We are IntechOpen,

the world’s leading publisher of

Open Access books
Built by scientists, for scientists

4,400
Open access books available
117,000
International authors and editors
130M Downloads

Our authors are among the

154
Countries delivered to
TOP 1%
most cited scientists
12.2%
Contributors from top 500 universities

Selection of our books indexed in the Book Citation Index

in Web of Science™ Core Collection (BKCI)

Interested in publishing with us?

Contact book.department@intechopen.com
Numbers displayed above are based on latest data collected.
For more information visit www.intechopen.com
 7

Applications of Equations of State

in the Oil and Gas Industry
Ibrahim Ashour1, Nabeel Al-Rawahi2, Amin Fatemi1
and Gholamreza Vakili-Nezhaad1,3
1Department
of Petroleum and Chemical Engineering
College of Engineering, Sultan Qaboos University, Oman
2Department of Mechanical & Industrial Engineering,

College of Engineering, Sultan Qaboos University, Oman

3Department of Chemical Engineering, Faculty of Engineering, University of Kashan, Kashan

I. R. Iran

1. Introduction
Reservoir fluids contain a variety of substances of diverse chemical nature that include
hydrocarbons and nonhydrocarbons. Hydrocarbons range from methane to substances that
may contain 100 carbon atoms. The chemistry of hydrocarbon reservoir fluids is very complex.
In spite of the complexity of hydrocarbon fluids found in underground reservoirs, equations of
state have shown surprising performance in the phase-behavior calculations of these complex
fluids. An equation of state (EOS) is an analytical expression relating pressure to the volume
and temperature. The expression is used to describe the volumetric behavior, the vapor/liquid
equilibria (VLE), and the thermal properties of pure substances and mixtures. Numerous EOS
have been proposed since Van der Waals introduced his expression in 1873. Currently, a
number of EOS are used in reservoir engineering which have shown more reliability in
reservoir fluids calculations. In this chapter, a review over the most commonly used EOS in the
oil and gas industry has been provided. We explore their strengths and weaknesses and to
examine the predictive capability of these equations. A brief introduction to Soave-Redlich-
Kwong (SRK), Peng-Robinson (PR), Patel-Teja (PT), Schmit-Wenzel (SW), and Esmaeilzadeh-
Roshanfekr (ER) equations of state has been provided with intention to compare their
efficiency in predicting different reservoir fluids properties. The Progress in developing EOS
for the calculation of thermodynamic data and phase behavior is also reviewed. Effect of
characterization on VLE predictions as well as advances in application of equations of state for
heavy hydrocarbons has been considered in this work. Finally, as a case-study, phase behavior
of a typical Omani crude oil as well as application of EOS with proper characterization method
for this real oil sample has been examined.

2. Overview of EOS
Consider the plot of pressure versus total volume of a pure substance shown in Fig.1. An
equation of state (EOS) is desired to represent the volumetric behavior of the pure substance
in the entire range of volume both in the liquid and in the gaseous state.

www.intechopen.com
166 Thermodynamics – Kinetics of Dynamic Systems

Single Phase
Pressure

Two Phase Region

Volume

Fig. 1. Pressure volume diagram of a pure component

An EOS can represent the phase behavior of the fluid, both in the two-phase envelope (i.e.,
inside the binodal curve), on the two-phase envelope, and outside the binodal curve.
Numerous EOS have been proposed to represent the phase behavior of pure substances and
mixtures in the gas and liquid states since Van der Waals introduced his expression in 1873.
These equations were generally developed for pure fluids and then extended to mixtures
through the use of mixing rules. The mixing rules are simply a means of calculation mixture
parameters equivalent to those of a pure substance. The equations of state are divided into
two main groups: cubic and noncubic. Noncubic equations can better describe the
volumetric behavior of pure substances but may not be suitable for complex hydrocarbon
mixtures (Firoozabadi, 1989). For instance, the modified Benedict-Webb-Rubin equation
(Starling, K.E. 1973) is admittedly more accurate than the cubic EOS (such as the Peng-
Robinson EOS) for the PVT description of pure substances, but it may be less accurate than
the two-constant cubic equations for VLE computation of complex reservoir fluid systems
(Katz and Firoozabadi, 1978). The application of BWRS type equations demands a high
computational time and effort, due to their high powers in volume and large number of
parameters, hence, unsuitable for reservoir fluid studies where many sequential equilibrium
calculations are required. More importantly, for multi-component systems each parameter
must be determined using a mixing rule, which at best is quite arbitrary (Danesh, 1998).
Although acceptable phase behavior results can be obtained by BWRS (Starling, 1966), it has
been surpassed by the simpler, yet more reliable van der Waals type cubic equation of state.
There are many examples in the literature where EOS are compared (Sing, 2005; Ahmed,
2004). The findings all highlight the fact that there is currently no “all in one” EOS that will
give the best prediction of all thermodynamic properties of different types of reservoir
fluids. It seems that some EOS can do better than the others only for certain reservoir fluid
types and some EOS are advantageous for particular properties. For example, the PR-EOS
for superior phase transitions (O’Reilly, 2009). This may also lead to entire PVT experiments
being better represented by a particular EOS. The objective is to review literature for a
number of common cubic EOS used in reservoir engineering calculations and compare their
strengths and weaknesses.

www.intechopen.com
Applications of Equations of State in the Oil and Gas Industry 167

2.1 Commonly used EOS in reservoir engineering calculations

Since 1949 when Redlich and Kwong (RK) formulated their two-parameter cubic equation of
state (EOS), many investigators have introduced various modifications to improve ability of
RK-EOS. Two other well-known cubic equations are Soave (SRK) (1972) and Peng-Robinson
(PR) (1976) equations. Although many modified forms of RK-EOS are reported in the
literature, but at least for hydrocarbon systems and their mixtures, only SRK and PR
equations have been widely accepted. Both SRK and PR equations use Pitzer acentric factor
as the third parameter to obtain parameter a in their equations. Acentric factors are
calculated through critical properties; therefore, for heavy compounds where critical
properties should be estimated, errors in critical properties will be contributed to acentric
factor. Probably, the most successful cubic EOS for vapor liquid equilibria (VLE)
calculations have been those proposed by Soave, Redlich and Kwong and Robinson and
Peng (Esmaeilzadeh et al., 2005). Both of these EOS assumed a fixed value of the critical
compressibility factor for all substances and as a result the predicted values for saturated
liquid density differs considerably from their experimental values.

2.1.1 Soave-Redlich-Kwong (SRK) EOS

In 1972, Soave improved on the RK-EOS which represents an attempt to take molecular
geometry and polarity into account by replacing the term . in RK-EOS with a more
general temperature-dependent term . He showed that a simple expression for the
temperature dependency of attraction parameter “a” enabled the equation to represent
vapor pressure of a wide class of substances. The proposed equation known as SRK-EOS is
as follows:

= − (1)
− +
Where

= . (2)

= . (3)

Soave proposed a simple form for ≡ , for all pure substances, taking advantage of
the concept of the acentric factor of Pitzer (Pitzer et al., 1955) . Soave compared the predicted
vapor pressure from his modification and the original RK EOS for a number of substances,
showing that his modification greatly improved vapor pressure predictions. In this
modification α T is extrapolated for the supercritical temperatures. Soave compared only
the measured and computed saturation pressures of several binary systems that showed
good agreement. SRK is quite capable of predicting vapour-liquid equilibria, but it does not
provide reliable liquid density. (Danesh, 1998)

2.1.2 Peng-Robinson (PR) EOS

Another important variation of the van der Waals EOS was introduced in 1976 by Peng and
Robinson. SRK-EOS fails to predict liquid densities accurately. Improved density prediction

www.intechopen.com
168 Thermodynamics – Kinetics of Dynamic Systems

was the main motivation of the authors of PR-EOS which in general is superior in density
predictions of reservoir fluid systems. Although this equation improves the liquid density
prediction, it cannot describe volumetric behavior around the critical point. The PR-EOS is
perhaps the most popular and widely used EOS. In terms of the molar volume Vm, Peng and
Robinson proposed the following two-constant cubic EOS:

= − (4)
− + + −
Where

= . (5)

= . (6)

The generalized expression for the temperature-dependant parameter is given by

= (7)
where

= + − (8)

With

= . + . − . (9)
Comparison of the vapor-pressure prediction of several substances by the SRK EOS and the
PR EOS with experimental data shows that the error is small for both equations, although
the PR EOS performs better by a small margin (Firoozabadi A., 1988). Peng and Robinson
also compared enthalpy departures for five pure substances from both their proposed EOS
and the SRK EOS. Both equations generate enthalpy values of about the same reliability.
According to different researchers’ experience, PR-EOS enjoys more simplicity and
reliability than many other equations. However, both PR and SRK equations break-down at
C10 – C11and heavier compounds. Peneloux and Rauzy (1982) introduced a constant for
each substance to be subtracted from the volume obtained in the SRK equation. Their
modification greatly improves liquid density predictions, but it requires a fourth parameter
beside critical temperature, critical pressure and acentric factor required by SRK equation.
2.1.2.1 Volume shift
A comparison of the predicted liquid molar volume by leading two parameter EOS with
experimental data of pure compounds generally shows a systematic deviation. The
deviation is almost constant over a wide pressure range away from the critical point. Hence,
subtracting the predicted molar volume by a constant correction term can improve the
predicted liquid density. The effect on the predicted vapor volume is generally insignificant
due to its large value relative to that of liquid away from the critical point. Peneloux et al.

www.intechopen.com
Applications of Equations of State in the Oil and Gas Industry 169

[26] were the first who introduced the volume shift concept, i.e. shifting the volume axis,
and applied it to SRK,

vc = v-c (10)
where vc is the corrected molar volume, and c is the correction term determined by
matching the measured and predicted saturated liquid volumes at Tr = 0.7. The volume shift
generally improves the predicted liquid density, and has a minimal effect on the vapor
density at low and moderate pressures as its molar volume is relatively large compared to
the value of c. At high pressure condition, the inclusion of c parameter may not necessarily
improve the predicted gas density as it is just a correction term for the liquid density.
However, it is advisable to adjust the gas phase volume by the third parameter to maintain
consistency, particularly near the critical point where properties of the two phases approach
each other. Peneloux et al. correlated the volume translation parameter c as,

c = 0.40768(0.29441- ZRA ) RTc/Pc (11)

where ZRA is the Rackett compressibility factor. For a more detailed discussion, reader is
suggested to refer to Peneloux et al. (1982).

2.2 Three-parameter EOS

A two-parameter EOS predicts the same critical compressibility factor, Z, for for all
substances, i.e. 0.307 and 0.333 by PR and SRK respectively, whereas Zc varies within a
range of 0.2 to 0.3 for hydrocarbons. Although the inaccuracy of predicted volume at the
critical point, not necessarily leads to unreliable volumetric data at all conditions, it
demonstrates the inflexibility of two-parameter EOS for matching both the vapor pressure
and volume. The inclusion of a third parameter relaxes the above limitation. The third
parameter is generally determined by employing volumetric data.

2.2.1 Esmaeilzadeh-Roshanfekr (ER) EOS

Both of PR and SRK equations assume a fixed value of the critical compressibility factor for
all substances and, as a result, the predicted values for saturated liquid density differ
considerably from their experimental values. On the other hand, some equations of state
proposed by Schmit and Wenzel (Schmit G. & Wenzel H., 1980) and Patel and Teja (Patel
N.C., Teja A.S., 1982) introduced a third parameter to their equations. This suggestion led to
the introduction of a substance dependent critical compressibility which allowed them to
reproduce more accurate the experimental saturate liquid density at a particular temper-
ature. Their work showed that the optimum value of substance critical compressibility was
not equal to the experimental critical compressibility of the fluid of interest. Using the
generalized Van der Walls theory, Esmaeilzadeh and Roshanfekr used a mathematically
simple cubic EOS to model attractive interactions between molecules. The proposed
equation of state in their work is as follows (Esmaeilzadeh & Roshanfekr, 2006)

= − (12)
− + + −
Where “ ” is a function of temperature and “b” and “c” are constants. In this EOS and
b are derived as:

www.intechopen.com
170 Thermodynamics – Kinetics of Dynamic Systems

= . (13)

= (14)

= (15)

This EOS predicts saturated liquid density more accurately than the PT and PR EOS. The
results for the calculation of vapor pressure of pure components for light hydrocarbons
show that Eq. (12) has the lowest deviation and for heavy hydrocarbons the PT EOS yields
the lowest deviation (for Tr < 0.75). The prediction of thermodynamic properties of light and
intermediate hydrocarbons by Eq. (12) is superior to other EOS studied in this work.
Moreover, It is found that Esmaeilzadeh-Roshanfekr EOS is most accurate for predicting
gas-condensate properties, while the original SRK and PR equations remain reliable for oil
samples. (Bonyadi et al., 2007)

2.2.2 Schmidt-Wenzel EOS (SW)

Liquid density prediction at Tr=0.7 by SRK and PR for pure substances is associated with
noticeable deviation from reliable values. Note that SRK is more reliable for substances with
small acentric factors, whereas PR gives reliable data for compounds with acentric factors
around (1/3). Based on the above observation, Schmidt and Wenzel incorporated the
acentric factor as the third parameter in the attractive term as,

= − (16)
− + + −
Substituting acentric factor values of zero and 1/3 in the Schmidt-Wenzel EOS (SW) will
reduce it to SRK and PR respectively, where these equations predict the liquid density
reliably. SW can, therefore, be considered a general form of SRK and PR (Danesh, 1998). The
authors used the boundary conditions at the critical point, Eq.(4.9) to determine , and b, as

= (17)

= (18)
Where

= − − (19)

= (20)
In above equations η is the critical compressibility factor, and is related to the correlating
parameter q, by

= + (21)

www.intechopen.com
Applications of Equations of State in the Oil and Gas Industry 171

and q, defined as b/vc, is the smallest positive root of the following equation,

(6ω+ 1) q3 + 3q2 + 3q- 1 = 0 (22)

with an approximate value of,

q = 0.25989 - 0.0217 ω + 0.00375ω2 (23)

Schmidt and Wenzel selected the same form of α as proposed by Soave, but correlated, m,
with the acentric factor and reduced temperature by matching vapor pressure data of pure
compounds as is discussed in details in Schmidt et al, 1980. The inclusion of ω in EOS as the
third parameter by Schmidt and Wenzel resulted in a variable calculated critical
compressibility, according to the value of acentric factor. The predicted values are, however,
about 15% higher than the true values. This was known to the authors, but was accepted as
the price for an overall optimum accuracy in predicted volumes (Danesh, 1998).

2.2.3 Patel-teja (PT) EOS

Patel N.C., Teja A.S. (1982) modified the attractive term by including a more flexible third
parameter. (Patel et al., 1982) The authors found that the use of true critical compressibility
factor will result in the overall loss of accuracy in predicted density, a conclusion also
reached by Schmidt and Wenzel. For more details the reader is recommended to referred to
Patel N.C., Teja A.S.(1982).

3. Heavy oil characterization

Heavy-oil fluids contain large concentrations of high-molecular weight components,
including a large content of the plus fractions, such as C7+. For crude oils and reservoir
fluids, the basic laboratory data are usually presented in the form of the composition of
hydrocarbons up to hexanes and the heptane-plus fraction (C7+), with its molecular weight
and specific gravity calculations (Danesh 1998; Ahmed 2007). The constituents of a
hydrocarbon system are classified in two categories: the well-defined components and the
undefined petroleum fractions, which are those heavy compounds lumped together and
identified as the plus-fraction [i.e., C7+ (Ahmed 2007)]. Several samples of heavy oil indicate
that the plus fraction C10+ contains a molar fraction close to 70% and that the fraction C80+
is also representative with values close to 2% (Pedersen et al. 2004). The importance of
characterizing the plus fraction arises when the modeled fluid has high molecular weight
and high density (heavy oil). Characterization of plus fraction usually consists of three parts:
(1) splitting the fraction into a certain number of component groups called SCNs; (2)
estimation of the physicochemical properties of the SCN; and (3) lumping of the generated
SCNs (Pedersen et al. 2006).

3.1 Splitting method

Several methods have been developed to estimate the mole distribution of the compounds
in the plus fraction (Katz et al. 1978; Pedersen et al. 1982; Ahmed et al. 1985; Whitson 1983).
Heptanes plus (C7+) fractions are expressed by a distribution model and the fractions
heavier than C6 have been lumped into pseudo-components with approximately equal
weight fraction of each pseudo-component (i.e. molar averaging). Often, the exact chemical
composition of a HC fraction is not known, therefore, pseudoization defines these HC
fractions and allows the determination of EOS parameters Splitting and lumping are the two

www.intechopen.com
172 Thermodynamics – Kinetics of Dynamic Systems

main types of the pseudoization. A common feature among these methods is that
components with the same number of carbon atoms are lumped in groups called SCNs with
a single predefined value for properties like Pc, Tc, ω, Tb, M, and density ρ. Whitson (1983)
proposed a method using the TPG distribution in order to estimate the mol fraction as a
function of the molecular weight. The molecular weights used are the generalized values
presented for each SCN (Katz and Firoozabadi 1978). Generalized correlations have been
developed to generate critical properties for the SCN including those by Twu (1984), Ahmed
(1985), Kesler-Lee (1976), Riazi-Daubert (1987), and Edmister (1958). Riazi-Daubert, and
Edmister correlations are used.
Whitson (1983) used TPG distribution to estimate the mole fraction of the SCNs within the
Cn+ fraction. TPG is defined (Whitson 1983) as a function of the molecular weight (M) by
the following equation:

−
− exp − (24)
=
Г
where is the minimum molecular weight present in the Cn+ fraction, is used to fit the
shape of the distribution, and Г is the gamma function. Whitson recommended Г = 92, the
molecular weight of toluene, as a good estimation of , if C7+ is the plus fraction; for other
plus fractions, following is used as approximation:

= 14n – 6 (25)
and

− (26)
=

where MCn+ is the molecular weight of the Cn+ fraction. The mole fraction of an SCN is then
generated by calculation of the cumulative frequency of occurrence between the limits Mi−1
and Mi multiplied by the mole fraction of the Cn+ fraction.

= + (27)

where i is the SCN and Mi is the molecular weight of the SCN usually defined as the
molecular weight of the normal component.

3.2 Correlations used to estimate physicochemical properties of the SCN

In a hydrocarbon mixture, the critical properties (critical pressure “Pc”, critical temperature
“Tc” and accentric factor “ω”) must be given for each component. These properties are well
known for pure compounds (like methane, ethane, etc.), but nearly all naturally occurring
gas and crude oil fluids contain some heavy fractions that are not well defined. There arises
the need of adequately characterizing these undefined plus fractions in terms of their critical
properties (Gastón, 2007).
Several correlations have been developed to estimate the physical properties of petroleum
fractions and are in principal function of the specific gravity, the boiling point temperature
and the molecular weight Riazi-Daubert (1987), Twu (1984), Ahmed (1985), Kesler-Lee
(1976), and Edmister (1958); in this study, the Riazi-Daubert (1986) has been used.

www.intechopen.com
Applications of Equations of State in the Oil and Gas Industry 173

3.2.1 Riazi-Daubert correlation

Riazi-Daubert’s correlation is utilized to obtain physical properties of the plus fraction using
the laboratory reported MW and SG as heavy fraction parameters. This study uses Riazi and
Daubert, since it is the one mostly used in the industry; for calculating the accentric factor,
Riazi-Daubert uses the Edmister’s correlation (Riazi, M. R., Daubert, T. E. (1987)). The
proposed relationship is:

Θ = aMWbSGc exp [dMW + eSG + f (MW . SG)] (28)

Where:
Θ = some physic property.
a-f = coefficients for each physic property (Table 1).
The Edmister’s correlation for the accentric factor is Pc and Tc dependent is given by
(Edmister, W.C., 1958):

log .
= − (29)
−

Θ Tc Pc Tb
a 544.4 45203 6.77857
b 0.2998 -0.8063 0.401673
c 1.0555 1.6015 -1.58262
d -0.00013478 -0.0018078 0.00377409
e -0.61641 -0.3084 2.984036
f 0.0 0.0 -0.00425288
Table 1. Riazi and Daubert’s coefficients

3.3 Lumping methods and mixing rules

The generation of an appropriate mole distribution that represents the plus fraction usually
requires splitting the plus fraction into large number of components (SCN) with their
respective mole fractions and physical properties. The use of a large number of components
in a reservoir simulation is time consuming. Lumping is defined as the reduction of the
number of components used in EOS calculations for reservoir fluids. After lumping many
components into a minimum number of hypothetical components, it is necessary to
determine the characterization parameters (critical temperature, critical pressure, and
acentric factor) for each lumped hypothetical component for use in the equations of state
using some mixing rules. Phase equilibrium calculations are very sensitive to the values of
the characterization parameters in the equations of state. Conventional mixing rules, which
are inconsistent with the equation of state itself, are usually applied to calculate the
characterization parameters of the lumped pseudocomponents. The inadequacy of this
characterization method often results in inaccurate predictions of phase equilibria. Another
problem is that the binary interaction parameters between the lumped hypothetical
components, which are often needed in the phase behavior calculations, are difficult to
obtain. The common practice is to set the binary interaction parameters equal to zero for all
hydrocarbon-hydrocarbon interactions, while nonzero values may be used for interactions

www.intechopen.com
174 Thermodynamics – Kinetics of Dynamic Systems

with non-hydrocarbons (Chorng H. Twu and John E. Coon, 1996). Pedersen et al. (2006)
states that lumping consists of
 Deciding what carbon number fractions are to be lumped into same pseudocomponent.
 Deciding the mixing rules that will average Tc, Pc, ω of the individual carbon number
fractions to one Tc, Pc, ω to represent the lumped pseudocomponents.
Whitson’s method is described for estimating the number of MCN groups needed for
adequate plus-fraction description, as well as which SCN groups belong to the MCN group.
The proposed distribution model is similar to a folded log-normal distribution. The number
of MCN groups, Ng , is given by

Ng = Int [ 1 + 3.3 log10 (N - n) ] (30)

For black-oil systems, this number probably can be reduced by one (Whitson 1983).
The molecular weights separating each MCN group are taken as

Ml = Mn {Exp [( 1 / Ng . ln (MN / Mn) ]}l (31)

where MN is the molecular weight of the last SCN group (which may actually be a plus
fraction), and 1= I, 2 ... Ng. Molecular weights of SCN groups falling within the boundaries
of these values are included in the MCN group, I.
Recently, Rudriguez et al. developed a method based on a modification of Whitson’s
approach. The approach is based on the fact that single carbon number groups (SCN), may
represent hundreds of different compounds with the same number of carbon atoms. These
compounds can be classified in different types: paraffins, naphtenes and aromatics.
Uncertainty of the types and distribution of compounds present in each single carbon number
indicates that the average value of molecular weight of a single carbon number is different
from one sample to another. The modification of Whitson’s method includes a simple
procedure to determine the value of the fitting parameter (α); and a new definition of the limits
used to calculate the frequency of occurrence for each single carbon number. The developed
method is based on that the molecular weight is not uniquely related to carbon numbers due
to the hidden exponential increase of number of isomers/components with increasing the
carbon numbers. In the method, TPG distribution from Whitson’s approach is used to
characterize the plus fraction and generate molecular weight / carbon number function. It is,
also used to find the best trend fit to the experimental data by solving for parameter. The
limiting molecular weight, for each carbon number, is determined to fit the mole fraction that
is corresponding to the carbon number. Linear extrapolation of the limiting molecular weight
as a function of the carbon number is used here to extend the characterization to the missing
data of the higher carbon number (Rodriguez et al., 2010). The reader is recommended to refer
to Rodriguez et al. 2010, for further discussion of the proposed method.

3.4 Mixing rules

Mixing rule for calculating critical properties (including acentric factor and specific gravity)
of MCN groups is discussed here. Molar and volumetric properties of MCN groups are
always calculated using the mixing rules

= (32)

www.intechopen.com
Applications of Equations of State in the Oil and Gas Industry 175

=
(33)
∑

pseudocritical volume should be calculated using weight fractions

. (34)

where zl and fwl are the sums of zi and fwi found in MCN group l. MCN acentric factors are
usually calculated using Kay's mixing rule.
In the next section, a case study is presented in order to implement correct characterization
procedures using the described method in previous sections. The sample is a black oil
sample collected from an Omani reservoir with specified plus fraction analyzed in the
laboratory.

4. Case study: Fahud oil sample characterization

A typical reservoir oil sample collected from an Omani reservoir (Fahud) has been taken
into consideration for VLE analysis and characterization scheme.

4.1 Sample selection

A set of PVT reports from different fields in north and central of Oman have been reviewed
to choose a sample for our case study having an API of 37.76. The selected sample is a bottom
hole sample (BHS) at the depth of 2550 m and the recorded reservoir temperature of
95 0C.

4.2 Laboratory measurement

The sample is analyzed to indentify the components through the Liquid Gas
Chromatograph, AGILENT Technologies, model 7890A. The column name is DB-1 with
length of 60 (m) with a diameter of 0.250 (mm) and film thickness of 0.25 (um) column
temperature is -60 t0 3250C. The compositional analysis defined the mole composition of
several SCN until it reaches to C7. The critical properties of these elements were obtained
from Reid et al. (1986). Lastly the pseudo-component (which represents the heptanes plus-
fraction of the fluid, in this case C7+) is characterized using the later described Riazi-
Daubert correlation (Riazi, M. R., Daubert, T. E. (1987)). Table 2 shows the results of the
compositional analysis of this crude oil sample.

4.3 Methodology
The compositional simulator utilized is reservoir simulation Eclipse (Property of
Schlumberger) PVTi module. It uses the PR-EOS with the modifications on the volume shift,
the quadratic mixing rule and Lorenz-Bray-Clark viscosity correlation. For estimation of the
undefined element properties, Riazi-Daubert correlation is used (Riazi, M. R., Daubert, T. E.
(1987)). This software has been used to find the phase envelop of the reservoir sample and
estimation of different characteristics of the oil sample.

www.intechopen.com
176 Thermodynamics – Kinetics of Dynamic Systems

No. Component [mol %]

1 N2 1.67
2 CO2 0.24
3 CH4 41.2
4 C2H6 3.45
5 C3H8 1.65
6 I-C4H10 0.56
7 N-C4H10 1.75
8 I-C5H12 0.82
9 N-C5H12 1.56
10 C6H14 3.32
11 C7+ 43.78
C7+ MW (gr/mol): 271
C7+ SG (gr/cm3): 0. 848

Table 2. compositional analysis of Fahud crude oil sample

4.4 Phase envelop of the Fahud oil sample

The oil sample analyzed in this study is initially composed of more than about 20 mole%
heptanes and heavier compounds which is representative of Black oil type of reservoir fluid.
Its phase envelope, therefore, is the widest of all types of reservoir fluids, with its critical
temperature well above the reservoir temperature (Tc=828K compared to Tres=366K). Phase
diagram of this sample is plotted using the Eclipse software as in fig. 1.

Fig. 1. Phase envelope of Fahud oil sample generated by Eclipse-PVTi.

www.intechopen.com
Applications of Equations of State in the Oil and Gas Industry 177

5. Acknowledgment
The Research leading to these results has received funding from Petroleum Development
Oman (PDO), Sultanate of Oman, through research agreement no. [CTR # 2009/111].

6. References
Ahmed T. (1997). Hydrocarbon Phase behavior, Gulf publishing Company, London.
Danesh A. (1998). PVT and Phase Behavior of Petroleum Reservoir Fluids, Elsevier Science B.V.,
London.
Edmister, W.C. (April 1958). Applied Hydrocarbon Thermodynamic, Part 4: Compressibility
Factors and Equations of State, Petroleum Refinery, Vol.(37): 173-
179.
Esmaeilzadeh F., Roshanfekr M. (2006). A new Cubic Equation of State for Reservoir Fluids,
Fluid Phase Equilibria Vol.(239): 83–90
Firoozabadi A. (April 1988), Reservoir-Fluid Phase Behavior and Volumetric Prediction with
Equations of State, Journal of Petroleum Technology, pp 397-406.
Firoozabadi A. (1989). Thermodynamics of Hydrocarbon Reservoirs, McGraw-Hill.
Katz, D.L. and Firoozabadi, A. (Nov. 1978). Predicting Phase Behavior of Condensate Crude-
Oil Systems Using Methane Interaction Coefficients, Journal of Petroleum Technology
1649-55; Trans., AIME, 265.
Joffe, J., Schroeder, G.M., and Zudkevitch, D. (May 1970). Vapor-Liquid Equilibria with the
Redlich-Kwong Equation of State, AIChE J. 496-98.
Kesler, M.G. and Lee, B.I. (1976). Improve Prediction of Enthalpy of Fractions, Hydrocarbon
Processing: 55-59.
Krejbjerg K., Pedersen K. S. (2006). Controlling VLLE Equilibrium with a Cubic EOS in
Heavy Oil Modeling, 7th Canadian International Petroleum Conference,
Calgary,Canada.
O’Reilly D.I. (2009). Comparative PVT Simulation: An application to Australian Fluid
Samples, SPE Annual Technical Conference and Exhibition, New Orleans, Louisiana,
USA.
Patel N.C., Teja A.S.(1982). A new cubic equation of state for fluids and fluid mixtures,
Chem. Eng. Sci. Vol.(37): 463–473.
Peng, D.Y. and Robinson, D.B. (1976). A New Two-Constant Equation of State, Ind. & Eng.
Chem. 15, No.1, 59-64.
Peneloux A., Rauzy E. and Freze, R (1982). A Consistent Correction for Redlich-Kwong-
Soave Volumes. Fluid Phase Equilibria Vol.(8): 7-23.
Rafael A. Aguilar Zurita and William D. McCain, Jr. (2002). An Efficient Tuning Strategy to
Calibrate Cubic EOS for Compositional Simulation, SPE Annual Conference and
exhibition, San Antonio, Texas, SPE 77382.
Reid R.C., Prausnitz, J.M. and Sherwood, T.K (1986). The Properties of Gases and Liquids, 4th
edition, McGraw Hill.
Riazi, M. R., Daubert, T. E. (1987). Characterization Parameters for Petroleum Fractions, Ind.
Eng. Chem. Res. Vol.(26): 755-759.
Riazi M. R. (2005). Characterization and properties of Petroleum Fractions, ASTM Stock
Number: MNL50, ISBN: 2004059586, USA.

www.intechopen.com
178 Thermodynamics – Kinetics of Dynamic Systems

Rodriguez I. and Hamouda A.A. (2010). An Approach for Characterization and Lumping of
Plus Fractions of Heavy Oil, SPE 117446 Reservoir Evaluation & Engineering.
Schmit G., Wenzel H. (1980). A modified van der Waals type equation of state, Chem. Eng.
Sci. Vol.(35): 1503-1511.
Sing, B.P. (2005): Comparison of equations of state including the generalized Rydberg EOS,
Physica B Vol.(369): 111-116
Soave G (1972). Equilibrium Constants from a Modified Redlich-Kwong Equation of State,
Chem. Eng. Sci. 27, 1197-1203.
Starling, K.E (1966 ). A New Approach for Determining Equation-of-State Parameters Using
Phase Equilibria Data, SPE Journal Vol.(237), 363-371, Trans. AIME.
Starling, K.E. (1973). Fluid Thermodynamics Properties for Light Petroleum Systems, Gulf
Publishing Co., Houston.
Twu, C.H. (1984). An internally Consistent Correlation for Predicting the Critical Properties
and Molecular Weights of Petroleums and Coal-Tar Liquids, Fluid Phase Equilibria
Vol.(16): 137.
Twu, C.H., Coon, J.E. and Cunningham, J.R. (1995). A New Generalized Alpha Function for
a Cubic Equation of State. Part 1: Peng-Robinson EOS, Fluid Phase Equilibria,
Vol.(105): Number 1.
Whitson, C.H. (1982). Effect of C7+ Properties on Equation of State Predictions, SPE Annual
Technical Conference and Exhibition, SPE 11200.
Whitson, C.H.(Aug. 1983). Characterizing Hydrocarbon Plus Fractions, SPE Journal: 683-
94.
Zudkevitch, D. and Joffe, J. (Jan. 1970). Correlation and Prediction of Vapor Liquid
Equilibrium with the Redlich-Kwong Equation of State, AIChE J. 112-19.

www.intechopen.com
 Thermodynamics - Kinetics of Dynamic Systems
Edited by Dr. Juan Carlos Moreno Piraján

ISBN 978-953-307-627-0
Hard cover, 402 pages
Publisher InTech
Published online 22, September, 2011
Published in print edition September, 2011

Thermodynamics is one of the most exciting branches of physical chemistry which has greatly contributed to
the modern science. Being concentrated on a wide range of applications of thermodynamics, this book gathers
a series of contributions by the finest scientists in the world, gathered in an orderly manner. It can be used in
post-graduate courses for students and as a reference book, as it is written in a language pleasing to the
reader. It can also serve as a reference material for researchers to whom the thermodynamics is one of the
area of interest.

How to reference
In order to correctly reference this scholarly work, feel free to copy and paste the following:

Ibrahim Ashour, Nabeel Al-Rawahi, Amin Fatemi and Gholamreza Vakili-Nezhaad (2011). Applications of
Equations of State in the Oil and Gas Industry, Thermodynamics - Kinetics of Dynamic Systems, Dr. Juan
Carlos Moreno Piraján (Ed.), ISBN: 978-953-307-627-0, InTech, Available from:
http://www.intechopen.com/books/thermodynamics-kinetics-of-dynamic-systems/applications-of-equations-of-
state-in-the-oil-and-gas-industry

InTech Europe InTech China

University Campus STeP Ri Unit 405, Office Block, Hotel Equatorial Shanghai
Slavka Krautzeka 83/A No.65, Yan An Road (West), Shanghai, 200040, China
51000 Rijeka, Croatia
Phone: +385 (51) 770 447 Phone: +86-21-62489820
Fax: +385 (51) 686 166 Fax: +86-21-62489821
www.intechopen.com
© 2011 The Author(s). Licensee IntechOpen. This chapter is distributed
under the terms of the Creative Commons Attribution-NonCommercial-
ShareAlike-3.0 License, which permits use, distribution and reproduction for
non-commercial purposes, provided the original is properly cited and
derivative works building on this content are distributed under the same
license.