Neeraj Kumar Masters Thesis

COMPRESSIBILITY FACTORS FOR NATURAL AND SOUR
RESERVOIR GASES BY CORRELATIONS AND
CUBIC EQUATIONS OF STATE
by
NEERAJ KUMAR, B.Tech.
A THESIS
IN
PETROLEUM ENGINEERING
Submitted to the Graduate Faculty

of Texas Tech University in
Partial Fulfillment of
the Requirements for
the Degree of
MASTER OF SCIENCE
IN
PETROLEUM ENGINEERING
Approved
Akanni Lawal
Chairperson of the Committee
Paulus Adisoemarta
Accepted
John Borrelli
Dean of the Graduate School
December, 2004
ACKNOWLEDGEMENTS
There are many people who were associated with this thesis who deserve
recognition. I would like to thank Dr. Akanni S. Lawal for his direction, support and
training. Thanks to Dr. James F. Lea for helping me with industrial approach towards this
thesis. I would also like to thank Dr. Paulus Adisoemarta for serving on my committee
and for his guidance.
ii
TABLE OF CONTENTS
ACKNOWLEDGEMENTS ii
ABSTRACT vi
LIST OF TABLES vii
LIST OF FIGURES viii
LIST OF ABBREVIATIONS xii
CHAPTER
1. INTRODUCTION 1
1.1 Background Information 1
1.2 Use of Compressibility Factors in Engineering Analysis 2
1.2.1 Z-Factor for Sour and Acid Gases 2
1.2.2 Z-Factor for Geologic CO2 Storage 2
1.3 Significance of the Project 3
1.4 Objective of the Project 4
2. COMPRESSIBILITY FACTOR PREDICTION TECHNIQUES 5

2.1 Theoretical Analysis of Gas Law-Based Z-Factors 5
2.2 Experimental Method for Compressibility Factors 5
2.3 Empirical Correlation Methods 5
2.3.1 Standing-Katz Compressibility Factor Chart 5
2.3.2 Hall-Yarborough Z-Factor Correlation 6
2.3.3 Wichert -Aziz Z-Factor Correlation 7
2.3.4 Dranchuk-Abou-Kassem Z-Factor Correlation 7
2.3.5 Beggs-Brill Equation for SK Z-Factor Chart 8
2.3.6 Amoco Company Equation for SK Z-Factor Chart 9
2.3.7 Gopal Best-Fit Equation for SK Z-Factor Chart 9
2.3.8 Shell Oil Company Equation for SK Z-Factor Chart 10
2.3.9 Physical Properties of C7+ Fractions Correlations 11
iii
2.4 Corresponding State Prediction Methods 12
2.5 Equations of State Prediction Methods 19
3. STANDING-KATZ Z-FACTOR CORRELATION 20

3.1 Standing-Katz Representation of Z-Factor Chart 20
3.2 Best-Fit Equations for SK Z-Factor Chart 20
3.3 Mixture Critical Property Prediction Methods 23
3.3.1 Heptane-Plus Fraction Correlation Methods 25
3.3.2 Pseudocritical Mixing Parameter Methods 27
3.3.3 Pseudocritical Gas Gravity Correlation Methods 33
3.3.4 van der Waals Theory of Pseudocritical Methods 37
3.3.5 Improved Theory for Pseudocritical Mixture Parameter 37
3.4 Designed Scaling Parameter for Standing-Katz Z-Factor Chart 38
3.4.1 Design Procedure for Scaling Parameter 38
3.5 Designed PR/Z Versus Z-Factor Chart 42
3.6 Prediction Results for Z-Factor of Natural Gases 43
3.7 Prediction Results for Z-Factor of Reservoir Gases 45
4. Z-FACTOR PREDICTIONS FROM CUBIC EQUATIONS OF STATE 53

4.1 Selection of Cubic Equations-of-State 53
4.2 Lawal-Lake-Silberberg Equation of State 54
4.3 van der Waals Equation of State 56
4.4 Redlich-Kwong Equation of State 57
4.5 Soave-Redlich-Kwong Equation of State 58
4.6 Peng-Robinson Equation of State 61
4.7 Schmidt-Wenzel Equation of State 62
4.8 Patel-Teja Equation of State 63
4.9 Trebble-Bishnoi Equation of State 65
iv
4.10 Transformed Cubic Equations to the LLS EOS Form 66
4.11 Generalized Reduced State of Cubic Equations-of-State 67
4.12 Prediction Results for Z-Factor of Pure Substances 71
4.13 Development of Binary Interaction Parameters 74
4.14 Prediction Results of Z-Factor of Mixtures 75
4.15 Prediction Results for Z-Factor of Natural Gases 77
4.15. 1 Results for Excelsior Laboratory Data 78
4.15. 2 Results for TTU Laboratory Data 80
4.15. 3 Results for UCalgary Data 81
4.15. 4 Results for Elsharkawy Gas Data 88
4.15. 5 Results for Elsharkawy Miscellaneous Data 90
5. CONCLUSIONS AND RECOMMENDATIONS 94

5.1. Conclusions 94
5.2. Recommendations 95
REFERENCES 96
APPENDICES 106
A. REDUCED FORM OF CUBIC EQUATIONS OF STATE 106
B. PREDICTION RESULTS FOR PSEUDOCRITICAL PARAMETERS 117
C. SCALING FACTOR DEVELOPMENT AND RESULTS 122
D. PREDICTION OF Z-FACTOR FOR PURE SUBSTANCES 127
E. EXPERIMENTAL Z-FACTOR FOR MISCELLANEOUS GASES 137
F. PREDICTION OF Z-FACTOR FROM LLS EOS 171
G. FORTRAN PROGRAMS 174
v
ABSTRACT
Compressibility factor (z-factor) values of natural gases are necessary in most

petroleum engineering calculations. The most common sources of z-factor values are
experimental measurement, equations of state method and empirical correlations.
Necessity arises when there is no available experimental data for the required
composition, pressure and temperature conditions. Presented here is a technique to
predict z-factor values of pure substances, natural gases and sour reservoir gases
regardless of the composition of the acid gases at all temperatures and pressures.
Eight equations of state have been thoroughly examined and the results suggest
that the Lawal-Lake-Silberberg (LLS-EOS) equation of state is capable of predicting z-
factor values of both pure substances and mixtures of gases. This equation of state
method allows the determination of reduced temperature (TR) and reduced pressure (PR)
instead of the pseudo-reduced temperature (TPR) and pseudo-reduced pressure (PPR) both
for pure substances and mixtures of gases. This EOS is robust and the results are accurate
even if of acid gases present in high concentration. A comparative z-factor prediction
result of the various EOS methods for different gas samples is presented fortifying the
capability of the LLS-EOS method. Another method of predicting z-factor values is
based on the famous Standing-Katz (S-K) Chart (empirical methods). Law of
Corresponding States principle has formed the basis to develop a universal adjustable
parameter. This developed adjustable parameter forms the basis for using LLS-EOS to
be able to use S-K Chart to predict accurate z-factor values of pure substances and
mixtures of gases regardless of the concentration of acid gases. In contrast to the existing
methods derived from other equations of states (EOS methods) and S-K Chart (empirical
methods), this project provides a simple and universal technique for predicting z-factor
values for pure substances, natural gases and sour reservoir gases.
vi
LIST OF TABLES
2.1 Heavy Fraction Property Correlations. 10

3.1 Coefficients of Cavett’s correlation. 25
3.2 Sources of Experimental Z-Factor for Pure Substances 36
3.3 Rich Gas Condensate Composition (Elsharkawy) 45
3.4 Highly Sour Gas Composition (Elsharkawy) 46
3.5 Carbon Dioxide Rich Composition (Elsharkawy) 47
3.6 Very Light Gas Composition (Elsharkawy) 48
3.7 Property Prediction for Gas Composition Data (Elsharkawy) 49
4.1 Common Specialization Cubic Equation of State 66
4.2 Sources of Experimental Z-Factor 77
4.3 Gas Composition Data for Excelsior 6 Laboratory Data. 78
4.4 Gold Creek Gas Composition. 81
4.5 Results of Elsharkawy Gas Data. 88
4.6 Z-Factor Results for Miscellaneous Gases. 90
B.1 Gas Composition Description. 118
E.1 UCalgary Z-Factor Data. 137
vii
LIST OF FIGURES
1.1 Critical compressibility factor for pure hydrocarbons (alkanes). 3

2.1 Z-Factor of Pure Substances at Reduced Conditions(TR=0.65). 22
2.3 Z-Factor of Pure Substances at Reduced Conditions (TR=0.85). 24
3.1 Comparison of Six Correlations for Pseudocritical Pressure Parameters. 35
3.2 Compare of Six Correlations for Pseudocritical Temperature Parameters. 35
o
3.3 Scaled Z-Factor for Buxton & Campbell Data (Mix-5) at 160 F. 40
3.4 Scaled Z-Factor for Buxton and Campbell Data (Mix-5) at 130 oF. 40
3.5 Scaled Z-Factor for Buxton and Campbell Data (Mix-5) at 100 oF. 41
3.6 Scaled Z-Factor for Satter Data (Mix-E) at 160 oF. 41
3.7 SK Z-Chart Developed Based on Computation SK Technique. 42
3.8 Amount of gas produced. 43
o
3.9 Scaled Z-Factor Buxton & Campbell, Mix-2 Result, @ T = 130 F. 43
3.10 Scaled Z-Factor Buxton & Campbell, Mix-2 Result, @ T = 100 oF 44
3.11 Scaled Z-Factor Buxton & Campbell, Mix-3 Result, @ T = 100 oF 44
3.12 Scaled Z-Factor for Very Light Gas Composition. 50
3.13 Scaled Z-Factor for Carbon Dioxide Rich Gas Composition. 50
3.14 Scaled Z-Factor for Rich Gas Condensate Composition. 51
3.15 Scaled Z-Factor for Highly Sour Gas Composition. 51
4.1 Z-Factor comparison for LLS-EOS for Methane. 71
4.2 Z-Factor comparison for LLS-EOS for Carbon dioxide. 72
viii
4.3 Z-Factor comparison for LLS-EOS for Nitrogen. 72
4.4 Z-Factor comparison for vdW-EOS for Methane. 73
4.5 Z-Factor comparison for vdW-EOS for Carbon dioxide. 73
o
4.6 Z-Factor comparison for CO2-C1 mixture at 49 F. 75
4.7 Z-Factor comparison for CO2-C1 mixture at 70 oF. 75
4.10 Z-Factor for Sweet Natural Gas, Data from Excelsior 6 (FPP) at 581 oR. 79
4.11 Z-Factor Comparison Chart at 90 oF (Simon et. al.). 79
o
4.12 Z-Factor Comparison Chart at 120 F (Simon et. al.). 80
4.13 75% CO2 - Dry Gas at 100 oF for CO2 Sequestration. 80
4.14 25% CO2 - Dry Gas at 160 oF for CO2 Sequestration. 81
4.15 Z-Factor for sour natural gas, data from Excelsior 6 (FPP) at 581 oR. 82
4.16 Z-Factor comparison for sour natural gas mixture at 84 oF. 82
o
4.17 Z-Factor comparison for sour natural gas mixture at 73 F. 83
o
4.23 Z-Factor comparison for sour natural gas mixture at 175 F. 86
B.1 Critical temperature prediction for Gore Data (Mix 47-1). 118
B.2 Critical pressure prediction for Gore Data (Mix 47-1). 119
ix
C.1 Scaled z-factor result for Buxton & Campbell Data at 160 oF (Mix-4). 123
o
C.2 Scaled z-factor result for Buxton & Campbell Data at 130 F (Mix-4). 123
D.1 Z-Factor comparison for vdW-EOS for Nitrogen. 127
D.2 Z-Factor comparison for RK-EOS for Methane. 127
D.3 Z-Factor comparison for RK-EOS for Carbon dioxide. 128
D.4 Z-Factor comparison for RK-EOS for Nitrogen. 128
D.5 Z-Factor comparison for SRK-EOS for Methane. 129
D.6 Z-Factor comparison for SRK-EOS for Carbon dioxide. 129
D.7 Z-Factor comparison for SRK-EOS for Nitrogen. 130
D.8 Z-Factor comparison for PR-EOS for Methane. 130
D.9 Z-Factor comparison for PR-EOS for Carbon dioxide. 131
D.10 Z-Factor comparison for PR-EOS for Nitrogen. 131
D.11 Z-Factor comparison for SW-EOS for Methane. 132
D.12 Z-Factor comparison for SW-EOS for Carbon dioxide. 132
D.13 Z-Factor comparison for SW-EOS for Nitrogen. 133
D.14 Z-Factor comparison for PT-EOS for Methane. 133
D.15 Z-Factor comparison for PT-EOS for Carbon dioxide. 134
D.16 Z-Factor comparison for PT-EOS for Nitrogen. 134
D.17 Z-Factor comparison for TB-EOS for Methane. 135
D.18 Z-Factor comparison for TB-EOS for Carbon dioxide. 135
D.19 Z-Factor comparison for TB-EOS for Nitrogen. 136
F.1 Z-factor for pure substances (Methane). 171
x
F.2 Z-factor for pure substances (n-Decane). 171
F.3 Z-factor for pure substances (Carbon Dioxide). 172
F.4 Z-factor for pure substances (Hydrogen Sulfide). 172
F.5 Z-factor for pure substances (Nitrogen). 173
xi
LIST OF ABBREVIATIONS
Symbol Definition
a Attraction Parameter in EOS

⎛ a (T ) P ⎞
A Dimensionless Constant ⎜ 2 2 ⎟
⎝R T ⎠
ACF Acentric Factor
AF Acentric Factor
API Oil Gravity
b van der Waals co-volume
⎛ bP ⎞
B Dimensionless Constant ⎜ ⎟
⎝ RT ⎠
BIN Binary Interaction Number
BIP Binary Interaction Parameter
EOS Equation of State
G Gibbs Free Energy
k Parameter of SRK EOS
LLS Lawal-Lake-Silberberg
m Parameter of SRK EOS
Mw Molecular Weight
Mw Molecular Weight
p Pressure in psia
P Pressure in psia
PR Peng Robinson
R Universal Gas Constant (10.73 psiD.ft3/ (lb-
mol. oR))
RK Redlick-Kwong
SRK Soave-Redlich-Kwong
xii
SW Schmidt-Wenzel
t Inverse Absolute Temperature (1/T)
T Absolute Temperature
TB Trebble-Bishnoi
V Volume in cubic feet
vdW van der Waal
x Mole Fraction
z Compressibility Factor
Z Compressibility Factor
Greek Letter
α Parameter of LLS EOS
αij Binary Interaction Term
β Parameter of LLS EOS
Ω Dimensionless EOS Parameter
ω Acentric Factor
γg Specific Gravity
Subscripts
c Critical Property
pr Pseudo Reduced Property Identification
pc Pseudo Critical Property Identification
r Reduced Property Identification
m Mixture Definition
R Reduced State
i, j Component Identification
1, 2 Index for components 1 and 2
xiii
CHAPTER 1
INTRODUCTION
1.1 Background Information

Compressibility Factor is a measure of the amount the gas deviates from perfect
behavior. It is more commonly called as the gas deviation factor, represented as z (or) Z.
It is a dimensionless quantity and by definition the ratio of the volume actually occupied
by a gas at a given pressure and temperature to the volume it would occupy if it behaved
ideally. Therefore, a value of z = 1 would represent an ideal gas condition.
Va Actual volume of n moles of gas at T and p
z= =
Vi Ideal volume of n moles at same T and p
The kinetic theory of gases (basis for Ideal gas law) assumes that there are neither
attractive forces nor repulsive forces between the gas molecules.
In nature, ideal gases do not exist instead real gases exist. All molecules of real gases are
under two kinds of forces:
(a) to move apart from each other because of their constant kinetic motion, and
(b) to come together because of electrical attractive forces between the molecules.
At normal conditions, the molecules are quite far apart and the attractive forces are
negligible and same is the condition at high temperatures because of the greater kinetic
motion. Under these above mentioned conditions, the gas tends to approach ideal
behavior. While, at high pressures, the molecules come very close to each other resulting
in significant attractive forces. These theories qualitatively explain the behavior of non-
ideal (real) gases and a general representation of the gas law is as follows:
Ideal Gas Law: PV = nRT (1.1).
Real Gas Law: PV = znRT (1.2).
1
1.2 Use of Compressibility Factors in Engineering Analysis
Accurate information of compressibility factor values is necessary in engineering
applications like gas metering, pipeline design, estimating reserves, gas flow rate, and
material balance calculations. Some of the petroleum engineering applications which
involve use of z-factor values of gases are as follows:
1.2.1 Z-Factor for Sour and Acid Gases

If hydrogen sulfide is present in a natural gas mixture it is termed as sour natural
gas. The existing methods of calculating z-factor values when significant amounts of acid
gases like carbon dioxide (CO2) and hydrogen sulfide (H2S) are present in the natural gas
mixtures incur high deviations from the actual values.
1.2.2 Z-Factor for Geologic CO2 Storage

A high content of CO2 gas present in the atmosphere is the major cause for global
warming. A method to capture CO2 from the atmosphere or other sources of CO2
production and be able to store it into abandoned wells is called as CO2 sequestration.
CO2 gas in various concentrations can be required to be stored. Engineering this method
needs z-factor values.
Knowledge of accurate critical z-factor value for pure substances and mixtures is
essential in the determination of accurate z-factor values. Critical z-factor is unique for
each component and system. Figure 1.1 illustrates the capability of various equations-of-
states in predicting critical compressibility factor values.
2
0.38
VDW
0.36
Critical Compressibility Factor
0.34
RK
0.32
PR
SW
0.30
Twu PT
0.28
TB
EXP LLS
0.26
0.24
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10
Pure Substances
Figure 1.1: Critical compressibility factor for pure hydrocarbons (alkanes).
1.3 Significance of the Project

Today’s standard treatment of phase behavior in reservoir simulation is still based
on formation volume factors (FVF’s) and surface gas/oil ratios (GOR’s) which requires
the determination of z-factor and critical properties of mixtures, more importantly. As
more and more, sour environment reservoirs are discovered, it becomes a necessity to
have a simple and robust technique to be able to determine z-factor values accurately.
This project presents methods that allow accurate determination of z-factor values both
for pure components and gas mixtures including significant amounts of non-hydrocarbon
components for all ranges of pressures and temperatures.
3
1.4 Objective of the Project
This research project provides improved predictive techniques for z-factors based
on the approaches of cubic Equations-of-State (EOS) and empirical correlation of
Standing-Katz5 Chart. Eight EOS that are routinely used in reservoir calculations and
improved pseudocritical property methods for Standing & Katz (SK) Chart are utilized to
match experimentally determined z-factors for pure substances, natural and sour reservoir
gases. The experimental z-factors data for 3100 gas samples, including highly sour gases
(H2S), acid gases (CO2 and N2) and rich gas condensates (with significant amount of C7+)
are used to establish the improved predictive techniques for z-factors.
4
CHAPTER 2
COMPRESSIBILITY FACTOR PREDICTION TECHNIQUES
2.1 Theoretical Analysis of Gas Law-Based Z-Factors

The magnitude of deviation of real gases from the conditions of the ideal gas law
increases with increasing pressure and temperature and varies widely with the
composition of the gas.
Numerous equations-of-state have been developed in the attempt to correlate the
pressure-temperature-volume variables for real gases with experimental data. In order to
express a more exact relationship between the variables p, V, and T, z-factor must be
introduced into the ideal gas equation to account for the departure of gases from ideality.
This forms the basis for the real gas law and is represented as:
pV = zRT (1.2).
To account for this deviation factor (z-factor), numerous equations-of-state have
been proposed.
2.2 Experimental Method for Compressibility Factors

Among the existing method of determination of z-factors, experimental
measurement is one of the most accurate methods. It is hard to determine experimentally
measured z-factor values for all compositions of gases at all ranges of pressures and
temperatures. At the same time, this method is expensive and most of the time these
measurements are made at reservoir temperatures only.
2.3 Empirical Correlations Methods
2.3.1 Standing-Katz Compressibility Factor Chart

Standing and Katz5 presented a generalized z-factor chart, which has become an
industry standard for predicting the volumetric behavior of natural gases. To be able to
5
use this chart, knowledge of reduced temperature and reduced pressure are required,
which further needs determination of critical properties (namely, critical pressure and
critical temperature of the system). Numerous methods have been suggested to predict
pseudocritical properties of the gases as a function of their specific gravity. The point to
be noted here is that these methods predict pseudo critical values which are evidently not
accurate values of the gas mixtures. The existing methods fail to predict accurate values
of pseudocritical values when non-hydrocarbon components are present in significant
amounts. Improved technique to predict critical properties have been discussed in the
Chapter 3 of this thesis report.
2.3.2 Hall-Yarborough Z-Factor Correlation

Hall and Yarborough8 (1973) presented an equation-of-state that accurately
determined the Standing and Katz z-factor chart. This is based on the Starling-Carnahan21
equation-of-state. Best fit mathematical expressions were determined based on the data
taken from Standing and Katz z-factor chart. The mathematical form of the equation is:
⎡ 0.06125p pr t ⎤
Z=⎢ [
⎥ EXP − 1.2(1 − t )
2
]
⎣ Y ⎦ (2.1).
where pPR = pseudo-reduced pressure
⎛ Tpc ⎞
t = reciprocal of the pseudo-reduced temperature ⎜⎜ = ⎟⎟
⎝ T ⎠
[
F(Y) = −0.06125p pr T − 1.2(1 − t ) +
2
] Y + Y2 + Y3 − Y4
(1 − Y )3
( ) ( )
− 14.76t − 9.76t 2 4.58t 3 Y 2 + 90.7 t − 242.2t 2 + 42.4t 3 Y (2.18+ 2.82 t ) = 0 (2.2).
Hall and Yarborough pointed out that the method is not recommended for
application if the pseudo-reduced temperature is less than one.
6
2.3.3 Wichert-Aziz Z-Factor Correlation
Sour natural gases (containing H2S) and/or CO2 frequently exhibit different
compressibility factor behavior than do sweet natural gases. Wichert and Aziz22 (1972)
developed a calculation procedure to account for these differences. Wichert and Aziz
developed a pseudo-critcal temperature adjustment factor which is a function of the
concentration of CO2 and H2S in the sour gas. This correction factor is then used to adjust
the pseudo-critical temperature and pressure according to the following expressions:
Tpc′ = Tpc − ε (2.3).
p pc Tpc′
p′pc =
Tpc + B(1 − B)ε
(2.4).
where Tpc = pseudo-critical temperature, oR
ppc = pseudo-critical pressure, psia

Tpc′ = corrected pseudo-critical temperature, oR
p pc = corrected pseudo-critical pressure, psia
B = mole fraction of H2S in the gas mixture

ε = pseudo-critical temperature adjustment factor and is defined mathematically
by the following expression
( ) (
ε = 120 A 0.9 − A 1.9 + 15 B 0.5 − B 4.0 ) (2.5).
where the coefficient A is the sum of the mole fraction of H2S and CO2 in the gas
mixture, or
A = y H 2S + y CO 2
(2.6).
2.3.4 Dranchuk-Abu-Kassem Z-Factor Correlation

Dranchuk and Abu-Kassem23 (1975) proposed an eleven-constant equation-of-
state for calculating the gas compressibility factors. The equation is as follows:
7
⎡ A A A ⎤
z = ⎢A 1 + 2 + 33 + 55 ⎥ρ r
⎢⎣ Tpr Tpr Tpr ⎥⎦
⎡ A A ⎤ ⎡A A ⎤
+ ⎢A 6 + 7 + 28 ⎥ρ 2r − A 9 ⎢ 7 + 28 ⎥ρ 5r
⎢⎣ Tpr Tpr ⎥⎦ ⎢⎣ Tpr Tpr ⎥⎦
( ρ2
) [
+ A 10 1 + A 11ρ 2r 3r EXP − A 11ρ 2r + 1
Tpr
]
(2.7).
where ρ r = reduced gas density and is defined by the following relationship:
0.27p pr
ρr =
zTpr
(2.8).
The constants A1 through A11 were determined by fitting the equation, using non-
linear regression models, to 1,500 points from the Standing and Katz z-factor chart. The
coefficients values:
A1 = 0.3262 A2 = -1.0700 A3 = -0.5339 A4 = 0.01569
A5 = -0.05165 A6 = 0.5475 A7 = -0.7361 A8 = 0.1884
A9 = 0.1056 A10 = 0.6134 A11 = 0.7210
This method is applicable over the ranges
0.2 ≤ p pr < 30
1.0 < Tpr ≤ 3.0
with an average absolute error of 0.585 percent.
2.3.5 Beggs-Brill Equation for SK Z-Factor Chart

Beggs and Brill25 (1973) proposed a best-fit equation for the Standing and Katz z-
factor chart and is as follows:
z=A+
(1 − A ) + Cp D
pr
eB (2.9).
where
A = 1.39(Tpr − 0.92) − 0.36Tpr − 0.101
0.5
8
⎡ 0.066 ⎤
B = (0.62 − 0.23Tpr )p pr + ⎢
0.32
− 0.037⎥ p 2pr + 9 (Tpr −1) p 6pr
⎣⎢ (Tpr − 0.86 ) ⎦⎥ 10
C = (0.132 − 0.32 log (Tpr ))

(0.3016 −0.49 T
pr + 0.1824 Tpr
2
)
D = 10
This method is cannot be used for reduced temperature ( Tpr ) values less than
0.92.
2.3.6 Amoco Company Equation for SK Z-Factor Chart

Amoco Company uses the Hall and Yarborough z-factor determination method
and can be defined as follows:
⎡ 0.06125p pr t ⎤
Z=⎢ ⎥ EXP − 1.2(1 − t )
2
[ ]
⎣ Y ⎦ (2.10).
where ppr = pseudo-reduced pressure
⎛ Tpc ⎞
⎝ T ⎠
[
F(Y) = −0.06125p pr T − 1.2(1 − t ) +
2
] Y + Y2 + Y3 − Y4
(1 − Y )3
( ) (
− 14.76t − 9.76t 2 4.58t 3 Y 2 + 90.7 t − 242.2t 2 + 42.4t 3 Y (2.18+ 2.82 t ) = 0 ) (2.11).
It should be noted that this method is not recommended for application if the
pseudo-reduced temperature is less than one.
2.3.7 Gopal Best-Fit Equation for SK Z-Factor Chart

Gopal’s33 correlation for z-factor estimation was developed by dividing the
Standing-Katz chart into two parts by drawing a line isobarically for PR up to 5.4. For
various Tr values, several z-factor values were tabulated isobarically for Pr up to 5.4
because, for any Pr,, the z-factor values show a uniform trend. His objective was to come
9
up with two noniterative equations, one for Pr less than or equal to 5.4, and the other for
Pr greater than 5.4. To describe the chart accurately, the chart was further divided into 12
parts24. A general equation was developed and is of the form:
Z = Pr (ATr + B ) + CTr + D (2.12).
The values of constants A, B, C, and D for various combinations of PR and TR are
available in the reference33. For Pr greater than 5.4, harmonic equations are suggested to
be a good fit.
2.3.8 Shell Oil Company Equation for Z-Factor Chart

4
⎛ p pr ⎞
Z = ZA + ZB × p pr + (1 − ZA) × EXP(− ZG) − ZF × ⎜⎜ ⎟⎟
⎝ 10 ⎠ (2.13).
where,
ZA = −0.101 − 0.36 × Tpr + 1.3868 × (Tpr − 0.919)
0.04275
ZB = 0.021 +
(Tpr − 0.65)
ZC = 0.6222 − 0.224 × Tpr
0.0657
ZD = − 0.037
(Tpr − 0.86)
ZE = 0.32 × EXP (−19.53 × (Tpr − 1))
ZF = 0.122 × EXP ( −11.3 × (Tpr − 1))
ZG = p pr * ( ZC + ZD × p pr + ZE × p 4pr )
10
2.3.9 Physical Properties of C7+ Fractions Correlation
Table 2.1: Heavy Fraction Property Correlations.
6084
API = + 5 .9
MW
141.5
SG =
131.5 + API
( )
Tbp o R = e 0 MW e1 SG
e2
C = e 0 MW 1 SG 2 Tbpe3
e e
p c , ( psi) = e 0 MW 1 SG 2 Tbpe3 C e 4
e e
( )
Tc o R = e 0 MW 1 SG 2 Tbpe 3 Ce 4
e e
ω = e 0 MW 1 SG 2 Tbpe3 C e 4
e e
0.293 0.361
Zc = Ωw =
(1 + 0.375ω ) (1 + 0.0274ω )
Parameters
Property
e0 e1 e2 e3 e4
Tbp 108.701661 0.42244800 0.42682558 0.000000 0.000000
C 0.83282122 0.09255911 -0.0413045 0.12621158 0.000000
Pc 237031780 -0.028484 2.755309 -1.374444 -2.947221
Tc 6.206640 -0.059607 0.224357 0.968332 -0.802538
ω 1.5790E-13 -1.453063 -2.811708 4.883921 2.109476
ω 2.22065E-10 -0.45908 -2.25373 3.4452 0.000000
11
2.4 Corresponding States Prediction Methods
The theory of Corresponding States proposes that all gases will exhibit the same
behavior, e.g. z-factor, when viewed in terms of reduced pressure, reduced volume, and
reduced temperature. Mathematically, this principle can be defined as:
z = z c Ψ (p R , TR ) (2.14).
The mathematical derivation of the above expression is as follows:
Real gas law is,
PV = zRT (2.15).
Multiply and divide the LHS of the above equation by Pc Vc and RHS by zcTc, we get,
PV zRT
Pc Vc = z c Tc
Pc Vc z c Tc (2.16).
PV T T
= = zR c
Pc Vc Pc Vc Tc (2.17).
By definition
P T
PR = & TR =
Pc Tc (2.18).
z z c Tc
= PR VR = TR
z c Pc Vc (2.19).
we have from real gas law,
z c Tc 1
=
Pc Vc R (2.20).
z PR VR
= PR VR =
z c TR (2.21).
TR
= z = zc
PR VR
z = z c Ψ (p R , TR ) (2.22).
Based on the above derivation, the following relationship can be established,
12
p R1 VR1 p R 2 VR 2
=
Z R1TR1 Z R 2 TR 2 (2.23).
4
C om pressibility Factor
3
Exp
TR = 0.65 nC7
2 nC9
nC10
vdW
SRK
1
LLS
PT
PR
0
0 5 10 15 20 25 30
Reduced Pressure
Figure 2.1: Z-Factor of Pure Substances at Reduced Conditions (TR=0.65).
13
5
4
C om pressibility Factor
3 Exp
nC4
TR = 0.75 nC5
2 nC6
nC9
vdW
SRK
1
LLS
PT
PR
0
0 5 10 15 20 25 30
Reduced Pressure
Figure 2.2: Z-Factors of Pure Substances at Reduced Conditions (TR = 0.75).
14
5
Exp
C3
iC4
4 nC4
nC5
nC6
Compressibility Factor
nC7
nC9
3 nC10
vdW
SRK
TR = 0.85
LLS
2 PT
PR
0
0 5 10 15 20 25 30
Reduced Pressure
Figure 2.3: Z- Factor of Pure Substances at Reduced Conditions (TR=0.85).
1.8
1.4
Exp
1 CO2
H2S
C2
TR = 1.02 C3
nC5
0.6 vdW
SRK
LLS
PT
PR
0.2
0 4 8 12 16
Reduced Pressure
15
2.25
1.85
1.45
Exp
C2
1.05 C3
TR = 1.07 nC4
iC4
nC5
vdW
0.65 SRK
LLS
PT
PR
0.25
0 5 10 15 20
Reduced Pressure
2.03
1.75
1.47
Exp
CO2
1.19 H2S
C2
TR = 1.13 C3
nC4
0.91
iC4
vdW
SRK
0.63 LLS
PT
PR
0.35
0 5 10 15 20
Reduced Pressure
16
1.9
1.55
Exp
CO2
1.2 H2S
C2
C3
TR = 1.24 nC4
iC4
0.85 vdW
SRK
LLS
PT
PR
0.5
0 5 10 15 20
Reduced Pressure
1.64
1.31
Exp
CO2
TR = 1.55 C1
C2
C3
0.98
vdW
SRK
LLS
PT
PR
0.65
0 5 10 15 20
Reduced Pressure
17
1.60
1.36
Exp
CO2
C1
C2
1.12 TR = 1.98
vdW
SRK
LLS
PT
PR
0.88
0 3 6 9 12 15 18
Reduced Pressure
2.00
1.73
1.45 Exp
N2
TR = 2.03
C1
vdW
1.18 SRK
LLS
PT
PR
0.90
0 5 10 15 20 25 30
Reduced Pressure
18
2.5 Equations of State Prediction Methods
Cubic equations of state (EOS’s) are simple equations relating pressure, volume,
and temperature (PVT). They accurately describe the volumetric and phase behavior of
pure compounds and mixtures, requiring only critical properties and acentric factor of
each component. The same equation is used to calculate the properties of all phases,
thereby ensuring consistency in reservoir processes that approach critical conditions.
Multiple phase behavior, such as low-temperature CO2 flooding, can be treated with an
EOS, and even water-/hydrocarbon-phase behavior can be predicted accurately with a
cubic EOS.
Volumetric behavior is calculated by solving the simple cubic equation, usually
pV
expressed in terms of z = ,
RT
z 3 + A 2 z + A1z + A 0 = 0 (2.24).
where constants A0, A1, and A2 are functions of pressure, temperature, and phase
composition. Chapter 4 presents a detailed use of equations-of-state method for solving z-
factors.
19
CHAPTER 3
STANDING-KATZ Z-FACTOR CORRELATION
3.1 Standing-Katz Representation of Z-Factor Chart

The z-factor in the Standing and Katz5 (SK) chart is a function of reduced
pressure and temperature. To be able to predict z-factor using the SK chart requires the
appropriate reduced temperature and pressure. Information on the composition of the gas
used to design the Standing-Katz z-factor chart is not provided. A close study and
comparison of the experimental data with that of SK chart z-factor values suggests that
the SK chart was developed based on the natural gas mixture without any significant
amounts of non-hydrocarbon components and C7+ in it.
3.2 Best-Fit Equations for SK Z-Factor Chart

Many empirical equations and EOSs have been fit to the original Standing-Katz z-
factor chart. Some of the commonly used methods in the petroleum industry are:
Hall & Yarborough11 Best Fit Equation:
⎡ 0.06125p pr t ⎤
Z=⎢
Y
[
⎥ exp − 1.2(1 − t )
2
] (3.1)
⎣ ⎦
where ppr = pseudo-reduced pressure

⎛ Tpc ⎞
⎝ T ⎠
[
F(Y) = −0.06125p pr T − 1.2(1 − t ) +
2
] Y + Y2 + Y3 − Y4
(1 − Y )3
( ) ( )
− 14.76 t − 9.76 t 2 4.58t 3 Y 2 + 90.7 t − 242.2 t 2 + 42.4 t 3 Y (2.18+ 2.82 t ) = 0 (3.2).
20
Beggs-Brill25 Best-Fit Equation:
z=A+
(1 − A ) + Cp D
pr
eB (3.3)
where
A = 1.39(Tpr − 0.92)
0.5
− 0.36Tpr − 0.101
⎡ 0.066 ⎤
B = (0.62 − 0.23Tpr )p pr + ⎢
0.32
− 0.037⎥ p 2pr + 9 (Tpr −1) p 6pr
⎢⎣ Tpr − 0.86 ( ⎥⎦ ) 10
C = (0.132 − 0.32 log(Tpr ))

(0.3016−0.49T 2
pr + 0.1824 Tpr )
D = 10
Dranchuk-Abu-Kassem23 Best-Fit Equation:
⎡ A A A ⎤
z = ⎢ A1 + 2 + 33 + 55 ⎥ ρ r
⎢⎣ T pr T pr T pr ⎥⎦
⎡ A A ⎤ ⎡A A ⎤
+ ⎢ A6 + 7 + 28 ⎥ ρ r2 − A9 ⎢ 7 + 28 ⎥ ρ r5
⎣⎢ T pr T pr ⎥⎦ ⎣⎢ T pr T pr ⎥⎦
)ρ [ ]
2
(
+ A10 1 + A11 ρ r2 3
r
EXP − A11 ρ r2 + 1
T pr
(3.4)
where ρ r = reduced gas density and is defined by the following relationship:
0.27p pr
ρr =
zTpr
The constants A1 through A11 were determined by fitting the equation,
using non-linear regression models, to 1,500 points from the Standing and Katz z-factor
chart. The coefficients values:
A1 = 0.3262 A2 = -1.0700 A3 = -0.5339 A4 = 0.01569
A5 = -0.05165 A6 = 0.5475 A7 = -0.7361 A8 = 0.1884
A9 = 0.1056 A10 = 0.6134 A11 = 0.7210
Dranchuk-Purvis-Robinson Method:
21
Dranchuk, Purvis, and Robinson’s (1974) correlation was developed based on
Benedict-Webb-Rubin57 type of equation of state. It consists of eight coefficients which
were obtained based on a best-fit of 1500 data points from Standing-Katz Z-factor chart.
The correlation is,
⎡ A A ⎤ ⎡ A ⎤ ⎡A A ⎤
Z = 1 + ⎢A 1 + 2 + 33 ⎥ρ r + ⎢A 4 + 5 ⎥ρ 2r + ⎢ 5 6 ⎥ρ 5r
⎢⎣ Tpr Tpr ⎥⎦ ⎢⎣ Tpr ⎥⎦ ⎢⎣ Tpr ⎥⎦
⎡A ⎤
+ ⎢ 37 ρ 2r (1 + A 8 ρ 2r )EXP(− A 8 ρ 2r )⎥
⎣⎢ Tpr ⎦⎥ (3.5)
0.27p pr
where ρ r = and the coefficients A1 to A8 have the following values:
ZTpr
A1 = 0.31506237 A2 = -1.0467099 A3 = -0.57832729 A4 = 0.53530771

A5 = -0.61232032 A6 = -0.10488813 A7 = 0.68157001 A8 = 0.68446549
This method is valid with in a temperature and pressure range of:
1.05 ≤ Tpr < 3.0
0.2 ≤ Ppr ≤ 3.0 .
Shell Oil Company Best-Fit Equation:

4
⎛ p pr ⎞
Z = ZA + ZB × p pr + (1 − ZA) × exp(− ZG) − ZF × ⎜⎜ ⎟⎟ (3.6)
⎝ 10 ⎠
where,
ZA = −0.101 − 0.36 × TR + 1.3868 × (TR − 0.919)
0.04275
ZB = 0.021 +
(TR − 0.65)
ZC = 0.6222 − 0.224 × TR
0.0657
ZD = − 0.037
(TR − 0.86)
ZE = 0.32 × exp(−19.53 × (TR − 1))
22
ZF = 0.122 × exp(−11.3 × (TR − 1))
ZG = PR * ( ZC + ZD × PR + ZE × PR4 )
3.3 Mixture Critical Property Prediction Methods

Numerous correlations and methods have been suggested in the past to predict
mixture critical properties. These methods predict pseudocritical properties and do not
represent a correct estimation of the properties for various ranges of composition. In most
cases, each of the correlations are designed for a limited reduced pressure, reduced
temperature and a fixed range of composition of gases (in Chapter 2 is discussed the
procedure to calculate properties of C7+). This calls for a need to have a generalized
method to calculate mixture critical properties and presented here is a generalized method
to calculated pure component and mixture critical properties. The expressions for mixture
critical point (Pc and Tc) are established in the following equations:
am B c2
Pc =
b 2m [3Z c2 + (α m + β m )B c2 + α m B c ] (3.7)
am Bc
Tc =
b m R[3Z c + (α m + β m )B c2 + α m B c ]
2
(3.8).
The parameters going into the Equations 3.7 and 3.8 are calculated as shown
below:
The critical equation-of-state parameter Bc is obtained by solving the following cubic
equation:
φ 3 B 3c + φ 2 B c2 + φ1 B c + φ 0 = 0 (3.9)
where
φ3 = 8 + 12α m + 6α 2m + α 3m
φ2 = 15 + 15α m − 27βm − 3α 2m
φ1 = 6 + 3α m
φ0 = −1
Similarly, the expression for Zc (critical Z for mixtures) in terms of αm and βm are shown
in Equations 3.7 and 3.8 is obtained by solving the following cubic equation:
23
θ 3 Z 3c + θ 2 Z c2 + θ1 Z c + θ 0 = 0 (3.10)
where
θ 3 = 8 + 12α m + 6α 2m + α 3m
θ 2 = − (3 + 12α m + 12α 2m + 9β m − 9α m β m )
θ1 = 3α m + 6α 2m + 6β m − 6α m β m
θ 0 = − (α 2m + β m − α m β m )
where the mixture parameters am, bm, αm and βm are prescribed as
n n
a m = ∑∑ x i x j a (T )1i / 2 a (T )1j / 2 a ij
i =1 j=1
(3.11)
3
⎛ n ⎞
b m = ⎜ ∑ x i b1i / 3 ⎟
⎝ i =1 ⎠ (3.12).
n n
α m = ∑∑ x i x j α 1i / 2 α 1j / 2 α ij
i =1 j=1
(3.13)
n n
β m = ∑∑ x i x jβ1i / 2β1j / 2β ij
i =1 j=1
(3.14).
The temperature function essential in the determination of the mixture equation of
state parameter (attractive term ‘a’) is defined as:
R 2 Tc2 2 2
3 R Tc
a (T ) = Ω a = [1 + (Ω w − 1) Z c ] TR−θ
Pc Pc (3.15)
where θ = 0.19708+ 0.08627ω + 0.35714ω + 3.59015e − 03ωMw .
2
The pure component parameters are defined as follows:

RTc RTc
b = Ωb = Ω w Zc
Pc Pc (3.16)
1 + Ω w Z c − 3Z c
α=
Ω w Zc (3.17)
Z (Ω w − 1) + 2Ω Z + (1 − 3Z c )Ω w
2 3 2
β= c w c
Ω Z 2
w c (3.18)
0.361
Ωw =
1 + 0.0274ω (3.19).
24
A brief description of the previously used empirical correlations suggested is
given in the following paragraphs. It should be noted that only the commonly used
correlations are mentioned.
3.3.1 Heptane-Plus Fraction Correlation Methods

Cavett’s Correlation:
Cavett (1962) proposed correlations for estimating the critical pressure and
temperature of hydrocarbon fractions.
Tc = a 0 + a 1Tb + a 2 Tb2 + a 3 (API)(Tb ) + a 4 (Tb ) 3

(3.20)
+ a 5 (API)(Tb ) 2 + a 6 (API) 2 (Tb ) 2
Log(p c ) = b 0 + b1 (Tb ) + b 2 (Tb ) 2 + b 3 (API)(Tb ) + b 4 (Tb ) 3

(3.21).
+ b 5 (API)(Tb ) 2 + b 6 (API) 2 (Tb ) + b 7 (Tb ) 2
The coefficients in the above equations are tabulated below:
Table 3.1: Coefficients of Cavett’s correlation.
I ai bi
0 768.07121 2.8290406
1 1.7133693 0.94120109*10-3
2 -0.0010834003 -0.30474749*10-5
3 -0.0089212579 -0.20876110*10-4
4 0.38890584*10-6 0.15184103*10-8
5 0.53094290*10-5 0.11047899*10-7
6 0.32711600*10-7 -0.48271599*10-7
7 - 0.13949619*10-9
25
Kesler-Lee Correlations:
Kesler and Lee (1976) proposed a set of equations to estimate the critical
temperature, critical pressure, acentric factor, and molecular weight of petroleum
fractions.
Critical Pressure:
0.0566 ⎛ 2.2898 0.11857 ⎞ −3

ln ( p c ) = 8.3634 − − ⎜⎜ 0.24244 + + ⎟10 Tb
γ ⎝ γ γ 2 ⎟⎠
⎛ 3.648 0.47227 ⎞ −7 2 ⎛ 1.6977 ⎞ −10 3
+ ⎜⎜1.4685 + + ⎟⎟10 Tb − ⎜⎜ 0.42019 + ⎟10 Tb
⎝ γ γ 2
⎠ ⎝ γ 2 ⎟⎠
(3.22)
Critical Temperature:
105
Tc = 341.7 + 811.1γ g + (0.4244 + 0.1174γ g )Tb + (0.4669 − 3.26238γ g ) (3.23)
Tb
Molecular Weight:
M W = −12272.6 + 9486.4 γ g + (4.6523 − 3.3287 γ g )Tb

⎛ 720.79 ⎞ 10 7
( )
+ 1 − 0.77084 γ g − 0.02058γ g2 ⎜⎜1.3437 − ⎟
Tb ⎟⎠ Tb
(3.24).
⎝
2 ⎛ 181.98 ⎞ 1012
( ⎜ )
+ 1 − 0.80882 γ g + 0.02226γ g ⎜1.8828 −
T
⎟⎟ 3
⎝ b ⎠ Tb
Winn-Sim-Daubert Correlation:
Sim and Daubert (1980) represented the critical pressure, critical temperature, and
molecular weight as follows:
p c = 3.48242 × 109 Tb−2.3177 γ g2.4853 (3.25)
[
Tc = exp 3.994718Tb0.08615 γ 0g.04614 ] (3.26)
M w = 1.4350476 × 10 −5 Tb2.3776 γ g−0.9371 (3.27)
where Tb is the boiling point in oR.
26
Watansiri-Owens-Starling Correlation
Watansiri (1985) developed a set of correlations to estimate the critical properties

and acentric factor of coal compounds and other hydrocarbons and their derivatives.
Critical Temperature:
ln(Tc ) = −0.0650504 − 0.0005217Tb + 0.03905 ln(M w ) + 1.11067 ln(Tb )

(3.28)
M w ⎡0.078154γ g 2 − 0.061061γ g 3 − 0.016943γ g ⎤
1 1
⎢⎣ ⎥⎦
Critical Volume:
ln(Vc ) = 76.313887 − 129.8038γ g + 63.1750γ g2 − 13.175γ 3g

(3.29)
+ 1.10108 ln(M w ) + 42.1958 ln(γ g )
Critical Pressure:
0.8
⎛ Tc ⎞ ⎛Mw ⎞ ⎛ T ⎞
ln(P c ) = 6.6418853 + 0.01617283⎜ ⎟ − 8.712⎜ ⎟ − 0.08843889⎜ b ⎟
⎜V ⎟ ⎜ T ⎟ ⎜M ⎟
⎝ c ⎠ ⎝ c ⎠ ⎝ w ⎠
(3.30)
Acentric Factor:
⎡ ⎛ Tb ⎞ 382.904 ⎤
⎢5.1236667 × 10 Tb + 0.281826667⎜⎜ ⎟⎟ +
−4
+ ⎥
⎢ ⎝ Mw ⎠ Mw ⎥
⎢ 2 ⎥
⎢ ⎛ T ⎞ ⎥⎛ 5Tb ⎞
ω = ⎢0.074691 × 10− 5 ⎜ b ⎟ − 0.12027778 × 10 − 4 Tb M w + 0.001261γ g M w ⎥⎜⎜ 9M ⎟⎟
⎜γ ⎟
⎢ ⎝ g ⎠ ⎥⎝ w ⎠
⎢ 1 2 ⎥
⎢+ 0.1265 × 10− 4 M 2 + 0.2061 × 10− 4 γ M 2 − 66.29959 Tb − 0.00255452 Tb ⎥
3 3
⎢ w g w
Mw γ g2 ⎥⎦
⎣
(3.31)
3.3.2 Pseudocritical Mixing Parameters Methods
Empirical Methods
Gpc = Gideal + Gexcess (3.32)
27
Ppc = ∑ x i Pci + ∑ Φ i (Pci (IDEAL) x i )
n
(3.33)
i =1
Tpc = ∑ x i Tci + ∑ Φ i (Tci (IDEAL) x i )

n
(3.33)
i =1
Kay’s Rule (1936)

n
Ppc = ∑ x i Pci (3.34)
i
n
Tpc = ∑ x i Tci (3.35)
i
Joffe Method64 (1947)

⎛T ⎞ n ⎛ T ⎞
⎜ pc ⎟
⎜⎜ 12 ⎟⎟ = ∑i i ⎜⎜ 1c2 ⎟⎟
x
⎝ Ppc ⎠ m ⎝ Pc ⎠ i (3.36)
3
⎛ Tpc ⎞ 1 n n ⎡⎛ ⎞ 3 ⎛ Tc ⎞ 3 ⎤
1 1
⎜ ⎟ = ∑∑ x i x j ⎢⎜ Tc ⎟⎟ + ⎜⎜ ⎟⎟ ⎥
⎜P
⎝ pc
⎟ 8 i j
⎠ ⎢⎜⎝ Pc ⎠i ⎝ Pc ⎠ j ⎥⎦
⎣ (3.37)
Prausnitz-Gunn (1958)
n
Tpc = ∑ x i Tci
i =1 (3.38)
⎛ n
⎞ ⎛ n
⎞
⎜ ∑ x i Z ci ⎟R ⎜ ∑ x i Tci ⎟
Ppc = ⎝ i =1 ⎠ ⎝ i =1 ⎠
⎛ n
⎞
⎜ ∑ x i Vci ⎟
⎝ i =1 ⎠ (3.39)
Stewart-Burkhardt-Voo Method61 (1959)

2
⎡ c ⎛ T ⎞⎤
⎢∑ x i ⎜ c ⎟⎥
⎢ i ⎜ 12 ⎟⎥
⎣ ⎝ Pc ⎠i ⎦
Tpc = 2
⎞ 2 ⎡ nc ⎛ Tc ⎞ 2⎤
1
1 c ⎛ Tc
∑ x i ⎜⎜ P ⎟⎟ + ⎢∑ x i ⎜⎜ ⎟ ⎥
⎟ ⎥
3 i ⎝ c ⎠ i 3 ⎢⎣ i ⎝ Pc ⎠i ⎦
(3.40)
28
2
⎡ nc ⎛ T ⎞⎤
⎢∑ x i ⎜ c ⎟⎥
⎢ i ⎜ 12 ⎟⎥
⎣ ⎝ Pc ⎠i ⎦
Ppc = 2
⎡ nc 2
⎤
⎞ 2 ⎡ nc ⎛ Tc ⎤
1
⎢ 1 x ⎛⎜ Tc ⎞ 2
⎥
⎢3 ∑ i⎜
⎟⎟ + ⎢∑ x i ⎜⎜ ⎟
⎟
⎥
⎥
⎢⎣ i ⎝ Pc ⎠ i 3 ⎢⎣ i ⎝ Pc ⎠i ⎥
⎦ ⎥⎦
(3.41)
Leland-Mueller Method (1959)

1/ γ
⎡ n n ⎡ 1/ 3 1/ 3 3 ⎤
⎤
⎢
⎢ ∑∑
x x
i j T [T
ci c j ]
γ/2
⎢
1 ⎛
⎜
⎜
Z T
c c ⎞
⎟
⎟ +
1 ⎛
⎜
⎜
Z T
c c ⎞
⎟
⎟
2 ⎝ Pc ⎠ j ⎥ ⎥
⎥ ⎥
i j ⎢⎣ 2 ⎝ Pc ⎠ i ⎦ ⎥
Tpc = ⎢
⎢ n n ⎡ 1 ⎛ Z T ⎞1 / 3 1 ⎛ Z T ⎞1 / 3 ⎤
3
⎥
⎢ ⎥
⎢ ∑∑ x i x j ⎢ ⎜⎜
2 P
⎢⎣ ⎝ c ⎠ i
c c
⎟⎟ + ⎜⎜
2
c c
P
⎟⎟ ⎥
⎥
⎣ i j ⎝ c ⎠ j ⎥⎦ ⎦ (3.42)
⎡ ⎤
⎢ n ⎥
⎢ Tc ∑ x i Z ci ⎥
Ppc = ⎢ i ⎥
⎢ n n ⎡1 ⎛ Z T ⎞ 1/ 3 3 ⎥
1⎛Z T ⎞ ⎤
1/ 3
⎢ x i x j ⎢ ⎜⎜ c c ⎟⎟ + ⎜⎜ c c ⎟⎟ ⎥ ⎥
∑∑
⎢ i j ⎢⎣ 2 ⎝ Pc ⎠ i 2 ⎝ Pc ⎠ j ⎥ ⎥
⎣ ⎦ ⎦ (3.43)
where
⎡ n ⎤
⎢ P∑ x i (Tc )i ⎥
γ = Ψ ⎢ i =n1 ⎥
⎢ T x (P ) ⎥
⎢⎣ ∑ i c i ⎥
⎦
i =1 (3.44)
Leland and co-workers later reported the following relationship,
⎡ n ⎤
⎢ ∑ x i Tci ⎥
γ = −0.75⎢ ni ⎥ + 2.44
⎢ xP ⎥
⎢⎣ ∑ i ci ⎥
⎦
i (3.45).
Satter-Campbell Method46 (1963)

n n 1 1
Tpc = ∑∑ x i x j Tci 2 Tcj 2
i =1 i =1 (3.46)
29
n
Tc ∑ x i Z ci
Ppc = i
3
n n ⎡ ⎛Z T 1
⎞ 3 1 ⎛ Z c Tc ⎞ 3⎤
1
∑∑ x x ⎢1 ⎜ c c ⎟⎟ + ⎜⎜ ⎟⎟ ⎥
⎢ 2 ⎜⎝ Pc
i j
i =1 j=1
⎣ ⎠i 2 ⎝ Pc ⎠ j ⎥⎦
(3.47).
Lee-Kesler Method54 (1975)

Z ci = 0.2905 − 0.085ωi (3.48)
Z ci RTci
Vci =
Pci (3.49).
3
1 n n
∑ x x ⎛⎜⎝ V + Vcj 3 ⎞⎟
1 1
Vpc = ∑ 3
8 i =1
i j ci
⎠
j=1
(3.50)
n n 3
1
∑ ∑ x x ⎛⎜⎝ V + Vcj 3 ⎞⎟
1 1
Tpc = 3
Tci Tcj
8Vc
i j ci
⎠
i =1 j=1
(3.51)
T
Θ= b
Tc (3.52)
−1
− ln Pc (atm) − 5.92714 + 6.09648Θ + 1.28862 ln Θ − 0.169347Θ 6
ωi =
15.2518 − 15.6875Θ −1 − 13.4721 ln Θ + 0.43577Θ 6 (3.53).
n
ω = ∑ x i ωi
i =1 (3.54)
(0.2905 − 0.085ω)RTc
Ppc =
Vc (3.55)
Van Ness-Abbot Method63 (1982)

4
⎡n n ⎛ T 52 ⎞ 2 ⎛ T 52 ⎞ 2 ⎤
1 1 3
⎢ ⎜ c ⎟ ⎜ c ⎟ ⎥
⎢∑∑ x i x j ⎜ P ⎟ ⎜ P ⎟ ⎥
⎢⎣ i =1 j=1 ⎝ c ⎠ i ⎝ c ⎠ j ⎥⎦
Tpc =
2
2
⎡n n ⎛ Tc ⎞ ⎛ Tc ⎞ ⎤
3
⎢∑∑ x i x j ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎥
⎢⎣ i =1 j=1 ⎝ Pc ⎠ i ⎝ Pc ⎠ j ⎥⎦
(3.56)
30
4
⎡n n ⎛ T 52 ⎞ 2 ⎛ T 52 ⎞ 2 ⎤
1 1 3
⎢ ⎜ c ⎟ ⎜ c ⎟ ⎥
⎢∑∑ x i x j ⎜ P ⎟ ⎜ P ⎟ ⎥
⎢⎣ i =1 j=1 ⎝ c ⎠ i ⎝ c ⎠ j ⎥⎦
Ppc =
2
5
⎡n n ⎛ Tc ⎞ ⎛ Tc ⎞ ⎤ 3
⎢∑∑ x i x j ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎥
⎢⎣ i =1 j=1 ⎝ Pc ⎠ i ⎝ Pc ⎠ j ⎥⎦
(3.57)
Pedersen-Fredenslund-Christensen-Thomassen Method55,56 (1984)

3
n n ⎡⎛ T ⎞
1
3
⎛T ⎞
1
3 ⎤
∑∑ x i x j ⎢⎜⎜ c
⎢⎝ Pc
⎟⎟ + ⎜⎜ c ⎟⎟ ⎥
⎥
i j
⎣ ⎠i ⎝ Pc ⎠ j ⎦
Tpc = 3
Tci Tcj
n ⎡⎛ T
n
⎞
1
3
⎛T ⎞
1
3 ⎤
∑∑ x x ⎢⎜ c
i j ⎜
⎢⎝ Pc
⎟⎟ + ⎜⎜ c ⎟⎟ ⎥
⎥
i j
⎣ ⎠i ⎝ Pc ⎠ j ⎦ (3.58)
3
n n ⎡⎛ T ⎞ 13 ⎛ T ⎞ 13 ⎤
8∑∑ x i x j ⎢⎜⎜ c ⎟⎟ + ⎜⎜ c ⎟⎟ ⎥
i j ⎢⎝ Pc ⎠ i ⎝ Pc ⎠ j ⎥⎦
Ppc = ⎣ Tci Tcj
3 2
⎡n n ⎡⎛ T ⎞ 13 ⎛ T ⎞ 13 ⎤ ⎤
⎢ x i x j ⎢⎜⎜ c ⎟⎟ + ⎜⎜ c ⎟⎟ ⎥ ⎥
⎢∑∑ ⎢⎝ Pc ⎠ i ⎥
⎢⎣
i j
⎣ ⎝ Pc ⎠ j ⎥⎦ ⎥
⎦ (3.59)
Teja-Thurner-Pasumarti Method (1985)
Tpc n n Tcij
= ∑∑ x i x j
Ppc i =1 j=1 Pcij
(3.60)
2 2
T n n T
= ∑∑ x i x j
pc cij
Ppc i =i j=1 Pcij

(3.61)
where
Tcij = ξ ij (Tci Tcj )
1
2 (3.62)
8Tcij
Pcij = 3
⎡⎛ T ⎞ 3 ⎛ Tc ⎞ 3 ⎤
1 1
⎢⎜ c ⎟⎟ + ⎜⎜ ⎟⎟ ⎥
⎢⎜⎝ Pc ⎠i ⎝ Pc ⎠ j ⎥⎦
⎣ (3.63)
Sutton Method62 (1985)
31
2
⎡ c ⎛ T ⎞ ⎤
⎢∑ x i ⎜ c ⎟ −E ⎥
⎢ i ⎜ 12 ⎟ k
⎥
⎣ ⎝ Pc ⎠i ⎦
Tpc = 2
⎞ 2 ⎡ nc ⎛ Tc ⎞ 2⎤
1
1 c
⎛T
∑ x i ⎜⎜ c ⎟⎟ + ⎢∑ x i ⎜⎜ ⎟ ⎥ − EJ
⎟ ⎥
3 i ⎝ Pc ⎠ i 3 ⎢⎣ i ⎝ Pc ⎠i ⎦
(3.64)
2
⎡ nc ⎛ T ⎞ ⎤
⎢∑ x i ⎜ c ⎟ −E ⎥
⎢ i ⎜ 12 ⎟ k
⎥
⎣ ⎝ Pc ⎠i ⎦
Ppc = 2
⎡ nc 2
⎤
⎞ 2 ⎡ nc ⎛ Tc ⎤
1
⎢ 1 x ⎛⎜ Tc ⎞ 2
⎥ − EJ ⎥
⎢3 ∑ i⎜
⎟⎟ + ⎢∑ x i ⎜⎜ ⎟
⎟ ⎥
⎢⎣ i ⎝ Pc ⎠ i 3 ⎢⎣ i ⎝ Pc ⎠i ⎥
⎦ ⎥⎦
(3.65)
Lawal-Lake-Silberberg65 (2002)
a m Bc
Tc =
2
(3.66)
a m B c2
Pc = 2
b m [3Z c2 + (α m + β m )B c2 + α m B c ]
(3.67)
n n
a m = ∑∑ x i x j (a i a j ) 0.5 a ij
i j
(3.68)
3
⎛ n ⎞
b m = ⎜ ∑ x i b1/3
i ⎟
⎝ i ⎠ (3.69)
n n
α m = ∑∑ x i x j (α i α j ) 0.5 α ij
i j
(3.70)
n n
β m = ∑∑ x i x j (β i β j ) 0.5 β ij
i j
(3.71)
Θ 3 Z3c + Θ 2 Zc2 + Θ1Zc + Θ 0 = 0 (3.72)

where,
32
Θ 3 = (α 3m + 6α 2m + 12α m + 8)
Θ 2 = −3(1 + 4α 2m + 4α m + 3β m − 3α m β m )
Θ1 = 3(2α 2m + 2β m − 2α m β m + α m )
Θ 0 = (α m β m − β m − α 2m )
θ 3 B3c + θ 2 Bc2 + θ1Bc + θ 0 = 0 (3.73)

where,
θ 3 = (α 3m + 6α 2m + 12α m + 8)
θ 2 = −3(α 2m − 5α m + 9β m − 5)
θ1 = 3(α m + 2)
θ0 = −1
Redlich-Kwong-Abbott
4
⎡ n ⎛ 52 ⎞ 2⎤
1 3
⎢ x ⎜ Tc ⎟ ⎥
⎢∑ i
⎜ Pc ⎟ ⎥
⎣⎢
i ⎝ ⎠ i ⎦⎥
Tpc = 2
(3.74)
⎡ n ⎛T ⎞ ⎤ 3
⎢∑ x i ⎜ c P ⎟ ⎥
⎢⎣ i ⎝ c ⎠i ⎥
⎦
4
⎡ n ⎛ 52 ⎞
1
2 ⎤ 3
⎢ x ⎜ Tc ⎥
⎢∑
⎟
i
⎜ Pc ⎟ ⎥
⎣⎢
i ⎝ ⎠i ⎦⎥
Ppc = 5
(3.75)
⎡ n ⎛T ⎞ ⎤ 3
⎢∑ x i ⎜ c P ⎟ ⎥
⎣⎢ i ⎝ c ⎠i ⎥
⎦
3.3.3 Pseudocritical Gas Gravity Correlation Methods

The Standing90 gas gravity correlation is stated as:
Ppc (psia ) = 706 − 51.7S g − 11.1S g2 (3.76)
Tpc ( o R ) = 187 + 330S g − 71.5S g2 (3.77)
33
The Sutton90 gas gravity correlation is stated as:
Ppc (psia ) = 756.8 − 131.0S g − 3.6S g2 (3.78)
Tpc ( o R ) = 169.2 + 349.5S g − 74.0S g2 (3.79)
Elsharkawy-Hashem-Alikhan90 gas gravity correlation is stated as:

Ppc (psia ) = 787.06 − 147.34S g − 7.916S g2 (3.80)
Tpc ( o R ) = 149.18 + 358.14S g − 66.976S g2 (3.81)
Hankinson-Thomas-Philips91 gas gravity correlation is stated as:

Ppc (psia ) = 709.604 + 58.718S g (3.82)
Tpc ( o R ) = 170.491 + 307.344S g (3.83)
Brill-Beggs102 gas gravity correlation is stated as:

Ppc (psia ) = 708.75 − 57.5S g (3.84)
Tpc ( o R ) = 169.0 + 314.0S g (3.85)
This work:
Ppc (psia ) = 659.94 + 57.306S g − 63.012S g2 (3.86)
Tpc ( o R ) = 165.95 + 321.82S g + 0.7924S g2 (3.87)
The R2 for Ppc is 0.9821 and that for Tpc is 0.9999.
34
700
Stan
Sutt
ElHA
HaTPh
680
BrBe
ThisWork
Pc Calculated (psia)
660
640
620
600
600 620 640 660 680 700
Pc Experimental (psia)
Figure 3.1: Comparison of Six Correlations for Pseudocritical Pressure Parameters.
Stan
530
Sutt
ElHA
HaTPh
490
BrBe
ThisWork
Tc Calculated ( R)
o
450
410
370
330
330 370 410 450 490 530
o
Tc Experimental ( R)
Figure 3.2: Compare Six Correlations for Pseudocritical Temperature Parameters.
35
Table 3.2: Sources of Experimental Z-Factor for Pure Substances.
Authors Year System Reference

No.
Sage-Lacey 1950 C1 8
Sage-Lacey 1950 iC4, nC4 8
Sage-Lacey 1950 iC5, nC5 8
Stewart-Sage-Lacey 1954 nC6 10
Sage-Reamer- Nichols 1955 nC7 9
Sage-Lacey 1950 H2S 8
Sage-Lacey 1950 N2 8
Sage-Lacey 1950 CO2 8
36
3.3.4 van der Waals Theory of Pseudocritical Methods
Criticality Theory
1. van der Waals Pseudocritical Theory3 (1873)
⎛ ∂P ⎞
⎜ ⎟ =0
⎝ ∂V ⎠ T at T = Tc and P = Pc (3.88)
⎛ ∂ 2P ⎞
⎜⎜ 2 ⎟⎟ = 0
⎝ ∂V ⎠ T at T = Tc and P = Pc (3.89)
2. Gibbs Criteria (1928)
⎛ ∂G ⎞
⎜ ⎟ =0 (3.90)
⎝ ∂x ⎠ T ,P
⎛ ∂ 2G ⎞
⎜⎜ 2 ⎟⎟ = 0
⎝ ∂x ⎠ T ,P (3.91)
3. Wilson Renormalization Theory (1982)
3.3.5 Improved Theory for Pseudocritical Mixture Parameter

Mixture rules significantly affect the accuracy of mixture property determination.
Weighted average based on mole fraction has been the general rule since Kay but this
method is an approximate method and more rigorous methods are required for accurate
determination of mixture properties. Numerous methods have been proposed but none of
them present a generalized method for critical property prediction with high accuracy.
Most of the methods are either statistical or empirical and therefore are bound by errors.
In this project a method is presented which is based on LLS EOS. This method is capable
of predicting critical properties of mixtures irrespective of the component and its
composition.
Prediction method of binary interaction number is an essential parameter in
mixture critical property determination. The BIN can be function of molecular weights,
acentric factor or product of molecular weight and acentric factor. Care must be taken in
37
applying these rules of predicting BIN with gas mixtures containing very light and heavy
components. Other occasions of concern could be when isomers are present in a gas
mixture. It should be noted that in BIN can be equal to 1 only in case of pure
composition.
3.4 Designed Scaling Parameter for Standing-Katz Z-Factor Chart

In order to extend the use of SK chart to the prediction of z-factors for sour and
acid gases without resorting to the Wichert-Aziz2 correction formula for pseudocritical
pressures and temperatures parameters, a universal scaling parameter has been
established. This scaling parameter is developed by overlaying the experimental z-factor
curves for the same range of pressures and temperatures as that of SK chart and
measuring the deviation from of the SK chart curves. A mathematical quantification of
this deviation for hydrocarbon compounds, non-hydrocarbon compounds, and sour
reservoir gases resulted in a similar modification (or scaling) parameter requirement.
This observation establishes the fact that the SK chart is designed perfectly but most of
the time, it is used wrongly. The error is in the method of calculation of the pseudocritical
pressures and temperatures.
3.4.1 Design Procedure for Scaling Parameter

The scaling parameter for hydrocarbon components is developed based on wide
range of available experimental data and measuring the deviation of SK computational
methods from experimental data. In the design of a scaling parameter, non-hydrocarbon
components that are commonly found in the reservoir gases like nitrogen, hydrogen
sulfide, and carbon dioxide were considered. A wide range of experimental z-factor data
for natural gases containing significant amounts of acid gases, sour gas, and C7+ fraction
were collected and used in this project to develop the scaling parameter.
38
The step-by-step procedure for obtaining the scaling factor is as follows:
z SK
1. z SF = × zc .
z Expt .
2. A regression analysis of the reduced pressure and ZSK scaled z-factor (based on
step 1) is performed to obtain a quadratic expression for scaling factor at each
temperature of the mixture. The equation describing it is Equation 3.78.
3. The coefficients a0, a1 and a2 for each mixture is collected and is subjected to
linear regression analysis.
4. The general expressions for these coefficients are obtained by performing
regression analysis as functions of product of molecular weight and acentric
factor (ωMw).
5. The equations describing the final expressions are presented below.
SF = a 0 + a1PR + a 2 PR2 (3.92)
where
0.31
a0 =
1.04518 − 0.15675(ωM w ) (3.93)
9.40E − 05
a1 =
1.2722E − 02 − 4.4852E − 03(ωM w ) (3.94)
− 3.54E − 04
a2 =
0.83084 − 0.41702(ωM w ) (3.95)
The prediction results using the scaling factor technique is presented below. More
results on this can be seen in the Section C.1 of Appendix C.
39
1.42
Expt.
SK
1.32
Scaled
1.22
1.12
Z-Factor
1.02
0.92
0.82
0.72
0 2,000 4,000 6,000 8,000
Pressure (Psia)
Figure 3.3: Scaled Z-Factor for Buxton & Campbell Data (Mix-5) at 160 oF.
1.41
Expt.
1.31
SK
Scaled
1.21
1.11
Z-Factor
1.01
0.91
0.81
0.71
0 2,000 4,000 6,000 8,000
Pressure (psia)
Figure 3.4: Scaled Z-Factor for Buxton and Campbell Data (Mix-5) at 130 oF.
40
1.35
Expt.
1.25 SK
Scaled
1.15
1.05
Z-Factor
0.95
0.85
0.75
0.65
0 2,000 4,000 6,000 8,000
Pressure (Psia)
Figure 3.5: Scaled Z-Factor for Buxton and Campbell Data (Mix-5) at 100 oF.
1.2
Expt.
Scaled
1.1 SK
Z-Factor
0.9
0.8
0 3 6 9 12
Pressure (Psia)
Figure 3.6: Scaled Z-Factor for Satter Data (Mix-E) at 160 oF.
41
3.5Designed pR/z Versus Z-Factor Chart
This section provides a clear view of an ideal z-chart and the eventually the
capability of predicting amount of gas produced by a graphical means. Figure 3.5 is a z-
chart developed based on computation techniques developed based on a correlation
developed for SK Z-Chart.
1.1
0.9
Tr=1.0
Tr=1.05
Tr=1.1
Z-Factor Values
Tr=1.2
0.7 Tr=1.3
Tr=1.4
Tr=1.5
Tr=1.6
Tr=1.7
Tr=2.0
0.5 Tr=2.2
Tr=2.4
Tr=2.6
Tr=2.8
Tr=3.0
Tr=1.8
0.3 Tr=1.9
Tr=1.15
TR = 1.0 Tr=1.25
Tr=1.35
Tr=1.45
0.1
0 2 4 6 8
Reduced Pressure
Figure 3.7: SK Z-Chart Developed Based on Computation SK Technique.
42
Tr=1.0
Tr=1.05
1.00
Tr=1.1
Tr=1.15
Tr=1.2
Tr=1.25
0.80
Tr=1.30
Tr=1.35
Tr=1.40
Tr=1.45
Z-Factor
0.60
Tr=1.50
Tr=1.6
Tr=1.7
0.40 Tr=1.8
Tr=1.9
Tr=2.0
Tr=2.2
0.20 Tr=2.4
TR=1.0
Tr=2.6
Tr=2.8
Tr=3.0
0.00
0 2 4 6 8 10 12
PR/z
Figure 3.8: Amount of gas produced.
3.6 Prediction Results for Z-Factor of Natural Gases

1.4
Exp
Standing-Katzl
1.3
Scaledt
1.2
1.1
Z-Factor
0.9
0.8
0.7
0 2,000 4,000 6,000 8,000
Pressure (psia)
Figure 3.9: Scaled Z-Factor Buxton & Campbell, Mix-2 Result, @ T = 130 oF.
43
1.3
Exp
Standing-Katz
Scaled
1.2
1.1
Z-Factor
0.9
0.8
0 2,000 4,000 6,000 8,000
Pressure (psia)
1.26
Exp
Standing-Katzl
Scaled
1.16
1.06
Z-Factor
0.96
0.86
0.76
0 2,000 4,000 6,000 8,000
Pressure (psia)
44
45
3.7 Prediction Results for Z-Factor of Reservoir Gases
Scaling is done based on the law of corresponding states principle as follows:
⎡ Z Scaled ⎤ ⎡ Z SK ⎤
⎢ ⎥ = ⎢ SF ⎥ (3.96).
⎣ Z c ⎦ PR ,TR ⎣ Z ⎦ PR ,TR
Table 3.3: Rich Gas Condensate Composition (Elsharkawy71).

Serial No. 39
Rich gas Condensate
IND 281 282 283 284 285 286 287

H2S 0 0 0 0 0 0 0
CO2 0.0231 0.0242 0.0248 0.0253 0.0258 0.0262 0.0266
N2 0.0137 0.0155 0.0161 0.0166 0.0163 0.0155 0.0143
C1 0.6583 0.7074 0.738 0.7559 0.7583 0.7485 0.7292
C2 0.0803 0.0817 0.0821 0.0839 0.0863 0.0905 0.0944
C3 0.0417 0.0411 0.0404 0.0402 0.0415 0.0447 0.0495
iC4 0.0078 0.0073 0.007 0.0069 0.0073 0.0082 0.0091
nC4 0.0184 0.017 0.0162 0.0159 0.0167 0.0186 0.0208
iC5 0.0075 0.0067 0.0062 0.006 0.0062 0.007 0.008
nC5 0.0108 0.0097 0.0089 0.0084 0.0086 0.0096 0.0107
nC6 0.0116 0.011 0.0103 0.0086 0.0078 0.0082 0.0092
C7+ 0.1268 0.0784 0.05 0.0323 0.0252 0.023 0.0282
Mw+ 191 154 139 128 120 115 113
Sg+ 0.831 0.804 0.789 0.778 0.77 0.765 0.763
Pc C7+, (psia) 324.6 378.4 404.3 427.5 447.2 461.0 466.9
Tc C7+, (oR) 1264.0 1177.7 1136.4 1105.1 1081.6 1066.6 1060.5
o
T( F) 313 313 313 313 313 313 313
P (psia) 6010 5100 4100 3000 2000 1200 700
Z (Expt.) 1.212 1.054 0.967 0.927 0.93 0.952 0.97
ρ(lb/cu.ft.) 26.3 18.97 14.17 9.79 6.27 3.68 2.19
ZSK 1.0982 0.9806 0.9224 0.8964 0.9054 0.9311 0.9531
ZScaled(This Study) 1.0213 1.0931 0.5793 0.0725 0.4924 0.8660 0.9835
46
Table 3.4: Highly Sour Gas Composition (Elsharkawy71).
Serial No. 57
Highly sour gas condensate
IND 439 440 441 442 443 444 445

H2S 0.282 0.277 0.272 0.27 0.273 0.289 0.318
CO2 0.0608 0.0644 0.0669 0.0685 0.0694 0.0699 0.0679
N2 0.0383 0.0455 0.0476 0.0473 0.0461 0.0434 0.0394
C1 0.4033 0.4382 0.4641 0.4807 0.4844 0.4688 0.4331
C2 0.0448 0.0471 0.0481 0.0487 0.0493 0.0496 0.0494
C3 0.0248 0.0243 0.0239 0.0237 0.0239 0.0252 0.0277
iC4 0.006 0.0055 0.0051 0.0049 0.0049 0.0055 0.0067
nC4 0.0132 0.012 0.0111 0.0106 0.0106 0.0114 0.014
iC5 0.0079 0.0068 0.006 0.0055 0.0053 0.0058 0.0074
nC5 0.0081 0.0069 0.006 0.0054 0.0052 0.0057 0.0071
nC6 0.0121 0.0096 0.0078 0.0066 0.006 0.0063 0.0077
C7+ 0.0991 0.063 0.0412 0.0286 0.0217 0.0192 0.0214
Mw+ 165 121 116 112 109 107 107
Sg+ 0.818 0.778 0.773 0.768 0.764 0.762 0.762
Pc C7+, psia 365.4 453.2 467.1 477.8 486.0 492.7 492.7
Tc C7+, oR 1209.7 1090.7 1075.7 1062.7 1052.5 1046.3 1046.3
o
T( F) 250 250 250 250 250 250 250
P (psia) 4190 3600 3000 2400 1800 1200 700
Z (Expt.) 0.838 0.806 0.799 0.809 0.842 0.888 0.935
ρ(lb/cu.ft.) 27.34 19.52 15.06 11.3 7.95 5.06 2.91
ZSK 0.8295 0.9299 0.9615 0.9744 0.9755 0.9734 0.9742
47
Table 3.5: Carbon Dioxide Rich Gas Composition (Elsharkawy71).
Serial No. 124 Carbon Dioxide Rich Gas
IND 926 927 928 929 930 931 932

H2S 0.003 0.003 0.003 0.003 0.003 0.003 0.004
CO2 0.6352 0.6395 0.6514 0.6579 0.6639 0.6706 0.6716
N2 0.0386 0.0399 0.041 0.0417 0.0421 0.0411 0.0388
C1 0.1937 0.1988 0.2008 0.207 0.2084 0.2037 0.1994
C2 0.0303 0.0307 0.0308 0.0309 0.0313 0.0315 0.0318
C3 0.0174 0.0172 0.017 0.0169 0.017 0.0175 0.0184
iC4 0.0033 0.0032 0.0031 0.003 0.003 0.0032 0.0035
nC4 0.0093 0.0088 0.0085 0.0082 0.0082 0.0088 0.0097
iC5 0.0039 0.0036 0.0033 0.0031 0.003 0.0033 0.0039
nC5 0.0047 0.0042 0.0038 0.0036 0.0035 0.0038 0.0046
nC6 0.0051 0.0049 0.0046 0.0042 0.0036 0.003 0.0034
C7+ 0.0551 0.0458 0.0324 0.0202 0.0127 0.0101 0.0113
Mw+ 170 153 139 128 118 110 106
Sg+ 0.811 0.797 0.783 0.773 0.763 0.755 0.751
Pc C7+, psia 347.8 373.9 397.8 421.7 446.3 469.4 482.4
Tc C7+, oR 1211.6 1169.4 1131.0 1100.6 1071.2 1046.9 1034.5
o
T( F) 219 219 219 219 219 219 219
P (psia) 4825 4100 3300 2600 1900 1200 700
Z (Expt.) 0.851 0.777 0.72 0.719 0.775 0.851 0.915
ρ(lb/cu.ft.) 34.88 30.9 25.58 19.39 12.87 7.38 4.03
ZSK 0.7935 0.7739 0.7884 0.8247 0.8653 0.9084 0.9434
48
Table 3.6: Very Light Gas Composition (Elsharkawy71).
Very light gas
125
Serial No.
IND 933 934 935 936 937 938 939
H2S 0 0 0 0 0 0 0
CO2 0.0033 0.0033 0.0034 0.0035 0.0035 0.0036 0.0038
N2 0.0032 0.0033 0.0033 0.0033 0.0033 0.0033 0.0033
C1 0.942 0.9438 0.9451 0.9461 0.9468 0.9473 0.9467
C2 0.0231 0.023 0.023 0.0231 0.0232 0.0233 0.0236
C3 0.0082 0.0082 0.0082 0.0082 0.0082 0.0082 0.0083
iC4 0.0023 0.0023 0.0023 0.0023 0.0023 0.0023 0.0023
nC4 0.0025 0.0025 0.0025 0.0025 0.0025 0.0025 0.0026
iC5 0.0012 0.0012 0.0012 0.0012 0.0012 0.0012 0.0012
nC5 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0009
nC6 0.0014 0.0013 0.0013 0.0013 0.0013 0.0012 0.0013
C7+ 0.012 0.0103 0.0089 0.0077 0.0069 0.0063 0.006
Mw+ 143 133 126 120 116 114 114
Sg+ 0.787 0.777 0.769 0.763 0.76 0.758 0.758
Pc C7+, psia 390.5 409.7 423.9 438.6 450.5 456.2 456.2
Tc C7+, oR 1142.1 1114.1 1093.0 1075.4 1064.3 1058.3 1058.3
o
T( F) 209 209 209 209 209 209 209
P (psia) 4786 4000 3300 2600 1900 1300 700
Z (Expt.) 1.019 0.974 0.945 0.933 0.933 0.947 0.969
ρ(lb/cu.ft.) 12.13 10.42 8.76 6.92 5.03 3.37 1.78
ZSK 1.1235 1.0726 1.0375 1.0119 0.9955 0.9884 0.9883
ZScaled(This Work) 1.0007 0.9565 0.9310 0.9179 0.9170 0.9264 0.9458
49
Table 3.7: Property Prediction for Gas Composition Data (Elsharkawy71).
Data No. T,oR P,psia TR PR Tc, oR Pc, psia Zc ZExpt
Rich Gas Condensate
281 773 6010 1.6602 9.545 465.6188 629.6467 0.3137 1.212
282 773 5100 2.346 9.9547 329.4974 512.3187 0.3111 1.054
283 773 4100 2.679 8.5429 288.5443 479.9311 0.3093 0.967
284 773 3000 2.8195 6.3235 274.1664 474.4191 0.3079 0.927
285 773 2000 2.8615 4.2224 270.1407 473.6642 0.3077 0.93
286 773 1200 2.8533 2.5324 270.9140 473.8606 0.3083 0.952
287 773 700 2.7923 1.4711 276.8299 475.8504 0.3095 0.97
Highly Sour Gas
439 710 4190 1.4904 5.6376 476.3853 743.2255 0.3176 0.838
440 710 3600 1.8906 5.459 375.5364 659.4605 0.317 0.806
441 710 3000 2.0593 4.7129 344.7844 636.5490 0.3167 0.799
442 710 2400 2.156 3.8496 329.3079 623.4470 0.3163 0.809
443 710 1800 2.1873 2.8831 324.5952 624.3326 0.3162 0.842
444 710 1200 2.1462 1.8854 330.8097 636.4649 0.3161 0.888
445 710 700 2.0284 1.0567 350.0302 662.4678 0.3161 0.935
CO2 Rich Gas
926 679 4825 1.3607 5.5574 499.0157 868.2062 0.3012 0.851
927 679 4100 1.4475 4.8577 469.0735 844.0239 0.3014 0.777
928 679 3300 1.5372 3.9986 441.7072 825.2834 0.3013 0.72
929 679 2600 1.6176 3.2057 419.766 811.0509 0.3016 0.719
930 679 1900 1.6622 2.3661 408.4864 803.0142 0.3016 0.775
931 679 1200 1.6632 1.4895 408.2512 805.6412 0.3011 0.851
932 679 700 1.6418 0.8669 413.5822 807.5066 0.3006 0.915
Very Light Gas
933 669 4786 2.3565 8.9693 283.8983 533.5994 0.2935 1.019
934 669 4000 2.3535 7.4526 284.2594 536.7226 0.2933 0.974
935 669 3300 2.3506 6.1209 284.603 539.1324 0.2932 0.945
936 669 2600 2.3480 4.8043 284.9245 541.1855 0.2931 0.933
937 669 1900 2.3460 3.5019 285.1668 542.5596 0.2930 0.933
938 669 1300 2.3445 2.3914 285.3522 543.6069 0.2930 0.947
939 669 700 2.3454 1.288 285.2353 543.4760 0.2930 0.969
50
1.15
Expt.
SK
Scaled
1.1
1.05
Z-Factor
0.95
0.9
0 2 4 6 8 10
Pressure (Psia)
Figure 3.12: Scaled Z-Factor for Very Light Gas Composition.

1
Expt.
SK
Scaled
0.9
Z-Factor
0.8
0.7
0 2 4 6
Pressure (Psia)
Figure 3.13: Scaled Z-Factor for Carbon Dioxide Rich Gas Composition.
51
1.4
1.2
0.8
Z-Factor
0.6
0.4
Expt.
SK
0.2
Scaled
0
1 3 5 7 9 11
Pressure (Psia)
Figure 3.14: Scaled Z-Factor for Rich Gas Condensate Composition.

1.05
0.95
Z-Factor
0.9
0.85
Expt.
SK
Scaled
0.8
0 2 4 6
Pressure (Psia)
Figure 3.15: Scaled Z-Factor for Highly Sour Gas Composition.
52
CHAPTER 4
Z-FACTOR PREDICTION FROM CUBIC
EQUATIONS OF STATE
4.1 Selection of Cubic Equations-of-State

Some phase behavior applications require the use of an equation of state to predict
properties of petroleum reservoir fluids. Since the introduction of the van der Waals4
EOS, many cubic EOS’s have been proposed like the Redlich and Kwong13 EOS (RK
EOS) in 1949, the Peng and Robinson12 EOS (PR EOS) in 1976, to name only a few.
RT
Most of these equations retain the original van der Waals repulsive term ,
(V − b )
modifying only the denominator in the attractive term. With the advent of simulation
techniques in petroleum engineering, accuracy was the priority but a universal equation-
of-state method was required as most of the EOSs worked best in a certain range of
pressures and temperatures and compositions.
Most petroleum engineering relied on the PR EOS or a modification of the RK
EOS. Soave’s19 modification (SRK EOS) was the simplest and most widely used. A
major drawback of the SRK EOS was the poor liquid density prediction. PR EOS
reported that their EOS predicts better liquid densities than the SRK EOS but not accurate
enough for all ranges of pressures and temperatures including other phases. Many other
proposed equations of states relied on complex temperature functions to represent the
highly nonlinear correction terms for EOS constants.
The critical properties, acentric factor, molecular weight, and binary-interaction
parameters (BIP’s) of components in mixture are required for EOS calculations. With the
existing chemical-separation techniques, we usually cannot identify the many hundreds
and thousands of components found in reservoir fluids. Another problem with the
53
existing EOS and other methods of predicting EOS parameters is that they cannot predict
properties of components heavier than approximately C20.
Eight equations of state have been chosen which are commonly used in the
reservoir simulation and calculation purposes in the petroleum industry. Each of these
equations of state has been thoroughly examined in their ability to be able to predict z-
factor both for pure substances and gas mixtures (including natural gases and sour natural
gases with significant amounts of C7+). It is observed that the prediction of z-factor is
significantly dependent on the accuracy of the critical properties supplied/predicted.
Based on this observation, LLS29 EOS was observed to be capable of predicting accurate
critical properties for gas mixtures and therefore, more accurate z-factor prediction is
possible with this method for a wide range of pressures and temperatures and for any gas
composition. Hence, LLS EOS method can be adopted as a universal method for z-factor
determination.
4.2 Lawal-Lake-Silberberg Equation of State
RT a (T )
P= − 2 (4.1)
V − b V + αbV − βb 2
where
1 + Ω w Zc − 3Zc
α= (4.2)
Ω w Zc
Zc2 (Ω w − 1)3 + 2Ω 2w Zc + (1 − 3Zc )Ω w

β= (4.3)
Ω 2w Zc
Ω a = (1 + (Ω w − 1) Zc ) 3 (4.4)
R 2Tc2
a = Ωa (4.5)
Pc
Ω b RTc (4.6)
b=
Pc
54
Z-Form of the EOS:
Φ 3 Z 3 + Φ 2 Z 2 + Φ1 Z + Φ 0 = 0 (4.7)
where,
Φ 3 = 1.0 Φ 2 = −[1 + (1 − α)B]
[
Φ1 = A − αB − (β + α)B2 ]
Φ 0 = − ⎡AB − β(B2 + B3 ) ⎤
where,
a (T ) P bP
A= , B=
R 2T 2 RT .
Mixing Rules:
1 1
a m = ∑∑ x i x ja i 2 a j 2 a ij (4.8)
i j
3
⎡ 1 ⎤
b m = ⎢∑ x i bi 3 ⎥ (4.9)
⎣ i ⎦
ωi
a ij = for ωi ≤ ω j (4.10)
ωj
ωj
a ij = for ωi > ω j (4.11)
ωi
α m = ∑∑ x i x jα i 2 α j 2 (α i α j )
1 1 0.5
(4.12)
i j
β m = ∑∑ x i x jβ i 2 β j 2 (β i β j )
1 1 0.5
(4.13)
i j
a ij = (a i a j ) = (α i α j ) = (β i β j ) (4.14)
55
4.3 van der Waal Equation of State
van der Waals4 proposed the first cubic EOS in 1873. The van der Waals EOS
gives a simple, qualitatively accurate relation between pressure, temperature, and molar
volume. It can be mathematically expressed as:
RT a
p= − 2 (4.15)
V−b V
where a = attraction parameter
b = repulsion parameter
as compared to the ideal gas law, van der Waals EOS provides two important
improvements. First, the prediction of liquid behavior is more accurate because volume
approaches a limiting value, b, at high pressures,
lim V(p) = b (4.16)
p→∞
where be is referred to as the covolume.

a/V2 term in the vdW EOS represents the non-ideal gas behavior and is interpreted as the
attractive component of pressure.
van der Waals also stated that the critical criteria that are used to define the two
EOS constants a and b which are the first and second derivatives of pressure with respect
to volume equal to zero at the critical point of a pure component.
⎛ ∂p ⎞ ⎛ ∂ 2p ⎞
⎜ ⎟ = ⎜⎜ 2 ⎟⎟ =0 (4.17)
⎝ ∂V ⎠ pc ,Tc ,Vc ⎝ ∂V ⎠ pc ,Tc ,Vc
Martin and Hou show that this constraint is equivalent to the condition (z − z c ) = 0 at
3
the critical point. The constants a and b are given by:

27 R 2 Tc2
a=
64 p c
1 RTc
and b = (4.18)
8 pc
3
The critical compressibility results in z c = = 0.375 .
8
56
van der Waals EOS in terms of z can be written as:
z 3 − (B + 1)z 2 + Az − AB = 0 (4.19)
p 27 p R
where A = a = (4.20)
(RT ) 64 TR2
2
p 1 pR
B=b = (4.21)
RT 8 TR
vdW EOS has a fixed zc (=0.375) for all components which is not true and no
temperature function which is a drawback of vdW EOS.
4.4 Redlich-Kwong Equation of State

Redlich and Kwong13 (1948) developed an adjustment in the van der Waals’
attractive pressure term (a/V2), which could considerably improve the prediction of the
volumetric and physical properties of the vapor phase. This attractive pressure term has a
temperature dependence term and their equation can be represented as:
RT a (T )
p= −
V − b V ( V + b) (4.22)
where T is the system temperature in oR.
The authors in their development of the equation, noted that as the system
pressure becomes very large, i.e., p → ∞, the molar volume V of the substance shrinks to
about 26% of its critical volume regardless of the system temperature. The Equation 2.17
was accordingly constructed to satisfy the following condition:
b = 0.26Vc (4.23)
Applying the critical point conditions (as expressed by Equation 4.17) on
Equation 4.19, and solving the resulting equations simultaneously, gives
R 2 Tc2.5
a = Ωa a (TR ) (4.24)
pc
RTc
b = Ωb (4.25)
pc
where
57
Ω a = 0.42748
Ω b = 0.08664
Equating Equation 4.18 with Equation 4.21 gives
p c Vc = 0.333RTc (4.26)
The above expression shows that Redlich-Kwong EOS produces a universal critical
compressibility factor (Zc) of 0.333 for all substances.
Replacing the molar volume V in Equation 4.20 with ZRT/p gives
p
A=a
R T2
2
(4.27)
bp
B= (4.28).
RT
Redlich and Kwong extended the application of their equation to hydrocarbon
liquid or gas mixtures by employing the following mixing rules:
2
⎡n ⎤
a m = ⎢∑ x i a i0.5 ⎥ (4.29)
⎣ i =1 ⎦
⎡n ⎤
b m = ⎢∑ x i b i ⎥ (4.30)
⎣ i =1 ⎦
The Redlich-Kwong value of zc=1/3 is reasonable for lighter hydrocarbons but is
unsatisfactory for heavier components.
4.5 Soave-Redlich-Kwong Equation of State

A significant development of cubic equations of state was the publication by
Soave19 (1972) of a modification in the evaluation of the parameter a in the attractive
pressure term of the Redlich-Kwong equation of state (Equation 4.22). Soave replaced
the term (a/T0.5) in Equation 4.22 with a more general temperature-dependent term as
demonstrated by (aα), to give
RT aα(T)
p= − (4.31)
V − b V ( V + b)
58
where α is a dimensionless factor which becomes unity at T = Tc. At temperatures
other than critical temperature, the parameter α is defined by the following expression:
α = (1 + m(1 − Tr0.5 )) 2 (4.32)
The parameter m is correlated with the acentric factor, to give
m = 0.480 + 1.574ω − 0.176ω 2 (4.33)
where ω is the acentric factor of the substance.
For any pure component, the constants a and b in Equation 4.31 are found by
imposing the classical van der Waals’ critical point constraints (Equation 4.17), on
Equation 4.31 and solving the resulting equations, to give
R 2 Tc2
a = Ωa
pc (4.34)
RTc
b = Ωb
pc (4. 35)
where Ωa and Ωb are the Soave-Redlich-Kwong (SRK) dimensionless pure component
parameters and have the following values:
Ωa = 0.42747 (4.36)
Ωa = 0.08664 (4.37)
The Z-Form of the Equation 4.31 is:
Z 3 − Z 2 + (A − B − B 2 ) Z − AB = 0 (4.38)
where
A=
(aα )p
(RT) 2 (4.39)
bp
B= (4.40)
RT
To use the Equation 4.38 with mixtures, the following mixing rules were proposed by
Soave:
(a α )m ∑ ∑ [x x j (a i a j α i α j ) (k ]
− 1) (4.41)
0 .5
= i ij
i j
59
b m = ∑ [x i b i ]
i (4.42)
with
A=
(aα )m p (4.43)
(RT ) 2
bmp
B= (4.44)
RT
The parameter kij is an empirically determined correction factor called the binary
interaction coefficient, characterizing the binary formed by component i and component j
in the hydrocarbon mixture.
Modifications of the SRK EOS

Groboski and Daubert37 (1978) proposed a new expression for calculating the
parameter m of Equation 4.32 to improve the pure component vapor pressure predictions
by the SRK EOS. The proposed relationship has the following form:
m = 0.48508 + 1.55171ω − 0.15613ω2 (4.45)
Elliot and Daubert38 (1985) stated that the evaluation of optimal interaction
coefficients of asymmetric mixtures (components with significant difference in chemical
behavior), proposed the following set of expressions for calculating kij,
• For N2 systems:
k ij = 0.107089 + 2.9776k ij∞
• For CO2 systems:
( )
k ij = 0.08058 − 0.77215k ij∞ − 1.8407 k ij∞
2
• For H2S systems:

k ij = 0.07654 + 0.017921k ij∞
• For Methane systems with compounds of 10 or more:
( )
k ij = 0.17985 + 2.6958k ij∞ + 10853 k ij∞
2
where, for the above expression:
60
k ij∞ = −(ε i − ε j ) 2 /(2ε i ε j ) (4.46)
and
ε i = (a i log e (2)) 0.5 / b i (4.47).
The major drawback in the SRK EOS is that the critical compressibility factor
takes on the unrealistic universal critical compressibility of 0.333 for all substances.
Consequently, the molar volumes are typically overestimated, i.e., densities are
underestimated.
4.6 Peng-Robinson Equation of State

Peng and Robinson12 (1975) conducted a comprehensive study to evaluate the use
of SRK equation of state for predicting the behavior of naturally occurring hydrocarbon
systems. The authors showed emphasis on the ability of the equation to predict liquid
densities and other fluid properties particularly in the vicinity of the critical region. They
proposed the following expression:
RT aα(T)
p= − (4. 48)
V − b (V + b) 2 − cb 2
Equation 4.48 can be rewritten as:
RT aα(T)
p= − (4.49)
V − b V ( V + b ) + b( V − b)
Imposing the classical critical point conditions (Equation 4.17) on Equation 4.48
and solving for the parameters a and b, yields
R 2 Tc2
a = Ωa (4.50)
pc
RTc
b = Ωb
pc (4.51)
where
Ω a = 0.45724
Ω b = 0.07780 .
61
This equation predicts a universal critical gas compressibility factor of 0.307 compared to
0.333 for the SRK model. Peng and Robinson also adopted Soave’s approach for
calculating the parameter α:
α = (1 + m(1 − TR0.5 )) 2 (4.52)
where m = 0.3746 + 1.5423ω − 0.2699ω 2 (4.53)

This was later expanded by the investigators (1978) to give the following
relationship:
m = 0.379642 + 1.48503ω − 0.1644ω2 + 0.016667ω3 (4.54)
Rearranging Equation 2.37 into the compressibility factor form gives
Z 3 + (B − 1) Z 2 + (A − 3B 2 − 2B) Z − (AB − B 2 − B 3 ) = 0 (4.55)
The mixing rules for PR EOS are defined as follows:
a m = ∑∑ x i x j a 1i / 2 a 1j / 2 a ij (4.56)
b m = ∑ x i bi (4.57)
i
Although PR EOS is another widely used cubic EOSs in petroleum engineering

calculations, it underpredicts saturation pressure of reservoir fluids compared with SRK
EOS.
4.7 Schmidt-Wenzel Equation of State

Schmidt and Wenzel24 (1980) proposed an attractive pressure term that introduces
the acentric factor ω as a third parameter. The SW EOS has the following form:
RT a (T )
p= − 3 (4. 58)
V − b V + (1 + 3ω)bV − 3ωb 2
with
⎛ R 2 Tc2 ⎞
a = Ω a ⎜⎜ ⎟⎟α (4.59)
⎝ pc ⎠
62
⎛ RT ⎞
b = Ω b ⎜⎜ c ⎟⎟ (4.60)
⎝ pc ⎠
where
Ω a = (1 − ζ c (1 − β c )) 3 (4.61)
Ω b = βcξc (4.62)
The βc is given by the smallest positive root of the following equation:
(6ω + 1)β3c + 3β c2 + 3β c − 1 = 0 (4. 63)
and
1
ξc = (4.64)
3(1 + β c ω)
4.8 Patel-Teja Equation of State

Patel and Teja20 (1982) proposed the following three-parameter cubic equation:
RT a (T )
p= − (4.65)
V − b V2 + (b + c)V − bc
In this equation “a” is a function of temperature, and b and c are constants
characteristic of each component. Equation 4.65 was constrained to satisfy the following
conditions:
∂p
=0 (4.66)
∂VTC
∂ 2p
=0 (4.67)
∂VT2C
p c Vc
= ξc (4.68)
RTc
Patel and Teja pointed out that the third parameter c in the equation allows the
empirical parameter ξc to be chosen freely. Application of Equation 4.66 to Equation 4.67
yields:
63
R 2 Tc2
a = Ωa [1 + m(1 − TR0.5 )]2 (4.69)
pc
RTc
b = Ωb (4.70)
pc
RTc
c = Ωc (4.71)
pc
where
Ω c = 1 − 3ξ c (4.72)
Ωa = 3ξc2 + 3(1 − 2ξc )Ω b + Ω 2b + (1 − 3ξc ) (4.73)

and Ωb is the smallest positive root of the following equation:
Ω 3b + (2 − 3ξ c )Ω 2b + 3ξ c2 Ω b − ξ 3c = 0 (4.74)
Equation 4.74 can be solved for Ωb by using the Newton-Raphson iterative
method with an initial value for Ωb as given by
Ω b = 0.32429Z c − 0.002005 (4.75)
For non-polar fluids, the parameters m and, ξc are related to the acentric factor by
the following relationships:
m = 0.452413 + 1.30982ω − 0.295937ω 2 (4.76)
ξ c = 0.329032 − 0.0767992ω + 0.0211947ω 2 (4.77)
In terms of Z, Equation 4.65 can be rearranged to produce
Z3 + (C − 1)Z2 + (A − 2BC − B − C − B2 )Z + (BC + B2C − AB) = 0 (4.78)
where, for mixtures
a mp
A= (4.79)
(RT )2
bm p
B= (4.80)
RT
cm p
C= (4.81)
RT
with
64
[
a m = ∑∑ x i x j (a i a j ) 0.5 (1 − k ij ) ] (4.82)
b m = ∑ [x i bi ] (4.83)
i
cm = ∑ [x i ci ] (4.84)
i
An improved relationship for undefined components such as C7+, the parameters

m and ξc was proposed by Willman and Teja40 (1986) in terms of the boiling point Tb and
specific gravity γ. Therefore, a major drawback of PT EOS is that additional information
is required to be able to determine volumetric properties of composition involving C7+.
4.9 Trebble-Bishnoi-Salim Equation of State

Trebble and Bishnoi26 proposed a four parameter equation of state and it can be
represented as follows:
RT a (T )
p= − 2 (4.85)
V − b V + (b + c)V − bc − d 2
Parameters “a” and “b” are temperature dependent while “c” and “d” are
independent of temperature. Therefore, new temperature functions for “a(T)” and “b(T)”
have been proposed. The value of “d” was determined for all the components available in
the database along the critical isotherm. “d” values for the remaining components were
calculated from a linear fit of optimized “d” values versus the critical volume. The value
of “c” was directly determined from the experimental value of the critical
compressibility. Once the parameters “c” and “d” are set, optimal values of “a” and “b”
are then calculated.
This TB EOS offers increased correlational flexibility and allows for significant
improvements in PVT predictions. Trebble and Bishnoi do mention that the quality of an
equation-of-state largely depends on the data used in its preparation
65
4.10 Transformed Cubic Equations to the LLS EOS Form
Lawal-Lake-Silberberg EOS is represented as:
RT a (T )
P= − 2
V − b V + αbV − β b 2 (4.1)
It is the most general form of the EOSs described in this study. This can be
observed by substituting the values of α and β with numerical constants as described in
the Table 4.1.
Table 4.1: Common Specialization Cubic Equation of State
4.11 Generalized Reduced State of Cubic Equations-of-State

Described below is the derivation of reducing the general LLS EOS to the Z-
form:
66
RT a (T )
P= − 2
V − b V + αbV − β b 2 (4.1)
V
Multiply on both sides of Equation 4.1 by , we get
RT
V
a (T )
V RT V RT
P = −
RT V − b RT V 2 + αbV − βb 2 (4.86)
Real Gas Equation: PV = ZRT (4.87)
Using the real gas law, Equation 4.86 becomes,
a (T ) V
V RT
Z= −
V − b V 2 + αbV − β b 2 (4.88)
ZRT
Simplifying Equation 4.88 using the real gas law: V = ,
P
a (T) ZRT
P
1 RT
Z= −
1−
b (ZRT )2 +
αbZRT
− βP 2
ZRT P2 P
P (4.89)
Further simplifying Equation 4.89,
a (T) ZRT
P P2
1 RT
Z= −
bp ( ZRT ) 2
+ α ZbPRT − β(bP) 2
1−
RTZ (4.90)
a (T ) P
A=
Defining (RT )2 (4.91)
bP
B=
and RT (4.92)
1
Using these definitions in Equation 4.90 and dividing the 2nd part of RHS by ,we
(RT )2
get,
67
a (T ) P
Z
Z=
1
−
(RT )2
B ( ZRT) 2 αZbPRT β(bP) 2
1− + −
Z (RT )2 (RT )2 (RT )2 (4.93)
Simplifying Equation 4.93,

a (T ) P
Z
Z=
1
−
(RT )2
B αZbP β(bP) 2
1− Z2 + −
Z (RT ) (RT )2 (4.94)
Using the definitions of A and B and further simplifying Equation 4.94, we get
Z AZ
Z= − 2
Z − B Z + αBZ − β B 2 (4.95)
Canceling Z on the numerators on both sides in Equation 4.95, we get
1 A
1= − 2
Z − B Z + αBZ − β B 2 (4.96)
Simplifying Equation 4.96 by cross-multiplication, we get
Z 3 + (− B + αB)Z 2 + (− β B 2 − αB 2 )Z + β B 3 = Z 2 + αBZ − β B 2 − AZ + AB (4.97)
= Z 3 + (− 1 − B + αB)Z 2 + (A − αB − βB 2 − αB 2 )Z + (β B 3 + β B 2 − AB) = 0 (4.98)
The reduced form of the real-gas law can be expressed as

Z = Z c f ( PR , TR ) (4.99)
In order to use Equation 4.99 to predict Z-factors of pure substances, natural and
sour gases by utilizing cubic equations of state, the computation of Z-factor from the
reduced form of Equation 4.1 requires composition-dependent critical compressibility
factor as well as mixture critical pressure, temperature and volume for the reduced
parameters (PR, νR, TR). The task is accomplished in the next paragraph
68
The reduced compressibility factor (ZR) equation for pure substances can be
derived from Equation 4.1 by dividing the expression of Equation 4.100 by Zc:
1 + Ω w Zc − 3Zc
α=
Ω w Zc (4.100)
θ 3 Z 3R + θ 2 Z 2R + θ1 Z R + θ 0 = 0 (4.101)
where
θ3 = 1
⎛ 1 Ω P ⎞
θ 2 = − ⎜⎜ + (1 − α) b R ⎟⎟
⎝ Zc Z c TR ⎠
⎛ Ω P Ω P ⎧ Ω P ⎫
2
⎞
θ1 = ⎜ 2 2+ θc − α 2
a R b R
− ( α + β) ⎨ b R
⎬
⎟
⎜ Z c TR Z c TR ⎩ c R ⎭ ⎟⎠
Z T
⎝
⎛ Ω Ω P2 ⎡ 1 ⎧ Ω P ⎫ 2 ⎧ Ω P ⎫3 ⎤ ⎞
θ 0 = − 3 3+ θ c − β ⎢ ⎨ b R ⎬ + ⎨ b R ⎬ ⎥ ⎟
⎜ a b R
⎜ ZT ⎢⎣ Z c ⎩ Z c TR ⎭ ⎩ Z c TR ⎭ ⎥⎦ ⎟⎠
⎝ c R
The reduced compressibility factor (ZR) equation for mixtures can be derived
from Equation 4.101 by replacing pure substance parameters with mixture parameters:
θ3 = 1
⎛ 1 BP ⎞
θ 2 = − ⎜⎜ + (1 − α m ) c R ⎟⎟
⎝ Zc Z c TR ⎠
⎛ A P B P ⎧ B P ⎫
2
⎞
θ1 = ⎜ 2 2+ θm − α m 2 − (α m + β m )⎨
c R c R c R
⎬
⎟
⎜ Z c TR Z c TR ⎩ c R ⎭ ⎟⎠
Z T
⎝
⎛ A B P2 ⎡ 1 ⎧ B P ⎫ 2 ⎧ B P ⎫3 ⎤ ⎞
θ 0 = − 3 3+ θ m − β m ⎢ ⎨ c R ⎬ + ⎨ c R ⎬ ⎥ ⎟
⎜ c c R
⎜Z T ⎢⎣ Z c ⎩ Z c TR ⎭ ⎩ Z c TR ⎭ ⎥⎦ ⎟⎠
⎝ c R (4.102)
In Equations 4.102, the composition-dependent parameters Ac, Bc and Zc are

defined by Equations 4.103-4.105.
69
A c = (α m + β m )B c2 + α m B c + 3Z c2 (4.103)
θ 3 Z 3c + θ 2 Z c2 + θ1 Z c + θ 0 = 0 (4.104)
where
θ 3 = 8 + 12α m + 6α 2m + α 3m
θ 2 = − (3 + 12α m + 12α 2m + 9β m − 9α m β m )
θ1 = 3α m + 6α 2m + 6β m − 6α m β m
θ 0 = − (α 2m + β m − α m β m )
φ 3 B 3c + φ 2 B c2 + φ1 B c + φ 0 = 0 (4.105)
where
φ 3 = 8 + 12α m + 6α 2m + α 3m
φ 2 = 15 + 15α m − 27β m − 3α 2m
φ1 = 6 + 3α m
φ 0 = −1
The expressions for mixture critical pressure and temperature are thereby established in
Equations 4.99 and 4.102
am B c2
Pc = 2
b m [3Z c2 + (α m + β m )B c2 + α m B c ] (4.106)
am Bc
Tc =
2
(4.107)
4.12 Prediction Results for Z-Factor of Pure Substances

A graphical comparative result of the eight EOSs is shown with the experimental
values for the components as shown below. More results on this can been seen in
Appendix D.
70
Z-Factor Comparison Graph (Expt. vs. LLS-EOS)
1.35
1.25
1.15
Z-Factor
1.05
LLS 560 R
LLS 680 R
0.95 LLS 920 R
Expt. T=560
Expt. T=680
0.85
Expt. T=920
0.75
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure, P (Psia)
Figure 4.1: Z-Factor comparison for LLS-EOS for Methane.

Z-Factor Comparison Graph (Expt. vs. LLS)
1.13
1.03
0.93
0.83
Z-Factor
0.73
0.63 LLS 560 R
LLS 680 R
0.53 LLS 920 R
Expt. T=560
0.43
Expt. T=680
Expt. T=920
0.33
0.23
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure, P (Psia)
Figure 4.2: Z-Factor comparison for LLS-EOS for Carbon dioxide.
71
Z-Factor Comparison Graph (Expt. vs. LLS-EOS)
1.45
1.35
Z-Factor
1.25
LLS 560 R
LLS 680 R
1.15
LLS 920 R
Expt. T=560
1.05 Expt. T=680
Expt. T=920
0.95
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure, P (Psia)
Figure 4.3: Z-Factor comparison for LLS-EOS for Nitrogen.

1.7
Z-Factor Comparison (Expt. Vs. VdW-EOS)
1.6
1.5
1.4
1.3
Z-Factor
1.2
1.1
VdW-EOS T=100 F
1 VdW-EOS T=220 F
VdW-EOS T=460 F
100 F EXP
0.9
220 F EXP
460 F EXP
0.8
0.7
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Pressure (psia)
Figure 4.4: Z-Factor comparison for vdW-EOS for Methane.
72
1.6
Z-Factor Comparison (Expt. Vs. vdW-EOS)
1.4
1.2
1
Z-Factor
0.8
VdW-EOS T=100 F
0.6
VdW-EOS T=220 F
VdW-EOS T=460 F
100 F EXP
0.4
220 F EXP
460 F EXP
0.2
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Pressure, (psia)
Figure 4.5: Z-Factor comparison for vdW-EOS for Carbon dioxide.
4.13 Development of Binary Interaction Parameters
Binary Interaction Coefficient/Number (BIN):

These binary interaction coefficients are used to model the intermolecular
interaction through empirical adjustment of the (aα)m term as represented mathematically
by Equation 4.38. They are dependent on the difference in molecular size of components
in a binary system and they are characterized by the following properties, as summarized
by Slot-Petersen39 (1987):
• The interaction between hydrocarbon components increases as the relative
difference between their molecular weights increases:
k,j+1 > ki,j
• Hydrocarbon components with the same molecular weight have a binary
interaction coefficient of zero:
ki,j = 0
73
• The binary interaction coefficient matrix is symmetric:
ki,j = kj,i
4.14 Prediction Results for Z-Factor of Mixtures
Z-Factor Comparison Chart at 49 oF (Simon et. al.)
1.0 Expt. Measured

Corresponding states
BWR EOS
0.9 VdW
LLS
PR
0.8 PT
RK
SRK
0.7 SW
Z-Factor
TB
0.6
0.5
0.4
0.3
0.2
1000 1250 1500 1750 2000 2250 2500 2750 3000
Pressure (Psia)
Figure 4.6: Z-Factor comparison for CO2-C1 mixture at 49 oF.
74
1.0
Expt. Measured
0.9 BWR EOS
VdW
LLS
0.8 PR
PT
RK
0.7 SRK
SW
Z-Factor
TB
0.6
0.5
0.4
0.3
0.2
800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800
Pressure (Psia)
1.0 Expt. Measured

BWR EOS
0.9 VdW
LLS
TB PR
PT
0.8 RK
SRK
SW
Z-Factor
0.7 TB
0.6 VdW
RK
SRK
0.5 PT
PR
LLS
0.4
0.3
1250 1500 1750 2000 2250 2500 2750 3000
Pressure (Psia)
75
1.2
Expt. Measured
1.1 BWR EOS
VdW
LLS
1.0 PR
PT
0.9 RK
SRK
SW
Z-Factor
0.8 TB
TB
0.7
VdW
0.6
SRK
PT
0.5 LLS PR
0.4
0.3
500 1000 1500 2000 2500 3000
Pressure (Psia)
76
4.15 Prediction Results for Z-Factor of Natural Gases
Table 4.2: Sources of Experimental Z-Factor.

Authors Year System Reference
No.
Sage-Reamer-Lacey 1950 C1-C2 8
Sage-Lacey-Schfaasma 1934 C1-C3 79
Reamer-Olds-Sage-Lacey 1944 C1-CO2 75
Reamer-Sage-Lacey 1951 C1-H2S 80
Reamer-Olds-Sage-Lacey 1942 C1-nC10 82
Reamer-Olds-Sage-Lacey 1945 C2-CO2 76
Reamer-Selleck-Sage-Lacey 1952 C2-N2 83
Reamer-Sage 1962 C2-nC10 84
Sage-Reamer-Lacey 1951 C3-CO2 77
Reamer-Olds-Sage-Lacey 1949 nC4-CO2 78
Reamer-Selleck-Sage-Lacey 1953 nC10-H2S 81
Wichert 1970 CO2-H2S-N2-C1-C2-C3-iC4-nC4- 86

iC5-nC5-nC6-C7+
Elsharkawy 2002, 2004 CO2-H2S-N2-C1-C2-C3-iC4-nC4- 41, 71

iC5-nC5-nC6-C7+
Elsharkawy-Foda 1998 CO2-H2S-N2-C1-C2-C3-iC4-nC4- 74

iC5-nC5-nC6-C7+
Satter-Campbell 1963 H2S-C1-C2 46
Buxton-Campbell CO2-N2-C1-C2-C3
Simon-Fesmire-Dicharry-Vorhis 1977 CO2-N2-C1-C2-C3-nC4-nC5-nC6 87
Fluid Prop. Package (Shell) 2003 CO2-N2-C1-C2-C3-iC4-nC4-iC5- Private

nC5-nC6-C7+
77
4.15.1 Results for Excelsior Laboratory Data
Table 4.3: Gas Composition for Excelsior 6 Laboratory Data.

COMPARISON
OF
LABORATORIES
AND FLUID
PROPERTIES
PACKAGE
Pressure (Psia) 3317 2615
Fluid Prop. Core Fluid Prop.
Core Lab. Package Lab. Package
BHT, oF 121
0.802 0.7942 0.768 0.7767
Z-Factor 0 0 0.171 0.2048
Produced
Fraction of Dew
Point Gas 0 0 0.042 0.05
Liquid Saturation
Vapor Phase
Composition 0.0005 0.0005 0.0005 0.0005
Carbon Dioxide 0.0069 0.0069 0.0073 0.0071
Nitrogen 0.813 0.813 0.8321 0.8325
Methane 0.063 0.063 0.0625 0.0627
Ethane 0.0343 0.0343 0.0325 0.0334
Propane 0.0195 0.0195 0.0179 0.0185
iso-Butane 0.0153 0.0153 0.0137 0.0143
n-Butane 0.0102 0.0102 0.0085 0.0091
iso-Pentane 0.0052 0.0052 0.0042 0.0045
n-Pentane 0.0079 0.0079 0.0059 0.0063
Hexane (s) 0.0242 0.0242 0.0149 0.0111
Heptane plus 0 0 0 0
78
1.20
Lab. vdW
LLS PR
PT RK
1.09
SRK SW
Z-Factor
0.98
0.87
0.76
715 1235 1755 2275 2795 3315
Pressure(psia)
Figure 4.10: Z-Factor for Sweet Natural Gas, Data from Excelsior 6 (FPP) at 581 oR
Expt. Measured
1.0 Corresponding states
BWR EOS
VdW
0.9 LLS
PR
TB
PT
0.8 RK
SRK
SW
Z-Factor
TB
0.7
0.6 VdW
RK
SRK
0.5 PT
PR
LLS
0.4
0.3
1250 1500 1750 2000 2250 2500 2750 3000
Pressure (Psia)
Figure 4.11: Z-Factor Comparison Chart at 90 oF (Simon et al.).
79
o
Z-Factor Comparison Chart at 120 F (Simon et. al.)
1.2
Expt. Measured
1.1 BWR EOS
VdW
LLS
1.0 PR
PT
0.9 RK
SRK
SW
Z-Factor
0.8 TB
TB
0.7
VdW
0.6
SRK
PT
0.5 LLS PR
0.4
0.3
500 1000 1500 2000 2500 3000
Pressure (Psia)
Figure 4.12: Z-Factor Comparison Chart at 120 oF (Simon et al.).
4.15.2 Results for TTU Laboratory Data
0.9 LLS EOS
PE Lab.
0.8
Z-Factor
0.7
0.6
0.5
0 1000 2000 3000 4000 5000
Pressure, psia
Figure 4.13: 75% CO2 - Dry Gas at 100 oF for CO2 Sequestration.
80
1
LLS
PE Lab.
0.95
Z-Factor
0.9
0.85
0 1000 2000 3000 4000 5000
Pressure, psia
Figure 4.14: 25% CO2 - Dry Gas at 160 oF for CO2 Sequestration.
4.15.3 Results for UCalgary Data
Table 4.4: Gold Creek Gas Composition.

GOLD CREEK 10-5
T (210
o
P (Psia) F)
4496 0.93
4815 0.948
4515 0.966
5015 0.984
5215 1.003
5515 1.032
6015 1.061
CO2 H2S N2
Total Acid Gas
0.0318 0.0704 0.0401 0.1022
C1 C2 C3 IC4 NC4 IC5 NC5 C6 C7+
0.7069 0.0303 0.0209 0.0057 0.0109 0.006 0.0057 0.0093 0.046
C7+ Mole. Sp. Gr. 0.785
Fraction Wt. 131
81
1.7
Expt.
VdW
LLS
PR
PT
VdW
RK
1.5
SRK
SW
Z-Factor
RK
SRK
1.3
PT
SW
PR
1.1
LLS
0.9
4400 4700 5000 5300 5600 5900 6200
Pressure (Psia)
Figure 4.15: Z-Factor for sour natural gas, data from Excelsior 6 (FPP) at 581 oR
Shell Marmattan 10-33 @ 84 oF
1.6
Expt.
VdW-EOS
1.4
LLS-EOS
PR-EOS
PT-EOS
1.2
RK-EOS
SRK-EOS
SW-EOS
1.0
Z-Factor
TB-EOS
TB
VdW
0.8
SRK
0.6 RK
SW
PR
PT LLS
0.4
0.2
2014 2514 3014 3514 4014 4514 5014
Pressure (Psia)
Figure 4.16: Z-Factor comparison for sour natural gas mixture at 84 oF.
82
Shell Marmattan 10-33 @ 73 oF
1.6
Expt.
VdW-EOS
1.4 LLS-EOS
PR-EOS
PT-EOS
RK-EOS
1.2
SRK-EOS
SW-EOS TB
Z-Factor
TB-EOS
1.0
VdW
0.8 SRK
RK
SW
PR
PT
0.6 LLS
0.4
2014 2514 3014 3514 4014 4514 5014
Pressure (Psia)
Sutte Plant, H,P Injection Line
1.23
VdW
Expt. SW
1.18 LLS TB
PR
PT
1.13 RK PT
RK
SRK
SW
1.08 SRK
TB
Z-Factor
VdW
1.03 PR
0.98 LLS
0.93
0.88
0.83
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Pressure (Psia)
83
Fina WindFall Processing Plant (510 oR)
1.12
VdW
1.02 TB
SW SRK
0.92
PR
Z-Factor
RK LLS
0.82
PT
Expt.
0.72
LLS-EOS
VdW-EOS
0.62 PR-EOS
RK-EOS
SRK-EOS
0.52 PT-EOS
SW-EOS
TB-EOS
0.42
1014 1514 2014 2514 3014 3514 4014 4514 5014
Pressure (Psia)
o
Fina WindFall Processing Plant (560 R)
1.18
TB VdW
1.08
SW SRK
0.98
RK
Z-Factor
LLS
0.88 PR
PT
Expt.
LLS-EOS
0.78 VdW-EOS
PR-EOS
RK-EOS
SRK-EOS
0.68
PT-EOS
SW-EOS
TB-EOS
0.58
1014 1514 2014 2514 3014 3514 4014 4514 5014
Pressure (Psia)
84
1.19
TB VdW
1.09
SW SRK
0.99
RK
Z-Factor
LLS
0.89 PT
PR
Expt.
LLS-EOS
0.79 VdW-EOS
PR-EOS
RK-EOS
SRK-EOS
0.69
PT-EOS
SW-EOS
TB-EOS
0.59
1014 1514 2014 2514 3014 3514 4014 4514 5014
Pressure (Psia)
1.20
1.15
1.10 TB VdW
1.05
SW SRK
1.00
RK
Z-Factor
0.95
PT
0.90 LLS
PR Expt.
LLS-EOS
0.85 VdW-EOS
PR-EOS
0.80 RK-EOS
SRK-EOS
PT-EOS
0.75
SW-EOS
TB-EOS
0.70
1014 1514 2014 2514 3014 3514 4014 4514 5014
Pressure (Psia)
85
o
1.24
Expt.
1.19 LLS-EOS
VdW-EOS
PR-EOS VdW
1.14 TB
RK-EOS
SRK-EOS
1.09
PT-EOS
SRK
SW-EOS SW
1.04 RK
TB-EOS
Z-Factor
0.99
0.94 PT
LLS
PR
0.89
0.84
0.79
0.74
1014 1514 2014 2514 3014 3514 4014 4514 5014
Pressure (Psia)
1.24
Expt.
1.19 LLS-EOS
VdW-EOS
PR-EOS VdW
1.14 TB
RK-EOS
SRK-EOS
1.09
PT-EOS
SW SRK
SW-EOS
1.04 TB-EOS
RK
Z-Factor
0.99
PT
0.94 LLS
PR
0.89
0.84
0.79
0.74
1014 1514 2014 2514 3014 3514 4014 4514 5014
Pressure (Psia)
86
o
1.24
Expt.
1.19 LLS-EOS
VdW-EOS
PR-EOS VdW
1.14 TB
RK-EOS
SRK-EOS
1.09
PT-EOS SRK
SW-EOS SW
1.04 RK
TB-EOS
Z-Factor
0.99
PT
0.94 LLS
PR
0.89
0.84
0.79
0.74
1014 1514 2014 2514 3014 3514 4014 4514 5014
Pressure (Psia)
o
1.24
Expt.
LLS-EOS
1.19 VdW-EOS
PR-EOS
TB VdW
RK-EOS
1.14
SRK-EOS
PT-EOS
1.09 SW-EOS SRK
TB-EOS SW
Z-Factor
RK
1.04
0.99 PT
LLS
0.94 PR
0.89
0.84
1014 1514 2014 2514 3014 3514 4014 4514 5014
Pressure (Psia)
87
4.15.4 Results for Elsharkawy Gas Data
Table 4.5: Results of Elsharkawy Gas Data.

IND 1 84 416 439 504 752 817
H2S 0 0.0708 0.0383 0.2816 0 0.1693 0.1047
CO2 0.0017 0.0096 0.0058 0.0608 0.0097 0.0576 0.0163
N2 0.015 0.0064 0.002 0.0383 0.0041 0.0011 0.0244
C1 0.7284 0.6771 0.7564 0.4033 0.8616 0.6619 0.7352
C2 0.0847 0.0871 0.0706 0.0448 0.0355 0.0412 0.0498
C3 0.0418 0.0384 0.0336 0.0248 0.0154 0.0188 0.0181
IC4 0.011 0.005 0.0104 0.006 0.0046 0.0044 0.0059
NC4 0.0171 0.0156 0.0135 0.0132 0.0046 0.0076 0.0073
IC5 0.0088 0.0056 0.0072 0.0079 0.0026 0.0032 0.004
NC5 0.0084 0.0082 0.0055 0.0081 0.002 0.0036 0.0037
C6 0.0124 0.0083 0.0077 0.0121 0.0035 0.0052 0.0053
C7+ 0.0707 0.0656 0.049 0.0991 0.0564 0.0261 0.0253
Mw+ 152 154 158 165 253 144 132
Sg+ 0.81 0.776 0.783 0.818 0.85 0.788 0.774
Tc C7+, oR 1179.581 1151.75 1165.19 1209.73 1368.64 1144.9 1109.426
Pc C7+, 381.99 350.86 373.99 398.74 487.02 362.72 409.55
psia
T (oF) 221 296 325 250 271 255 290
P (psia) 4973 4669 5095 4190 11830 4050 4255
Z (Expt.) 0.997 0.97 1.011 0.838 1.775 0.914 0.968
LLS (This
Study) 1.0052 0.9883 1.0651 0.7349 1.5917 0.9749 1.0172
88
Table 4.5 (Contd.)
Component Mole Fraction
IND 1275 1277 1280 1714 1788 1866
H2S 0.068 0.1078 0.1826 0.2327 0.273 0.5137
CO2 0.0209 0.0616 0.0866 0.0287 0.0451 0.0319
N2 0.1019 0.004 0.0037 0.0304 0.0061 0.0258
C1 0.6857 0.7414 0.5213 0.5601 0.6459 0.4241
C2 0.059 0.0327 0.1165 0.082 0.0084 0.0024
C3 0.0282 0.0121 0.0142 0.0345 0.0093 0.0007
iC4 0.0047 0.0022 0.0039 0.0085 0.0027 0.0002
nC4 0.0116 0.0061 0.0083 0.011 0.002 0.0003
iC5 0.0085 0.0057 0.0095 0 0.002 0.0002
nC5 0 0 0 0.0071 0.001 0.0001
nC6 0.0035 0.0046 0.0103 0.0028 0.0012 0.0002
C7+ 0.008 0.0218 0.0431 0.0022 0.0032 0.0004
Mw+ 125 125 125 145 103 120
Sg+ 0.75 0.75 0.75 0.85 0.7 0.75
Tc C7+, oR 1074.0 1074.02 1074.0 1202.56 983.27 1063.8
Pc C7+, psia 405.26 405.26 405.26 394.76 272.93 422.82
T (oF) 157 189 216 120 250 230
P (psia) 2347 5065 5385 1000 5014 3514
Z (Expt.) 0.823 0.95 0.942 0.802 0.931 0.711
LLS (This Study) 0.9151 1.0328 0.9984 0.8768 1.0095 0.8330
89
4.15.5 Results for Elsharkawy Miscellaneous Data
Table 4.6: Z-Factor Results for Miscellaneous Gases.

Rich Gas Condensate
Serial No. 281 282 283 284 285 286 287
H2S 0 0 0 0 0 0 0
CO2 0.0231 0.0242 0.0248 0.0253 0.0258 0.0262 0.0266
N2 0.0137 0.0155 0.0161 0.0166 0.0163 0.0155 0.0143
C1 0.6583 0.7074 0.738 0.7559 0.7583 0.7485 0.7292
C2 0.0803 0.0817 0.0821 0.0839 0.0863 0.0905 0.0944
C3 0.0417 0.0411 0.0404 0.0402 0.0415 0.0447 0.0495
iC4 0.0078 0.0073 0.007 0.0069 0.0073 0.0082 0.0091
nC4 0.0184 0.017 0.0162 0.0159 0.0167 0.0186 0.0208
iC5 0.0075 0.0067 0.0062 0.006 0.0062 0.007 0.008
nC5 0.0108 0.0097 0.0089 0.0084 0.0086 0.0096 0.0107
nC6 0.0116 0.011 0.0103 0.0086 0.0078 0.0082 0.0092
C7+ 0.1268 0.0784 0.05 0.0323 0.0252 0.023 0.0282
Mw+ 191 154 139 128 120 115 113
Sg+ 0.831 0.804 0.789 0.778 0.77 0.765 0.763
Pc C7+, 324.60 378.39 404.34 427.52 447.21 460.98 466.85
psia
Tc C7+, oR 1264.023 1177.662 1136.436 1105.09 1081.6 1066.586 1060.503
o
T ( F) 313 313 313 313 313 313 313
P (psia) 6010 5100 4100 3000 2000 1200 700
Z (Expt.) 1.212 1.054 0.967 0.927 0.93 0.952 0.97
ρ (lb/cu.ft.) 26.3 18.97 14.17 9.79 6.27 3.68 2.19
LLS (This
Study) 1.0614 1.0612 1.0239 0.9815 0.9595 0.9588 0.9675
90
Table 4.6 (Contd.)
Highly Sour Gas Condensate
Serial No. 439 440 441 442 443 444 445
H2S 0.282 0.277 0.272 0.27 0.273 0.289 0.318
CO2 0.0608 0.0644 0.0669 0.0685 0.0694 0.0699 0.0679
N2 0.0383 0.0455 0.0476 0.0473 0.0461 0.0434 0.0394
C1 0.4033 0.4382 0.4641 0.4807 0.4844 0.4688 0.4331
C2 0.0448 0.0471 0.0481 0.0487 0.0493 0.0496 0.0494
C3 0.0248 0.0243 0.0239 0.0237 0.0239 0.0252 0.0277
iC4 0.006 0.0055 0.0051 0.0049 0.0049 0.0055 0.0067
nC4 0.0132 0.012 0.0111 0.0106 0.0106 0.0114 0.014
iC5 0.0079 0.0068 0.006 0.0055 0.0053 0.0058 0.0074
nC5 0.0081 0.0069 0.006 0.0054 0.0052 0.0057 0.0071
nC6 0.0121 0.0096 0.0078 0.0066 0.006 0.0063 0.0077
C7+ 0.0991 0.063 0.0412 0.0286 0.0217 0.0192 0.0214
Mw+ 165 121 116 112 109 107 107
Sg+ 0.818 0.778 0.773 0.768 0.764 0.762 0.762
Pc C7+, 365.42 453.28 467.1 477.79 486.02 492.70 492.70
psia
Tc C7+, oR 1209.732 1090.741 1075.735 1062.661 1052.522 1046.28 1046.28
o
T ( F) 250 250 250 250 250 250 250
P (psia) 4190 3600 3000 2400 1800 1200 700
Z (Expt.) 0.838 0.806 0.799 0.809 0.842 0.888 0.935
ρ(lb/cu.ft.) 27.34 19.52 15.06 11.3 7.95 5.06 2.91
LLS (This
Study) 0.8055 0.8698 0.8837 0.8920 0.9009 0.9156 0.9361
91
Table 4.6 (Contd.)
Carbon Dioxide Rich Gas
Serial No. 926 927 928 929 930 931 932
H2S 0.003 0.003 0.003 0.003 0.003 0.003 0.004
CO2 0.6352 0.6395 0.6514 0.6579 0.6639 0.6706 0.6716
N2 0.0386 0.0399 0.041 0.0417 0.0421 0.0411 0.0388
C1 0.1937 0.1988 0.2008 0.207 0.2084 0.2037 0.1994
C2 0.0303 0.0307 0.0308 0.0309 0.0313 0.0315 0.0318
C3 0.0174 0.0172 0.017 0.0169 0.017 0.0175 0.0184
iC4 0.0033 0.0032 0.0031 0.003 0.003 0.0032 0.0035
nC4 0.0093 0.0088 0.0085 0.0082 0.0082 0.0088 0.0097
iC5 0.0039 0.0036 0.0033 0.0031 0.003 0.0033 0.0039
nC5 0.0047 0.0042 0.0038 0.0036 0.0035 0.0038 0.0046
nC6 0.0051 0.0049 0.0046 0.0042 0.0036 0.003 0.0034
C7+ 0.0551 0.0458 0.0324 0.0202 0.0127 0.0101 0.0113
Mw+ 170 153 139 128 118 110 106
Sg+ 0.811 0.797 0.783 0.773 0.763 0.755 0.751
Pc C7+, 347.8288 373.929 397.8203 421.6873 446.3173 469.4246 482.3509
psia
Tc C7+, 1211.601 1169.445 1131.005 1100.627 1071.227 1046.943 1034.515
o
R
T (oF) 219 219 219 219 219 219 219
P (psia) 4825 4100 3300 2600 1900 1200 700
Z (Expt.) 0.851 0.777 0.72 0.719 0.775 0.851 0.915
ρ(lb/cu.ft.) 34.88 30.9 25.58 19.39 12.87 7.38 4.03
LLS (This
Study) 0.7551 0.7276 0.7222 0.7483 0.7882 0.8437 0.8975
92
Table 4.6 (Contd.)
Very light gas
Serial No. 933 934 935 936 937 938 939
H2S 0 0 0 0 0 0 0
CO2 0.0033 0.0033 0.0034 0.0035 0.0035 0.0036 0.0038
N2 0.0032 0.0033 0.0033 0.0033 0.0033 0.0033 0.0033
C1 0.942 0.9438 0.9451 0.9461 0.9468 0.9473 0.9467
C2 0.0231 0.023 0.023 0.0231 0.0232 0.0233 0.0236
C3 0.0082 0.0082 0.0082 0.0082 0.0082 0.0082 0.0083
iC4 0.0023 0.0023 0.0023 0.0023 0.0023 0.0023 0.0023
nC4 0.0025 0.0025 0.0025 0.0025 0.0025 0.0025 0.0026
iC5 0.0012 0.0012 0.0012 0.0012 0.0012 0.0012 0.0012
nC5 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0009
nC6 0.0014 0.0013 0.0013 0.0013 0.0013 0.0012 0.0013
C7+ 0.012 0.0103 0.0089 0.0077 0.0069 0.0063 0.006
Mw+ 143 133 126 120 116 114 114
Sg+ 0.787 0.777 0.769 0.763 0.76 0.758 0.758
Pc C7+, psia 390.4827 409.7106 423.93 438.5907 450.5163 456.162 456.162
Tc C7+, oR 1142.133 1114.075 1093.042 1075.419 1064.345 1058.3 1058.3
o
T ( F) 209 209 209 209 209 209 209
P (psia) 4786 4000 3300 2600 1900 1300 700
Z (Expt.) 1.019 0.974 0.945 0.933 0.933 0.947 0.969
ρ(lb/cu.ft.) 12.13 10.42 8.76 6.92 5.03 3.37 1.78
LLS (This Study) 1.0018 0.9569 0.9252 0.9046 0.8995 0.9113 0.9411
93
CHAPTER 5
CONCLUSIONS AND RECOMMENDATIONS
5.1 Conclusions
This project establishes the need and a solution for a simple and robust technique
of predicting z-factor values for sour reservoir gases and natural reservoir gases.
1. Z-factor from Equations of state has been established. Eight equations-of-state

routinely used in the reservoir simulators have been examined and the most
general EOS has been established.
2. LLS EOS is the most generalized EOS. Every other EOS can be derived from
LLS EOS by substituting for α and β.
3. Best-fit equations for Standing and Katz Z-Chart have been established. Eight
computational techniques available has been examined and Beggs and Brill
computation technique has been used in the development of the scaling factor.
4. A universal scaling factor has been developed for S-K Z-Chart which is capable
of predicting z-factors of
a. Natural gases
b. Sour reservoir gases
5. Determination of accurate critical parameters of mixtures is an essential step to
obtain accurate z-factor values.
6. Improved technique for mixture critical property has been established. 3100
experimental data from various sources were used in the development of scaling
factor and also used for comparison purposes.
94
5.2 Recommendations
The following points can be based for further studies:
1. design of a generalized chart for predicting the amount of gas produced,
2. improvement in the generalized scaling of z using Standing-Katz chart based on
law of corresponding principles.
95
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Fractions,” Ind. Eng. Chem. Res., 26 (24), 755-759 (1987).
102. Brill, J. P., and Beggs, H. D., “Two-Phase flow in pipes,” INTERCOMP
Course, The Huge (1974).
103. Katz, D. L., “High Pressure Gas Measurement,” Pet. Refin., 21 (6) 64-70
(1942).
104. Ahmed, T., Hydrocarbon Phase Behavior, Gulf Publishing Co., Houston
(1989).
105. Buxton, T. S., and Campbell, J. M., “Compressibility Factors for Naturally
Occurring Petroleum Gases,” SPEJ, 80-86, March (1967).
106. Dranchuk, P. M., Purvis, R. A., and Robinson, D. B., “Computer Calculation of
Natural Gas Compressibility Factors Using the Standing and Katz
Correlations,” Inst. of Petroleum Technical Institute Series, No. IP74-008, 1-13
(1974).
107. Elsharkawy, A. M., Hashem, Y. S. K. S, and Alikhan, A. A., “Compressibility

Factor for Gas Condensates,” Paper SPE 59702 presented at the SPE 2000
Permian Basin Oil and Gas Recovery Conference, Midland, TX, March 21-23
(2000).
108. Kay, W. B., “Density of Hydrocarbon Gases and Vapor at High Temperature
and Pressure,” Ind. Eng. Chem., 1014-1019, Sept. (1936).
109. MacCain, W. D. Jr., The Properties of Petroleum Fluids, (2nd Ed.), PennWell
Books: Tulsa (1990).
110. McLeod, W. R., Application of Molecular Refraction to the Principle of

Corresponding States, Ph.D Thesis, University of Oklahoma (1968).
111. Pedersen, K. S., Thomassen, P., and Fredenslund, Aa., Advances in

Thermodynamics, 1, 137 (1989).
104
112. Robinson, R. L., Jr., and Jacoby, R. H., “Better Compressibility Factors,”
Hydro. Proc., 44 (4), April, 141-145 (1965).
113. Simon, R., and Briggs, J. E., “Application of Benedict-Webb-Rubin Equation of

State to Hydrogen Sulfide Mixtures,” AIChE J., 10 (4), July, 548-550 (1964).
114. Sutton, R. P., “Compressibility Factors for High Molecular Weight Reservoir
Gases,” Paper SPE 14265 presented at the SPE Annual Technical Meeting and
Exhibition, Las Vegas, Sept. 22-25 (1985).
115. Takacs, G., “Comparison Made for Computer Z-Factor Calculation,” Oil & Gas
J., 20, December, 64-66 (1976).
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83, March, 610-620 (1972).
105
APPENDIX A
REDUCED FORM OF CUBIC EQUATIONS OF STATE
A.1 Lawal-Lake-Silberberg Reduced Equation of State

RT a (T )
P= − 2
V − b V + αbV − βb 2 (A.1)
1 + Ω w Z c − 3Z c
α=
Ω w Zc (A.2)
Z (Ω w − 1) + 2Ω Z + (1 − 3Z c )Ω w
2 3 2
β= c w c
Ω Z 2
w c (A.3)
Ω a = (1 + (Ω w − 1) Z c ) 3
(A.4)
2 2
R T
a = Ωa c
Pc (A.5)
Ω b RTc
b=
Pc (A.6)
− θc
a (T) = aTR 2
(A.7)
where,
ω
θc = 0.309833 + 1.763758ω + 0.720661ω2 − 1.363589ω3 − 4.005783
Mw
(A.8)
Z-Form of the LLS-EOS is as follows:

Φ 3 Z 3 +Φ 2 Z 2 + Φ 1 Z + Φ 0 = 0
(A.9)
where,
Φ 3 = 1.0 (A.10)
Φ 2 = −[1 + (1 − α)B] (A.11)
[
Φ1 = A − αB − (β + α )B2 ] (A.12)
Φ 0 = − ⎡AB − β( B 2 + B3 ) ⎤
(A.13)
106
a (T ) P
A=
R 2T 2 (A.14)
bP
B=
RT (A.15)
Mixing Rules
a m = ∑∑ x i x j a i 2 a j 2 a ij
1 1
i j
(A.16)
3
⎡ 1 ⎤
b m = ⎢∑ x i b i 3 ⎥
⎣ i ⎦ (A.17)
ωi
a ij = for ωi ≤ ω j
ωj
(A.18)
ωj
a ij = for ωi > ω j
ωi
(A.19)
α m = ∑∑ x i x jα i 2 α j 2 (α i α j )
1 1 0 .5
i j
(A.20)
β m = ∑∑ x i x jβ i 2 β j 2 (β i β j )
1 1 0 .5
i j
(A.21)
a ij = (a i a j ) = (α i α j ) = (β i β j )
(A.22)
A.2 van der Waals Reduced Equation of State

RT a (T )
P= − 2
V−b V (A.23)
α=0 (A.24)
β=0 (A.25)
Ω a = (1 + (Ω w − 1) Z c ) 3 = (1 + (Ω w − 1)0.375) 3
(A.26)
a (T ) = a (A.27)
2 2
R T
a = Ωa c
Pc (A.28)
Ω Z RT
b= w c c
Pc (A.29)
Z-Form of the vdW-EOS is as follows:
107
Φ 3 Z 3 +Φ 2 Z 2 + Φ 1 Z + Φ 0 = 0
(A.30)
where,
Φ 3 = 1.0 (A.31)
Φ 2 = −[1 + (1 − α)B] = −[1 + B] (A.32)
[
Φ1 = A − αB − (β + α)B2 = [A] ] (A.33)
Φ 0 = − ⎡AB − β( B + B ) ⎤ = −[ AB]
2 3
(A.34)
where
a(T)P
A= 2 2
R T (A.35)
bP
B=
RT (A.36)
Mixing Rules:
a m = ∑∑ x i x ja i 2 a j 2 a ij
1 1
i j
(A.37)
b m = ∑ x i bi
i (A.38)
ωi
ωj
(A.39)
ωj
ωi
(A.40)
α m = ∑∑ x i x j α i 2 α j 2 (α i α j )
1 1 0 .5
i j
(A.41)
β m = ∑∑ x i x jβ i 2 β j 2 (β i β j )
1 1 0 .5
i j
(A.42)
(A.43)
A.3 Redlich-Kwong Reduced Equation of State

RT a (T )
P= − 2
V − b V + bV (A.44)
108
α = 1.0 (A.45)
β = 0.0 (A.46)
Ω a = 0.42751 (A.47)
2 2
R T
a = 0.42747 c
Pc (A.48)
RTc
b = 0.08664
Pc (A.49)
1
a (T ) = a
TR
(A.50)
Z-Form of the RK-EOS is as follows:

Φ 3 Z 3 + Φ 2 Z 2 + Φ1 Z + Φ 0 = 0
(A.51)
where,
Φ 3 = 1.0 (A.52)
Φ 2 = −1.0 (A.53)
Φ1 = [ A − B − B ] 2
(A.54)
Φ 0 = −[AB] (A.55)
where,
a (T ) P
A=
R 2T 2 (A.56)
bP
B=
RT (A.57)
Mixing Rules
1 1
i j
(A.58)
b m = ∑ x i bi
i (A.59)
ωi
ωj
(A.60)
ωj
ωi
(A.61)
109
α m = ∑∑ x i x jα i 2 α j 2 (α i α j )
1 1 0 .5
i j
(A.62)
β m = ∑∑ x i x jβ i 2 β j 2 (β i β j )
1 1 0 .5
i j
(A.61)
(A.62)
A.4 Soave-Redlich-Kwong Reduced Equation of State

RT a (T )
P= − 2
V − b V + bV (A.63)
α = 1.0 (A.64)
β = 0.0 (A.65)
Ω a = 0.42751 (A.66)
2 2
R T
a = 0.42747 c
Pc (A.67)
RT
b = 0.08664 c
Pc (A.68)
a (T) = [1.0 + (0.48 + 1.574ω − 0.176ω )(1.0 − T )] a 2 0.5
R
2
(A.69)
Z-Form of the SRK-EOS is as follows

Φ 3 Z 3 + Φ 2 Z 2 + Φ1 Z + Φ 0 = 0
(A.70)
Φ 3 = 1.0
Φ 2 = −1.0
Φ 1 = [A − B − B 2 ]
Φ 0 = −[AB]
where,
a (T ) P bP
A= 2 2 , B=
R T RT
Mixing Rules:
1 1
i j
(A.71)
b m = ∑ x i bi
i (A.72)
110
ωi
ωj
(A.73)
ωj
ωi
(A.74)
α m = ∑∑ x i x jα i 2 α j 2 (α i α j )
1 1 0 .5
i j
(A.75)
β m = ∑∑ x i x jβ i 2 β j 2 (β i β j )
1 1 0 .5
i j
(A.76)
(A.77)
A.5 Peng-Robinson Reduced Equation of State

RT a (T )
P= − 2
V − b V + 2bV − b 2 (A.78)
α = 2.0 (A.79)
β = 1 .0 (A.80)
Ω a = 0.45724 (A.81)
Ω b = 0.07780 (A.82)
2 2
R T
a = 0.45724 c
Pc (A.83)
RT
b = 0.07780 c
Pc (A.84)
a (T) = [1.0 + (0.37464 + 1.54226ω − 0.26992ω )(1.0 − T )] a
2 0.5
R
2
(A.85)
Z-Form of the PR-EOS
Φ 3 Z 3 + Φ 2 Z 2 + Φ1 Z + Φ 0 = 0
(A.86)
Φ 3 = 1.0
Φ 2 = − [1 − B]
Φ1 = [A − 2B − 3B 2 ]
Φ 0 = − [ AB − ( B 2 + B3 )]
a (T ) P bP
A= , B=
R 2T 2 RT
111
Mixing Rules
1 1
i j
(A.87)
b m = ∑ x i bi
i (A.88)
ωi
ωj
(A.89)
ωj
ωi
(A.90)
β m = ∑∑ x i x jβ i 2 β j 2 (β i β j )
1 1 0 .5
i j
(A.91)
(A.92)
A.6 Schmidt-Wenzel Reduced Equation of State

RT a (T )
P= − 2
V − b V + (1 + 3ω)bV − 3ωb 2 (A.93)
(6ω + 1)β3c + 3β c2 + 3β c − 1 = 0
(A.94)
βc = smallest positive root of the above equation.
1
ζc =
3(1 + β c ω) (A.95)
Ω b = ζ cβ c (A.96)
Ω a = (1 − ξ c (1 − β c )) 3
(A.97)
R 2 Tc2
a = Ωa
Pc (A.98)
R.Tc
b = Ωb
Pc (A.99)
a (T) = aα(TR , k ) (A.100)
α (TR , k ) = (1 + k (TR , k 0 )(1 − TR )) 2
(A.101)
where,
k 0 = 0.465 + 1.347ω − 0.528ω2
(A.102)
112
(5TR − 3k 0 − 1) 2
k (TR , k 0 ) = k 0 + , for TR ≤ 1.0
70 (A.103)
k (TR , k 0 ) = k (1, k 0 ) for TR > 1.0
(A.104)
Z-Form of SW-EOS:
Z 3 − [1.0 + (1.0 − (1.0 + 3ω))B]Z 2 + [A − (1.0 + 3ω)B − (1 + 6ω)B 2 ]
− [AB − 3ω(B 2 + B 3 )] = 0 (A.105)
Φ1 : 1.0
Φ2 : − [1.0 + (1.0 − (1.0 + 3ω))B]
Φ3 : A − (1.0 + 3ω) B − (1 + 6ω)B 2
Φ0 : − [AB − 3ω(B 2 + B 3 )]
a (T ) P
A=
(RT ) 2
bP
B=
RT
Mixing Rules:
1 1
i j
(A.106)
b m = ∑ x i bi
i (A.107)
ωi
ωj
(A.108)
ωj
ωi
(A.109)
α m = 1 + 3ωm (A.110)
β m = −3ωm (A.111)
∑ x ω (M ) i i w i
ωm = i
x i (M w )i
(A.112)
where Mwi is the component’s molecular weight.
113
A.7 Patel-Teja Reduced Equation of State
RT a (T )
P= − 2
V − b V + (b + c)V − cb (A.113)
Z-Form of PT-EOS
Z3 − (1.0 − C) Z 2 + (A − 2BC − B2 − B − C) Z − [AB − (B + B2 )C] = 0 (A.114)
Φ1 : 1.0
Φ 2: -(1.0-C)
Φ 3: A − 2BC − B 2 − B − C
Φ 0: - AB + (B + B 2 )C
where,
α (TR ) = [1 + F(1 − TR1 / 2 )]2 (A.115)
F = 0.452413 + 1.30982 ω − 0.295937 ω 2
(A.116)
Z c = 0.329032 − 0.076799 ω + 0.0211947 ω 2
(A.117)
Ω c = 1− 3Zc (A.118)
Ω b , solve Ω + (2 − 3Z c )Ω + 3Z Ω b − Z = 0
3 2 2 3
b b c c (A.119)
2
Ω a = 3 Zc + 3(1 − 2Zc )Ω b + Ω + 1 − 3Zc 2
b (A.120)
pick the smallest positive root = Ω b
a (T) = aα(TR ) (A.121)

a (T ) P Ω a (RTc ) 2
A= a=
(RT ) 2 Pc
bP Ω b RTc
B= b=
RT Pc
cP Ω c RTc
C= c=
RT Pc
Mixing Rules:
1 1
i j
(A.122)
b m = ∑ x i bi
i (A.123)
cm = ∑ x ici
i (A.124)
114
ωi
ωj
(A.125)
ωj
ωi
(A.126)
α m = ∑∑ x i x jα i 2 α j 2 (α i α j )
1 1 0 .5
i j
(A.127)
β m = ∑∑ x i x jβ i 2 β j 2 (β i β j )
1 1 0 .5
i j
(A.128)
(A.129)
A.8 Trebble-Bishnoi-Salim Reduced Equation of State

RT a (T )
P= − 2
V − b V + (b + c)V − bc − d 2 (A.130)
Z-Form of the TB-EOS Equation

Z3 − (1 − C)Z 2 + (A − 2BC − B2 − B − C − D 2 )Z − [AB − (B + B2 )C − (B + 1)D 2 ] = 0 (A.131)
Φ1 : 1.0
Φ 2 : − (1 − C)
Φ 3 : (A − 2BC − B 2 − B − C − D 2 )
Φ0 : − [AB − (B + B 2 )C − (B + 1)D 2 ]
where,
a (T ) P bP cP dP
A= 2 2
;B= ; C= ; D=
R T RT RT RT
where ,
R 2 Tc2 Ω RT Ω RT Ω RT
a ( T ) = Ω a α ( TR ) ;b = b c ;c = c c ;d = d c
Pc Pc Pc Pc
2
m = 0.662 + 3.12ω − 0.854ω + 9.3( ZC − 0.3) (A.132)
p = 0.475 + 2.0ω for M ≤ 128 g mol -1
(A.133)
p = 0.613 + 0.62ω + 4.06ω for M > 128 g mol
2 -1
(A.134)
α (TR ) = [[1 + m(1 − T )] + p{(0.7)
1/ 2
R
1/ 2
− (TR ) }{1 − (TR ) }]
1/ 2 1/ 2
(A.135)
ξ c = 1.063 × Zc
(A.136)
115
Ω c = 1.0 − 3.0ξ c (A.137)
Ω + ( 2 . 0 − 3 . 0ξ c ) Ω + 3. 0 ξ Ω b − ( Ω + ξ ) = 0
3 2 2 2 3
b b c d c (A.138)
Ω b = the smallest positive root in the above equation.
Ω a = 3ξ c2 + 2Ω b Ω c + Ω b + Ω c + Ω 2b + Ω d2
Vc
Ωd =
3 .0
Mixing Rules
1 1
i j
(A.139)
b m = ∑∑ x i x j b i 2 b j 2 b ij
1 1
i j
1 1
c m = ∑∑ x i x j c i 2 c j 2 c ij
i j
ωi
ωj
ωj
ωi
α m = ∑∑ x i x jα i 2 α j 2 (α i α j )
1 1 0 .5
i j
β m = ∑∑ x i x jβ i 2 β j 2 (β i β j )
1 1 0 .5
i j
a ij = b ij = c ij = (a i a j ) = (α i α j ) = (β i β j )
116
APPENDIX B
PREDICTION RESULTS FOR
PSEUDOCRITICAL PARAMETERS
B.10 Pseduocritical Parameter Results
Table B.1: Gas Composition Description.
Mix No. 47-1 26-1 26-2 26-3 47-2 26-4 26-5

CO2 0.0120 0.0109 0.0100 0.0091 0.0044 0.0030 0.0020
N2 0.0000 0.0884 0.1611 0.2441 0.0000 0.1130 0.2400
C1 0.9089 0.8286 0.7625 0.6870 0.9668 0.8580 0.7364
C3 0.0191 0.0174 0.0160 0.0144 0.0070 0.0060 0.0053
iC4 0.0033 0.0030 0.0028 0.0030 0.0014 0.0012 0.0010
nC4 0.0060 0.0055 0.0051 0.0040 0.0020 0.0018 0.0015
iC5 0.0021 0.0019 0.0018 0.0016 0.0007 0.0006 0.0005
nC5 0.0013 0.0012 0.0011 0.0010 0.0005 0.0004 0.0004
nC6 0.0015 0.0014 0.0012 0.0011 0.0005 0.0004 0.0004
C7+ 0.0018 0.0016 0.0015 0.0014 0.0007 0.0006 0.0005
He 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Table B.1 (Contd.)

Mix No. 26-6 26-7 26-8 Mix-1 Mix-2 Mix-3 Mix-4
CO2 0.0013 0.0020 0.0025 0.0069 0.0069 0.0079 0.0079
N2 0.1146 0.1350 0.0705 0.0150 0.0148 0.0149 0.0143
C1 0.7665 0.7515 0.8532 0.9027 0.8906 0.8313 0.7961
C3 0.0335 0.0327 0.0198 0.0134 0.0139 0.0365 0.0399
iC4 0.0035 0.0038 0.0037 0.0037 0.0040 0.0080 0.0101
nC4 0.0090 0.0060 0.0039 0.0034 0.0039 0.0108 0.0149
iC5 0.0017 0.0000 0.0000 0.0019 0.0023 0.0033 0.0065
nC5 0.0015 0.0020 0.0022 0.0012 0.0019 0.0023 0.0052
nC6 0.0000 0.0000 0.0000 0.0020 0.0038 0.0028 0.0087
C7+ 0.0033 0.0000 0.0000 0.0029 0.0110 0.0029 0.0171
He 0.0100 0.0060 0.0031 0.0000 0.0000 0.0000 0.0000
117
Table B.1 (Contd.)
Mix No. Mix-5 Mix-6 Mix-7

CO2 0.0079 0.0079 0.0014
N2 0.0138 0.0135 0.0000
C1 0.7644 0.7507 0.4534
C3 0.0430 0.0443 0.1961
iC4 0.0120 0.0128 0.0936
nC4 0.0186 0.0202 0.0825
iC5 0.0094 0.0106 0.0542
nC5 0.0078 0.0089 0.0343
nC6 0.0140 0.0164 0.0129
C7+ 0.0299 0.0355 0.0011
He 0.0000 0.0000 0.0000
Mixture 47-1 (Gore Data)

500
400 LM LLS Expt.

Kay Joffe PG LK SBV VNA Pedersen Sutton
SC
C ritical T em p eratu re ( o R )
TTP
300
200
100
0
Kay Joffe PG LK SBV Critical
TTP Property
VNA Methods
Pedersen LM SC Sutton LLS Expt.
Figure B.1: Critical temperature prediction for Gore Data (Mix 47-1).
118
1000
LLS Expt.
800
LM
Kay Joffe LK SBV VNA Pedersen Sutton
PG SC
Critical Pressure (psia)
600
TTP
400
200
0
TTP Property
VNA Methods
Figure B.2: Critical pressure prediction for Gore Data (Mix 47-1).
1000
LLS Expt.
800
LM
PG SC
600
TTP
400
200
0
TTP Property
VNA Methods
119
400
LM LLS Expt.
SC
300
TTP
Critical Temperature ( R)
o
200
100
0
TTP Property
VNA Methods

1000 Expt.
LLS
800
LM
PG
SC
600
TTP
400
200
0
TTP Property
VNA Methods
Figure B.5: Critical pressure prediction for Gore Data (Mix 26-2.
120
400
LM
Joffe LK SBV VNA Pedersen LLS Expt.
Kay PG Sutton
SC
300
Critical Temperature ( R)
o
TTP
200
100
0
TTP Property
VNA Methods
1075
LLS Expt.
860
LM
645 SC
TTP
430
215
0
TTP Property
VNA Methods
121
APPENDIX C
SCALING FACTOR DEVELOPMENT
AND RESULTS
The following three forms of the scaling parameter were tested and the
exponential form was selected based on its prediction and matching capability:
[ (
Z SF = 1 + k 1 − TR )]2
… (3.18).
Z SF = TRθ … (3.19).
Z SF = aEXP(bTR ) … (3.20).
The step-by-step procedure for obtaining the scaling factor is as follows:
z SK
1. z SF = × zc
z Expt .
2. Plot zSF vs. TR graph; obtain the best fit-curve and the corresponding equation in
the form of z SF = a × e − bTR for each pure component. Obtain a and b for each
component.
3. Plot a vs. ωMw graph; obtain the best fit-curve and the corresponding equation of
the form a = coeff1 (ωM w ) − coeff 2 .
4. Plot b vs. ω graph; obtain the best fit-curve and the corresponding equation of the
form b = [Aω 2 + Bω + C]
where A, B, and C are constants.
5. The scaling factor expressions for:
a. Pure Components
z SF = a exp(bTR )
where,
a = coeff1 (ωM w ) coeff 2
b = [Aω 2 + Bω + C]
b. Mixtures follow the following Mixing rule:
122
2 2
⎛ n ⎞
[ω M w ] = ⎛⎜ ∑ x i [ω M w ]i0.5 ⎞⎟
n
ω m = ⎜ ∑ x i ω i0.5 ⎟
⎝ i ⎠ ⎝ i ⎠
where a, b, A, B, and C belong to the above described procedure only.
C.1 Scaled Z-Factor Results

Buxton & Campbell at 160 oF (Mix-4)
1.45
Expt.
SK
1.35
Scaled
1.25
1.15
Z-Factor
1.05
0.95
0.85
0.75
0 2,000 4,000 6,000 8,000
Pressure (Psia)
Figure C.1: Scaled z-factor result for Buxton & Campbell Data at 160 oF (Mix-4).
123
Buxton & Campbell, Mix-4, T = 130 F, Quadratic
1.42
Exp
SK
1.32
Scaled
1.22
1.12
Z-Factor
1.02
0.92
0.82
0.72
0 2,000 4,000 6,000 8,000
Pressure (psia)
Buxton & Campbell, Mix-3, T = 160 F
1.4
Exp
SK
1.3 Scaled
1.2
Z-Factor
1.1
0.9
0.8
0 2,000 4,000 6,000 8,000
Pressure (psia)
124
Buxton & Campbell, Mix-3, T = 130 F
1.36
Exp
SK
1.26 Scaled
1.16
Z-Factor
1.06
0.96
0.86
0.76
0 2,000 4,000 6,000 8,000
Pressure (psia)
Buxton & Campbell, Mix-3, T = 100 F, Quadratic
1.36
Exp SK
Scaled
1.21
Z-Factor
1.06
0.91
0.76
0 2,000 4,000 6,000 8,000
Pressure (psia)
125
Buxton & Campbell, Mix-2, T = 130 F,Quadratic
1.2
Exp
SK
1.1 Scaled
Z-Factor
0.9
0.8
0 2,000 4,000 6,000 8,000
Pressure (psia)
Buxton and Campbell Data, Mix-1, Quadratic
o
160 F
1.35
Expt.
SK
1.25 Scaled
1.15
Z-Factor
1.05
0.95
0.85
0 2,000 4,000 6,000 8,000
Pressure (Psia)
126
APPENDIX D
PREDICTION OF Z-FACTOR FOR PURE SUBSTANCES
D.1 Prediction Results by Equations of State Method

Z-Factor Comparison (Expt. Vs. vdW-EOS)
1.55
1.45
1.35
Z-Factor
1.25
1.15
VdW-EOS T=100 F
1.05 VdW-EOS T=220 F
VdW-EOS T=460 F
100 F EXPT.
0.95 220 F EXPT.

460 F EXPT.
0.85
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Pressure (psia)
Figure D.1: Z-Factor comparison for vdW-EOS for Nitrogen.

Z-Factor Comparison Graph (Exp. vs. RK-EOS)
1.37
1.29
1.22
Z-Factor
1.14
RK-EOS 560 R
1.07
RK-EOS 680 R
RK-EOS 920 R
0.99
Expt. T=560
Expt. T=680
0.92
Expt. T=920
0.84
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure, P (Psia)
Figure D.2: Z-Factor comparison for RK-EOS for Methane.
127
Z-Factor Comparison Graph (Expt. vs. RK-EOS)
1.13
0.98
0.83
Z-Factor
0.68
RK-EOS 560 R
RK-EOS 680 R
0.53 RK-EOS 920 R
Expt. T=560
Expt. T=680
0.38
Expt. T=920
0.23
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure, P (Psia)
Figure D.3: Z-Factor comparison for RK-EOS for Carbon dioxide.

Z-Factor Comparison Graph (Expt. vs. RK-EOS)
1.43
1.36
1.28
Z-Factor
1.21
RK-EOS 560 R
RK-EOS 680 R
1.13 RK-EOS 920 R
Expt. T=560
Expt. T=680
1.06
Expt. T=920
0.98
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure, P (Psia)
Figure D.4: Z-Factor comparison for RK-EOS for Nitrogen.
128
1.5
SOAVE-REDLICH-KWONG(C1) vs. Experimental Z-Factor Plot
1.4
1.3
1.2
Z-Factor
1.1
T=100 F
T=220 F
T=460 F
1
100 F EXP
220 F EXP
460 F EXP
0.9
0.8
0 2000 4000 6000 8000 10000
Pressure(psia)
Figure D.5: Z-Factor comparison for SRK-EOS for Methane.

1.3
SOAVE-REDLICH-KWONG(CO2) vs. Experimental Z-Factor Comparison Plot
1.08
0.86
Z-Factor
0.64 T=100 F
T=220 F
T=460 F
100 F EXP
0.42 220 F EXP
460 F EXP
0.2
0 2000 4000 6000 8000 10000
Pressure(psia)
Figure D.6: Z-Factor comparison for SRK-EOS for Carbon dioxide.
129
SOAVE-REDLICH-KWONG(N2) vs. Experimental Z-Factor Comparison Plot
1.55
1.45
1.35
Z-Factor
1.25
T=100 F
T=220 F
1.15 T=460 F
100 F EXP
220 F EXP
1.05 460 F EXP
0.95
0 2000 4000 6000 8000 10000
Pressure(psia)
Figure D.7: Z-Factor comparison for SRK-EOS for Nitrogen.

Z-Factor Comparison Graph (Expt. vs. PR-EOS)
1.25
1.20
1.15
1.10
Z-Factor
1.05
1.00 PR-EOS 560 R
PR-EOS 680 R
0.95
PR-EOS 920 R
Expt. T=560
0.90
Expt. T=680
0.85 Expt. T=920
0.80
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure (Psia)
Figure D.8: Z-Factor comparison for PR-EOS for Methane.
130
1.0
0.9
0.8
0.7
Z-Factor
0.6 T = 560 R
T = 680 R
0.5
T = 920 R
Expt. T=560
0.4
Expt. T=680
0.3 Expt. T=920
0.2
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure, P (Psia)
Figure D.9: Z-Factor comparison for PR-EOS for Carbon dioxide.

1.4
1.3
1.3
1.2
Z-Factor
1.2
1.1
PR-EOS 560 R
PR-EOS 680 R
1.1
PR-EOS 920 R
Expt. T=560
1.0 Expt. T=680
Expt. T=920
1.0
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure (Psia)
Figure D.10: Z-Factor comparison for PR-EOS for Nitrogen.
131
1.5
Z-Factor Comparison (Expt. Vs. SW-EOS)
1.4
1.3
1.2
Z-Factor
1.1
SW-EOS 100 F
SW-EOS 220 F
1
SW-EOS 460 F
100 F EXP
220 F EXP
0.9
460 F EXP
0.8
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
P (psia)
Figure D.11: Z-Factor comparison for SW-EOS for Methane.

1.2
1.1
0.9
0.8
Z-Factor
0.7
0.6
SW-EOS 100 F
0.5
SW-EOS 220 F
SW-EOS 460 F
0.4 100 F EXP
220 F EXP
0.3 460 F EXP
0.2
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Pressure (psia)
Figure D.12: Z-Factor comparison for SW-EOS for Carbon dioxide.
132
1.55
1.45
1.35
Z-Factor
1.25
SW-EOS 100 F
1.15 SW-EOS 220 F
SW-EOS 460 F
100 F EXP
1.05
220 F EXP
460 F EXP
0.95
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
P (psia)
Figure D.13: Z-Factor comparison for SW-EOS for Nitrogen.

Z-Factor Comparison Graph (Exp. vs. PT-EOS)
1.33
1.23
1.13
Z-Factor
PT-EOS 560 R
1.03 PT-EOS 680 R
PT-EOS 920 R
Expt. T=560
0.93 Expt. T=680
Expt. T=920
0.83
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure, P (Psia)
Figure D.14: Z-Factor comparison for PT-EOS for Methane.
133
Z-Factor Comparison Graph (Exp. vs. PT-EOS)
1.13
1.03
0.93
0.83
Z-Factor
0.73
0.63 PT-EOS 560 R
PT-EOS 680 R
0.53 PT-EOS 920 R
Expt. T=560
0.43
Expt. T=680
0.33 Expt. T=920
0.23
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure, P (Psia)
Figure D.15: Z-Factor comparison for PT-EOS for Carbon dioxide.

Z-Factor Comparison Graph (Expt. vs. PT-EOS)
1.46
1.36
Z-Factor
1.26
PT-EOS 560 R
1.16 PT-EOS 680 R
PT-EOS 920 R
Expt. T=560
1.06 Expt. T=680
Expt. T=920
0.96
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
Pressure, P (Psia)
Figure D.16: Z-Factor comparison for PT-EOS for Nitrogen.
134
TB-EOS (METHANE)
1.35
1.25
1.15
Z-Factor
1.05
100 F
0.95
220 F
460 F
100 F EXP
0.85 220 F EXP
460 F EXP
0.75
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Pressure (psia)
Figure D.17: Z-Factor comparison for TB-EOS for Methane.

1.1
TB-EOS (CO2)
0.9
0.8
0.7
Z-Factor
0.6
T=100 F
T=160 F
0.5
T=220 F
100 F EXP
0.4 220 F EXP
460 F EXP
0.3
0.2
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
P(psia)
Figure D.18: Z-Factor comparison for TB-EOS for Carbon dioxide.
135
1.5
TB-EOS (NITROGEN)
1.4
100 F
220 F
460 F
1.3
100 F EXP
220 F EXP
Z-Factor
460 F EXP
1.2
1.1
0.9
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Pressure (psia)
Figure D.19: Z-Factor comparison for TB-EOS for Nitrogen.
136
APPENDIX E
EXPERIMENTAL Z-FACTOR FOR
MISCELLANEOUS GASES
Table E.1: UCalgary Z-Factor Data.

Thesi Cmp CO nC nC nC C7
o
s T ( F) nt. 2 H2S N2 C1 C2 C3 iC4 4 iC5 5 6 +
Mcle
od- Mole 0.5 0.4 0.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Mix-1 40 % 0 22.60 6 75.61 1 8 2 2 0 0 0 0
P Zexpt
(psia) .
600 0.847
1000 0.748
1500 0.639
2000 0.586
2500 0.595
3000 0.632
4000 0.732
5000 0.845
Com
Thesi pone CO nC nC nC C7
o
s T ( F) nt 2 H2S N2 C1 C2 C3 iC4 4 iC5 5 6 +
Mcle
od- Mole 0.5 0.4 0.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Mix-1 100 % 0 22.60 6 75.61 1 8 2 2 0 0 0 0
P Zexpt
(psia) .
600 0.895
1000 0.836
1500 0.779
2000 0.731
2500 0.713
3000 0.722
4000 0.783
5000 0.876
137
Table E.1 (Contd.)
Thesis T (oF) Cmpnt. CO2 H2S N2 C1 C2 C3 iC4 nC4 iC5 nC5 nC6 C7+
Mcleod-Mix-1 40 Mole % 0.50 22.60 0.46 75.61 0.71 0.08 0.02 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.847
1000 0.748
1500 0.639
2000 0.586
2500 0.595
3000 0.632
4000 0.732
5000 0.845
Thesis T (oF) Component CO2 H2S N2 C1 C2 C3 iC4 nC4 iC5 nC5 nC6 C7+
Mcleod-Mix-1 100 Mole % 0.50 22.60 0.46 75.61 0.71 0.08 0.02 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.895
1000 0.836
1500 0.779
2000 0.731
2500 0.713
3000 0.722
4000 0.783
5000 0.876
Mcleod-Mix-1 175 Mole % 0.50 22.60 0.46 75.61 0.71 0.08 0.02 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.933
1000 0.9
1500 0.865
2000 0.839
2500 0.826
3000 0.825
4000 0.856
5000 0.914
Mcleod-Mix-2 40 Mole % 0.30 14.38 0.46 84.14 0.59 0.08 0.03 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
626 0.866
848 0.82
1022 0.787
1521 0.706
2021 0.662
2521 0.663
3021 0.69
4021 0.781
5021 0.887
Mcleod-Mix-2 65 Mole % 0.30 14.38 0.46 84.14 0.59 0.08 0.03 0.02 0.00 0.00 0.00 0.00
138
Table E.1 (Contd.)
P (psia) Zexpt.
624 0.889
823 0.859
1022 0.828
1521 0.763
2021 0.722
2522 0.716
3022 0.732
4022 0.807
5022 0.903
Mcleod-Mix-2 100 Mole % 0.30 14.38 0.46 84.14 0.59 0.08 0.03 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
607 0.911
625 0.909
824 0.886
1023 0.864
1522 0.815
2021 0.783
2521 0.773
3021 0.781
3521 0.805
4021 0.837
4521 0.876
5021 0.919
Mcleod-Mix-2 135 Mole % 0.30 14.38 0.46 84.14 0.59 0.08 0.03 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
655 0.926
824 0.911
1023 0.894
1522 0.858
2021 0.834
2521 0.826
3021 0.83
4021 0.873
5021 0.941
Mcleod-Mix-2 175 Mole % 0.30 14.38 0.46 84.14 0.59 0.08 0.03 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
565 0.946
823 0.93
1023 0.918
1522 0.891
2021 0.874
2521 0.867
3021 0.869
4021 0.903
5021 0.958
139
Table E.1 (Contd.)
Mcleod-Mix-3 40 Mole % 1.31 5.70 0.52 91.51 0.84 0.08 0.02 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.892
1000 0.819
1500 0.751
2000 0.711
2500 0.707
3000 0.73
4000 0.814
5000 0.918
Mcleod-Mix-3 100 Mole % 1.31 5.70 0.52 91.51 0.84 0.08 0.02 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.913
1000 0.883
1500 0.843
2000 0.816
2500 0.808
3000 0.815
4000 0.867
5000 0.945
Mcleod-Mix-3 100 Mole % 1.31 5.70 0.52 91.51 0.84 0.08 0.02 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.913
1000 0.883
1500 0.843
2000 0.816
2500 0.808
3000 0.815
4000 0.867
5000 0.945
Mcleod-Mix-3 175 Mole % 1.31 5.70 0.52 91.51 0.84 0.08 0.02 0.02 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.951
1000 0.929
1500 0.909
2000 0.896
2500 0.892
3000 0.897
4000 0.932
5000 0.986
Mcleod-Mix-22 88 Mole % 1.80 0.00 0.81 84.99 6.64 2.67 1.07 0.91 0.82 0.00 0.19 0.10
P (psia) Zexpt.
500 0.902
140
Table E.1 (Contd.)
1000 0.823
1500 0.756
2000 0.725
2500 0.728
3000 0.755
3500 0.787
Mcleod-Mix-22 113 Mole % 1.80 0.00 0.81 84.99 6.64 2.67 1.07 0.91 0.82 0.00 0.19 0.10
P (psia) Zexpt.
500 0.925
1000 0.862
1500 0.811
2000 0.775
2500 0.772
3000 0.797
3500 0.821
Mcleod-Mix-22 200 Mole % 1.80 0.00 0.81 84.99 6.64 2.67 1.07 0.91 0.82 0.00 0.19 0.10
P (psia) Zexpt.
500 0.96
1000 0.927
1500 0.9
2000 0.884
2500 0.882
3000 0.891
3500 0.91
Mcleod-Mix-24 81 Mole % 0.61 0.00 0.00 85.00 6.00 3.32 0.85 1.29 0.57 0.66 1.09 0.62
P (psia) Zexpt.
500 0.918
1000 0.842
1500 0.777
2000 0.742
2500 0.739
3000 0.765
3500 0.802
Mcleod-Mix-24 152 Mole % 0.61 0.00 0.00 85.00 6.00 3.32 0.85 1.29 0.57 0.66 1.09 0.62
P (psia) Zexpt.
500 0.947
1000 0.903
1500 0.868
2000 0.848
2500 0.843
3000 0.853
3500 0.877
141
Table E.1 (Contd.)
Mcleod-Mix-24 200 Mole % 0.61 0.00 0.00 85.00 6.00 3.32 0.85 1.29 0.57 0.66 1.09 0.62
P (psia) Zexpt.
500 0.96
1000 0.929
1500 0.906
2000 0.892
2500 0.89
3000 0.889
3500 0.916
Mcleod-Mix-25 91 Mole % 0.40 0.00 0.00 94.32 3.90 1.17 0.08 0.13 0.00 0.00 0.00 0.00
P (psia) Zexpt.
500 0.929
1000 0.875
Mcleod-Mix-25 110 Mole % 0.40 0.00 0.00 94.32 3.90 1.17 0.08 0.13 0.00 0.00 0.00 0.00
P (psia) Zexpt.
500 0.939
1000 0.895
Mcleod-Mix-25 150 Mole % 0.40 0.00 0.00 94.32 3.90 1.17 0.08 0.13 0.00 0.00 0.00 0.00
P (psia) Zexpt.
500 0.958
1000 0.925
Reservoir T (oF) Component CO2 H2S N2 C1 C2 C3 iC4 nC4 iC5 nC5 nC6 C7+
S & B T4 160 Mole % 0.00 10.00 0.00 90.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.955
1000 0.929
1500 0.899
2000 0.879
3000 0.874
4000 0.911
5000 0.969
S & B T4 220 Mole % 0.00 10.00 0.00 90.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.971
1000 0.953
1500 0.937
2000 0.926
3000 0.924
4000 0.955
5000 1.002
S & B T4 280 Mole % 0.00 10.00 0.00 90.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
142
Table E.1 (Contd.)
P (psia) Zexpt.
600 0.981
1000 0.972
1500 0.963
2000 0.957
3000 0.96
4000 0.989
5000 1.027
S & B T4 160 Mole % 0.00 20.00 0.00 80.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.945
1000 0.909
1500 0.87
2000 0.842
3000 0.825
4000 0.863
5000 0.925
S & B T4 220 Mole % 0.00 20.00 0.00 80.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.963
1000 0.941
1500 0.917
2000 0.899
3000 0.887
4000 0.912
5000 0.959
S & B T4 280 Mole % 0.00 20.00 0.00 80.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
600 0.976
1000 0.963
1500 0.948
2000 0.937
3000 0.931
4000 0.953
5000 0.99
Mix-2-API-PRJ-
37 157 Mole % 2.09 6.80 10.19 68.57 5.90 2.82 0.47 1.16 0.85 0.00 0.35 0.80
P (psia) Zexpt.
2115 0.829 MC7+ 125
2347 0.823 SgC7+ 0.7500
Mix-17-API-PRJ-
37 189 Mole % 6.16 10.78 0.4 74.14 3.27 1.21 0.22 0.61 0.57 0 0.46 2.18
P (psia) Zexpt.
4915 0.938 MC7+ 125
5065 0.95 SgC7+ 0.7500
143
Table E.1 (Contd.)
Mix-25-API-PRJ-
37 191 Mole % 4.16 9.13 0 78.77 2.97 1.27 0.27 0.6 0.43 0 0.43 1.97
P (psia) Zexpt.
4945 0.955 MC7+ 125
SgC7+ 0.7500
Mix-2-API-PRJ-
37 216 Mole % 8.66 18.26 0.37 52.13 11.65 1.42 0.39 0.83 0.95 0.00 1.03 4.31
P (psia) Zexpt.
4515 0.852 MC7+ 125
5385 0.942 SgC7+ 0.7500
Mix-402-API-
PRJ-37 230 Mole % 2.06 2.44 10.70 70.72 6.91 3.38 0.52 0.67 0.64 0.00 0.37 1.59
P (psia) Zexpt.
3000 0.903 MC7+ 125
3270 0.91 SgC7+ 0.7500
3400 0.914
3600 0.918
3800 0.925
4000 0.934
4200 0.946
4400 0.954
4600 0.97
4800 0.981
5130 1.006
Mix-601-API-
PRJ-37 276 Mole % 6.61 4.53 15.58 41.72 7.12 5.42 2.23 3.10 2.85 0.00 2.68 8.17
P (psia) Zexpt.
4000 0.875 MC7+ 125
5000 0.98 SgC7+ 0.7500
Mix-705-API-
PRJ-37 190 Mole % 4.24 2.90 0.98 70.90 7.34 2.84 0.66 1.40 1.43 0.00 1.13 6.18
P (psia) Zexpt.
4720 0.948 MC7+ 125
4743 0.95 SgC7+ 0.7500
4774 0.955
4815 0.959
4915 0.969
5015 0.981
5115 0.991
5315 1.014
5515 1.039
Mix-707-API-
PRJ-37 218 Mole % 3.17 18.5 2.18 56.22 4.83 2.5 0.56 1.49 1.48 0 1.15 7.82
P (psia) Zexpt.
4475 0.884 MC7+ 125
4515 0.887 SgC7+ 0.7500
4565 0.893
144
Table E.1 (Contd.)
4615 0.899
4715 0.91
4915 0.933
5215 0.97
5515 1.006
6015 1.067
Mix-722-API-
PRJ-37 179 Mole % 2.30 13.21 8.71 65.57 3.07 1.77 0.35 1.00 1.01 0.00 0.78 2.23
P (psia) Zexpt.
3025 0.812 MC7+ 125
3115 0.814 SgC7+ 0.7500
3215 0.818
3315 0.824
3515 0.834
3815 0.853
4215 0.883
4615 0.916
5015 0.951
Mix-727-API-
PRJ-37 143 Mole % 2.06 6.21 10.15 70.52 5.38 2.8 0.37 0.95 0.64 0 0.3 0.62
P (psia) Zexpt.
2399 0.831 MC7+ 125
2415 0.831 SgC7+ 0.7500
2515 0.832
2615 0.834
3015 0.844
3515 0.868
4015 0.903
4515 0.943
5015 0.986
Mix-729-API-
PRJ-37 181 Mole % 5.11 6.56 4.52 77.85 2.50 0.77 0.12 0.45 0.42 0.00 0.31 1.39
P (psia) Zexpt.
3099 0.859 MC7+ 125
3115 0.859 SgC7+ 0.7500
3215 0.861
3515 0.872
3586 0.875
4115 0.906
4415 0.927
4715 0.946
5015 0.968
Mix-735-API-
PRJ-37 206 Mole % 5.05 2.05 25.15 49.35 6.49 3.22 1.05 1.7 1.59 0 1.18 3.17
P (psia) Zexpt.
4430 0.987 MC7+ 125
4515 0.994 SgC7+ 0.7500
4715 1.011
145
Table E.1 (Contd.)
4915 1.029
5215 1.056
5515 1.083
Shell-Et.Al-
Marmattan-10-
33 73 Mole % 3.19 51.37 2.58 42.41 0.24 0.07 0.02 0.03 0.02 0.01 0.02 0.04
P (psia) Zexpt.
2114 0.402 MC7+ 120
2514 0.438 SgC7+ 0.7500
3014 0.495
3514 0.553
4014 0.612
4514 0.67
5014 0.728
Shell-Et.Al-
Marmattan-10-
33 84 Mole % 3.19 51.37 2.58 42.41 0.24 0.07 0.02 0.03 0.02 0.01 0.02 0.04
P (psia) Zexpt.
2114 0.426 MC7+ 120
2514 0.454 SgC7+ 0.7500
3014 0.507
3514 0.562
4014 0.62
4514 0.677
5014 0.734
Shell-Et.Al-
Marmattan-10-
33 95 Mole % 3.19 51.37 2.58 42.41 0.24 0.07 0.02 0.03 0.02 0.01 0.02 0.04
P (psia) Zexpt.
2114 0.458 MC7+ 120
2514 0.478 SgC7+ 0.7500
3014 0.526
3514 0.578
4014 0.632
4514 0.685
5014 0.737
Shell-Et.Al-
Marmattan-10-
33 110 Mole % 3.19 51.37 2.58 42.41 0.24 0.07 0.02 0.03 0.02 0.01 0.02 0.04
P (psia) Zexpt.
2114 0.495 MC7+ 120
2514 0.485 SgC7+ 0.7500
3014 0.534
3514 0.586
4014 0.639
4514 0.693
5014 0.747
146
Table E.1 (Contd.)
Shell-Et.Al-
Marmattan-10-
33 147 Mole % 3.19 51.37 2.58 42.41 0.24 0.07 0.02 0.03 0.02 0.01 0.02 0.04
P (psia) Zexpt.
2114 0.61 MC7+ 120
2514 0.568 SgC7+ 0.7500
3014 0.585
3514 0.619
4014 0.662
4514 0.707
5014 0.756
Shell-Et.Al-
Marmattan-10-
33 186 Mole % 3.19 51.37 2.58 42.41 0.24 0.07 0.02 0.03 0.02 0.01 0.02 0.04
P (psia) Zexpt.
2114 0.69 MC7+ 120
2514 0.665 SgC7+ 0.7500
3014 0.651
3514 0.666
4014 0.696
4514 0.731
5014 0.77
Shell-Et.Al-
Marmattan-10-
33 230 Mole % 3.19 51.37 2.58 42.41 0.24 0.07 0.02 0.03 0.02 0.01 0.02 0.04
P (psia) Zexpt.
2114 0.749 MC7+ 120
2514 0.722 SgC7+ 0.7500
3014 0.71
3514 0.711
4014 0.73
4514 0.755
5014 0.786
147-Sutte-Plant 198 Mole % 4.2 3.32 1.06 77.91 7.74 2.99 0.58 1.45 0.25 0.23 0.16 0.11
P (psia) Zexpt.
200 0.991 MC7+ 125
500 0.968 SgC7+ 0.7340
1000 0.924
1500 0.895
2000 0.878
2500 0.869
3000 0.876
3500 0.893
4000 0.918
4500 0.951
5000 0.988
147-Waterton 156 Mole % 8.03 29.66 1.04 52.75 3.48 0.82 0.15 0.6 0.22 0.23 0.45 2.57
P (psia) Zexpt.
147
Table E.1 (Contd.)
3914 0.749 MC7+ 130
4014 0.757 SgC7+ 0.8340
4214 0.774
4414 0.792
4714 0.82
4914 0.839
5064 0.853
5114 0.858
5214 0.868
5414 0.888
5714 0.917
6014 0.948
Gold Creek 210 Mole % 3.18 7.04 4.81 70.69 3.83 2.09 0.57 1.09 0.60 0.57 0.93 4.60
P (psia) Zexpt.
4496 0.938 MC7+ 131
4615 0.948 SgC7+ 0.7850
4815 0.966
5015 0.984
5215 1.003
5515 1.032
6015 1.061
HOME-ET.AL-6-
8(L) 77 Mole % 3.08 49.35 2.66 44.47 0.23 0.06 0.02 0.03 0.02 0.01 0.03 0.04
P (psia) Zexpt.
1014 0.667 MC7+ 125
1514 0.455 SgC7+ 0.7500
2014 0.421
2514 0.457
3014 0.408
3514 0.562
4014 0.618
4514 0.674
5014 0.73
HOME-ET.AL-6-
8(L) 120 Mole % 3.08 49.35 2.66 44.47 0.23 0.06 0.02 0.03 0.02 0.01 0.03 0.04
P (psia) Zexpt.
1014 0.75 MC7+ 125
1514 0.622 SgC7+ 0.7500
2014 0.537
2514 0.529
3014 0.557
3514 0.597
4014 0.643
4514 0.691
5014 0.74
HOME-ET.AL-6-
8(L) 144 Mole % 3.08 49.35 2.66 44.47 0.23 0.06 0.02 0.03 0.02 0.01 0.03 0.04
P (psia) Zexpt.
148
Table E.1 (Contd.)
1014 0.802 MC7+ 125
1514 0.692 SgC7+ 0.7500
2014 0.612
2514 0.584
3014 0.596
3514 0.626
4014 0.665
4514 0.707
5014 0.752
HOME-ET.AL-6-
8(L) 230 Mole % 3.08 49.35 2.66 44.47 0.23 0.06 0.02 0.03 0.02 0.01 0.03 0.04
P (psia) Zexpt.
1014 0.884 MC7+ 125
1514 0.832 SgC7+ 0.7500
2014 0.786
2514 0.751
3014 0.739
3514 0.74
4014 0.757
4514 0.78
5014 0.809
DICK-LAKE-A-
15(SMOOTHED-
DATA) 93 Mole % 1.23 1.62 2.52 77.48 10.32 3.94 0.54 1.30 0.27 0.24 0.54 0.00
P (psia) Zexpt.
615 0.882
715 0.872
815 0.861
915 0.849
DICK-LAKE-A-
15(SMOOTHED-
DATA) 105 Mole % 1.23 1.62 2.52 77.48 10.32 3.94 0.54 1.30 0.27 0.24 0.54 0.00
P (psia) Zexpt.
615 0.888
715 0.878
815 0.868
915 0.858
DICK-LAKE-A-
15(SMOOTHED-
DATA) 120 Mole % 1.23 1.62 2.52 77.48 10.32 3.94 0.54 1.30 0.27 0.24 0.54 0.00
P (psia) Zexpt.
615 0.896
715 0.888
815 0.879
915 0.87
RIMBEY-GAS-
PLANT 84 Mole % 1.21 1.50 2.08 78.14 10.29 4.05 0.62 1.23 0.29 0.29 0.30 0.00
149
Table E.1 (Contd.)
DICK-LAKE-A-
15(SMOOTHED-
DATA) P (psia) Zexpt.
500 0.926
750 0.885
1000 0.841
1250 0.805
1400 0.787
RIMBEY-GAS-
PLANT 95 Mole % 1.86 3.29 2.28 80.34 6.56 3.02 0.52 1.07 0.37 0.34 0.35 0.00
DICK-LAKE-A-
23(SMOOTHED-
DATA) P (psia) Zexpt.
500 0.945
750 0.911
1000 0.873
1250 0.842
1500 0.816
HOMEGLEN-
RIMBEY-A-
25(SMOOTHED-
DATA) 83 Mole % 1.61 3.26 2.75 80.52 6.61 2.92 0.42 0.99 0.21 0.21 0.50 0.00
P (psia) Zexpt.
615 0.881
715 0.872
815 0.862
915 0.853
1015 0.844
HOMEGLEN-
RIMBEY-A-
25(SMOOTHED-
DATA) 100 Mole % 1.61 3.26 2.75 80.52 6.61 2.92 0.42 0.99 0.21 0.21 0.50 0.00
P (psia) Zexpt.
615 0.892
715 0.883
815 0.874
915 0.865
1015 0.856
HOMEGLEN-
RIMBEY-A-
25(SMOOTHED-
DATA) 120 Mole % 1.61 3.26 2.75 80.52 6.61 2.92 0.42 0.99 0.21 0.21 0.50 0.00
P (psia) Zexpt.
615 0.905
715 0.896
815 0.887
915 0.878
1015 0.869
150
Table E.1 (Contd.)
SHELL-LOW-
WATERTON-
NO.5-17 156 Mole % 3.48 16.03 0.97 65.49 3.93 1.53 0.32 0.92 0.52 0.50 1.12 5.19
P (psia) Zexpt.
4560 0.864 MC7+ 140
4596 0.868 SgC7+ 0.9050
4650 0.874
4714 0.881
4814 0.892
4914 0.903
5114 0.926
5514 0.973
6014 1.03
SHELL-NO.3-
BURNT-
TIMBER 196 Mole % 5.78 6.42 0.33 81.87 3.64 0.74 0.22 0.19 0.10 0.07 0.13 0.51
P (psia) Zexpt.
936 0.935 MC7+ 118
1058 0.929 SgC7+ 0.7580
1203 0.923
1363 0.915
1557 0.906
1733 0.899
1912 0.894
2275 0.886
2772 0.885
3199 0.893
3506 0.901
3781 0.912
3827 0.914
3851 0.915
4014 0.923
4514 0.95
5014 0.981
5514 1.014
6014 1.051
SHELL-NO.4-
W.J.P.2-23 120 Mole % 6.17 5.40 0.49 81.07 3.74 0.94 0.32 0.34 0.18 0.12 0.23 1.00
P (psia) Zexpt.
4279 0.882 MC7+ 127
4295 0.883 SgC7+ 0.8050
4314 0.885
4330 0.886
4346 0.887
4414 0.893
4514 0.902
5014 0.948
5514 0.995
6014 1.044
6514 1.094
151
Table E.1 (Contd.)
WIMBORNE-
NO.6-11-
(UPPER) 162 Mole % 2.06 12.96 9.63 66.34 3.11 1.80 0.34 0.94 0.33 0.45 0.56 1.48
P (psia) Zexpt.
2899 0.82 MC7+ 115
2916 0.82 SgC7+ 0.7610
2945 0.821
2984 0.823
3014 0.823
3064 0.825
3114 0.827
3214 0.831
3314 0.836
3514 0.846
4014 0.878
4514 0.916
5014 0.958
5514 1.003
6014 1.048
ROYALITE-
EDSON-6-4-52-
17 160 Mole % 4.34 1.04 0.17 90.31 2.70 0.66 0.16 0.18 0.09 0.07 0.11 0.17
P (psia) Zexpt.
514 0.959 MC7+ 125
1014 0.925 SgC7+ 0.7500
1514 0.898
2014 0.88
2514 0.873
3014 0.878
3514 0.896
4014 0.918
ROYALITE-
EDSON-6-4-52-
17 220 Mole % 4.34 1.04 0.17 90.31 2.70 0.66 0.16 0.18 0.09 0.07 0.11 0.17
P (psia) Zexpt.
514 0.975 MC7+ 125
1014 0.955 SgC7+ 0.7500
1514 0.939
2014 0.929
2514 0.926
3014 0.931
3514 0.943
4014 0.961
HB-UNION-
KAYBOS-S-7-
14 250 Mole % 3.13 16.82 1.12 60.09 7.72 3.12 1.00 1.44 0.41 0.63 1.10 3.42
P (psia) Zexpt.
3542 0.94 MC7+ 124
4014 0.971 SgC7+ 0.7940
4514 1.009
5014 1.051
152
Table E.1 (Contd.)
5514 1.096
6014 1.144
HB-UNION-
KAYBOS-S-11-
1 230 Mole % 3.12 15.62 1.01 60.12 7.85 3.28 0.82 1.56 0.67 0.75 1.11 4.09
P (psia) Zexpt.
3457 0.821 MC7+ 125
4014 0.848 SgC7+ 0.7950
4514 0.89
5014 0.936
5514 0.984
6014 1.033
6514 1.082
PANTHER-
RIVER-5-23 50 Mole % 12.86 35.99 1.54 49.53 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
434 0.851
PANTHER-
RIVER-5-23 50 Mole % 12.01 38.37 2.35 46.98 0.29 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
464 0.85
PANTHER-
RIVER-5-23 50 Mole % 10.77 30.28 3.09 55.80 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
764 0.778
R&J-Mixture-17 200 Mole % 1.18 20.27 0.23 76.30 1.29 0.73 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
246 0.979
363 0.97
532 0.956
776 0.938
1125 0.915
1623 0.846
R&J-Mixture-18 100 Mole % 7.44 7.35 0.61 83.03 1.30 0.07 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
252 0.967
369 0.952
536 0.931
772 0.902
1101 0.864
1556 0.821
153
Table E.1 (Contd.)
R&J-Mixture-19 100 Mole % 15.55 14.91 0.41 67.92 1.11 0.10 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
194 0.968 MC7+
285 0.953 SgC7+
414 0.932
597 0.903
849 0.863
1188 0.812
1640 0.854
R&J-Mixture-20 100 Mole % 2.87 23.27 3.04 56.01 8.20 3.45 0.85 1.10 0.00 0.71 0.28 0.22
P (psia) Zexpt.
400 0.912 MC7+
600 0.867 SgC7+
800 0.82
1000 0.874
R&J-Mixture-20 120 Mole % 2.87 23.27 3.04 56.01 8.20 3.45 0.85 1.10 0.00 0.71 0.28 0.22
P (psia) Zexpt.
400 0.922
600 0.883
800 0.842
1000 0.902
R&J-Mixture-11 150 Mole % 22.30 0.00 0.50 75.59 1.40 0.21 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
250 0.975
360 0.964
538 0.949
783 0.927
1130 0.9
1622 0.869
R&J-Mixture-12 200 Mole % 28.14 0.00 0.82 69.93 1.06 0.05 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
233 0.962
344 0.974
505 0.963
739 0.947
1076 0.927
1559 0.903
R&J-Mixture-13 100 Mole % 0.08 4.09 0.96 89.26 1.54 0.07 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
231 0.972
339 0.959
154
Table E.1 (Contd.)
495 0.941
717 0.916
1029 0.883
1464 0.845
R&J-Mixture-14 100 Mole % 1.44 16.30 0.77 79.48 1.53 0.48 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
258 0.962
377 0.945
547 0.921
785 0.889
1111 0.847
1558 0.798
R&J-Mixture-15 100 Mole % 2.10 26.96 0.68 68.68 1.15 0.43 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
197 0.965
288 0.95
418 0.927
600 0.894
848 0.851
1178 0.794
1609 0.829
R&J-Mixture-16 150 Mole % 1.27 18.99 0.77 77.26 1.32 0.39 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
255 0.972
375 0.959
547 0.941
791 0.916
1135 0.884
1617 0.846
R&J-Mixture-5 100 Mole % 10.18 10.33 10.66 49.06 9.55 10.22 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
248 0.965
363 0.949
526 0.926
754 0.895
1074 0.854
1511 0.808
R&J-Mixture-6 100 Mole % 0.04 0.00 0.95 97.48 1.53 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
352 0.964
515 0.948
749 0.926
155
Table E.1 (Contd.)
1000 0.898
1550 0.867
R&J-Mixture-7 100 Mole % 5.36 0.00 0.84 92.22 1.49 0.09 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
342 0.963
500 0.946
726 0.924
1049 0.894
1496 0.86
R&J-Mixture-8 100 Mole % 11.46 0.00 0.68 86.16 1.46 0.04 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
256 0.97
376 0.956
548 0.937
792 0.911
1134 0.877
1614 0.84
R&J-Mixture-9 100 Mole % 19.72 0.00 0.55 78.30 1.39 0.04 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
254 0.967
371 0.952
540 0.931
779 0.902
1111 0.865
1570 0.822
R&J-Mixture-10 100 Mole % 54.46 0.00 0.26 44.60 0.68 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
154 0.97
225 0.956
328 0.935
473 0.907
672 0.866
937 0.811
1275 0.843
1703 0.867
B&C-Mixture-1 100 Mole % 5.06 0.00 0.53 89.77 4.64 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.861
1526 0.844
2026 0.816
2526 0.811
3026 0.822
156
Table E.1 (Contd.)
3526 0.846
4026 0.878
4526 0.917
5026 0.959
6026 1.05
7026 1.146
B&C-Mixture-1 130 Mole % 5.06 0.00 0.53 89.77 4.64 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.904
1526 0.875
2026 0.855
2526 0.851
3026 0.857
3526 0.877
4026 0.904
4526 0.937
5026 0.974
6026 1.056
7026 1.143
B&C-Mixture-1 160 Mole % 5.06 0.00 0.53 89.77 4.64 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.925
1526 0.899
2026 0.885
2526 0.874
3026 0.905
3526 0.901
4026 0.923
4526 0.954
5026 1.009
6026 1.064
7026 1.143
B&C-Mixture-2 100 Mole % 10.13 0.00 0.57 85.20 4.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.881
1526 0.838
2026 0.812
2526 0.864
3026 0.875
3526 0.908
4026 0.921
4526 0.96
5026 1.002
6026 1.095
7026 1.19
157
Table E.1 (Contd.)
B&C-Mixture-2 130 Mole % 10.13 0.00 0.57 85.20 4.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.904
1526 0.872
2026 0.85
2526 0.844
3026 0.851
3526 0.879
4026 0.897
4526 0.93
5026 0.969
6026 1.052
7026 1.139
B&C-Mixture-2 160 Mole % 10.13 0.00 0.57 85.20 4.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.923
1526 0.899
2026 0.882
2526 0.877
3026 0.883
3526 0.899
4026 0.921
4526 0.949
5026 0.983
6026 1.058
7026 1.139
B&C-Mixture-3 100 Mole % 20.16 0.00 0.52 74.58 4.74 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.865
1526 0.814
2026 0.878
2526 0.862
3026 0.878
3526 0.904
4026 0.938
4526 0.979
5026 0.923
6026 1.114
7026 1.214
B&C-Mixture-3 130 Mole % 20.16 0.00 0.52 74.58 4.74 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.889
1526 0.852
2026 0.925
2526 0.914
3026 0.92
158
Table E.1 (Contd.)
3526 0.939
4026 0.967
4526 1.002
5026 1.041
6026 1.126
7026 1.214
B&C-Mixture-3 160 Mole % 20.16 0.00 0.52 74.58 4.74 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.91
1526 0.882
2026 0.86
2526 0.95
3026 0.955
3526 0.97
4026 0.993
4526 1.024
5026 1.056
6026 1.134
7026 1.215
B&C-Mixture-4 100 Mole % 10.91 0.00 0.00 75.93 0.00 13.16 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.913
1526 0.85
2026 0.814
2526 0.814
3026 0.837
3526 0.875
4026 0.821
4526 0.971
5026 1.023
6026 1.131
7026 1.241
B&C-Mixture-4 130 Mole % 10.91 0.00 0.00 75.93 0.00 13.16 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.951
1526 0.899
2026 0.87
2526 0.863
3026 0.878
3526 0.906
4026 0.945
4526 0.989
5026 1.036
6026 1.035
7026 1.136
159
Table E.1 (Contd.)
B&C-Mixture-4 160 Mole % 10.91 0.00 0.00 75.93 0.00 13.16 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.974
1526 0.934
2026 0.91
2526 0.904
3026 0.913
3526 0.936
4026 0.967
4526 1.003
5026 1.045
6026 1.136
7026 1.228
B&C-Mixture-5 100 Mole % 12.92 0.00 0.00 58.41 28.67 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.893
1526 0.815
2026 0.776
2526 0.778
3026 0.808
3526 0.851
4026 0.901
4526 0.955
5026 1.01
6026 1.124
7026 1.138
B&C-Mixture-5 130 Mole % 12.92 0.00 0.00 58.41 28.67 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.93
1526 0.872
2026 0.836
2526 0.83
3026 0.848
3526 0.882
4026 0.924
4526 0.971
5026 1.021
6026 1.125
7026 1.231
B&C-Mixture-5 160 Mole % 12.92 0.00 0.00 58.41 28.67 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1026 0.961
1526 0.913
2026 0.883
2526 0.875
3026 0.886
160
Table E.1 (Contd.)
3526 0.911
4026 0.947
4526 0.989
5026 1.033
6026 1.129
7026 1.227
FINA-ET.AL-
Creek-10-7 236 Mole % 3.4 16 1.15 59.09 7.59 3.09 0.78 1.69 0.67 0.78 1.2 4.56
P (psia) Zexpt.
3514 0.914
4014 0.955
4514 0.999
5014 1.042
5514 1.092
6014 1.142
6514 1.193
FINA-
WINDFALL-T-3 219 Mole % 7.74 11.83 1.62 63.00 4.20 2.69 0.69 1.80 0.70 0.79 0.92 4.02
P (psia) Zexpt.
3814 0.843 MC7+ 139.0
3854 0.845 SgC7+ 0.7880
3914 0.849
4014 0.857
4514 0.901
5014 0.946
FINA-
WINDFALL-
PILOT-PLANT-
INJECTION-
GAS-T-3 150 Mole % 5.13 15.67 2.68 66.84 4.55 3.01 0.47 0.83 0.22 0.23 0.15 0.22
P (psia) Zexpt.
3014 0.764 MC7+ 125.0
3514 0.787 SgC7+ 0.7500
4014 0.82
4514 0.859
5014 0.901
FINA-
WINDFALL-
PILOT-PLANT-
INJECTION-
GAS-T-3 200 Mole % 5.13 15.67 2.68 66.84 4.55 3.01 0.47 0.83 0.22 0.23 0.15 0.22
P (psia) Zexpt.
3014 0.824 MC7+ 125.0
3514 0.839 SgC7+ 0.7500
4014 0.864
4514 0.894
5014 0.928
161
Table E.1 (Contd.)
FINA-
WINDFALL-
PILOT-PLANT-
INJECTION-
GAS-T-3 250 Mole % 5.13 15.67 2.68 66.84 4.55 3.01 0.47 0.83 0.22 0.23 0.15 0.22
P (psia) Zexpt.
3014 0.877 MC7+ 125.0
3514 0.888 SgC7+ 0.7500
4014 0.907
4514 0.931
5014 0.96
FINA-
WINDFALL-
PILOT-PLANT-
INJECTION-
GAS-T-3 300 Mole % 5.13 15.67 2.68 66.84 4.55 3.01 0.47 0.83 0.22 0.23 0.15 0.22
P (psia) Zexpt.
3014 0.912 MC7+ 125.0
3514 0.922 SgC7+ 0.7500
4014 0.939
4514 0.96
5014 0.985
FINA-
WINDFALL-
PROCESSING-
PLANT-
INJECTION-
GAS-T-3 50 Mole % 4.51 27.30 0.61 64.59 0.84 0.93 0.27 0.20 0.20 0.11 0.12 0.32
P (psia) Zexpt.
1014 0.714 MC7+ 103.0
2014 0.63 SgC7+ 0.7000
2514 0.655
3014 0.7
4014 0.715
5014 0.834
FINA-
WINDFALL-
PROCESSING-
PLANT-
INJECTION-
GAS-T-3 100 Mole % 4.51 27.30 0.61 64.59 0.84 0.93 0.27 0.20 0.20 0.11 0.12 0.32
P (psia) Zexpt.
1014 0.816 MC7+ 103.0
2014 0.764 SgC7+ 0.7000
2514 0.752
3014 0.769
4014 0.748
5014 0.846
162
Table E.1 (Contd.)
FINA-
WINDFALL-
PROCESSING-
PLANT-
INJECTION-
GAS-T-3 125 Mole % 4.51 27.30 0.61 64.59 0.84 0.93 0.27 0.20 0.20 0.11 0.12 0.32
P (psia) Zexpt.
1014 0.847 MC7+ 103.0
2014 0.722 SgC7+ 0.7000
2514 0.703
3014 0.708
4014 0.771
5014 0.857
FINA-
WINDFALL-
PROCESSING-
PLANT-
INJECTION-
GAS-T-3 150 Mole % 4.51 27.30 0.61 64.59 0.84 0.93 0.27 0.20 0.20 0.11 0.12 0.32
P (psia) Zexpt.
1014 0.871 MC7+ 103.0
2014 0.768 SgC7+ 0.7000
2514 0.747
3014 0.747
4014 0.795
5014 0.869
FINA-
WINDFALL-
PROCESSING-
PLANT-
INJECTION-
GAS-T-3 175 Mole % 4.51 27.30 0.61 64.59 0.84 0.93 0.27 0.20 0.20 0.11 0.12 0.32
P (psia) Zexpt.
1014 0.895 MC7+ 103.0
2014 0.809 SgC7+ 0.7000
2514 0.788
3014 0.784
4014 0.819
5014 0.885
FINA-
WINDFALL-
PROCESSING-
PLANT-
INJECTION-
GAS-T-3 200 Mole % 4.51 27.30 0.61 64.59 0.84 0.93 0.27 0.20 0.20 0.11 0.12 0.32
P (psia) Zexpt.
1014 0.913 MC7+ 103.0
2014 0.842 SgC7+ 0.7000
2514 0.824
3014 0.818
4014 0.844
5014 0.902
163
Table E.1 (Contd.)
FINA-
WINDFALL-
PROCESSING-
PLANT-
INJECTION-
GAS-T-3 225 Mole % 4.51 27.30 0.61 64.59 0.84 0.93 0.27 0.20 0.20 0.11 0.12 0.32
P (psia) Zexpt.
1014 0.925 MC7+ 103.0
2014 0.865 SgC7+ 0.7000
2514 0.848 0.748
3014 0.841 0.741
4014 0.864 0.764
5014 0.914 0.814
FINA-
WINDFALL-
PROCESSING-
PLANT-
INJECTION-
GAS-T-3 250 Mole % 4.51 27.30 0.61 64.59 0.84 0.93 0.27 0.20 0.20 0.11 0.12 0.32
P (psia) Zexpt.
1014 0.944 MC7+ 103.0
2014 0.894 SgC7+ 0.7000
2514 0.88
3014 0.873
4014 0.889
5014 0.931
CHEVRON-
CLARK-LAKE-
11-33 228 Mole % 3.44 17.6 1.02 57.41 7.55 3.24 0.87 1.63 0.63 0.79 1.31 4.51
P (psia) Zexpt.
3366 0.79 MC7+ 150.0
3414 0.793 SgC7+ 0.8000
3469 0.797
3514 0.8
3814 0.822
4214 0.857
4514 0.883
4672 0.899
4714 0.902
4814 0.912
5014 0.931
5514 0.982
6014 1.034
6514 1.086
7014 1.139
NEVIS-NO.110-
30 143 Mole % 2.06 6.21 10.15 70.52 5.38 2.8 0.37 0.95 0.29 0.35 0.3 0.62
P (psia) Zexpt.
2354 0.832 MC7+ 125.0
164
Table E.1 (Contd.)
2404 0.832 SgC7+ 0.7500
2414 0.832
2514 0.832
2614 0.834
3014 0.844
3514 0.869
4014 0.903
4514 0.944
5014 0.987
Panther River5-
23 50 Mole % 10.67 31.08 3.37 54.78 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
864 0.759
Panther River5-
23 50 Mole % 9.67 27.72 4.34 58.21 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1114 0.702
Panther River5-
23 50 Mole % 9.29 26.77 4.63 59.24 0.07 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1189 0.674
Panther River5-
23 100 Mole % 11.27 63.57 1.09 23.90 0.17 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
664 0.779
Panther River5-
23 100 Mole % 10.53 50.44 1.98 36.86 0.19 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
984 0.7
Panther River5-
23 100 Mole % 11.10 49.80 1.80 37.18 0.12 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1014 0.697
Panther River5-
23 100 Mole % 10.22 45.47 2.56 41.64 0.11 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1344 0.613
Panther River5-
23 100 Mole % 10.13 44.74 2.75 42.26 0.12 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1454 0.589
165
Table E.1 (Contd.)
Panther River5-
23 150 Mole % 7.96 73.85 0.75 17.27 0.17 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
714 0.758
Panther River5-
23 150 Mole % 8.74 69.95 0.89 20.27 0.15 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1064 0.635
Panther River5-
23 150 Mole % 9.14 67.16 1.04 22.53 0.13 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1374 0.543
Panther River5-
23 150 Mole % 9.12 66.84 1.06 22.85 0.13 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1414 0.518
Panther River5-
23 150 Mole % 9.14 65.87 1.08 23.73 0.18 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
1594 0.452
Panther River5-
23 175 Mole % 8.65 70.03 0.92 20.24 0.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
664 0.829
1014 0.726
1364 0.606
Jeff Lake Et.Al

Cross 11-25-25-
29 W4M
(Smoothed
Data) 100 Mole % 10.16 33.16 2.16 53.41 1.11 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
200 0.958
600 0.871
1000 0.786
1500 0.681
2000 0.611
2500 0.598
3000 0.619
3500 0.656
4000 0.7
166
Table E.1 (Contd.)
Jeff Lake Et.Al

Cross 11-25-25-
29 W4M
(Smoothed
Data) 176 Mole % 10.16 33.16 2.16 53.41 1.11 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
200 0.972
600 0.92
1000 0.873
1500 0.816
2000 0.77
2500 0.744
3000 0.74
3500 0.752
4000 0.776
Jeff Lake Et.Al

Cross 6-32-25-
28 W4M
(Smoothed
Data) 100 Mole % 9.23 26.59 2.64 59.57 1.97 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
200 0.956
600 0.876
1000 0.804
1500 0.719
2000 0.66
2500 0.645
3000 0.66
3500 0.695
4000 0.735
Jeff Lake Et.Al

Cross 6-32-25-
28 W4M
(Smoothed
Data) 176 Mole % 9.23 26.59 2.64 59.57 1.97 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
200 0.972
600 0.924
1000 0.883
1500 0.837
2000 0.801
2500 0.78
3000 0.78
3500 0.795
4000 0.816
167
Table E.1 (Contd.)
Jeff Lake Et.Al

Cross 11-3-25-
28 W4M
(Smoothed
Data) 100 Mole % 13.47 10.38 3.00 70.69 2.46 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
200 0.963
600 0.902
1000 0.851
1500 0.795
2000 0.755
2500 0.74
3000 0.749
3500 0.775
4000 0.809
Jeff Lake Et.Al

Cross 11-3-25-
28 W4M
(Smoothed
Data) 176 Mole % 13.47 10.38 3.00 70.69 2.46 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P (psia) Zexpt.
200 0.976
600 0.942
1000 0.915
1500 0.884
2000 0.86
2500 0.846
3000 0.849
3500 0.863
4000 0.884
Imperial FINA
Wildcat Hills 6-
35-27-6 W5M
(Smoothed
Data) 75 Mole % 6.60 3.95 0.68 83.74 2.86 0.75 0.25 0.23 0.06 0.08 0.08 0.72
P (psia) Zexpt.
513 0.913
1013 0.835 7+ Fraction Mole Wt. 139
1513 0.772 Sp. Gr. 0.7860
2013 0.736
2513 0.73
3013 0.748
3513 0.781
4013 0.825
168
Table E.1 (Contd.)
Imperial FINA
Wildcat Hills 6-
35-27-6 W5M
(Smoothed
Data) 99 Mole % 6.60 3.95 0.68 83.74 2.86 0.75 0.25 0.23 0.06 0.08 0.08 0.72
P (psia) Zexpt.
513 0.928
1513 0.808 Sp. Gr. 0.7860
2013 0.773
2513 0.762
3013 0.774
3513 0.801
4013 0.837
Imperial FINA
Wildcat Hills 6-
35-27-6 W5M
(Smoothed
Data) 132 Mole % 6.60 3.95 0.68 83.74 2.86 0.75 0.25 0.23 0.06 0.08 0.08 0.72
P (psia) Zexpt.
513 0.934
1513 0.845 Sp. Gr. 0.7860
2013 0.82
2513 0.812
3013 0.821
3513 0.842
4013 0.872
Imperial FINA
Wildcat Hills 6-
35-27-6 W5M
(Smoothed
Data) 189 Mole % 6.60 3.95 0.68 83.74 2.86 0.75 0.25 0.23 0.06 0.08 0.08 0.72
P (psia) Zexpt.
513 0.949
1513 0.889 Sp. Gr. 0.7860
2013 0.878
2513 0.874
3013 0.876
3513 0.89
4013 0.914
Imperial Mobil
Brazeau River
6-11
(Smoothed
Data) 210 Mole % 3.66 2.16 0.00 89.34 3.52 0.50 0.21 0.23 0.10 0.08 0.20 0.00
P (psia) Zexpt.
169
Table E.1 (Contd.)
813 0.948
1516 0.913 Sp. Gr. 0.7860
2085 0.904
2513 0.898
2828 0.9
3013 0.901
3429 0.906
3743 0.919
4013 0.935
170
APPENDIX F
PREDICTION OF Z-FACTOR FROM LLS EOS
Methane Z-Factor (LLS EOS)

1.088
1.033
0.978 400 Expt.

LLS 400 psia
1500 Expt.
Z-Factor
LLS 1500 psia

0.923
2000 Expt
LLS 2000 psia
3000 Expt
0.868
LLS 3000 psia
4000 Expt
LLS 4000 Psia
0.813
0.758
1.5 1.7 1.9 2.1 2.3 2.5 2.7
Reduced Temperature
Figure F.1: Z-factor for pure substances (Methane).
n-Decane Z- Factor (LLS EOS)

2.5
2.0
400 Expt.
LLS 400 psia
1.5
1500 Expt.
Z-Factor
LLS 1500 psia

2000 Expt
LLS 2000 psia
1.0
3000 Expt
LLS 3000 psia
4000 Expt
0.5 LLS 4000 Psia
0.0
0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85
Reduced Temperature
Figure F.2: Z-factor for pure substances (n-Decane).
171
Carbon Dioxide Z-Factor (LLS EOS)
1
0.8
400 Expt.
LLS 400 psia
1500 Expt.
Z-Factor
LLS 1500 psia

0.6
2000 Expt
LLS 2000 psia
3000 Expt
LLS 3000 psia
0.4 4000 Expt
LLS 4000 Psia
0.2
0.9 1.1 1.3 1.5 1.7
Reduced Temperature
Figure F.3: Z-factor for pure substances (Carbon Dioxide).
Hydrogen Sulfide Z-Factor (LLS EOS)

0.9375
0.75
400 Expt.
LLS 400 psia
0.5625
1500 Expt.
Z-Factor
LLS 1500 psia

2000 Expt
LLS 2000 psia
0.375
3000 Expt
LLS 3000 psia
4000 Expt
0.1875 LLS 4000 Psia
0
0.74 0.83 0.92 1.01 1.10 1.19
Reduced Temperature
Figure F.4: Z-factor for pure substances (Hydrogen Sulfide).
172
Nitrogen Z-Factor (LLS EOS)
1.145
1.11
400 Expt.
LLS 400 psia
1500 Expt.
Z-Factor
1.075
LLS 1500 psia
2000 Expt
LLS 2000 psia
1.04 3000 Expt
LLS 3000 psia
4000 Expt
LLS 4000 Psia
1.005
0.97
2.40 3.00 3.60 4.20 4.80
Reduced Temperature
Figure F.5: Z-factor for pure substances (Nitrogen).
173
APPENDIX G
FORTRAN PROGRAMS
! Z-FACTOR PROGRAM BY LLS EOS METHOD FOR MIXTURES

DIMENSION root(3),coeff(4),XC(20),P(30), ac(20), bc(20), zc(20), omgw(20)
Dimension PPR(40),TTR(20),PP(30),Zexpt(30,30),Corr(20),BWR(20),XCMP(20),BIJA(15,15),&
BIJB(15,15),BIJC(15,15),BIJD(15,15)
Dimension Alp(20), Bet(20), AF(20), wm(20), tc(20), pc(20),APDB(5),ZZV(5,30)
Data PPR/0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0&
,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0,7.5,8.0,8.5,9.0,9.5,10,15,20,25,30/
Data TTR/0.1,0.5,1,1.5,2,3,4,5/
OPEN (UNIT=5,FILE='Input_SageLaceyC1-C2_ZFactData.TXT',STATUS='old')
OPEN (UNIT=6,FILE='OUTPUT_SageLaceyC1-C2_ZFactData.TXT',STATUS='unknown')
WRITE (6,*) 'LLS-MIXTURE-Sage and LaceyC1-C2_ZFactData'

Read (5,*)NData
do 20 I = 1,2
Read (5,*)wm(I),zc(I),AF(I),omgw(I),pc(I),tc(I)
20 Continue
R = 10.73
! BIJA = Average Acentric Factor
! BIJB = Average Molecular Weight
! BIJC = Average of Acentric Factor X Molecular Weight
! BIJD = Average of Tc / Sqrt(Pc)
Do 100 K=1,NData
Read (5,*)Ncomp,TT,NDataP
Read (5,*) (XCMP(J),J=1,9)
Do 220 I=1,2
! Write (6,*)wm(I),zc(I),AF(I),omgw(I),pc(I),tc(I)
Call Para(AF(I),zc(I),wm(I),tc(I),pc(I),R,TT,Alp(I),Bet(I),ac(I),bc(I))
! write(6,*)I,TT,AF(I),zc(I),wm(I),tc(I),pc(I),Alp(I),Bet(I),ac(I),bc(I)
! write(6,*)I,TT,PP,Alp(I),Bet(I),ac(I),bc(I)
220 continue
! Computation of Binary Interaction Parameter
Call BinIJ(Ncomp,AF,wm,tc,pc, BIJA,BIJB,BIJC,BIJD)
!
If( K .GT. 1) GO TO 122
Do 121 I=1,Ncomp
Do 121 J=1,Ncomp
write(6,*) BIJA(I,J),BIJB(I,J),BIJC(I,J),BIJD(I,J)
121 Continue
122 Continue
Do 120 J=1,NDataP
Read (5,*)PP(J),(Zexpt(J,I),I=1,9)
! Write (6,*) TT,PP(J),(Zexpt(J,I),I=1,9)
120 Continue
Do 160 J=1,9
AAPD=0.0
IT=0
XC(1)=XCMP(J)
XC(2)=1.0-XC(1)
Write (6,125)
Write (6,*)' C1 Mole Fraction = ',XC(1),' C2 Mole Fraction = ',XC(2)
125 Format(/)
Do 145 IB=1,4
IT=0
AAPD=0.0
Do 140 I=1,NDataP
174
If(IB .EQ. 1)Call Mixrule(Ncomp, XC, ac, bc,tc,pc, Alp, Bet, AF, wm,BIJA, am, bm, Alpm, Betm,wmix,AFmix)
If(IB .EQ. 2)Call Mixrule(Ncomp, XC, ac, bc,tc,pc, Alp, Bet, AF, wm,BIJB, am, bm, Alpm, Betm,wmix,AFmix)
If(IB .EQ. 3)Call Mixrule(Ncomp, XC, ac, bc,tc,pc, Alp, Bet, AF, wm,BIJC, am, bm, Alpm, Betm,wmix,AFmix)
If(IB .EQ. 4)Call Mixrule(Ncomp, XC, ac, bc,tc,pc, Alp, Bet, AF, wm,BIJD, am, bm, Alpm, Betm,wmix,AFmix)
call Zfactr (Alpm, Betm, am, bm, PP(I), TT, R, ZV, ZL)
call TcPcMix(am,bm,Alpm,Betm,R,Tcm,Pcm)
DenV=PP(I)*wmix/(ZV*R*TT)
APD=((ZV-Zexpt(I,J))/Zexpt(I,J))*100.0
AAPD=AAPD+ABS(APD)
! write (6,*)
! write (6,15) TT,PP(I),ZV,ZL,Zexpt(I,J),APD
ZZV(IB,I)=ZV
15 Format(2F8.1,5F8.4)
140 Continue
DatP=NDataP
AAPD=AAPD/DatP
APDB(IB)=AAPD
! write(6,*)'End of Data = ',K
! write(6,*)'Average Absolute Percent Deviation = ',AAPD
145 Continue
Do 146 I=1,NDataP
write (6,15) TT,PP(I),(ZZV(N1,I),N1=1,4),Zexpt(I,J)
146 Continue
write(6,51)(APDB(N1),N1=1,4)
51 Format(16X,5F8.2)
write(6,25)
160 Continue
25 Format(/)
100 Continue
close(5)
close(6)
STOP
END
Subroutine Zfactr (Alp, Bet, AT, BC, P, T, R, ZV, ZL)
Dimension Coef(4),RT(3)
AA = AT*P/(R**2*T**2)
BB = BC*P/(R*T)
Coef(1) = 1.
Coef(2) = -(1.+(1-Alp)*BB)
Coef(3) = AA-(Alp*BB)-(Bet+Alp)*BB**2
Coef(4) = -(AA*BB-Bet*(BB**2+BB**3))
Call Cubic (MTYPE, Coef, RT)
! write(6,*) 'Root=',RT
Rmin = 1.E+10
Rmax = 1.E-10
Do 70 I=1,3
if (RT(I).LE. 0.0) Go to 70
if (RT(I).LT. BB) Go to 70
if (RT(I).GT. Rmax) Rmax = RT(I)
if (RT(I).LT. Rmin) Rmin = RT(I)
70 Continue
ZV=Rmax
ZL=Rmin
Return
End
Subroutine ZRedMix (Alp, Bet,AF,wm, Zc,Pr,tr, ZV, ZL)

w=AF
theta = 0.309833 + 1.763758*w + 0.720661*w*w - 1.363589*w**3 - 4.005783*w/(sqrt(wm))
tmp = tr ** (-theta/2.0)
omgW=0.361/(1.0+0.0274*w)
omga=(1.0+(omgW-1.0)*Zc)**3
omgb = omgW*Zc
175
Coef(1) = 1.0
Coef(2) = -(1.0/Zc+(1.0-Alp)*omgb*Pr/(Zc*tr))
Coef(3) = omga*Pr/(Zc**2*tr**(2+theta))-Alp*omgb*Pr/(Zc**2*tr)-(Alp+Bet)*(omgb*Pr/(Zc*tr))**2
Coef(4) = -(omga*omgb*Pr**2/(Zc**3*tr**(3+theta))-Bet*(1.0/Zc*(omgb*Pr/(Zc*tr))**2+(omgb*Pr/(Zc*tr))**3))
Rmin = 1.E+10
Rmax = 1.E-10
Do 70 I=1,3
70 Continue
ZV=Rmax*Zc
ZL=Rmin*Zc
Return
End
Subroutine Zcfactr (Alp, Bet, Zc, RT)

Coef(1) = Alp**3 + 6*Alp**2+ 12*Alp + 8.
Coef(2) = -(12*Alp**2+12 *Alp + 9*Bet- 9*Alp*Bet+ 3.)
Coef(3) = 6*Alp**2 + 3*Alp + 6*Bet - 6*Alp*Bet
Coef(4) = -(Alp**2+Bet-Alp*Bet)
Rmin = 1.E+10
Rmax = 1.E-10
Do 70 I=1,3
! if (RT(I).LT. BB) Go to 70
70 Continue
ZV=Rmax
ZL=Rmin
Zc = Rmax
Return
End
Subroutine Bcfact (Alp, Bet, Bc,RT)

Coef(1) = Alp**3 + 6*Alp**2+ 12*Alp + 8.
Coef(2) = -(3*Alp**2-15 *Alp+27*Bet-15.)
Coef(3) = 3*Alp+6.
Coef(4) = -1.
Rmin = 1.E+10
Rmax = 1.E-10
Do 70 I=1,3
70 Continue
ZV = Rmax
ZL = Rmin
Bc = Rmax
Return
End
Subroutine TcPcMix(am,bm,alpm,betm,R,Tcm,Pcm)
Dimension RTB(3), RTZ(3)
call Bcfact (alpm, betm, Bc,RTB)
call Zcfactr (alpm, betm, Zc, RTZ)
denom = 3*zc**2+(alpm+betm)*Bc**2+alpm*Bc
176
Pcm = (am*Bc**2)/(bm**2*denom)
Tcm = (am*Bc)/(bm*R*denom)
return
End
Subroutine Para(AF,zc,wm,tc,pc,R,TT,Alp,Bet,ac,bc)
omgww = 0.361/(1.0+0.0274*AF)
Alp = (1.0+omgww*zc-3.0*zc)/(omgww*zc)
Bet = (zc*zc*(omgww-1.0)**3.0+(2.0*zc*omgww**2)+&
omgww*(1.0-3.0*zc))/(omgww**2*zc)
omga = (1.0+(omgww-1.0)*zc)**3.0
omgb = omgww*zc
tr = TT/tc
theta = 0.309833 + 1.763758*AF + 0.720661*AF*AF - 1.363589*AF**3 - 4.005783*AF/sqrt(wm)
! theta = 0.19708+0.08627*AF+0.35714*AF**2+3.59015E-03*AF*wm
! tmp = tr**(-theta)
CB = omgb*R*tc/pc
CA = omga*R**2*tc**2/pc
ac = CA*tmp
bc = CB
Return
End
Subroutine Mixrule(Ncomp, x, ac, bc,tc,pc, Alp, Bet, AF, wm,BIN, Sumam,bmLLS, SumAlpm, SumBetm,wmmix,AFmix)
Dimension x(20), ac(20), bc(20), Alp(20), Bet(20), AF(20), wm(20),tc(20),pc(20),BIN(15,15)
Sumam = 0.0
SumbmLLS = 0.0
SumAlpm = 0.0
SumBetm = 0.0
wmmix = 0.0
AFmix = 0.0
Do 10 I = 1,Ncomp
Sumbm = Sumbm + x(I)*bc(I)
AFmix=AFmix+x(I)*sqrt(AF(I))
wmmix=wmmix+x(I)*sqrt(wm(I))
SumbmLLS = SumbmLLS + x(I)*bc(I)**(1.0/3.0)
Do 10 J = 1,Ncomp
Sumam = Sumam + x(I)*x(J)*sqrt(ac(I))*sqrt(ac(J))*BIN(I,J)
SumAlpm = SumAlpm + x(I)*x(J)*sqrt(Alp(I))*sqrt(Alp(J))*BIN(I,J)
SumBetm = SumBetm + x(I)*x(J)*sqrt(Bet(I))*sqrt(Bet(J))*BIN(I,J)
10 Continue
bmLLS = (SumbmLLS)**3.0
AFmix=AFmix**2
wmmix=wmmix**2
Return
End
Subroutine BinIJ(Ncomp,AF,wm,tc,pc, BIJA,BIJB,BIJC,BIJD)
Dimension AF(20),wm(20),tc(20),pc(20)
Dimension BIJA(15,15),BIJB(15,15),BIJC(15,15),BIJD(15,15)
Do 10 I = 1,Ncomp
Do 10 J = 1,Ncomp
AFI=AF(I)
AFJ=AF(J)
WMI=wm(I)
WMJ=wm(J)
AFWI=wm(I)*AF(I)
AFWJ=wm(J)*AF(J)
TPCI=tc(I)/sqrt(pc(I))
TPCJ=tc(J)/sqrt(pc(J))
!
If(AFI.LE.AFJ) BIJA(I,J) = (AFI/AFJ)**0.5
If(AFI.GT.AFJ) BIJA(I,J)= (AFJ/AFI)**0.5
!
177
If(WMI.LE.WMJ) BIJB(I,J) = (WMI/WMJ)**0.5
If(WMI.GT.WMJ) BIJB(I,J) = (WMJ/WMI)**0.5
!
If(AFWI.LE.AFWJ) BIJC(I,J) = (AFWI/AFWJ)**0.5
If(AFWI.GT.AFWJ) BIJC(I,J) = (AFWJ/AFWI)**0.5
!
If(TPCI.LE.TPCJ) BIJD(I,J) = (TPCI/TPCJ)**0.5
If(TPCI.GT.TPCJ) BIJD(I,J) = (TPCJ/TPCI)**0.5
10 Continue
Return
End
Subroutine Cubic(MTYPE,A,Z)
DIMENSION B(3), A(4), Z(3)
B(1)=A(2)/A(1)
B10V3=B(1)/3.0
B(2)=A(3)/A(1)
B(3)=A(4)/A(1)
ALF=B(2)-B(1)*B10V3
BBT=2.0*B10V3**3-B(2)*B10V3+B(3)
BETOV=BBT/2.0
ALFOV=ALF/3.0
CUAOV=ALFOV**3
SQBOV=BETOV**2
DEL=SQBOV+CUAOV
IF (DEL) 90,10,40
10 MTYPE = 0
! Three Equal Roots
GAM=SQRT(-ALFOV)
IF (BBT) 30,30,20
20 Z(1) = -2.0*GAM-B10V3
Z(2) = GAM-B10V3
Z(3) = Z(2)
GO TO 130
30 Z(1) = 2.0*GAM-B10V3
Z(2) = -GAM-B10V3
Z(3) = Z(2)
GO TO 130
40 MTYPE = 1
! One Real Root & 2 Imaginary Conjugate Roots
EPS=SQRT(DEL)
TAU=-BETOV
RCU=TAU+EPS
SCU=TAU-EPS
SIR=1.0
SIS=1.0
IF (RCU) 50,60,60
50 SIR=-1.0
60 IF (SCU) 70,80,80
70 SIS=-1.0
80 R=SIR*(SIR*RCU)**0.3333333333
S=SIS*(SIS*SCU)**0.3333333333
Z(1)=R+S-B10V3
Z(2)=-(R+S)/2.0-B10V3
Z(3)=0.86602540*(R-S)
GO TO 130
90 MTYPE = -1
! Three Dissimilar and Real Roots
QUOT=SQBOV/CUAOV
RCOT=SQRT(-QUOT)
IF (BBT) 110,100,100
100 PEI=(1.5707963+ATAN(RCOT/SQRT(1.0-RCOT**2)))/3.0
GO TO 120
110 PEI=ATAN(SQRT(1.0-RCOT**2)/RCOT)/3.0
120 FACT=2.0*SQRT(-ALFOV)
Z(1)=FACT*COS(PEI)-B10V3
178
PEI=PEI+2.0943951
PEI=PEI+2.0943951
130 CONTINUE
IF (MTYPE .EQ. 1) Z(2) = -99.99
IF (MTYPE .EQ. 1) Z(3) = -99.99
RETURN
END
! Z-FACTOR PROGRAM BY LLS EOS METHOD FOR MIXTURES

DIMENSION root(3),coeff(4),XC(20),P(20), ac(20), bc(20), zc(20), omgw(20)
Dimension PPR(40),TTR(20),Zexpt(20),BIJA(15,15),BIJB(15,15),BIJC(15,15),BIJD(15,15)
Dimension APDB(5,20),ZZV(5,30),DEV(5),TT(30),PP(30)
Dimension Alp(20), Bet(20), AF(20), wm(20), tc(20), pc(20)
Data PPR/0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0&
,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0,7.5,8.0,8.5,9.0,9.5,10,15,20,25,30/
Data TTR/0.1,0.5,1,1.5,2,3,4,5/
OPEN (UNIT=5,FILE='Input-Elsh_SPE74369.TXT',STATUS='old')
OPEN (UNIT=6,FILE='OUTPUT-LLS-Elsh-SPE74369.TXT',STATUS='unknown')
WRITE (6,*) 'LLS-Elsh-SPE74369'
Read (5,*)NData
Read (5,*)(Zexpt(I),I=1,NData)
R = 10.73
AAPD=0.0
! BIJA = Average Acentric Factor
! BIJB = Average Molecular Weight
! BIJC = Average of Acentric Factor X Molecular Weight
! BIJD = Average of Tc / Sqrt(Pc)
IT=1
Do 100 K=1,NData
Read (5,*)Ncomp,PP(K),TT(K)
! Write (6,*) Ncomp,TT(K),PP(K)
do 20 I = 1,Ncomp
Read (5,*)XC(I),wm(I),zc(I),AF(I),omgw(I),pc(I),tc(I)
! Write (6,*)XC(I),wm(I),zc(I),AF(I),omgw(I),pc(I),tc(I)
Call Para(AF(I),zc(I),wm(I),tc(I),pc(I),R,TT,Alp(I),Bet(I),ac(I),bc(I))
! write(6,*)I,TT(K),AF(I),zc(I),wm(I),tc(I),pc(I),Alp(I),Bet(I),ac(I),bc(I)
! write(6,*)I,TT(K),PP(K),Alp(I),Bet(I),ac(I),bc(I)
20 continue
! Computation of Binary Interaction Parameter
Call BinIJ(Ncomp,AF,wm,tc,pc, BIJA,BIJB,BIJC,BIJD)
!
If(IT .GT. 1) GO TO 122
Do 121 II=1,Ncomp
121 write(6,126) (BIJA(II,JJ),JJ=II,Ncomp)
write(6,127)
Do 123 II=1,Ncomp
123 write(6,126) (BIJB(II,JJ),JJ=II,Ncomp)
write(6,127)
Do 124 II=1,Ncomp
124 write(6,126) (BIJC(II,JJ),JJ=II,Ncomp)
write(6,127)
Do 125 II=1,Ncomp
125 write(6,126) (BIJD(II,JJ),JJ=II,Ncomp)
write(6,127)
126 Format(12F6.3)
127 Format(/)
IT=IT+1
122 Continue
! write(6,*)'End of Data = ',K
Do 145 IB=1,4
AAPD=0.0
179
If(IB .EQ. 1)Call Mixrule(Ncomp, XC, ac, bc,tc,pc, Alp, Bet, AF, wm,BIJA, am, bm, Alpm, Betm,wmix,AFmix)
If(IB .EQ. 2)Call Mixrule(Ncomp, XC, ac, bc,tc,pc, Alp, Bet, AF, wm,BIJB, am, bm, Alpm, Betm,wmix,AFmix)
If(IB .EQ. 3)Call Mixrule(Ncomp, XC, ac, bc,tc,pc, Alp, Bet, AF, wm,BIJC, am, bm, Alpm, Betm,wmix,AFmix)
If(IB .EQ. 4)Call Mixrule(Ncomp, XC, ac, bc,tc,pc, Alp, Bet, AF, wm,BIJD, am, bm, Alpm, Betm,wmix,AFmix)
! call Mixrule(Ncomp, XC, ac, bc,tc,pc,Alp, Bet, AF, wm, am, bm, Alpm, Betm,wmix,AFmix)
call Zfactr (Alpm, Betm, am, bm, PP(K), TT(K), R, ZV, ZL)
call TcPcMix(am,bm,Alpm,Betm,R,Tcm,Pcm)
! DenV=PP*wmix/(ZV*R*TT(K))
APD=((ZV-Zexpt(K))/Zexpt(K))*100.0
AAPD=AAPD+ABS(APD)
APDB(IB,K)=AAPD
! write (6,*);write (6,*)
! write (6,15) TT(K),PP(K),ZV,ZL,Zexpt(K),APD
ZZV(IB,K)=ZV
15 Format(2F8.1,5F8.4)
145 Continue
100 continue
Dat=NData
AAPD=AAPD/Dat
! write(6,*)'Average Absolute Percent Deviation = ',AAPD
Do 146 I=1,NData
write (6,15) TT(I),PP(I),(ZZV(N1,I),N1=1,4),Zexpt(I)
146 Continue
APDA2=0.0
APDB2=0.0
APDC2=0.0
APDD2=0.0
Do 147 I=1,NData
APDA2=APDA2+APDB(1,I)
APDB2=APDB2+APDB(2,I)
APDC2=APDC2+APDB(3,I)
APDD2=APDD2+APDB(4,I)
147 Continue
DEV(1)=APDA2/Dat
DEV(2)=APDB2/Dat
DEV(3)=APDC2/Dat
DEV(4)=APDD2/Dat
write(6,51)(DEV(N1),N1=1,4)
51 Format(16X,5F8.2)
close(5)
close(6)
STOP
END
Subroutine Zfactr (Alp, Bet, AT, BC, P, T, R, ZV, ZL)
AA = AT*P/(R**2*T**2)
BB = BC*P/(R*T)
Coef(1) = 1.
Coef(2) = -(1.+(1-Alp)*BB)
Coef(3) = AA-(Alp*BB)-(Bet+Alp)*BB**2
Coef(4) = -(AA*BB-Bet*(BB**2+BB**3))
Rmin = 1.E+10
Rmax = 1.E-10
Do 70 I=1,3
70 Continue
ZV=Rmax
ZL=Rmin
Return
End
180
Subroutine ZRedMix (Alp, Bet,AF,wm, Zc,Pr,tr, ZV, ZL)
w=AF
theta = 0.309833 + 1.763758*w + 0.720661*w*w - 1.363589*w**3 - 4.005783*w/(sqrt(wm))
omgW=0.361/(1.0+0.0274*w)
omga=(1.0+(omgW-1.0)*Zc)**3
omgb = omgW*Zc
Coef(1) = 1.0
Coef(2) = -(1.0/Zc+(1.0-Alp)*omgb*Pr/(Zc*tr))
Coef(3) = omga*Pr/(Zc**2*tr**(2+theta))-Alp*omgb*Pr/(Zc**2*tr)-(Alp+Bet)*(omgb*Pr/(Zc*tr))**2
Coef(4) = -(omga*omgb*Pr**2/(Zc**3*tr**(3+theta))-Bet*(1.0/Zc*(omgb*Pr/(Zc*tr))**2+(omgb*Pr/(Zc*tr))**3))
Rmin = 1.E+10
Rmax = 1.E-10
Do 70 I=1,3
70 Continue
ZV=Rmax*Zc
ZL=Rmin*Zc
Return
End
Subroutine Zcfactr (Alp, Bet, Zc, RT)

Coef(1) = Alp**3 + 6*Alp**2+ 12*Alp + 8.
Coef(2) = -(12*Alp**2+12 *Alp + 9*Bet- 9*Alp*Bet+ 3.)
Coef(3) = 6*Alp**2 + 3*Alp + 6*Bet - 6*Alp*Bet
Coef(4) = -(Alp**2+Bet-Alp*Bet)
Rmin = 1.E+10
Rmax = 1.E-10
Do 70 I=1,3
70 Continue
ZV=Rmax
ZL=Rmin
Zc = Rmax
Return
End
Subroutine Bcfact (Alp, Bet, Bc,RT)

Coef(1) = Alp**3 + 6*Alp**2+ 12*Alp + 8.
Coef(2) = -(3*Alp**2-15 *Alp+27*Bet-15.)
Coef(3) = 3*Alp+6.
Coef(4) = -1.
Rmin = 1.E+10
Rmax = 1.E-10
Do 70 I=1,3
70 Continue
ZV = Rmax
ZL = Rmin
Bc = Rmax
181
Return
End
Subroutine TcPcMix(am,bm,alpm,betm,R,Tcm,Pcm)
Dimension RTB(3), RTZ(3)
call Bcfact (alpm, betm, Bc,RTB)
call Zcfactr (alpm, betm, Zc, RTZ)
denom = 3*zc**2+(alpm+betm)*Bc**2+alpm*Bc
Pcm = (am*Bc**2)/(bm**2*denom)
Tcm = (am*Bc)/(bm*R*denom)
return
End
Subroutine Para(AF,zc,wm,tc,pc,R,TT,Alp,Bet,ac,bc)
omgww = 0.361/(1.0+0.0274*AF)
Alp = (1.0+omgww*zc-3.0*zc)/(omgww*zc)
Bet = (zc*zc*(omgww-1.0)**3.0+(2.0*zc*omgww**2)+&
omgww*(1.0-3.0*zc))/(omgww**2*zc)
omga = (1.0+(omgww-1.0)*zc)**3.0
omgb = omgww*zc
tr = TT/tc
theta = 0.309833 + 1.763758*AF + 0.720661*AF*AF - 1.363589*AF**3 - 4.005783*AF/sqrt(wm)
! theta = 0.19708+0.08627*AF+0.35714*AF**2+3.59015E-03*AF*wm
! tmp = tr**(-theta)
CB = omgb*R*tc/pc
CA = omga*R**2*tc**2/pc
ac = CA*tmp
bc = CB
Return
End
Subroutine Mixrule(Ncomp, x, ac, bc,tc,pc, Alp, Bet, AF, wm,BIN, Sumam,bmLLS, SumAlpm, SumBetm,wmmix,AFmix)
Dimension x(20), ac(20), bc(20), Alp(20), Bet(20), AF(20), wm(20),&
tc(20),pc(20),BIN(15,15)
Sumam = 0.0
SumbmLLS = 0.0
SumAlpm = 0.0
SumBetm = 0.0
wmmix = 0.0
AFmix = 0.0
Do 10 I = 1,Ncomp
Sumbm = Sumbm + x(I)*bc(I)
AFmix=AFmix+x(I)*sqrt(AF(I))
wmmix=wmmix+x(I)*sqrt(wm(I))
SumbmLLS = SumbmLLS + x(I)*bc(I)**(1.0/3.0)
Do 10 J = 1,Ncomp
Sumam = Sumam + x(I)*x(J)*sqrt(ac(I))*sqrt(ac(J))*BIN(I,J)
SumAlpm = SumAlpm + x(I)*x(J)*sqrt(Alp(I))*sqrt(Alp(J))*BIN(I,J)
SumBetm = SumBetm + x(I)*x(J)*sqrt(Bet(I))*sqrt(Bet(J))*BIN(I,J)
10 Continue
bmLLS = (SumbmLLS)**3.0
AFmix=AFmix**2
wmmix=wmmix**2
Return
End
Subroutine BinIJ(Ncomp,AF,wm,tc,pc, BIJA,BIJB,BIJC,BIJD)
Dimension AF(20),wm(20),tc(20),pc(20)
Dimension BIJA(15,15),BIJB(15,15),BIJC(15,15),BIJD(15,15)
Do 10 I = 1,Ncomp
Do 10 J = 1,Ncomp
AFI=AF(I)
AFJ=AF(J)
WMI=wm(I)
182
WMJ=wm(J)
AFWI=wm(I)*AF(I)
AFWJ=wm(J)*AF(J)
TPCI=tc(I)/sqrt(pc(I))
TPCJ=tc(J)/sqrt(pc(J))
!
If(AFI.LE.AFJ) BIJA(I,J) = (AFI/AFJ)**0.5
If(AFI.GT.AFJ) BIJA(I,J)= (AFJ/AFI)**0.5
!
If(WMI.LE.WMJ) BIJB(I,J) = (WMI/WMJ)**0.5
If(WMI.GT.WMJ) BIJB(I,J) = (WMJ/WMI)**0.5
!
If(AFWI.LE.AFWJ) BIJC(I,J) = (AFWI/AFWJ)**0.5
If(AFWI.GT.AFWJ) BIJC(I,J) = (AFWJ/AFWI)**0.5
!
If(TPCI.LE.TPCJ) BIJD(I,J) = (TPCI/TPCJ)**0.5
If(TPCI.GT.TPCJ) BIJD(I,J) = (TPCJ/TPCI)**0.5
10 Continue
Return
End
Subroutine Cubic(MTYPE,A,Z)
DIMENSION B(3), A(4), Z(3)
B(1)=A(2)/A(1)
B10V3=B(1)/3.0
B(2)=A(3)/A(1)
B(3)=A(4)/A(1)
ALF=B(2)-B(1)*B10V3
BBT=2.0*B10V3**3-B(2)*B10V3+B(3)
BETOV=BBT/2.0
ALFOV=ALF/3.0
CUAOV=ALFOV**3
SQBOV=BETOV**2
DEL=SQBOV+CUAOV
IF (DEL) 90,10,40
10 MTYPE = 0
! Three Equal Roots
GAM=SQRT(-ALFOV)
IF (BBT) 30,30,20
20 Z(1) = -2.0*GAM-B10V3
Z(2) = GAM-B10V3
Z(3) = Z(2)
GO TO 130
30 Z(1) = 2.0*GAM-B10V3
Z(2) = -GAM-B10V3
Z(3) = Z(2)
GO TO 130
40 MTYPE = 1
! One Real Root & 2 Imaginary Conjugate Roots
EPS=SQRT(DEL)
TAU=-BETOV
RCU=TAU+EPS
SCU=TAU-EPS
SIR=1.0
SIS=1.0
IF (RCU) 50,60,60
50 SIR=-1.0
60 IF (SCU) 70,80,80
70 SIS=-1.0
80 R=SIR*(SIR*RCU)**0.3333333333
S=SIS*(SIS*SCU)**0.3333333333
Z(1)=R+S-B10V3
Z(2)=-(R+S)/2.0-B10V3
Z(3)=0.86602540*(R-S)
GO TO 130
90 MTYPE = -1
183
! Three Dissimilar and Real Roots
QUOT=SQBOV/CUAOV
RCOT=SQRT(-QUOT)
IF (BBT) 110,100,100
100 PEI=(1.5707963+ATAN(RCOT/SQRT(1.0-RCOT**2)))/3.0
GO TO 120
110 PEI=ATAN(SQRT(1.0-RCOT**2)/RCOT)/3.0
120 FACT=2.0*SQRT(-ALFOV)
PEI=PEI+2.0943951
PEI=PEI+2.0943951
130 CONTINUE
IF (MTYPE .EQ. 1) Z(2) = -99.99
IF (MTYPE .EQ. 1) Z(3) = -99.99
RETURN
END
184
PERMISSION TO COPY
In presenting this thesis in partial fulfillment of the requirements for a master’s
degree at Texas Tech University or Texas Tech University Health Sciences Center, I
agree that the Library and my major department shall make it freely available for
research purposes. Permission to copy this thesis for scholarly purposes may be granted
by the Director of the Library or my major professor. It is understood that any copying
or publication of this thesis for financial gain shall not be allowed without my further
written permission and that any user may be liable for copyright infringement.
Agree (Permission is granted.)
_______Neeraj Kumar_________ ____09-30-2005___

Student Signature Date
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COMPRESSIBILITY FACTORS FOR NATURAL AND SOUR

RESERVOIR GASES BY CORRELATIONS AND

CUBIC EQUATIONS OF STATE

NEERAJ KUMAR, B.Tech.

Submitted to the Graduate Faculty

2. COMPRESSIBILITY FACTOR PREDICTION TECHNIQUES 5

3. STANDING-KATZ Z-FACTOR CORRELATION 20

4. Z-FACTOR PREDICTIONS FROM CUBIC EQUATIONS OF STATE 53

5. CONCLUSIONS AND RECOMMENDATIONS 94

Compressibility factor (z-factor) values of natural gases are necessary in most

2.1 Heavy Fraction Property Correlations. 10

1.1 Critical compressibility factor for pure hydrocarbons (alkanes). 3

a Attraction Parameter in EOS

1.1 Background Information

1.2.1 Z-Factor for Sour and Acid Gases

1.2.2 Z-Factor for Geologic CO2 Storage

Figure 1.1: Critical compressibility factor for pure hydrocarbons (alkanes).

1.3 Significance of the Project

COMPRESSIBILITY FACTOR PREDICTION TECHNIQUES

2.1 Theoretical Analysis of Gas Law-Based Z-Factors

2.2 Experimental Method for Compressibility Factors

2.3 Empirical Correlations Methods

2.3.1 Standing-Katz Compressibility Factor Chart

2.3.2 Hall-Yarborough Z-Factor Correlation

ppc = pseudo-critical pressure, psia

p pc = corrected pseudo-critical pressure, psia

B = mole fraction of H2S in the gas mixture

2.3.4 Dranchuk-Abu-Kassem Z-Factor Correlation

with an average absolute error of 0.585 percent.

2.3.5 Beggs-Brill Equation for SK Z-Factor Chart

C = (0.132 − 0.32 log (Tpr ))

2.3.6 Amoco Company Equation for SK Z-Factor Chart

2.3.7 Gopal Best-Fit Equation for SK Z-Factor Chart

2.3.8 Shell Oil Company Equation for Z-Factor Chart

ZC = 0.6222 − 0.224 × Tpr

ZE = 0.32 × EXP (−19.53 × (Tpr − 1))

ZF = 0.122 × EXP ( −11.3 × (Tpr − 1))

Table 2.1: Heavy Fraction Property Correlations.

Tbp 108.701661 0.42244800 0.42682558 0.000000 0.000000

C 0.83282122 0.09255911 -0.0413045 0.12621158 0.000000

Pc 237031780 -0.028484 2.755309 -1.374444 -2.947221

Tc 6.206640 -0.059607 0.224357 0.968332 -0.802538

ω 1.5790E-13 -1.453063 -2.811708 4.883921 2.109476

ω 2.22065E-10 -0.45908 -2.25373 3.4452 0.000000

Figure 2.1: Z-Factor of Pure Substances at Reduced Conditions (TR=0.65).

Figure 2.2: Z-Factors of Pure Substances at Reduced Conditions (TR = 0.75).

Figure 2.3: Z- Factor of Pure Substances at Reduced Conditions (TR=0.85).

Figure 2.5: Z-Factor of Pure Substances at Reduced Conditions (TR=1.07).

Figure 2.6: Z-Factor of Pure Substances at Reduced Conditions (TR=1.13).

Figure 2.7: Z-Factor of Pure Substances at Reduced Conditions (TR=1.24).

Figure 2.10: Z-Factor of Pure Substances at Reduced Conditions (TR=2.03).

STANDING-KATZ Z-FACTOR CORRELATION

3.1 Standing-Katz Representation of Z-Factor Chart

3.2 Best-Fit Equations for SK Z-Factor Chart

Hall & Yarborough11 Best Fit Equation:

where ppr = pseudo-reduced pressure

C = (0.132 − 0.32 log(Tpr ))

Dranchuk-Abu-Kassem23 Best-Fit Equation:

A1 = 0.31506237 A2 = -1.0467099 A3 = -0.57832729 A4 = 0.53530771

0.2 ≤ Ppr ≤ 3.0 .

Shell Oil Company Best-Fit Equation:

ZA = −0.101 − 0.36 × TR + 1.3868 × (TR − 0.919)