltenes and n-alkanes. All samples of {asphaltenes
+ n-alkanes} were heated to the melting temperature
and then were quenched with liquid nitrogen. This
preparation of samples should freeze a partial im- Figure 9. DSC thermal curve of (a) pure C28H58 and (b)
{asphaltene + C28H58, 70 mol %}.
mobilization of n-alkanes attained during the n-alkane
melting. The thermal curve of asphaltenes determined
between 330 and 570 K, Figure 7, does not show
significant heat effects below 400 K. Thus, no heat effect
inherent to asphaltenes themselves would interfere with
the melting process of n-alkanes. Enthalpies of n-alkane
fusion were investigated with a series of mixtures
{asphaltenes + (n-CmHm+2; m ) 20, 28, and 36)}
containing between 10 and 90 mol % of asphaltenes. The
mole compositions were calculated assuming for as-
phaltenes M ) 1000. Thermal curves corresponding to
the melting of pure n-alkanes are presented in Figures
8a, 9a, and 10a. In the case of n-octacosane and of
n-hexatriacontane, a first-order solid-solid transition
is observed a few Kelvins below the melting tempera-
ture. Selected results obtained with n-eicosane, n-
octacosane, and n-hexatriacontane are presented in
Figures 8b, 9b, and 10b. Neither melting nor rotator Figure 10. DSC thermal curve of (a) pure C20H42 and (b)
transition temperature of n-alkanes are significantly {asphaltene + C20H42, 60 mol %}.
altered by the presence of asphaltenes. A small lowering
of melting temperatures is probably due to the presence lower in respect to the expected value. As stated above,
of small quantities of hydrocarbons in asphaltene. In this difference might be attributed to n-alkanes-as-
most cases, the enthalpy of fusion of n-alkane is slightly phaltenes interactions.
2478 Energy & Fuels, Vol. 19, No. 6, 2005 Mahmoud et al.

Figure 11. P, mole percent of n-alkane (CnH2n+2) bonded to

asphaltene in function of the n-alkane concentration in the
sample O: n ) 20, 9: n ) 28, 2: n ) 36.

The number of CH2 segments of the alkyl chain

trapped in the asphaltene structure was previously
estimated to be between seven and nine.11 Assuming
that eight segments of each molecule of n-alkane are
partly immobilized, the observed enthalpy of melting
should be, respectively, 12/20, 20/28, and 28/36 of the
enthalpy of melting of pure n-eicosane, n-octacosane,
and n-hexatriacontane, respectively. These values would
be observed if all molecules of the n-alkane were bonded
to asphaltenes. Experimental results of the heat of
fusion data obtained with DSC were usually lower than
∆FUSH of the pure n-alkane but higher than [(n-8)/n]
∆FUSH and probably corresponded to the melting of both
species. Accordingly, the actual value of the ∆FUSH was
used to calculate P, the percent of alkane molecules
trapped in the asphaltene network.
As is shown in Figure 11, results obtained with three
n-alkanes studied follow the same curve.
The maximum of this curve is located at 40% of
asphaltenes and corresponds to 25% of immobilized
molecules of n-alkane. In reality, this value is probably
higher because of the partial compensation of exother-
mic and endothermic effects. The negatives values of P
observed at low and high asphaltene concentrations
indicate that in these ranges the endothermic effect is
predominant. Consequently, the more realistic value of
P might be obtained by shifting the experimental curve
toward higher values in a way to math its extremities
with the coordinate origin (X ) 0, P ) 0 and X ) 1, P )
0). In this case, the maximum value of P is of about 44%.
Thus, the ratio of bonded to free n-alkanes of about 1 is
observed at the molar ratio asphaltenes/alkanes of about
1 (40 mole percent of asphaltenes), This implies that
one monomeric asphaltene can bond one-half of n-
alkane molecule. However, asphaltenes aggregate eas-
ily, and the number of contacts between n-alkanes and
stable aggregates of asphaltenes is physically more
relevant. Assuming that the smallest stable aggregate
is composed of five to six monomers, we conclude that
one elementary asphaltene aggregate may bound three
molecules of n-alkane.
3.4. Influence of Asphaltenes on the Liquid-
Solid Solubility Diagram {n-Eicosane or n-Hexatri-
acontane + Dibenzofuran}. According to previously
discussed results, the presence of asphaltenes should
influence phase equilibria of mixtures {aromatics +
n-alkanes}. We verified this assumption determining
solubility diagrams at 400 K of the systems {(95%,
Figure 12. (a) Solid liquid equilibrium diagrams of b:
{dibenzofuran (1) + C20H42 (2)} and O: {(dibenzofuran, 95 mol
% + asphaltene) (1) + C20H42 (2)}. (b) Solid liquid equilibrium
diagrams of b: {dibenzofuran (1) + C36H74 (2)} and O:
{(dibenzofuran, 95 mol % + asphaltene) (1) + C36H74 (2)}
dibenzofuran + 5%, asphaltenes) + n-eicosane or n-
hexatriacontane}. In the case of ternary mixtures, all
samples contain the constant ratio aromatic/asphaltene
) 20. Results obtained are compared in Figure 12 with
binary data {dibenzofuran + n-eicosane or n-hexatria-
contane} published previously.13
A small systematic deviation exists between two
solubility curves. In the presence of asphaltenes, the
aromatic deposing curve is lowered and the alkane
deposing curve is raised. The hypothesis that asphaltene
(dissolved or precipitated) retains a part of n-alkane
implies that the material balance of the phase equilib-
rium has changed. This means that a certain quantity
of n-alkane does not participate in establishing the
phase equilibrium. This hypothesis explains satisfac-
torily a shift of the solubility diagram induced by
asphaltenes.
4. Conclusions
All calorimetric results presented and discussed in
this work may be explained on the basis of the hypoth-
esis that interactions of asphaltenes with n-alkanes lead
to a partial immobilization of the n-alkane chains. This
phenomenon can be attributed to a partial “dissolution”
of n-alkanes in the protecting shell formed by aliphatic
lateral chains of asphaltenes. The “quasi-solid” charac-
Calorimetric Probing of n-Alkane-Petroleum Interactions
ter of partly immobilized n-alkanes facilitates the
nucleation and the subsequent deposition of waxes.
On the other hand, dissolution of n-alkanes in the
protecting shell of asphaltenes may modify the stability
of asphaltenes and induce flocculation.
Present results are consistent with previously pub-
lished results11 and confirm the idea that the presence
of asphaltenes modifies not only solvent properties of
Energy & Fuels, Vol. 19, No. 6, 2005 2479
the crude oil but also structures resulting from the self-
assembling of petroleum molecules.
Acknowledgment. We thank the Centre National
de Recherche Scientifique and Total for financing this
research. R.M. acknowledges the Ministère de la Re-
cherche et la Technologie d’Algérie for the fellowship.
EF050161U