2 Petroleum

Much appreciation and a big thank you to Dr. Oliver Mullins,

Schlumberger-Doll Research.

Petroleum contains the following components:

• Paraffins (also known as alkanes, saturated hydrocarbons)
• Naphthenes (also known as cycloalkanes, cycloparaffins,
saturated hydrocarbons)
• Aromatics (also known as arenes)
• Asphaltenes and resins (also known as polynuclear compounds)
Some quantities of carbon dioxide, nitrogen, and/or hydrogen sulfide are often
present in petroleum. Hydrogen or helium may also occasionally be present.
Notice that chemicals with double or triple covalent bonds such as alkenes,
cycloalkenes, etc. are not present in petroleum. Although compounds with these
distinguishing features may have been present in the original organic source material,
the processes of diagenesis, catagenesis, and geologic time have served to allow any
of these chemically weaker double and triple bonds to react and become single bonds.
Many of the compounds found in petroleum, especially those with larger molecules,
contain heteroatoms (sulfur, oxygen, and/or nitrogen) or even metallic ions. While
carbon and hydrogen atoms are the predominant constituents, the proper descriptor
for these naturally occurring chemical mixtures is petroleum and not hydrocarbon.
The first three of the chemical families listed above as components of petroleum
were discussed in chapter 1; the asphaltenes and resins (which are not homologous
series) will be discussed next.

Asphaltenes and Resins

The basic structures of asphaltenes and resins are similar. Both can be formed
by oxidation of polycyclic aromatic hydrocarbons. On the other hand, both can
be reduced to hydrocarbons by hydrogenation, which yields moderate to large
hydrocarbon molecules, hydrogen sulfide, and water. Further, resins can be
converted to asphaltenes by oxidation.

39
tHe ProPertIeS oF Petroleum FluIDS, tHIrD eDItIoN

There are, however, important differences between asphaltenes and resins.

Asphaltenes do not dissolve in petroleum but are dispersed as colloids. Resins
readily dissolve in petroleum. Pure asphaltenes are solid, dry, black powders and
are nonvolatile; as temperature is increased they tend to disintegrate before boiling.
Pure resins are heavy liquids or sticky solids and are as volatile as other petroleum
molecules of the same size. The resins of high molecular weight are red; the lighter
resins are often yellow or orange.
Figure 2–1 shows four different petroleum oils from which the gas (lighter
components) has been removed. These are fractions separated from a heavy oil.
Petroleum 1 has no resins or asphaltenes and thus no color. The color of petroleum
2 (which is yellow) is due to the presence of lighter resins in the mixture. Petroleum
3 (which is mostly red) contains primarily heavier (larger) resins and is mixed
with some asphaltenes (notice the black asphaltenes which have flocculated and
dropped to the bottom). And the dark color of petroleum 4 is caused by asphaltenes
suspended (colloidal action) in the mixture, with possibly some heavy resins since
the color is not totally black and the mixture is not solid.

3
1
2

Fig. 2–1. Four petroleum liquids1

Asphaltenes
This section will discuss asphaltenes found in petroleum. There are other natural
sources of asphaltenes, such as coal, but these other asphaltenes, although similar
to petroleum asphaltenes, have different average sizes, divergences in heteroatom
composition, and so on.
Petroleum asphaltenes are defined according to solubility. They are soluble
in toluene (sometimes benzene or pyridine is used) and insoluble in n-heptane
(sometimes n-pentane is used). The toluene solubility captures the most aromatic
components of the petroleum. The n-alkane insolubility captures those molecules
that have asphaltene properties, although if n-pentane is used (rather than n-heptane)

40
 Chapter 2 | Petroleum

to define asphaltenes, a greater fraction of asphaltene-like molecules are captured

along with increased non-asphaltene molecules.
An asphaltene molecule consists of a single polycyclic aromatic hydrocarbon
(PAH) surrounded by alkane-like substituents. This is sometimes called a
“like-your-hand” model in which the PAH represents the palm of the hand and the
alkane-like chain structures represent the fingers.
The PAH structures are fused rings, primarily aromatic with some cycloalkane
rings. On average there are 7 fused rings in the PAH of a petroleum asphaltene
molecule with a range of 5 to 10 rings found in individual asphaltene molecules.
The chain structures are alkyls with up to 8 to 10 carbon atoms per alkyl group.
There is often heteroatom content; nitrogen atoms are entirely contained within
the PAH, replacing carbon atoms in the ring structures. Sulfur atoms are also
primarily within the PAH replacing carbon atoms, and the relatively small oxygen
content appears in various groups, including alcohol structures.
The carbon-carbon bonds within the PAH are primarily benzene bonds (sextets)
with a few double bonds. On average, the molecular weight of an asphaltene
molecule is 750 lb/lb mole with a range of 500–1,000 lb/lb mole for individual
asphaltene molecules.
In the past, asphaltenes were thought to be very much larger (heavier) than
mentioned above. This is because, with some concentration of asphaltenes within
the petroleum, the asphaltene molecules form nanoaggregates. The PAHs are
physically attracted (not covalently connected) and are bound together fairly
tightly. The predominately alkyl substituents create steric hindrance (i.e., they get
in the way), preventing close approach of the PAHs embedded in the nanoaggregate
structure. Thus the nanoaggregates grow to contain eight asphaltene molecules2
and then their growth stops. Thus a “fuzzy tennis ball” is created—eight attractive
PAHs encased by repulsive alkyl substituents. If additional asphaltene molecules
are present in the petroleum, they form additional nanoaggregates. A few of the
heaviest resin molecules (less than about 15% by mass) can become embedded
along with the asphaltene molecules in the center of a nanoaggregate.
At higher concentrations of asphaltenes in the petroleum, the nanoaggregates
can form clusters. Clusters can contain several nanoaggregates, physically (not
covalently) crosslinked, that have rather small bonding energy and vary in size. This
variability causes the enormous dependence of the viscosity of heavy petroleum on
temperature and asphaltene composition.
Large quantities of clusters can flocculate and become too heavy to be held in
suspension by colloidal action. These floccules will attach to any solid surface or
precipitate to the bottom.
Asphaltene instability within petroleum oils is a major contributor to several
issues that plague the petroleum industry, including plugging the pores in reservoir
rock, deposition in the wellbores and gathering systems, strengthening of oil-water
emulsions, sedimentation and plugging during oil storage, and many other problems.

41
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

Resins
Resins may be thought of as small asphaltenes; the exact definition depends
on the precipitating solvent used to define resins (usually n-heptane soluble,
n-pentane insoluble, but this is not consistent within the industry). The PAH/alkyl/
heteroatom structures are present in resins, although the number of fused rings in
the PAHs is smaller (three to five rings). The alkyl structures may be somewhat
larger than in asphaltenes since the hydrogen/carbon ratios in resins are greater than
in asphaltenes. Further, resin molecules may contain smaller ratios of heteroatoms
than asphaltene molecules. Resin molecules can have molecular weights up to
500 lb/lb mole but most are smaller.
Resins do not contribute to the problems in the petroleum industry that
asphaltenes cause.
Asphaltenes are considered to be colloids (i.e., colloidally suspended in
petroleum oil). Asphaltene colloidal particles were thought to be stabilized by a
coating of resin molecules, with resins acting as surfactants for asphaltenes. Recent
research has shown that this is not true; resins are not necessary for stabilizing
asphaltene colloidal particles in petroleum oil.3

The Origin of Petroleum

In the calmest portions of a body of water, the smallest fragments of rock settle
to the bottom. These calm portions of the water become depleted of oxygen so
that the remnants of plankton remain intact and settle with the rock fragments.
The process of the formation of petroleum from this organic matter is described in
figure 2–2.

Diagenesis
As these sediments become deeper (and thus hotter) due to continued
sedimentation from above, the rock fragments begin to cement together to create
a porous solid called shale, and in the pores among the rock fragments, anaerobic
bacteria work the organic remains to create a solid called kerogen. This process,
called diagenesis, continues to about 125°F, at which point the bacteria cease to
exist due to the temperature. This process is sometimes called organic diagenesis.
Kerogen is composed of large nonvolatile organic molecules that are insoluble in
organic solvents.
Methane is also formed during this process; this is biogenic methane, probably
more correctly called microbial methane. At these depths, the rocks are generally
unconsolidated, thus there are no traps, and most of this methane migrates to the
surface and is lost. A few low-temperature chemical reactions also participate in the
diagenesis process.

42
 Chapter 2 | Petroleum

LIFE

Hydrocarbons and Lipids, proteins,

protohydrocarbons carbohydrates
in organisms
DIAGENESIS

Bacterial activity and low-temperature chemical reactions

50°C KEROGEN

BITUMEN
High-temperature
Reactions
CATAGENESIS
PETROLEUM
(Maturation)

Light oil and gas Heavy oil

Gas 200°C Pyrobitumens

METAGENESIS
Methane 250°C Graphite

Fig. 2–2. The origin of petroleum4

Catagenesis
As the depth of burial increases, the organic matter is subjected to increasingly
higher temperatures. The higher temperatures cause thermal degradation of kerogen
to yield petroleum molecules. This is basically a disintegration chemical reaction
which is called catagenesis. In most procedures the kerogen is decomposed to
bitumen, which is nonvolatile organic matter that is soluble in organic solvents.
The reaction proceeds to form petroleum-sized molecules (oil and gas) from
the bitumen. Catagenesis starts at about 125°F and ends at temperatures just
under 400°F. Having formed during this process, these petroleum molecules are
therefore thermogenic.
Most of the petroleum oil is formed between 140°F and 320°F (corresponding
to approximate depths of 6,000 to 22,000 feet); this is called the oil window.
The increase in the number of molecules formed during the disintegration of
kerogen to petroleum causes pressure buildup within the shale which in turn

43
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

causes minute cracks to form. The smaller petroleum molecules are able to escape
through these cracks and begin their migration, usually upward, to be trapped in
geological structures.

Metagenesis
Metagenesis is the last stage in the natural thermal disintegration of organic
matter. The products are essentially methane and graphite-like structures. Some
hydrogen sulfide is also formed. This process starts at temperatures slightly below
400°F (a depth of approximately 30,000 feet).
The black graphite-like structures remain in the source rock, thus shales are
black as a result of the remaining organic matter, not from the original color of the
rock fragments.
It is interesting that the high-temperature end of the alteration of organic
matter (~400°F) overlaps with the low-temperature beginning of the alteration of
inorganic matter, metamorphism, which is the transformation of sedimentary rocks
to metamorphic rocks, such as shale converted to slate.

The catagenesis/metagenesis process

The chemical reaction involved in the process of converting natural organic
matter into petroleum wants to proceed to the production of methane as an end
point. However, each carbon atom in methane requires four hydrogen atoms. But
since the precursor organic matter does not have enough hydrogen atoms to satisfy
all the carbon atoms, petroleum, consisting of many organic molecules, is formed
rather than just methane. The larger petroleum molecules require fewer hydrogen
atoms for each carbon atom.
Hunt proposed a hypothetical description of the process as shown in figure 2–3.
The process begins at the top of the figure with a hypothetical kerogen structure
which has 1.43 hydrogen atoms for each carbon atom (H/C ratio). The thermal
process between lines one and two forms a few petroleum-type molecules illustrated
on the right. In order to provide sufficient hydrogen to create these molecules, the
remaining kerogen must begin to condense into fused aromatic rings as shown
on the left. This process continues from lines two through four until the original
kerogen molecule has become a graphite-like structure and the resultant petroleum
product is only methane. The temperature at the end of the process (the fourth line)
will be approximately 400°F. The decrease in H/C ratio of the remaining kerogen
molecules as shown on the right of the figure is typical of the process as temperature
is increased.
If the cracks in the shale become large enough that the remains of the kerogen
between lines two and three can escape, an asphaltene-like molecule will join the
migrating petroleum.

44
 Chapter 2 | Petroleum

H/C of
kerogen

1.43

1.29

0.96

CH 4 0.47

Fig. 2–3. The thermal alteration of kerogen in which the kerogen molecules condense and
aromatize into ring structures in order release hydrogen to form petroleum-type molecules5
45
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

Determining the Composition of Petroleum

The techniques for measuring the compositions of petroleum have evolved over
the years. Originally a process of distillation was used. This has been superseded
by chromatography and/or mass spectrometry.

Low-temperature distillation
For many years, the composition of petroleum was determined using
low-temperature laboratory distillation equipment developed by W. J. Podbielniak.6
This device is typically called a pod-column (appropriate because he was usually
called Dr. Pod in his professional life). In this device, the lower boiling components
of petroleum are separated by distillation and the weights of the resulting pure
components are determined. The resulting calculation of the composition is in
weight fraction, not mole fraction, which is usually used by petroleum chemists
and engineers.
As the distillation process proceeds, the temperature required to separate the
isomers of hexane becomes high enough, even with the use of a vacuum, to cause
the larger molecules of the sample to begin to disintegrate (this is called “cracking”
by chemists). Obviously, at this point the procedure cannot be continued; once
cracking starts the sample is ruined. Thus the process results in the determination
of the composition of the more volatile (smaller) components with all the larger
components lumped together into a pseudocomponent called heptanes plus (C7+).
Values of the molecular weights of the components are necessary to convert the
weight fractions to mole fractions. The molecular weights of the pure components
are known; however, the molecular weight of the remaining heptanes plus must be
measured each time composition is measured.

Example 2–1. Calculate the composition in mole fraction for the petroleum with
measured composition in weight fraction given below.

Component Composition weight fraction

Carbon dioxide 0.0012
Nitrogen 0.0029
Methane 0.0196
Ethane 0.0156
Propane 0.0236
i- Butane 0.0046
n- Butane 0.0194
i- Pentane 0.0090
n- Pentane 0.0154
Hexanes 0.0244
Heptanes plus 0.8643
1.0000

46
 Chapter 2 | Petroleum

Properties of heptanes plus

 Molecular weight 215
  Specific gravity 0.8629

Solution

Composition weight Molecular weight, Composition

Component wj/Mj
fraction, wj Mj mole fraction, xj
Carbon 0.0012 44.010 0.0000273 0.0037
dioxide
Nitrogen 0.0029 28.0135 0.0001035 0.0139
Methane 0.0196 16.042 0.001222 0.1638
Ethane 0.0156 30.069 0.0005188 0.0696
Propane 0.0235 44.096 0.0005329 0.0714
i- Butane 0.0046 58.122 0.0000791 0.0106
n- Butane 0.0194 58.122 0.0003338 0.0447
i- Pentane 0.0090 72.149 0.0001247 0.0167
n-Pentane 0.0154 72.149 0.0002134 0.0286
Hexanes 0.0244 86.175 0.0002831 0.0380
Heptanes plus 0.8644 215.000 0.004020  0.5390
1.0000 0.0074586 1.0000

This procedure is seldom used today; however, the process is of interest because
the petroleum industry learned a valuable lesson from the results: the quantity
(and to a lesser extent the molecular weight) of the heptanes plus fraction controls
the values of nearly all the fluid properties of the petroleum. Exceptions are the
bubblepoint pressures of oils and the dewpoint pressures of gases, which are
strongly influenced by the quantities of the lightest components of the petroleum.

Chromatography
There are several techniques currently available to determine the compositions
of petroleum. The procedure most often used is chromatography. A schematic of
gas chromatography equipment is shown in figure 2–4.
The heart of the equipment is the column. This is typically coiled ⅛ in. stainless
steel tubing (approximately 20 feet in length) filled with a granular material
impregnated with a heavy liquid which will adsorb the components of petroleum.
The column is contained in a sealed temperature-controlled oven. A carrier gas,
usually helium, flows into the column to assist in moving the sample through the
column. The sample is injected into the column and is adsorbed on the granular
material. The more volatile components of the sample desorb and move through
the column. The heavier of these components re-adsorb and then desorb again
according to volatility. The components of the sample progress through the column,

47
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

pushed by the carrier gas, and are separated by volatility. Near the outlet end of the
column, the flow stream consists of a series of pure components separated in the
carrier gas. The mass of each of these components is measured by a detector. The
signals from the detector are processed electronically and a graph of the results,
called a chromatogram, is produced. The mass of each component is determined
electronically and tabulated.

Sample Injector

Flow Controller
Computer
Waste
Column
Detector

Column Oven
Carrier Gas

Fig. 2–4. Simplified schematic of a gas chromatographic system7

Several different devices are available for use as detectors. Often equipment
based on thermal conductivity is used.
The physical property most closely related to volatility is the normal boiling
point temperature. So, although the process separates the components by volatility,
the separation can be thought of as occurring according to the normal boiling point
temperature. The components with the lowest boiling point temperatures come out
first. For instance, all the structural isomers of a particular alkane come out before
the normal isomer, since the n-structure always has the highest boiling point of that
set of isomers.
Liquid chromatography is somewhat more complicated than gas chromatography;
however, the basic process, separation by volatility, remains.
A simplified version of a chromatogram is shown in figure 2–5.
The chromatogram shows a peak for each component of the mixture. The area
under each peak divided by the total area under all peaks is the weight fraction
(i.e., the lbj/lb total of that component). That is, as a component passes through the
detector, its mass is measured, not its volume.
Figure 2–6 shows a chromatogram of a petroleum oil. Apparently this is a
surface oil (i.e., nearly all of the lighter components of the oil have been removed).

48
 Chapter 2 | Petroleum

Column: 7 ft molecular sieve 13x

Methane
Temperature: 35*c
Flow rate: 60 ml/min
Sample size: 0.5 ml

Carbon Monoxide

Nitrogen

Hydrogen
Oxygen
11 10 9 8 7 6 5 4 3 2 1 0

Minutes

Fig. 2–5. A simple gas chromatogram. Note: Contemporary chromatograms show decreasing
volatility from left to right rather than from right to left as shown here (American Society for
Testing and Materials 1977, 194)

Notice that there are two peaks for the pentanes, representing n-pentane and
iso-pentane. The third structural isomer of pentane, neo-pentane (dimethylpropane)
is not present. Also notice that there are only three peaks for structural isomers of
hexane; these are n-hexane (which appears last in this grouping), 2-methylpentane,
and 3-methylpentane. The other two structural isomers of hexane, 2,2-dimethylbutane
and 2,3-dimethylbutane, are not present. This is typical of the presence of the
structural isomers of the alkanes in petroleum; the more complicated isomers are
not usually present.
The peak named “REFERENCE” between n-pentane and n-hexane in figure
2–6 is a solvent doped into the sample to assist in determining the compositions of
the components.
The most significant feature of the chromatogram is that the n-alkanes are the
most common components. Notice all the larger peaks of the n-alkanes throughout
the chromatogram. This is true of all petroleum: if the n-alkanes are not present in
large quantities, the petroleum has been biodegraded (i.e., bacteria have eaten the
normal alkanes). Bacteria are like children: they want to eat the desert first, and
they are fondest of normal alkanes.

49
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

Fig. 2–6. A chromatogram of a petroleum oil (from Weatherly, Blackstone A-1).

50
 Chapter 2 | Petroleum

Fig. 2–6. Cont.

51
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

Fig. 2–6. Cont.

Notice that the peaks for methylcyclopentane (MECYPEN), benzene, and

cyclohexane appear between the peaks of n-hexane and n-heptane mixed with the
peaks of some of the structural isomers of heptane. Compare the normal boiling point
temperatures for these components with the normal boiling point temperatures of
the heptanes listed in appendix A. This is the first appearance in the chromatographic

52
 Chapter 2 | Petroleum

column of the smallest (lightest) naphthenes and aromatics. The quantities of these
smallest fragments are often quite large (in this example, the quantity of benzene is
relatively small, but this is not always the case with petroleum).
Notice that the normal boiling point temperature of cyclopentane (see appendix
A) is less than that of n-hexane and thus the peak for cyclopentane should appear
among the peaks of the structural isomers of hexane. However, the amount of
cyclopentane in most petroleum is insignificant (as in this case).

Reporting the Composition of Petroleum

The page labeled 7/17 of table 8–1 shows that the compositions of all components
through n-pentane are determined (weight fraction) and reported (mole fraction or
mole percent). These pure components are all either paraffins or nonhydrocarbons.
There are so many components heavier than n-pentane that they are usually
grouped into pseudocomponents and the compositions of these pseudocomponents
are reported. As before, the list of components ends with a plus component which
groups all heavier components of that petroleum, in this case eicosanes plus, C20+.
Sometimes the composition is reported to tricosanes plus, C30+.

The pseudocomponents
The area of the chromatogram used to determine the compositions of these
pseudocomponents starts to the right of an n-alkane and goes through the next
larger n-alkane. For instance, the composition of the pseudocomponent called
heptane is determined by adding the area under the curve starting just to the right of
the n-hexane peak and ending with the n-heptane peak.
These pseudocomponents have been given several names; all these names are
poorly representative of the constituents of the pseudocomponents.
One system, used in table 8–1, pages 4/17, 5/17, and 7/17, names each
pseudocomponent according to the name of the n-alkane at the right end of the
area used to determine the composition. This implies that all members of that
pseudocomponent are alkanes; however, naphthenes and aromatics are also included
in that pseudocomponent. For instance, the pseudocomponent named Heptanes has
several of the structural isomers of heptane but also includes methylcyclopentane,
benzene, and cyclohexane. Thus this naming system is not correctly descriptive.
Another system, used in reference 8, names each pseudocomponent according
to the number of carbon atoms in the n-alkane to the right of the area. For instance,
Heptanes is named C7 or C7. This implies that there are seven carbon atoms in
every molecule of that pseudocomponent. This system is inexact; for instance, the
two naphthenes and one aromatic in C7 all have six carbon atoms.
In another naming system, the pseudocomponents are called single carbon
number groups, or SCNs. For instance, the Heptanes discussed above would be

53
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

identified as SCN7, using the number of carbon atoms in the n-heptane at the end of
the area. This naming system is also not properly descriptive since the number seven
implies seven carbon atoms in all constituents of that group and this is not true.
It is doubtful that a truly descriptive system for naming these pseudocomponents
will be available in the foreseeable future.

The compositions of the pseudocomponents

The pseudocomponents (let’s call them SCNs) are mixtures of paraffins,
naphthenes, and aromatics. The naphthenes and aromatics in a particular SCN
generally have one less carbon atom than the paraffins in that SCN. Thus the name
single carbon number is a misnomer. In fact, the fused ring structures that appear in
the single carbon number groups of SCN13 and higher contain even fewer carbon
atoms than indicated by the SCN number. This problem is also true of the Cn and
n-alkane naming systems described above.

The relationship between composition and the pseudocomponent

numbers (SCN)
Figure 2–7a gives a plot of the composition of the petroleum reported in table
8–1 as mole percent versus either the number of carbon atoms or the SCN. The
numbers from 1 to 5 on the horizontal axis represent methane through pentanes (the
iso- and n- are combined). The numbers 6 and larger refer to SCNs. The vertical axis
has a logarithmic scale simply because of the very large range of the compositions
in the oil, in this case varying from less than 0.1 to almost 70 mole percent.
Common understanding in the petroleum industry is that a semi-log plot such
as figure 2–7b has a straight line from SCN6 out to the end. This is not correct.7
There is always a bump in this curve at SCN7 and SCN8. This is caused by the
large quantities of the smallest fragments of aromatics and naphthenes that
appear in the chromatographic column at this point. These include benzene,
toluene, methylcyclopentane (MECYPEN), cyclohexane, and methylcyclohexane
(MEXYHEX) (see fig. 2–6).
The line from SCN8 through SCN12 is straight (exponential). There is always
a discontinuity and a change of slope between SCN12 and SCN13. This occurs
due to the first appearance in the chromatographic column of enough of the fused
ring structures to affect the composition of SCN13. These are two-ring fused
structures, either two fused benzene rings (naphthalene), one benzene ring fused
to a cyclohexane ring (tetrahydronaphthalene), or two fused cyclohexane rings
(decahydronaphthalene).
The fused ring compounds that could possibly be found in SCN13 are
naphthalene and some of the structural and geometric isomers of methyltetrahy-
dronaphthalene, dimethyltetrahydronaphthalene, methyldecahydronaphthalene,
dimethyldecahydronaphthalene, and ethyldecahydronaphthalene.

54
 Chapter 2 | Petroleum

Smaller versions of these two-ring structures could be found in SCN12 but

their compositions in petroleum are usually negligible. Larger versions of these
fused-ring structures will be found in SCN groups heavier than SCN13.
The data from SCN13 to the heaviest SCN will form a straight line (exponential)
even out to SCN29 or SCN35 on a plot like figure 2–7b. Unfortunately the round-off
error for the heaviest pseudocomponents causes a lot of scatter in the plot (due to
very small compositions).

100

10
Composition, mole percent

1.0

0.1

0.01
0 5 10 15 20
SCN

Fig. 2–7a. Composition of a petroleum oil (from page 7/17 of table 8–1)

55
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

1.0
Composition, mole percent

0.1

0 5 10 15 20
SCN

Fig. 2–7b. The SCN part of the composition of figure 2–7a (Note that the data point plotted over
SCN20 is in reality Eicosanes plus)

Molecular weights of the pseudocomponents

Table 8–1, pages 4/17, 5/17, and 7/17, gives the values of molecular weights
used to convert the measured values of weight fraction to the reported values of
mole fraction (mole percent). The top ten of these molecular weights are for pure
components and may be found in many fluid property tabulations (see, for instance,
appendix A).
The next group of molecular weights, for SCN6 (hexanes) through SCN19
(nonadecanes), was obtained from the tabular correlation in table 2–1.

56
 Chapter 2 | Petroleum

Table 2–1. Generalized properties of the single carbon number groups9

Hydrocarbon Boiling Range Average Boiling Point Density Molecular
Group °C °F °C °F (g/ml) Weight
C6 36.5 to 69.2 97.7 to 156.7 63.9 147 0.685 84
C7 69.2 to 98.9 156.7 to 210.1 91.9 197.5 0.722 96
C8 98.9 to 126.1 210.1 to 259.1 116.7 242 0.745 107
C9 126.1 to 151.3 259.1 to 304.4 142.2 288 0.764 121
C10 151.3 to 174.6 304.4 to 346.4 165.8 330.5 0.778 134
C11 174.6 to 196.4 346.4 to 385.5 187.2 369 0.789 147
C12 196.4 to 216.8 385.5 to 422.2 208.3 407 0.800 161
C13 216.8 to 235.9 422.2 to 456.7 227.2 441 0.811 175
C14 235.9 to 253.9 456.7 to 489.2 246.4 475.5 0.822 190
C15 253.9 to 271.1 489.2 to 520 266 511 0.832 206
C16 271.1 to 287.3 520 to 547 283 542 0.839 222
C17 287 to 303 547 to 577 300 572 0.847 237
C18 303 to 317 577 to 603 313 595 0.852 251
C19 317 to 331 603 to 628 325 617 0.857 263
C20 331 to 344 628 to 652 338 640.5 0.862 275
C21 344 to 357 652 to 675 351 664 0.867 291
C22 357 to 369 675 to 696 363 686 0.872 305
C23 369 to 381 696 to 717 375 707 0.877 318
C24 381 to 392 717 to 737 386 727 0.881 331
C25 392 to 402 737 to 756 397 747 0.885 345
C26 402 to 413 756 to 775 408 766 0.889 359
C27 413 to 423 775 to 793 419 784 0.893 374
C28 423 to 432 793 to 810 429 802 0.896 388
C29 432 to 441 810 to 826 438 817 0.899 402
C30 441 to 450 826 to 842 446 834 0.902 416
C31 450 to 459 842 to 857 455 850 0.906 430
C32 459 to 468 857 to 874 463 866 0.909 444
C33 468 to 476 874 to 888 471 881 0.912 458
C34 476 to 483 888 to 901 478 895 0.914 472
C35 483 to 491 901 to 915 486 908 0.917 486
C36 493 922 0.919 500
C37 500 934 0.922 514
C38 508 947 0.924 528
C39 515 959 0.926 542
C40 522 972 0.928 556
C41 528 982 0.930 570
C42 534 993 0.931 584
C43 540 1,004 0.933 598
C44 547 1,017 0.935 612
C45 553 1,027 0.937 626

57
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

The labels on the last two columns of table 2–1 should include the word average
since the numbers listed are based on averages of the properties of the components
included in each SCN.
This correlation is based on limited data and is therefore somewhat suspect. For
instance, the SCN labeled C6 contains n-hexane, a couple of the structural isomers
of hexane (all with molecular weights of slightly over 86), and cyclopentane
(molecular weight slightly over 70). In order for the average molecular weight of
this SCN to be 84 (as reported), the cyclohexane content of the SCN would have
to be about 0.4 mole fraction. This quantity of cyclopentane would never exist in a
petroleum oil. However, this correlation is currently the best available.10
The value of the molecular weight of the heaviest fraction (in the case of
table 8–1, Eicosanes plus) is based on a molecular weight measurement. The
laboratory separates a liquid fraction (a grouping of the components heavier
than C7 and lighter than the desired plus fraction) from the original reservoir
fluid sample. The molecular weight of this liquid is measured and the molecular
weight of the reported plus fraction is calculated using the weight fractions and
average molecular weights of the SCN groups that were included in the separated
liquid. The laboratory procedure for measuring this molecular weight is not very
precise, and its error plus the errors in the SCN molecular weights (tabulated in the
correlation) are propagated into the reported molecular weight of the plus fraction.
So the accuracy of the reported value of the molecular weight of the plus fraction
is even more suspect.

So What Does the Refiner Do?

The first thing that happens to petroleum oil at a refinery is separation into
fractions by distillation. Table 2–2 gives the fractions that are typically separated
in this first step.

Table 2–2. Typical petroleum oil fractions

Boiling point, °F Approximate chemical
Crude fraction Uses
(melting point) composition
Hydrocarbon gas C1–C2 Fuel gas
to 100 C3–C6 Bottled fuel gas, solvent
Gasoline 100–350 C5–C10 Motor fuel, solvent
Kerosene 350–450 C11–C12 Jet fuel, cracking stock
Light gas oil 450–580 C13–C17 Diesel fuel, furnace fuel
Heavy gas oil 580–750 C18–C25 Lubricating oil, bunker fuel
Lubricants and 750–950 C26–C238 Lubricating oil, paraffin wax,
waxes (100) petroleum jelly
Residuum 950+ C38+ Tars, roofing compounds, paving
(200+) asphalts, coke, wood preservatives

58
 Chapter 2 | Petroleum

These fractions are submitted to further processing, either physical or chemical, in

the refinery to produce saleable products.

Classification of Crude Oils

Crude oils may be classified by physical properties or by the chemical structure
of the constituent molecules. Chemical structures are much more difficult to
measure than physical properties.

Physical classification
Commercial value of a petroleum liquid can be estimated quickly through
measurement of the following physical characteristics:
• Specific gravity (API gravity)
• Gasoline and kerosene content
• Sulfur content
• Asphalt content
• Pour point
• Cloud point
The specific gravity and API gravity of a liquid are defined in chapter 10. The
next three of these properties have already been discussed. Pour point is the lowest
temperature, expressed as a multiple of 5°F, at which the liquid is observed to flow
when cooled under prescribed conditions. Cloud point is the temperature at which
paraffin wax begins to solidify. This state is identified by the onset of turbidity as
the temperature is lowered. Both tests qualitatively measure the paraffin content of
the liquid.

Chemical classification
Chemical classifications of petroleum relate to the molecular structures of the
molecules in the oil. Of course, the smaller molecules, six carbon atoms and less,
are predominately paraffins. So chemical classification is usually based on analysis
of the petroleum after most of the light molecules (the gas) are removed.
Terms such as paraffinic, naphthenic, naphthenic-aromatic, and aromatic-
asphaltic are used in the several classification methods that have been proposed.
These terms obviously relate to the molecular structure of the chemical species
most prominent in the crude oil mixture. However, such classification is made
difficult because the large molecules usually consist of condensed aromatic and
naphthenic rings with paraffinic side chains. The characteristic properties of the
molecules depend on the proportions of these structures.

59
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

One classification method treats a large molecule as aromatic if it has a single

benzene ring, regardless of the other content. Another method considers the
fraction of each molecule that is aromatic, naphthenic, or paraffinic. Obviously, in
either case the analysis procedure is tedious. A third classification method simply
measures the specific gravities of several fractions separated by distillation and
attempts to relate chemical structure to specific gravity.
Another classification system, called SARA, describes the composition of
petroleum as weight fractions of Saturates (paraffins and naphthenes), Aromatics,
Resins, and Asphaltenes. The procedure for separating an oil into these fractions
does not give precise results; however, this classification system is sometimes
helpful in predicting the performance of various recovery processes.
The petroleum industry has not agreed on a standard classification system.
Further, the classification of crude oil is of little importance to its production, with
the exceptions that paraffinic crudes can precipitate wax and plug the production
string and asphaltic crudes can cause several problems with regard to asphaltene
precipitation. Consequently, classification systems will not be examined in detail.
Kinghorn gives a good review of chemical classification systems (1983).

Exercises
2–1. The table below gives the composition measured in a laboratory of
a petroleum oil (a reservoir oil–bottom-hole sample). Calculate the
composition of this oil in mole fraction.
Component composition Weight fraction
Methane 0.0688
Ethane 0.0400
Propane 0.0398
i- Butane 0.0047
n- Butane 0.0221
i- Pentane 0.0076
n- Pentane 0.0134
Hexanes 0.0196
Heptanes plus 0.7840
1.0000
Properties of heptanes plus
 Molecular weight 248
  Specific gravity 0.8340

2–2. A lot of experience has shown that the reported value of the molecular
weight of heptanes plus (C7+) can be in error by as much as 20%.11 Repeat
exercise 2–1 using a molecular weight for the heptanes plus of 200 lb/lb

60
 Chapter 2 | Petroleum

mole—approximately 20% less than the value reported. Compare your

results with the results of exercise 2–1.
2–3. Figure 2–6 is the chromatogram of a petroleum oil (probably a separator
oil). Shade the area that will be used to calculate the composition of SCN8
(Octanes, C8).
2–4. Repeat exercise 2–3 for SCN10 (Decanes, C10).

Nomenclature
Latin
Mj Molecular weight of component j, lb/lb mole
wj Composition of component j, weight fraction, lb of j/lb total
xj Composition of component j in liquid, mole fraction,
lb mole of j/lb mole total

General References
Hunt, J. M. Petroleum Chemistry and Geology. 2nd Ed. New York: W. H. Freeman and
Company, 1996.
Mullins, O. C., Sheu, E. Y., Hammami, A., and Marshall, A. G., eds. Asphaltenes, Heavy
Oils, and Petroleomics. New York: Springer, 2007.
Kinghorn, R. R. F. An Introduction to the Physics and Chemistry of Petroleum. New York:
John Wiley, 1983.

Notes
1. Hascakir, B., Texas A&M University, personal communication.
2. Freed, D. E., Lisitza, N. V., Sen, P. N., and Song, Y.-Q., “Molecular Composition and
Dynamics of Oils from Diffusion Measurements,” in Asphaltenes, Heavy Oils, and
Petroleomics, edited by O. C. Mullins et al. (New York: Springer, 2007), 279–300.
2. Mullins, O. C., The Modified Yen Model (Cambridge, MA: Schlumberger-Doll
Research, 2011), 6.
3. Hunt, J. M., Petroleum Chemistry and Geology, 2nd ed. (New York: W. H. Freeman
and Company, 1996), 61.
4. Ibid., 208.
5. Podbielniak, W. J., “Low Temperature Fractional Analysis of Liquids and Gases,
II Fundamentals of Operating Technique, Causes and Cures of Errors,” Petroleum
Refiner 30 (1951), 145–155.
61
THE PROPERTIES OF PETROLEUM FLUIDS, THIRD EDITION

6. Hosein, R., and McCain, W. D., Jr., “Extended Analysis for Gas Condensate
Systems,” SPE Reservoir Evaluation and Engineering, 12 (2009), 159–166.
7. Hascakir, B., personal communication.
8. Katz, D. L., and Firoozabadi, A., “Predicting Phase Behavior of Condensate/
Crude-Oil Systems Using Methane Interaction Coefficients,” Journal of Petroleum
Technology (1978), 1649–1655.
9. Al-Meshari, A. A., and McCain, W. D., Jr., “Validation of Splitting the Hydrocarbon
Plus Fraction: First Step in Tuning Equation of State,” paper SPE104631 presented at
the 15th SPE Middle East Oil & Gas Show and Conference, Bahrain, March 11–14,
2007.
10. Al-Meshari, A. A., and McCain, W. D., Jr., “New Strategic Method to Tune Equation-
of-State for Compositional Simulation,” paper SPE106332 presented at the SPE
Technical Symposium of Saudi Arabia Section, Dhahran, Saudi Arabia, May 14–16,
2005; Pedersen, K. S., Fredenslund, A., and Thomassen, P., “Properties of Oil and
Natural Gases,” Contributions in Petroleum Geology & Engineering 5 (1989), 167.
11. Hascakir, B., personal communication.

62