1

On the Molecular Nature of

Petroleum Asphaltenes
JAMES G. SPEIGHT1

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Publication Date: January 1, 1982 | doi: 10.1021/ba-1981-0195.ch001

Corporate Research-Science Laboratories, Exxon Research and Engineering

Company, P.O. Box 45, Linden, NJ 07036
SPEROS E. MOSCHOPEDIS
Coal Research Department, Alberta Research Council, 11315-87th Avenue,
Edmonton, Alberta T6G 2C2, Canada
A survey of the methods used to determine asphaltene "structure" indicates that there are serious shortcomings in all of the
methods because of the assumptions required to derive the
molecular formulae. The continued insistence that a complex
fraction such as asphaltenes, derived in a one-step process
from petroleum as a consequence of its insolubility in nonpolar solvents, has a definitive molecular structure is of questionable value to petroleum technology, and it is certainly beyond
the scope of the available methods to derive such formulae.
Asphaltenes would best be described in terms of several
structural types rather than definite molecular structures.

he molecular nature of the asphaltene fractions of p e t r o l e u m a n d b i t u mens has been the subject of numerous investigations (J, 2) b u t determ i n i n g the actual structures of the constituents of the asphaltene fraction has
p r o v e d to be difficult. It is, no doubt, the great c o m p l e x i t y of the asphaltene
fraction that has h i n d e r e d the f o r m u l a t i o n of the i n d i v i d u a l molecular
structures. Nevertheless, the various investigations have brought to light some
significant facts about asphaltene structure; there are indications that asphaltenes consist of condensed aromatic n u c l e i that c a r r y a l k y l a n d a l i c y c l i c
systems w i t h heteroelements (i.e., nitrogen, oxygen, a n d sulfur) scattered
throughout i n various, i n c l u d i n g heterocyclic, locations.
O t h e r basic generalizations also have been noted; w i t h increasing m o l e c u lar weight of the asphaltene fraction, both a r o m a t i c i t y a n d the proportion of
heteroelements increase (S, 4, 5). I n addition, the proportion of asphaltenes i n
Author to whom correspondence should be sent.

0065-2393/81/0195-0001$05.00/0
1981 American Chemical Society
In Chemistry of Asphaltenes; Bunger, J., et al.;
Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

CHEMISTRY OF

ASPHALTENES

petroleum varies w i t h source, depth of b u r i a l , the specific (or A P I ) gravity of

the crude o i l , and the sulfur content of the crude o i l as w e l l as a nonasphaltene
sulfur (5). H o w e v e r , m a n y facets of asphaltene structure still r e m a i n u n k n o w n ,
and it is the purpose of this chapter to b r i n g together the pertinent i n f o r m a t i o n
on asphaltene structure as w e l l as the part p l a y e d b y asphaltenes i n the
physical structure of petroleum and bitumens.
Asphaltene Composition
Asphaltenes are dark b r o w n to black friable solids that have no definite
m e l t i n g point, a n d w h e n heated, usually intumesce, then decompose l e a v i n g a
carbonaceous residue. T h e y are obtained f r o m petroleums and bitumens by
addition of a nonpolar solvent (such as a hydrocarbon) w i t h a surface tension
lower than 25 dynes c m " at 2 5 C (such as liquefied petroleum gases, the
l o w - b o i l i n g petroleum naphthas, petroleum ether, pentane, isopentane, and
hexane) but are soluble i n l i q u i d s h a v i n g a surface tension above 25 dynes
cm
(such as p y r i d i n e , carbon disulfide, carbon tetrachloride, and benzene)
(6, 7).

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- 1

Asphaltenes are, by definition, a solubility class (<S, 9, 10) that is p r e c i p i tated f r o m petroleums and bitumens by the a d d i t i o n of a m i n i m u m of forty
volumes of the l i q u i d hydrocarbon. In spite of this, there are still reports of
"asphaltenes" being isolated f r o m crude o i l b y m u c h lower proportions of the
precipitating m e d i u m (11), w h i c h leads to errors not only i n the determination
of the amount of asphaltenes i n the crude o i l but also i n the determination of
the c o m p o u n d type. F o r example, w h e n insufficient proportions of the
precipitating m e d i u m are used, resins (a fraction isolated at a later stage of the
separation procedure by adsorbtion chromatography) also m a y appear w i t h i n
the asphaltene fraction b y adsorbtion onto the asphaltenes f r o m the supernatant l i q u i d and can be released by reprecipitation i n the correct manner (12).
Thus, questionable isolation techniques throw serious doubt on any conclusions
d r a w n f r o m subsequent work done on the isolated material.
T h e elemental compositions of asphaltenes isolated b y use of excess
(greater than 40) volumes of n-pentane as the p r e c i p i t a t i n g m e d i u m shows
that the amounts of carbon a n d hydrogen usually vary over only a narrow
range: 82 3% carbon; 8.1 0.7% hydrogen (J3,14). These values correspond
to H / C ratios of 1.15 0.05, although values outside of this range sometimes
are f o u n d . T h e near constancy of the H / C ratio is surprising w h e n the n u m b e r
of possible molecular permutations i n v o l v i n g the heteroelements are considered. In fact, this property, more than any other, is the cause for the general
belief that unaltered asphaltenes f r o m v i r g i n petroleum have a definite
composition and that asphaltenes are precipitated by hydrocarbon solvents
because of this composition, not only because of solubility properties. H o w e v er, notable variations do occur i n the proportions of the heteroelements, i n
particular i n the proportions of oxygen a n d sulfur. O x y g e n contents vary f r o m
0.3% to 4.9%, so the O / C ratios vary f r o m 0.003 to 0.045; sulfur contents vary
f r o m 0.3% to 10.3%, so S/C ratios range f r o m 0.001 to 0.049.

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

1.

SPEIGHT A N D

MOSCHOPEDis

Petroleum Asphaltenes

T a b l e I. E l e m e n t a l C o m p o s i t i o n s of A s p h a l t e n e F r a c t i o n s
P r e c i p i t a t e d b y D i f f e r e n t Solvents

Source
Canada
Iran
Iraq

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Kuwait

Precipitating
Medium
n-pentane
n-heptane
n-pentane
n-heptane
n-pentane
n-heptane
n-pentane
n-heptane

Composition

Atomic

(wt %)

Ratios

H/C

N/C

O/C

S/C

79.5
78.4
83.8
84.2
81.7
80.7
82.4
82.0

8.0
7.6
7.5
7.0
7.9
7.1
7.9
7.3

1.2
1.4
1.4
1.6
0.8
0.9
0.9
1.0

3.8
4.6
2.3
1.4
1.1
1.5
1.4
1.9

7.5
8.0
5.0
5.8
8.5
9.8
7.4
7.8

1.21
1.16
1.07
1.00
1.16
1.06
1.14
1.07

0.013
0.015
0.014
0.016
0.008
0.010
0.009
0.010

0.036
0.044
0.021
0.012
0.010
0.014
0.014
0.017

0.035
0.038
0.022
0.026
0.039
0.046
0.034
0.036

In contrast, the nitrogen content of the asphaltenes appears to r e m a i n

relatively constant; the amount present varies f r o m 0.6% to 3.3% at the
extremes, a n d N / C ratios are usually about 0.015 0.008. H o w e v e r , exposing
asphaltenes to atmospheric oxygen can substantially alter the oxygen content,
and exposing a crude o i l to elemental sulfur, or even to sulfur-containing
minerals, c a n result i n excessive sulfur uptake. Perhaps oxygen a n d sulfur
contents vary more m a r k e d l y than do nitrogen contents because of these
conditions.
In addition, the use of heptane as the p r e c i p i t a t i n g m e d i u m yields a
product that is substantially different f r o m the pentane-insoluble material
(Table I). F o r example, the H / C ratios of the heptane precipitate are
m a r k e d l y lower than those of the pentane precipitate, i n d i c a t i n g a higher
degree of aromaticity i n the heptane precipitate. N / C , O / C , a n d S / C ratios
are usually higher i n the heptane precipitate, i n d i c a t i n g higher proportions of
the heteroelements i n this material (13, 14).
Asphaltene Structure
A s p h a l t e n e Structure b y S p e c t r o s c o p i c M e t h o d s . M u c h of the infor
mation available on the carbon skeleton of asphaltenes has been d e r i v e d f r o m
spectroscopic studies of asphaltenes isolated f r o m various petroleums a n d
natural asphalts (1,2). T h e data f r o m these studies support the hypothesis that
asphaltenes, v i e w e d structurally, are condensed polynuclear aromatic r i n g
systems bearing a l k y l sidechains. T h e n u m b e r of rings apparently varies f r o m
as l o w as six i n smaller systems to fifteen to twenty i n more massive systems
(13,14).
Attempts have also been m a d e to describe the total structures of asphal
tenes ( F i g u r e 1) i n accordance w i t h N M R data a n d results of spectroscopic a n d
analytical techniques, a n d it is difficult to visualize these postulated structures
as part of the asphaltene molecule. T h e fact is that a l l methods e m p l o y e d for
structural analysis involve, at some stage or another, assumptions that,
although based on data c o n c e r n i n g the more volatile fractions of petroleum,
are of questionable validity w h e n a p p l i e d to asphaltenes.

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

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Publication Date: January 1, 1982 | doi: 10.1021/ba-1981-0195.ch001

CHEMISTRY O F

(C

7 9

g 2

N S 0)
2

ASPHALTENES

mol wt. 3449

Figure 1. Hypothetical structure of a petroleum asphaltene

Asphaltenes have also been subjected to x-ray analyses to gain a n insight

into their macromolecular structure (15); the method is reputed to y i e l d
i n f o r m a t i o n about the dimension of the unit cell such as interlamellar distance
(c/2), layer diameter ( L J , height of the unit cell ( L ) , a n d n u m b e r of lamellae
( N ) c o n t r i b u t i n g to the micelle ( F i g u r e 2).
c

Fractionation of an asphaltene b y stepwise precipitation w i t h hydrocarbon solvents (heptane to decane) allows separation of the asphaltene b y
molecular weight. T h e structural parameters d e t e r m i n e d using the x-ray
method (Table II) show a relationship to the molecular weight (16). F o r the
particular asphaltene i n question (Athabasca), the layer diameters
(L )
increase w i t h molecular weight to a l i m i t i n g value; similar relationships also
appear to exist for the interlamellar distance (c/2), m i c e l l e height ( L ) , a n d
even the n u m b e r of lamellae (N ) i n the micelle.
a

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

1.

SPEIGHT A N D

MOSCHOPEDis

Petroleum Asphaltenes

aromatic sheets
aliphatic

\-

chains

3.6 - 3.8 (c/2)

w w w

6-15A(LJ
N = L / c / 2 = 3-5

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Analytical Chemistry

Figure 2. Representation of an asphaltene from x-ray analysis

A p p l i c a t i o n of Diamonds's x-ray diffraction matrix m e t h o d to the probl e m of d e t e r m i n i n g asphaltene structure p r o d u c e d some novel results (17). F o r
example, asphaltenes (precipitated b y n-pentane f r o m Athabasca b i t u m e n a n d
conventional A l b e r t a crude oils) that are soluble i n decane gave histograms
completely different f r o m those obtained w i t h the decane-insoluble material
( F i g u r e 3), suggesting the existence of at least two different molecular types i n
the asphaltene fraction. T h e molecular types p r e d o m i n a n t i n the decanesoluble material appear to be based on simple condensed aromatic units w i t h
only about six aromatic rings per unit. O n the other h a n d , the decane-insoluble
fraction contained aromatic systems of m u c h greater c o m p l e x i t y , but these
systems appeared to be collections of simpler units that were actually similar to
those i n the lower molecular weight material but l i n k e d head-to-tail i n a c y c l i c
system.

Table II. Structural Parameters of Asphaltene Fractions

Derived by the X-ray Method
Structural
Molecular
2694
2704
3185
4338
6427
6530
7603
8158

Weight

L.(A)
6.0
6.3
7.3
9.1
13.9
14.5
14.7
14.8

()
3.81
3.79
3.79
3.74
3.65
3.65
3.64
3.64

Parameters

L.(A)

10.7
10.2
11.0
11.6
12.5
13.8
13.8
14.0

2.8
2.7
2.9
3.1
3.4
3.8
3.8
3.9

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

CHEMISTRY O F ASPHALTENES

100

100 r

50

50

8.4
15
5.8
10
20

'
3

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15

8.4

A
(a)

5.8

10

30
20

Figure 3. Histograms and hypothetical aromatic units for (a) decane-soluble

asphaltenes, and (b) decane-insoluble asphaltenes from Alberta crude oils
In the case of asphaltenes of lower molecular weight, the absence of any
evidence i n the histograms to support hole structures clearly suggests that a n y
heteroatoms located i n the c y c l i c systems are f o u n d at peripheral sites.
H o w e v e r , there is some evidence of hole structures w i t h i n the carbon lamellae
of the higher molecular weight asphaltenes. T o accommodate heteroatoms i n
such holes w o u l d require a significant modification of the N M R m o d e l to a
m u c h larger, more ponderous structure. I n contrast, insertion of the heteroele
ments into the x-ray m o d e l ( F i g u r e 3) c o u l d be achieved quite conveniently
without any significant structural alterations. H o w e v e r , structural acceptabil
ity is not the only criterion f o r proof of structure w h e n d e d u c i n g structural
f o r m u l a e b y any of the physico-chemical techniques. Indeed, the method
itself m a y require proof of acceptability.
Investigations of the x-ray diffraction patterns of various low temperature
( 4 5 0 - 7 5 0 C ) synthetic carbons (18), carbon black b l e n d e d w i t h polyethylene
(15), condensed aromatics of k n o w n structure where the m a x i m u m diameter
of the sheets is approximately 14 (15) as w e l l as mixtures of condensed
aromatics and porphyrins (19) indicate that the x-ray diffraction patterns c a n
be reproduced thereby supporting the concept of condensed aromatic sheets
(having a tendency to stack) as the structure of asphaltenes. H o w e v e r , it is
perhaps this ease w i t h w h i c h the x-ray diffraction of the asphaltenes c a n be
reproduced w h i c h dictates that caution is necessary i n the interpretation of the
data. Indeed, a n y e m p t y polyethylene sample holder w i l l exhibit a similar

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

1.

SPEIGHT A N D

MOSCHOPEDis

Petroleum Asphaltenes

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x-ray diffraction pattern to that of the asphaltenes (19). Therefore, it appears

debatable whether the data d e r i v e d b y this m e t h o d , or b y a n y other m e t h o d ,
are absolute or their sole value is l i m i t e d to comparison between the various
parameters.
Indeed, an excellent example of inconsistency between a spectroscopic
method (i.e., N M R ) a n d other data is p r o v i d e d b y a n examination of the
asphaltenes f r o m Athabasca b i t u m e n where a l k y l sidechains are d e d u c e d to
contain approximately four carbon atoms (20, 21). T h e pyrolysis ( 3 5 0 8 0 0 C ) of this asphaltene produces substantial amounts of alkanes (< C34) i n
the distillate (22, 23, 24). T h e presence of these alkanes i n the pyrolysates is
thought to reflect the presence of such chains i n the original asphaltene (24)
but this is difficult to rationalize o n the basis of a n " a v e r a g e " structure d e r i v e d
f r o m N M R data. Obviously, recognition of the inconsistencies of the spectroscopic method w i t h respect to the paraffinic moieties must lead to recognition
of s i m i l a r inconsistencies w h e n considering the aromatic nucleus.
A k e y feature i n the current concept of asphaltene structure is believed to
be the occurrence of condensed polynuclear aromatic clusters, w h i c h m a y
contain as m a n y as twenty i n d i v i d u a l rings a n d account for a p p r o x i m a t e l y
50% of the asphaltene carbon (J, 2, 13, 14). H o w e v e r , it w o u l d be naive to
presume that precise (or m e a n i n g f u l " a v e r a g e " ) molecular structures c a n be
d e d u c e d b y means of a n y spectroscopic technique (J, 2, 13, 14) w h e n too
m a n y assumptions (incorporating several u n k n o w n factors) are r e q u i r e d to
derive the structural formulae.
Asphaltene Structure b y Chemical Methods.
tenes b e i n g a sulfur p o l y m e r of the type:

T h e concept of asphal-

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

CHEMISTRY OF

ASPHALTENES

has arisen because of the nature of the products obtained by reacting an

asphaltene w i t h potassium naphthalide (25). H o w e v e r , it was erroneously
assumed that this particular organometallic reagentone of several k n o w n to
participate i n r a p i d , complex reactions w i t h organic substratescleaved only
c a r b o n - s u l f u r - c a r b o n bonds, a n d not c a r b o n - c a r b o n bonds, that is:

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or

It has been proved that potassium naphthalide cleaves c a r b o n - c a r b o n bonds i n

various diphenylmethanes (26) a n d the cleavage of c a r b o n - c a r b o n bonds i n
1,2-diarylethanes has been d o c u m e n t e d (27). In each case the isolation of
well-defined organic reaction products confirms the nature of the reaction.
F u r t h e r m o r e , the possibility of transmetallation f r o m the a r y l n a p h t h a l i d e to
the aromatic centers of the asphaltenes (27) complicates the situation a n d
undoubtedly leads to more complex reactions and to reaction products of
questionable composition. F o r m u l a t i n g the structure of the u n k n o w n reactant
(asphaltenes) under such conditions is extremely difficult. Indeed, it is evident
that reacting asphaltenes w i t h any particularly active reagents (e.g., the a l k a l i
aryls) leads to complex reactions, and it m a y be difficult, if not impossible, to
predict accurately the course of these reactions (28). In fact, the reaction of
potassium naphthalide w i t h tetrahydrofuran a l o n e u n d e r conditions i d e n t i cal to those reported where asphaltenes were also present (25)produces a
light b r o w n amorphous p o w d e r (29) that c o u l d erroneously be identified as a
major product had any asphaltene been present.
T h e r e have also been attempts to substantiate the concept of a sulfurcontaining p o l y m e r b y virtue of the t h e r m a l decomposition i n the presence of
tetralin (30). H o w e v e r , aliphatic c a r b o n - c a r b o n bonds (such as those i n
1,2-diphenylethane) w i l l cleave under similar conditions, w h i l e reactions
i n v o l v i n g alteration of the h y d r o c a r b o n structure also occur (31). Indeed, an
investigation of the nature of the t h e r m a l dissociation of tetralin indicates that
the reaction is quite complex (32) a n d the presence of an a d d e d material (such
as coal or asphaltene) c o u l d render any attempt to rationalize the reaction i n
simple terms to be of extremely dubious value.
Nitrogen, Oxygen, and Sulfur in Asphaltenes. U n f o r t u n a t e l y , i n a l l
these studies, too little emphasis has been placed on d e t e r m i n i n g the nature
a n d location of the nitrogen, oxygen, a n d sulfur atoms i n the asphaltene
structure. H o w e v e r , mass spectroscopic investigations (33) of a petroleum
asphaltene have a l l o w e d the identification of fragment peaks, w h i c h indicate
that at least some of the heteroatoms exist i n the r i n g systems ( F i g u r e 4). A
study of the t h e r m a l decomposition of the asphaltenes f r o m a natural b i t u m e n
(22, 23) indicated that only 1% of the nitrogen was lost d u r i n g the t h e r m a l
treatment, w h i l e substantially more sulfur (23%) and almost a l l of the oxygen
(81%) were lost as a result of this treatment. T h e tendency for nitrogen a n d

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

1.

SPEIGHT A N D

MOSCHOPEDIS

mass

Petroleum Asphaltenes

possible nuclei

93

241

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185

285

Analytical Chemistry

Figure 4. Suggested heteroatom locations from mass spectroscopic

peaks

fragmentation

sulfur to r e m a i n d u r i n g thermal decomposition, as opposed to the easy

e l i m i n a t i o n of oxygen, supports the concept that nitrogen a n d sulfur have
stability because of their location i n r i n g systems (24, 34, 35); if a sulfur-type
p o l y m e r (25) existed, it w o u l d be expected to lose m u c h , but not necessarily
all, of its sulfur content to the v o l a t i l e s m a i n l y as h y d r o g e n sulfide (24).
Such a sulfur-type p o l y m e r m i g h t also be expected to lose m u c h of the
sulfur b y treatment w i t h Raney n i c k e l (36). H o w e v e r , these particular
(Athabasca) asphaltenes are difficult to desulfurize w i t h R a n e y n i c k e l (26) as
c o m p a r e d w i t h a variety of aromatic/aliphatic thioether polymers of the
type:

w h i c h can lose sulfur quite conveniently under the same conditions (37,
Polymers of the type:

desulfurize very slowly w i t h Raney n i c k e l (37, 38) a n d others, for instance:

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

38).

10

CHEMISTRY OF

ASPHALTENES

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lose n o n r i n g sulfur relatively readily c o m p a r e d w i t h the heterocyclic sulfur

(37, 38, 39).
If these results, w i t h the data f r o m t h e r m a l decomposition experiments
(22,23, 24), can be projected to the particular asphaltenes i n question, it w o u l d
be i n d i c a t i v e of sulfur existing p r e d o m i n a n t l y i n the heterocyclic f o r m .
O f the heteroelements i n petroleum, there are more data p e r t a i n i n g to
the locations of the oxygen atoms than to the sulfur a n d nitrogen atoms.
H o w e v e r , the majority of the data relates to oxygen functions i n b l o w n
(oxidized) asphalts a n d residua (40, 41), w h i c h m a y be of little relevance to the
oxygen functions i n the native materials. O f the l i m i t e d data available, there
are indications that oxygen i n asphaltenes can exist as nonhydrogen-bonded
phenolic h y d r o x y l groups (42, 43). O t h e r i n f o r m a t i o n on the presence a n d
nature of oxygen i n asphaltenes has been d e r i v e d f r o m i n f r a r e d spectroscopic
examination of the products after interaction of the asphaltenes w i t h acetic
a n h y d r i d e (42, 44). T h i s has p r o d u c e d evidence for the presence of ketones
and/or quinones as w e l l as indications that a considerable portion of the
h y d r o x y l groups present i n asphaltenes m a y exist as collections of two or more
h y d r o x y l functions on the same aromatic r i n g , or on adjacent p e r i p h e r a l sites
on a condensed r i n g system:
O H

O-H

or even on sites adjacent to a c a r b o n y l f u n c t i o n i n a condensed r i n g system:

O H

0-H

In the context of p o l y h y d r o x y aromatic n u c l e i existing i n Athabasca

asphaltenes, it is of interest to note that pyrolysis at 8 0 0 C results i n the
f o r m a t i o n of resorcinols (24) i m p l y i n g that such functions m a y i n d e e d exist i n
the asphaltenes.
T h e f o r m i n w h i c h nitrogen exists i n asphaltenes is even less w e l l
understood than those of oxygen a n d sulfur. Attempts have been m a d e to
define organic nitrogen i n terms of basic a n d nonbasic types (45). Spectroscopic investigations (46) suggest that carbazoles m i g h t be a p r e d o m i n a n t
nitrogen type i n asphaltenes f r o m Athabasca b i t u m e n , w h i c h supports earlier
mass spectroscopic evidence (33) for nitrogen-types i n asphaltenes.

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

1.

SPEIGHT A N D

MOSCHOPEDis

Petroleum

Asphaltenes

11

Asphaltene Molecular Weights

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D e t e r m i n i n g the molecular weights of asphaltenes is a p r o b l e m because

they have a l o w solubility i n the liquids often used for determination. Also,
adsorbed resins lead to discrepancies i n molecular-weight determination, a n d
precipitated asphaltenes should be reprecipitated several times prior to the
determination (12). Thus, careful precipitation a n d c a r e f u l choice of the
determination m e t h o d are both very important for o b t a i n i n g m e a n i n g f u l
results.
Asphaltenes tend to associate, even i n d i l u t e solution (47, 48) so there has
been considerable conjecture about the actual molecular weights of these
materials, but the data are fragmented a n d m a n y different asphaltenes have
been e m p l o y e d for the investigations. Nevertheless, for any one particular
study, there are large variations i n asphaltene molecular weights. F o r example,
molecular weight investigations using an ultracentrifuge gave values u p to
300,000 (47, 49, 50) w h i l e an osmotic pressure m e t h o d (51) i n d i c a t e d m o l e c u lar weights of approximately 80,000 a n d a m o n o m o l e c u l a r film m e t h o d (52)
y i e l d e d values of 80,000-140,000. H o w e v e r , other procedures have y i e l d e d
lower values: 2500-4000 b y the ebullioscopic m e t h o d (53); 6 0 0 - 6 0 0 0 b y the
cryoscopic method (5J, 54-57); 9 0 0 - 2 0 0 0 b y viscosity determinations (49, 58,
59); 1000-4000 b y light adsorption coefficients (60); 1000-5000 b y vapor
pressure osmometry (5, 61); a n d 2000-3000 b y a n isotonic (62) or e q u a l vapor
pressure (63) method.
A f a i r l y comprehensive study of asphaltene molecular weights b y vapor
pressure osmometry has been reported a n d shows that the molecular weights
of various asphaltenes are dependent not only o n the nature of the solvent but
also o n the solution temperature at w h i c h the determinations were p e r f o r m e d
(64). H o w e v e r , data f r o m later work, i n v o l v i n g molecular weight d e t e r m i n a tions b y the cryoscopic m e t h o d (48), indicate that the molecular nature of
asphaltenes is not conducive to the determination of absolute molecular
weights b y any one method. F o r any one m e t h o d , the observed molecular
weights suggest that asphaltenes f o r m molecular aggregates, even i n d i l u t e
solution, a n d this association is influenced b y solvent polarity, asphaltene
concentration, a n d the temperature of the determination. I n fact, w o r k b y
Ignasiak et a l . (65), has c o n f i r m e d the earlier w o r k of Moschopedis a n d
Speight (66) a n d Moschopedis et a l . (64), w h i c h showed that intermolecular
h y d r o g e n - b o n d i n g is i n v o l v e d i n asphaltene association a n d has a significant
effect o n observed molecular weights. T h i s requires that serious reconsideration be g i v e n to ideas such as the concept of these particular asphaltenes
existing as a sulfur p o l y m e r (25). T h i s s u l f u r - p o l y m e r concept, i n spite of
evidence to the contrary (64), was based o n the erroneous statement that
solvent type d i d not affect asphaltene molecular weight a n d c o u l d not account
for the observed decreases i n molecular weight w i t h increases i n solvent
polarity.

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

12

CHEMISTRY OF

ASPHALTENES

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The Physical Structure of Asphaltenes in Petroleum

A l t h o u g h the evidence available i n the literature appears to indicate that
the hydrocarbon structures and some features, such as the various condensed
r i n g systems, i n different petroleums are similar (from the asphaltenes a n d
resins to the constituents of the o i l fraction), the variety of source materials
involved i n petroleum genesis implies that, on an i n d i v i d u a l molecular scale,
there m a y be substantial structural differences a m o n g the constituents of the
various crude oils and bitumens. As well, the difficulty w i t h w h i c h resins f r o m
one crude o i l peptize (As i n a colloid, the terms peptization, dispersion, and
solubilization are often used interchangeably to describe the means b y w h i c h
asphaltenes exist w i t h i n petroleum.) asphaltenes f r o m a different crude o i l ,
and the instability of the " b l e n d " (5) are evidence for significant structural
differences a m o n g the asphaltenes and resins of various crude oils.
Some researchers, i n a d d i t i o n to d e r i v i n g broad generalities f r o m the use
of various analytical techniques, are attempting to assign specific total
molecular configurations to the asphaltene constituents. Perhaps it is of little
value to petroleum technology a n d certainly b e y o n d the scope of the available
methods to derive such formulae. H o w e v e r , w i t h i n any one petroleum, a
variety of structures exist i n the asphaltene fraction (in w h i c h there is a
decided hydrogen deficiency), but the close relationships of the various
hydrocarbon series c o m p r i s i n g the asphaltenes, resins, a n d oils gives rise to
m u c h o v e r l a p p i n g of fractions into neighboring series, both i n molecular
weight and i n H / C ratio.
T h e asphaltenes appear to be the final (excluding carbenes a n d carboids,
those organic fractions of petroleum that are insoluble i n toluene or benzene)
condensation product as indicated f r o m oxidation where the scheme of
reaction (66, 67) is:
oils resins asphaltenes
H i g h aromaticity is generally prevalent i n the asphaltenes a n d the resins, but
i n some resins the hydrocarbons show an increase i n aliphatic material (more
sidechains, for example) u n t i l , w i t h considerable saturation, the oils, w h i c h
contain numerous a l k y l chains of v a r y i n g length, are reached. T h e degree of
aromaticity is important w h e n the resins are b e i n g adsorbed b y the asphaltene
particles, just as paraffinicity is important w h e n the resins are desorbed. H i g h
aromaticity of the maltenes (i.e., that part of petroleum r e m a i n i n g after the
asphaltenes have been removed, often referred to as the deasphalted oil)
indicates good solvency for the asphaltenes, a n d the solvent power of the
maltenes is one of the most important factors i n d e t e r m i n i n g the physicoc h e m i c a l behavior of the petroleum colloid system.
T h e means by w h i c h the asphaltenes r e m a i n dispersed i n the o i l m e d i u m
[asphaltenes are, i n fact, insoluble i n the o i l fraction (5)] has been the subject of
m u c h speculation, but it is n o w clear that this is m a i n l y attributable to the

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

1.

SPEIGHT A N D MOSCHOPEDIS

Petroleum Asphaltenes

13

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resins. In fact, it is possible to b r i n g about dispersion of asphaltenes i n their

corresponding o i l fractions only b y addition of resins. T h e general indications
are that the degree of aromaticity of, a n d the p r o p o r t i o n of heteroelements i n ,
the resins appear to play an important part i n the ability of these materials to
b r i n g about solubility of the asphaltenes i n an o i l . F u r t h e r m o r e , if the a d d e d
resins are less aromatic than the natural resins, asphaltenes w i l l not disperse;
for resins of equal aromaticity, those h a v i n g higher heteroelement content are
better for dispersion purposes. Therefore, it appears that a crude o i l is a
complex system w i t h i n each fraction, dependent u p o n other systems for
complete m o b i l i t y a n d solubility (5). It is presumed that the resins associate
w i t h the asphaltenes i n the m a n n e r of an electron donor-acceptor, a n d that
there c o u l d w e l l be several points of structural s i m i l a r i t y between the
asphaltenes a n d resins that w o u l d have an adverse effect on the a b i l i t y of the
resins to associate w i t h asphaltenes f r o m a different crude o i l (5, 43).
A n early hypothesis of the physical structure of petroleum (52) i n d i c a t e d
that asphaltenes are the centers of micelles f o r m e d b y adsorption, or even b y
absorption of part of the maltenes, that is, resin material, onto the surfaces or
into the interiors of the asphaltene particles. Thus, most of those substances
w i t h greater molecular weight a n d w i t h the most p r o n o u n c e d aromatic nature
are situated closest to the nucleus a n d are surrounded b y lighter constituents of
less aromatic nature. T h e transition of the i n t e r m i c e l l u l a r (dispersed or oil)
phase is gradual a n d almost continuous. C o n t i n u e d attention to this aspect of
asphaltene chemistry has led to the assumption that asphaltenes exist as
clusters w i t h i n the micelle. T h i s arises m a i n l y because of the tendency for
asphaltenes to associate i n dilute solution i n solvents of l o w polarity a n d f r o m
possible misinterpretation of viscosity data (58, 64). T h e presence of asphaltene "stacks" i n the solid phase, as d e d u c e d f r o m x-ray diffraction patterns
(68), also seemed to support the concept of the widespread existence of
asphaltene clusters i n the micelle.
T h e concept of h y d r o g e n - b o n d i n g interactions b e i n g one of the means of
association between the asphaltenes a n d resins has, however, l e d to a reconsideration of the assumed cluster as part of the m i c e l l e (43). Indeed, it appears
that w h e n resins a n d asphaltenes are present together, h y d r o g e n - b o n d i n g m a y
be one of the mechanisms b y w h i c h resin-asphaltene interactions are
achieved. Resin-asphaltene interactions are preferred over asphaltene-asphaltene interactions (43). Thus, if the same intermolecular forces are present i n
petroleums a n d bitumens, it w o u l d perhaps not be surprising that asphaltenes
exist not as the more cumbersome agglomerations but more nearly single
entities that are peptized, a n d effectively dispersed, b y the resins.

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In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

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14

CHEMISTRY OF ASPHALTENES

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21. Ibid.,1971, 50, 102.
22. Ibid.,1970, 49, 134.
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1971) 15(1),57.
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26. Moschopedis,S. E.; Speight,J. G . ,unpublished data, 1977.
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Francisco,Aug.-Sept.,1976) 21(6),198.
43. Moschopedis,S. E.; Speight,J. G. Fuel 1976, 55, 187.
44. Ibid.,334.
45. Nicksic,S. W.; Jeffries-Harris,M. J. J. Inst. Pet., London 1968, 54, 107.
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(Washington,D.C.,Sept.,1979) 24(4), 1007.
47. Winniford,R. S. Inst. of Pet. Rev. 1963, 49, 215.

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.

1.

SPEIGHT AND MOSCHOPEDIS

Petroleum Asphaltenes

48. Speight, J. G.; Moschopedis, S. E. Fuel 1977, 56, 344.

49. Ray, B. R.; Witherspoon, P. .; Grim, R. E. Phys. Chem. 1957, 61, 1296.
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65. Ignasiak, T.; Strausz, O. P.; Montgomery, D. S. Fuel 1977, 56, 359.
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;

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15

RECEIVED June 23,

1980.

In Chemistry of Asphaltenes; Bunger, J., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1982.