Fuel 85 (2006) 1–11

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Molecular size and weight of asphaltene and asphaltene solubility

fractions from coals, crude oils and bitumen
Sophie Badrea, Cristiane Carla Goncalvesa, Koyo Norinagab,
Gale Gustavsona, Oliver. C. Mullinsa,*
a
Schlumberger-Doll Research, OFS, Old quarry Road, Ridgefield, CT 06877, USA
b
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Sendai 980-8577, Japan
Received 4 May 2005; received in revised form 31 May 2005; accepted 31 May 2005
Available online 28 June 2005

Abstract
The molecular weight of asphaltenes has been a controversy for several decades. In recent years, several techniques have converged on the
size of the fused ring system; indicating that chromophores in virgin crude oil asphaltenes typically have 4–10 fused rings. Consequently, the
molecular weight debate is equivalent to determining whether asphaltenes are monomeric (one fused-ring system per molecule) or whether
they are polymeric. Time-resolved fluorescence depolarization (FD) is employed here to interrogate the absolute size of asphaltene molecules
and to determine the relation of the size of the fused ring system to that of the corresponding molecule. Coal, petroleum and bitumen
asphaltenes are compared. Molecular size of coal asphaltenes obtained here by FD-determined rotational diffusion match closely with
Taylor-dispersion-derived translational diffusion measurements with UV absorption [1]. Coal asphaltenes are smaller than petroleum
asphaltenes. N-methyl pyrrolidinone (NMP) soluble and insoluble fractions are examined. NMP soluble and insoluble fractions of
asphaltenes are monomeric. It is suggested that the ‘giant’ asphaltene molecules reported from SEC studies using NMP as the eluting solvent
may actually be the expected flocs of asphaltene which are not soluble in NMP. Data is presented that intramolecular electronic relaxation in
asphaltenes does not perturb FD results.
q 2005 Elsevier Ltd. All rights reserved.

Keywords: Asphaltene; Molecular weight; bitumen

1. Introduction changes, viscosity, and interfacial properties of crude oils

Asphaltenes are the most complex component of crude
oil [2–5]. The term asphaltene is defined operationally;
asphaltenes are defined to be toluene soluble and n-heptane
insoluble. Other similar asphaltene definitions exist impact-
ing derived properties somewhat. This definition is actually
quite useful and not arbitrary in that it captures the most
aromatic component of crude oil. This definition does
correspond to a fraction of coal, but asphaltene is not the
most aromatic component of coal. Asphaltenes are a friable,
infusible solid microcolloidally suspended in crude oil.
They are characterized by complex chemistry and their
presence in crude oils impacts the oil properties. Phase
* Corresponding author. Tel.: C1 20 3431 5572; fax: C1 20 3438 3819.
E-mail address: omullins@ridgefield.oilfield.slb.com (O.C. Mullins).
0016-2361/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2005.05.021
are strongly affected by asphaltenes. The lack of proper
understanding of asphaltenes has limited the predictive
capabilities of petroleum science. Francis Crick advises “if
you want to understand function, study structure” [6].
Correspondingly, if the structure of asphaltenes is unknown
to within one or several orders of magnitude, then predictive
science is precluded and phenomenological approaches
prevail. Such is the case particularly for properties of crude
oils where asphaltenes play a key role. The new field of
petroleomics necessarily requires resolution of the asphalt-
ene molecular weight debate. The premise of petroleomics
is the prediction of structure based on function. First, one
must have proper asphaltene molecular structures.
Many bulk properties of asphaltenes are known well.
The saturate to aromatic carbon is known from 13C NMR
studies [7]. X-ray Raman spectroscopy (XRRS) has shown
that the overall geometry of the ring systems is largely
pericyclic [8] as expected from chemical stability
considerations. The sulfur [9] and nitrogen [10] chemical
2 S. Badre et al. / Fuel 85 (2006) 1–11
moieties are known from X-ray absorption near edge
structure (XANES). Infrared spectroscopy (IR) and NMR
has shown that (petroleum) asphaltene hydrogen resides
mostly on saturated carbon [7]. The size of the aromatic
ring systems has been imaged directly by scanning
tunneling microscopy (STM) [11]. High-resolution, trans-
mission electron microscopy (HRTEM) studies yield the
same size of the rings systems as STM; although of lower
resolution, HRTEM can naturally sample a much larger
sample size [12]. STM [11] and HRTEM [12] both
indicate that there are about 6–7 fused rings in petroleum
asphaltenes on average. Optical absorption and fluor-
escence spectroscopy [13–15], when coupled with mol-
ecular orbital calculations [16] provide guidance as to the
ring size within the standard quantum-particle-in-a-box
precepts. At present, there is little controversy surrounding
these bulk parameters. All techniques that speak to ring
size support a conclusion of 4–10 rings in typical virgin
crude oil asphaltene molecules.
The one area of asphaltene molecular structure that has
been the most controversial is that of asphaltene molecular
weight. Results in the literature vary by significantly more
than one order of magnitude for asphaltene molecular
weight. Because there is general agreement about the
constituent molecular fragments of asphaltenes (e.g. size of
fused ring systems, size of alkane substituents, etc.), the
debate regarding asphaltene molecular weight reduces to
whether asphaltenes are monomeric or polymeric. For
instance, one structure proposed for asphaltenes from
athabasca bitumen showed a cross-linked network of
aromatic ring systems—essentially a polymer, although
the authors of the report expressed significant uncertainty
regarding their determination of the proper molecular
weight [17]. (We thank the authors for pointing this out.)
The chemical and physical properties of monomers differ
enormously from the corresponding polymers; it is essential
for the advancement of petroleum science to resolve the
debate on the molecular weight of asphaltenes.
In a series of publications, our laboratory has shown that
FD strongly supports the monomeric description of
asphaltenes. The FD technique works by measuring the
rate of rotational diffusion of molecules in dilute solution.
First, FD has shown that asphaltene molecules undergo rapid
rotational diffusion, approximately the same rate as
molecules in w750 g/mol range [18–22]. Second, the large
wavelength dependence of the rotational diffusion times
shows that for each asphaltene molecule, a single chromo-
phore is a large part of the molecule, thus, there must be one
or sometimes two chromophores (fused ring system) per
molecule [18–22]. Third, FD has shown that large
chromophores require substantial alkane substitution while
small chromophores mandate minimal alkane substitution
[20]. This is interpretable in terms counterbalancing forces
controlling molecular solubility. In asphaltenes, there is a
balance of opposing effects; p-bond stacking (via Van der
Waal’s force) reducing solubility vs steric repulsion of
alkane chains increasing solubility. Fourth, the trend towards
smaller asphaltenes in mildly thermally cracked feedstock
results from the loss of alkane groups reducing steric
disruption thereby mandating smaller ring systems for the
same solubility class [22]. Fifth, the FD analysis of solubility
subfractions of asphaltenes shows that asphaltene properties
grade continuously from one subclass to the next; there is no
large discontinuity of asphaltene properties [21]. Monomeric
asphaltenes, but not polymeric asphaltenes are consistent
with these extensive FD results. Furthermore, Taylor-
dispersion measurements of translational diffusion [1]
performed on coal asphaltenes match the FD-derived
rotational diffusion measurements. Agreement between
two very different techniques with very different detection
methods confirms the validity of both sets of studies.
Of course, mass spectroscopy (MS) can also be used
to obtain molecular weight. In an early study, field-
ionization mass spectroscopy (FIMS) was used and an
asphaltene molecular weight of w700 g/mol was obtained
[23]. Laser-desorption mass spectroscopy (LDMS) has
resulted in various and inconsistent asphaltene molecular
weights [1,24–26]. One LDMS study obtained w500 g/mol
for asphaltenes [24]. This study noted the extreme care that
is required for baseline subtraction. Electrospray-ionization
Fourier-transform ion-cyclotron resonance mass spec-
troscopy (ESI-FT-ICR-MS) has been used on heavy oils
and similar materials finding molecular mass consistent
with the monomeric description of asphaltenes [27,28].
Atmospheric pressure chemical ionization mass spec-
troscopy (APCI-MS) has been used on asphaltenes yielding
molecular weights w700 g/mol [29]. The only mass
spectral technique that seems to provide self-contradictory
results is LDMS; ironically, this technique remains popular
for determination of asphaltene molecular weight in certain
laboratories.
One sustaining source for the molecular weight
controversy is that asphaltenes are known to aggregate at
low concentrations. Surface tension measurements have
shown that asphaltenes exhibit a critical nanoaggregate
concentration (CNAC) at w400 mg/l in pyridine [30]. (A
terminology change is being attempted per reviewers’
request; the term nanoaggregate is replacing micelle for
asphaltenes.) Microcalorimetry also shows asphaltene
aggregation (likely not primary aggregation) but at much
higher concentrations and in the presence of some dissolved
water in the toluene [31]. Recent high-Q, ultrasonic spectral
studies of asphaltenes clearly show asphaltene CNAC in the
range of 50–150 mg/l [32,33]. Furthermore, it has been
shown that removing the more soluble component of a
whole asphaltene leads to a remaining fraction that exhibits
a much lower solubility [34]. The likely explanation is that
above CNAC, a nanocolloidal dispersion is stable for the
whole asphaltene—appearing to be a solution, but for the
more monodisperse low solubility asphaltene component,
initial aggregation above the CNAC, does not result in a
stable nanocolloid but proceeds to floc formation.
 S. Badre et al. / Fuel 85 (2006) 1–11
Any techniques that report molecular weight by making
measurements on solutions such as vapor pressure osmo-
metry (VPO) or Size Exclusion Chromatography (SEC)
need to account for aggregation. The large molecular
weights reported for asphaltenes from these techniques are
most likely due in part to the measurement of aggregate
weight, not molecular weight. This problem is exacerbated
for asphaltene fractions whose preparation is based on low
solubility, such as for NMP-insoluble asphaltene fractions.
Any description of asphaltenes must be consistent with
the observation that properties of asphaltenes vs resins and
asphaltene subfractions vary continuously. The defining
characteristic of asphaltenes—solubility—necessarily
grades continuously from resins—by definition. Further-
more, subfractions of asphaltenes obtained by changing
solvent ratios necessarily grade continuously in solubility.
Asphaltene solubility subfractions have also been shown to
grade continuously one into the next with respect to
molecular size [21]. Asphaltene molecular properties have
also been shown to grade continuously into resins, the next
heaviest fraction of crude oil [19]. That is, there is no large
discontinuity in asphaltene properties. One should not be
confused with the distinct rheological properties of
asphaltenes and resins that most likely simply have to do
with intermolecular binding energy vs temperature. Con-
sider the rheological difference of the oil n-hexadecane and
the waxy n-heptadecane, all at room temperature; their
chemistry is nearly identical. Furthermore, crude oils and
asphaltenes exhibit the Urbach tail phenomenon in the
electronic absorption edge [15]—a result familiar in
condensed matter physics [35]. This observation indicates
large ring systems grow from small ring systems. Again, the
electronic absorption edge of crude oils grades continuously
into that of asphaltene; there is no large discontinuity.
Consequently, the view that asphaltenes are bimodal in
properties [26] is inconsistent with many observations and
with the solubility classification of asphaltenes.
There is a study based on Size Exclusion Chromatog-
raphy (SEC) that claims there is a large molecular weight
fraction of asphaltenes [36]. In fact, this study finds that
asphaltenes and other comparable carbonaceous species are
bimodal in their molecular weight distribution. In this SEC
study, the two very different ‘molecular’ weight components
are separated rather cleanly by many SEC peak widths [36].
We find such description of asphaltene molecular weight to
be highly improbable and view one should search for
alternate explanations. For some reason, this study
employed NMP as the eluting solvent. As is established
here and elsewhere [37], asphaltenes are not totally soluble
in NMP. There is an NMP-soluble fraction and an NMP-
insoluble fraction in asphaltene. We view that the far more
likely explanation for a strongly bimodal distribution of
mass obtained in these NMP SEC studies is due to partial
dissolution of asphaltene in the NMP. Perhaps the
description is: the NMP-soluble component eluted slowly
in accord with its low molecular weight. The NMP-insoluble
3
asphaltene forms floc in NMP which then went rapidly
through the column. This explanation should be tested by
using an SEC solvent that asphaltenes are known to dissolve
in—say toluene—and comparing with the study cited using
an SEC solvent that asphaltenes are known not to dissolve
in—NMP. The authors did note that this SEC peak for the
very large asphaltene molecules was not obtained when
THF was used as the solvent (although other difficulties
were mentioned) [36].
Previously, a single coal asphaltene was compared to
several petroleum asphaltenes [20]. The principle finding
was that alkane chain length scaled with the size of the
asphaltene molecule and also with the asphaltene chromo-
phore (the aromatic ring system). The solubility classifi-
cation of asphaltenes mandates a balance between
intermolecular attraction via van der Waals interaction vs
steric hindrance disrupting binding. Direct observation of
ring stacking via HRTEM supports the contention that
alkanes disrupt stacking [12]. It is conventional wisdom that
in general coal asphaltenes are smaller than petroleum
asphaltenes; this must be tested.
In this report, we extend our FD results comparing
several coal asphaltenes with petroleum asphaltenes; certain
systematics are obtained. FD interrogation of asphaltene
solubility subfractions is extended to include N-methyl
pyrrolidinone (NMP) solubility as the solvent. We also
include Athabasca bitumen as the source material to test
systematics of asphaltene properties. The FD results
obtained here bolster conclusions drawn from previous FD
work.
2. Experimental section
The specifics of how we employ FD have been described
elsewhere [18–22]. Here, the fundamentals of FD are
briefly described. FD employs a laser polarized in the lab
frame to define a unique axis. The solvent used for FD was
toluene at room temperature unless otherwise specifically
stated. Absorption of polarized photons gives an ensemble
of polarized asphaltene molecules. Rotational diffusion
reduces the extent of molecular alignment; after a
sufficiently long period of time, no polarization remains.
The time dependence of the polarization is measured using
a fast pulse on a photomultiplier tube (PMT) attached to the
emission monochromator of a fluorescence system. Our
measurements were made using a PTI time-resolved
fluorescence spectrometer. The system contains a C-72
fluorescence lifetime spectrometer with a PTI A-720
steady-state fluorescence spectrometer. The C-72 system
employs a nitrogen-pumped dye laser to excite the
fluorescence. Various Exciton dyes were used to cover
our excitation range. The dye laser output was sent through
a Glan–Thompson polarizer of known orientation and then
used to excite a dilute solution of asphaltenes. The
fluorescence emission at 908 was imaged onto an entrance
4 S. Badre et al. / Fuel 85 (2006) 1–11
slit of the emission monochromator fitted with a second
Glan–Thompson polarizer. The corresponding photomulti-
plier was pulsed so as to acquire signal only over a short
time window. With the polarization decay from a standard
to characterize the laser pulse, deconvolution software from
PTI was employed to obtain the rotational correlation.
We utilize several wavelengths in order to interrogate
different asphaltene fractions in a single solution. A red shift
of 40 nm (increase in emission wavelength over excitation
wavelength) is typically employed. This is essentially the
Stokes shift—the energy difference between excitation and
emission between two electronic states of a molecule in
solution. A larger red shift can lead to electronic thus,
polarization relaxation in the excited state manifold. A
smaller red shift can give rise to improper detection of
scattered excitation light in the emission channel altering
the polarization curve. In these experiments, the asphaltenes
are typically in a concentration range of 10 mg/l. Using
750 g/mol (our result) for asphaltene molecular weight, this
gives a solution of w13 mM. Recent ultrasonic experiments
show that the CNAC of asphaltenes is significantly higher in
concentration than this (CNACw100 mg/l) [32,33].
Fig. 1 shows a typical set of decay curves that are acquired
in order to determine fluorescence depolarization. The four
possible (908) combinations of the two polarizers, one on the
excitation side, the other on the emission side, are employed.
The horizontal excitation, vertical emission (designated as
H–V) and the H–H configurations produce curves that
overlay. The initial polarization that decays away with time is
shown by the initial separation in the V–H and V–V curves.
This polarization decay and the fitted curve are also shown in
Fig. 1.
To measure the decay curve, it is always necessary to
measure the response from a system that yields scattering
100
VV
Difference
HV Least SquareFit
80 VH
HH
Counts (/103)
60
40
20
0 0
64 66 68 70 72 74
Time (ns)
Fig. 1. The raw data curves utilized in FD. By measuring the time
dependence of the four 908 linear polarization combinations for incident
and fluorescent photons, one can measure the rate of polarization decay
(also shown) due to molecular rotation.
alone. We have used two candidate references, deionized
water and ludox (colloidal suspension of latex spheres).
They give slightly different results for several wavelengths;
the ludox scatterer often shows slightly better performance
at several wavelengths, but much worse results at one
wavelength. Consequently, we have chosen to keep water as
our reference because the dispersion is a very important part
of the results. The standard is not that important in our
experiments because (1) this choice has relatively small
effect on absolute rotational correlation times; and (2) the
depolarization curves for the model compound used for
comparison are influenced in exactly the same way as the
corresponding curves for asphaltenes—thus, the differential
comparison does not change at all.
The asphaltene samples were prepared using 40cc
n-heptane added per gram of crude oil (or bitumen). After
24 h with occasional stirring, the resulting asphaltene
precipitate was washed with n-heptane until it was colorless.
The resulting asphaltene was dissolved and the same
precipitation process was followed a second time. We
refer to these samples as n-heptane asphaltenes. We have
performed various FD and sulfur XANES studies on the first
and second precipitations but we have never observed any
effect from this second precipitation process. Nevertheless,
we do so for completeness.
The N-methyl pyrrolidinone (NMP) samples (all from
UG8 asphaltene) were prepared by dissolving 25 mg of
n-heptane UG8 asphaltenes in 50 ml of toluene. 100 ml of
NMP was then added. After 18 h, the solution was filtered.
The precipitated solid was then filtered. After drying, this
solid was dissolved in minimum toluene and precipitated
with excess NMP. The resulting solid was labeled as NMP
insoluble. The solution from this second process was labeled
as NMP soluble. The soluble portion from the first solution
is comparable in spectra and in tr, consequently, we list
parameters and spectra for the second solution only.
25
Coal asphaltenes were prepared from Illinois (IL) and
Pocahantas (POC)coals (Argonne Premium Coal Samples,
20
http://www.anl.gov/PCS/) and liquefaction products from
Banko coal. Extraction and fractionation procedures were
followed by Iino et al. [38]. Dried Illinois and Pocahantas
coals were extracted with pyridine. The pyridine soluble
15
portions were subsequently fractionated into toluene
solubles and insolubles. The toluene solubles were further
10 fractionated into n-hexane solubles and insolubles (asphalt-
ene). The yields of asphaltenes were 8 and !1 wt% (daf)
from IL and POC coals, respectively. Banko (BA) coal was
5 liquefied with tetralin at 400 8C, under 9 MPa hydrogen
pressure for 30 min [39]. The liquefaction products were
recovered with THF. The THF soluble portions were
76 extracted with toluene and further fractionated with
n-hexane to get asphaltene (toluene soluble/n-hexane
insoluble). The asphaltene yield from Banko coal was
30 wt% (daf).
Table 1 lists the elemental weight percent for the various
asphaltenes and Athabasca bitumen. These data were
 S. Badre et al. / Fuel 85 (2006) 1–11 5

Table 1
The elemental mass fractions various petroleum asphaltenes, coal asphaltenes and a bitumen

Asph sample C H N O S C:H

UG8 81.07 7.11 1.02 1.6 8.94 1:1.045
Athabasca 77.03 8.01 1.27 3.00 8.18 1:1.239
Ven20 84.75 7.81 1.75 1.72 4.57 1:1.098
Denver Citya 72.63 6.58 0.75 3.19 5.32 1:1.1080
Iino 90.35 5.53 2.23 1.9 !0.23 1:0.729
Ill #8 80.98 6.52 1.33 8.80 0.39 1:0.960
BA 79.23 6.19 1.49 1.36 0.39 1:0.931
Athasaca Bitumenb 83.72 10.39 !0.5 15.03 4.73 1:1.479
a
Pipeline deposit.
b
Bitumen sample, not an asphaltene.

obtained from Galbraith Laboratories, Knoxville, TN. The
petroleum asphaltenes; UG8, Athabasca, Ven20 and Denver
City have H–C atomic ratios exceeding one, while the coal
asphaltenes; Ill#8, BA and Iino have H–C ratios less than
one. The Iino coal sample (from Tanito Harum coal) has an
H–C ratio much less than one.
Some fluorescence lifetime data shown herein which will
be identified was acquired on Beamline U9B at the National
Synchrotron Light Source at Brookhaven National Labs.
3. Data interpretation
As described elsewhere [18 and references therein], the
following definitions are used
TðtÞ Z Is ðtÞ K It ðtÞ
experiment, can now be written as:
Vh
tr Z (6)
kT
It is straightforward to check this analysis by measuring
known dye compounds and comparing the resulting
molecular size with calculated results. These known
references allow the molecular weight to molecular size
correlation to be made.
Finally, the impact on the rotational correlation time of
having asymmetric tops has been discussed in detail. (cf
Ref. [18, 21] and references therein). From Eq. (6) one can
obtain a molecular radius from the rotational correlation
time assuming the molecule is a sphere. The derived radius
increases by 12.4% for the long axis if assumes an oblate
spheroid shape with an aspect ratio of 2 [21]. We presume
asphaltenes are oblate spheroids with an aspect ratio of 2 for
(1) our analysis.

SðtÞ Z Is ðtÞ C 2It ðtÞ (2)

4. Results and discussion
and
4.1. Asphaltenes; coal vs petroleum
TðtÞ
rðtÞ Z (3)
SðtÞ Fig. 2 shows the FD data for several coal asphaltenes vs
where Ijj ðtÞ and It ðtÞ denote the detection of intensity of UG8 (petroleum) asphaltene; the coal asphaltenes exhibit
light linearly polarized parallel and perpendicular to the trends similar to the petroleum asphaltenes. The trs are not
polarization axis of the excitation beam and r(t) represents large when compared to those of model compounds and
the anisotropy of the fluorescence emission. For spherical increase as the emission wavelength increases. Coal
rotors, the following equation applies: asphaltenes have tr smaller than those for petroleum
asphaltenes meaning that at a given interrogation wave-
2 length, coal asphaltene molecules are smaller than those of
rðtÞ Z eK6Dt : (4)
5 petroleum asphaltenes. Furthermore, the coal fluorescence
spectra peak at shorter wavelengths than the petroleum
The impact of molecular asymmetry has been checked asphaltenes as seen in Fig. 3. Consequently, the coal
[18,21]; it is not large. For a sphere, the following equation centroid for molecular size is shifted to shorter wavelength
applies: and smaller tr compared to petroleum asphaltenes. (More
kT extensive fluorescence spectra of petroleum asphaltenes are
6D Z ; (5) published elsewhere [13]; UG8 asphaltene exhibits a typical
Vh
petroleum asphaltene fluorescence spectrum.) Conse-
where V is volume of the molecule, h is viscosity of the quently, coal asphaltenes are characterized by a much
solvent, and D is solute rotational diffusion coefficient. The smaller tr, roughly comparable to that of OEP which has a
decay time of the anisotropy, tr, the parameter of our molecular weight of 535 g/mol. It is possible the coal
6 S. Badre et al. / Fuel 85 (2006) 1–11

Asphaltene w0.7 nm. Fig. 2 confirms that the coal asphaltene molecules
0.8 are smaller. Fig. 3 shows that the coal asphaltenes have
UG8 CrudeOil
0.7 BA Coal shorter wavelength emission indicating that coal asphaltene
POC Coal ring systems are smaller than petroleum ring systems. Fig. 4
IL Coal
0.6 solar dye shows the coal asphaltenes are much lower in coloration
OEP (optical absorption in the visible) than petroleum asphalt-
− τr 0.5
enes, even though coal source materials for these
(ns)
0.4 asphaltenes are black. Thus, petroleum asphaltenes have
larger fused ring systems than coal asphaltenes. As shown
0.3 previously, coal asphaltenes lack alkane substitution
0.2 relative to petroleum asphaltenes [20]. The universal
asphaltene solubility definition mandates a balance of
0.1 attractive and repulsive molecular forces. Coal asphaltenes,
0
lacking alkanes, lack intermolecular repulsion. Conse-
400 450 500 550 600 quently, they must exhibit weaker intermolecular attractive
Emission Wavelength forces; this mandates smaller fused ring systems. The lack
Fig. 2. Rotational correlation times tr for several coal asphaltenes, one of long wavelength absorption in coal asphaltenes relative to
crude oil asphaltene and two known compounds. petroleum asphaltenes in Fig. 4 shows the lack of large
fused ring systems in coal asphaltenes relative to petroleum
asphaltenes are smaller than OEP; the limits of our time- asphaltenes.
resolved fluorescence depolarization system is approxi- The molecular size obtained here for coal asphaltenes
mately 100 ps, which is our measured correlation time for matches exactly the results obtained previously using a very
OEP. Thus, we lose resolving power for molecules smaller different technique. Taylor-dispersion measurements with
than OEP. The molecular size of OEP obtained by FD is UV absorption have been performed on dilute solutions of
very close to that obtained for OEP and other similar coal asphaltenes in a variety of solvents [1]. Taylor diffusion
porphyrins by a very different technique; perturbed angular determines the translational diffusion constant, FD deter-
correlation of gamma rays [40]. Thus, we believe we have mines the rotational diffusion constant. The Taylor diffusion
accurately measured the correlation time for OEP here. experiments used UV absorption for detection of asphalt-
Table 2 lists the parameters that are measured and enes; FD relies on fluorescence emission. The fact that these
derived for the coal asphaltenes, UG8 petroleum asphaltene very different techniques obtain the same centroid and range
and the model compounds. These values for both the coal of asphaltene molecular size is very encouraging. Table 1
and the crude oil asphaltene molecular size are consistent shows that coal asphaltene molecular size is w12 Å in
with corresponding HRTEM results [12]. Direct imaging of diameter (at the fluorescence maxima); Taylor-dispersion
the fused aromatic ring systems by HRTEM shows that the finds coal asphaltene molecular diameters to be w11 Å [1].
petroleum asphaltene ring systems are w1 nm in linear In addition, LDMS was used on the coal asphaltenes to
dimension while the coal asphaltene fused ring systems are obtain the molecular weight.
Petroleum asphaltenes have a correlation time compar-
able to the solar dye which has a molecular weight of
1
755 g/mol. These results support what was observed for one
coal asphaltene previously [20]. As shown previously, the
smaller fraction of alkane carbon in coal shown by 13C
Fluorescence Intensity (norm)

0.8
NMR yields less steric repulsion [20]. The smaller steric
repulsion must be balanced by smaller intermolecular
0.6 attraction to maintain constant solubility; thus, coal
aromatic ring systems are smaller. That is, alkane steric
UG8 repulsion balances p–p intermolecular attractive inter-
0.4
POC actions to maintain the same solubility—which is the
BA property that defines asphaltenes. At a given interrogation
0.2 wavelength in Fig. 2, the coal asphaltenes are seen to be
smaller than the petroleum asphaltenes. This is due in part to
the smaller alkane fraction of coal asphaltenes. The C:H
0 ratios for coal asphaltenes are much higher than for
350 400 450 500 550 600
petroleum asphaltenes (cf. Table 1) reflecting the lack of
Fluorescence Emission Wavelength (nm)
alkane substituents in coals.
Fig. 3. The fluorescence spectra of different asphaltenes, UG8 petroleum By spanning a large range in wavelength in Fig. 1, we can
asphaltene and POC and BA coal asphaltenes. interrogate different chromophores. Small chromophores
 S. Badre et al. / Fuel 85 (2006) 1–11 7

Table 2
tr values and corresponding molecular diametersa or known compounds and for different coal and oil asphaltene samples at different wavelengths

l Emission OEP (ns) (Å) Solar Dye (ns) (Å) UG8 (ns) (Å) BA (ns) (Å) POC (ns) (Å) IL (ns) (Å)
410 0.18 ns 14.9 Å
450 0.088 ns 11.7 Å 0.32 ns 18.1 Å 0.13 ns 13.4 Å 0.11 ns 12.7 Å 0.092 ns 11.9 Å
480 0.4 ns 19.5 Å 0.24 ns 16.4 Å 0.21 ns 15.7 Å 0.165 ns 14.5 Å
520 0.56 ns 21.8 Å 0.36 ns 18.8 Å 0.35 ns 18.6 Å 0.22 ns 16.0 Å
570 0.7 ns 23.5 Å
530 0.48 ns 20.7 Å
a
Long axis assuming oblate spheroid, aspect ratioZ2.

are investigated with blue light and large chromophores
with red light. But Fig. 2 also shows that there is roughly an
order of magnitude increase of tr, thus large increase in
molecular size, in going from short wavelength to long
wavelength for the asphaltenes. This indicates that the small
and large chromophores are not linked to each other. If they
were, then (1) large tr would result and (2) little dependence
of tr on wavelength would be observed. Thus, both the
zeroth moment (small magnitude of tr) and first moment
(large wavelength dependence of tr) in Fig. 2 indicate
asphaltenes are monomeric, not polymeric.
Comparison of Table 2 to previous work on the Iino coal
asphaltene sample (Tanito Harum) shows that the samples
that have smaller H–C ratios are characterized by smaller
molecules. That is, the tr for the Iino coal asphaltene sample
[20] are less than for the coal asphaltenes presented here.
Table 1 shows that this Iino coal sample has a much smaller
H–C ratio (0.729) than the other coal asphaltenes measured
here. And all coal asphaltenes we have measured have both
smaller tr and smaller H–C ratios than all petroleum
asphaltenes we have measured. Less alkane substituents
produces smaller asphaltene molecules.
2 1
0.8
1.5
Transmission
4.2. NMP
There has been the suggestion that NMP insoluble
asphaltene fractions are inaccessible to fluorescence
techniques [37]; and that possibly the NMP insolubles are
of a very different molecular weight than the NMP solubles.
This suggestion would be that NMP mysteriously separates
the presumed bimodal asphaltene molecular distribution
into low and high molecular weight fractions. This all seems
improbable to us; we have previously obtained solubility
subfractions of asphaltenes from various solvent systems
and found no large mass fraction [21,22]. Only subtle
differences were found in molecular weight among the
different solubility fractions independent of solvents used.
Again, all mass spectral techniques except laser desorption
ionization exhibit only small molecular masses for
asphaltenes [23,27–29]. And laser desorption techniques
in the literature are conflicting most likely due to the
enormous baseline subtraction issue [24–26]. In any event,
we have obtained rotational correlation data for NMP
solubility fractions.
Table 3 lists this data; molecular diameters for NMP
soluble and NMP insoluble fractions are listed; the
diameters for the NMP insoluble component is somewhat
bigger than the NMP soluble component but the difference
is not nearly an order of magnitude. Note that the tr of the
NMP soluble component is obtained in NMP solvent. We
have previously shown that, as expected, Eq. (6) properly
accounts for viscosity variations [20]. All measured tr are
all quite small and comparable indicating molecules in the
500–1000 g/mol range. Table 3 shows that, as expected,

0.6
Absorption

1
Table 3
tr values for 410 nm excitation, 450 nm emission for UG8 asphaltene and
UG8 Petroleum 0.4 solubility fractions
illinois #8
Iino Coal
Sample tr (ns) Solvent vis- Diameter Diameter
0.5
cosity (cp) (sphere) (Å) (oblate
0.2 spheroidc
Toluene 0.32 0.59 16.1 18.1
soluble
0 NMP 0.65 1.67 14.4 16.2
0
300 400 500 600 700 800 900 1000 soluble
Wavelength (nm) NMP 0.47 0.59 18.3 20.6
insoluble
Fig. 4. The optical absorption and transmission spectra of various petroleum
a
and coal asphaltenes. Long axis, aspect ratioZ2.
8 S. Badre et al. / Fuel 85 (2006) 1–11

the whole asphaltene lies in the middle of the NMP soluble acquired in the same conditions. It is evident the NMP
and NMP insoluble fractions in terms of molecular size. insoluble fraction has a lower fluorescence intensity. This
The NMP insoluble asphaltenes have a much smaller issue needs to be addressed. Some reduction in quantum
fluorescence quantum yield in the concentration range yield is observed when isolating the less soluble asphaltene
where we perform our measurements. Fig. 5 shows the subfractions from toluene–n-heptane mixtures. The larger
fluorescence spectra of the whole asphaltene, the NMP aromatic ring systems are known to be of lower quantum
soluble fraction and the NMP insoluble fraction; all yield due to the Energy Gap Law [13,41]. This basic
photophysical phenomenon does not impede our measure-
ments for interrogating different asphaltene solubility
5
fractions [21,22]. In our experiments, we utilize concen-
λex = 370 nm
trations 10 times below aggregation limits of whole
Fluorescence Instensity (arb.units)

4 NMP Soluble asphaltenes [32,33]. However, if one were to use higher

Whole Asphaltene concentrations, the fluorescence yield can be reduced to
NMP Insoluble
very low values due to collisional quenching [13]. This
3
photophysical effect has been studied in detail using
measurements of quantum yields, fluorescence lifetimes
2 and fluorescence spectra as a function of concentration, oil
type, and excitation wavelength [13]. If experiments do not
prove use of low concentrations, then the corresponding
1
results are in doubt. Furthermore, it has been shown that
asphaltene subfractions can have very different solubility
0 characteristics than the whole asphaltene [34]. In other
350 400 450 500 550 600 650 words, the aggregation and flocculation phenomena can
Wavelength (nm)
4 change depending on the asphaltene fractionation. It is
plausible that the concepts stating NMP insoluble asphalt-
λex = 410 nm enes are not fluorescent and polymeric are incorrect because
Fluorescence Instensity (arb.units)

the corresponding concentrations are too high, the asphalt-

3 NMP Soluble
Whole Asphaltene
enes are aggregated resulting in (1) no fluorescence and (2)
NMP Insoluble large apparent mass (aggregate mass). Recent high-Q
ultrasonic determination of aggregation limits for asphalt-
2 enes in toluene show the petroleum [32] and coal
asphaltenes [33] aggregate at w100 mg/l in toluene, much
lower than previously thought.
1
4.3. Bitumen

0 Fig. 6 compares athabasca bitumen asphaltenes to UG8

400 450 500 550 600 650 asphaltenes; this somewhat different source material gives
Wavelength (nm)
3 asphaltenes of essentially the same size as those of UG8
crude oil. There has been the suggestion that athabasca
λex = 440 nm
asphaltenes consist of aromatic rings systems that are
Fluorescence Instensity (arb.units)

covalently cross-linked [17]. Our data directly refute this

NMP Soluble
2 Whole Asphaltene model. Athabasca bitumen asphaltenes are similar to all
NMP Insoluble other crude oil asphaltenes we have measured; they are
monomeric and are small. Again the wavelength depen-
dence of tr indicates that the single chromophore (aromatic
ring system) interrogated is a large part of the entire
1
asphaltene molecule; there is one chromophore per
molecule.
The prevailing concept is that the solubility classification
of asphaltenes is fairly restrictive chemically thereby
0 preventing wild variations in corresponding molecular
450 500 550 600 650
structure. For grossly different source materials, coal vs
Wavelength (nm)
crude oil, some differences in asphaltene molecular
Fig. 5. The fluorescence spectra for asphaltene fractions; NMP soluble, structure exist, but still the differences are not large. For
NMP insoluble and whole UG8 asphaltene at three excitation wavelengths. asphaltene science, this result is good news. Asphaltenes,
 S. Badre et al. / Fuel 85 (2006) 1–11 9

0.8
UG8 Asphaltene λex=316 nm, λem = 370 nm
0.7
Athabasca
Bitumen UG8 Asphaltene

Fluorescence Intensity
Asphaltene Concentration
0.6
Dilute
1%
τr 0.5
2.5%
(ns)
10%
0.4

0.3

0.2
0.1
400 450 500 550
Fluorescence Emission Wavelength (nm)
Fig. 6. Comparison of Athabasca bitumen asphaltene and UG8 crude
oil asphaltene.
while complex, have underlying simple governing
principles.
It is known that fluorescence quantum yields vary as a
function of various parameters in crude oils and asphaltenes.
There has been speculation in the literature [43], rather
extensive speculation at that, as to whether large ‘archipe-
lago type’ molecular structures could have excessive
intramolecular quenching of fluorescence. These structures
have been proposed for asphaltenes where there are various
islands of fused ring systems cross-linked by alkane chains.
It is known that individual fluorophores can interact in
solution if they become physically close enough—say by
diffusion. Electronic excitation energy of fluorophores can
be transferred to a fluorophore of smaller energy excited
states resulting in red shifted fluorescence emission [14]. In
addition, fluorophore or chromophore interaction in solution
can result in quenching, thus reduced quantum yields [41].
Both processes of energy transfer and electronic energy
quenching are additional decay processes of the electronic
0 10 20 30 40 50
Time (nano seconds)
600
Fig. 7. The fluorescence decay curves for asphaltene toluene solutions at
various concentrations. Intermolecular energy transfer and quenching at
high concentrations cause a dramatic reduction in fluorescence lifetimes.
By measuring lifetimes of dilute asphaltene solutions and
comparing those to deasphaltened crude oil (maltene)
solutions, we can determine if we see a reduction of
lifetimes due to intramolecular relaxation. Thus, we can test
the speculation regarding intramolecular relaxation in
asphaltenes [43]. Fig. 8 shows the fluorescence decay
curves for very dilute solutions of UG8 asphaltenes and the
corresponding UG8 crude oil without asphaltenes (UG8
maltenes). The lifetimes of the two solutions are very
similar and much larger than the fluorescence lifetimes of
concentrated asphaltene solutions [42]. Thus, there is little
or no measurable intramolecular relaxation in asphaltenes.
First, long fluorescence lifetimes as listed in Fig. 8 for dilute
asphaltene solutions are not compatible with extensive
intramolecular relaxation. Second, nobody is (yet) propos-
ing extra large molecular weight components in maltenes.
λ ex=390 ns,
b) λ em = 430 ns
UG8 De-Asphaltened Crude Oil
τ=1.8 ns, 10.1 ns
Fluorescence Intensity

excited state thus necessarily give rise to a reduction of

fluorescence lifetime [44]. Fig. 7 shows what happens to the
fluorescence lifetimes of asphaltenes as relaxation processes UG8 Asphaltene (Dilute Soln.)
increase. By increasing asphaltene concentrations in τ=2.0 ns, 9.4 ns
toluene, relaxation processes of excited electronic states
increase. Fig. 7 shows the fluorescence decay curves for a
series of asphaltene solutions at different concentrations. A
UG8 Asphaltene (10% Soln.)
large reduction of asphaltene fluorescence lifetimes with
τ=0.7 ns
higher concentrations is observed. At the highest concen-
trations, the asphaltene fluorescence decay curve is 5 15 25 35 45 55 65
essentially the lamp function, the lifetime is below Time (nanoseconds)
measurement limit of the system. This occurs because of
the rapid concentration-dependent relaxation mechanisms Fig. 8. The fluorescence decay curves for (top) a dilute toluene solution of
deasphaltened crude oil UG8 (UG8 maltene); (middle) a dilute solution of
that speed up the decay of the fluorescent state. The ‘lamp’ UG8 asphaltenes in toluene; and (bottom) UG8 asphaltene in high
here is Beamline U9B at the National Synchrotron Light concentration (10%) in toluene. Intramolecular quenching effects are
Source at Brookhaven National Labs. absent from the dilute solution lifetime data.
10
a) λex =290 nm, λem= 330 nm
104
NS De-Asphaltened Crude Oil
τ =3.6 ns, 13.5 ns
Fluorescence Intensity
103
NS Asphaltene (Dilute Soln.)
τ = 3.5 ns, 12.1 ns
102
NS Asphaltene (10% Soln.)
τ =0.6 ns
101
5 15 25 35 45
Time (nanoseconds)
Fig. 9. The fluorescence decay curves for (top) a dilute toluene solution of
deasphaltened crude oil NS (NS maltene); (middle) a dilute solution of NS
asphaltenes in toluene and; (bottom) NS asphaltene in high concentration
(10%) in toluene. Intramolecular quenching effects are absent from the
dilute solution lifetime data.
The maltene chromophores are presumed not to be
crosslinked. By comparison, the asphaltene chromophores
are not crosslinked. Monomeric asphaltene molecules
prevail.
Fig. 9 shows the fluorescence decay curves for dilute
solutions of NS asphaltene and for the NS crude oil without
asphaltenes (NS maltenes). This data is for a different
excitation and emission wavelengths than Fig. 8. Again, the
asphaltene and maltene fluorescence decay curves are very
similar and exhibit much longer lifetimes than the
concentrated solution of asphaltene. These data show
there is no intramolecular relaxation in asphaltenes. The
speculations in the literature that intramolecular relaxation
in asphaltenes is dominant are contradicted by this data. The
likely reason is that asphaltenes are primarily monomeric as
all FD results suggests. In addition, other considerations
argue against intramolecular relaxation.
Certainly, energy transfer can take place from blue-
emitting chromophores (large HO–LU gap) [45] to small
HO–LU gap fluorophores. However, red-emitting chromo-
phores cannot transfer energy to large HO–LU gap
chromophores. Toluene is an example of a large HO–LU
gap chromophore (and possible quencher). But energy
transfer to toluene from visible fluorophores does not occur;
in accord with energy conservation. For example, toluene
solutions of fluorophores are highly fluorescent. Thus, our
longest wavelength FD results would be unaffected in any
event by other blue-emitting asphaltene fluorophores. In
addition, the study of bichromophoric molecules connected
by a single alkane chain exhibit the ‘Hirayama’ rule [46].
The Hirayama rule which is generally applicable states that
upon electronic excitation of the bichromophoric molecules,
eximers form only for the connecting chain length of three
carbons, for example, 1,3-diphenyl propane. Other connect-
ing chain lengths preclude eximer formation due to the
difficulty of the linked chromophores to find each other
S. Badre et al. / Fuel 85 (2006) 1–11
within the radiative lifetime. This exact chain length would
not be generally expected in an asphaltene molecule that
possesses two chromophores. Moreover, asphaltenes exhibit
steric interactions further impeding an eximer equivalent.
And asphaltenes would contain multiple alkane links in the
archipelago model further reducing flexibility. Our rather
large anisotropies also indicate that intramolecular energy
transfer is not so large as energy transfer with subsequent
fluorescence greatly reduces anisotropy [18,19]. The
archipelago model for asphaltene molecular structure is
inconsistent with our data.
55 65
5. Conclusions
Fluorescence depolarization studies have proven to be a
powerful and consistent tool to unravel asphaltene complex-
ities. Asphaltene molecules are monomeric with relatively
small molecular weight. Independent of which source
material or which solubility fraction, asphaltenes are
consistently found by FD to be relative small molecules.
Both the zeroth moment (absolute tr) and the first moment
(wavelength dispersion of tr) provide independent, compel-
ling data. These conclusions are in accord with mass
spectral techniques, FI-MS, ESI-FT-ICR-MS, APCI-MS.
Only LD-MS yields self-contradictory results in the
literature most likely over the issue of proper baseline
subtraction. The coal asphaltene results presented here
match closely those previously reported which were
obtained by Taylor-dispersion (coupled with UV absorption
detection). Attempts to disqualify time-resolved fluor-
escence depolarization have the additional problem to
similarly disqualify the Taylor-dispersion studies as well
as most mass spec studies. In addition, both direct molecular
imaging techniques, HRTEM and STM, provide corrobora-
tive results consistent with the FD results. Asphaltenes are
monomeric, not polymeric.
Acknowledgements
We are deeply indebted to Prof. Masashi Iino for
providing us with one of the coal asphaltene samples.
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