1.
Composition and physical properties
of hydrocarbons
1.1.1 Introduction
Petroleum is a naturally occurring liquid, gaseous
or even solid mixture, composed principally
of hydrocarbons, that accumulates in subterranean
reservoirs. As a generic term that keeps varying
with time, petroleum is difficult to define precisely.
In this text, it is used interchangeably
with hydrocarbons when these compounds represent
the predominant portion in the mixture.
However, our discussion will not be exclusive
to hydrocarbons but will also include relevant
non-hydrocarbons.
The constituents of a natural reservoir fluid form
an almost continuous hydrocarbon spectrum
from the lightest one, methane, through intermediate
molecular weights and up to very large molecules.
The relative proportion of these different parts
can vary in a large range, which results in petroleum
fluids showing very different features.
For instance, the simplest reservoir fluids
are natural gas, while the most complex molecular
mixtures are those of black oil and bitumen.
As can be seen from this example, the physical
properties of a petroleum fluid are determined
by its composition and, moreover, many of these
vary significantly as a function of temperature
and pressure. Petroleum reservoirs have temperatures
that vary from ambient to more than 200C
and a pressure that can be as high as 150 MPa.
The reservoir conditions depend on the depth
of the reservoir and on the geological processes
that the reservoir has experienced since it was filled
by the reservoir fluid.
The temperature and pressure change dramatically,
relative to the reservoir conditions, during production
where the pressure is lowered to fulfil transport
and storage conditions. These changes in temperature
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
and pressure will often lead to a change in the state of
the mixture from a single phase state to a two-phase
state where the two phases will each have a different
composition in comparison to the original petroleum
fluid. Therefore, the properties of the new phases
will change with the change in composition,
temperature and pressure. Even within the reservoir
the physical state of the mixture (gas, liquid or solid)
can change due to varying composition, temperature
and pressure.
1.1.2 Composition of petroleum
fluids
Two important questions regarding the composition
of petroleum fluids are what is in the mixture?
(qualitative chemical analysis) and how can the
amount of each component be quantitatively
determined? (quantitative chemical analysis).
The chemical composition of petroleum is largely
speculative due to the difficulty of a complete
identification caused by the enormous number
of components. For a hydrocarbon with a given
molecular formula CxHy, the number of possible
isomers increases dramatically as the molecule
becomes larger. To illustrate this point, Fig. 1 shows
how drastically the number of possible isomers
increases in the paraffin group alone. Even though not
all of them exist in real oils, the presence of other
hydrocarbon groups and heterocompounds
will complicate the task. Even for the paraffins in the
C5-C12 range, the number of possible isomers is
greater than 600 (Altgelt and Boduszynski, 1994),
around 200-400 of which have been experimentally
observed (though not all identified).
Fortunately, in most cases, we do not need an
all-out effort to identify and quantify all of the
31
GEOSCIENCES

1040 (Speight, 2001) as shown by the following values

of percentage weight:
5.92.1039
1030
number of isomers

1.06.1031
1020
2.21.1022
6.24.1013
1010 .
4.11 109
3.66.103
3
75
1
0 10 20 30 40 50 60 70 80 90 100 110
carbon number
Fig. 1. Increase in the number of isomers
with carbon number in paraffin.
components. Hydrocarbons up to and including C5
are easily determined on a molar basis.
The remaining identified components, which
normally go up to 20, or in some cases 30, carbon
atoms, are not individual molecular compounds
but rather fractions defined by a normal boiling
point range. These fractions are defined based on
the normal boiling point of the normal alkanes and
are called the C6 , C7, etc. fractions (or components)
according to the carbon number of the normal alkane
within the fraction. Finally, the part of the oil
that cannot be analysed is called the residue
or plus fraction: for example, the symbol C20
indicates the residue that includes the C20 fraction
and all of the material in the oil less volatile than
this. The above compositional analysis is generally
considered to be sufficient in terms of oil
characterization for physical property studies.
However, some laboratories systematically identify
all components up to C12 by the use of gas
chromatography combined with mass spectroscopy.
Chemical composition
Gases produced from a petroleum reservoir mainly
contain alkanes lighter than heptane, with methane and
ethane being the predominant components. However,
light non-hydrocarbons including nitrogen, carbon
dioxide, and hydrogen sulphide are also common, their
proportions being related to the reservoir where they
originate from.
Petroleum liquid, or crude oil, contains larger
molecules and its appearance, composition,
and other properties vary a lot with different
petroleum reservoirs. Nevertheless, nearly
all naturally occurring petroleum liquids have fairly
narrow limits of elemental composition
Carbon: 83.0-87.0%
Hydrogen: 10.0-14.0%
Nitrogen: 0.1-2.0%
Oxygen: 0.05-1.5%
Sulphur: 0.05-6.0%
The narrow range of the carbon to hydrogen ratio
reflects the fact that CH2 group is the primary
unit in various organic molecules in crude oils.
Generally speaking, components in petroleum
liquids can be classified into hydrocarbons
and heterocompounds. The term hydrocarbon
is used for molecules made up only of carbon
and hydrogen atoms. On the other hand,
heterocompounds are compounds which, in addition
to carbon and hydrogen, also contain one or more
heteroatoms such as sulphur, nitrogen, oxygen,
vanadium, nickel or iron.
The principal chemical and physical characteristics
of three crudes originating from three different
oilfields and the hydrocarbon fractions obtained
from these using the true boiling point distillation
method (see below) are reported in Table 1.
Hydrocarbon components
The hydrocarbon components of petroleum fall
into three groups: paraffins, naphthenes and aromatics.
Olefins (also called alkenes) are so scarce in naturally
occurring petroleum that they may be neglected.
Also, the presence of dienes (RCHCHR')
and acetylenes (RCCR') is considered to be
extremely unlikely.
Paraffins, also known as acyclic alkanes, are
saturated hydrocarbons with straight (normal paraffin)
or branched (isoparaffin) chains, but without any ring
structure. Both normal and isoparaffins have the same
molecular formula CnH2n+2.
Naphthenes, also known as cycloalkanes
or alicyclic hydrocarbons, are saturated hydrocarbons
containing one or more rings, each of which may have
one or more paraffinic side chains. Naphthenes
are present in all fractions in which the constituent
molecules contain more than five carbon atoms.
Aromatics are compounds containing at least
one benzene ring. Many of the aromatic hydrocarbons
in petroleum consist of aromatic and naphthenic
rings and bear normal and/or branched alkane side
chains.
The proportions of the above three groups vary
with the type of crude, but within any crude oil,
the proportion of paraffinic hydrocarbons usually
decreases with increasing molecular weight or boiling

32 ENCYCLOPAEDIA OF HYDROCARBONS
 Table 1. Chemical and physical characteristics of three crudes originating in different fields

Crude A Yields and characteristics of products

Crude
Oil Gas Naphthas Kerosines Gasoils V. Dist. Residues
TBP range C1-C4 C5-80 80-160 80-180 160-230 180-230 230-370 370-416 370-530 370+ 410+ 530+
TBP Distillation A
TBP yield % wt 0.29 0.97 2.04 3.12 7.18 6.10 24.23 5.14 21.47 65.31 60.17 43.84
TBP yield % vol 0.50 1.37 2.65 3.98 8.54 7.20 26.71 5.35 21.52 60.28 54.93 38.77 Cut %Wt Cum
point
Density at 15C kg/l 0.9624 0.5491 0.6800 0.7408 0.7531 0.8090 0.8149 0.8730 0.9248 0.9603 1.0426 1.0541 1.0883
API Gravity at 60F 15.5 C1
Viscosity at 20C cSt 1585.94 C2

VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT

Viscosity at 50C VBN 4.31 5.25 15.80 25.69 32.12 48.76 50.73 56.90 C3 0.08
Sulphur % wt 6.70 0.0500 0.3850 0.4506 1.7650 1.8700 3.35 4.85 6.22 8.66 8.99 9.36 i-C4 0.16
Mercaptan sulphur ppm 310 168 108 93 52 36 n-C4 0.28
Hydrogen sulphide % wt 0.001 i-C5 0.40
Acidity mgKOH/g 2.13 0.77 0.79 0.78 1.50 1.62 n-C5 0.55
Paraffins % vol 82.2 70.7 66.1 80 1.25
Naphthenes % vol 13.8 21.1 22.9 100 1.45
Aromatics % vol 4.0 8.2 11.0 23.8 25.1 120 1.81
N+2A index 21.7 37.5 44.9 140 2.45
Smoke Pt. mm 24 23 160 3.29
Freezing Pt. C 56 53 180 4.37
Cloud Pt. C 6 21 210 7.91
Pour Pt. C 15 9 18 53 68 >100 230 10.47
Cetane index 46.7 48.5 250 13.33
Total nitrogen % wt 0.00003 0.00003 0.00003 0.00003 0.3854 0.4796 270 16.82
Basic nitrogen ppm 399 521 290 20.67
Nickel ppm 75.8 0.14 16.1 126.0 172.9 320 26.75
Vanadium ppm 105.3 1.9 161.2 175.0 240.2 350 31.34
P. Value 3.0 3.3 2.9 370 34.69
Asphaltenes % wt 12.89 19.73 21.42 29.40 390 37.39
R.C.C. % wt 8.66 1.07 13.26 14.78 19.76 410 39.83
Penetration at 25C dmm 530 56.16
UOP K factor 12.05 11.89 11.40 11.30 550 61.89
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS

33
34
Table 1. Chemical and physical characteristics of three crudes originating in different fields
GEOSCIENCES

Crude B Yields and characteristics of products

Crude
Oil Gas Naphthas Kerosines Gasoils V. Dist. Residues
TBP range C1-C4 C5-80 80-160 80-180 160-230 180-230 230-370 370-416 370-530 370+ 410+ 530+
TBP yield % wt 1.11 4.39 13.78 17.79 13.40 9.39 24.72 5.05 21.55 42.61 36.56 21.06 TBP Distillation B
TBP yield % vol 1.72 5.74 16.19 20.66 14.70 10.23 24.78 5.71 19.73 37.15 31.44 17.42
Density at 15C kg/l 0.8652 0.5549 0.6606 0.7368 0.7449 0.7883 0.7945 0.8630 0.9170 0.9452 0.9924 1.0061 1.0460
Cut %Wt Cum
point
API gravity at 60F 32.0
Viscosity at 20C cSt 8.77 C1 0.00

Viscosity at 50C VBN 2.81 4.23 15.25 25.08 30.62 38.57 40.80 46.70 C2 0.02

Sulphur % wt 2.80 0.0350 0.0380 0.0787 0.1850 0.2250 2.25 3.46 3.72 5.06 5.33 6.44 C3 0.30

Mercaptan sulphur ppm 186 264 224 241 306 305 i-C4 0.46

Hydrogen sulphide % wt 0.001 n-C4 1.10

Acidity mgKOH/g 0.09 0.11 0.14 0.07 0.08 0.06 i-C5 1.69

Paraffins % vol 90.4 74.2 70.5 n-C5 2.75

Naphthenes % vol 7.4 13.4 15.7 80 5.49

Aromatics % vol 2.3 12.4 13.8 21.0 21.9 100 8.52

N+2A index 11.9 38.2 43.3 120 11.74

Smoke Pt. mm 26 25 140 15.42

Freezing Pt. C 54 48 160 19.27

Cloud Pt. C 4 25 180 23.28

Pour Pt. C 15 9 24 30 33 67 210 29.06

Cetane index 49.7 52.2 230 32.67

Total nitrogen % wt 0.00003 0.00003 0.00003 0.00003 0.2446 0.3329 250 36.39

Basic nitrogen ppm 190 302 270 40.26

Nickel ppm 4.8 0.14 11.2 13.0 22.6 290 43.82

Vanadium ppm 2.9 1.9 6.9 8.0 13.9 320 48.13

P. Value 4.8 5 350 54.21

Asphaltenes % wt 0.56 1.32 1.54 2.67 370 57.39

R.C.C. % wt 4.39 0.44 10.31 12.28 20.87 390 60.45

Penetration at 25C dmm 410 63.44

UOP K factor 12.38 12.02 11.73 11.89 530 78.94

550 81.90

ENCYCLOPAEDIA OF HYDROCARBONS
 Table 1. Chemical and physical characteristics of three crudes originating in different fields

Crude C Yields and characteristics of products

Crude
Oil Gas Naphthas Kerosines Gasoils V. Dist. Residues
TBP range C1-C4 C5-70 70-160 160-230 180-230 230-370 370-416 370-530 370+ 410+ 530+
TBP yield % wt 2.60 4.80 17.57 16.25 11.57 29.56 6.64 19.91 29.22 22.58 9.31 TBP Distillation C
TBP yield % vol 3.86 5.95 19.49 16.84 11.89 28.66 6.16 18.09 25.81 19.65 7.72
Density at 15C kg/l 0.8110 0.5447 0.6544 0.7311 0.7825 0.7894 0.8364 0.8741 0.8926 0.9181 0.9320 0.9780 Cut %Wt Cum
point
API gravity at 60F 42.9
Viscosity at 20C cSt 3.56 C1

Viscosity at 50C VBN 4.99 15.56 24.28 28.43 32.96 35.52 42.67 C2

VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT

Sulphur % wt 0.24 0.0009 0.0006 0.0156 0.0210 0.19 0.42 0.46 0.62 0.68 0.98 C3 0.05

Mercaptan sulphur ppm 10 3 i-C4 0.90

Hydrogen sulphide % wt n-C4 1.67

Acidity mgKOH/g 0.05 0.04 0.04 0.03 i-C5 2.60

Paraffins % vol 93.7 74.3 n-C5 3.66

Naphthenes % vol 4.1 21.0 70 5.03

Aromatics % vol 2.2 4.7 8.5 9.1 100 7.40

N+2A index 8.5 30.4 120 11.87

Smoke Pt. mm 32 30 140 15.74

Freezing Pt. C 51 45 160 20.24

Cloud Pt. C 2 180 24.97

Pour Pt. C 36 5 26 30 33 39 210 29.65

Cetane index 61.3 72.3 230 36.99

Total nitrogen % wt 0.0001 0.0001 0.0053 0.0274 0.0303 0.1300 0.1600 0.3200 250 13.33

Basic nitrogen ppm 104 162 270 41.22

Nickel ppm 0.5 1.5 2.0 4.8 290 45.73

Vanadium ppm 3.4 12.0 15.0 35.0 320 50.56

P. Value 1.1 1.1 1.2 350 54.80

Asphaltenes % wt 0.73 2.50 7.90 370 61.69

R.C.C. % wt 1.46 0.05 50.01 6.48 15.60 390 67.05

Penetration at 25C dmm 410 73.99

UOP K factor 12.15 12.00 11.90 11.90 530 77.42

530 90.69
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS

35
GEOSCIENCES
paraffins
weight (%)
naphthenes
naphtheno-aromatics
aromatics
heteroatomic
compounds
boiling point
Fig. 2. Distribution of various compound types
throughout petroleum (Speight, 2001).
point (Fig. 2). As the boiling point of the petroleum
fraction increases, not only will the number of
constituents increase but so also will the molecular
complexity of the constituents.
Non-hydrocarbon components
(heterocompounds)
The non-hydrocarbon components of petroleum
consist of: sulphur compounds commonly including
thiols, sulphides, cyclic sulphides, disulphides,
benzothiophene, dibenzothiophene and
naphthobenzothiophene; oxygen compounds
including alcohols, ethers, carboxylic acids, esters,
ketones and furans; and nitrogen compounds
including pyrrole, indole, carbazole,
benzo(a)carbazole, pyridine, quinoline, indoline, and
benzo(f)quinoline. Among the non-hydrocarbon
species present in petroleum certain metals can also
be found. These heterocompounds, as well as metals,
are generally found only in the non-volatile portion
of crude oil (Speight, 2001).
The concentration of these heterocompounds is
usually quite small, although it tends to increase with
increasing boiling point (see again Fig. 2).
Furthermore, their presence mainly influences the
processibility of the crude oil and the quality of the
petroleum products rather than the physical properties
of petroleum.
Compositional analysis
Reservoir fluid samples at elevated pressure cannot
be introduced into a Gas Chromatography instrument
for direct analysis unless a special high pressure
injection technique is employed. Therefore, the high
pressure samples are generally separated into
atmospheric gas and oil which are analysed separately.
Sampling, recombination and analysis of hydrocarbon
36
gases and oils constitute the main aspects in obtaining
the representative overall composition of a reservoir
fluid. For a discussion of the sampling and
recombination procedures, see chapters 3.3 and 4.2.
Analysis of hydrocarbon
gases and oils
The composition of hydrocarbon gases can be
determined by Gas Chromatography (GC) and that of
oils by True Boiling Point (TBP) distillation or
simulated distillation. Furthermore, Mass
Spectroscopy (MS) can be used together with GC for
the most detailed analysis.
Gas Chromatography. GC is a chromatographic
method for separating volatile components using a gas
as a mobile phase. A small amount of sample is
introduced into the gas chromatograph through a
heated injection port, where the liquid (if any) is
vaporized. This sample is then transported by a carrier
gas, e.g. helium, into a column coated or packed with
a stationary phase. Components in the sample are
retained by the stationary phase, then released and
displaced forward by the upstream carrier gas, and,
finally, elute in the reverse order of their affinity to the
stationary phase, that is, with respect to the force with
which they are retained. Gas chromatography can have
up to one million theoretical equilibrium stages and
thus has a high separation ability. The eluted
components can be identified by their retention times,
which are calibrated in advance, and quantified by
different detectors. The two most commonly used
detectors are the Flame Ionization Detector (FID) and
the Thermal Conductivity Detector (TCD), where the
former is usually employed for hydrocarbons and the
latter for non-hydrocarbons.
True Boiling Point (TBP) distillation. True Boiling
Point distillation is traditionally used in analysing oil
by fractionating it into relatively narrow fractions or
cuts. These TBP fractions can then be treated as
components with specific boiling points, molecular
weights and critical properties, that is, in the same way
as a pure component.
Distillation separates molecules by their difference
in volatility (vapour pressure, boiling point). However,
it cannot be taken for granted that distillation is based
on molecular weight difference. Although the volatility
of hydrocarbons decreases with molecular weight
within each homologous series, the difference between
boiling points in the different homologous series is
quite substantial. An increase in aromaticity and
polarity decreases the volatility and increases the
boiling point.
TBP distillation consists of distillations both at
atmospheric pressure and at reduced pressure.
Atmospheric distillation is confined to a maximum
ENCICLOPEDIA DEGLI IDROCARBURI

reboiler temperature of 345C to avoid decomposition.
Subsequently, vacuum distillation at pressures ranging
from 5 to 200 mmHg (~0.7-27 kPa) is usually used to
separate higher fractions. The boiling points
determined at reduced pressure are converted to so-
called Atmospheric Equivalent Temperatures (AET),
which are hypothetical boiling points at atmospheric
pressure if decomposition could be avoided.
The standard American Society for Testing
Materials (ASTM) D-2892 describes the TBP
distillation procedure in detail. In practice, different
variations can be implemented.
In general, TBP distillation is a standard method of
oil analysis, which fractionates oil truly according to
their boiling points. Moreover, physical samples of
each fraction can be obtained and further
determination of their physical properties, e.g.
molecular weight and specific gravity, is possible.
However, the drawback of TBP distillation is that it
requires large amounts of sample (1-10 litres) and a
long analysis time (100 hours). Pedersen et al. (1989b)
suggested using a mini-distillation apparatus which
only requires 100 ml sample.
The normal boiling points of paraffin plus 0.5C,
as suggested by Katz and Firoozabadi (1978), are
generally accepted as boundaries between different
fractions, and the resulting narrow fractions are often
called Single Carbon Number (SCN) fractions, to
emphasize that they contain compounds whose boiling
points fall within a narrow range. Each of these SCN
fractions is named after the number of carbon atoms of
the n-alkane in the fraction, e.g. C7, C8, etc.
Simulated distillation. Simulated distillation is
essentially a low resolution gas chromatography
method. The method is based on the observation that
hydrocarbons are sequentially eluted from a non-polar
column almost in the order of their boiling points.
After calibration with normal alkanes, the retention
times for an oil sample can be readily converted to
boiling points. In the case where complete elution of
heavy ends is impossible, an internal standard must be
used to determine the amount of eluted fractions.
Simulated distillation is preferred to the TBP
method since it is quick and requires only a small
amount of sample. On the other hand, no physical
fractions can be obtained with this method and
therefore their molecular weights and specific
gravities are unavailable.
ASTM D-2887 is a simulated distillation standard
up to approximately 540C (1,000F) atmospheric
equivalent boiling point. However, recent efforts have
focused on extending the range up to 800C (1,470F).
Gas Chromatography coupled to Mass
Spectrometry (GC-MS) and others. In the GC-MS
method, a gas chromatography instrument and a mass
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS
spectrometer are employed in series. GC serves as a
separation procedure of different compounds,
whereas MS provides the molecular weight, the
chemical formula and the amount of each compound.
The GC-MS analysis can be applied to gas or oil
samples. Using this method, each individual
substance in the mixture can, in principle, be
detected quantitatively if the amount is above the
detection limit. However, with increasing boiling
point, the number of possible molecular structures
increases dramatically, while the concentration of the
compounds generally decreases, and thus the MS
analysis becomes increasingly difficult. Therefore, a
significant fraction of the oil will be unrecognized by
the GC-MS and its amount will be determined by a
mass balance in which all of the detected compounds
are subtracted from the total oil.
GC-MS can determine the distribution of paraffins,
naphthenes and aromatics (indicated by the acronym:
PNA) in a SCN fraction. Information about the PNA
distribution can be used to improve the C7+
characterization. However, a complete PNA
distribution of the whole oil is difficult to obtain and
even if it is available, many uncertainties still exist in
evaluating the properties of heavy components. In this
sense, PNA analysis has limited usefulness in practical
characterization.
A more detailed discussion of different analysis
methods, especially for heavy petroleum fractions can
be found in Altgelt and Boduszynski (1994).
1.1.3 Physical properties
of hydrocarbons
In quantitative simulations of the production and
processing of petroleum fluids, two approaches to
the description of petroleum fluids are usually
employed: the black oil approach, where the fluid is
described by only two components, oil and gas, and
the compositional approach, where the fluid is
described by a number of components. The black oil
approach is directly based on Pressure-Volume-
Temperature (PVT) experiments (see Chapter 4.2),
however, its modelling of phase equilibria and
physical properties is approximate. On the other
hand, the compositional approach employs
Equations Of State (EOS) and provides a more
accurate fluid estimation.
EOS modelling requires a detailed knowledge of
the molar composition of the mixture and the critical
properties and the acentric factor of all the
components. The next section discusses how to obtain
the required information either experimentally or
through a characterization procedure.
37
GEOSCIENCES
A major step in modelling the physical properties
of reservoir fluids is to calculate volumetric properties
and associated phase equilibria (PVT modelling) as
well as other important physical properties such as
viscosity and interfacial tension. A discussion of these
issues is presented in the following.
Physical properties of narrow distillation
cuts and their characterization
The compositional analysis cannot provide the
required information for all of the real components in
a petroleum mixture. The compositional information
obtained varies with boiling point range. Hydrocarbon
components up to C6 and non-hydrocarbon gases (N2,
CO2 and H2S) can be quantified discretely and the
properties of these well-defined components are
readily found in handbooks. The low boiling range in
the C7+ fractions (e.g. up to C30) can be fractionated in
terms of narrow TBP fractions and their molecular
weights and specific gravities can be experimentally
determined. For the heavy end of the C7+ fractions,
TBP residue, no further analysis of the molar
distribution is made and only the molecular weight and
specific gravity of the whole residue are
experimentally determined. It is also very common
that the only available information about the C7+
fraction is its molar composition, specific gravity and
molecular weight.
To create a set of components, which can be
directly used by the EOS method, from the limited
compositional information, proper characterization of
the C7+ fraction is needed. This characterization
roughly includes two steps: determination of the molar
composition of all components (including the C7+
fractions) and estimation of the critical properties and
the acentric factor (see below) of the C7+ fractions. In
practice, the number of components in a characterized
oil is too high for simulation purposes and lumping to
a lower number of pseudocomponents is generally
undertaken. Each pseudocomponent is a mixture
rather than a pure compound, however, they are treated
as pure compounds with specific physical properties
in the calculations.
The properties involved in characterization include
the molecular weight, M, the normal boiling point Tb,
the specific gravity g, the critical temperature Tc, the
critical pressure Pc, and the acentric factor w. M is
used to convert weight fractions from compositional
analysis to molar fractions. Tb and g are used for
estimating Tc, Pc and w, which are used almost
exclusively for EOS modelling. In the following
sections, the properties mentioned above will be
defined and the experimental methods used to
determine the measurable properties will be described;
38
moreover, correlations between these properties will
be discussed, and different characterization methods
will be introduced.
Properties
Molecular weight (M). For well defined molecular
structures the molecular weight is easily calculated
from the atomic masses of the constituents. In the case
of the fractions, the average molecular weight can be
measured by the following methods: vapour pressure
osmometry, freezing point depression, boiling point
elevation, gel permeation chromatography and non-
fragmenting mass spectrometry (Speight, 2001). The
different methods have advantages and drawbacks,
which make them suitable for different molecular
weight ranges.
Vapour pressure osmometry, freezing point
depression and boiling point elevation are all based on
the assumption that the change in the corresponding
properties (vapour pressure, freezing point, and
boiling point) in a pure solvent caused by introduction
of a solute at low concentration is directly proportional
to the concentration of the solute. Gel permeation
chromatography, also known as size exclusion
chromatography, takes advantage of the difference in
elution time between molecules with different sizes.
Non-fragmenting mass spectrometry principally
provides detailed information of the hydrocarbon
types, the formulae and the concentration of all the
components in a fraction.
Normal boiling point (Tb ). The normal boiling
point of a pure substance is the temperature at which
the substance changes state from liquid to vapour at a
pressure of 1 atm (0.1013 MPa). This property is
known and tabulated for all the pure components
normally considered in petroleum engineering except
for the high boiling substances that do not have a
boiling point at atmospheric pressure. For the
distillation fractions the normal boiling point is
usually chosen to be a certain average value of the
temperature interval of the distillation fraction.
Density (r) and specific gravity (g). The density r
is defined as the mass divided by the volume at a
certain temperature and pressure. This can be
measured for pure components, fractions and
petroleum fluids by different methods. The most
widely used techniques are the following:
Pycnometry, where the mass of a calibrated volume
is determined before and after filling with the
substance to be investigated. Pycnometers for high
pressure and high temperature are available but have
to be calibrated carefully at the relevant conditions.
Oscillating tube or vibrating tube densimetry,
where a tube of glass, for low pressure, and
of metal, for high pressure, is exposed to forced
ENCYCLOPAEDIA OF HYDROCARBONS

oscillations. The resonance frequency is measured
and if the apparatus has been calibrated with a fluid
of similar density, the resonance frequency of the
sample can be converted into its density. The
method is convenient for high pressure measurements
since it can be connected directly to other high pressure
equipment. It should be noted that for measurements
at very high pressure and high temperature the
calibration has to be repeated frequently.
Displacement method, where a known volume is
transferred into a vessel that is weighed before and
after the transfer. This method can be used at high
pressure and high temperature conditions.
Specific gravity g, or relative density, is the ratio
of the density of a material at temperature T and
pressure P to the density of a reference material at
reference temperature Tref and reference pressure Pref :
[1] gr(P,T )/rref (Pref ,Tref)
Specific gravities of oil and gas are measured at
standard conditions of 14.7 psia (0.1013 MPa) and
60F (15.6C) with respect to water and air at the
same conditions. In the petroleum industry, API
gravity is often used:
[2] API141.5/go131.5
where go is the specific gravity of the oil measured at
standard conditions.
Figs. 3 and 4 show change of density and of
molecular weight, respectively, versus carbon number
for different oils. It can be seen that the density varies
Fig. 3. Density versus carbon
number for North Sea oils
and condensates
(Pedersen et al., 1989a).
density (g/cm3)
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS
considerably with the PNA distribution of the
hydrocarbon fraction as compared to the molecular
weight. The narrow range of molecular weight for a
given carbon number has been used as a basic
assumption in Pedersens characterization method (see
below). However, other studies show that the
molecular weight can also vary considerably
(Dandekar et al., 2000).
Critical temperature (Tc ). For a pure component
the critical point is the point that terminates the vapour
pressure curve, while the critical temperature Tc is the
highest temperature at which the substance can exist
simultaneously as vapour and liquid. Therefore, at
temperatures above Tc no phase transition can occur
between vapour and liquid. For pure components, Tc
can be measured in principle and compilations of Tc
are readily available (Poling et al., 2000). Critical
point measurement of heavy hydrocarbons is hindered
by their decomposition temperature. Recently
developed techniques, using extremely short exposure
to high temperature (a few milliseconds), make it
possible to measure the critical temperature
of n-alkanes (Nikitin et al., 1994) up to tetracosane
(n-C24). Fig. 5 shows how Tc increases with carbon
number in the n-alkanes.
Critical pressure (Pc ). Similarly the critical
pressure Pc of a pure component is the highest
pressure at which the pure component has a vapour-
liquid phase transition or, in other words, the highest
possible vapour pressure of the component. For the
same reasons explained above for the critical
1
0.98
0.96
0.94
0.92
0.90
0.88
0.86
0.84
aromatic oils
0.82
medium paraffinic oils
paraffinic oils
0.80
aromatics
0.78 aliphatics
Katz and Firoozabadi (1978)
0.76
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
carbon number
39
GEOSCIENCES

400 Fig. 4. Molecular weight versus

380 carbon number for North Sea oils
and condensates
360 (Pedersen et al., 1989b).
340

320

300
molecular weight

280

260

240

220

200 aromatic oils

180 medium paraffinic oils
paraffinic oils
160 aromatics
aliphatics
140 Katz and Firoozabadi (1978)
120
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
carbon number

temperature, the critical pressure cannot be measured
for large hydrocarbon molecules. Pc decreases with
carbon number in n-alkanes after ethane (see again
Fig. 5).
Acentric factor (w). The acentric factor w is
defined as follows:
[3] wlog(Prsat )T 0.70.1
r but caution must be taken since g is usually
where Prsat is the reduced vapour pressure and Tr is the
reduced temperature. The value of w reflects a
deviation in the vapour pressure compared to the
behaviour of ideal spherical molecules (e.g. noble
gases) for which w is always zero. The factor w can be
explained as the non sphericity of a molecule and
generally increases with increasing molecular weight.
required for the characterization of a narrow petroleum
fraction. Sometimes, experimental values of two of
them (typically Tb and g, or M and g), are unknown
and have to be estimated. TBP data for oils from a
similar region can be used as a good reference. The
generalized properties up to C45 proposed by Katz and
Firoozabadi (1978) can be used as a rough estimation
oil-specific. In any case, properties for C45 are still
needed if the oil is heavy.
Pedersen et al. (1989a, 1992) have assumed a very
simple molecular weight correlation for SCN
fractions:
[4] MC 14i4
i

Tc, Pc and w are the three basic input parameters for the where i is the carbon number. The SCN fractions
cubic equations of state which are widely used in the
petroleum industry (see below).
Critical volume (vc ). The critical volume vc is the 800 50
critical temperature (K)

critical pressure (bar)

molar volume of a component at its Tc and Pc. 700

Experimental values of vc are fewer and less accurate 600 40
than Tc and Pc. The volume vc is generally not used as 500 30
an input parameter in the EOS method, but it is used 400
by some property estimation semiempirical models, 300 20
e.g. the Lohrenz-Bray-Clark (LBC) correlation for
200 10
viscosity estimation (see below).
100
5 10 15 20 25
Correlations between properties carbon number
Estimation of the missing quantities: g, M and Tb. Fig. 5. Change of critical temperature
The specific gravity g, the molecular weight M, and and critical pressure with carbon number
the normal boiling point Tb form the minimum set in n-alkanes.

40 ENCYCLOPAEDIA OF HYDROCARBONS

are defined using Katz and Firoozabadis Tb
up to C45 and extrapolating the successive values by
adding 6 K for each carbon number from C45 to C80.
Pedersen et al. also suggested a logarithm
distribution for g:
[5] gC C+Dlni
i
where the two coefficients C and D are determined by
a measured or assumed gC and the volume additivity
n
constraint on the experimental gC
n
zC MC gC1 zC MC gC1
[6]
n n n in i i n
where z is the molar composition.
Another approach to estimating g is to relate
g to M through a unique characterization factor
(Whitson and Brule, 2000), which can be determined
by the constraint in (6). Several empirical
correlations employed when estimating Tb
are also reviewed in detail by Whitson and
Brule (2000).
Correlations between Tc , Pc and w. Abundant
correlations exist for the estimation of critical
properties. The most popular of these include
the Lee-Kesler correlations (Kesler and Lee, 1976;
Lee and Kesler, 1980), the Riazi-Daubert
correlations (1980) and Twus perturbation
expansion correlations (1984). All of these
correlations express Tc and Pc in terms of Tb and g.
At the same Tb, the difference in g reflects the
difference in aromaticity. Furthermore, fractions with
high aromaticity tend to have higher g, Tc and Pc. In
Twus correlations, critical properties of normal
alkanes are correlated only in terms of Tb, while g
only appears in the perturbation step to correct for the
deviation of the critical properties from those of
n-alkanes.
Acentric factors can be estimated using either the
Lee-Kesler correlations or the Edmister correlation
(1958).
Pedersen et al. (1989a) argued that using Tb as an
intermediate variable to estimate Tc and Pc is not
necessary and expressed Tc and Pc directly in terms of
g and M. Instead of correlating w, they directly
correlate the m parameter in the SRK EOS (see
below). Recently, another set of correlations for high
temperature high pressure reservoirs were proposed by
Pedersen et al. (2002).
Due to the intrinsic limitation of any EOS,
the true Tc , Pc and w will not necessarily give a
reasonable reproduction of the vapour pressure for
heavy components. Soave (1998) proposed a set of
correlations in which the values of Pc are adjusted so
that boiling points at both 10 and 760 mmHg can be
reproduced.
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS
Characterization
For Cnwhere the molar distribution is unknown or
incomplete, different distribution functions can be
assumed. A simple approach adopted by Pedersen et al.
(1989a, 1992) is to assume an exponential molar
distribution:
[7] zC Aexp(Bi)
i
where i refers to the carbon number, and A and B are
two constants determined by the two constraints on
zC and MC :
n n
zC  zC
[8]
n in i
[9] zC MC  zC MC
n n in i i
Whitson (1983; Whitson and Brule, 2000)
suggested a more general three-parameter gamma
distribution. Therefore, after determination of the
molar distribution, Tc, Pc and w of each SCN fraction
can be evaluated using the correlations introduced in
the previous section.
The characterized SCN components are usually
too numerous and thus are grouped into a number of
pseudo components which are manageable for process
or reservoir simulations. For reservoir simulations the
number is currently limited to around 10 components,
while for process simulations it is in general limited
to around 50 components, even though for some
process calculations it can be feasible to use up to 100
components for the description of the oil. Each
lumped fraction can contain several SCN fractions
and its properties are obtained using different
averaging methods: from the simple weight or molar
average to very sophisticated ones (Montel and
Gouel, 1984; Leibovici, 1993). As a reversal process
of lumping, delumping can be performed to retrieve
the detailed compositional information after a
simulation with lumped components (Leibovici et al.,
1996).
PVT experiments
In the case of petroleum fluids in reservoirs under
pressure, it is essential to know very early in the
production phase how the fluid will respond to the
pressure reduction that will occur when the reservoir is
depleted. A set of simple, yet informative experiments
are used to reveal the nature of the fluid. The
experiments have the common name PVT experiments
since they investigate the relationship between the
pressure and the phase volumes at one or more
temperatures. During each experiment the temperature
is kept constant. Further details on these types of
experiments can be found in chapter 4.2.
41
GEOSCIENCES
PVT modelling
Empirical correlations
Empirical correlations were extensively used in
calculating PVT properties before the widespread
application of more theoretically sound models based
on EOS. Unlike general EOS models, empirical
correlations usually treat gas properties and oil
properties as two separate categories. The properties of
major concern include the volumetric property and the
viscosity for both gas and oil, gas solubility, as well as
bubble point pressure and surface tension in the case
of oils. An extensive description of these empirical
correlations can be found in chapter 4.2.
Basics of phase equilibrium
For a heterogeneous closed system consisting of Nc
components and Np phases, it can be proven that the
temperature T and the pressure P must be uniform
throughout the system and that the chemical potential
m of the individual components must be the same in all
of the phases at equilibrium:
[10] mijmik i1,,Nc, j,k1,,Np with jk
The chemical potential of component i, mi, is
usually expressed as ( G/ ni)T,P,nji o ( A/ ni)T,V,nji,
where V is the total volume, ni is the molar number of
component i, and G and A are the Gibbs energy and
the Helmholtz energy respectively. In practical
equilibrium calculation, a less abstract concept,
fugacity, is often used instead of chemical potential.
Fugacity, literally meaning escaping tendency, is
related to chemical potential by the following
definition:
i f fi
[11] mimiRT ln 1 with 13 1 as P 0
fi yi P
where mi fi
and are the chemical potential and the
fugacity of component i, respectively, at a reference
state of the same temperature, and yi is the
composition of component i in the mixture. Fugacity
can be understood as a corrected pressure. The
dimensionless ratio /ifi / yiP is called the fugacity
coefficient. The ratio aifi /fi is known as the activity
of component i and giai /xi is called the activity
coefficient where xi is the molar fraction.
If the reference states for different components are
at the same temperature, it can be shown that Eq. [10]
is equivalent to the equality of the fugacities:
[12] fijfik i1,,Nc, j,k1,,Np with jk
The fugacity and other thermodynamic functions,
such as the internal energy and the enthalpy, can be
expressed rigorously in terms of volumetric
properties, e.g.:
42
 1nP 

fi 1 RT
[13] ln/iln 13  1 1 dVlnZ
yi P RT V i T,V,n V
j
where Z is the compressibility factor given by
ZPv/RT, in which v is the molar volume.
In principle, all of the thermodynamic properties
can be calculated if the necessary volumetric data are
available. However, experimental measurement of
volumetric data over the full range of the integral in
Eq. [13] is unrealistic in most cases. The necessary
volumetric data are usually provided by an EOS which
describes the mathematical relation between pressure,
temperature, volume, and composition.
Finally, it should be noted that criteria [10] and
[12] are only necessary conditions (and not sufficient)
for phase equilibrium since a stable equilibrium state
is not only a stationary point but also a global
extremum, e.g. dAT,V 0, dGT, P 0.
Equations of state (EOS)
Since the introduction of the van der Waals EOS
in 1873, numerous EOS have been proposed. General
reviews of EOS are readily available in the literature
(Anderko, 1990; Wei and Sadus, 2000). The EOS
encountered in modelling petroleum fluids roughly
fall into three families: vdW (van der Waals) -type
EOS, the virial EOS and its modifications, and EOS
based on the Principle of Corresponding States
(PCS).
All vdW-type EOS consist of a repulsive term and
an attractive term like their common predecessor van
der Waals EOS:
RT a
[14] P 12  12
vb v
repulsiv attractive
term term
where b is a co-volume parameter and a/v 2 is an
expression for the attractive pressure. Many vdW-type
EOS, including the vdW EOS itself, take a cubic form
in terms of the volume or the compressibility factor Z
and are referred to as cubic EOS. Despite their
simplicity and empirical nature, cubic EOS are the
most widely used EOS in the petroleum industry. The
two most successful examples are the Soaves
modification of the Redlich-Kwong EOS i.e. the SRK
EOS (Redlich and Kwong, 1949; Soave, 1972) and the
PR EOS (Peng and Robinson, 1976), which will be
discussed in detail below.
The virial EOS can be expressed as an expansion
in terms of molar density r:
[15] Z1BrCr2
or pressure P:
[16] Z1BPCP2
ENCYCLOPAEDIA OF HYDROCARBONS
 COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS

where coefficients B, C, etc. are called the second,
third, etc. virial coefficients, and B, C, etc.
are coefficients related to B, C etc. Since the third
and higher virial coefficients are generally
unavailable from experimental data, application of
the virial EOS is limited to the low density region
and, thus, is of little use in most practical
applications. However, the rigorous statistical
mechanics basis of the virial EOS has inspired many
empirical extensions which are valid over wide
ranges of density. Amongst these extensions are the
Benedict-Webb-Rubin EOS i.e. BWR EOS
(Benedict et al., 1940) and Starlings modification
(1973) of this EOS (BWRS EOS).
The third class of EOS is based on PCS.
The classical two-parameter PCS assumes
that two different systems have the same reduced
pressure if they are at corresponding states,
i.e. if they have the same reduced volume and
temperature. Depending on the number
of parameters used in defining the corresponding
states, there are three-parameter and even
four-parameter PCS. The PCS is actually implicated
in most EOS, while it is in this third family
that EOS are formulated explicitly using the PCS.
The EOS in this family usually employ
very accurate equations for suitable reference fluids
and relate the final fluid properties
with the properties of reference fluids by the shape
factor method or the perturbation method.
The main advantage of this family of EOS is that the
properties of the fluid of interest can be accurately
reproduced provided the substance is not very
different from the reference fluids. The EOS
proposed by Mollerup and Rowlinson (1974) for
liquefied natural gas and low molecular weight
hydrocarbon mixtures, and that proposed
by Lee and Kesler (1975), for hydrocarbons
and their mixtures, belong to this family.
Cubic equations of state: the SRK EOS
and the PR EOS. These EOS can be written
in a general form:
[18] acWa R2Tc2/Pc
[19] bWb RTc /Pc
where Wa 0.42747 and Wb 0.08664
for the SRK EOS, and Wa 0.45724 and Wb 0.07780
for the PR EOS. The temperature dependency
of a(T) is expressed by the following functional
form:
[20] a(T)ac a(Tr,w)
where the temperature function a(Tr,w) is assumed
to be a function of the reduced temperature Tr
and the acentric factor w has the following form:
23
[21] a(Tr,w)[1m(1Tr)]2
[22] mSRK0.4801.574w0.175w2
[23] mPR0.374641.54226w0.26992w2
The function a(Tr,w) can be determined by fitting
the pure component vapour pressures.
Finally, Eq. (17) can be expressed in terms
of the compressibility factor as
[24] Z 3[1(1d1)B]Z 2[Ad1BB2(d1d2)]Z
(ABd2 B2d2 B3)0
where d1d1d2, d2d1d2 and two dimensionless
parameters, A and B, are defined as:
AaP/(RT)2
[25]
BbP/RT
Eq. [24] is in cubic form and can be solved
analytically, which is generally believed to be an
advantage of the cubic EOS. In fact, numerical
solutions using the Netwon-Raphson method can be
equally efficient.
Quadratic mixing rules, also known as van der
Waals one-fluid mixing rules or random mixing rules,
are generally used for a and b in an Nc component
mixture:
Nc

RT a(T) [26] b xi bi

[17] P11 1111121 i1
nb (nd1b)(nd2 b)
Nc Nc

where a(T) and b are two EOS parameters. d1 and d2
are constants: d11 and6d21 for the SRK EOS, while
d11
2 and d21
2 for the PR EOS. where aij
aiaj (1kij) e kij is the binary interaction
6 5
Since the critical point of a pure component is an
inflexion point of the pressure-volume isotherm,
which requires the first and second derivatives to be
equal to zero, the two parameters aca(Tc ) and b can
be determined through these two constraints and,
finally, expressed in terms of critical temperature and
pressure as follows:
[27] a  xi xj aij
i1 j1
parameter with kii0 and kijkji. The value of kij can
be obtained by fitting binary vapour-liquid
equilibrium data. Usually, kij0 is a good
approximation for most hydrocarbon-hydrocarbon
pairs except for C1-C7+ pairs.
Fugacity coefficients of component i in a mixture
are given by:

VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT 43

GEOSCIENCES

fi b32i An alternative to three-parameter cubic EOS is the

[28] ln/iln 12  (Z1)ln(ZB) volume translation method which can be used to
yi P b
Nc separate the application of an EOS to vapour-liquid


2 xj aij b


equilibrium calculations from the application to density

A j1 Zd1B
1212333 12123 32i ln 1212
(d2d1)B a b Zd2 B
Expressions for other thermodynamic properties
are easily found in the original papers. The above
expressions are commonly adopted in phase
equilibrium calculations. However, a more systematic
and efficient way to formulate these properties exists,
especially when a large number of thermodynamic
properties, including derivatives of fugacity
coefficients, are required (Michelsen and Mollerup,
1986; Mollerup and Michelsen, 1992).
The SRK and PR EOS give similar vapour-liquid
equilibrium calculation results, however, the major
improvement offered by the PR EOS is in the liquid
density calculation. This can be attributed to the fact
that the critical compressibility factor predicted by the
PR EOS (0.307) is closer to the real hydrocarbon value
(<0.290) than that determined by the SRK EOS
(0.333). On the other hand, volume translation (see
below) can improve the density prediction in the SRK
EOS and, in many cases, it is required by both types of
EOS to obtain acceptable volumetric results. In
conclusion, the choice of the SRK or PR EOS is
largely determined by personal preference.
Improvement of cubic EOS. Modifications of cubic
EOS have been performed mainly in two directions.
The first is to introduce a better temperature
dependency a(T) in order to improve the reproduction
of the vapour pressure; the second is to modify the
functional form of the EOS in order to improve liquid
density prediction.
It should be noted that Soaves modification of the
RK EOS is actually a modification of the a(T)
function. In a similar way Mathias and Copeman
(1983), and Stryjek and Vera (1986), have proposed
better a(T) functions for the RK and the PR EOS,
respectively. Recently, Twu et al. (1995a, 1995b)
proposed new a(T) functions for both the RK and the
PR EOS. These modifications usually incorporate
compound specific parameters which significantly
improve the vapour pressure accuracy, especially for
polar molecules. However, their effect on supercritical
temperatures is still open to question.
The PR EOS improves the density calculation by
modifying the attractive form in the SRK EOS.
Further improvement of density prediction can be
achieved by introducing additional EOS parameters.
The Schmidt-Wenzel EOS (1980) and the Patel-Teja
EOS (1982) are two commonly used three-parameter
EOS.
44
calculations. The method proposed by Martin (1979),
and elaborated further by Peneloux et al. (1982),
consists in translating the molar volume from the
original EOS, vEOS along the volume axis as follows:
[29] nCORn EOSc
The mixture translation parameter c is calculated
from the pure component translation parameters ci
through a linear mixing rule:
Nc
[30] c xi ci
i1
where ci can be determined by matching the measured
saturated liquid volumes at Tr0,7 or from different
correlations (Peneloux et al., 1982; Jhaveri and
Youngren, 1988). ci can also be treated as tuning
parameters to match experimental densities.
Since vapour volume is generally much larger than
liquid volume, the above translation will mainly
improve the liquid density without much affecting the
gas density. The elegance of this method is found in
the fact that the translation will increase the fugacity
of component i in all the phases by the same factor
exp(ci P/RT) and thus will not affect the phase
equilibrium calculations. Also, the same formulation
and code for the original EOS can be utilized directly.
Phase equilibrium calculation
Several frequently used phase equilibrium
calculations are introduced below. More detailed
discussion can be found in the work by Michelsen and
Mollerup (2004).
T-P flash calculation. In an isothermal flash (or
T-P flash) calculation, a feed with a given
composition is brought to a specified T and P, the
resultant number of phases, and the amount and
composition of each phase, then need to be
determined. The isothermal flash is probably the most
common and important equilibrium calculation.
Therefore, robust and reliable algorithms are available
for this type of calculation.
In many practical calculations, it is either assumed
or can be known in advance that there are, at most, one
liquid phase and one vapour phase. The two-phase
flash calculation for these situations consists of a
stability analysis step and a phase split calculation
step (Michelsen, 1982a and 1982b). Multiphase
isothermal flash calculations also have similar steps,
but they require more extensive stability analysis and
more demanding phase split calculation. The
discussion here is limited to two-phase equilibrium.
ENCYCLOPAEDIA OF HYDROCARBONS

The stability analysis step is carried out as follows:
a stable equilibrium mixture of molar composition z is
subject to the following TPD (Tangent Plane Distance)
criterion:
Nc
[31] TPD(w) wi [mi (w)mi (z)]0
i1
which means that the appearance of any infinitesimal
amount of a new phase of any molar composition w
should always increase the Gibbs energy.
Fig. 6 shows the geometric meaning of TPD(w). A
tangent plane (line) to the Gibbs energy surface
(curve) can be made at composition z, while TPD(w)
is the distance from the tangent plane (line) to the
Gibbs energy surface (curve) at composition w.
Stability requires that all points on the tangent plane
are lower than the Gibbs energy surface, in other
words, that TPD(w) is always positive. In real
calculations, it is impossible and also unnecessary to
check all of the compositions. Only the stationary
points (possible minima) of the tangent plane
distances are checked. The search for stationary
points should start from a set of initial estimates
representing a possible incipient phase. At high
pressures, a priori phase identification is difficult.
Therefore, both vapour-like and liquid-like initial
estimates are used in the stability analysis for a two-
phase vapor-liquid flash calculation. Once instability
is found in the located stationary point, the fugacity
coefficients at this point are used to generate the
initial estimates for the equilibrium factors Ki in the
phase split calculation step. Ki is defined as the mole
fraction ratio of component i between vapour and
liquid phases.
Whereas the TPD criterion specified by Eq. (31)
requires constraint minimization, in practice, it is
modified to a form which only needs unconstrained
minimization.
The phase split calculation is usually started with a
successive substitution algorithm. This algorithm
consists of an inner loop, which solves for phase
amounts and compositions at fixed Ki, and an outer
loop, which updates the K-factors using the new phase
compositions. The equation solved in the inner loop
can be written as follows:
z (K 1)
Nc
[32]  i i
11111
i1 1(K 1)b
0
i
and is known as the Rachford-Rice equation. b is the
molar amount of vapour phase. The Rachford-Rice
equation can readily be solved by the Newton-
Raphson method.
Successive substitution can be accelerated by the
general dominant eigenvalue method. If the iteration
does not converge after two or three accelerations, it is
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS
recommended to switch to a second order
minimization of the Gibbs energy.
Saturation points and the phase envelope. In the
early days, saturation points (the bubble point and the
dew point) calculations were thought to be simple and
were even used to initiate a flash calculation by
checking if the specified condition is situated in the
two-phase region. The true situation, however, is just
the opposite: calculations of bubble or dew points at
elevated pressures are much more difficult. One
obvious difficulty is that the number of solutions to
the saturation point calculation is not known in
advance. For example, there is no dew point at
temperatures higher than the cricondentherm while the
number of dew points increases to two below the
cricondentherm. Furthermore, stability analysis cannot
be performed in an easy and reliable manner as in the
case of an isothermal flash calculation since a primary
variable, T or P, is always missing. Currently, there is
no entirely satisfactory method for calculation of
saturation points at arbitrary conditions.
With proper initial estimates, saturation point
calculations can be performed using a partial Newtons
method, in which saturation T or P converges faster
than composition. Wilson K-factors can be used as
initial estimates, however, their accuracy is poor at
high pressure or near the critical point. Dew point
calculation is generally more difficult than bubble
point calculation due to the non-ideality of the
incipient liquid phase. A search of the unstable P (or
T) range by stability analysis can also be used to
initiate the saturation calculation. This procedure
wsp w mole fraction z
molar gibbs energy of mixing
TPD(w)
TPD(wsp)
Fig. 6. Illustration of Tangent Plane
Distance (TPD) concept. TPD
at composition w for the feed composition z
is shown as TPD(w).
TPD at the stationary point wsp is TPD(wsp).
The dashed tangent at wsp is parallel
to the tangent at z.
45
GEOSCIENCES
obviously needs more computation effort and a priori
knowledge of a reasonable search region.
A more reliable procedure to locate all saturation
points is to perform phase envelope calculation. The
phase envelope is a curve in the pressure-temperature
plane showing the transition boundary between the
vapour and the liquid phase. Further explanation of
phase envelopes for multicomponent systems is given
in Section 1.1.5. Michelsen (1980) developed an
efficient algorithm to construct the entire phase
envelope. The calculation starts at readily obtained low
pressure saturation points, while the subsequent
saturation points are generated by a full Newtons
method using initial estimates generated from
information obtained in earlier steps. This type of
calculation can cross the critical point smoothly.
Critical point. A preferable algorithm, proposed by
Heidemann and Khalil (1980), expresses the critical
point criteria in terms of the Helmholtz energy instead
of the Gibbs energy, as had been done in earlier work
(Peng and Robinson, 1977). After further improvement
by Michelsen and Heidemann (1981), the critical point
calculation algorithm is comparable to flash
calculation in computation time.
PVT simulation and EOS tuning
All of the conventional PVT experimental results
can be simulated based on an EOS model. Simulation
of a specific PVT experiment is simply one of, or a
combination of, several phase equilibrium calculations
described above. Commercial PVT softwares are
widely available nowadays. Calculations using cubic
EOS with a proper characterization procedure can
generally reproduce the experimental data
qualitatively. Quantitatively, several percent errors are
common in calculated saturation pressures, densities,
and mole percent of key components (Whitson and
Brule, 2000; Pedersen et al., 1989b). Near the critical
region, it is likely that the EOS method will incorrectly
identify dew points or bubble points even if there is
only a small calculation error.
The disagreement between the measured and the
calculated results may originate from inaccurate
properties deduced from characterization, limitations
of the cubic EOS, incomplete compositional analysis,
and last but not least, erroneous experimental data.
Nearly all PVT reports are flawed to some extent,
however, consistency checks before a PVT simulation
can help to rule out some poor experimental data. The
remaining deviations between predictions and
measurements can be reduced further by adjusting the
parameters entering the calculation model. This
method is known as EOS tuning.
Tuning of EOS parameters is not an exact science
in the sense that there is no unique way of tuning, and
46
the engineer decides how much and which parameters
to tune based on his experience. However, we attempt
to give some guidelines to tuning below:
The common tuning parameters are the properties
of C7+ fractions including critical properties,
acentric factors, their interaction coefficients with
methane, and volume shift parameters. Coats and
Smart (1986) suggested direct tuning of Wa and
Wb, both for methane and the heaviest C7+ fraction.
However, the magnitude of tuning is generally
large and may cause undesirable results outside the
regression region.
The properties of the greatest interest in terms of
further application and those of higher
experimental accuracy should be assigned a higher
weighting factor. Saturation pressure, densities,
and gas/oil ratio are examples of important
properties for reservoir simulation. Coats and
Smarts suggestion (1986) of a weighting factor of
40 for saturation pressures, around 10 for densities
and 1 for composition can serve as a rough guide
to the setting of weighting factors.
The number of parameters tuned and the extent of
tuning should be as few as possible. Tuning should
be focused on the most sensitive parameters, while
the insensitive ones can be removed. Furthermore,
one should be aware of the errors in experimental
data and avoid overfitting.
Although automatic non-linear regression is the
prevailing technique, common sense should be the
guide throughout and manual trial-and-error
should also be attempted. The tuning of parameters
should correspond to reasonable trends in
properties, such as the increase of Tc, Pc with the
carbon number.
Pedersen et al. (1989b) suggested tuning of the C7+
molecular weight by arguing that the molecular
weight measurement usually suffers from an error
of 5-10%. The overall composition must be
changed after C7+ tuning since the molar
composition is actually converted from the original
weight composition data using molecular weights.
For a sample from a well-studied reservoir,
however, the range of molecular weight is
relatively certain.
A consistent way of tuning kij between the C7+
fraction and methane is preferred, i.e. tuning of the
coefficients of the empirical correlation which
generates these kij instead of tuning them
separately. It should be realized that kij tuning may
cause spurious results at other temperatures.
Volume shift parameters will not change phase
equilibrium calculation. Also, the critical volume
will only influence viscosity calculation through
the LBC correlation (see below).
ENCYCLOPAEDIA OF HYDROCARBONS
 COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS

Viscosity, interfacial tension gas can be evaluated strictly based on gas kinetic
and diffusion theory. On the other hand, viscosity models for dense
fluids, including the LBC correlation and the f-theory,
Viscosity are generally semi-empirical in form.
Viscosity is a measure of the resistance which a The Lohrenz-Bray-Clark (LBC) correlation. The
fluid exhibits to flow. The dynamic viscosity, h, of a LBC correlation is given by:
Newtonian fluid is defined as the ratio of the local
shear stress driving the fluid flow to the velocity [33] [(hh*)x104]1/4
gradient in its perpendicular direction. Viscosity is not a0a1rra2 rr2a3 rr3a4 rr4
an equilibrium property. However, the viscosity of a
Newtonian fluid is still a state function and has a where a0a4 are empirical coefficients, rrvc/v is the
definite value once the state is fixed. The most reduced density, xTc1/6M1/2Pc2/3 is the viscosity-
common unit of h used in the oil industry is the poise
(P), which is equivalent to 0.1 Pas, and its submultiple 66
the centipoise (cP), 1 cP1 mPas. The kinematic hx
56
viscosity is the ratio of the viscosity to density and its
unit is the stoke (St), where 1 stoke 104 m2/s. 46
Fig. 7, a generalized viscosity plot calculated using 36
Lucas corresponding-states viscosity correlation, and 26
Fig. 8, the smoothed viscosity of propane, illustrate 16
how fluid viscosity varies with pressure and
6
temperature. An increase in pressure always increases 100
the fluid viscosity; however, the influence of
temperature is different for liquid and gas, and in the 5
70
latter case depends on the pressure. For a liquid phase,
or a gas phase at relatively high pressure, an increase 4 50
in temperature will reduce the viscosity. For a gas 40
phase at low pressure or a dilute gas, viscosity will 30
3 25
increase with temperature. 20
Abundant viscosity models, ranging from highly 2.0
15
10
theoretical ones to simple empirical correlations, are 2 1.7 8.0
1.4 6.0
available in the literature. Many of them are only 1.2 4.0
3.0
suitable for predicting either the liquid or the gas 1.0
1 0.8
phase viscosity. However, viscosity calculation for 0.5
both hydrocarbon gas and liquid using a single model Pr0
is often required in the petroleum industry, especially
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
in processes involving high pressure phase reduced temperature
equilibrium. The following discussion will focus only
on this type of model. Reviews of other viscosity hx 100
models can be found in the literature (Monnery et al., 5
70
1995; Poling et al., 2000).
The Lohrenz-Bray-Clark correlation (LBC, 4
50
Lohrenz et al., 1964) is traditionally used in the oil
3 40
industry. Nevertheless, a number of new viscosity 20
Pr0 10 30
models appeared recently, including the model based
on the corresponding states principle (Aasberg- 5 6 7 8 9 10 11 12 13 14
Petersen et al., 1991), the model based on the graphical reduced temperature
similarity between PvT and ThP plots (Guo et
al., 2001) and the friction-theory Fig. 7. Generalized viscosity plot based on Lucas
(f-theory) viscosity model (Quiones-Cisneros et al., corresponding states correlation (Poling et al., 2000).
2000; Quiones-Cisneros, 2001). Only the LBC The vertical axis represents the product of the dynamic
viscosity h and the parameter x0.176 Tc1/6M1/2Pc2/3,
correlation and the f-theory model are discussed below. where h is given in mP, Tc in K, and Pc in bar.
Both the LBC correlation and the f-theory model The lower part of the figure
incorporate the dilute gas viscosity as the lower shows the behaviour
density limit. Actually, only the viscosity of the dilute for high temperature values.

VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT 47

GEOSCIENCES

reducing parameter and h* is the low-pressure gas EOS) by means of three temperature dependent
mixture viscosity. friction coefficients as follows:
When the LBC correlation is applied to a
[36] hf kr Prepkrr Prep2ka Pattr
mixture, linear mixing rules are used for M, Tc, Pc
and vc , and the following special mixing rule is Quiones-Cisneros et al. (2001) further introduced the
applied to h*: concept of corresponding states into the model and
Nc Nc developed a general one-parameter f-theory. The
[34] h* zi hi*Mi1/2/ zi Mi1/2 one-parameter f-theory expresses the friction term of
i1 i1
a pure component in the reduced form:
Lohrenz et al. (1964) also suggest a correlation for
[37] hf hf /hc
the critical molar volumes of the C7+ fractions.
However, in practice, the C7+ critical volumes are where hc is the characteristic critical viscosity. hf is
generally treated as tuning parameters. related to Prep and Pattr in a way similar to that shown in
As can be seen from Eq. [33], the LBC Eq. [36]:
correlation actually expresses h as a 16-degree Prep 2
  
Prep Pattr
polynomial in the reduced density and thus is very [38] hf kr 12 krr 12 ka 12
Pc Pc Pc
sensitive to the density calculation results. It tends to
underpredict viscosities especially for highly viscous where kr, krr, ka are EOS-specific and
fluids. temperature dependent coefficients.
The friction theory viscosity model (f-theory). For mixtures, the h0 is calculated by:
The friction theory considers dense fluid viscosity as Nc

a mechanical property rather than a transport [39] lnh0 xi lnh0,i

i1
property. It is not until the dilute gas limit that the
kinetic theory of gases becomes important. and the hf is calculated using Eq. [36], while kr,
According to f-theory, the total viscosity h of dense krr, ka are calculated from the following mixing
fluids can be separated into a dilute gas term h0 and rules:
a friction term hf : Nc
xi hc,i kr,i Nc xi 1
[35] hh0hf
[40] 
kr  111
i1 M
0.3P
c,i
 12
i1 M

0.3
where the dilute gas model of Chung et al. (1988) is Nc
x h k Nc 1

i1111
M 0.3P i1 M 0.3
x
used to calculate h0. [41] ka
i c,i a,i
 12i

By analogy with the Amontons-Coulomb friction c,i

law, the viscosity friction term has been related to the Nc

x h k Nc 1

i1111
M 0.3P 2 i1 M 0.3
x
repulsive pressure term Prep and the attractive term Pattr [42] krr
i c,i rr,i
 12 i

in a vdW type EOS (e.g. the SRK EOS or the PR c,i

Fig. 8. Viscosity of propane Tr0.3

at different reduced pressures
and temperatures. 10,000 0.4

0.5
dynamic viscosity (mP)

0.6
0.7
0.8
0.9
1,000 1.0
1.1
1.2
1.29

Tc369.82 K
100 Pc42.4953 bar

0 2 4 6 8 10
reduced pressure

48 ENCYCLOPAEDIA OF HYDROCARBONS

Although the one-parameter f-theory loses
some accuracy in comparison to the original
f-theory, it reduces the required number of
input parameters to a single compound-specific
hc. For normal alkanes, hc can be evaluated by
the following empirical equation:
1 H
MPc 2/3
[43] hc7.94830104 1321
Tc1/6
where the units are M in g/mol, Pc in bar, Tc in K and hc
in cP. The f-theory has also been extended to model
viscosities of petroleum fluids (Quiones-Cisneros et
al., 2004).
Interfacial tension
Interfacial tension originates from the
unbalanced force at the interfacial layer between two
phases. For molecules in the surface layer between a
low dense gas phase and a high dense liquid phase, the
attraction from neighbouring gas molecules is less
than that from neighbouring liquid molecules. In
macroscopic terms, the result is a tension at the
boundary, pointing inside the bulk liquid phase.
The tension between a pure liquid and its vapour (or
air saturated with its vapour) is referred to as surface
tension, while that between two liquids is referred to as
interfacial tension. However, both terms have been
applied to other situations and a consistent
nomenclature does not seem to exist. Here, interfacial
tension is accepted as a general term for all situations
and surface tension specifically refers to a pure
component.
Interfacial tension is closely related to the flow
behaviour of reservoir fluids at the pore level, e.g.
the important capillary function is determined both
by the interfacial tension and the pore
characteristics.
Surface or interfacial tension is interpreted as the
tension force on a unit length on the surface, or the
Gibbs energy change with unit increase in surface
area. Traditionally, the units corresponding to the
above two definitions are the dyne/cm and the
erg/cm2, respectively. In SI unit, 1 dyne/cm=1
erg/cm2=1 mN/m.
Interfacial tension is roughly related to the density
difference between two phases and vanishes at the
critical point. For a gas-oil system, interfacial tension
usually decreases with increasing pressure, whereas the
temperature effect depends on the position relative to
the critical point. For example, for gas condensates, s
is expected to decrease with decreasing temperature,
while the opposite is expected for an oil sample.
Interfacial tension at high pressure is commonly
measured using the pendant drop method, which
consists of measuring the shape of a suspended drop
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS
of the heavier phase (or a standing bubble of the
lighter phase) formed in its equilibrium phase, as
shown in Fig. 9. The interfacial tension is related to
the drop dimensions by:
Drgde2
[44] s111
where Dr is the density difference between two
phases, de is the equatorial diameter, and 1/H is a
tabulated function of ds /de, where ds is the diameter of
the drop measured at the height de above the bottom of
the drop (see again Fig. 9). In the case of small
interfacial tension near the critical point, laser light
scattering techniques are preferred (Fotland and
Bjorlykke, 1989; Haniff and Pearce, 1990).
Traditional interfacial tension modelling consists
of relating surface tensions of pure compounds to
various properties, such as density, compressibility
and latent heat of vaporization and then extending this
concept to mixtures by some arbitrary mixing rules. A
more recent attempt is to use a theoretically sound
gradient theory and its simplifications.
Parachor method. The Macleod-Sugden equation
(Poling et al., 2000), which is widely employed to
estimate the vapour-liquid interfacial tension, is given by:
[45] s1/4Ps(rML rMV )
where rML and rMV are the molar densities of the liquid
and vapour phase, respectively. [Ps] is known as the
parachor, which is supposed to be temperature
independent. Eq. (45) has been extended to mixtures
by Weinaug and Katz (1943) using simple molar
averaging for the parachor:
Nc Nc
[46] s1/4rML  xi PsirMV  yi Psi
i1 i1
Nc

i1
Psi (xi rML yi rMV )
ds
de
de
Fig. 9. The principle of the pendant drop method
for the measurement of the surface tension.
49
GEOSCIENCES
The above equation is widely used in the petroleum
industry.
Parachor values can be estimated by group
contribution methods. Ali (1994) also reviews the
parachor values reported by different investigators. For
homologous hydrocarbons, an almost linear
relationship with molecular weight is usually found.
However, in real oils, the PNA distribution varies in
various SCN groups and the linearity is distorted.
Firoozabadi et al. (1988) give an equation that can be
used to approximate the parachor of pure
hydrocarbons from C1 through C6 and for C7+
fractions.
It should be noted that since s is proportional to
Ps4(rML rMV )4, the result obtained from Eq. [45] is
very sensitive to the density calculation and the choice
of parachor values.
Other modifications of Weinaug and Katzs
parachor method have been made, including
modification of the exponent 1/4 on the left-hand side
of Eq. [46] and improvement of the parachor mixing
rule. However, Firoozabadi et al. (1988) comment that
for reservoir fluid without asphaltene, the Weinaug-
Katz correlation is sufficient.
Finally, it should be noted that generalized
correlations are not expected to provide a reliable
parachor value for the oil heavy end, which generally
contains a high concentration of asphaltic and surface
active materials. Therefore, it is advisable to determine
it experimentally.
The gradient theory and its simplification. The
gradient theory (Carey et al., 1978, 1980; Guerrero
and Davis, 1980) assumes that there is a continuous
density variation for each component across the
interface between two equilibrium bulk phases. The
density profiles of all the components must take
specific forms in order to minimize the Helmholtz
energy at fixed T, V and N. Interfacial tension is by
definition the partial derivative of the minimized
Helmholtz energy with respect to surface area. After
some derivation, it can be expressed in terms of the
density profiles of all of the components:
 are available and their prediction ability is difficult to
[47] s  C(n)
i j

proposed a linear gradient theory, which assumes
that the number densities of each component are
linearly distributed across the interface.
These authors have applied this model to a variety
of mixtures including hydrocarbon-water
mixtures.
Diffusion and thermodiffusion
Diffusion describes the process of relative motion
of different components in a mixture in the absence of
mixing. Diffusion fluxes are determined as relative
fluxes of different components in a mixture. For
example, if Ji is the molar flux of component i in a
mixture of Nc component, then one determines the
molar convective flux using (Haase, 1969):
Nc
[48] Jc Ji
i1
and the diffusive flux of component i using:
[49] JD,iJizi Jc
where zi is the molar fraction of component i. The
mass flux of each component can be similarly defined.
Ficks law expresses the molar diffusion fluxes in
terms of the gradients of the molar fractions:
Nc1
[50] JD,ir  Dik zk
k1
where r is the molar density and Dik is the Fickian
molar diffusion coefficient of component i. Although
D12D21 holds for binary systems, it is seldom
pointed out that Dij is not necessarily equal to Dji for
n3. On the other hand, the study on
multicomponent diffusion is rare, both
experimentally and theoretically, in contrast to the
fact that large databases of experimental values, and
many models and correlations for diffusion
coefficients exist for binary mixtures (Hsu and Chen,
1998; Poling et al., 2000).
For dilute gases, diffusion coefficients can easily
be evaluated based on the strict framework of gas
kinetic theory. For liquids, only approximate models
 dxdn
 dndx
dx
11i 11j
where C(n) is the influence parameter for
inhomogeneous fluid, ni is the number density of
component i and x is the distance from the interface.
When combined with a specific EOS to calculate
, the density profiles are first calculated by solving a
set of partial differential equations or algebraic
equations. The interfacial tension is then readily
obtained using Eq. [47].
To avoid the difficulty in the density profile
calculation, Zuo and Stenby (1996a, 1996b, 1998)
50
verify due to the lack of experimental data on
diffusion coefficients in multicomponent mixtures.
The free volume theory has been used in modelling
liquid diffusion coefficients for a long time
(Hirschfelder et al., 1954; Bondi, 1968) and recent
models for multicomponent diffusion are available
(Wesselingh and Bollen, 1997). In engineering
practice, effective diffusion coefficients estimated
from binary diffusion coefficients are often used
(Whitson and Brule, 2000). Estimation of liquid
diffusion coefficients is believed to have only orders of
magnitude accuracy.
ENCYCLOPAEDIA OF HYDROCARBONS

Thermodiffusion, or the Soret effect, which is
induced by temperature gradients, is analogous to
diffusion induced by concentration gradients.
Thermodiffusion is often negligible but it can be
important under specific situations, e.g. the
compositional grading of thick oil reservoir (Georis et
al., 1998). Accurate measurements of thermodiffusion
are rare since they are easily ruined by the natural
convection which occurs under the gravity
environment.
1.1.4 Heavy petroleum fraction
The most complex chemistry of petroleum is found
in the heavy fraction. This part contains several
classes of compounds. The detailed molecular
structure cannot always be determined and it may be
necessary to define a group of compounds as a
solubility class rather than a class of molecular
structures. From a technological point of view the
most important heavy fractions are waxes and
asphaltenes, but resins also play a significant role.
These three classes of compounds will be defined
and described below.
Wax
Definition and chemical structure
Waxes are crystalline materials separated from
petroleum by cooling a mixture of the oil, a ketone,
and another polar or aromatic solvent. Several
different solvent types and solvent pairs are used in the
literature, such as acetone-toluene,
methylisobutylketone (MIBK)-methylene chloride,
etc. Due to the differences in the solvent pairs and
other conditions the wax content will vary according
to the method employed, and may even contain
co-precipitated and entrapped oil and asphaltenes. As
the separation temperature decreases the amount of
solid material recovered increases.
The term paraffins is often used synonymously
with waxes since the long chain normal alkanes
largely dominates the composition of waxes. Most
waxes consist of normal alkanes with a carbon number
in the range from 20 to 50, but there is discussion in
the scientific community whether a different class of
waxes exists, namely, the so-called microcrystalline
waxes. To avoid confusion the term paraffin waxes
will be used in the following. Branched alkanes do not
fit into the crystal structures formed by the normal
alkanes and, therefore, are not found in paraffin wax.
As a result, the class of molecules are generally very
well defined when paraffin wax problems have to be
addressed.
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS
Paraffin waxes in petroleum production
The fraction referred to as paraffin waxes is
important because it represents a potential
production or transport problem in relation to oil and
gas condensate production. As commercial products,
paraffin waxes are valuable, for instance, as
lubricants; however, this will not be covered further
in this section. Paraffin wax formation in a
petroleum fluid is observed as a solid phase that
appears when the fluid is cooled down. The
temperature at which the first paraffin wax is
observed is called the Wax Appearance Temperature
(WAT). In Fig. 10, a temperature-pressure diagram is
shown for a petroleum fluid where both the solid-
liquid phase transition boundary and the vapour-
liquid phase envelope are reported (for a detailed
discussion of the latter, see Section 1.1.5). The slope
of the solid-liquid curve is rather steep, which
indicates that the WAT is neither very sensitive to
the pressure nor to the dissolved gas in the oil. If the
WAT is higher than the process or transport
temperature there will be precipitation and
deposition of paraffin wax in the process equipment
or transport pipelines. Therefore, the control of
paraffin wax is covered by the term flow assurance.
Since deposited paraffin wax can only be removed
mechanically or by heating, it is crucial that the
deposition of paraffin wax does not get out of
control. Off shore pipelines are particularly
vulnerable since the costs of remediation are
considerable. The level of paraffin wax deposition in
pipelines is controlled mechanically by pigging; a
process in which a tool with a diameter slightly
smaller than the inner pipe diameter also known as
700
600
500
pressure (bar)
400
model
data
300
200 solidliquid liquid
100
solid
liquid
vapour liquidvapour
0
0 100 200 300 400 500 600 700
temperature (K)
Fig. 10. Entire phase envelope
with consideration of the wax precipitation
(Lindeloff et al., 1999).
51
GEOSCIENCES
the pig is pushed through the pipeline. The pig
scrapes the paraffin wax off the pipe walls and
pushes it to the end of the pipeline where it is
collected. Another way to secure flow assurance is
the use of chemical additives that affect the paraffin
wax precipitation, or the growth or agglomeration of
paraffin wax crystals. Such chemicals can keep the
paraffin wax dispersed as small crystals that will be
carried along with the flowing oil. The basic
mechanisms are not completely understood and the
use of these chemical additives requires
Modelling of wax precipitation
Accurate thermodynamic modelling of paraffin
wax precipitation is possible. The requirement is that
the balance between the paraffins, naphthenes, and
aromatic compounds is known for the fraction of the
fluid in which the paraffin wax components are
present.
The fugacity equality condition for the solid-liquid
equilibrium between solid wax and liquid hydrocarbon
can be written as
i ni
xiS 1giL 12
fiL


PL S
n112
experimental testing for each specific oil. Different [51] 1  exp dP
xiL giS fiS P RT
oils will contain a varying amount of paraffin wax
components but since accumulation over time will where xi is the mole fraction, giis the activity
occur in pipelines, even small amounts of paraffin coefficient, fi is the fugacity at the reference state (T,
wax in an oil can represent a significant risk for the P), and vi is the molar volume. The superscripts L and
flow assurance. S represent the liquid and solid phases, respectively.
The exponential term in Eq. [51] corrects the effect of
Experimental determination of the wax appearance pressure on the fugacity. The fugacity ratio fiL/fiS can
temperature be expressed as:
A number of methods can be used to determine the
fiL Dhf T
ht



T
WAT, including differential scanning calorimetry, [52] ln 11S 11 11 11 11 
visual observation using microscopy, cross polar fi RT Tf RT Tt
microscopy, light transmittance or scattering,
Cp

viscometry, cold finger, and filter plugging. Only the
microscopy, light transmittance and filter plugging
methods are briefly introduced below.
In general, microscopy is only used at atmospheric
pressure. A small fluid sample is studied under the
microscope while being either heated or cooled. Since
subcooling will occur, the most accurate
measurements are obtained when a cold fluid sample
is melted. The WAT can be identified as the
temperature at which the last crystal melts. Since
paraffin wax is a multicomponent mixture, the melting
or freezing will take place over a range of
temperatures and not at a single temperature as for a
pure substance.
Laser light of different wavelengths can easily be
transmitted through petroleum fluids if a small light
path is chosen. If the fluid is cooled uniformly, and
is mixed well, the WAT can be determined by the
fact that the transmitted light is disturbed by
scattering from the paraffin wax crystal in the fluid.
This method has been developed for high pressure
applications.
In the filter plugging method, petroleum fluid is
pumped or circulated through a filter while the whole
setup is cooled down in a controlled manner. The WAT
can be detected by a sudden resistance to the flow
through the filter. This method has also been
developed for use at high pressure. It is possible to
design the setup in such a way that the paraffin wax on
the filter can be collected and its composition
analysed.
52
T T
222 11f ln1f
1
R T T
where Dhf is the molar heat of fusion or melting
enthalpy at the melting temperature of the solute Tf ,
Dht is the molar enthalpy change of phase transition
at the temperature of phase transition Tt and DCp is
the difference between the heat capacity of the liquid
phase and that of the solid phase. The Dht term is
important in modelling wax precipitation since the
solid-solid phase transition usually occurs below the
melting temperature for heavy n-alkanes. The
contribution from the DCp term is usually small and
often neglected.
Eq. [51] and Eq. [52] provide the framework of
modelling wax precipitation in terms of the activity
coefficients model. Early wax models (Won, 1986;
Pedersen et al., 1991; Coutinho and Stenby, 1996;
Coutinho et al., 1996) have been developed mainly for
low pressure applications. The key problem lies in
proper modelling of the activity coefficients in
addition to reasonable estimation of Tf , Tt , Dhf and Dht
for the n-alkanes in the oil. Coutinho et al. (1995) gave
a comprehensive evaluation of the different activity
coefficient models utilized in the prediction of alkane
solid-liquid equilibria.
To model the precipitation in live oils, where the
effects of pressure and dissolved gas are present, it is
convenient to modify the above framework by
modelling the vapour and liquid phase using an EOS
(Pedersen, 1995; Lindeloff et al., 1999; Pauly et al.,
2000; Daridon et al., 2001). In this method the liquid
ENCYCLOPAEDIA OF HYDROCARBONS

activity coefficients terms are replaced by liquid
fugacities.
Asphaltene and resin
Definition, composition and structure
Asphaltenes are operationally defined as the solid
material precipitated from crude when mixed with an
excess of a low boiling hydrocarbon, such as
n-heptane or n-pentane. This fraction should be
soluble in toluene or benzene (Fig. 11). The amount of
asphaltene separated is a function of the n-alkane
carbon number, the time of contact (especially for
viscous heavy oils), the ratio of oil to solvent, and the
temperature. Although some standards, such as the
Institute of Petroleum (IP) 143, are prevailing in the
determination of the asphaltene content of crudes,
most of the above separation conditions are often
varied in the literature on asphaltene research. This
leads to some additional confusion regarding the
actual behavior and nature of this fraction, as the gross
composition of the asphaltene will vary considerably.
The number of different compounds inside the
asphaltene fraction is estimated to be over 100,000.
These compounds are characterized by high molecular
weight, polarity and aromaticity. Despite the
complexity of asphaltene fractions, their ratio of
hydrogen to carbon varies only in a narrow range, say,
around 1.0 to 1.2. The heteroatoms N, S, O and trace
metals are concentrated in the asphaltene fraction,
while their quantity can vary from oil to oil in almost
one order of magnitude. Sulphur is usually the most
concentrated among all heteroatoms.
feedstock
n-heptane
insolubles
benzene or toluene
insolubles asphaltenes
carbon disulphide
or pyridine
carboids carbenes
(insolubles) (solubles)
Fig. 11. Simplified representation of the separation of petroleum into six major fractions according to the solubility in different
solvents (n-heptane, benzene, etc.) or the adsorption on solid substrates (Speight, 1999).
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS
The molecular weight of asphaltene is directly
related to the molecular size of asphaltene and is a
crucial parameter in any asphaltene model.
Unfortunately, its experimental determination is
difficult. Asphaltenes tend to self associate even in
dilute solution. The mechanism is not well
understood but hydrogen bonding and charge-transfer
are believed to be responsible. The association is
influenced by solvent polarity, asphaltene
concentration, and the temperature at which the
determination is made (Speight, 1999). Methods like
vapour pressure osmometry are only able to provide
the molecular weights of aggregates and the
measured values are dependent on the above
mentioned factors. Other methods have their own
specific problems. In general, none of the current
technologies can answer the challenge of determining
the true molecular weights of asphaltenes. Values
from different methods differ significantly, even by
orders of magnitude.
Not much is known about the asphaltene
structure. Investigations have shown that asphaltenes
consist of condensed aromatic nuclei that carry alkyl
and alicyclic systems with heteroelements scattered
throughout in various locations (Speight, 1999).
However, the formulation of the individual
molecular structure is still impossible. An example
of a hypothetical asphaltene molecule is given
in Fig. 12. Different types of structures have
appeared in the literature.
Generally, resins refer to the more strongly
adsorbed oil fraction in a deasphaltened oil which is
subject to subdivision using a surface active
deasphaltened
oil
silica or alumina
1. heptane 2. benzene 3. benzene
or toluene and methanol
saturates aromatics resins
53
GEOSCIENCES
material, such as fullers earth or alumina. The
absorbed resin is recovered by a more polar solvent
and, therefore, eluted last (see again Fig. 11). Resins
are believed to have molecular structures similar to
asphaltenes but with longer alkyl non-polar chains
and smaller aromatic rings. The molecular weight of
resins is in the range of 100-600 u, according to
vapour pressure osmometry measurements (Speight,
1999). These resins can be considered to be a
transition type between asphaltenes and the simpler
fractions, and hence an overlap between resins and
asphaltenes is expected.
Resins play an important role in dispersing
asphaltenes in crude oil (Andersen and Speight,
2001). It is generally believed that asphaltenes are
dispersed in crude oil as centres of micelles
surrounded by resins and other lighter and less
aromatic molecules. The transition from the
asphaltene centres to the bulk phase oil is gradual,
with the size and aromaticity decreasing outwards
from the aggregate. The concept of Critical Micellar
Concentration (CMC) has been widely used in
describing the association of asphaltenes. However,
recent studies suggest a step-wise mechanism rather
than the formation of finite-size micelles (Andersen,
1994; Acevedo et al., 1999; Groenzin and Mullins,
2000).
Asphaltene precipitation
The importance of asphaltene is unfortunately
justified by the many problems it causes. Apart
from poisoning of catalysts and destabilization of
products in the refining process, the major problem
caused by asphaltene in oil production and transport
is its precipitation. Asphaltene precipitation is
OH
N
S multicomponent mixtures.
mole
S
C 84.9%
H 8.2%
N 1.0%
O 1.2%
Fig. 12. A hypothetical S 4.7%
asphaltene molecule H/C 1.15
(Speight, 1999). molecular weight: 1,370
54
complex, and the possibility of precipitation is not
necessarily proportional to the content of the
asphaltene. For example, oils with a smaller
percentage of asphaltene may be more likely to
precipitate. Both depletion and gas injection can
trigger precipitation of asphaltene. The reason is
usually attributed to unfavourable changes in
solvent properties with a change in pressure or the
addition of injection gas.
Experimental data on the onset of asphaltene
precipitation are scarce in the literature. The data can
be measured by different methods, e.g. visual
observation through microscopy, light transmission
or scattering, electrical conductivity, viscometry, and
capillary flow measurements.
The modelling of asphaltene precipitation is less
developed in comparison to the modelling of wax
precipitation. Among the major difficulties is the
lack of understanding of the actual mechanisms
responsible for the precipitation. Moreover, little is
known about the true dispersion state of asphaltene in
oil, while data on the physical properties of
asphaltene are virtually unavailable. There is even
debate on whether the precipitation is a reversible
process. The limited experimental data make it more
difficult to evaluate the existing models.
1.1.5 Reservoir fluids
This section describes the different types of
petroleum reservoir fluids which are commonly
encountered by exploration. A proper classification
of a reservoir is important since the fluid type is a
deciding factor in the production scheme. The
properties of interest also differ between different
types of reservoirs. As will be seen below, the
classification of reservoir fluids is closely related to
the Pressure-Temperature (P-T) phase diagram of
The P-T phase diagram
of a multicomponent system
Fig. 13 shows a typical pressure-temperature
phase diagram of a multicomponent system with a
specific overall composition. In the phase diagram,
the two-phase region is enclosed by a continuous
boundary called the phase envelope. This phase
envelope consists of a bubble point branch and a dew
point branch, with the two branches connected at the
critical point where the coexisting liquid and vapour
become identical in terms of intensive properties. In
contrast to a single component system, the critical
point of a multicomponent system is generally not
ENCYCLOPAEDIA OF HYDROCARBONS

the maximum temperature and the maximum
pressure of the two-phase region. The maximum
temperature point and the maximum pressure point
are called the cricondentherm and the cricondenbar,
respectively.
In the two-phase region, a set of quality lines
(dashed lines) can be drawn to indicate constant
percentage liquid volume. The bubble point and the
dew point branches correspond to the two special
quality lines with 100% and 0% liquid, respectively.
All of the quality lines converge to the critical point.
The single phase region can be further divided
into a liquid region and a gas region, where the
former refers to the region above the bubble point
curve with temperatures lower than the critical
temperature and the latter refers to the remaining part
of the diagram.
A special phenomenon called retrograde
condensation can be observed for mixtures due to the
existence of two dew point pressures at temperatures
higher than the critical temperature but lower than
the cricondentherm. As shown in Fig. 13, both a low
pressure dew point D1 and a high pressure dew point
D2 exist at temperature T1. For a depletion process
A D2 B C D1 at constant temperature T1, an
infinitesimal amount of liquid will form when the
system reaches D2, and a further decrease in pressure
will increase the liquid volume fraction until it
reaches its maximum at B. The increase of the
condensed liquid (usually called the liquid dropout)
with decreasing pressure is contrary to the common
intuition and named retrograde condensation. It
should be noted that B is only the maximum in the
liquid volume fraction rather than the absolute
Fig. 13. Typical pressure-
temperature phase diagram
for a multicomponent system.
single phase
The quality lines can be more
evenly spaced for other systems.
critical point
pressure
% liquid
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS
amount of the liquid dropout. The absolute liquid
dropout can still increase after B but the increase is
not enough to counteract the expansion effect so that
the liquid volume fraction decreases. After C, further
decrease in pressure will reduce the absolute liquid
dropout due to the re-vaporization. The decrease
continues until an infinitesimal amount of liquid is
left at D1.
Classification of reservoir fluids
Petroleum reservoirs are described or classified
based on the composition of the petroleum fluid, and
the temperature and pressure prevailing in the
reservoir. However, the dimensions of a petroleum
reservoir are large and the composition of the
petroleum fluid varies depending on the location in the
reservoir due to the influence of gravity, the
geothermal gradient and the geologic history of the
reservoir. The classification, into the categories
described below, is therefore a simplification which
should be kept in mind.
When a petroleum reservoir is discovered, it is
common practice to classify the reservoir into one of
the following types: natural gas, gas condensate,
volatile oil or black oil, based on the location of initial
reservoir conditions with respect to the phase envelope
of the reservoir fluid. Natural gas is further subdivided
into wet gas and dry gas, while black oil will, here,
also cover heavy oil and extra heavy oil. The
classification has a direct impact on the economical
and technical evaluation, and thereby on the
production strategy. For example, some aspects of the
fluid properties, such as volumetric properties, are
single phase
region region A
(liquid) (gas) cricondenbar
D2
B
100
80 30
C
15 two-phase
20
region cricondentherm
10
2
1
0 D1
temperature T1
55
GEOSCIENCES

Table 2. Typical molar composition of petroleum reservoir fluids

Component Dry gas Wet gas Gas Volatile Black

condensate oil oil
N2 0.0292 0.0150 0.0050 0.0161 0.0070
CO2 0.0107 0.0100 0.0393 0.0217 0.0200
C1 0.8763 0.9010 0.7257 0.6065 0.3300
C2 0.0477 0.0420 0.0850 0.0796 0.0660
C3 0.0185 0.0210 0.0493 0.0471 0.0700
i-C4 0.0049 0.0020 0.0102 0.0210 0.0240
n-C4 0.0058 0.0015 0.0105 0.0220 0.0280
i-C5 0.0020 0.0021 0.0035 0.0210 0.0180
n-C5 0.0020 0.0024 0.0045 0.0110 0.0170
C6 0.0029 0.0020 0.0050 0.0190 0.0290
C7+ 0.0010 0.0620 0.1350 0.3910
C7+ molecular weight 128 182 199 249
C7+ specific gravity 0.750 0.807 0.802 0.853

important for the estimation of the petroleum reserves.
Others are of importance for the flow assurance.
Potential production problems have to be addressed as
early as possible.
Table 2 shows the typical molar composition of
petroleum reservoir fluids and the corresponding
calculated phase envelopes are shown in Fig. 14. It
should be noted that the same initial reservoir
conditions and separator conditions are used for all
fluids in Fig. 14, whereas in fact, they vary from field
to field.
Dry gas and wet gas
For both dry gas and wet gas, the initial reservoir
temperature is higher than the cricondentherm of the
reservoir fluid and the reservoir conditions never fall
inside the two-phase region during a depletion
procedure (the vertical line in Fig. 14). Furthermore,
for a dry gas, the process conditions are typically
outside the two-phase envelope. Compared with a dry
gas, a wet gas contains a larger fraction of C2-C6
components, and its phase envelope is larger and
reaches higher temperatures. The separator conditions
are inside the two-phase region for a wet gas. The
typical gas/oil ratio of a wet gas is 60,000-100,000
scf/stb (11,000-18,000 sm3/m3) and its stock tank oil is
usually water-white with a specific gravity higher than
60 API.
It can be seen that there is no gas-liquid critical
point on the phase envelope of the wet gas in
Fig. 14. This is due to the three-phase equilibrium at
the low temperature. Actually, phase envelopes in
real hydrocarbon mixtures can be much more
complicated than the phase envelops shown in
Fig. 13. For example, multiphase equilibria as well
as multiple critical points or no critical point are
very common in reality, and at low temperature one
or more solid phases will usually form. These points
are not considered in the two-phase envelopes
in Fig. 14.
Gas condensate
The initial temperature of a gas condensate
reservoir lies between the critical temperature and the
cricondentherm of the reservoir fluid. In such a case
the fluid exists as a gas at initial conditions, but
during pressure depletion, liquid will drop out due to
retrograde condensation below the high pressure dew
point. A typical gas condensate has a gas/oil ratio in
the range 8,000-70,000 scf/stb (1,400-12,000
sm3/m3). The stock tank oil is usually slightly
coloured and its API gravity is usually greater than
50.
Volatile oil and black oil
In the case of both volatile oil and black oil, the
initial reservoir temperature is below the critical
temperature of the reservoir fluid. The fluid therefore
exists as a liquid at initial conditions, however, on
pressure depletion, the bubble point will eventually
be reached.
Volatile oil differs from black oil quantitatively
only in terms of having a relatively larger fraction
of light and intermediate hydrocarbon components.
As a result, its critical temperature is much closer
to the reservoir temperature. During the depletion,
volatile oils show a larger shrinkage factor due
to the large amount of gas released. The typical
gas/oil ratio for a volatile oil is 2,000-3,500 scf/stb
(360-620 sm3/m3). Its stock tank oil is usually
greenish to orange in colour with an API gravity
between 45 and 55.

56 ENCYCLOPAEDIA OF HYDROCARBONS

The gas/oil ratio for a black oil is usually below
700 scf/stb (120 sm3/m3) and the stock tank oil
colour can range from brown to black with an API
gravity between 15 to 40. Black oils with a gas/oil
ratio less than 200 scf/stb (36 sm3/m3) and an API
gravity less than 15 are sometimes known as low
shrinkage oils.
Heavy oils and extra heavy oils
The definition of heavy oil is quite arbitrary.
Generally, it refers to petroleum with an API gravity of
less than 20 and usually, but not always, a sulphur
content higher than 2 wt% (Speight, 1999). The term
heavy oil has also been arbitrarily used to describe
both heavy oils that require thermal stimulation of
recovery from the reservoir and bitumen in bituminous
sand (tar sand) formations from which the heavy
bituminous material is recovered by a mining
operation. Speight (1999) gives a detailed discussion
of the difference between the terms heavy oil,
bitumen, mineral wax, asphaltite, asphaltoid, and
bituminous sand.
Near critical fluid
A reservoir fluid with its critical temperature very
close to the reservoir temperature is called a near
critical fluid. Such a near critical fluid can be either a
gas condensate or a volatile oil, and is characterized by
a dramatic change in the liquid volume fraction just
below the saturation pressure. For the near critical gas
50
reservoir conditions
gas
condensate
40
pressure (MPa)
30
20
wet gas
separator
conditions
10
reservoir
temperature
dry gas
0
100 0 100 200
temperature ( C)
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS
condensate, as shown in Fig. 15, a small pressure drop
below the dew-point will give rise to a large amount of
liquid dropout.
Compositional grading
A reservoir at static equilibrium can show
significant compositional variations known as
compositional grading. Compositional grading is
mainly due to gravity, as the temperature gradient in a
reservoir is usually small (0.025 K/m), and therefore
plays a less important role. However, the temperature
can significantly influence the fluid distribution in
some specific situations (Georis et al., 1998).
The isothermal compositional grading can be
described by
[53] mi (Pref , zref ,T )Mi ghref mi (P, z,T )Mi gh
i1,, Nc
where mi is the chemical potential of component i, Mi
is the molecular weight, zref is the known composition
of a single phase fluid at reference depth href with
reference pressure Pref , and P and z are the pressure
and composition at depth h.
In general, the heavy components tend to
accumulate at the bottom while the light components
tend to accumulate in the top. Therefore, saturation
pressure and solution gas/oil ratio can change
considerably as they are associated with
compositional change. Fig. 16 shows two typical
Fig. 14. Phase envelopes for
different types of reservoir fluids.
The dashed line indicates the
depletion line for an isothermal
phase envelope reservoir. Fluids with critical points
gas-liquid critical point to the right of the depletion line
three-phase point belong to oil reservoirs, while the
rest belongs to gas reservoirs.
volatile oil
black oil
300 400 500
57
GEOSCIENCES

profiles of saturation pressure and reservoir Contact (GOC) is formed, whereas in the right-hand
pressure. On both profiles, the dew point pressure profile, the saturation pressure is always below the
increases with depth (i.e. with an increasing amount reservoir pressure and the transition from oil to gas
of heavy components) and the bubble pressure takes place through a local critical point.
decreases with depth (i.e. with decreasing methane Compositional change is discontinuous at the GOC
content). The reservoir pressure increases with depth in the left-hand profile while that in the right-hand
and shows different slopes in the gas and oil regions. profile is always continuous.
The difference between two profiles is that in the
left-hand profile, the saturation pressure reaches the
reservoir pressure at a depth where a clear Gas Oil 1.1.6 Formation water
Water is always associated with petroleum
volume critical point
2,600 liqui
d by hydrocarbons in their production. Not only is water
100% % found almost invariably in reservoirs in appreciable
90% 0%
2,400 80% quantities as connate, interstitial, or formation water,
70%
60% but it is also deliberately injected to improve oil
pressure (psi)

2,200
50% recovery. Water interacts with hydrocarbon fluids in
2,000 terms of flow, expansion, and sometimes dissolution
1,800 40% and release of soluble gases. Furthermore, solid
precipitation including scaling and hydrate formation
1,600 due to temperature and pressure change may cause
30%
1,400 20% considerable damage during the production process.
10%
Knowledge of the physical properties of the formation
60 80 100 120 140 160 180 200 220 240 260 water and its phase equilibrium is therefore important
A a temperature ( F)
to petroleum engineers. Some of these aspects are
2,700 discussed in the following paragraphs. Further details
171 F 169 F 166 F on the characteristics of the layer waters (salinity,
2,600 18 solubility of gas in the water, volumetric parameters
19 1
9
F F
2,500 21
2
F 11
and viscosity) are reported in chapter 4.2.
2
F

2
F F
5
14

10
2,400 Composition
F
85 Formation water contains dissolved salts
2,300
(primarily sodium chloride) and dissolved gases
2,200 (primarily methane and ethane). It bears little
2,100 relationship to sea water although both are generally
pressure (psi)

called brine or salt water. The formation water has

2,000 much higher salinity, ranging from 200 to 300,000
1,900 ppm (around saturation), compared with around
35,000 ppm of sea water.
1,800 The cations dissolved in formation waters usually
1,700 include Na, Ca2 and Mg2, and occasionally K,
Ba2, Li, Fe2 and Sr2. The anions commonly
1,600 include Cl, SO42 and HCO 2 
3 , while CO3 , NO3 ,
  3 2
Br , I , BO3 and S are also often present.
1,500
Finally, the concentration of salts in formation
1,400 water is called salinity and can be specified using
1,300 different quantities. Table 3 gives definitions of some
of the most commonly used quantities.
1,200
0 10 20 30 40 50 60 70 80 90 100
B b percent liquid by volume
Volumetric property of formation water
Unlike water density, which is only a function of
Fig. 15. P-T phase diagram for
temperature and pressure and can be easily determined
a near critical gas condensate fluid (A) with high accuracy, formation water density is also
and its corresponding volume isotherms (B) influenced by the amount and composition of
(Katz et al., 1959). dissolved salts and gases. The large range of dissolved

58 ENCYCLOPAEDIA OF HYDROCARBONS
 COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS

Fig. 16. Typical saturation

gas
pressure and reservoir

de
gas

de

w
pressure change with

pre
pre
depth.

ssu
ssu

r e s er v
re
re
gas/oil contact

depth

depth
critical

o ir p
point

r e ss
re

res

re
su

er

su
res

ur e
vo

s
p

pre
ir
le

pr
bb

le
es

bb
bu

su
oil

bu
re
oil

pressure pressure

components brings difficulty in developing a general
model. Fortunately, the volumetric property of
formation water varies within a relatively small range,
with the isothermal compressibility being typically
2-4 106 psi1 (3-6 1010 Pa1) and the formation
volume factor, which is defined as the volume of the
formation water at reservoir conditions divided by the
volume of the water produced from the formation
water at surface conditions, typically ranging from
1.00 rm3/m3 at high pressure to 1.07 rm3/m3 at low
pressure. Engineering correlations (McCain, 1990;
Whitson and Brule, 2000) can give reasonable
estimations in practice when experimental data are not
available. These engineering correlations often
simplify the dissolved salts to NaCl or neglect the salt
effect on the formation volume factor.
Mutual solubility of formation water
and hydrocarbons
The solubility of hydrocarbons in water is very
low, while that of methane in water is no more than
1 mol% at common reservoir conditions. From methane
to propane, the solubility decreases by a factor of two
to three on going from one hydrocarbon gas to the next
Table 3. Different commonly used expressions
of salinity.
Term Definition
moles of solute
Molality
mass of pure water (kg)
moles of solute
Molarity
volume of brine (l)
mass of solute
Weight percent 
mass of brine
Parts per million (ppm) mass of solute (g)
mass of brine (t)
mass of solute (mg)
Milligrams per liter
mass of brine (l)
heavier one, and the solubility of heavier liquid
hydrocarbons is much smaller. Furthermore, the
solubility of hydrocarbons increases with pressure, this
effect being more prominent for lighter hydrocarbons
and at low pressures. On the other hand, at constant
pressure, the solubility of hydrocarbons has a
temperature minimum, before which it decreases with
temperature and after which it increases. Within
common reservoir temperature and pressure ranges, an
increase in hydrocarbon solubility with temperature is
usually observed. Finally, the solubility of CO2 in
water is almost one order of magnitude larger than that
of methane.
The equilibrium water content in hydrocarbons is
generally larger than the corresponding hydrocarbon
solubility in water, especially at low pressure and
high temperature. Therefore, in the case of liquid
hydrocarbons, the water content can be orders of
magnitude higher. However, since the water content
decreases with pressure and increases dramatically
with temperature, the water content in light
hydrocarbon gases can be lower at low temperature
and high pressure. Fig. 17 illustrates the mutual
solubility of methane and water within the usual
reservoir temperature and pressure ranges. The
presence of salt reduces both the solubility of the
hydrocarbons and the equilibrium water content.
The plot of methane solubility in water prepared by
Culberson and McKetta (1952) is commonly used to
estimate the solubility of natural gas in water.
Application of the salinity correction can be
performed subsequently by introducing salting out
coefficients (Whitson and Brule, 2000). The solubility
of CO2 in brine can be estimated by the empirical
correlation of Chang et al. (1996), while that of water
100
in natural gas and hydrocarbon liquids can be
estimated using empirical charts (Hoot et al., 1957;
McKetta and Wehe, 1962; GPA, 1980).
Cubic EOS with the conventional quadratic
mixing rules cannot simultaneously correlate the

VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT 59

GEOSCIENCES
1 inclusion, using Debye-Hckel terms, is
10-1
mole fraction
10-2
10-3
10-4
0 200 400
pressure (bar)
Fig. 17. Solubility of methane in water
(solid lines) and water content in methane
(dashed lines) (Olds et al., 1942; Culberson
and McKetta, 1951; Sultanov et al., 1971;
Sultanov et al., 1972).
composition both in the hydrocarbon phase and in
the aqueous phase. Therefore, when the water
content in the hydrocarbon phase is accurately
correlated, the solubility in the acqueous phase will
often be underestimated by orders of magnitude. A
conventional engineering solution to the above
problem is to use different sets of interaction
parameters for the hydrocarbon phase and the
aqueous phase, where the interaction parameter in
the aqueous phase is usually assumed to be
temperature dependent. Sreide and Whitsons
modification (1992) of the PR EOS is such an
example. Unconventional mixing rules can also be
applied to the problem (Kabadi and Danner, 1985).
Sreide and Whitsons model only accounts for the
salt effect empirically by constricting the interaction
parameters to be salinity dependent. More rigorous
75
interfacial tension (mN/m)
70
65
60
55
50
45
40
35
30
0 200 400
pressure (bar)
Fig. 18. Pressure and temperature dependency
of interfacial tension in the methane-water
system (Jennings and Newman, 1971;
Sachs and Meyn, 1995). Obvious disagreement
can be observed between the data
at 23.3C and 25C.
60
implemented in other engineering models (Zuo and
Guo, 1991; Zuo et al., 1996).
200 C
In the production process, the hydrocarbons and
150 C water may coexist with glycols, which are added for
the purposes of inhibiting hydrate formation,
104.44 C
depressing water freezing point, and dehydrating
71.1 C
natural gas. Modelling glycol-hydrocarbon-water
37.78 C systems is theoretically difficult due to the self
association and cross association in these systems. The
600 800 1,000 Cubic-Plus-Association (CPA) EOS (Kontogeorgis et
al., 1999), a recent EOS, developed by combination of
the SRK EOS and the Wertheim association term, has
succeeded in the description of this system. The most
impressive aspect of the CPA EOS is its ability to
simultaneously describe hydrocarbon-water mutual
solubility using a single interaction parameter and to
accurately predict multicomponent phase behaviour
(Derawi et al., 2003).
Viscosity
The viscosity of formation water at reservoir
conditions is virtually less than 1 cP, generally lower
than the viscosity of oil. Within the normal reservoir
temperature and pressure ranges, the viscosity of
formation water increases with pressure and decreases
with temperature. Furthermore, an increase in salinity
will increase the viscosity, while the effect of
dissolved gas is also believed to increase the viscosity.
To account for this Whitson and Brule (2000)
recommend a modified version of the empirical
correlation by Kestin et al. (1981) for brine viscosity
calculation.
Interfacial tension between hydrocarbon
and formation water
The interfacial tension of water/hydrocarbon
systems varies from approximately 72 mN/m
Sachs and Meyn (1995) for water/brine/gas systems at surface conditions
25 C
Jennings and Newman (1971) to 20 to 30 mN/m for water/brine/stock-tank-oil
23.3 C systems at reservoir conditions. Fig. 18 shows
106.0 C the experimental data on the interfacial tension
176.7 C
between methane and water, which is largely
representative of the case of reservoir gas and
formation water. The interfacial tension decreases
with pressure and temperature in the tested region.
Due to the experimental difficulty,
the published data are often in significant
600 800 1,000
discrepancy as indicated by Fig. 18. The interfacial
tension between liquid hydrocarbon and water
decreases with temperature but slightly increases
with pressure, while it generally increases in the
presence of salts.
The parachor method is not suitable to model
interfacial tension between hydrocarbons and water.
ENCYCLOPAEDIA OF HYDROCARBONS

On the other hand, Firoozabadi and Ramey (1988)
suggested a graphical relation with limited success.
The empirical correlation uses density difference and
reduced temperature as correlation parameters. Finally,
more recently, Zuo and Stenby (1998) applied the
linear gradient theory to the modelling of interfacial
tension between hydrocarbon and formation water and
obtained fairly good results.
Mineral scaling
Scale formation, the precipitation of inorganic
minerals from brine, either in production facilities or
in reservoir pores, is a serious problem in oil
production. As an example, Fig. 19 illustrates the result
of serious scale formation in a well tube.
The most common types of scale found are
CaCO3, BaSO4, SrSO4, CaSO4 and CaSO42H2O.
Formation of these scales is usually caused by
temperature and pressure change during production,
which not only induces supersaturation of one or
several dissolved minerals, but also changes the
solubility of CO2 and H2S, and thus modifies the pH
in the aqueous phase. The solubility of minerals such
as carbonates is dependent on the pH and, therefore,
scale may be formed after a change in the pH. Another
common reason for scale formation is the mixing of
incompatible water, which can happen during sea
water injection.
Thermodynamic modelling of scale formation
mainly concerns whether, and how much, scale will
form under certain conditions. Most of the modelling
work uses a general model for electrolyte solutions
(Atkinson et al., 1991; Yuan and Todd, 1991;
Haarberg et al., 1992; Atkinson and Mecik, 1997;
Kaasa, 1998). Scale formation modelling of
sulphates is relatively simple while that of carbonates
needs additional consideration of the pH and the
phase distribution of CO2.
Fig. 19. Scale formation in a well tube
(Kaasa, 1998).
VOLUME I / EXPLORATION, PRODUCTION AND TRANSPORT
COMPOSITION AND PHYSICAL PROPERTIES OF HYDROCARBONS
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Erling Halfdan Stenby
Wei Yan
Department of Chemical Engineering
Technical University of Denmark
Lyngby, Denmark
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