Talal Hassoun Diss PDF

CLOSED-FORM VAN DER WAALS CRITICAL POINT
FOR PETROLEUM RESERVOIR FLUIDS
by
TALAL HUSSEIN HASSOUN, B.S., M.S.
A DISSERTATION
IN
PETROLEUM ENGINEERING
Submitted to the Graduate Faculty

of Texas Tech University in
Partial Fulfillment of
the Requirements for
the Degree of
DOCTOR OF PHILOSOPHY
Approved
Akanni S. Lawal
Chairperson of the Committee
Lloyd R. Heinze
James F. Lea
Accepted
John Borrelli
Dean of the Graduate School
May, 2005
ACKNOWLEDGEMENTS
I wish to express my sincere thanks for the advice, guidance, and encouragement
given by my supervisor, Dr. Akanni S. Lawal. I would also like to thank the members of
my committee, Dr. Lloyd R. Heinze, and Dr. James F. Lea for their time and efforts. A
special thanks is extended to Dr. U. Mann for his assistance and willingness to help.
Finally, I thank Mr. S. Andreas, Mr. N. Kumar, and Mr. Tarek Hassoun for their help and
discussion contributed to this dissertation. I would like to acknowledge the Petroleum
Engineering Department for providing the financial support during the course of my
doctoral studies.
This Dissertation is dedicated to my father, my mother, my wife, Majida, my
daughter Amani, and to my sons, Ashraf, Heitham, and Tarek for providing me with
inspiration and confidence.
ii
TABLE OF CONTENTS
ACKNOWLEDGEMENTS ii
ABSTRACT v
LIST OF TABLES vii
LIST OF FIGURES ix
NOMENCLATURE xi
CHAPTER
I. INTRODUCTION 1
1.1 Importance of Critical State 7
1.2 Approaches to Critical State Prediction 12
1.3 Retrograde Reservoir Fluids 14
1.4 Objectives of Work 16
II. CRITICAL PROPERTY CORRELATION METHODS 18
2.1 Criteria of the Critical State 19
2.2 Empirical Models 22
2.3 Corresponding States 25
2.4 Convergence Pressure 31
2.5 Equation of State Models 45
III. CLOSED-FORM VAN DER WAALS EXPRESSIONS 54
3.1 Van der Waals Equations of State Theory 54
3.2 Closed-Form Equations for Fluid Critical Point 61
iii
3.3 Closed-Form Critical Property Computation Methods 69
IV. CRITICAL PROPERTIES FOR RESERVOIR FLUIDS 74
4.1 Critical Pressure Data for Complex Hydrocarbon Mixtures 74
4.2 Calculation of Critical Properties
4.3 Results and Discussion 75
4.4 Comparison Between Calculated and Experimental Data 80
83
V. CONCLUSIONS AND RECOMMENDATIONS 86
5.1 Conclusions 86
5.2 Recommendations 88
REFERENCES 89
APPENDICES
A. ANALYTICAL SOLUTION FOR CUBIC EQUATIONS 99
B. VAN DER WAALS EXPRESSIONS FOR FLUID CRITICAL POINT 112
C. PREDICTION RESULTS OF CRITICAL PRESSURE, CRITICAL 130
TEMPERATURE, AND HEPTANE PLUS PROPERTIES
iv
ABSTRACT
The prediction of critical points is of great practical importance because the
classification of petroleum reservoir fluids as a dry gas, gas condensate, volatile oil, and
crude oil depends largely on the knowledge of the critical properties of the reservoir
fluid. Also, the critical pressure and critical temperature of reservoir fluids are important
properties for describing the reservoir fluid phase behavior, predicting volumetric
properties of reservoir fluids and designing supercritical fluid processes.
Previous work for determining critical pressure, and critical temperature for
reservoir fluids include, empirical correlations, corresponding states method, and pseudo-
critical property methods. The generality of these previous correlations is limited to the
range of conditions and parameters used in the establishment of the correlations. Methods
based on the Gibbs criteria have also been used with Redlich-Kwong and Peng-Robinson
equations for prediction of critical properties. However, the Gibbs criteria have not been
applied to predicting critical properties of reservoir fluids.
A closed-form equation is developed for predicting the critical properties (Tc, Pc)
of complex reservoir fluids by using the Lawal-Lake-Silberberg (LLS) equation of state
with the criticality criteria established by Nobel Laureates van der Waals (VDW) in 1873.
By inverting the parameters of the LLS EOS in terms of the mixing parameters that are
based on the constituent substances and composition of the reservoir fluids, experimental
critical pressures and temperatures are predicted with interaction parameters expressed in
terms of molecular weight ratios of the binary constituent of reservoir fluids.
v
The prediction results of critical pressures and temperatures based on the VDW
criticality criteria show that experimental data consisting of 85 reservoir fluid mixtures
are within average absolute percent deviation of 3% to 5% of the measured critical
pressures and temperatures. In contrast to the previous work, this research project
provides an accurate method for computing the critical properties of reservoir fluids and
it is easy to use because the parameters of the criticality equation are readily available.
This project is useful for unifying near-critical flash routine with phase equilibria of the
compositional reservoir models. The project is also very attractive for establishing
reservoir models that are based on the critical composition convergence pressure concept.
vi
LIST OF TABLES
2.1 Modification to the Attractive Term of van der Waals Equation of State ................52
2.2 Modification to the Repulsive Term of van der Waals Equation of State ................53
3.1 Parameter of Selected Equations of State ..................................................................62
3.2 Relationship of EOS Constants to Critical Parameters..............................................64
4.1 Sample of Experimental Data Used in Calculations of Mixture 1.............................76
4.2 Calculated Critical Data of Heptane-plus Fraction Correlation.................................77
4.3 Calculated Critical Data of Heptanes-Plus Fraction for Data Set 1...........................78
4.4 Calculated Results for Pure Component parameters .................................................78
4.5 Calculated Results for Mixtures Parameters..............................................................79
4.6 Predicted Critical Pressure, Pc, Critical Temperature, Tc for Mixtures .....................81
C.1 Critical Pressure Prediction for Complex Mixtures………………………………130
C.2 Critical Pressure Prediction for Complex Mixtures ……………………………...131
C.3 Critical Pressure Prediction for Complex Mixtures...….…………………………132
C.4 Critical Pressure Prediction for Complex Mixtures...… …………………………133
C.5 Critical Pressure Prediction for Complex Mixtures……………………………....134
C.6 Critical Pressure Prediction for ComplexMixture………………………………...135
C.7 Critical Pressure Prediction for Complex Mixtures ……………………………...136
C.8 Critical Pressure Prediction for Complex Mixtures ……………………………137
C.9 Critical Pressure Prediction for Complex Mixtures ……………………………138
C.10 Critical Temperature Prediction for Complex Mixtures ……………………….139
vii
C.11 Critical Temperature Prediction for Mixtures ………………………………….140
C.12 Critical Temperature Prediction for Complex Mixtures………………………..141
C.13 Critical Temperature Prediction for Complex Mixtures…………………….….142
C.19 Critical Pressure, Temperature, and Properties Prediction

for Heptane Plus....….….….….….….….….….….….….….….….….….….….148

for Heptane Plus……………………………………………………………. ….149

for Heptane Plus…………………………………………………………...……150

for Heptane Plus…………………………………………………...……….. ….151

for Heptane Plus …………………………………………………………….….152

for Heptane Plus …………………………………………………………….….153
C.25 Critical Pressure, Temperature, and properties Prediction

for Heptane Plus……………………………………………………………. ….154

for Heptane Plus……………………………………………………………. ….155

for Heptane Plus……………………………………………………………. ….156
viii
LIST OF FIGURES
1.1 Pressure-Temperature Phase Diagram of Petroleum Reservoir Fluids……………5
1.2 Pressure-Volume Diagram of Pure Components………………………………... 8
1.3 Pressure-Volume Diagram of Mixtures………………………………………….10
1.4 Specific Weight of Liquid and Gas for Propane in the Critical Region………....12
1.5 Pressure-Temperature Diagram of Retrograde Gas Condensate………………...14
2.1 Pressure-Volume Plot for a Single-Component System…………………………19
2.2 Critical Point Representation in a Multi-Component System……………………22
2.3 Compressibility Factors of Methane, Ethane, and Propane as a Function of

Reduced Pressure………………………………………………………………...27
2.4 A Deviation Chart for Hydrocarbon Gases…………………………………… 28
2.5 Approximate Temperature of the Reduced Vapor Pressure…………………… 30
2.6 Equilibrium Ration for a Low-Shrinkage Oil……………………………………33
2.7 Equilibrium Ratio for a Condensate Fluid……………………………………….34
2.8 Illustration of Quasi-Convergence Pressure Concept……………………………38
2.9 Comparison of Equilibrium Ratios at 100°F for 1000 and 5000 psi
Convergence Pressure……………………………………………………………40
2.10 Equilibrium Ratios of Heptanes-plus Fraction…………………………………. 42
2.11 K vs Pressure with C10+ Curve Required to Match Check Point Data…………...43
2.12 K vs Pressure with Curve Showing Effect of Choosing a Convergence

Too High or Too Low for Condensate Depletion………………………………..44
3.1 Pressure-Volume Diagram for Pure Component………………………………. 58
3.2 Algorithm for Computation of Critical Parameters…………………………….. 73
ix
4.1 Predicted Critical Pressure of Complex Mixtures………………………….……82
4.2 Predicted Critical Temperature of Complex Mixtures…………………………...83
C.1 Critical Pressure Prediction for Complex Mixtures

(All Data)…………………………………………………….…………………157
C.2 Critical Pressure Prediction for Complex Mixtures

(Mixture 145 – 1)………………………………………………….....…………158
C.3 Critical Pressure Prediction for Complex Mixture

(Mixture 145 – 10)…………………………………………………… ……… 159

(Mixture 4 –6)…………………………………………………… ……………160

(Mixture75 – 6)…………………………………………………… …………..161

(Mixture141 – 7)…………………………………………………… ……….…162

(Mixture 141 – 16)……………………………………………………………...163

(Mixture 141 – 25)…………………………………………………… ………. 164

(Mixture 58 – 1) ………………………………………………………………..165

(Mixture 47 - 1)…...……………………………………………………………166
C.11 Critical Temperature Prediction for Complex Mixture

(All Data)……………………………………………………………………….167

(Mixture 145 –1)..………………………………………………………………168

(Mixture 145 –10)………………………………………………………………169
x
(Mixture 4 – 6).. …….………………………………………………………….170

(Mixture 75 - 6).. ……………………………………………………………….171

(Mixture 141 – 7).. ….………………………………………………………….172

(Mixture 141 - 25)………………………………………………………………173

(Mixture 58 - 1) ………………………………………………………………...174

(Mixture 47 –1) …….…………………………………………………………..175
xi
NOMENCLATURE
Symbol Definition
a Attraction Parameter Term of EOS
⎛ aP ⎞
A Dimensionless Constant ⎜ 2 2 ⎟
⎝R T ⎠
AD Absolute Deviation
API Oil Gravity
b van der Waals co-volume
⎛ bP ⎞
B Dimensionless Constant ⎜ ⎟
⎝ RT ⎠
C Characterization Factor
K Watson Characterization Factor
MW Molecular Weight
P Pressure
Pc Critical Pressure
R Gas Constant
Sg Specific Gravity
T Absolute Temperature
Tc Critical Temperature
Tbp Boiling Temperature
V Molar Volume
xii
x Mole Fraction
Z Compressibility Factor
Zc Critical Compressibility Factor
Greek Letter
α Parameter of LLS EOS
αij Binary Interaction
β Parameter of LLS EOS
βij Beta Binary Interaction
Ω Dimensionless Parameter
ω Acentric Factor
Subscripts
c Critical Property
m Mixture Identification
r Reduced State
VDW van der Waals Symbol
ij Component Identification
xiii
CHAPTER I
INTRODUCTION
Petroleum reservoir fluids contain a variety of substances of diverse chemical
nature that include hydrocarbons and non-hydrocarbons. Hydrocarbons (carbon-
hydrogen molecules) range from methane to asphalt. Non-hydrocarbons include
substances such as nitrogen, carbon dioxide, and sulfur compounds. The chemistry of
hydrocarbon reservoir fluids is very complex. However, the mixtures of these complex
hydrocarbons may be in gaseous or liquid state at the pressures and temperatures often
encountered in petroleum reservoirs.
In spite of the complexity of hydrocarbon fluids found in reservoir rocks, simple
cubic equations of state have shown surprising performance in the phase behavior
calculations for both the vapor-liquid and vapor-liquid-liquid equilibria of these reservoir
fluids.
Knowledge of the phase equilibria of two-phase system is very important in the
design of a separation process and petroleum reservoir studies. Our interests are
properties of the state at which two phases of vapor and liquid become indistinguishable.
This state is termed critical at which the intensive properties of the liquid and vapor
phases become identical. Hence, mixtures consist of two phases of identical composition
are called critical mixtures. Predicting critical properties such as critical pressure, Pc ,
critical temperature, Tc , and critical volume, Vc of the composition of a system in which
two phases become indistinguishable is very difficult and costly to determine
1
experimentally. Also, it is particularly difficult to determine the critical state
experimentally for multi-component mixtures.
Many methods have been reported for predicting critical properties of fluid
mixtures. These methods have ranged from empirical correlations, 29 98,111,122 , 31

to rigorous
thermodynamic conditions. Currently, there are three fundamental approaches, namely,
van der Waals criterion, Gibbs free energy, and the Wilson renormalization-group (RG)
theory. The Gibbs, 36 Wilson, 1120 and Jiang & Prausnitz 46

approaches were highly
considered and gained the attention of researchers in the field but their techniques have
46 ,100
failed, in determining the critical points of reservoir fluids that contain heptane-plus
(C7+) fractions because their method not based on ideal gas law. The van der Waals
approach proved to be practical in resolving critical states in binary systems 114,115,116,117
and therefore can be applicable for predicting the critical properties of multi-component
systems and the more complex reservoir fluids.
In order to predict adequately the critical properties ( Pc ,Tc ,Vc ) of complex
reservoir fluids, a background in phase behavior is needed to understand numerous
surface and subsurface aspects of petroleum engineering. A knowledge of reservoir fluid
properties and phase behavior is necessary to calculate fluid in place, fluid recovery by
primary depletion, and fluid recovery by enhanced oil recovery (EOR) techniques such as
gas cycling, hydrocarbon solvent injection, and carbon dioxide (CO2) displacement. An
example is given for clarification is that, many reservoirs have problems need
compositional treatment to increase accuracy and obtain more realistic description of
their fluids. This compositional treatment is of two types: depletion and/or cycling of
2
volatile oil and gas condensate and the other is miscible flooding with Multi-contact
miscibility (MCM). The difference between these two types of treatment is that the
depletion of volatile oil and gas condensate involves the removal of composition from the
critical region, while the second type requires calculation of phase composition and
properties converging at the critical point. The compositional model is capable of solving
the problem of miscibility where the original reservoir fluid and injected fluid are
miscible on first contact. There is difficulty in modeling the MCM process in achieving
stable convergence of gas and oil phase compositions, densities, and viscosities near the
critical point. The use of an equation of state in the MCM process, the vapor liquid
equilibrium ratios (K-values), and phase densities can be calculated near the critical
point. Therefore, in light of the advantages of van der Waals equations of state in solving
reservoir problems and the fact that a priori knowledge of the location of mixtures critical
points is required for volatile oil and gas condensate, the van der Waals criticality
conditions is applied as a tool to develop a closed-form solution of equation of state for
the critical points of fluid mixtures.
The prediction of critical properties of petroleum reservoir fluids is an important
factor in understanding the overall phase behavior of EOR miscibility fluid injection
projects. 10 In many chemical and petroleum processes, the knowledge of the critical
behavior of hydrocarbon mixtures is useful in settling the operating ranges in the process
equipment. Furthermore, in compositional reservoir simulation, the appearance and
disappearance of phases (single phase or two-phases) in the reservoir grid block is
important. The critical state is required in K- values correlations that use the
3
convergence pressure concept, because the convergence pressure is the critical pressure
under certain specified conditions. 39,66,94 Several methods, such as that of Hadden and
Grayson, 39 for finding K-values depend on the use of convergence pressure as a
correlating parameter.
At the present time, the major area of research study in petroleum and chemical
industries is the high-pressure phase equilibria, phase density and composition of fluid
mixtures, and the effects of changes in pressure and temperature in which they exist. The
most practical tool used by scientists and researchers in high-pressure phase equilibria
studies is the cubic equation of state. This equation is an expression relates pressure,
temperature, and volume of the fluid (PVT). Many papers and books have been
published on the study of phase behavior of single, binary and ternary systems, as well as
for multi-component and complex reservoir fluids under a wide variety of conditions of
pressures and temperatures. Majority of these scientific publications deals with the
determination and prediction of fluid critical point.
The critical state of multi-component mixture is important from theoretical and
practical point of view, and an ability to predict this condition is highly desirable. Even
though the van der Waals criterion for critical state was enunciated by van der Waals 116 ,
no satisfactory analytical method for predicting the critical condition in multi-component
systems based on this criterion has ever been formulated. The object of the work
undertaken in this study was to develop a closed-form solution to the problem of
predicting the critical properties of defined multi-component mixtures from the van der
Waals criticality condition together with a four parameters Lawal-Lake-Silberberg (LLS)
4
cubic equation of state. The van der Waals on-fluid theory is employed in this project
and the application of mixing rules allows the pure component parameters of the LLS
equation of state to be extended to mixture parameters.
We can best illustrate what the effects various system compositions have on the
phase behavior of petroleum hydrocarbons by presenting schematically the phase
diagrams for particular systems. Figure 1.1 is a pressure-temperature diagram, which
shows the relative boundaries of the two phase-phase region for typical reservoir fluids.
These include a dry gas, a gas condensate, a volatile oil, and a crude oil.
Figure 1.1. Pressure-Temperature Phase-Diagram of Petroleum Reservoir Fluids. 7
Schematic phase diagrams for each of the four reservoirs fluid classifications are
shown in Figure 1.1, which relates the reservoir fluid state to the reservoir pressure and
temperature. The vertical dotted line on the Figure 1.1 represents pressure depletion in
5
the reservoir at a constant temperature. The area within the phase envelope for each type
of reservoir fluid represents the pressure and temperature conditions at which both liquid
and vapor phases can exist. Point C on each envelope represents the critical point,
where the properties of liquid and vapor become identical. The solid line to the left of the
critical point C , represents 100 percent liquid (the bubble-point line); the solid line to the
right of the critical point C , represents 100 percent vapor (the dew-point line).
As the fluid composition becomes richer in the high molecular weight
hydrocarbons, the phase envelope is changed such that the critical point shifts toward
higher temperatures and lower pressures. The location of the reservoir temperature and
pressure with respect to the critical temperature and pressure on the phase diagram for
any given fluid dictates the phase state of the fluid in the reservoir. Generally speaking,
the fluid above and to the left of the critical is considered liquid; fluid above and to the
right of the critical point is considered gas. Refer again to Figure 1.1, the gas reservoir
envelope lies completely to the left of the reservoir temperature line largely because the
main gas constituent, methane, has a low critical temperature (−116 o F ) . Therefore, only
one phase can exist at reservoir temperature regardless of pressure. Any liquid recovered
from a gas reservoir is the result of surface condensation after the gas has left the
reservoir.
Criticality is an important concept in phase behavior that is closely related to
equilibrium and stability concepts. In this introductory chapter, the importance of critical
state criteria, and the background and approach to critical state predictions are introduced.
6
The retrograde reservoir fluid phenomena, is demonstrated, and the objective of this work
is defined.
1.1 Importance of Critical State

The prediction of the critical properties of hydrocarbon mixtures is an important
aspect of the general problem of predicting the overall phase behavior of petroleum
reservoir fluids. The critical state is the unique condition about which the liquid and
vapor phases are defined, and hence has theoretical and practical significance. In
hydrocarbon processing and producing operations, a knowledge of the critical condition
is necessary because many of these operations take place under conditions which are at or
near the bubble-point or upper dew point regions and are frequently accompanied by
isobaric (constant pressure) or isothermal (constant temperature) retrograde phenomena.
Fluid property predictions and design calculations in this region are often the most
difficult one to make, and knowledge of the precise location of the critical point for the
reservoir under study is of the utmost help.
From a theoretical point of view, the changes of many of the thermodynamics and
transport properties take on a special significance as the critical state is approached. In an
empirical method the critical state has formed an integral part of many useful generalized
correlations such as those based on the theorem of corresponding states or the
convergence pressure concept in vapor-liquid equilibrium calculations.
In many ways the characteristics of the critical state that make it theoretically and
practically important are also the characteristics that make it one of the more difficult
conditions to measure experimentally. The very fact that density differences between
7
phases disappear, that the rate of volume change with respect to pressure approaches
infinity, or that infinitesimal temperature gradients can be responsible for a transition
from 100 percent liquid to 100 percent vapor all make the critical condition that one of
the more difficult to measure or observe accurately. For obvious economic reasons, it is
a condition that cannot be obtained by experiment in any special way for the many
systems for which it is required. Consequently, many attempts have been made to
develop methods for predicting the critical properties based on generalized empirical or
semi-empirical procedures. Consider the plot of pressure versus volume of a pure
component shown in Figure 1.2.
Figure 1.2. Pressure-Volume Phase Diagram of Pure Components. 32
8
Figure 1.2 illustrates the variation of volume with pressure and temperature
throughout the critical region. It is of interest to note that T1 < Tc ; Tc is the critical
temperature is tangent to the saturation line at the critical state. At point S , the liquid is
compressed (this state is referred to as under-saturated liquid because more gas is
dissolved in it). As the pressure is decreased, the volume increases. At point A, the
liquid is in the saturated and stable state. To the right of point A, as the pressure is
lowered, the component might follow one of two routs. It might follow the line AD , in
which case point D represents the saturated and stable vapor, or it might follow curve
AB , for which the fluid will be in a meta-stable condition. In this case, the limit of
⎛ ∂P ⎞
stability is determined by the condition that ⎜ ⎟ vanishes (i.e., point B ). Similarly,
⎝ ∂V ⎠ T1
at point R one can observe that as the pressure increases, condensation may not occur up
⎛ ∂P ⎞
to point C , where again ⎜ ⎟ will vanish. Curve DC represents the locus of meta-
⎝ ∂V ⎠ T1
stability and point C is the limit of meta-stability at T1 for the vapor. As the temperature
⎛ ∂V ⎞
is increased above that of the critical state there is a rapid increase in the slope ⎜ ⎟ of
⎝ ∂T ⎠ p
the isobars at the critical volume. Both the isobaric thermal expansion and the isothermal
compressibility are infinite at the critical state.
The pressure-volume diagram of mixture differs from that of pure component.
The pure component pressure-volume diagram can be seen in Figure 1.2, while the
pressure-volume diagram for mixtures is shown in Figure 1.3. The main differences
9
between Figure 1.2 and Figure 1.3 are: (1) V L and V G of Figure 1.3 do not represent the
equilibrium states and (2) the critical points have different features.
Figure 1.3. Pressure-Volume Diagram of Mixtures. 32
∂P ∂ 2 P
For a pure component, = = 0 , at the critical point. For a mixture, this
∂V ∂V 2
does not occur at the top of the two-phase envelope. The Z-factors in Figure1.2 of the
equilibrium gas and liquid phases always meet the condition Z L < Z G . However, for
mixtures, when gas and liquid phases are at equilibrium, Z L might be smaller or larger
than Z G . At equilibrium, the density of the liquid phase is higher than the density of the
gas phase, ρ L > ρ G . Then from
PM
ρ= (2.1)
ZRT
it follows that
10
M L MG
> G (2.2)
ZL Z
When Z-factors are less than one, then, Z L could be smaller or larger than Z G .
Variation in density of the liquid phase and gas phase at the critical region is
shown in Figure 1.4. It has been observed, experimentally, that there is a nearly linear
relationship between the average density of the coexisting phases and the vapor pressure
∂ρ avg
near to the critical state. It can be shown that will reach a constant value as the
∂P
critical state is approached. This relation of the average density of the liquid and gas
phases to the prevailing pressure and temperature has been called the “Law of Rectilinear
Diameters”. 101,102 This relation gives an acceptable basis for the experimental
determination of the critical volume of a pure component. It is necessary only to plot the
average specific weight of the coexisting phases as a function of pressure and to
extrapolate from the accurate experiment to the critical state. Such a plot for propane is
given in Figure 1.4. In this Figure 1.4, notice the slight curvature in the relation of the
average specific weight to pressure at the lower temperatures, but near the critical point
the relation becomes linear. In the light of this discussion it is seen that the critical point
is truly a state of the system.
11
Figure 1.4. Specific Weight of Liquid and Gas for Propane in the Critical Region. 102
1.2 Approaches to Critical State Prediction
Because of the difficulty of measuring the critical properties of hydrocarbon
mixtures experimentally, the ability to have reliable methods for correlating and
predicting these properties is highly desirable. A survey of the literature indicates many
correlations have been advanced for predicting the phase behavior, 77 predicting physical
properties, 69 , 49 developing equations of state, and designing supercritical fluid processes.
For many pure components, these critical properties have been experimentally
determined. 91 However, experimental determinations of the critical properties of
mixtures are impractical because of the limitations in terms of time and costs. Even
though experimental data for some mixtures are available, but with less coverage of
composition range of data points.
In addition to the direct measurements, critical properties of mixtures are usually
estimated utilizing various correlations methods, which have been reviewed in terms of
12
their estimation procedure and accuracy 108 . These correlation methods relied primarily
on many approaches, namely, graphical approach, 38 equation of state approach, 20,84, 79
empirical procedures involving the use of excess property approach, 54 the use of
conformal solution theory (corresponding states principle) approach 58 based on the
concept that all thermodynamic properties of mixtures can be evaluated from pure
component properties if the components conform to certain postulates of statistical
mechanics, and rigorous thermodynamic potential approach for the critical state, that is,
the second and third partial derivatives of the molar Gibbs free energy with respect to
composition at constant temperature and pressure must be equal to zero. Determination
of Tc , Pc , and Vc for the mixtures involves a simultaneous solution of an extended form
of derivatives and an equation of state such as reported by Spear et al. 107 There are two
setbacks in these approaches. First, most of these approaches are limited to estimating
critical properties of hydrocarbon mixtures. Even in the case of hydrocarbon mixtures,
most of the methods tend to yield higher order of errors when used to estimate the critical
properties of methane-containing mixtures. 107
In this work, a new concept for the development of a methodology for predicting
petroleum reservoir fluids critical properties for cubic equations of state consistent with
the criterion of van der Waals’ equation of state. The use of this concept is illustrated by
its application to the Lawal-Lake-Silberberg equation of state, and also the use of van der
Waals one-fluid theory and the application of mixing rules which allows the pure
component parameters of the LLS equation of state to be extended to mixtures
parameters.
13
1.3 Retrograde Reservoir Fluids
To illustrate retrograde reservoir fluid phenomena, Figure 1.5 shows the pressure-
temperature phase diagram for a mixture at fixed composition.
Figure 1.5. Pressure-Temperature Diagram of Retrograde Gas Condensation. 6
The solid thick line is the bubble- point curve (100 % liquid, 0 % vapor) and the thin line
is the dew-point curve (100 % vapor, 0 % liquid); they meet at critical point C where the
two phases become identical. The basic criterion for the critical point (point C ) is the
limiting condition where the system can exist in two phases. Near the critical point,
hydrocarbon mixtures exhibit a more complex behavior usually opposite to what would
be expected from observed behavior at low pressures. This reverse behavior comprises
retrograde phenomena. Retrograde phenomena always exist when the critical point of a
mixture is not at the highest pressure and temperature possible for the coexistence of two
14
phases. Also, near the critical point, the density-dependent properties change with small
changes in temperature and pressure.
More than a century ago Kuenen 62 , 61 first observed the isothermal (constant
temperature) retrograde condensation shown in the dashed ABDE line, and isobaric
vaporization, shown in line AGH were observed by Duhen (1896, 1901). The definitions
of these phenomena are:
1. Retrograde condensation occurs when a denser reservoir fluid phase is formed by
the isothermal decrease in pressure or the isobaric increase in temperature.
2. Retrograde vaporization occurs when a less dense of reservoir fluid phase is
formed by the isothermal increase in pressure or the isobaric decrease in
temperature.
The maximum pressure at point N is the cricondenbar, and the maximum
temperature at point M is called cricondentherm. 102 These points represent the upper
bounds where phase separation can take place.
Refer again to Figure 1.5, at point a , a single phase (vapor) exists. If we increase
the pressure on this vapor isothermally to point E , we encounter a dew-point state. As
pressure is increased beyond E , more and more of the vapor will condense until reach to
point D. Continue pressure increase from point D causes retrograde vaporization of
liquid that had previously been condensed. This process continues until point B , where
an upper dew point is reached. Continued pressure increase from point B to A which
compresses a single-phase fluid (vapor). If now reduce the temperature isobarically from
point A to point G , the volume of the single- phase fluid will contract. At point G a
15
bubble-point is encountered. With continued decrease in temperature isobarically, less
dense fluid (vapor) will continue to form until point H is reached. As conditions change
from point G to point H , retrograde vaporization occurs. Reduction of temperature
beyond H continue isobarically will cause a more dense phase to increase until the
bubble-point is reached. We could demonstrate retrograde condensation by reversing the
above-described procedure, that is, by proceeding from point N to point b. Quantitative
understanding of these phase-equilibrium phenomena is useful for design of production,
storage, and transportation of crude products.
Several observations can be made from Figure 1.5. The bubble-point line
coincides with the dew-point line at the critical point C. The shaded areas represent
regions of retrograde phenomena. The region defined by points CBMD in the region of
isothermal retrograde condensation.
1.4 Objectives of Work
The objective of this work is to develop a robust computational technique for
predicting the critical properties, critical pressure, Tc , critical pressure, Pc , and critical
volume, Vc for complex petroleum reservoir fluids. This objective consists of three
major elements:
1. Development of a comprehensive closed-form solution to the criticality criteria
established by Nobel Laureates van der Waals in 1873. Utility of the concept is
illustrated by its application to:
16
• Lawal-Lake-Silberberg (LLS) equation of state using van der Waals one-
fluid theory
2. Establish interaction parameters for hydrocarbon and non-hydrocarbon and for
hydrocarbon with pseudo-components..
3. Develop an algorithm for calculating these critical properties for reservoir fluids
(gases, gas condensate, volatile oils, and crude oils).
In order to achieve these objectives, this research work has been organized into five
chapters. Thus, after an overview of the critical property correlation methods and
illustrate the criteria of the critical state in Chapter 2, a review of the critical models,
corresponding state theory, convergence pressure concept, and the equations of state is
introduced. The van der Waals equation of state theory and the resulting derived
equations for the closed form-solution are presented in Chapter 3 with computational
procedure is described. Chapter 4 presents the results of calculations and analysis of the
predicted critical properties and compared with experimental calculations. Finally, in
Chapter 5 conclusions and recommendations were made on the equation of state
approach to critical points predictions, the general level of accuracy and applicability, and
the implications for future work in this area of phase behavior research.
17
CHAPTER II
CRITICAL PROPERTY CORRELATION METHODS
Several investigators have developed correlation techniques for predicting critical
properties of complex reservoir hydrocarbon mixtures. Many of these correlation
techniques were essentially both empirical and theoretical procedures in nature and were
aimed at predicting the critical properties of naturally hydrocarbon systems. The well
known of these was the method of Kurata and Katz 63 for the critical properties of volatile
hydrocarbon mixtures, and of Organic 80 for complex hydrocarbon systems. Later, Davis
et al., (1954) modified the original Kurata-Katz method to make it applicable to lighter
natural gas systems. All of these correlation methods make use of graphical correlations
with parameters such as pseudo critical temperature and pressure, molal average boiling
point, or weight average equivalent molecular weight.
In this chapter, a review of correlation methods for predicting critical properties
of complex petroleum reservoir fluids is undertaken to help understand their phase
behavior calculations. First, the criterion of the critical state is introduced, and the
empirical models of correlations are presented. If the critical state can be predicted for a
given mixture, the separation between the bubble-point and the dew point regions will be
defined, and physical properties of the mixture can be obtained by using the law of
corresponding states. Then the law of corresponding states and the convergence pressure
are presented in detail.
18
2.1 Criteria of the Critical State
At a critical point, the fluid does not exist in a particular state, either gas or liquid,
but has characteristics of both. Hence, it is called a supercritical fluid. To see at what
temperature, pressure, and volume, this supercritical behavior is observed, we use the fact
that at the critical point, the isotherm is both horizontal (zero slope) and has no curvature.
These two conditions are interpreted mathematically as follows:
∂P
=0 (2.1)
∂V
∂2P
=0 (2.2)
∂V 2
The criteria of criticality can be analyzed by two approaches: a simple approach
that relies on geometrical presentation, and an alternative approach more reliable for
multi-component and complex mixtures. Consider a p-v diagram for a two-phase critical
point of a single-component system shown in Figure 2.1.
Figure 2.1. Pressure-Volume Plot for a Single-component System. 32
In this pressure-volume phase diagram, the dashed curve is the spinodal curve
and the solid curve is the binodal curve. The p-v isotherms at four different temperatures
19
T1 , T2 , Tc , and T3 , are shown. Points B and C represents the limits of stability at
temperature T1 . Points B` and C` represent the limit of stability at temperature T2 . Based
on the criteria of stability, 32 the limits of stability at T1 and T2 are obtained from
⎛ ∂p ⎞ ⎛ ∂p ⎞ ⎛ ∂p ⎞
⎜ ⎟ = 0 and ⎜ ⎟ = 0 , respectively. Between points B and C, ⎜ ⎟ > 0 and
⎝ ∂v ⎠ T1 ⎝ ∂v ⎠ T2 ⎝ ∂v ⎠ T1
⎛ ∂p ⎞
between B` and C` ⎜ ⎟ > 0, and these are therefore the unstable segment of the
⎝ ∂v ⎠ T2
isotherms. Note that the changes in curvature between B and C indicates an inflection
⎛ ∂2 p ⎞
point where ⎜⎜ 2 ⎟⎟ = 0 exists between these two points. This inflection point is an
⎝ ∂v ⎠ T1
unstable. As the temperature approaches the critical point (i.e., Tc ), the limits of stability
and un-stability points coincide, and since the inflection point is now located on the
⎛ ∂2 p ⎞
bimodal curve, the inflection point ⎜⎜ 2 ⎟⎟ = 0 is a stable point. Points A, D and A`
⎝ ∂v ⎠ Tc
and D` represent equilibrium phases at T1 and T2 , respectively. Approaching toward the
critical point, the points A and A` and D and D` coincide also with the limit of stability.
At the critical point, the gas phase and liquid phase can be transformed into each other
without going through the two-phase region, and that the continuity of gas and liquid
state. The criteria of the critical state of a pure component are, therefore,
⎛ ∂p ⎞
⎜ ⎟ =0 (2.3)
⎝ ∂v ⎠ Tc
20
⎛ ∂2 p ⎞
⎜⎜ 2 ⎟⎟ = 0 (2.4)
⎝ ∂v ⎠ Tc
⎛ ∂3 p ⎞
⎜⎜ 3 ⎟⎟ < 0. (2.5)
⎝ ∂v ⎠ Tc
⎛ ∂3 p ⎞
Where ⎜⎜ 3 ⎟⎟ < 0 indicates that the critical point is neither a maximum nor a
⎝ ∂v ⎠ Tc
minimum.
In 1980, Heidmann and Khalil 43 proposed an alternative approach for the
calculation of critical point that is mathematically different from the expressions of the
Criticality conditions in Equation 2.6 32 , and Equation 2.7 32
(1) (1)
y 22 y 23 L y 2(1,c) +1
M M M M
λ ( c +1) = =0 (2.6)
y c(1, 2) y c(1,3) L y c(1,c) +1
y c(1+)1, 2 y c(1+)1,3 L y c(1+)1,c +1
and
(1) (1)
y 22 y 23 L y 2(1,c) +1
M M L M
=0 (2.7)
y c(1, 2) y c(1,3) (1)
L y c ,c +1
λ (2c +1) λ (3c +1) L λ (cc++11)
⎛ ∂C ⎞ ⎛ ∂C ⎞
(1)
where y 22 = ⎜⎜ 2 ⎟⎟ (1)
, y 23 = ⎜⎜ 2 ⎟⎟ , y (1) = A(T ,V , N , L , N c ) is the
⎝ ∂X 2 ⎠ c1 , x3L, xc + 2 ∂
⎝ 3 ⎠ c1 , x2 ,L, xc + 2
X
Helmholtz free energy, and λ (cc++11) = 0 , at the critical point but the concept is not different.
As we have already seen, the critical point is a stable point at the limit of stability. To
elaborate more on this concept, let us consider the pressure-volume diagram of multi-
component system of fixed composition sketched in Figure 2.2. The thick solid line on
21
the left represents the bubble-points and the thin line represents the dew points. The
bubble-points and dew points are stable equilibrium states; a perturbation in pressure,
thus, results in a stable state. Critical point CP is the point at which bubble-point and
dew point converge and being a stable state, it is at the limit of stability. These two
concepts of stable and limit of stability were used by Gibbs in 1876 to derive the
expressions for the critical point.
Figure 2.2. Critical Point Representation in a Multi-component System. 32
2.2 Empirical Models
Many correlations have been developed for predicting critical properties of pure
components and mixtures. These correlations have relied on three approaches: (1) an
empirical approaches involving the use of excess properties, (2) the use of conformal
solution theory based on the concept that all thermodynamic properties of mixtures can
be evaluated from component properties if the components conform to certain postulates
22
of statistical mechanics, (3) a rigorous thermodynamic condition based on the second and
third partial derivatives of all molar Gibbs free energy with respect to composition.
The empirical approach involves calculations of the following model:
n
G c = ∑ x i G ci + G corr (2.8)
i =1
where Gc is the critical property desired and G corr is a correction term which is called the
excess property of the mixture. Excess properties are usually estimated from empirical
relations. 122 Many correlations have been proposed based on Equation 2.6 to predict the
critical properties of mixtures. The critical temperature of defined mixtures predicted by
Li 71 , was simplified by Chueh-Prausnitz, 21 for all empirical approaches. All of these
correlations yielded results with large errors and the chemical nature and sizes of
components limit the use of these results. Li’s 71 correlation gave the most accurate
predictions with the method of Prausnitz gave satisfactory results. All other correlations
gave poor results for systems containing ethane.
Prausnitz’s 85 method for determining the pseudo-critical temperature can be
generalized for mixtures having any number of components. The generalized equation is
n n n
Tcm = ∑ θ i Tci + ∑∑θ iθ jτ ij (2.9)
i =1 i j
where
2
xV 3
θ i = i ci (2.10)
∑ x iVci
23
and τ ij for each interacting pair of molecules. 21 Equation 2.7 was tested by Prausnitz
with data set of six ternary system, two quaternary systems, and two quinary systems and
reported 0.4% deviation.
Li’s equation a pseudo-critical temperature for any mixture, has the following
form:
n
Tcm = ∑ φ i Tci (2.11)
i
where
x iVci
φi = n
(2.12)
∑xV
i
i ci
The critical state correlation models for mixtures are much more important than is
the case for pure components. A wide variety of empirical correlation models, usually
with an average boiling temperature and composition of the mixture as parameters, have
been proposed. These types of correlations are of two types: 1) correlation models
which apply to simple mixtures of known composition and 2) correlation models which
apply to complex petroleum hydrocarbon fractions. In general, the correlations for both
types of mixtures are limited to hydrocarbons and often only to aliphatic and simple
aromatic hydrocarbons.
For simple hydrocarbon mixtures, several empirical correlations for critical
temperature and pressure have been proposed. The correlations suggested by Pawlewski,
and Kay 53 is the most important from a historical point of view. More accurate
correlation models have been proposed by Joffe, 48 Grieves, 38 and Organick, 80 Etter and
24
Kay. 29 Edmister 27 summarized the critical point correlations available for hydrocarbon
mixtures up to 1949. The best of these correlations are accurate within 1% for the critical
temperature and 3-5% for the critical pressure.
Correlation models for predicting the critical point of complex petroleum
hydrocarbon fractions also have been proposed. Significant correlations have been
suggested by Smith, 105 Kurata-Katz, 63 Edmister, and Pollock. 27 Organick 80

also
proposed a correlation and introduced a comparison of his method with the Kurata-Katz.
Equations of state were involved in the critical state correlation in order to
integrate vapor-liquid equilibrium behavior with the critical point. The prediction of the
critical point on the basis of van der Waals critical condition and the use of a suitable
equation of state is considered the first step toward the work carried out in this
investigation.
2.3 Corresponding States
Van der Waals 116 in 1873 developed the theorem of corresponding states based
on experimental observation, which shows that compressibility factor Z for different
fluids exhibit similar behavior when correlated as a function of reduced temperature Tr
and reduced pressure Pr . By definition,
T
Tr = (2.13)
Tc
P
Pr = (2.14)
Pc
25
and
V
Vr = (2.15)
Vc
Where the subscript r represents the reduced state, and subscript c represents
critical state. These dimensionless reduced conditions of temperature, pressure, and
volume provide the basis for the simplest form of the theorem of corresponding states:
“All fluids, when compared at the same reduced temperature and reduced pressure, have
approximately the same compressibility-factor, and all deviate from ideal-gas behavior to
about the same degree.” 105 The term “reduced state” means that each reduced value of an
intensive property of a system may be defined as the ratio of the value of that property in
a given state to the value of that property at the critical state. The theorem of
corresponding states does not hold for big ranges of pressure for real gases, and at the
same time is not perfect. However, when applied to gases with similar chemical structure
(as paraffin hydrocarbons), it offers a correlation with close agreement (satisfactory for
engineering work) permits the use of reduced properties as the basis for correlating
experimentally compressibility factor. This is illustrated by the reduced PVT data on
methane, ethane, and propane shown in Figure 2.3. In Figure 2.3 is a plotted of values of
Z for methane, ethane, and propane as a function of reduced pressure for reduced
temperatures to show the degree of correlation.
26
Figure 2.3. Compressibility Factors of Methane, Ethane, and Propane as a Function of
Reduced Pressure and Reduced Temperature. 109
The theory of corresponding states was extended to cover mixtures of gases.
Kay invented the concept of pseudo-critical Temperature and pseudo-critical pressure for
real gases. These pseudo-critical properties are obtained by using the Amagat’s law of
partial volumes for mixtures to the critical properties of the composition of the mixture.
These quantities are defined as
n
T pc = ∑ y i Tci (2.16)
i =1
and
n
Ppc = ∑ y i Pci (2.17)
i =1
where Ppc is the pseudo-critical pressure, T pc is the pseudo-critical temperature, Tci and
Pci are the critical temperature and critical pressure respectively of ith component, y i
mole fraction of ith component in mixture, and n number of components. The physical
27
properties of gas mixtures are correlated with pseudo-critical pressure and pseudo-critical
temperature in the same way that properties for pure gases are correlated with reduced
pressure and reduced temperature. Thus, these pseudo-critical properties are defined as
follows:
P
Ppr = (2.18)
Ppc
T
T pr = (2.19)
T pc
Compressibility factors, experimentally obtained, for natural gas have been
correlated with pseudo-reduced pressure and temperature. 14,85 The petroleum industry has
universally adopted the correlations shown in Figures 2.4, to determine the
compressibility factor Z .
Figure 2.4. A Deviation-Chart for Hydrocarbon Gases. 109
28
Correlations of Z - factor based on the theory of corresponding states are called
two-parameter correlations, because of the use of two reducing parameters Tr and Pr .
These correlations are shown to be close for the simple fluids (argon, xenon), but
systematic deviations are observed for more complex fluids. A third corresponding-
states parameter concept characteristic of molecular structure (in addition to Tc and Pc ),
has been introduced by K. S. Pitzer 63 is the acentric factor ω .
The Pitzer acentric factor for a pure fluid is defined with reference to its vapor
pressure. Because the logarithm of the vapor pressure of pure fluid is linear in the
reciprocal of absolute temperature,
sat
d log p r
=m (2.20)
1
d( )
Tr
where pr is the reduced vapor pressure, Tr is the reduced temperature, and m is the
sat 1
slope of the plot of log Pr vs. .
Tr
It has been observed that if the two-parameters corresponding states were valid,
the slope m would be the same for all pure fluids. This is not true 63 ; because according
to Pitzer each fluid has its own characteristic value of m. Pitzer has noted that all vapor
sat 1
pressure data for simple fluids lie on the same line when plotted as log Pr vs. and
Tr
= −1.0 at Tr = 0.7. This is shown in Figure 2.5. Data

sat
the line passes through log Pr
for other fluids define other lines whose locations can be fixed in relation to the line for
the simple fluids (SF) by the difference:
29
( SF ) − log Pr
sat sat
log Pr (2.21)
The acentric factor is defined as the difference evaluated at Tr = 0.7 :
ω ≡ −1.0 − log( Pr sat ) T =0.7 r

(2.22)
Therefore, ω can be determined for any fluid from Tc , Pc and vapor pressure
measurement made at Tr = 0.7.
Figure 2.5. Approximate Temperature Dependence of the reduced Vapor Pressure. 105
30
2.4 Convergence Pressure
This section first discusses some fundamental thoughts on the equilibrium ratios
(K-values), and reviews the basic sources for obtaining these values. This followed by
providing a discussion about the convergence pressure (Hadden, 1953), 40 and remarks on
the interdependency of K-values of heavy (plus) fractions and convergence pressures.
In order to evaluate the equilibrium behavior of multi-component two-phase
systems and obtain an expression for K-values; Dalton’s and Raoult’s laws can be
combined. Dalton’s law is defined by the Equations 2.23, and 2.24
n
P = ∑ pi (2.23)
i =1
and
pi
yi = (2.24)
P
or
pi = y i P (2.25)
and Raoult’s equation is stated as “the partial pressure exerted by a constituent of liquid
phase is equal to the vapor pressure of that constituent times the mole fraction of that
constituent in the liquid phase. That is,
Pi = x i Pvi (2.26)
Where p i is the partial pressure of the ith component, x i is the mole fraction of the ith
component in liquid phase, y i is the mole fraction of ith component in vapor phase and
31
p vi is vapor pressure of ith component. By combining Equation 2.24 and Equation 2.26
we obtain:
py i = p i x i (2.27)
By definition,
yi
Ki = (2.28)
xi
Where K is defined as the distribution of a component, “i”, between vapor and liquid
phases is given by the equilibrium ratio, K, described by Equation 2.28.
The value of K i is dependent on the pressure, temperature, and composition of
the hydrocarbon system. Equilibrium ratios ( K values) for low-shrinkage oil and a
condensate at 200 o F are shown in Figures 2.6 6 and 2.7 6 as functions of pressure. The
equilibrium ratios ( K values) for both types of fluids are shown to converge to a point
value of 1. This point is called convergence pressure, defined on page 162 of the
NGSMA Data book. “Early high pressure experimental work revealed that if a
hydrocarbon system of fixed overall composition were held at constant temperature and
the pressure varied, the K - values of various components converged toward a common
value of unity at some high pressure. This pressure has been termed the convergence
pressure of the system “. If the temperature at which the K - values were presented is the
critical temperature of the hydrocarbon mixture, then the convergence pressure will be
the critical pressure. For all temperature other than the critical temperature, the
convergence of K - values is then an apparent convergence pressure. At a pressure less
than convergence pressure, the system will be at either dew point or bubble point, and
32
exists as a single-phase fluid at the conditions expressed by the point of apparent
convergence.
Figure 2.6. Equilibrium Ratio for Low-Shrinkage Oil. 6
33
Figure 2.7. Equilibrium Ratio for a condensate Fluid. 92
A widely accepted definition of convergence pressure by Hadden 39 in 1953 was
proposed. In fact, Hadden 39 defined the critical mixture, from which the convergence
pressure would be estimated, as that resulting from adding methane or nitrogen to the
equilibrium liquid. In such an addition always result in reaching the critical state, and
hence a convergence pressure is defined, and satisfies the phase rule requirement. If
these two lightest components methane (or nitrogen) were in every system of interest, this
definition of convergence pressure is adequate. But, for purposes of general correlation
of data, many of which are from binary or ternary that have neither methane nor nitrogen,
the adequately of Hadden’s definition is questionable.
34
Rowe, 93 in 1964 proposed a definition based on what he called critical
composition method. In this method, the convergence pressure is estimated from the
critical mixture, which would give the same equilibrium phases. That means the critical
mixture lies in the tie line. This definition is general and applicable to binaries or higher-
order systems without regard to which components may be present. Unfortunately, this
definition does not always define the convergence pressure. This limitation caused most
frequently at low pressure, where K - values are not sensitive to convergence pressure,
but can occur at high pressure as well Lawal, 1981 66 .
The critical mixture is determined by the intersection of the tie line with the locus
of critical compositions at the equilibrium temperature. Fair 31 has developed an equation
for the isothermal locus of critical composition in hydrocarbon systems that calculated
the critical composition. The general Fair’s equation is stated as
∑A z
i =1, j ≠1
i ci =1 (2.29)
Where Ai is the critical composition locus coefficient for component i , z ci is the mole
fraction of component in the critical mixture. In this notational form, j indicates the
component chosen as dependent; that is z c j is determined from z ci .
For an equilibrium state with liquid mole fractions x i and vapor mole fraction
y i , the interaction of the equations for the tie line (actually N = 1 component balance
equations) with the isothermal critical composition locus Equation 2.28 is represented by
z ci =
[
( x i − y i ) 1 − ∑ Ai y i ]+ y (2.30)
∑ A (x − yi )
i
i i
35
Where the summation is understood to be over all components except nitrogen. Equation
2.28 was used to calculate the critical mixture for all ternary, multi-component, and
complex mixture equilibrium states.
Fair, 30 presented correlations for binary data, which are considered more accurate
than the generalized locus functions. The critical compositions of the binaries were
calculated from the equilibrium temperature by the expression
m
z c L = θ + ∑ c iθ (θ i − 1) (2.31)
i =1
where z c L = mole fraction of light component
Tc H − T
θ= (2.32)
Tc H − Tc L
T = Equilibrium temperature
Tc H = Critical temperature of the heavy component
Tc L = Critical temperature of the light component
The convergence pressure characteristic of a particular equilibrium sate is
determined as the critical pressure of the critical mixture calculated either by Equation
2.26 or Equation 2.27. Methods of predicting critical pressures range from rigorous
thermodynamic to completely empirical, with methods having some degree of success.
The method we choose to present here is the one developed by Zais 122 because of its
general applicability and convenience of calculation. Zais’ equation is written in the
form
36
N N −1 N wi w j
Pcm = ∑ Pci w i + ∑ ∑
2
(2.33)
i =1 i =1 j = i +1 Aij + Bij ( w i − w j ) + c ij ( w i − w j ) 2
where
Pcm = Critical pressure for mixture
Pc i = Critical pressure of component i
w i = Weight fraction of component i
w j = Weight fraction of component j
Aij = Binary interaction coefficient
B ij = Binary interaction coefficient
C ij = binary interaction coefficient
After testing mole fraction, surface fraction, and volume fraction, Zais selected
weight fraction as the composition variable to use in Equation 2.31. To calculate
convergence pressure from Equation 2.31, it is necessary to convert the mole fractions
from Equation 2.27 or Equation 2.31to weight fraction.
By fitting Equation 2.31 to binary data, Zais was able to obtain values for the
coefficients Aij , B ij , and C ij for all hydrocarbon binary combinations from methane
through eicosane plus nitrogen and carbon dioxide. These coefficients and component
critical pressures for use in Equation 2.31 are tabulated. 122 Binary coefficients for binary
heavy fractions in complex mixtures are obtained by interpolation on a molecular weight
basis. Zais predicted the critical pressures of 298 ternary, multi-component, and complex
mixtures with an average absolute deviation of 5.2%.
37
In hydrocarbon systems, there is no critical pressure at temperatures below the
critical temperature of the lightest component. For this reason, it is impossible to derive a
convergence pressure as we described. Lawal, 66 in order to include such a data in the
new correlations he developed, a quasi-convergence pressure was defined which is
illustrated in Figure 2.8. The quasi- convergence pressure is read at the equilibrium
temperature from the binary critical locus reflected across an axis through the critical
temperature of the light component.
Figure 2.8. Illustration of Quasi-Convergence Pressure Concept. 66
38
In effect, for equilibrium at temperature T less than critical temperature of the
light component Tc L , the quasi-convergence pressure is defined as the critical pressure at
T p K , where
T pK − 2Tc L − T (2.34)
This definition of the quasi-convergence pressure is consistent with the
observation of Lenoir and White (1958) that quasi-convergence pressure should increase
with decreasing temperature. For systems higher than binaries, this definition of quasi-
convergence pressure is readily applied by determining the isothermal locus of critical
compositions at T p K rather than at equilibrium temperature T , according to Equation
2.32.
The fluid composition effects on the K - values as shown in Figure 2.9, 6 where
values for 1000 psia and 5000 psia convergence pressures are compared at 100 o F. The
differences in K values for the two convergence pressures shown at pressures below 100
psia are not significant for the lighter hydrocarbons. The equilibrium ratios for fluids
with convergence pressures of 4000 psia or greater, are the same to fluids with 1000 psia.
Therefore, it is apparent that at low pressures and temperatures the equilibrium ratios are
closely independent of composition.
39
Figure 2.9. Comparison of Equilibrium Ratios at 100 o F for 1000- and 5000-psia
convergence Pressure. 6
It is of practical value at this point to present brief remarks on the
interdependency of heavy (plus) fractions and convergence pressure concept. Because
the vapor-pressure curves and critical properties of hydrocarbon heavier than hexane are
fairly close together, it is possible to characterize the mixture by an average set of K -
values. Properties of heptanes plus fractions can be estimated from the properties of
heavier hydrocarbons such as decane. But, normally a more satisfactory procedure for
characterizing the heptanes plus is to use correlated experimental data heptanes plus
fraction of fluids with similar properties to those predicted. For this purpose equilibrium
ratios for the heptanes-plus fraction reported by Katz and Hachmuth, 50 and Roland,
40
Smith, and Kaveller, 6 are plotted in Figure 2.10. 6 The data of Katz are preferred for crude
oil system, and the data of Roland et al. are preferred for condensate fluids.
Figure 2.10. Equilibrium Ratios of Heptanes-Plus Fraction.6
The heavy (plus) fraction controls the behavior of the system as liquid (mostly the
plus-fraction) begins to drop out at the dew point. If a given set of K - values with
convergence pressure close enough to the correct convergence pressure is used methane
through decane, the entire adjustment in the – values system can be made by adjusting the
K - value for the plus- fraction only. Then, it is easy to determine whether or not the K -
value system chosen for methane through decane is near enough to the correct
convergence pressure set by inspecting the decane K - values curve that was required to
match check-point data. If the selected convergence pressure is too low, the C10+ K -
41
curve required to match checkpoint data will fall below the given published decane K -
curve. This shown in Figure 2.11 30 by the curve marked “ Pk too low”. If the
convergence pressure is too high (i.e., too close to the dew point pressure) the determined
C10+ K - values curve will have the correct shape but will fall above the given decane
curve. This shown in the Figure 2.12 30 by the curve marked “ Pk too high”. A set of K
- values for the correct convergence pressure will result in the C10+ K - values curve as
shown in Figure 2.11. Typically, the C 10 + K - value will, to some extent, cut across the
constant temperature lines on the given Natural Gasoline Supply Men’s Association
(NGSMA) decane curve. This phenomena caused by the fact that the plus-fraction that
first drop at the dew point is generally less volatile than the plus-fraction that drops out as
pressure declines.
42
Figure 2.11. K vs Pressure with C10+ Curve Required to Match Check-Point Data.
43
Figure 2.12. K vs Pressure with Curve Showing Effect of Choosing a Convergence
Too High or Too Low for Condensate Depletion. 30
44
2.5 Equation of State Models
An equation of state (EOS) can be defined as an algebraic equation that can
describe the relationship between pressure, temperature and volume for both a pure
component and a mixture. EOS may be used to describe the state of the fluid phase. The
volumetric phase behavior of a pure component and a multi-component mixture is
directly given by the equation of state. There are many families of EOS. The van der
Waals family is characterized by simple cubic form, and most have two to three
parameters. Basic parameters of these equations are the critical properties and the normal
boiling point or vapor pressure. For mixtures, the interaction coefficients between
constituents should be included to account for highest accuracy. There are many
equations of state used for calculating vapor-liquid equilibrium, Reid et al 91 give review
of several practical equations for chemical and petroleum industries. 10,11,12,51,52
One of the first and simplest, perhaps the best known equation of state model
is the ideal gas law,
PV = RT (2.35)
This law was derived by assuming that the molecules that make up the gas have
negligible sizes, that their collision with themselves and the wall are perfectly elastic, and
that the molecules have no interactions with each other. It has small applicability to
describe the volumetric phase behavior of petroleum reservoir fluids, because this law is
only valid for substances at low pressures and high temperatures. The petroleum industry
has adopted the concept of compressibility factor Z , or gas deviation factor for
45
describing the behavior of mixtures or gases at moderate high pressures. The
compressibility factor Z is a correction factor for the ideal gas law, that is
PV = ZRT (2.36)
and, by definition
PV
Z= (2.37)
RT
The limitations in the use of Equation 2.34 to describe the behavior of natural
gases gave the chance of the earliest attempts to represent the behavior of real gases by an
equation was that of van der Waals equation of state mode.
Since the proposal of van der Waals equation (1873) 116 , several
investigators 5,18, 27 , 64 have proposed many equations of state for representation of fluid
volumetric, thermodynamics, and phase equilibrium behavior. These equations, many of
them a modification of the van der Waals EOS, range in complexity from simple
equations containing two or three constants to complicated form having more than thirty
constants. Even though with this large number of EOS, not so many are considered by
engineers and researchers. Because of its computational problem, many prefer the
simplicity found in van der Waals cubic model while improving the accuracy through
modifications.
The van der Waals equation of state, is the first equation capable of representing
vapor-liquid coexistence
RT a
P= − 2 (2.38)
V −b V
46
The parameters a and b are constants that characterize the molecular properties
of the substance in question. The first term on the right side of Equation 2.36 represents
RT a
the repulsive interaction force ( ), and the other term ( 2 ) is the attractive forces
V −b V
between molecules. The parameters a and b can be obtained from the critical properties
of the fluid. Also, these parameters can be determined mathematically using Equation
2.1. In the development of cubic equations of state, modifications in the evaluation of the
parameter a in the attractive term by Soave is considered the most accurate results in
Redlich-Kwong, 86 Soave-Redlich-Kwong, 106 and Peng-Robinson. 83 Redlich-Kwong 87
equation is the most important and successful model for the modification of the van der
Waals equation of state.
Redlich-Kwong (1949) replaces the attractive term of the van der Waals EOS
with a temperature-dependent term. The R-K EOS has the form
RT a
P= − (2.39)
V − b V (V + b)T 0.5
For pure components, the Equation 2.37 constant parameters a and b usually
expressed as
2 .5
R 2Tc
a = Ωa (2.40)
Pc
RTc
b = Ωb (2.41)
Pc
where Ω a and Ω b are dimensionless parameters with the following computed values:
Ω a = 0.4278 and Ω b = 0.0867.
47
Soave, 94 modified the R-K EOS and published the Soave-Redlich-Kwong (SRK)
equation of state
RT aα
P= − (2.42)
V − B V (V + b)
where the dimensionless factor α is a function of temperature:
[
α = 1 + m (1 − Tr 0.5 ) ]
2
(2.43)
In the Equation 2.41, m is the slope and Tr is the reduced temperature.
Soave correlated the slope, m , against the acentric factor, ω , by the generalized form
m = 0.480 + 1.57ω − 0.176ω 2 (2.44)
As the case in the Redlich-Kwong equation of state, the constant parameters a
and b are determined at the critical conditions in the form
2
R 2Tc
a = Ωa (2.45)
Pc
RTc
b = Ωb (2.46)
Pc
where the values of dimensionless pure component parameters Ω a and Ω b do not
change as shown in Equations 2.43 and 2.44 due to the introduction of function a (T ).
Peng and Robinson 83 introduced an improved Redlich-Kwong EOS capable of
predicting the liquid volumes and a critical compressibility factor of Z c = 0.307. Their
equation is given by
RT aα
P= − (2.47)
V − b V (V + b) + b(V − b)
48
with
2
R 2Tc R 2Tc
a = Ωa = 0.4724 (2.48)
Pc Pc
and
RTc RT
b = Ωb = 0.07780 c (2.49)
Pc Pc
Peng and Robinson adopted Soave’s- Redlich-Kwong approach for computing α
as shown in Equation 2.45, where they used ω as the correlating parameter for the slope,
m , as given by
m = 0.379642 + 1.48503ω − 0.1644ω 2 + 0.001667ω 3
Usdin and McAuliffe (UM), 101 proposed a new parameter d , to replace b in the
second term (attractive term) of the Soave-Redlich-Kwong 106 equation:
RT aα
P= − (2.50)
V − b V (V + d )
where
2
R 2Tc
a = Ωa (2.51)
Pc
RTc
b = Ωb (2.52)
Pc
RTc
d = Ωd (2.53)
Pc
They argued that the two terms of the SRK equation are interconnected by
parameter b, concluding that all substances possess a value of critical compressibility
49
factor Z c = 0.333. They stated that severing the tie created by the shaping of the
parameter b and replacing it with d would cause accurate liquid density.
UM proved the dimensionless parameters Ω a , Ω b , and Ωd can be related to the
critical compressibility parameter, Z c , by the following expression:
3 2
[ ]
Ω d + (6 Z c − 1)Ω d + 12( Z c ) 2 − 3Z c Ω d + (8 Z c − 3)( Z c ) 2 = 0 (2.54)
Ω b = Ω c + 3Z c − 1, (2.55)
and
(Z c )3
Ωa = (2.56)
Ωb
Usdin and McAuliffe also adopted Soave’s formulation of α as Equation 2.45
with
m = 0.48049 + 4.516ωZ c + [0.67713(ω − 0.35) − 0.02](Tr − 0.7), (2.57)
for Tr ≤ 0.7
and
[ ]
m = 0.4049 + 4.516ωZ c + 37.7846ω ( Z c ) 3 + 0.78662 (Tr − 0.7) 2 , (2.58)
for 0.7 ≤ Tr ≤ 1.0
Patel and Teja 81 introduced the following form of EOS:
RT aα
P= − (2.59)
V − b V (V + b) + c (V − b)
where
50
2
R 2Tc
a = Ωa (2.60)
Pc
RTc
b = Ωb (2.61)
Pc
RTc
c = Ωc (2.62)
Pc
where
Ω c = 1 − 3ζ c (2.63)
Ω a = 3ζ c + 3(1 − 2ζ c )Ω b + Ω b + (1 − 3ζ c )
2 2
(2.64)
PcVc
ζc = (2.65)
RTc
and Ω b is the smallest positive root of the cubic expression:
Ω b + (2 − 3ζ c )Ω b + 3ζ c Ω b − ζ c = 0
3 2 2 3
(2.66)
A value of Ω b is given by
Ω b = 0.3243ζ c − 0.0225. (2.67)
Finally, α is determined by the following:
[
α = 1 + F (1 − Tr 0.5 ) ]
2
(2.68)
The Patel-Teja equation of state therefore requires four parameter constants
Tc , Pc , ζ c , and F for any fluid desired.
There are many other equations of state models with modifications of the
attractive term, repulsive term, and combination of both of the van der Waals EOS with
51
more than two or three parameters. Some of these are summarized in Table 2.1 and Table
2.2.
Table 2.1. Modifications to the Attractive Term of van der Waals Equation of State. 117
Equation Attractive Term
Redlich-Kwong (RK, 1949) a

RT 1 .5
(V + b)
a (T )
Soave (SRK, 1972)
RT (V + b)
a (T )V
Peng-Robinson (PR, 1976) RT [V (V + b) + b(V − b)]
a (T )V
RT (V + cb)
Fuller, (1970)
a (T )V
[
RT V + (b(T ) + c )V − b(T )c
2
]
Heyen, 1980-Sandler, (1994)
a (T )V
RT (V + ubV + wb 2 )
2
Schmidt-Knapp (1980)
a (T )V
Kubic (1982) RT (V + c ) 2
a (T )V
RT [V (V + b) + c (V − b)]
Patel-Teja (PT)(1982)
a (T )V
Yu and Lu (1987)
RT [V (V + c ) + b(3V + c )]
a (T )
Lawal-Lake-Silberberg (LLS)(1985) V + αbV + β b 2
2
52
Table 2.2. Modifications to the Repulsive Term of the van der Waals EOS. 117
Equation Repulsive Term
Reiss et al (1959) 1+η +η 2

(1 − η ) 3
Thiele (1963) 1+η +η 2

(1 − η ) 3
1
Guggenheim (1965)
(1 − η ) 4
1+η +η 2 −η 3
Carnahan-Starling (1969) (1 − η ) 3
53
CHAPTER III
CLOSED-FORM VAN DER WAALS EXPRESSIONS
This chapter presents the derived equations, which form the basis of critical point
calculations. These include the van der Waals equations of state theory, the parameters
that characterize the individual components in the Lawal-Lake-Silberberg (LLS)
generalized cubic equation of state, and the algorithm developed for computing the
critical properties of petroleum reservoir fluids. Using the LLS equation of state as a
basis, a closed-form solution for the van der Waals critical point is presented. This is
accomplished by introducing the “VDW closure parameters” (that is, parameters α , β
developed for the purpose of resolving critical point in fluids) into the original van der
Waals equation of state.
3.1 Van der Waals Equations of state Theory
The ideal gas law, PV = nRT , can be derived by assuming that the molecules
that make up the gas have negligible sizes, that their collision with themselves and the
wall of the vessel are perfectly elastic, and that the molecules have no interactions with
each other.
An early attempt, to take these intermolecular forces into account was that of Van
der Waals (1873), who proposed that the ideal gas equation of state be replaced by
⎛ ⎞
⎜P + a2 ⎟(V M − b) = RT (3.1)
⎜ ⎟
⎝ VM ⎠
54
a
This equation differs from the ideal gas equation by the addition of the term to
V2
pressure and the subtraction of the constant V to b from molar volume.
Here the parameters a and b are constants particular to a given gas, where R is
a
the universal gas constant. The term represents an attempt to correct pressure for the
V2
forces of attraction between the molecules. The actual pressure exerted on the wall of the
a
vessel by real gas is less, by the amount , than the pressure exerted by an ideal gas.
V2
The parameter b (or the so called co-volume parameter) is related to the size of each
molecule and represents the intermolecular repulsive forces in the sense that it is the
volume that the molecules have to move around in is not just the volume of the container
V , but is reduced to (V − nb ) . The parameter a has a more difficult meaning and is
related to intermolecular attractive force between the molecules. The net effect of the
intermolecular attractive forces is to reduce the pressure for a given volume and
n
temperature. When the density of the gas is low (i.e., when is small and nb is small
V
compared to V ) the Van der Waals equation reduces to that of the ideal gas law. The
a and b parameters can be obtained from the critical properties of the fluid.
On the basis of the available volume ( V − b ), Van der Waals was able to show
that Equation 3.1 is appropriate for the hard-sphere gas at low density. To see that this
leads to a pressure reduction, simply solve for P:
55
RT a
P= − 2 (3.2)
V −b V
a
Since a > 0 , and b << V , then will be a reduction in pressure by approximately .
V2
It is clear that the Van der Waals equation predicts a deviation from ideal
behavior. This deviation can be analyzed by defining a quantity Z , called the
compressibility factor, as
PV
Z= (3.3)
RT
For an ideal gas, it is clear that Z = 1 .
To derive Z , start with Equation 3.2, then multiply both sides by V and divide by
RT :
PV V a
Z= = − (3.4)
RT V − b RTV
or
1 a
Z= − (3.5)
b RTV
1−
V
b 1
For very low density << 1 , so we can use a Taylor series to approximate . In
V b
1−
V
general, for X << 1
1
≈ 1+ X (3.6)
1− X
56
Using this approximation, the compressibility factor becomes
b a
Z = 1+ − (3.7)
V RTV
or
a
(b − )
Z = 1+ RT (3.8)
V
a
The quantity b − is an observable and calculable quantity, which measures
RT
a a
deviation from ideal behavior of a gas. Note that if b − >> 0 , then b > and the
RT RT
a
pressure is larger than ideal gas pressure. However, the condition b > tells that
RT
excluded volume effects, as measured by the constant b , so an increase in pressure is
a a
what we would have predicted. On the other hand: if b − < 0 , then b < , then
RT RT
the pressure is less than the ideal gas pressure.
Real gases can have both positive and negative deviations from ideal behavior,
depending on the pressure and temperature and the particular system. Strongly attractive
forces will lead to a lowering of the pressure and hence a negative deviation from
ideality, where as strongly repulsive forces can lead to a positive deviation. What do the
isotherm of the Van der Waals equation look like? Recall that the isotherms are curves
corresponding to P vs. V at various fixed temperatures. For the Van der Waals
equation, some of the isotherms are shown in Figure 3.1.
57
Figure 3.1. Pressure-Volume Diagram for Pure Component.
For the isotherms where T > Tc appear similar to those of an ideal gas, i.e., there
is a monotonic decrease of pressure with increasing volume. The T = Tc isotherm
exhibits an unusual feature not present in any of the ideal gas isotherms – a small region
where the curve is essentially horizontal (flat) with no curvature. At this point, there is
no change in pressure as the volume changes. Below this isotherm, the Van der Waals
starts to exhibit unphysical behavior. The T < Tc isotherm has a region where the
pressure decreases with decreasing volume, behavior that is not expected on physical
grounds. What is observed experimentally, in fact, is that at a certain pressure, there is a
dramatic discontinuous change in the volume. This dramatic jump in volume signifies
that a phase transition has occurred, in this case, a change from a gaseous to a liquid state.
The T = Tc isotherm just represents a boundary between those isotherms along which no
such phase transition occurs and those that exhibit phase transitions in the form of
58
discontinuous changes in the volume. For this reason, the T = Tc isotherm is called the
critical isotherm, and the point at which the isotherm is flat the slope of the curve is zero,
and the isotherm has zero curvature at the critical point. Mathematically these two
situations correspond to zero values of the first and second derivatives of pressure with
respect to volume.
At the critical point, the system does not exist in a particular state, either gas or
liquid, but has characteristics of both. Hence, it is called a supercritical fluid. To see at
what temperature, pressure and volume, this supercritical behavior is observed, we use
the fact that at the critical point, the isotherm is both horizontal (zero slope) and has no
curvature. These two conditions (i.e., criteria of criticality) for a pure component are:
⎛ ∂P ⎞
⎜ ⎟ =0 (3.9)
⎝ ∂V ⎠ cp
⎛ ∂2P ⎞
⎜⎜ ⎟ =0
2 ⎟
(3.10)
⎝ ∂V ⎠ cp
Solving Van der Waals’ equation, Equation 3.1 for pressure yield for 1 mole
RT a
P= − 2 (3.11)
V −b V
To estimate a , b , and R at the critical point, it is necessary to obtain the first
and second derivatives with respect to volume of Equation B.1 in Appendix B and set
them equal to zero. The first of these conditions leads to
⎛ ∂P ⎞ ⎛ 2a RTc ⎞
⎜ ⎟ = ⎜⎜ 3 − ⎟ =0
⎟ (3.12)
⎝ ∂V ⎠ cp ⎝ Vc (Vc − b) 2 ⎠ cp
or
59
2a RTc
= (3.13)
Vc
3
(Vc − b) 2
The second condition leads to
⎛ ∂2P ⎞ 6a 2 RTc
⎜⎜ ⎟ = 4 −
2 ⎟
=0 (3.14)
⎝ ∂V ⎠ cp Vc (Vc − b) 3
or
6a 2 RTc
= (3.15)
Vc
4
(Vc − b)3
Consider the Van der Waals equation of state at the critical state
⎛ ⎞
⎜ Pc + a ⎟(Vc − b) = RTc (3.16)
⎜ 2 ⎟
⎝ Vc ⎠
The three equations Equation 3.13, through Equation 3.16 apply at the critical
point and by combination results in
2
27 R 2Tc
a= (3.17)
64 Pc
and
RTc
b= (3.18)
8 Pc
These equations for the constant parameters will only work for pure component at
the critical point. For mixtures, the two equations, Equation 3.9 and Equation 3.10 do not
hold. The pressure-volume diagram for the mixtures does not exhibit horizontal
inflection at the critical point.
60
3.2 Closed-Form Equations for Fluid Critical Point
Another development of van der Waals modification is the single component
form of the Lawal-Lake-Silberberg (LLS) equation of state. This generalized cubic
equation is used in this research project is presented in Equation 3.19. Related work to
this equation of state has been given in the literature. 62 The LLS equation has the form
RT a
P= − 2 (3.19)
V − b V + αbV − β b 2
where parameters a , b, α and β are established for pure component as follows
2
R 2Tc
a = [1 + (Ω ω − 1) Z c ]
3
: (3.20)
Pc
RTc
b = (Ω ω Z c ) (3.21)
Pc
1 + Ω ω Z c − 3Z c
α= (3.22)
Ωω Z c
2 2
Z c (Ω ω − 1) 3 + 2Ω ω Z c + (1 − 3 Z c )Ω ω
β= 2
(3.23)
Ωω Z c
0.361
Ωω = (3.24)
1 + 0.0274ω
where P is the pressure, T is the temperature, V is the molar volume, Z c , is the critical
compressibility factor, Pc and Tc are the critical pressure and temperature of the
components, Ω ω is a constant equals to 0.325, and R is the universal gas constant. The
units used in this work for the LLS EOS are psia for pressure, a degree Rankin, o R for
temperature, cu-ft/1b-mole for molar volume, and the constant R = 10.73 psia-cu-ft/1b-
mole o R. The experimental data are reported in psia of pressure, mol fractions, and o F,
61
therefore, the data had to be converted to the units used in this work. The composition
and critical points obtained by the researchers, Simon-Yarborough,98 Etter and Kay,29
and Zais for 85 hydrocarbon/non-hydrocarbon reservoir fluid mixtures are shown in
Tables C 1 through C 27 in Appendix C.
The Equation 3.19 has four independent parameters ( a, b, α , and β ) and it is a
generalized form and cubic in terms of molar volume. The LLS equation, Equation 3.19,
can be viewed as a generalized cubic equation of state from which many known
equations of state can be derived. Moreover, “the term generalized” cubic equations of
state is used when the equation can be reduced or modified to the form of any of the
known cubic equations of state by assigning specific integer to the parameters α and β .
3
It is interesting to find out that when α = β = 0 and Z c = the generalized form of LLS
8
equation of state reduces to van der Waals equation of state. Similarly for the PR EOS
for α = 2, β = 1. The resulting parameters from the application of the criticality
conditions to various forms of cubic EOS are presented in Table 3.1. 75
Table 3.1. Parameters of Selected Equations of State.

Equations of State Year Zc Ωa Ωb Ωc
van der Waals 1873 0.375 0.4218 0.1250 0.333
Dieterici 1896 0.271 0.6461 0.1355 0.500
Berthelot 1900 0.281 0.5365 0.936 0.333
Redlich-Kwong 1949 0.333 0.4275 0.0866 0.260
Peng-Robinson 1976 0.307 0.4572 0.0778 0.253
Harmens 1979 0.286 0.4831 0.0706 0.247
62
For example, when α = 0 and β = 0 in the LLS equation of state, the equation
reduced to the van der Waals equation of state previously shown in Equation 3.1.
Applying the criticality conditions to van der Waals equation of state yield the following
expressions: 98
⎛ ∂P ⎞ − RTc 2a
⎜ ⎟ = + 3 =0 (3.25)
⎝ ∂V ⎠ Tc (Vc − b)
2
Vc
⎛ ∂2P ⎞ 2 RTc 6a
⎜⎜ ⎟ =
2 ⎟
− 4 =0 (3.26)
⎝ ∂V ⎠ Tc (Vc − b) Vc
3
Solving simultaneously Equations 3.25 and 3.26 for a and b parameters, yield
Vc
b= (3.27)
3
9 RTcVc
a= (3.28)
8
Combining Equations 3.27and 3.28 with van der Waals Equation 3.1, a universal
compressibility factor, Z = 0.375 is obtained and calculating the parameters a and b
from the following equations:
2
R 2Tc
a = 0.4218 (3.29)
Pc
RTc
b = 0.125 (3.30)
Pc
where Ω a = 0.4218 and Ω b = 0.125 are constants at the critical point from the van der
Waals original equation. The parameter Ω ω is determined by dividing the parameter Ω b
by the critical compressibility factor, Z c . In the case of van der Waals,
63
Ω ω = 0.125 / 0.375 = 0.333. Solving Equation 3.28 and Equation 3.29 for the critical
properties for the original van der Waals and for those classical equations of state listed
in Table 3.1, the results are shown in Table 3.2.
Table 3.2. Relationship of EOS constants with Critical Parameters.

η pam ηT a m
Pc = 2
Tc = V c = η v bm
bm Rbm
EOS Year ηp ηT ηv
van der Waals 1973 1/27 8/27 3.0
Dietrich 1896 1/29.56 16.61/27 2.0
Berthelot 1900 1/27.04 10.67/27 3.0
Redlich-Kwong 1949 1/58.8 5.48/27 3.84
Peng-Robinson 1976 1/62.6 5.56/27 3.94
Harmens 1977 1/97.1 3.95/27 4.05
The criticality constraints for deriving the equations to predict the critical
properties for pure components or mixtures in this context of document are the
compressibility and volume forms of criticality conditions. The derivation of the critical
properties equations is presented in Appendix B. In this appendix, two methods for
deriving critical properties expressions are shown in terms of critical compressibility-
factor, Z c , and critical volume, Bc to the corresponding ( Z − Z c ) = 0 .
The critical compressibility- factor form at critical condition is derived by the
expansion of the LLS cubic equation of state in term of Z c and by comparison with the
64
expansion of ( Z − Z c ) 3 = 0. This procedure is shown in Appendix B and the resulting
cubic equation as Equation 3.30 where Z c = f (α , β ) .
Z c θ 1 + Z c θ 2 + Z cθ 3 + θ 4 = 0
3 2
(3.31)
where,
θ 1 = (8 + 12α + 6α 2 + α 3 ) (3.32)
θ 2 = −(3 + 12α + 12α 2 + 9 β − 9βα ) (3.33)
θ 3 = (3α + 6α 2 + 6 β − 6 βα ) (3.34)
θ 4 = −( β + α 2 − βα ) (3.35)
The critical volume form of the criticality condition is also determined by the
expansion of the LLS equation of state in terms of molar volume ( Bc ) and by comparison
of the ( Z − Z c ) 3 = 0 . This procedure is presented in Appendix B and the resulting cubic
equation is shown as Equation 3.36
Bc θ 1 + Bc θ 2 + Bc θ 3 + θ 4 = 0
3 2
(3.36)
where
θ 1 = (8 + 12α + 6α 2 + α 3 ) (3.37)
θ 2 = (15 + 15α − 27 β − 3α 2 ) (3.38)
θ 3 = (6 + 3α ) (3.39)
θ 4 = −1 (3.40)
65
The equations derived to predict the critical pressure, Pc , critical temperature,
Tc , and critical volume, Vc pure components and mixtures are presented with the
following dimensionless parameter:
aP
A= (3.41)
R 2T 2
bP
B= (3.42)
RT
PV
Z= (3.43)
RT
Applying Equation 3.19 at the critical Point we have
PcVc
Zc = (3.44)
RTc
aPc
Ac = 2
(3.45)
R 2Tc
bPc
Bc = (3.46)
RTc
Where subscript c denotes the gas-liquid critical state. Solving for single component
critical pressure, Pc , critical Temperature, Tc , and critical volume, Vc from Equations
3.43, 3.44, and 3.45, give the following expressions:
Bc RTc
Pc = (3.47)
b
Solving for Pc from Equation 3.44, obtain
2
Ac R 2Tc
Pc = (3.48)
a
66
Equating Equation 3.46 and Equation 3.47 yield
aBc
Tc = (3.49)
bRAc
and substituting Equation 3.48 into Equation 3.46 yield
2
aB
Pc = 2 c (3.50)
b Ac
Replacing Pc and Tc expressions previously obtained in Equation 3.48 and
Equation 3.49 in Equation 3.43, the critical volume equation is obtained as:
Zcb
Vc = (3.51)
Bc
The Equations 3.48, 3.49, and 3.50 can be expressed in terms of Ac , Bc , Z c , a,
b, α , and β . In the derivation of the criticality expressions in Appendix B Equation
B.48, the parameter Ac has been presented in term of Bc , Z c , α and β .
Ac = 3Z c + αBc + β Bc + αBc
2 2 2
(3.52)
By substituting Ac in the equations for Pc , Tc and Vc , the critical property
equations are expressed in terms of Bc , Z c , α and β . Then, Equations 3.48, 3.49 and
3.50 can be rewritten in the form
2
aBc
Pc =
(
b 2 3Z c + β Bc + αBc + αBc
2 2 2
) (3.53)
aBc
Tc =
(
bR 3Z c β Bc + αBc + αBc
2 2 2
) (3.54)
67
Zcb
Vc = (3.55)
Bc
or
2
aΩ b
Pc =
(
b 2 3Z c + β Ω b + αΩ b + αΩ b
2 2 2
) (3.56)
aΩ b
Tc =
(
bR 3Z c + β Ω b + αΩ b + αΩ b
2 2 2
) (3.57)
Zcb
Vc = (3.58)
Ωb
Where, Ω b is a constant parameter of the van der Waals equation of state. These
equations Equation 3.56 through Equation 3.58 to calculate Pc , Tc , and Vc are practical
and directly obtained once the composition and the pure components are given.
For the mixtures, the expressions for determining the critical properties are
expressed in terms of the parameters a m , bm , α m , and β m . These mixture parameters
require the LLS mixing rules to establish the following equations for the critical
properties for mixture:
2
a m Bc
Pc =
(
bm 3 Z c 2 + β m Bc + α m B c + α m B c
2 2 2
) (3.59)
a m Bc
Tc =
(
bm R 3 Z c + β m B c + α m B c + α m B c
2 2 2
) (3.60)
Z c bm
Vc = (3.61)
Bc
By LLS mixing rules,
68
n n
a m = ∑∑ x i x j a i 2 a 2 a ij
1 1
(3.62)
i j
3
⎛ n ⎞
bm = ⎜ ∑ xi bi1 / 3 ⎟ (3.63)
⎝ i =1 ⎠
n n
α m = ∑∑ x i x jα i α j α ij
1 1
2 2
(3.64)
i =1 j =1
n n
β m = ∑∑ x i x j β i β j β ij
1 1
2 2
(3.65)
i =1 j =1
The prediction of critical properties for hydrocarbon mixtures can now be
achieved since all the necessary equations have been developed. In this project, the
iterative methods have been utilized to match the experimental critical pressure, Pc ,
critical temperature, Tc and critical volume Vc for multi-component systems.
The algorithm constructed for calculating critical properties for reservoir fluids
(gases, gas condensate, volatile oils, and crude oils) are discussed next.
3.3 Closed-Form Critical Property Computation Methods
The type of data that are often available from laboratory work on reservoir fluid
samples for pure components are critical pressure, Pc , Tc , acentric factor, ω , Critical
compressibility factor, Z c , critical volume, Vc , and molecular weight. Additional
information that may be available is the analysis of the equilibrium liquid and gas. These
data will permit critical properties to be calculated directly at reservoir conditions of
pressure and temperature. Usually, however, laboratory critical point values are
69
furnished, and the critical volume of the reservoir fluids will be the most valuable data
available for reservoir study purposes.
Computer program provides speed and accuracy in predicting the critical
properties for pure components and complex mixtures by the closed-form Van der Waals
method. However, the following procedure (algorithm) is included to show the
calculation procedure followed by flowcharts of the main program:
The following is the step-by-step procedure to calculate the critical point of pure
components given the components measured Tc , Pc , ω .
Step1. From the single component critical data, calculate the pure components parameters
a, b, α , and β using Equation 3.20, Equation 3.21, Equation 3.22, and Equation3.22,
Step 2. Calculate the dimensionless critical volume, Bc using Equation 3.66.
bPc
Bc = (3.66)
RTc
Step 3. Calculate the Dimensionless Parameter Ac in terms of Bc , Z c , α , and β .
Ac = 3Z c + (α + β ) Bc + αBc
2 2
(3.67)
Step 4. Calculate the critical pressure, Pc , the critical temperature, Tc , and the critical
Vc using Equation 3.53, Equation 3.54, and 3.55.
Step 5. Once the pure components parameters are calculated, the mixture parameters for
a m , bm , α m , and β m are calculated using Equation 3.62, Equation 3.63, Equation 3.64,
and Equation 3.65.
70
Step 6. With the calculated values of α m and β m , the coefficients of Equations 3.64 and
3.65 are calculated.
Step 7. Calculate the dimensionless critical volume, Bc for the mixture using Equation
3.68. The solution of this cubic equation consists of two imaginary roots and one real
root. The real root is chosen as the value for Bc : Bc = f (α m , β m ) .
θ 3 Bc 3 + θ 2 Bc 2 + θ1 Bc + θ 0 = 0 (3.68)
where
θ 3 = (α m 3 + 6α m 2 + 12α m + 8) (3.69)
θ 2 = −3(α m 2 − 5α m + 9β m − 5) (3.70)
θ 1 = 3(α m + 2) (3.71)
θ 0 = −1 (3.72)
Step 8. Solve the cubic Equation 3.73 of the mixtures for Z c . The solution has two
imaginary roots and one real root. The real root is chosen as the value for Z c :
Z c = f (α m , β m ) ,
θ 3 Z c 3 + θ 2 Z c 2 + θ1 Z c + θ 0 = 0 (3.73)
where
θ 3 = (α m 3 + 6α m 2 + 12α m + 8) (3.74)
θ 2 = −3(1 + 4α m 2 + 4α m + 3β m − 3α m β m ) (3.75)
71
θ 1 = 3(2α m 2 + 2β m − 2α m β m + α m ) (3.76)
θ 0 = (α m β m − β m − α m 2 ) (3.77)
Step 9. Determine the constant Ac for mixtures using the equation
Ac = 3Z c + β m Bc + α m Bc + α m Bc
2 2 2
(3.78)
Step 10. Calculate the critical temperature, Tc , critical pressure, Pc , and critical
volume, Vc for the mixtures:
a m Bc
Tc = (3.79)
bm R(3Z c + β m Bc + α m Bc + α m Bc
2 2 2
2
a m Bc
Pc = (3.80)
bm (3Z c + β m Bc + α m Bc + α m Bc )
2 2 2 2
and
Z c bm
Vc (3.81)
Bc
Step 11. Calculate the average absolute deviations as Follows:
⎡ Pc , pred − Pc ,exp ⎤
Absolute Deviation (AD) = ABS ⎢ ⎥ (100) (3.82)
⎣⎢ Pc ,exp ⎦⎥
⎡ Tc , pred − Tc ,exp ⎤
Absolute Deviation (AD) = ABS ⎢ ⎥ (100) (3.83)
⎣⎢ Tc ,exp ⎥⎦
Figure 3.2 is an algorithm summarizes the step-by-step procedure presented above
to calculate the critical point of petroleum reservoir fluids.
72
Start
Input Tc Pc Vc Zc ω Read Parameters am bm αm βm
Read parameters a b α β
Call equations of parameters am
bm αm βm and calculate am bm αm
βm for mixtures
Call equations of parameters a b
α β calc. a b α β for pure
components
Read coefficients θ3 θ2 θ1 θ0 and
constant Bc for mixtures
constant Bc
Call cubic equation and calculate

Bc for mixtures
Call cubic equation and calculate Bc
for pure components

constant Zc for mixtures
constant Zc
Call cubic equation and calculate

Zc for mixtures
Call cubic equation and calculate Zc for
pure components
Read constant Ac for mixtures

Read constant Ac
Call equation Ac and calculate

Ac for mixtures
Call equation Ac and calculate Ac for
pure components
Read critical properties Tc Pc Vc
Call equations of Tc Pc Vc
calculate for Tc Pc Vc for
Call equations of Tc Pc Vc and calculate mixtures
for Tc Pc Vc for pure components
End
Figure 3.2. Algorithm for Computation of Critical Parameters.
73
CHAPTER IV
CRITICAL PROPERTIES FOR RESERVOIR FLUIDS
The critical point calculations using the modified Lawal-Lake-Silberberg (LLS)
equation of state introduced in Chapter 3 were carried for each pure component and
complex mixtures such as alkanes +, heptanes plus +, nitrogen and carbon dioxide. The
general behavior of the experimental parameters, and calculated critical properties for
these mixtures are presented in Tables C 1-C 27 and Figures C 1-C 19 in Appendix C. In
general, qualitative results were obtained for the critical pressure and critical temperature.
A detailed comparison and discussion of the results of each of the calculated critical
properties with respect to the corresponding experimental results, and with respect to the
other correlation predictions of Simon and Yarborough, Terry and Kats, and Zais are
presented in the following sections:
4.1 Critical Pressure Data for Complex Hydrocarbon Mixtures
In appendix C, tables and cross-plots are displayed for complex mixtures with the
results of critical pressures and critical temperatures. Each of the tables corresponds to 9
and 10 complex mixtures and each mixture is subdivided into different compositions.
Each table has the composition in mole fraction, the experimental values of the mixture
critical pressure, temperature, and the calculated values of critical pressure, critical
temperature for each complex mixture. The predicted critical properties and acentric
factor for C7 + of complex mixtures are also presented. The methane concentrations in
these mixtures varied from 19 to 96.6 mol percent. The intermediate hydrocarbon
74
groups, consisting of ethane, propane, and butane varied from a low of 3 to 59 mol
percent, and the concentrations of pentane and hexane fractions from 1 to 3 mole percent,
and the fraction heptane plus (C7+) varied from 2 to 14 mol percent. The non-
hydrocarbon mixtures consist of nitrogen and carbon dioxide. The concentration of non-
hydrocarbon mixtures varied from less than 1 to 22 mol percent. The physical properties
of the components fraction covered the range from light, paraffin to heavy, aromatic, and
asphalt.
4.2 Calculation of Critical Properties
In order to clarify the procedure to be followed when applying the methodology
of predicting the critical properties to an actual problem, an illustrative example of
calculation performed using the algorithm presented in Section 3.3 is given here.
To predict the critical pressure and critical temperature of a naturally occurring
mixture, it is given the following information for mixture 1 of the given data in Table 4.1.
As a step one, to compute the critical properties for complex mixtures, it is
desirable first to determine these properties for the C 7 + fraction in the mixture. In
complex mixtures, components heavier than the n-heptane have been summed into a C 7 +
fraction. These C 7 + fractions required for the parameters of equations of state are
59 62
obtained from the previously determined correlations TR-4-99 Lawal, and Lawal,
and the critical compressibility Z c required as additional input for the equation of state
used in this work is obtained from Rowlinson correlation of ACS Symposium Series,
316, 1977. In this project, the critical properties of the C 7 + fractions in the complex
75
mixtures are calculated on the basis of the reported molecular weight of the fraction
( MW c7+ ) . The empirical expressions shown in the Table 4.1 are used to estimate the
critical properties for the hydrocarbon fractions.
Table 4.1. A Sample of Experimental Data Used for Calculations of mixture 145-1.
Hydrocarbon Mixture Composition

Component Mole Fraction
Nitrogen 0.001
Carbon Dioxide 0.004
Methane 0.193
Ethane 0.032
Propane 0.585
i-Butane 0.007
n-Butane 0.012
i-Pentane 0.005
n-Pentane 0.007
Hexane 0.013
Heptane + 0.141
Heptanes + Properties:
Mo. Wt. 243
Characterization
Factor 11.6
o
Critical Temp., Tc , ( R) 725
Critical Temp. This work 725.39
Critical Pressure, Pc ( psia ) 2100
Predicted Pc ( psia ) :
(S. Yarborough) 2002
(Etter and Kay) 2911
(Zais) 2175
This Work 2101
76
Table 4.2. Physical properties of C 7 + Fractions Correlation. 62
6084 141.5
API = + 5.9 Sg = Tbp = e o MW e1 S ge2
MW API + 131.5
C = e o MW e1 S ge2 Tbpe3 Pc = e 0 MW e2 S g 2 Tbp 3 C e4 Tc = e 0 MW e1 S g 2 Tbp 3 C e4

e e e e
ω = e 0 MW e S g e Tbp e C e
1 2 3 4
Parameters e0 e1 e2 e3 e4
Tbp 108.701661 0.4224480 0.42682558 0.0000 0.0000
C 0.83282122 0.09255911 -0.0413045 0.12621158 0.0000
Pc 237031780 -0.028484 2.755309 -1.374440 -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
The C 7 + critical properties and acentric factors are estimated from the correlation
shown in Table 4.2. Bu using the given Mw of the C 7 + as basis, the critical pressure,
critical temperature, critical compressibility factor, and acentric factor of C 7 + were
obtained. The heptane-plus C 7 + is treated as a lumped single pseudo-component for all
the prediction results shown in this work. Table 4.2 displays some of the predicted
critical properties for the heptane-plus fraction.
From the given single component critical data, the pure component parameters
77
a , b, α , β , Ω ω , the dimensionless critical parameters Ac and Bc are calculated from
Equations 3.20, 3.18, 3.21, 3.22, 3.23, 3.24, 3.67, and 3.66 respectively. The resulting
parameters are presented in Table 4.4.
Table 4.3. Calculated Critical Data of Heptane-Plus Fraction for Data Set 1.
Heptanes + Properties
Mol. Wt. 243 243 243 243 191 191 191 191 191
Gravity(API) 33.31 33.31 33.31 33.31 39.98 39.98 39.98 39.98 39.98
SG 0.86 0.86 0.86 0.86 0.83 0.83 0.83 0.83 0.83
Characterization Factor 11.6 11.6 11.6 11.6 11.9 11.9 11.9 11.9 11.9
Tb 1037.0 1037.0 1037.0 1037.0 920.9 920.9 920.9 920.9 920.9
C 3.3475 3.3475 3.3475 3.3475 3.2304 3.2304 3.2304 3.2304 3.2304
Pc, (psia) 271.0 271.0 271.0 271.0 319.8 319.8 319.8 319.8 319.8
Tc, (oR) 1364.4 1364.4 1364.4 1364.4 1258.4 1258.4 1258.4 1258.4 1258.4
ω 0.5673 0.5673 0.5673 0.5673 0.4676 0.4676 0.4676 0.4676 0.4676
Zc 0.2416 0.2416 0.2416 0.2416 0.2493 0.2493 0.2493 0.2493 0.2493
Ωw 0.3555 0.3555 0.3555 0.3555 0.3564 0.3564 0.3564 0.3564 0.3564
Table 4.4. Calculated Results of Pure Component Parameters.
Component a b α β Ωω Ac Bc
N2 6506.50 0.520 2.21 5.32 0.361 0.569 0.105
CO2 18107.70 0.540 2.81 6.02 0.360 0.587 0.098
C1 11111.20 0.567 2.42 5.56 0.361 0.576 0.103
C2 26880.60 0.854 2.43 5.58 0.360 0.576 0.102
C3 46045.90 1.140 2.75 5.96 0.355 0.583 0.098
i-C4 64482.90 1.513 2.49 5.66 0.359 0.577 0.102
n-C4 109225.70 1.850 2.81 6.02 0.359 0.587 0.983
i-C5 90386.27 1.770 2.86 6.07 0.358 0.588 0.978
n-C5 139353.34 1.786 3.02 6.26 0.358 0.593 0.096
C6 130104.33 2.013 3.77 7.11 0.358 0.614 0.090
C7+ 475160.996 4.614 4.222 7.630 0.3535 0.6222 0.085
Once the pure components parameters are calculated, the mixture parameters for
a m , bm , α m and β m can be determined by using Equations 3.62 through Equation 3.65.
78
Since equations of state are developed for pure components, the use of mixing rules is
necessary to make proper application of the equations of state for mixtures. Another
important parameter in every geometric and quadratic mixing rule is the interaction
parameter. This binary interaction term is empirical and does not have any theoretical
basis but it is necessary in mixing rules application. A mixing rule is an algebraic
expression that relates the pure components’ parameters to the mixture composition when
the mixture parameter is established. In this work, the binary interaction terms, a ij , α ij ,
and β ij were assumed as constants, and assigned a value of 1. Then, using the Equation
3.52 the constant Ac was estimated. The Equations 3.59 through 3.61, for calculating the
critical properties are expressed in terms of the mixture parameters, a m , bm , α m , and β m
after LLS mixing rules (Equations 3.62 through 3.65) are applied. Table 4.4 presents the
results of a sample calculations of a hydrocarbon mixture performed using the algorithm
developed in section 3.3. The prediction results are in agreement with the experimental
values. The absolute percent deviation of the results is in the neighborhood of 1.
Table 4.5. Calculation Results for Mixture Parameters (Mixture 1).
Parameter Mixture 1
am 31177.9123
bm 0.11728247
αm 99.1126855
βm 0.69748539
Bc 0.269
Zc 0.2985
Ac 34.15
79
4.3 Results and Discussion
The variation in behavior of the calculated critical pressure and temperature
agreed both qualitatively and quantitatively with experimental data. Deviation errors in
the predictions of both critical pressure and temperature, as shown in Figures 4.5-4.6
were in the range of 0.03 to 0.13 percent. In Figure 4.1, the predicted critical pressure
obtained from Simon and Yarborough, Etter and Kay, Zais, and this work using Lawal-
Lake-Silberberg (LLS) is plotted against Critical experimental data. As shown in Figure
4.1, this work shows better agreement with the experimental data than the other three
correlations. Consequently, the LLS equation of state is selected for this work.
A comparison of the accuracy of predicted critical properties of this work with the
other correlations indicates that the mixing rules used with the LLS equation of state lead
to accurate predictions of mixture behavior. Furthermore, the influence of the values of
interaction parameters on the accuracy of the prediction of critical properties was
adjusted. Adjustment of the interaction parameter associated with the constant b of the
LLS equation of state, had an effect on the critical point calculations. Also, adjustments
of the interaction parameter associated with the constant a , improved significantly the
prediction of the critical properties, especially the critical pressure.
The results of the predicted critical pressure, Pc , and critical temperature, Tc , for
complex mixtures are presented in Table 4.6. The prediction results are in agreement
with the experimental values. The absolute percent deviation of the results ranges from
0.03 to 0.13 percent.
80
Table 4.6. Predicted Critical Pressure, Pc , Critical Temperature, Tc , for Mixtures.
Properties Mix. 1 Mix. 2 Mix. 3 Mix. 4 Mix.5 Mix. 6 Mix. 7 Mix. 8 Mix. 9
Tc, exp. 725 725 725 725 694 660 660 660 660
Tc, pred. 725.39 725.45 724.58 725.81 694.91 694.44 659.17 661.13 659.22
AD (%) 0.054 0.062 0.058 0.112 0.131 5.218 0.126 0.171 0.118
Pc, exp. 2100 2500 3400 1920 2420 3430 4355 4295 4630
Pc, pred. 2101.12 2501.55 3398.03 1922.15 1423.18 3432.17 4349.55 4302.33 4624.49
AD (%) 0.053 0.062 0.058 0.112 0.131 0.063 0.125 0.171 0.119
Eighty-five mixture sets of experimental data are analyzed for hydrocarbon
mixtures. Table C.1 through C. 27 in Appendix C show the prediction results for critical
pressures, critical temperatures. Also, these results are displayed in Figures C. 1-through
C. 10 for critical pressure, and in Figures C. 11 through C. 19 for critical temperature in
Appendix C. Figure 4.1 is a cross-plot shows the prediction results for the critical
pressures for all data.
81
8500
7500
Calculated Critical Pressure (psia)
6500
5500
4500
3500
2500
Simon-Yarborough
1500 Etter-Kay
Zais
This w ork
500
500 1500 2500 3500 4500 5500 6500 7500 8500
Experimental Critical Pressure (psia)
Figure 4.1. Predicted Critical Pressure of Complex Mixtures.
The match of the predicted critical pressure against the experimental critical
pressure gives an absolute deviation between 0.03 and 0.13 %. Similarly, the prediction
results for the critical temperature are in agreement with the experimental data. Figure
4.2 is a cross-plot which displays the prediction results for critical temperatures for all
data.
82
800
750
This w ork
700
Calculated Critical Temperature (oR)
650
600
550
500
450
400
350
300
300 350 400 450 500 550 600 650 700 750 800
o
Experimental Critical Temperature ( R)
Figure 4.2. Predicted Critical Temperature of Complex Mixtures.
4.4 Comparison Between Calculated and Experimental Data
To test the accuracy of the calculations of critical points of hydrocarbon mixtures,
a comparison of calculated with experimental values of the pressure and temperature at
the critical points of mixtures of known compositions was made. For this purpose, the
critical pressure and critical temperature on the hydrocarbon paraffin mixtures which
were determined in the laboratory was employed. A total of about 85 mixtures of non-
hydrocarbon and hydrocarbon components were studied. The results of these mixtures
are given in Table 4.6. Table 4.6 gives a summary of the results for all mixtures.
83
In general, the agreement between the calculated critical properties and the
experimental critical properties is very good. The over all deviation of the calculated
values from the experimental is about 0.03-0.13% of both the pressure and temperature.
Figure 4.1 is a cross-plot shows the comparison between the calculated critical pressures
and experimental critical pressures for all data points. Also, Figure 4.2 is a cross-plot
compares the calculated critical temperatures with the experimental critical temperatures
for all data.
The comparison of the results of the critical point predictions using the LLS
equation of state and the Simon-Yarborough, Etter-Kay, and Zais empirical calculation
methods was necessary to provide guidelines for critical point predictions of complex
reservoir fluids. The most important factor to be considered was the relationship between
the complexity of the equations of state used in the critical point equations and the
accuracy of the predictions of the critical properties. The critical point equations derived
from the LLS equation of state proved to be more simple and easy to derive than was the
case of many other equations of state. However, the results of the critical point
predictions proved to be in good agreement with the experimental critical points than the
Simon-Yarborough, Etter-Kay, and Zais.
The most comprehensive comparison of the critical point predictions of the LLS
equation of state approach and the Simon-Yarborough, Etter-Kay, and Zais correlations
can be made for the critical pressure calculations for each class of mixtures. In this work,
for the hydrocarbon/non-hydrocarbon class of mixture the LLS equation predicted more
accurate critical pressure- mole fraction relationship than did the Simon-Yarborough,
84
Etter-Kay, and Zais correlations in all the mixtures in the basic calculations (with
adjustment of binary interaction parameters).
One of the most significant features of the critical point calculations is that the
values of the interaction parameters are not equal to 1 as suggested in the original binary
mixing rules of the Redlich-Kwong and Benedict-Webb-Rubin (BWR) equations of state.
The assumption of a value of 1 to the binary interaction terms is equivalent to the
assumption that the intermolecular energy can be described by the geometric means of
the pure component energies. Chueh and Prausnitz 21 point out that the geometric mean
relationship is accurate only for simple, spherically, and symmetric molecules of nearly
equal size. Thus, for most multi-component systems, the best value of the interaction
parameters will not equal to 1, which agrees with the results of this investigation.
A comparison of the accuracy of the critical point prediction using LLS equation
of state approach and three other empirical correlation methods appears in Tables C. 1
through C. 9 in Appendix C. In general, the accuracy of critical pressure predictions
from the empirical calculation methods of Simon-Yarborough, Etter-Kay, and Zais was
not comparable to that obtained by this work with the equation of state approach using
Lawal-Lake-Silberberg equation of state. The advantages of the equation of state
approach are that the critical properties are determined simultaneously, including the
critical temperature, and critical volume are not restricted to any particular equation of
state.
85
CHAPTER V
CONCLUSIONS AND RECOMMENDATION
5.1 Conclusions
The purpose of this work was to integrate the thermodynamic criteria of the
critical state criteria of mixtures with a LLS EOS to predict the critical properties of
complex petroleum reservoir fluids. The major conclusions drawn from each of the
objectives are presented along with recommendations for future study in the following
sections:
The first objective, to develop a closed-form solution to the van der Waals
criticality conditions and perform numerical calculations to predict the critical properties
was achieved by using the Lawal-Lake-Silberberg (LLS) equation of state on complex
mixtures of hydrocarbons. Analysis of the results of the critical calculations showed that
qualitative and quantitative agreement with experimental data was obtained. In general,
the average error levels in the predictions of the critical properties were comparable to
those obtained experimentally and not comparable to those obtained from other
correlations (Simon and Yarborough, Etter and Kay, and Zais) 98, 29,122 . The conclusion
drawn from this result was that the ability of the equation of state to predict the critical
points of complex mixtures is directly related to the ability of the equations to predict the
corresponding critical properties of pure components of the mixtures. Thus, because of
its simplicity and the fact that the Lawal-Lake-Silberberg equation applicability yields
accurate and exact critical temperature and pressure for any pure component, the LLS
86
equation proved by this work to be much more satisfactory equation of state for critical
point predictions of petroleum reservoir fluids.
The second objective, to determine the need to establish interaction parameters for
hydrocarbon and non-hydrocarbon mixtures and for hydrocarbon with pseudo-
components was achieved. The best estimations of the critical properties were obtained
by adjusting the value of the interaction parameters to be equal to one in the mixing rules
of the constants a m and bm of the LLS equation. The binary interaction parameters are
expressed in terms of the ratio of molecular weights in the Equation B.91 through
Equation B.93 presented in Appendix B.
The third objective, to develop an algorithm for calculating the critical properties
of reservoir fluids was also achieved, and the procedural approach for computing the
step-by-step method was efficiently performed.
The equation of state approach to the prediction of critical points of mixtures
offers several advantages over the empirical and semi-empirical correlations methods in
use today. The general level of accuracy in the critical properties prediction carried out
in this work proved to be comparable to the experimental measurements.
5.2 Recommendations
The results obtained from this investigation are useful for PVT analysis of
reservoir fluids especially in resolving retrograde behavior. Therefore, several
recommendations can be made regarding future work:
87
1. Study should continue toward the implementation of this technique developed
in this search in a flash routine to resolve the convergence pressure problem for
near the critical region and retrograde behavior of reservoir fluids.
2. Based on the modified LLS equation of state used here in this work is
sufficiently reliable for predicting the vapor-liquid equilibrium and volumetric
reservoir fluids without the use of pseudodization. Instead, utilize heptane-
plus fraction as a lumped single-pseudo-component in equation of state by
predicting liquid dropout, constant volume depletion (CVD), constant
composition expansion (CCE), and flash-differential liberation (FL-DL) tests.
3. A possible use of the technique developed in this work into a reservoir
simulation model to perform gas cycling, gas- condensate simulation, and
multi-contact miscibility studies.
88
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APPENDIX A
ANALYTICAL SOLUTION FOR CUBIC EQUATIONS
The general cubic equation is given by Dunham, 24
a 3 X 3 + a 2 X 2 + a1 X + a 0 = 0 (A.1)
Divide the entire equation by a 3 ,
a 2 2 a1 a
X3 + X + X + 0 =0 (A.2)
a3 a3 a3
To find the roots of this equation, we first eliminate the quadratic term, X 2 . To do this,
we make the substitution
a2
X = y− (A.2)
3a 3
then, by substituting in Equation A.1, to obtain
a2 3 a a
a3 ( y − ) + a 2 ( y − 2 ) 2 + a1 ( y − 2 ) + a 0 = 0 (A.3)
3a 3 3a 3 3a 3
Expanding Equation A.3 and simplifying
a2 3 ⎛a ⎞ 2 ⎛ a2 2 ⎞ a
3
(y − ) = y 3 − ⎜⎜ 2 ⎟⎟ y + ⎜ ⎟y − 2 (A.4)
3a 3 ⎜ 3a 2 ⎟ 27a 3
3
⎝ a3 ⎠ ⎝ 3 ⎠
2
⎛ a2 ⎞ ⎛ a2 ⎞ a2
2
⎜⎜ y − ⎟ = y − 2⎜⎜
2
⎟⎟ y + (A.5)
⎝ 3a 3 ⎟⎠ ⎝ 3a 3 ⎠ 9a 3
2
Substituting in Equation A.3
99
⎛ a a
2
a ⎞
3
⎛ a a
2
⎞
a3 ⎜⎜ y 3 − 2 y 2 + 2 2 y − 2 3 ⎟⎟ + a 2 ⎜⎜ y 2 − 2 2 y + 2 2 ⎟
⎟
⎝ a3 3a3 27 a3 ⎠ ⎝ 3a3 9a 3 ⎠ (A.6)
⎛ a ⎞
+ a1 ⎜⎜ y − 2 ⎟⎟ + a 0 = 0
⎝ 3a3 ⎠
or
⎛ − a22 ⎞ ⎛ 2a 2
3
aa ⎞
⎜
a3 y + ⎜
3
⎟ ⎜
+ a1 ⎟ y + ⎜ a 0 + − 1 2 ⎟=0 (A.7)
2 ⎟
⎝ 3a 3 ⎠ ⎝ 27a 3 3a 3 ⎠
Equation A.7 is called the “depressed” cubic equation since the quadratic term, y 2 is
eliminated. Divide Equation A.7 by a 3 , then
1 ⎛ a ⎞
2
⎛ 2a 2
3
⎞
⎜ a1 − 2 ⎟ y + 1
aa
y +
3
⎜ a0 + − 1 2 ⎟=0 (A.8)
a3 ⎜ 3a 3 ⎟⎠ a3 ⎜ 27a 3
2
3a 3 ⎟
⎝ ⎝ ⎠
Let
1 ⎛ a ⎞
2
e= ⎜ a1 − 2 ⎟ (A.9)
a3 ⎜ 3a 3 ⎟⎠
⎝
And
1 ⎛ 2a 2
3
aa ⎞
f = ⎜ a0 + − 1 2 ⎟ (A.10)
a3 ⎜ 27a 3
2
3a 3 ⎟
⎝ ⎠
Substituting Equations A.9 and A.10 into Equation A.8 and obtain
y 3 + ey + f = 0 (A.11)
Reducing Equation A.11 using Vieta’s Substitution
s
y=z+ (A.12)
z
100
The constant s is an undefined constant for right now. Substituting Equation A.12 in
Equation A.11, yield
3
⎛ s⎞ ⎛ s⎞
⎜z + ⎟ + e⎜ z + ⎟+ f =0 (A.13)
⎝ z⎠ ⎝ z⎠
Expanding Equation A.13
3
⎛ s⎞ s2 s3 3s 2 s 3
⎜ z + ⎟ = z − 3sz + 3 − 3 = z − 3sz + − 3
3 3
(A.14)
⎝ z⎠ z z z z
Multiplying the right side of Equation A.14 by z 3 , yield
⎛ s⎞ 3 sz 3
⎜z + ⎟ z = z − 3sz + 3s z − s = z + s = ez 4 + esz 2
6 4 2 2 3 4
⎝ z⎠ z
Then
z 6 + (3s + e ) z 4 + s (3s + e ) z 2 + fz 3 + s 3 = 0 (A.15)
e
Now let s = − to simplify Equation A.15 into a “tri-quadratic” equation, then
3
e3
z 6 + fz 3 + =0 (A.16)
27
By substituting w = z 3 , then we have a general quadratic equation which we can solve
using the quadratic formula.
e3
w 2 + fw − =0 (A.17)
27
Solve for the quadratic Equation A.17 and will give two roots for w , hence using
w = z 3 would then give three roots for each of the two roots of w , hence will give
101
six root values for z . But the six root values of z would give only three values of y (for
s
y = z + ), and three values of x in Equation A.2.
z
Illustrative Problem
Find the roots of the following cubic equation
x 3 − 0.03 x 2 + 2.4 x10 −6 = 0 (A.18)
Solution
For the general form of the cubic equation
ax 3 + bx 2 + cx + d = 0 (A.19)
Where a = 1, b = −0.03, c = 0, d = 2.4 x10 −6
To find the roots of this equation, first eliminate the quadratic term (i.e., depress the cubic
equation). Let
b
x= y−
3a
− 0.03
x= y−
3(1)
x = y + 0.01 (A.20)
Substituting the above value of x Equation A.20 into the cubic Equation A.18 and
simplify, yield
y 3 − (3 x10 −4 ) y + (4 x10 −7 ) = 0 (A.21)
Convert this depressed cubic equation into the form
y 3 + ey + f = 0 (A.22)
102
Where the coefficients of Equation A.22 are e = −3 x10 −4 , f = 4 x10 −7
Now solve the depressed equation by using Vieta’s substitution as,
s
y=z+
z
and obtain
z 6 + (3s − 3 x10 −4 ) z 4 + (4 x10 −7 ) z 3 + s(3s − 3 x10 −4 ) z 2 + s 3 = 0 (A.23)
Let
e − 3 x10 −4
s=− =− = 10 − 4 (A.24)
3 3
Substituting Equation A.24 into Equation A.24 to obtain the “tri-quadratic” equation
z 6 + (4 x10 −7 ) z 3 + 1x10 −12 = 0 (A.25)
Convert Equation A.25 into a general quadratic equation by using w = z 3
w 2 + (4 x10 −7 ) w + (1x10 −12 ) = 0 (A.26)
Using the quadratic equation, the values for w are
4 x10 −7
w1 = − ± (4 x10 −7 ) 2 − 4(1x10 −12 )
2
w1 = −2 x10 −7 + i (9.797958 x10 −7 ) (A.27)
and
w 2 = −2 x10 −7 − i (9.797958 x10 −7 ) (A.28)
The solution of w = z 3 gives three values of z . These values in rectangular form are:
w = a + bi
w = ze iθ = z (cosθ + i sin θ )
103
b
Where θ = arctan +π
a
Then,
⎡ ⎛ θ 2πn ⎞ ⎛ θ 2πn ⎞⎤
3
w = 3 z ⎢cos⎜ + ⎟ + i sin⎜ + ⎟
⎣ ⎝3 3 ⎠ ⎝3 3 ⎠⎥⎦
Then, the three values from w1 are in rectangular form
z1 = −0.008976 + 0.00440i
z 2 = 6.707 x10 −4 0.009977i
z 3 = 0.008305 + 0.005569i
The values of z from w 2 are in rectangular form
z 4 = −0.008976 − 0.0044079i
z 5 = 6.70689228 x10 −4 − 0.0099775 i
z 6 = 0.0083054 − 0.00556957i
Using Vieta’s substitution,
s
y=z+
z
1x10 −4
y=z+ (A.29)
z
Substituting into Equation A.29 the value of z to find three values for y , choosing
z1 = −0.008976098 + 0.0044079 yields
1x10 −4
y1 = −0.008976 + 0.0044079i + = −0.01795
− 0.008976 + 0.0044i
104
1x10 −4
y 2 = 6.706892 + 0.00997748i + = 0.0013414
6.706892 + 0.00997748i
Similarly, the other value of z 3 gives
y 3 = 0.016611
With the substitution in Equation A.20
x = y + 0.01 (A.20)
The three roots of the given Equation A.19 are
x1 = −0.0079522
x 2 = 0.0113414
x 3 = 0.02661112
Method 2
The general cubic equation is given by
a 3 Z 3 + a 2 Z 2 + a1 Z + a 0 = 0 (A.30)
Divide the entire equation by a 3 ,
a 2 2 a1 a
Z3 + Z + Z+ 0 =0 (A.31)
a3 a3 a3
Eliminate a 2 by making substitution of the form
Z = x−λ (A.32)
By substituting Equation A.32 into Equation A.30,
( x − λ ) 3 + a 2 ( x − λ ) 2 + a1 ( x − λ ) + a 0 = 0 (A.33)
By expanding Equation A.33,
105
( x 3 − 3λ x 2 + 3λ 2 x − λ 3 ) + a 2 ( x 2 − 2λ x + λ 2 ) + a1 ( x − λ ) + a 0 = 0 (A.34)
x 3 + (a 2 − 3λ ) x 2 + (a1 − 2a 2 λ + 3λ 2 ) x + (a 0 − a1λ + a 2 λ 2 − λ 3 ) = 0 (A.35)
a2
Let λ = in order to eliminate the x 2 , so
3
1
Z ≡ x − a2 (A.36)
3
2 3
a a x a
x = ( x − 2 )3 = x 3 − a2 x 2 + 2 − 2
3
(A.37)
3 3 27
1 2 2 1 3
a2 Z 2 = a2 ( x − a2 )2 = a2 x 2 − a2 x + a2 (A.38)
3 3 9
1 1
a1 Z = a 1 ( x − a 2 ) = a1 x − a 2 a1 (A.39)
3 3
Substituting back into Equation A.30, becomes
1 2 2 2 1 3
x 3 + ( − a 2 + a 2 ) x 2 + ( a 2 − a 2 + a1 ) x − ( a 2
3 3 27
(A.40)
1 3 1
− a 2 + a1 a 2 − a 0 ) = 0
9 3
1 2 1 2 3
x 3 + ( a1 − a 2 ) x − ( a1 a 2 − a2 − a0 ) = 0 (A.41)
3 3 27
2 3
3a1 − a 2 9a a − 27a 0 − 2a 2
x3 + − 1 2 =0 (A.42)
3 27
Let,
2
3a1 − a 2
P= (A.43)
3
and,
106
3
9a a − 27a 0 − 2a 2
q= 1 2 (A.44)
27
then Equation A.42 can be written as
x 3 + Px = q (A.45)
Make Vieta’s substitution to simplify the derivation by letting:
P
x =W − (A.46)
3W
Substituting for x in Equation A.45, obtain
P 3 P
(W − ) + P (W − )−q = 0
3W 3W
or
P3
W −3
−q = 0 (A.47)
27W 3
Multiplying through Equation A.47 by W 3 to obtain a quadratic equation in W 3 ,
P3
(W ) − q (W ) −
3 2
=0
3
(A.48)
27
Apply the quadratic formula (Birkhoff & Mclane 1996, P.106):
1 4 3
W3 = (q ± q 2 + P
2 27
1 1 2 1 3
= q± q + P
2 4 27
= R ± R2 + Q3 (A.49)
Let:
107
1
R= q
2
1
R2 = q2
4
P3
Q =
3
27
By Vieta’s “magic” substitution, first define the intermediate variables from Equation
A.42
Let:
3
3a1 − a 2
Q= (A.50)
9
3
9a 2 a1 − 27a 0 − 2a 2
R= (A.51)
54
The cubic Equation A.42 then becomes,
x 3 + 3Qx − 2 R = 0 (A.52)
Let B and C be arbitrary constants. An identity, which is satisfied by perfect cubic
polynomial equations, is
x 3 − B 3 = ( x − B )( x 2 + Bx + B 2 ) (A.53)
Since Q ≠ 0 , add a multiple of (x-B) by C to both sides of Equation A.23 to give
( x 3 − B ) 3 + C ( x − B ) = ( x − B )( x 2 + Bx + B 2 + C ) = 0 (A.54)
Regrouping terms, becomes
x 3 + Cx − ( B 3 + BC ) = ( x − B )(x 2 + Bx + ( B 2 + C ) ) = 0 (A.55)
Match the coefficients C and − ( B 3 + BC ) with those of Equation A.52, so we must have
C = 3Q (A.56)
108
B 3 + BC = 2 R (A.57)
Then by substituting Equation A.56 into Equation A.57,
B 3 + 3QB = 2 R (A.58)
Now, find a value for B and reduce Equation A.58 to a quadratic equation.
( ) + (R − )
1 1
B = R + Q3 + R2 3
Q3 + R2 3
(A.59)
Taking the second and third powers of B gives
( ) ( )
2 2
( )
1
B = R+ Q +R
2 3 2 3
+ 2 R − (Q + R )
2 3 2 3 + R− Q +R 3 2 3
(A.60)
( ) + (R − )
2 2
= R+ Q +R 3 2 3
Q +R
3 2 3
− 2Q (A.61)
⎧⎪
( ) ( ) ⎫⎪⎬⎪
1 1
B = −2QB + ⎨ R + Q + R
3 3 2 3
+ R − Q3 + R2 3
⎪⎩ ⎭
(A.62)
⎧⎪
( ) ( ⎫⎪
)
1 1
× ⎨ R + Q3 + R2 3 + R − Q3 + R2 3 ⎬
⎪⎩ ⎪⎭
( )( )( ) (R − ) (A.63)
1 3
= R + Q3 + R2 + R − Q3 + R2 + R + Q3 + R 2 3
Q3 + R2
+ (R + ) (R − )
2 1
Q3 + R2 3
Q3 + R2 2
− 2QB
1⎛
( ) + (R − ) ⎞⎟⎟ (A.64)
1 1
= −2QB + 2 R + (R 2 − (Q 3 + R 2 ) )3 ⎜ R + Q 3 + R 2 3
Q3 − R2 3
⎜
⎝ ⎠
= −2QB + 2 R − QB = −3QB + 2 R (A.65)
Plugging B 3 and B into the left side of Equation A.58 gives:
( −3QB + 2 R ) + 3QB = 2 R (A.66)
109
Now, plugging C = 3Q into the quadratic part of Equation A.55 gives:
x 2 + Bx + ( B 2 + 3Q ) = 0 (A.67)
which provides the solution.
x=
1
2
(
− B ± B 2 − 4( B 2 + 3Q ) ) (A.68)
1 1
=− B± − 3B 2 − 12Q (A.69)
2 2
1
= − B ± 3i B 2 − 4Q (A.70)
2
These can be simplified by defining
( ) − (R − )
1 1
A≡ R+ Q +R 3 2 3
Q +R
3 2 3
(A.71)
( ) ( )
2 2
( )
1
A = R+ Q +R
2 3 2 3
− 2 R − (Q + R ) + R − Q + R
2 3 2 3 3 2 3
(A.72)
( ) + (R − )
2 2
= R + Q3 + R2 3
Q3 + R2 3
+ 2Q (A.73)
A 2 = B 2 + 4Q (A.74)
So the solutions to the quadratic portion of Equation A.55 can be written as
1 1
x =− B± 3i A (A.75)
2 2
Defining:
D ≡ Q3 + R2 (A.76)
S ≡3 R+ D (A.77)
T ≡3 R− D (A.78)
110
where
B = S +T (A.79)
A = S −T (A.80)
Therefore, at least, the roots of the original equation A.37 are given by:
1
Z1 = − a 2 + ( S + T ) (A.81)
3
1 1 1
Z 2 = − a2 − (S + T ) + i 3(S − T ) (A.82)
3 2 2
1 1 1
Z 3 = − a 2 − ( S + T ) − i 3( S − T ) (A.83)
3 2 2
With a 2 as the coefficient of Z 2 in Equation A.1 and S and T as defined above; these
three equations providing the three roots of the cubic equation are sometimes known as
Candamo’s formula. If the equation is in the standard form of Vieta,
x 3 + Px = q (A.84)
111
APPENDIX B
VAN DER WAALS EXPRESSIONS FOR FLUID CRITICAL POINT
The van der Waals equation of state (VDW-EOS), proposed in 1873, was the first
equation to represent vapor-liquid coexistence. The VDR-EOS is a two-parameter
equation with pressure given by a cubic function of molar volume in the form
RT a (T )
P= − 2 (B .1)
V −b V
The first term on the right hand side is the repulsive term and the second term is
the attractive term is temperature dependent.
V
Multiplying both sides of Equation B.1 by to obtain the VDW-EOS in Z
RT
form
V a
Z= − (B.2)
V − b RTV
by definition, where
PV
Z= (B.3)
RT
and
ZRT
V = (B.4)
P
Where Z is the compressibility factor, T is temperature, V is volume, P is
pressure, and R is the molar universal gas constant. The parameter a is a measure of the
112
attractive forces between molecules, and the parameter b is the co-volume occupied by
the molecules (if the molecules are represented by hard-spheres of diameter d, then
( 2πNσ 3 )
b= .
3
Substituting Equation B.4 into Equation B.2 leaves
ZRT aP
Z= − (B.5)
ZRT − Pb ZR 2T 2
or
1 ap
Z= − 2 2 (B.6)
Pb R T
1−
ZRT
with
aP
A= (B.7)
R 2T 2
and
bP
B= (B.8)
RT
Substituting Equation B.7 and Equation B.8 into Equation B.6 leaves
1 A
Z= − (B.9)
B Z
1−
Z
or
Z A
Z= − (B.10)
Z−B Z
or
113
Z 2 − A( Z − B )
Z= (B.11)
( Z − B) Z
and Z ( Z − B ) Z = Z 2 − A( Z − B ) (B.12)
or
Z 3 − BZ 2 = Z 2 − AZ + AB (B.13)
or
Z 3 − BZ 2 − Z 2 + AZ − AB = 0 (B.14)
then
Z 3 − (1 + B ) Z 2 + AZ − AB = 0 (B.15)
Equation B.1 was expanded to Equation B.15 form, which is a cubic equation.
When specialized to the critical state, has three equal roots, that is, that it be of the form
(Z − Z c )3 = 0 (B.16)
Expanding Equation (A.16), gives
3
( Z − Z c ) 3 = Z 3 − 3Z c Z 2 + 3Z c Z − Z c = 0 (B.17)
Equating the coefficients of Equation B.15 to the coefficients of Equation B.17, leaves
3 Z c = 1 + Bc (B.18)
2
3Z c = Ac (B.19)
and
3
Z c = Ac Bc (B.20)
There are three equations B.18, B.19, and B.20 with three unknowns Bc, Ac, and
Zc. To find these unknowns, substituting Ac of Equation B.19 into Equation B.20, obtain
114
3 2
Z c = 3 Z c Bc (B.21)
then
Z 3c Zc
Bc = 2
= (B.22)
3Z c 3
Substituting Equation (B.22) into Equation (B.18), leaves
Zc
3Z c = 1 + (B.23)
3
and
9Z c = 3 + Z c (B.24)
then
3
Zc = (B.25)
8
Substituting the value of Zc in Equation B.25 into Equation B.19, obtain
9 27
Ac = 3 = (B.26)
64 64
Substituting Equation B.25 into Equation B.18, gives
1
Bc = (B.27)
8
Now, consider the generalized form of the Lawal-Lake-Silberberg (LLS) cubic
equation of state. That is,
RT a
P= − 2 (B.28)
V − b V + αbV − βb 2
and the gas law is given,
PV = ZRT (B.29)
115
where, by definition
PV
Z= (B.30)
RT
and
ZRT
V = (B.31)
P
V
Multiplying both sides of Equation B.28 by the value
RT
V RT V a V
⋅P = ⋅ − 2 ⋅ (B.32)
RT V − b RT V + αbV − β b RT
2
then
V aV
Z= − (B.33)
V − b RT (V + αbV − β b 2 )
2
Substituting Equation B.31 into Equation B.33, yields
ZRT ZRT
a⋅
Z= P − P (B.34)
− b RT ⎡⎢( ⎤
ZRT ZRT 2 ZRT
) + αb( ) − βb 2 ⎥
P ⎣ P P ⎦
or
Z AZ
Z= − 2 (B.35)
Z − B Z + αBZ − β B 2
1
Multiplying both sides of Equation B.35 by , gives
Z
1 A
1= − 2 (B.36)
Z − B Z + αBZ − β B 2
or
116
( Z − B )( Z 2 + α BZ − β B 2 ) − ( Z 2 + α BZ − β B 2 ) + A( Z − B ) = 0 (B.37)
Consider that at the critical point, the coefficients of the expanded form of the
cubic equation of state Equation B.37 can be compared to the coefficients of the
expansion ( Z − Z c ) 3 = 0 shown in Equation B.38.
2
Z 3 − 3Z c Z 2 + 3Z c Z − Z 3 = 0 (B.38)
The coefficients of Equation B.37 are:
Z 3 :1 (B.39)
Z 2 : αB − B − 1 (B.40)
Z 1 : β B 2 − αB 2 − αB + A (B.41)
and
Z 0 : β B 3 + β B 2 − AB (B.42)
Substituting these coefficients B.39, B.40, B.41, and B.42 back in Equation B.37, leaves
Z 3 + (αB − B − 1) Z 2 + ( A − β B 2 − αB 2 − αB ) Z + ( β B 3 + β B 2 − AB ) = 0
(B.43)
Equate the coefficients of Equation B.43 to the coefficients of Equation B.38,
obtain
− 3Z c = αBc − Bc − 1
3 Z c = 1 + Bc − αBc (B.44)
3Z c = Ac − β Bc − αBc − αBc
2 2 2
(B.45)
− Z c = β Bc + β Bc − Ac Bc
3 3 2
(B.46)
117
where the subscript c represents the conditions at the critical state. Solve for Zc, Bc, and
Ac. From Equation B.44,
αBc − Bc − 1
− Zc = (B.47)
3
or
1 − αBc + Bc
Zc = (B.48)
3
From Equation B.45
Ac = 3Z c + β Bc + αBc + αBc
2 2 2
(B.49)
Substituting Equation B.48 into Equation B.46, gives
3
⎛ 1 − αBc + Bc ⎞
−⎜
3
⎟ = β Bc + β Bc − 3Z c + β Bc + αBc + αBc Bc
3 2 2 2 2
( ) (B.50)
⎝ ⎠
or
3 2
[
− (1 − αBc + Bc ) = 27 β Bc + 27 β Bc − 9(1 − αBc + Bc ) + 27 β Bc + αBc + αBc Bc
3 2
( 2 2
)]
(B.51)
and
α 3 Bc 3 − 3α 2 Bc 3 + 3αBc 3 − Bc 3 − 3α 2 Bc 2 + 6αBc 2 − 3Bc 2 + 3αBc − 3Bc

− 1 − 27 β Bc − 27 β Bc + 9α 2 B c +9 Bc − 18αBc − 18αBc + 18 Bc + 9 Bc
3 2 2 3 3 2 2
+ 27 β Bc + 27αBc + 27αBc = 0
3 3 2
(B.52)
or
118
(α 3
)
− 3α 2 + 3α − 1 − 27 β + 9α 2 + 9 − 18α + 27 β + 27α Bc + (−3α 2 + 6α
3
− 3 − 27 β − 18α + 18 + 27α ) Bc + (3α + 6 ) − 1 = 0

2
(B.53)
and
(α 3
) ( )
+ 6α 2 + 12α + 8 Bc + − 3α 2 + 15α − 27 β + 15 Bc + (3α + 6)Bc − 1 = 0
3 2
(B.54)
or
(α 3
) ( )
+ 6α 2 + 12α + 8 Bc + 3 − α 2 + 5α − 9β + 5 Bc + 3(α + 2)Bc − 1 = 0
3 2
(B.55)
Which can be further simplified to the following expression of the terms and appropriate
grouping of the variables:
θ 1 Bc 3 + θ 2 Bc 2 + θ 3 B c + θ 4 = 0 (B.56)
where
θ 1 = (α 3 + 6α 2 + 12α + 8) (B.57)
θ 2 = (15 + 15α − 27 β − 3α 2 ) (B.58)
θ 3 = (6 + 3α ) (B.59)
θ 4 = −1
(B.60)
Critical Condition by the Critical Compressibility Form
From equation B.44,
− 3Z c = Bc (α − 1) − 1, (B.43)
119
the following expressions can be deduced:
(1 − 3 Z c )
Bc =
(α − 1)
3Z c − 1
Bc = (B.61)
1−α
Substituting of Equation B.61 into Equation B.55, yield
(1 − 3 Z c ) 3 (1 − 3 Z c ) 2
(α 3 + 6α + 12α + 8)( ) + (−3α 2 + 15α − 27 β + 15)( ) +
(α − 1) (α − 1)
(1 − 3 Z c )
(3α + 6)( ) −1 = 0
(α − 1)
(B.62)
or
(α 3 + 6α 2 + 12α + 8)(1 − 3 Z c )3 + (−3α 2 + 15α − 27 β + 15)(1 − 3 Z c ) 2 (α − 1) +

(B.63
(3α + 6)(1 − 3 Z c )(α − 1) 2 − (α − 1)3 = 0
Let
A = (α 3 + 6α 2 + 12α + 8)(1 − 3Z c ) 3
B = (−3α 2 + 15α − 27 β + 15)(1 − 3Z c ) 2 (α − 1)
(B.64)
C = (3α + 6)(1 − 3Z c )(α − 1) 2
D = (α − 1) 3
And,
( A) + ( B ) + (C ) − ( D ) = 0 (B.65)
Expanding A, B, C, and D, then
120
A = (α 3 + 6α + 8)(1 − 3Z c ) 3
= (−27α 3 Z c − 162α 2 Z c − 324 Z c − 216 Z c + 27α 3 Z c + 162α 2 Z c + 324αZ c + 216 Z c −
3 3 3 3 2 2 2 2
9α 3 Z c − 54α 2 Z c − 108αZ c − 72 Z c + α 3 + 6α 2 + 12α + 8
B = (−3α 2 + 15α − 27 β + 15)(1 − 3Z c ) 2 (α − 1)

= (−27α 3 Z c + 162α 3 Z c − 243αβ Z c + 243β Z c − 135 Z c − 18α 3 Z c
2 2 2 2 2
− 108α 2 Z c − 162αβ Z c − 162 β Z c + 90αZ c + 90 Z c − 3α 3 + 18α 2 − 15α − 27αβ

− 27 β − 15)
C = (3α + 6)(1 − 3Z c )(α − 1) 2

= (−9α 3 Z c + 27αZ c − 18 Z c + 3α 3 − 9α + 6)
D = (α − 1) 3 = (α 3 − 3α 2 + 3α − 1)
substituting A, B, C, and D in Equation B.65, obtain
(−27αZ c − 162α 2 Z c − 324αZ c − 216 Z c + 27α 3 Z c + 162α 2 Z c + 324αZ c

3 3 3 3 2 2 2
+ 216 Z c − 9α 3 Z c − 54α 2 Zc − 108αZ c − 72 Z c + α 3 + 6α 2 + 12α + 8) +

2
(−27α 3 Z c + 162α 2 Z c − 243αβ Z c − 243β Z c − 135 Z c + 18α 3 Z c − 18α 2 Z c − 162αβ Z c

2 2 2 2 2
− 162 β Z c + 90 Z c − 3α 3 + 3α 2 + 18α 2 − 27αβ − 27 β − 15) + ( −9α 3 Z c + 27αZ c − 18 Z c

+ 3α 3 − 9α + 6) − (α 3 − 3α 2 + 3α − 1) = 0
(B.66)
or
( −27α 3 − 162α 2 − 324α − 216) Z c − (324α 2 + 324α + 243β − 243αβ + 81) Z c

3 2
− ( −162α 2 − 81α − 162αβ − 162 β ) Z c + ( 27α 2 − 27αβ − 27 β ) = 0
(B.67)
or
(α 3 + 6α 2 + 12α + 8) Z c − (12α 2 + 12α + 9 β − 9αβ + 3) Z c

3 2
(B.68)
+ (6α 2 + 3α − 6αβ + 6 β ) Z c − ( β + α 2 − αβ ) = 0
121
Let
θ 1 = (8 + 12α + 6α 2 + α 3 )
θ 2 = −(3 + 12α + 12α 2 + 9 β − 9βα )
(B.69)
θ 3 = (3α + 6α 2 + 6β − 6αβ )
θ 4 = −( β + α 2 − αβ )
Then the critical condition by the critical compressibility form is
θ1 Z c 3 + θ 2 Z c 2 + θ 3 Z c + θ 4 = 0 (B.70)
Derivation No.2
From Equation B.44
(1 − 3 Z c )
Bc = (B.44)
(α − 1)
From Equation B.46
− Z c = β Bc + β Bc − Ac Bc
3 3 2
(B.46)
Substituting for Ac = 3Z c + β Bc + αBc + αBc , obtain

2 2 2
2
[
− Z c = β Bc + β Bc − Bc 3Z c + β Bc + αBc + αBc
3 3 2 2 2
] (B.71)
Substituting Equation B.61 into Equation B.68, then

3 2
⎛ (1 − 3 Z c ) ⎞ ⎛ (1 − 3 Z c ) ⎞ ⎛ (1 − 3 Z c ) ⎞
= β ⎜⎜ ⎟⎟ + β ⎜⎜
3
− Zc ⎟⎟ − ⎜⎜ ⎟⎟
⎝ (α − 1) ⎠ ⎝ (α − 1) ⎠ ⎝ (α − 1) ⎠
⎡ ⎛ (1 − 3 Z c ) ⎞
2
⎛ (1 − 3 Z c ) ⎞
2
⎛ (1 − 3 Z c ) ⎞ ⎤
⎢ 3 Z c + β ⎜⎜
2
⎟⎟ + α ⎜⎜ ⎟⎟ + α ⎜⎜ ⎟⎟ ⎥ (B.72)
⎢⎣ ⎝ (α − 1) ⎠ ⎝ (α − 1) ⎠ ⎝ (α − 1) ⎠ ⎥⎦
Multiply both sides of Equation B.68 by (α − 1) 3 , obtain
122
− 3 Z c (α − 1) 3 = β (1 − 3 Z c ) 3 + β (1 − 3 Z c )(α − 1) − (1 − 3 Z c )
3 2
(B.73)
[3Z c
2
(α − 1) 2 + β (1 − 3 Z c ) 2 + α (1 − 3 Z c ) 2 + α (1 − 3 Z c )(α − 1) 2 ]
or
− 3 Z c (α − 1) 3 − β (1 − 3 Z c ) 3 − β (1 − 3 Z c ) 2 (α − 1) + (1 − 3Z c )
3
(B.74)
[3Z c
2
]
(α − 1) 2 + β (1 − 3 Z c ) 2 + α (1 − 3 Z c ) 2 + α (1 − 3 Z c )(α − 1) 3 = 0
2 3
where, (1 − 3Z c ) 3 = 1 − 9 Z c + 27Z c − 27 Z c (B.75)
(α − 1) 3 = α 3 − 3α 2 + 3α − 1 (B.76)
(α − 1) 2 = α 2 − 2α + 1 (B.77)
2
(1 − 3Z c ) 2 = 1 − 6 Z c + 9 Z c (B.74)
substituting Equations, B.75, B.76, B.77 into Equation B.74, obtain
− Z c (α 3 − 3α 2 + 3α − 1) − β (1 − 9 Z c + 27 Z c − 27Z c ) − β (1 − 6Z c
3 2 3
⎡3Z c 2 (α 2 − 2α + 1) + β (1 − 6 Z c + 9 Z c 2 )⎤
⎢ ⎥ (B. 75)
+ 9 Z c )(α − 1) + (1 − 3Z c ) ⎢+ α (1 − 6 Z c + 9 Z c )
2 2
⎥=0
⎢ ⎥
⎢⎣+ α (1 − 3Z c )(α − 3α + 3α − 1
3 2
⎥⎦
or
− Z c (α 3 − 3α 2 + 3α − 1) − β (1 − 9 Z c + 27 Z c − 27 Z c ) − β (1 − 6 Z c
3 2 3
⎡3Z c 2 (α 2 − 2α + 1)(1 − 3Z c ) + β (1 − 6 Z c + 9 Z c 2 )⎤
⎢ ⎥ (B.76)
+ 9 Z c )(α − 1) + ⎢(1 − 3Z c ) + α (1 − 6 Z c + 9 Z c )(1 − 3Z c )
2 2
⎥=0
⎢ ⎥
⎢⎣+ α (1 − 3Z c )(α − 2α + 1)(1 − 3Z c )
2
⎥⎦
where,
(α − 1)(1 − 6 Z c + 9 Z c ) = α − 6αZ c + 9αZ c − 1 + 6 Z c − 9 Z c

2 2 2
(B.77)
123
(1 − 3 Z c )(α 2 − 2α + 1) = α 2 − 2α + 1 − 3α 2 Z c + 6αZ c − 3 Z c (B.78)
(1 − 3Z c )(1 − 6 Z c + 9 Z c )(α 2 − 2α + 1) = 1 − 9 Z c + 27 Z c − 27 Z c
2 2 3
(B.79)
and,
(1 − 6 Z c + 9 Z c )(α 2 − 2α + 1) = α 2 − 2α + 1 − 6α 2 Z c + 12αZ c
2
(B.80)
+ 9α 2 Z c − 18αZ c + 9 Z c
2 2 2
Substituting Equations B.77, B.78, B.79, and B.80 into Equation B.76, obtain
− Z c (α 3 − 3α 2 + 3α − 1) − β (1 − 9 Z c + 27 Z c − 27 Z c ) − β (α − 6αZ c
3 2 3
⎡3 Z c 2 (α 2 − 2α + 1 − 3α 2 Z c + 6αZ c − 3Z c ) ⎤
⎢ ⎥
⎢+ β (1 − 9 Z c + 27 Z c − 27 Z c ) + α (1 − 9 Z c ⎥
2 3
+ 9αZ c
2 2
− 1 + 6Z c − 9Z c ) + ⎢ ⎥=0
⎢+ 27 Z c − 27 Z c ) + α (α − 2α + 1 − 6α
2 3 2 2
⎥
⎢ 2 ⎥
⎣+ 12αZ c − 6 Z c + 9α Z c − 18αZ c + 9 Z c )⎦
2 2 2
(B.81)
and,
(α 3 − 3α 2 + 3α + 27 β + 9α 2 − 18α + 9 + 27α ) Z c −
3
(−9αβ + β + 3 + 12α 2 + 12α ) Z c + (3α + 6α 2 + 6β − 6αβ ) Z c

2
(B.82)
− (α 2 + β − αβ ) = 0
Then,
(α 3 + 6α + 8) Z c − (3 + 12α + 12α 2 + 9 β − 9αβ ) Z c

3 2
(B.83)
+ (6α 2 + 3α + 6 β − 6αβ ) Z c − (α 2 + β − αβ ) = 0
Let,
θ1 = (8 + 12α + 6α 2 + α 3 )
124
θ 2 = −(3 + 12α + 12α 2 + 9 β − 9αβ )
θ 3 = (3α + 6α 2 + 6 β − 6αβ ) (B.84)
θ 4 = −(α + β − αβ )
2
Then,
θ1 Z c 3 + θ 2 Z c 2 + θ 3 Z c + θ 4 = 0 (B.85)
Critical Condition by the Critical Compressibility Form For Mixtures
The generalized cubic equation of state for mixtures is in the following form:
RT am
P= − 2 (B.86)
V − bm V + α m bmV − β m bm 2
By van der Waals mixing rules, the mixture parameters a m , bm , α m , β m take the
following forms:
n a 1 1
a m = ∑∑ x i x j a i 2 a j 2 a ij (B.87)
i j
n
bm = ( ∑ x i x j ) 3 (B.88)
i
n n 1 1
α m = ∑∑ x i x j α i 2 α j 2 α ij (B.89)
i j
n n 1 1
β m = ∑∑ x i x j β i 2 β j 2 β ij (B.90)
i j
and the binary interaction parameters established in terms of Mw ratios of components
form
125
na
⎛ MW i ⎞
a ij = ⎜ ⎟ MW i ≤ MW j (B.91)
⎜ MW ⎟
⎝ j ⎠
nα
⎛ MW i ⎞
α ij = ⎜⎜ ⎟ MW i ≤ MW j
⎟
(B.92)
⎝ MW j ⎠
nβ
⎛ MW i ⎞
β ij = ⎜⎜ ⎟ MW i ≤ MW j
⎟
(B.93)
⎝ MW j ⎠
where na , nα , and na are the exponents of the respective interaction terms.
Expanding Equation B.86 into Z terms and by multiplying both sides of the equations by
V
,
RT
VP V ⎛ RT ⎞ V ⎛ am ⎞
= ⎜ ⎟⎟ − ⎜ ⎟ (B.94)
RT RT ⎜⎝ V − bm ⎜
⎠ RT ⎝ V + α m bmV − β m bm
2 2 ⎟
⎠
⎛ V ⎞ V ⎛ am ⎞
Z = ⎜⎜ ⎟⎟ − ⎜ ⎟ (B.95)
⎜ ⎟
⎝ V − bm ⎠ RT ⎝ V + α m β mV − β m bm
2 2
⎠
by definition,
ZRT
V = ,
P
then,
⎛ ZRT ⎞ ⎛ ⎛ ZRT ⎞ ⎞⎛⎜ ⎞

⎟
⎜ ⎟ ⎜⎜ ⎟⎟
Z =⎜ P ⎟ − ⎜ ⎝ P ⎠ ⎟⎜ am ⎟
⎜ ⎛ ZRT ⎞ ⎟ ⎜ RT ⎟ ⎛ ⎜ 2 ⎟ (B.96)
⎜⎜ ⎟ − bm ⎟ ⎜ ⎟⎜ ⎜ ZRT ⎞⎟ + α m β m ⎛⎜ ZRT ⎞⎟ − β m bm 2 ⎟
⎝⎝ P ⎠ ⎠ ⎝ ⎠⎜⎝ ⎜⎝ p ⎟⎠ ⎝ P ⎠
⎟
⎠
P p2
Multiplying by and by 2 2 , obtain,
RT RT
126
⎛ ⎞ ⎛ ⎛ P2 ⎞ ⎞
⎜ m⎜
⎟
⎜ ⎟ a ⎜ R 2T 2 ⎟⎟
⎜ Z ⎟ ⎛ ZRT ⎞⎜ ⎝ ⎠ ⎟
Z= −⎜ ⎟⎜ ⎟ (B.97)
⎜ ⎟
⎛ P ⎞ ⎝ RT ⎠⎜ 2 ⎛ ZP ⎞ 2⎛ P
2
⎞⎟
⎜ Z − bm ⎜ ⎟⎟
⎜ Z + α β ⎜ ⎟ − β b
m m ⎜ ⎜ ⎟⎟
⎟
⎝ ⎝ RT ⎠ ⎠ 2 2
m m
⎝ ⎝ RT ⎠ ⎝R T ⎠⎠
⎛a P2 ⎞ ⎛b P⎞
since A = ⎜⎜ m2 2 ⎟⎟ and B = ⎜ m ⎟ , then
⎝R T ⎠ ⎝ RT ⎠
⎛ Z ⎞ ⎛⎜ ZA ⎞
⎟
Z =⎜ ⎟−⎜ 2 (B.98)
⎝ Z − B ⎠ ⎝ Z + α m ZB − β m B ⎟⎠
2
or
Z ( Z − B )( Z 2 + α m ZB − β m B 2 ) = Z ( Z 2 + α m ZB − β m B 2 ) − ZA( Z − B ) (B.99)
Z 3 + α m Z 2 B − ZB 2 β m − BZ 2 − α m ZB 2 + B 3 β m − Z 2 − α m ZB + B 2 β m
(B.100)
+ AZ − AB = 0
Z 3 + Z 2 (α m B − B − 1) + Z ( B 2 β m + α m B 2 + α m B − A) + B 3 β m + B 2 β m − AB = 0
(B.101)
Z 3 + Z 2 (1 + B − α m B ) + Z ( A − α m B − α m B 2 − B 2 β m ) + ( AB − B 2 β m − B 3 β m = 0
(B.102)
At the critical point, the generalized cubic equation of state in terms of Zc takes the form:
Z c + (1 + Bc − α m Bc ) Z c + ( Ac − α m Bc − α m Bc − Bc β m ) Z c
3 2 2 2
(B.103)
+ ( Ac Bc − Bc β m − Bc β m = 0
2 3
Now, comparing the coefficients of Equation B.103 with the coefficients of the expansion
( Z − Z c ) 3 =0 shown in Equation B.100
2 2 3
Z 3 − 3Z c Z 2 + 3Z c + 3Z c Z − Z c = 0 (B.104)
127
where,
3 Z c = 1 + Bc − α m Bc (B.105)
3Z c = Ac − α m Bc − α m Bc − Bc β m
2 2 2
(B.106)
and,
Z c = Ac Bc − Bc β m − Bc β m
3 2 3
(B.107)
From Equation B.106 and Equation B.107, Bc and Ac can be solved to give,
3Z c − 1
Bc = (B.105)
1−αm
Ac = 3Z c + α m Bc + β m Bc
2 2 2
(B.106)
By substitution of Ac and Bc with Equation B.98 and simplifying the terms, the analytical
function of Z c = ∫ (α m , β m ) is obtained.
⎛ ⎛ 3Z c − 1 ⎞ ⎛ 3Z c − 1 ⎞
2
⎛ 3Z c − 1 ⎞ ⎞⎟⎛ 3 Z c − 1 ⎞
2
3 ⎜
Z c = 3Z c + α m ⎜⎜
2
⎟ + α m ⎜⎜ ⎟ + β m ⎜⎜ ⎟ ⎜ ⎟
⎜ ⎝ 1 − α m ⎟⎠ ⎝ 1 − α m ⎟⎠ ⎝ 1 − α m ⎟⎠ ⎟⎜⎝ 1 − α m ⎟⎠
⎝ ⎠ (B.107)
2 3
⎛ 3Z − 1 ⎞ ⎛ 3Z − 1 ⎞
− β m ⎜⎜ c ⎟⎟ − β m ⎜⎜ c ⎟⎟
⎝ 1−αm ⎠ ⎝ 1−αm ⎠
and can be further simplified to the following expression by expanding the terms by
grouping,
θ1 Z c 3 + θ 2 Z c 2 + θ 3 Z c + θ 4 = 0 (B.108)
where:
128
θ 1 = (8 + 12α m + 6α m 2 + α m 3 )
θ 2 = −(3 + 12α m + 12α m 2 + 9 β m − 9 β m α m )
(B.109)
θ 3 = (3α m + 6α m 2 + 6 β m − 6α m β m )
θ 4 = −( β m + α m 2 − β m α m )
129
APPENDIX C
PREDICTION RESULTS OF CRITICAL PRESSURE, CRITICAL

TEMPERATURE, AND HEPTANE PLUS PROPERTIES
Table C. 1. Critical Pressure Predictions for Complex Mixtures by Four Methods

(Compositions in Mole Fractions)
Mixture No. 145-1 145-2 145-3 145-4 145-5 145-6 145-7 145-8 145-9
Nitrogen 0.001 0.001 0.001 0.001 0.004 0.001

Carbon Dioxide 0.004 0.005 0.005 0.004 0.006 0.002 0.0149 0.014 0.0156
Methane 0.193 0.271 0.363 0.229 0.365 0.482 0.5248 0.5335 0.5921
Ethane 0.032 0.034 0.038 0.029 0.058 0.065 0.145 0.0679 0.066
Propane 0.585 0.482 0.374 0.407 0.242 0.167 0.157 0.2035 0.1043
I-Butane 0.007 0.007 0.009 0.006 0.007 0.007 0.0055 0.0063 0.0058
n-Butane 0.012 0.015 0.015 0.172 0.215 0.14 0.0179 0.204 0.0831
I-Pentane 0.005 0.006 0.006 0.005 0.004 0.006 0.0055 0.0062 0.0054
n-Pentane 0.007 0.007 0.008 0.006 0.007 0.008 0.0079 0.0092 0.0078
Hexane 0.013 0.015 0.016 0.012 0.01 0.012 0.0082 0.0094 0.0081
Heptanes + 0.141 0.157 0.165 0.129 0.082 0.11 0.1133 0.1296 0.1118
Avg. Mol. Wt. 67.3 68.5 67.5 66.1 48.8 48.8 45 48.4 44.9
Mol. Wt. 243 243 243 243 191 191 191 191 191
Gravity(API)
Critical Temp., Tc (F) 265 265 265 265 234 200 200 200 200
Critical Temp., Tc (o R) 725 725 725 725 694 660 660 660 660
Critical Pc (psia) 2100 2500 3400 1920 2420 3430 4355 4295 4630
Predicted Pc (psia) :
Simon and Yarborough 2002 2550 3280 2113 2452 3490 3984 4261 4691
Etter and Kay 2911 3272 3658 2806 2509 3268 3909 3886 4040
Zais 2175 2613 3203 2298 2418 3480 4073 3982 4357
This work 2101.12 2501.55 3398.03 1922.15 2423.18 3432.17 4349.55 4302.33 4624.49
130
Table C. 2. (Continued)
Mixture No. 145 - 10 145 - 11 145 - 12 145 - 13 145 - 14 4-1 4-2 4-3 4-4 4-5
Nitrogen 0.0016 0.002

Carbon Dioxide 0.0153 0.0008 0.0139 0.0006 0.0008 0.0066 0.0067 0.0061 0.0061 0.0059
Methane 0.5774 0.6298 0.6165 0.4786 0.5808 0.7243 0.7292 0.8227 0.8165 0.795
Ethane 0.0631 0.0858 0.0602 0.082 0.0562 0.0557 0.0556 0.0284 0.0284 0.0281
Propane 0.1178 0.0672 0.0961 0.1359 0.0919 0.0308 0.0306 0.0124 0.0124 0.0128
I-Butane 0.0055 0.023 0.0055 0.0076 0.0081
n-Butane 0.0976 0.0305 0.0773 0.1273 0.082 0.0241 0.0226 0.0091 0.0092 0.0098
I-Pentane 0.005 0.0114 0.0053 0.0066 0.0071
n-Pentane 0.0073 0.0122 0.0077 0.0069 0.0073 0.015 0.0147 0.0067 0.007 0.0078
Hexane 0.0075 0.0206 0.008 0.0139 0.0148 0.0179 0.0183 0.0125 0.0131 0.015
Heptanes + 0.1035 0.1187 0.1095 0.139 0.1488 0.1256 0.1223 0.1021 0.1073 0.1247
Avg. Mol. Wt. 44.3 44.4 43.4 54.7 53.1 39.9 39.3 33 33.8 36.5
Mol. Wt. 191 167 191 205 205 167 167 158 158 158
Gravity(API)
Characterization Fact. 11.9 11.7 11.9 11.6 11.6 11.8 11.8 11.9 11.9 11.9
Critical Temp., Tc (F) 200 292 200 180 180 285 251 100 160 212
Critical Temp., Tc (oR) 660 752 660 640 640 745 711 560 620 672
Critical Press., Pc (psia) 4364 4850 4745 3500 4800 5130 5350 6000 5820 5620
Predicted Pc:
Simon and Yarborough 4413 4789 4930 3568 4735 5388 5412 5696 5695 5685
Etter and Kay 3865 4198 4169 3598 4209 4660 4679 5102 5094 5040
Zais 4150 4870 4592 3662 4488 5070 5083 5027 5980 5947
This work 4355.37 4848.37 4735.61 3495.07 4804.54 5134.45 5341.33 5988.62 5821.98 5608.11
131
Mixture No. 4-6 4-7 4-8 4-9 4-10 75 - 1 75 - 2 75 - 3 75 - 4 75 - 5
Nitrogen 0.0128 0.0058 0.0053 0.0054 0.0038

Carbon Dioxide 0.0035 0.0156 0.0008 0.0075 0.0074 0.0045
Methane 0.6433 0.6865 0.657 0.7164 0.8213 0.788 0.724 0.728 0.597 0.83
Ethane 0.0638 0.0603 0.0869 0.0548 0.0637 0.059 0.0542 0.0546 0.089 0.0378
Propane 0.0605 0.0232 0.0537 0.031 0.0409 0.0315 0.03 0.0302 0.05 0.0144
I-Butane
n-Butane 0.0565 0.0309 0.0303 0.0258 0.0235 0.0265 0.031 0.0207 0.049 0.0089
I-Pentane
n-Pentane 0.0404 0.0243 0.0195 0.0216 0.0122 0.0425 0.071 0.0688 0.093 0.0436
Hexane 0.0366 0.0256 0.0173 0.0198 0.0103 0.0252 0.0456 0.0438 0.0308
Heptanes + 0.0954 0.1245 0.1217 0.1231 0.0234 0.0214 0.0388 0.0375 0.122 0.0263
Avg. Mol. Wt. 35.2 41.5 45.7 40.1 25 29.5 29.1 36.2 24.5
Mol. Wt. 114 171 207 167 114 106 106 106 100 106
Gravity (API)
Characterization Fact. 11.7 12 12 11.8
Critical Temp., Tc (oR) 655 699 605 703 515 569 569 629 514
Predicted Pc (psia)
Simon and Yarborough 2371 5557 6687 5375 2456 2467 2465 2821
Etter and Kay 3013 4490 4865 4560 2574 2725 2722 2020 2812
Zais 2641 5325 5623 4851 2272 2277 2441 2467 2356 2443
This work 2723.07 5096.27 5582.6 5147.51 2386.85 2572.96 2537.73 2514.61 2581.33
132
Mixture No. 75 - 6 75 - 7 75 - 8 141 - 1 141 - 2 141 - 3 141 - 4 141 - 5 141 - 6
Nitrogen 0.0038 0.0036 0.003 0.1101 0.0477 0.0156 0.0123

Carbon Dioxide 0.0044 0.0043 0.0035 0.0008 0.0019 0.0047 0.0028 0.0172 0.011
Methane 0.815 0.784 0.643 0.3465 0.4675 0.4656 0.6173 0.6527 0.586
Ethane 0.0372 0.0355 0.0294 0.1561 0.1306 0.1645 0.1024 0.0725 0.1309
Propane 0.0141 0.0136 0.0111 0.1499 0.105 0.1163 0.0673 0.0391 0.0699
I-Butane 0.0121 0.0112 0.0141 0.0085 0.0157 0.0081
n-Butane 0.0102 0.013 0.0252 0.0852 0.0472 0.0454 0.0352 0.0204 0.0349
I-Pentane 0.0084 0.0169 0.0112 0.0106 0.016 0.0097
n-Pentane 0.0501 0.0631 0.123 0.0109 0.0192 0.0182 0.0171 0.0123 0.0187
Hexane 0.0354 0.0447 0.0871 0.02 0.0373 0.0215 0.0226 0.029 0.0194
Heptanes + 0.0303 0.0382 0.0747 0.1 0.1155 0.1229 0.1039 0.1251 0.1114
Avg. Mol. Wt. 25.4 27.6 37.7

Mol. Wt. 106 106 106 164 142 168 144 157 184
Gravity (API) 40.6 42.5 40.1 47.3 49.5 42.2
Characterization Fact. 11.6 11.55 11.75 11.75 12 11.85
Critical Pressure, Pc (psia) 2675 2730 2900 2970 3010 3573 3470 4060 4335
Predicted Pc (psia)
Etter and Kay 2873 2930 2724 2932 3019 3528 3507 3959 3972
Zais 2513 2588 2355 2710 2668 3599 3410 4493 4680
This work 2671.26 2731.9 2897.64 2970.33 3012.3 3577.27 3469.13 4059.64 4342.19
133
Mixture No. 141 - 7 141 - 8 141 - 9 141 - 10 141 - 11 141 - 12 141 - 13 141 - 14 141 - 15
Nitrogen 0.0009 0.0012 0.0013

Carbon Dioxide 0.0088 0.0041 0.0048 0.0056 0.0043 0.0038 0.0962 0.0776 0.0701
Methane 0.722 0.7052 0.7175 0.6992 0.5564 0.4902 0.5431 0.4371 0.3954
Ethane 0.0474 0.0725 0.0748 0.0638 0.0523 0.0464 0.1149 0.0932 0.0848
Propane 0.0278 0.0465 0.0456 0.0404 0.2108 0.297 0.0768 0.216 0.2738
I-Butane 0.0105 0.019 0.0177 0.0081 0.0069 0.0062 0.0147 0.0123 0.0115
n-Butane 0.0158 0.0129 0.0136 0.0169 0.0147 0.0133 0.0257 0.0223 0.0207
I=Pentane 0.0112 0.0064 0.0073 0.0079 0.007 0.0064 0.0082 0.0076 0.0072
n-Pentane 0.008 0.008 0.0046 0.0058 0.0052 0.0047 0.0082 0.0078 0.0076
Hexane 0.0181 0.01 0.0099 0.011 0.01 0.0093 0.0126 0.013 0.013
Heptanes + 0.1297 0.1142 0.1031 0.1413 0.1324 0.1227 0.0996 0.1131 0.1159
Avg. Mol. Wt.

Mol. Wt. 178 211 211 202 202 202 253 253 253
Gravity (API) 42.2 36.7 36.7 35 35 35 29 29 29
Characterization Fact. 11.8 11.7 11.7 11.55 11.55 11.55 11.55 11.55 11.55
Critical Press., Pc (psia) 5420 6345 6560 8050 5130 4180 6715 4780 4310
Predicted Pc (psia)
Etter and Kay 4783 5201 5276 5095 4083 3659 4831 4051 3796
Zais 5470 7037 7299 5925 4436 3861 6250 4844 4380
This work 5416.47 6354.1 6569.65 8041.73 5129.18 4172.89 6708.13 4787.78 4315.78
134
Mixture No. 141 - 16 141 - 17 141 - 18 141 - 19 141 - 20 141 - 21 141 - 22 141 - 23 141 - 24
Nitrogen 0.0052 0.0007 0.0008 0.0004

Carbon Dioxide 0.0871 0.0776 0.0778 0.0006 0.0011 0.0008 0.0008 0.0023 0.0022
Methane 0.4911 0.4384 0.654 0.6091 0.5432 0.4789 0.3678 0.77 0.7247
Ethane 0.1041 0.0935 0.0889 0.0865 0.0706 0.0624 0.0488 0.0316 0.0371
Propane 0.0699 0.0632 0.061 0.0765 0.195 0.2786 0.4154 0.0228 0.0473
I-Butane 0.0135 0.0123 0.0198 0.0183 0.0078 0.0075 0.007 0.0149 0.026
n-Butane 0.1063 0.1768 0.0317 0.0304 0.014 0.0132 0.0124 0.019 0.028
I-Pentane 0.0078 0.0074 0.0189 0.0134 0.0077 0.0072 0.0067 0.0084 0.0148
n-Pentane 0.0077 0.0077 0.0172 0.0094 0.006 0.0057 0.0053 0.0137 0.0167
Hexane 0.0123 0.0128 0.0307 0.0184 0.0165 0.0156 0.0145 0.0212 0.0202
Heptanes + 0.1002 0.1103 0.0692 0.1374 0.1368 0.1293 0.1209 0.0961 0.083
Avg. Mol. Wt.

Mol. Wt. 253 253 126 229 229 229 229 152 152
Gravity (API) 29 29 60.4 30.2 30.2 30.2 30.2 51 51
Critical Temp. Tc (F) 280 280 144 221 221 221 221 183 183
Critical Press. Pc (psia) 5400 4130 2660 5700 5140 4040 2800 4120 3755
Predicted Pc (psia)
Etter and Kay 4219 3789 3009 4686 4333 3926 3315 4331 3845
Zais 5322 4527 2796 5497 4811 4202 3235 3963 3527
This work 5397.08 4137.16 2656.94 5693.09 5143.95 4043.34 2798.17 4118.03 3755.24
135
Mixture No. 141 - 25 141 - 26 141 - 27 141 - 28 141 - 29 141 - 30 141 - 31 93 - 1 37 - 1 158 - 1
Nitrogen 0.0487 0.0249 0.0526 0.0115 0.0017 0.1898 0.0052 0.0076

Carbon Dioxide 0.0014 0.0029 0.0149 0.2202 0.0073 0.003 0.0013
Hydrogen Sulfide .0068b
Methane 0.4534 0.4957 0.6414 0.5325 0.2756 0.695 0.4004 0.5832 0.6849 0.5391
Ethane 0.0705 0.1379 0.0733 0.1428 0.1144 0.0696 0.0767 0.1355 0.0971 0.142
Propane 0.1961 0.1015 0.0605 0.0926 0.2486 0.0426 0.0347 0.0761 0.0542 0.0964
I-Butane 0.0936 0.0222 0.0154 0.0183 0.085 0.0109 0.0064 0.0084 0.0086
n-Butane 0.0825 0.0403 0.0298 0.0349 0.1294 0.0157 0.0204 0.0319 0.0223 0.0554
I-Pentane 0.0542 0.0162 0.0142 0.0134 0.043 0.0102 0.0046 0.008 0.0088
n-Pentane 0.0343 0.0189 0.0178 0.0179 0.027 0.0086 0.0067 0.0161 0.0092 0.0299
Hexane 0.0129 0.0234 0.0233 0.0318 0.0161 0.0184 0.0084 0.019 0.0142 0.0272
Heptanes + 0.0011 0.0952 0.0994 0.0632 0.0465 0.1124 0.0181 0.1145 .0925a 0.1011
Avg. Mol. Wt.

Mol. Wt. 114 161 161 117 192 180 115 193 147 178.5
Sp. Gravity or API 68.7 47.4 47.4 59.4 41 0.825 0.76 0.8135
Characterization Fact. 12.6 11.9 11.9 12.1 11.85 11.9
Critical Temp., Tc (F) 183 161 161 161 171 240 35 190 120 + 30 193
Critical Temp., Tc (oR) 643 621 621 621 631 700 495 650 #VALUE! 653
Predicted Pc (psia)
Simon and Yarborough 1242 3157 4276 1899 2114 4862 3634
Etter and Kay 1478 3238 3861 2592 1843 4119 3430
Zais 1484 3364 4303 2263 1850 5136 1987 4528 3970 3839
This work 1409.62 3229.75 4084.59 2321.97 1977.91 4906.24 3450.08 4449.06 5503.58 3483.95
(a) Heptanes plus treated as individual components through hexadecane
(b) H2S treated as propane
136
Mixture No. 58 - 1 11 - 1 6-1 6-2 6-3 30 - 1 52 - 2 52 - 3 52 - 6
Nitrogen 0.0066 0.0024 0.0021 0.002 0.0018 0.0124 0.0027

Carbon Dioxide 0.018 0.0302 0.0084 0.0076 0.007 0.0065 0.0022 0.0003
Methane 0.5966 0.6073 0.7504 0.6822 0.6253 0.5772 0.5706 0.5428 0.604
Ethane 0.1289 0.1177 0.0537 0.0489 0.0448 0.0414 0.1496 0.149 ..0517
propane 0.0653 0.0891 0.0136 0.0124 0.0114 0.0105 0.0825 0.0912 0.0757
I-Butane 0.0173 0.0198 0.0021 0.0019 0.0018 0.0016 0.0092 0.0072 0.0455
n-Butane 0.0219 0.0279 0.0127 0.1025 0.1773 0.2405 0.0367 0.0456 0.0389
I-Pentane 0.01 0.0124 0.0106 0.0096 0.0088 0.0082 0.0064 0.0249
n-Pentane 0.0096 0.008 0.0099 0.009 0.0082 0.0076 0.018 0.0186 0.0182
Hexane 0.0132 0.0237 0.0215 0.0197 0.0182 0.0217 0.0255 0.0394
Heptanes + 0.1126 0.0878 .1125a .1023a .0937a .0865a 0.0907 0.1201 0.0897
Avg. Mol. Wt.

Mol. Wt. 155 172 118 118 118 118 173 166 133
Specific Gravity or API 0.7994 38 41.2 0.8126 51.9
Characterization Fact. 11.8 11.5 11.7 11.7 11.85
Critical Temp., Tc (F) 264 125 172.5 297.5 232.5 252.5 170 170 245
Critical Temp., Tc (oR) 724 585 632.5 757.5 692.5 712.5 630 630 705
Critical Pressure, Pc (psia) 3840 3940 4715 3950 3470 3140 4220 3875 2953
Predicted Pc (psia)
Etter and Kay 3720 3794 3794 3273 2901 2621 3642 3554 2987
Zais 3116 3905 4061 3501 3079 2753 4093 3768 2577
This work 3834.23 3945.43 4710.42 3947.13 3466.88 3140.71 4224.02 3871.53 2955.59
137
Mixture No. 47 - 1 26 - 1 26 - 2 26 - 3 47 - 2 26 - 4 26 - 5 26 - 6 26 - 7 26 - 8
Nitrogen 0.0884 0.1611 0.2441 0.113 0.24 0.1146 0.135 0.0705

Carbon Dioxide 0.012 0.0109 0.01 0.0091 0.0044 0.003 0.002 0.0013 0.002 0.0025
Methane 0.9089 0.8286 0.7625 0.887 0.858 0.7364 0.7364 0.7665 0.7515 0.8532
Ethane 0.044 0.0401 0.0369 0.0333 0.016 0.015 0.012 0.0551 0.061 0.0411
Propane 0.0191 0.0174 0.016 0.0144 0.007 0.006 0.0053 0.0335 0.0327 0.0198
I-Butane 0.0033 0.003 0.0028 0.003 0.0014 0.0012 0.001 0.0035 0.0038 0.0037
n-Butane 0.006 0.0055 0.0051 0.004 0.002 0.0018 0.0015 0.009 0.006 0.0039
I-Pentane 0.0021 0.0019 0.0018 0.0016 0.0007 0.0006 0.0005 0.0017
n-Pentane 0.0013 0.0012 0.0011 0.001 0.0005 0.0004 0.0004 0.0015 .0020c .0022c
Hexane 0.0015 0.0014 0.0012 0.0011 0.0005 0.0004 0.0004
Heptanes + 0.0018 0.0016 0.0015 0.0014 0.0007 0.0006 0.0005 .0033d
Helium 0.01 0.006 0.0031
Avg. Mol. Wt. 18.4 19.25 19.94 20.75 16.9 18.11 19.56 20.02 19.98 18.6
Mol. Wt. 115 115 115 115 115 115 115 100
Gravity (API)
Characterization Fact.
Critical Temp., Tc (F) -79 -92 -104 -120 -101 -117 -131 -84 -90 -96
Critical Pressure, Pc (psia) 925 955 968 973 765 790 815 1143 1107 918
Predicted Pc (psia)
Simon and Yarborough 3285 3337 3380 3431 3681 3701 3740 3060 3042 3316
Etter and Kay 1385 1340 1303 1260 995 958 919 1519 1357 1265
Zais 1207 1273 1327 1340 907 958 978 1419 1328 1107
This work 924.78 955.88 967.83 973.21 765.06 790.12 815.1 1142.64 1107.03 918.27
© Heavy fraction treated as n-pentane.
(d) Heavy fraction treated as n-heptane.
(e) Helium treated as methane.
138
Table C. 10. Critical Temperature Predictions for Complex Mixtures by LLS EOS Method
Mixture No. 145-1 145-2 145-3 145-4 145-5 145-6 145-7 145-8 145-9
Nitrogen 0.001 0.001 0.001 0.001 0.004 0.001

Carbon Dioxide 0.004 0.005 0.005 0.004 0.006 0.002 0.0149 0.014 0.0156
Methane 0.193 0.271 0.363 0.229 0.365 0.482 0.5248 0.5335 0.5921
Ethane 0.032 0.034 0.038 0.029 0.058 0.065 0.145 0.0679 0.066
Propane 0.585 0.482 0.374 0.407 0.242 0.167 0.157 0.2035 0.1043
I-Butane 0.007 0.007 0.009 0.006 0.007 0.007 0.0055 0.0063 0.0058
n-Butane 0.012 0.015 0.015 0.172 0.215 0.14 0.0179 0.204 0.0831
I-Pentane 0.005 0.006 0.006 0.005 0.004 0.006 0.0055 0.0062 0.0054
n-Pentane 0.007 0.007 0.008 0.006 0.007 0.008 0.0079 0.0092 0.0078
Hexane 0.013 0.015 0.016 0.012 0.01 0.012 0.0082 0.0094 0.0081
Heptanes + 0.141 0.157 0.165 0.129 0.082 0.11 0.1133 0.1296 0.1118
Avg. Mol. Wt. 67.3 68.5 67.5 66.1 48.8 48.8 45 48.4 44.9
Mol. Wt. 243 243 243 243 191 191 191 191 191
Gravity(API)
This work 725.39 725.45 724.58 725.81 694.91 694.44 659.17 661.13 659.22
139
Mixture No. 145 - 10 145 - 11 145 - 12 145 - 13 145 - 14 4-1 4-2 4-3 4-4 4-5
Nitrogen 0.0016 0.002

Carbon Dioxide 0.0153 0.0008 0.0139 0.0006 0.0008 0.0066 0.0067 0.0061 0.0061 0.0059
Methane 0.5774 0.6298 0.6165 0.4786 0.5808 0.7243 0.7292 0.8227 0.8165 0.795
Ethane 0.0631 0.0858 0.0602 0.082 0.0562 0.0557 0.0556 0.0284 0.0284 0.0281
Propane 0.1178 0.0672 0.0961 0.1359 0.0919 0.0308 0.0306 0.0124 0.0124 0.0128
I-Butane 0.0055 0.023 0.0055 0.0076 0.0081
n-Butane 0.0976 0.0305 0.0773 0.1273 0.082 0.0241 0.0226 0.0091 0.0092 0.0098
I-Pentane 0.005 0.0114 0.0053 0.0066 0.0071
n-Pentane 0.0073 0.0122 0.0077 0.0069 0.0073 0.015 0.0147 0.0067 0.007 0.0078
Hexane 0.0075 0.0206 0.008 0.0139 0.0148 0.0179 0.0183 0.0125 0.0131 0.015
Heptanes + 0.1035 0.1187 0.1095 0.139 0.1488 0.1256 0.1223 0.1021 0.1073 0.1247
Avg. Mol. Wt. 44.3 44.4 43.4 54.7 53.1 39.9 39.3 33 33.8 36.5
Mol. Wt. 191 167 191 205 205 167 167 158 158 158
Gravity(API)
Critical Temp., Tc (F) 200 292 200 180 180 285 251 100 160 212
This work 658.69 751.75 658.69 639.1 640.61 745.65 709.85 648.77 620.21 670.58
140
Mixture No. 4-6 4-7 4-8 4-9 4-10 75 - 1 75 - 2 75 - 3 75 - 4 75 - 5
Nitrogen 0.0128 0.0058 0.0053 0.0054 0.0038

Carbon Dioxide 0.0035 0.0156 0.0008 0.0075 0.0074 0.0045
Methane 0.6433 0.6865 0.657 0.7164 0.8213 0.788 0.724 0.728 0.597 0.83
Ethane 0.0638 0.0603 0.0869 0.0548 0.0637 0.059 0.0542 0.0546 0.089 0.0378
Propane 0.0605 0.0232 0.0537 0.031 0.0409 0.0315 0.03 0.0302 0.05 0.0144
I-Butane
n-Butane 0.0565 0.0309 0.0303 0.0258 0.0235 0.0265 0.031 0.0207 0.049 0.0089
I-Pentane
n-Pentane 0.0404 0.0243 0.0195 0.0216 0.0122 0.0425 0.071 0.0688 0.093 0.0436
Hexane 0.0366 0.0256 0.0173 0.0198 0.0103 0.0252 0.0456 0.0438 0.0308
Heptanes + 0.0954 0.1245 0.1217 0.1231 0.0234 0.0214 0.0388 0.0375 0.122 0.0263
Avg. Mol. Wt. 35.2 41.5 45.7 40.1 25 29.5 29.1 36.2 24.5
Mol. Wt. 114 171 207 167 114 106 106 106 100 106
Gravity (API)
This work 655.74 698.49 606.37 702.66 514.97 568.77 569.16 628.91 514.26
141
Mixture No. 75 - 6 75 - 7 75 - 8 141 - 1 141 - 2 141 - 3 141 - 4 141 - 5 141 - 6
Nitrogen 0.0038 0.0036 0.003 0.1101 0.0477 0.0156 0.0123

Carbon Dioxide 0.0044 0.0043 0.0035 0.0008 0.0019 0.0047 0.0028 0.0172 0.011
Methane 0.815 0.784 0.643 0.3465 0.4675 0.4656 0.6173 0.6527 0.586
Ethane 0.0372 0.0355 0.0294 0.1561 0.1306 0.1645 0.1024 0.0725 0.1309
Propane 0.0141 0.0136 0.0111 0.1499 0.105 0.1163 0.0673 0.0391 0.0699
I-Butane 0.0121 0.0112 0.0141 0.0085 0.0157 0.0081
n-Butane 0.0102 0.013 0.0252 0.0852 0.0472 0.0454 0.0352 0.0204 0.0349
I-Pentane 0.0084 0.0169 0.0112 0.0106 0.016 0.0097
n-Pentane 0.0501 0.0631 0.123 0.0109 0.0192 0.0182 0.0171 0.0123 0.0187
Hexane 0.0354 0.0447 0.0871 0.02 0.0373 0.0215 0.0226 0.029 0.0194
Heptanes + 0.0303 0.0382 0.0747 0.1 0.1155 0.1229 0.1039 0.1251 0.1114
Avg. Mol. Wt. 25.4 27.6 37.7

Mol. Wt. 106 106 106 164 142 168 144 157 184
Gravity (API) 40.6 42.5 40.1 47.3 49.5 42.2
This work 524.27 540.38 648.47 570.06 629.48 640.76 618.84 721.94 646.07
142
Mixture No. 141 - 7 141 - 8 141 - 9 141 - 10 141 - 11 141 - 12 141 - 13 141 - 14 141 - 15
Nitrogen 0.0009 0.0012 0.0013

Carbon Dioxide 0.0088 0.0041 0.0048 0.0056 0.0043 0.0038 0.0962 0.0776 0.0701
Methane 0.722 0.7052 0.7175 0.6992 0.5564 0.4902 0.5431 0.4371 0.3954
Ethane 0.0474 0.0725 0.0748 0.0638 0.0523 0.0464 0.1149 0.0932 0.0848
Propane 0.0278 0.0465 0.0456 0.0404 0.2108 0.297 0.0768 0.216 0.2738
I-Butane 0.0105 0.019 0.0177 0.0081 0.0069 0.0062 0.0147 0.0123 0.0115
n-Butane 0.0158 0.0129 0.0136 0.0169 0.0147 0.0133 0.0257 0.0223 0.0207
I=Pentane 0.0112 0.0064 0.0073 0.0079 0.007 0.0064 0.0082 0.0076 0.0072
n-Pentane 0.008 0.008 0.0046 0.0058 0.0052 0.0047 0.0082 0.0078 0.0076
Hexane 0.0181 0.01 0.0099 0.011 0.01 0.0093 0.0126 0.013 0.013
Heptanes + 0.1297 0.1142 0.1031 0.1413 0.1324 0.1227 0.0996 0.1131 0.1159
Avg. Mol. Wt.

Mol. Wt. 178 211 211 202 202 202 253 253 253
Gravity (API) 42.2 36.7 36.7 35 35 35 29 29 29
This work 724.53 686.98 676.99 661.32 661.89 660.87 739.24 741.2 740.99
143
Mixture No. 141 - 16 141 - 17 141 - 18 141 - 19 141 - 20 141 - 21 141 - 22 141 - 23 141 - 24
Nitrogen 0.0052 0.0007 0.0008 0.0004

Carbon Dioxide 0.0871 0.0776 0.0778 0.0006 0.0011 0.0008 0.0008 0.0023 0.0022
Methane 0.4911 0.4384 0.654 0.6091 0.5432 0.4789 0.3678 0.77 0.7247
Ethane 0.1041 0.0935 0.0889 0.0865 0.0706 0.0624 0.0488 0.0316 0.0371
Propane 0.0699 0.0632 0.061 0.0765 0.195 0.2786 0.4154 0.0228 0.0473
I-Butane 0.0135 0.0123 0.0198 0.0183 0.0078 0.0075 0.007 0.0149 0.026
n-Butane 0.1063 0.1768 0.0317 0.0304 0.014 0.0132 0.0124 0.019 0.028
I-Pentane 0.0078 0.0074 0.0189 0.0134 0.0077 0.0072 0.0067 0.0084 0.0148
n-Pentane 0.0077 0.0077 0.0172 0.0094 0.006 0.0057 0.0053 0.0137 0.0167
Hexane 0.0123 0.0128 0.0307 0.0184 0.0165 0.0156 0.0145 0.0212 0.0202
Heptanes + 0.1002 0.1103 0.0692 0.1374 0.1368 0.1293 0.1209 0.0961 0.083
Avg. Mol. Wt.

Mol. Wt. 253 253 126 229 229 229 229 152 152
Gravity (API) 29 29 60.4 30.2 30.2 30.2 30.2 51 51
Critical Temp. Tc (F) 280 280 144 221 221 221 221 183 183
This work 739.6 741.28 603.31 680.17 681.52 681.56 680.55 642.69 643.04
144
Mixture No. 141 - 141 - 141 - 141 - 141 - 141 - 141 - 93 - 1 37 - 1 158 - 1
25 26 27 28 29 30 31
Nitrogen 0.0487 0.0249 0.0526 0.0115 0.0017 0.1898 0.0052 0.0076

Carbon Dioxide 0.0014 0.0029 0.0149 0.2202 0.0073 0.003 0.0013
Methane 0.4534 0.4957 0.6414 0.5325 0.2756 0.695 0.4004 0.5832 0.6849 0.5391
Ethane 0.0705 0.1379 0.0733 0.1428 0.1144 0.0696 0.0767 0.1355 0.0971 0.142
Propane 0.1961 0.1015 0.0605 0.0926 0.2486 0.0426 0.0347 0.0761 0.0542 0.0964
I-Butane 0.0936 0.0222 0.0154 0.0183 0.085 0.0109 0.0064 0.0084 0.0086
n-Butane 0.0825 0.0403 0.0298 0.0349 0.1294 0.0157 0.0204 0.0319 0.0223 0.0554
I-Pentane 0.0542 0.0162 0.0142 0.0134 0.043 0.0102 0.0046 0.008 0.0088
n-Pentane 0.0343 0.0189 0.0178 0.0179 0.027 0.0086 0.0067 0.0161 0.0092 0.0299
Hexane 0.0129 0.0234 0.0233 0.0318 0.0161 0.0184 0.0084 0.019 0.0142 0.0272
Heptanes + 0.0011 0.0952 0.0994 0.0632 0.0465 0.1124 0.0181 0.1145 .0925a 0.1011
Avg. Mol. Wt.

Mol. Wt. 114 161 161 117 192 180 115 193 147 178.5
Sp. Gravity or API 68.7 47.4 47.4 59.4 41 0.825 0.76 0.8135
Critical Temp., Tc (F) 183 161 161 161 171 240 35 190 120 + 30 193
Critical Temp., Tc (oR) 643 621 621 621 631 700 495 650 #VALUE! 653
This work 642.83 620.95 620.18 620.19 630.34 700.18 494.44 650.59 580.38 651.87
145
Mixture No. 58 - 1 11 - 1 6-1 6-2 6-3 30 - 1 52 - 2 52 - 3 52 - 6
Nitrogen 0.0066 0.0024 0.0021 0.002 0.0018 0.0124 0.0027

Carbon Dioxide 0.018 0.0302 0.0084 0.0076 0.007 0.0065 0.0022 0.0003
Methane 0.5966 0.6073 0.7504 0.6822 0.6253 0.5772 0.5706 0.5428 0.604
Ethane 0.1289 0.1177 0.0537 0.0489 0.0448 0.0414 0.1496 0.149 ..0517
propane 0.0653 0.0891 0.0136 0.0124 0.0114 0.0105 0.0825 0.0912 0.0757
I-Butane 0.0173 0.0198 0.0021 0.0019 0.0018 0.0016 0.0092 0.0072 0.0455
n-Butane 0.0219 0.0279 0.0127 0.1025 0.1773 0.2405 0.0367 0.0456 0.0389
I-Pentane 0.01 0.0124 0.0106 0.0096 0.0088 0.0082 0.0064 0.0249
n-Pentane 0.0096 0.008 0.0099 0.009 0.0082 0.0076 0.018 0.0186 0.0182
Hexane 0.0132 0.0237 0.0215 0.0197 0.0182 0.0217 0.0255 0.0394
Heptanes + 0.1126 0.0878 .1125a .1023a .0937a .0865a 0.0907 0.1201 0.0897
Avg. Mol. Wt.

Mol. Wt. 155 172 118 118 118 118 173 166 133
Specific Gravity or API 0.7994 38 41.2 0.8126 51.9
Critical Temp., Tc (F) 264 125 172.5 297.5 232.5 252.5 170 170 245
Critical Temp., Tc (oR) 724 585 632.5 757.5 692.5 712.5 630 630 705
This work 722.91 585.81 631.89 667.01 691.88 712.66 630.6 629.44 705.62
146
Mixture No. 47 - 1 26 - 1 26 - 2 26 - 3 47 - 2 26 - 4 26 - 5 26 - 6 26 - 7 26 - 8
Nitrogen 0.0884 0.1611 0.2441 0.113 0.24 0.1146 0.135 0.0705

Carbon Dioxide 0.012 0.0109 0.01 0.0091 0.0044 0.003 0.002 0.0013 0.002 0.0025
Methane 0.9089 0.8286 0.7625 0.887 0.858 0.7364 0.7364 0.7665 0.7515 0.8532
Ethane 0.044 0.0401 0.0369 0.0333 0.016 0.015 0.012 0.0551 0.061 0.0411
Propane 0.0191 0.0174 0.016 0.0144 0.007 0.006 0.0053 0.0335 0.0327 0.0198
I-Butane 0.0033 0.003 0.0028 0.003 0.0014 0.0012 0.001 0.0035 0.0038 0.0037
n-Butane 0.006 0.0055 0.0051 0.004 0.002 0.0018 0.0015 0.009 0.006 0.0039
I-Pentane 0.0021 0.0019 0.0018 0.0016 0.0007 0.0006 0.0005 0.0017
n-Pentane 0.0013 0.0012 0.0011 0.001 0.0005 0.0004 0.0004 0.0015 .0020c .0022c
Hexane 0.0015 0.0014 0.0012 0.0011 0.0005 0.0004 0.0004
Heptanes + 0.0018 0.0016 0.0015 0.0014 0.0007 0.0006 0.0005 .0033d
Helium 0.01 0.006 0.0031
Avg. Mol. Wt. 18.4 19.25 19.94 20.75 16.9 18.11 19.56 20.02 19.98 18.6
Mol. Wt. 115 115 115 115 115 115 115 100
Gravity (API)
Critical Temp., Tc (F) -79 -92 -104 -120 -101 -117 -131 -84 -90 -96
This work 380.91 368.34 355.94 340.07 359.03 343.05 329.04 375.88 370.01 364.11
147
Table C.19. Critical Pressure, Temperature and Properties Predictions
for Heptane Plus
Mixture No. 145-1 145-2 145-3 145-4 145-5 145-6 145-7 145-8 145-9
Nitrogen 0.001 0.001 0.001 0.001 0.004 0.001

Carbon Dioxide 0.004 0.005 0.005 0.004 0.006 0.002 0.0149 0.014 0.0156
Methane 0.193 0.271 0.363 0.229 0.365 0.482 0.5248 0.5335 0.5921
Ethane 0.032 0.034 0.038 0.029 0.058 0.065 0.145 0.0679 0.066
Propane 0.585 0.482 0.374 0.407 0.242 0.167 0.157 0.2035 0.1043
I-Butane 0.007 0.007 0.009 0.006 0.007 0.007 0.0055 0.0063 0.0058
n-Butane 0.012 0.015 0.015 0.172 0.215 0.14 0.0179 0.204 0.0831
I-Pentane 0.005 0.006 0.006 0.005 0.004 0.006 0.0055 0.0062 0.0054
n-Pentane 0.007 0.007 0.008 0.006 0.007 0.008 0.0079 0.0092 0.0078
Hexane 0.013 0.015 0.016 0.012 0.01 0.012 0.0082 0.0094 0.0081
Heptanes + 0.141 0.157 0.165 0.129 0.082 0.11 0.1133 0.1296 0.1118
Avg. Mol. Wt. 67.3 68.5 67.5 66.1 48.8 48.8 45 48.4 44.9
Mol. Wt. 243 243 243 243 191 191 191 191 191
Gravity(API) 33.31 33.31 33.31 33.31 39.98 39.98 39.98 39.98 39.98
SG 0.86 0.86 0.86 0.86 0.83 0.83 0.83 0.83 0.83
Tb 1037.0 1037.0 1037.0 1037.0 920.9 920.9 920.9 920.9 920.9
C 3.3475 3.3475 3.3475 3.3475 3.2304 3.2304 3.2304 3.2304 3.2304
Pc, psia 271.0 271.0 271.0 271.0 319.8 319.8 319.8 319.8 319.8
Tc, oR 1364.4 1364.4 1364.4 1364.4 1258.4 1258.4 1258.4 1258.4 1258.4
ω 0.5673 0.5673 0.5673 0.5673 0.4676 0.4676 0.4676 0.4676 0.4676
Zc 0.2416 0.2416 0.2416 0.2416 0.2493 0.2493 0.2493 0.2493 0.2493
Ωω 0.3555 0.3555 0.3555 0.3555 0.3564 0.3564 0.3564 0.3564 0.3564
148
Mixture No. 145 - 10 145 - 11 145 - 12 145 - 13 145 - 14 4-1 4-2 4-3 4-4 4-5
Nitrogen 0.0016 0.002

Carbon Dioxide 0.0153 0.0008 0.0139 0.0006 0.0008 0.0066 0.0067 0.0061 0.0061 0.0059
Methane 0.5774 0.6298 0.6165 0.4786 0.5808 0.7243 0.7292 0.8227 0.8165 0.795
Ethane 0.0631 0.0858 0.0602 0.082 0.0562 0.0557 0.0556 0.0284 0.0284 0.0281
Propane 0.1178 0.0672 0.0961 0.1359 0.0919 0.0308 0.0306 0.0124 0.0124 0.0128
I-Butane 0.0055 0.023 0.0055 0.0076 0.0081
n-Butane 0.0976 0.0305 0.0773 0.1273 0.082 0.0241 0.0226 0.0091 0.0092 0.0098
I-Pentane 0.005 0.0114 0.0053 0.0066 0.0071
n-Pentane 0.0073 0.0122 0.0077 0.0069 0.0073 0.015 0.0147 0.0067 0.007 0.0078
Hexane 0.0075 0.0206 0.008 0.0139 0.0148 0.0179 0.0183 0.0125 0.0131 0.015
Heptanes + 0.1035 0.1187 0.1095 0.139 0.1488 0.1256 0.1223 0.1021 0.1073 0.1247
Avg. Mol. Wt. 44.3 44.4 43.4 54.7 53.1 39.9 39.3 33 33.8 36.5
Mol. Wt. 191 167 191 205 205 167 167 158 158 158
Gravity(API) 39.98 44.46 39.98 37.85 37.85 44.46 44.46 46.49 46.49 46.49
SG 0.83 0.80 0.83 0.84 0.84 0.80 0.80 0.79 0.79 0.79
Tb 920.9 860.6 920.9 953.9 953.9 860.6 860.6 836.6 836.6 836.6
C 3.2304 3.1667 3.2304 3.2644 3.2644 3.1667 3.1667 3.1407 3.1407 3.1407
Pc,psia 319.8 348.0 319.8 305.1 305.1 348.0 348.0 359.7 359.7 359.7
Tc, oR 1258.4 1200.2 1258.4 1289.4 1289.4 1200.2 1200.2 1176.3 1176.3 1176.3
ω 0.4676 0.4209 0.4676 0.4946 0.4946 0.4209 0.4209 0.4033 0.4033 0.4033
Zc 0.2493 0.2531 0.2493 0.2472 0.2472 0.2531 0.2531 0.2545 0.2545 212
Ωω 0.3564 0.3569 0.3564 0.3562 0.3562 0.3569 0.3569 0.3571 0.3571 5620
149
Mixture No. 4-6 4-7 4-8 4-9 4-10 75 - 1 75 - 2 75 - 3 75 - 4 75 - 5
Nitrogen 0.0128 0.0058 0.0053 0.0054 0.0038

Carbon Dioxide 0.0035 0.0156 0.0008 0.0075 0.0074 0.0045
Methane 0.6433 0.6865 0.657 0.7164 0.8213 0.788 0.724 0.728 0.597 0.83
Ethane 0.0638 0.0603 0.0869 0.0548 0.0637 0.059 0.0542 0.0546 0.089 0.0378
Propane 0.0605 0.0232 0.0537 0.031 0.0409 0.0315 0.03 0.0302 0.05 0.0144
I-Butane
n-Butane 0.0565 0.0309 0.0303 0.0258 0.0235 0.0265 0.031 0.0207 0.049 0.0089
I-Pentane
n-Pentane 0.0404 0.0243 0.0195 0.0216 0.0122 0.0425 0.071 0.0688 0.093 0.0436
Hexane 0.0366 0.0256 0.0173 0.0198 0.0103 0.0252 0.0456 0.0438 0.0308
Heptanes + 0.0954 0.1245 0.1217 0.1231 0.0234 0.0214 0.0388 0.0375 0.122 0.0263
Avg. Mol. Wt. 35.2 41.5 45.7 40.1 25 29.5 29.1 36.2 24.5
Mol. Wt. 114 171 207 167 114 106 106 106 100 106
Gravity (API) 61.04 43.63 37.57 44.46 61.04 64.98 64.98 64.98 68.35 64.98
SG 0.73 0.81 0.84 0.80 0.73 0.72 0.72 0.72 0.71 0.72
Tb 704.8 871.0 958.5 860.6 704.8 677.6 677.6 677.6 656.3 677.6
C 2.9917 3.1778 3.2691 3.1667 2.9917 2.9594 2.9594 2.9594 2.9337 2.9594
Pc,psia 427.1 343.0 303.1 348.0 427.1 441.1 441.1 441.1 452.0 441.1
Tc, oR 1038.0 1210.4 1293.6 1200.2 1038.0 1007.7 1007.7 1007.7 983.5 1007.7
ω 0.3158 0.4287 0.4985 0.4209 0.3158 0.2996 0.2996 0.2996 0.2874 0.2996
Zc 0.2620 0.2524 0.2469 0.2531 0.2620 0.2634 0.2634 0.2634 0.2645 212
Ωω 0.3579 0.3568 0.3561 0.3569 0.3579 0.3581 0.3581 0.3581 0.3582 5620
150
Mixture No. 75 - 6 75 - 7 75 - 8 141 - 1 141 - 2 141 - 3 141 - 4 141 - 5 141 - 6
Nitrogen 0.0038 0.0036 0.003 0.1101 0.0477 0.0156 0.0123

Carbon Dioxide 0.0044 0.0043 0.0035 0.0008 0.0019 0.0047 0.0028 0.0172 0.011
Methane 0.815 0.784 0.643 0.3465 0.4675 0.4656 0.6173 0.6527 0.586
Ethane 0.0372 0.0355 0.0294 0.1561 0.1306 0.1645 0.1024 0.0725 0.1309
Propane 0.0141 0.0136 0.0111 0.1499 0.105 0.1163 0.0673 0.0391 0.0699
I-Butane 0.0121 0.0112 0.0141 0.0085 0.0157 0.0081
n-Butane 0.0102 0.013 0.0252 0.0852 0.0472 0.0454 0.0352 0.0204 0.0349
I-Pentane 0.0084 0.0169 0.0112 0.0106 0.016 0.0097
n-Pentane 0.0501 0.0631 0.123 0.0109 0.0192 0.0182 0.0171 0.0123 0.0187
Hexane 0.0354 0.0447 0.0871 0.02 0.0373 0.0215 0.0226 0.029 0.0194
Heptanes + 0.0303 0.0382 0.0747 0.1 0.1155 0.1229 0.1039 0.1251 0.1114
Avg. Mol. Wt. 25.4 27.6 37.7

Mol. Wt. 106 106 106 164 142 168 144 157 184
Gravity (API) 64.98 64.98 64.98 40.6 42.5 40.1 47.3 49.5 42.2
SG 0.72 0.72 0.72 0.82 0.81 0.82 0.79 0.78 0.81
Tb 677.6 677.6 677.6 862.2 807.5 872.1 802.9 828.4 901.6
C 2.9594 2.9594 2.9594 3.1592 3.0931 3.1704 3.0983 3.1372 3.2123
Pc,psia 441.1 441.1 441.1 371.8 421.8 364.8 392.3 349.4 323.4
Tc, oR 1007.7 1007.7 1007.7 1211.9 1164.0 1220.9 1148.0 1162.3 1237.5
ω 0.2996 0.2996 0.2996 0.4076 0.3599 0.4159 0.3715 0.4057 0.4559
Zc 0.2634 0.2634 0.2634 0.2542 0.2582 0.2535 0.2572 0.2543 0.2502
Ωω 0.3581 0.3581 0.3581 0.3570 0.3575 0.3569 0.3574 0.3570 0.3565
151
Mixture No. 141 - 7 141 - 8 141 - 9 141 - 10 141 - 11 141 - 12 141 - 13 141 - 14 141 - 15
Nitrogen 0.0009 0.0012 0.0013

Carbon Dioxide 0.0088 0.0041 0.0048 0.0056 0.0043 0.0038 0.0962 0.0776 0.0701
Methane 0.722 0.7052 0.7175 0.6992 0.5564 0.4902 0.5431 0.4371 0.3954
Ethane 0.0474 0.0725 0.0748 0.0638 0.0523 0.0464 0.1149 0.0932 0.0848
Propane 0.0278 0.0465 0.0456 0.0404 0.2108 0.297 0.0768 0.216 0.2738
i-Butane 0.0105 0.019 0.0177 0.0081 0.0069 0.0062 0.0147 0.0123 0.0115
n-Butane 0.0158 0.0129 0.0136 0.0169 0.0147 0.0133 0.0257 0.0223 0.0207
i=Pentane 0.0112 0.0064 0.0073 0.0079 0.007 0.0064 0.0082 0.0076 0.0072
n-Pentane 0.008 0.008 0.0046 0.0058 0.0052 0.0047 0.0082 0.0078 0.0076
Hexane 0.0181 0.01 0.0099 0.011 0.01 0.0093 0.0126 0.013 0.013
Heptanes + 0.1297 0.1142 0.1031 0.1413 0.1324 0.1227 0.0996 0.1131 0.1159
Avg. Mol. Wt.

Mol. Wt. 178 211 211 202 202 202 253 253 253
Gravity (API) 42.2 36.7 36.7 35 35 35 29 29 29
SG 0.81 0.84 0.84 0.85 0.85 0.85 0.88 0.88 0.88
Tb 889.0 968.5 968.5 954.9 954.9 954.9 1066.8 1066.8 1066.8
C 3.1968 3.2784 3.2784 3.2581 3.2581 3.2581 3.3684 3.3684 3.3684
Pc,psia 334.8 300.5 300.5 321.3 321.3 321.3 274.9 274.9 274.9
Tc, oR 1228.0 1303.6 1303.6 1298.7 1298.7 1298.7 1400.4 1400.4 1400.4
ω 0.4423 0.5055 0.5055 0.4822 0.4822 0.4822 0.5778 0.5778 0.5778
Zc 0.2513 0.2463 0.2463 0.2481 0.2481 0.2481 0.2408 0.2408 0.2408
Ωω 0.3567 0.3561 0.3561 0.3563 0.3563 0.3563 0.3554 0.3554 0.3554
152
Mixture No. 141 - 16 141 - 17 141 - 18 141 - 19 141 - 20 141 - 21 141 - 22 141 - 23 141 - 24
Nitrogen 0.0052 0.0007 0.0008 0.0004

Carbon Dioxide 0.0871 0.0776 0.0778 0.0006 0.0011 0.0008 0.0008 0.0023 0.0022
Methane 0.4911 0.4384 0.654 0.6091 0.5432 0.4789 0.3678 0.77 0.7247
Ethane 0.1041 0.0935 0.0889 0.0865 0.0706 0.0624 0.0488 0.0316 0.0371
Propane 0.0699 0.0632 0.061 0.0765 0.195 0.2786 0.4154 0.0228 0.0473
I-Butane 0.0135 0.0123 0.0198 0.0183 0.0078 0.0075 0.007 0.0149 0.026
n-Butane 0.1063 0.1768 0.0317 0.0304 0.014 0.0132 0.0124 0.019 0.028
I-Pentane 0.0078 0.0074 0.0189 0.0134 0.0077 0.0072 0.0067 0.0084 0.0148
n-Pentane 0.0077 0.0077 0.0172 0.0094 0.006 0.0057 0.0053 0.0137 0.0167
Hexane 0.0123 0.0128 0.0307 0.0184 0.0165 0.0156 0.0145 0.0212 0.0202
Heptanes + 0.1002 0.1103 0.0692 0.1374 0.1368 0.1293 0.1209 0.0961 0.083
Avg. Mol. Wt.

Mol. Wt. 253 253 126 229 229 229 229 152 152
Gravity (API) 29 29 60.4 30.2 30.2 30.2 30.2 51 51
SG 0.88 0.88 0.74 0.88 0.88 0.88 0.88 0.78 0.78
Tb 1066.8 1066.8 736.3 1019.5 1019.5 1019.5 1019.5 814.3 814.3
C 3.3684 3.3684 3.0359 3.3194 3.3194 3.3194 3.3194 3.1221 3.1221
Pc,psia 274.9 274.9 387.6 300.1 300.1 300.1 300.1 355.0 355.0
Tc, oR 1400.4 1400.4 1064.6 1361.9 1361.9 1361.9 1361.9 1147.6 1147.6
ω 0.5778 0.5778 0.3454 0.5301 0.5301 0.5301 0.5301 0.3961 0.3961
Zc 0.2408 0.2408 0.2594 0.2444 0.2444 0.2444 0.2444 0.2551 0.2551
Ωω 0.3554 0.3554 0.3576 0.3558 0.3558 0.3558 0.3558 0.3571 0.3571
153
Mixture No. 141 - 25 141 - 26 141 - 27 141 - 28 141 - 29 141 - 30 141 - 31 93 - 1 37 - 1 158 - 1
Nitrogen 0.0487 0.0249 0.0526 0.0115 0.0017 0.1898 0.0052 0.0076

Carbon Dioxide 0.0014 0.0029 0.0149 0.2202 0.0073 0.003 0.0013
Methane 0.4534 0.4957 0.6414 0.5325 0.2756 0.695 0.4004 0.5832 0.6849 0.5391
Ethane 0.0705 0.1379 0.0733 0.1428 0.1144 0.0696 0.0767 0.1355 0.0971 0.142
Propane 0.1961 0.1015 0.0605 0.0926 0.2486 0.0426 0.0347 0.0761 0.0542 0.0964
I-Butane 0.0936 0.0222 0.0154 0.0183 0.085 0.0109 0.0064 0.0084 0.0086
n-Butane 0.0825 0.0403 0.0298 0.0349 0.1294 0.0157 0.0204 0.0319 0.0223 0.0554
I-Pentane 0.0542 0.0162 0.0142 0.0134 0.043 0.0102 0.0046 0.008 0.0088
n-Pentane 0.0343 0.0189 0.0178 0.0179 0.027 0.0086 0.0067 0.0161 0.0092 0.0299
Hexane 0.0129 0.0234 0.0233 0.0318 0.0161 0.0184 0.0084 0.019 0.0142 0.0272
Heptanes + 0.0011 0.0952 0.0994 0.0632 0.0465 0.1124 0.0181 0.1145 .0925a 0.1011
Avg. Mol. Wt.

Mol. Wt. 114 161 161 117 192 180 115 193 147 178.5
Sp. Gravity or API 68.7 47.4 47.4 59.4 41 0.825 0.76 0.8135
SG 0.71 0.79 0.79 0.74 0.82 0.825 0.76 0.8135 0.51 0.46
Tb 693.2 841.5 841.5 715.2 920.6 898.1 717.6 919.4 671.4 697.4
C 2.9903 3.1492 3.1492 3.0034 3.2326 3.2025 2.9968 3.2347 3.0905 3.1752
Pc,psia 393.0 348.9 348.9 423.3 314.0 340.0 454.6 306.9 150.5 98.7
Tc, oR 1012.8 1177.7 1177.7 1049.9 1255.3 1241.1 1062.2 1250.3 875.5 858.5
ω 0.3245 0.4118 0.4118 0.3215 0.4718 0.4429 0.3109 0.4768 0.5151 0.6618
Zc 0.2612 0.2538 0.2538 0.2615 0.2490 0.2513 0.2624 0.2486 0.2456 0.2347
Ωω 0.3578 0.3570 0.3570 0.3578 0.3564 0.3567 0.3580 0.3563 0.3560 0.3546
154
Mixture No. 58 - 1 11 - 1 6-1 6-2 6 - 3 30 - 1 52 - 2 52 - 3 52 - 6
Nitrogen 0.0066 0.0024 0.0021 0.002 0.0018 0.0124 0.0027

Carbon Dioxide 0.018 0.0302 0.0084 0.0076 0.007 0.0065 0.0022 0.0003
Methane 0.5966 0.6073 0.7504 0.6822 0.6253 0.5772 0.5706 0.5428 0.604
Ethane 0.1289 0.1177 0.0537 0.0489 0.0448 0.0414 0.1496 0.149 ..0517
propane 0.0653 0.0891 0.0136 0.0124 0.0114 0.0105 0.0825 0.0912 0.0757
I-Butane 0.0173 0.0198 0.0021 0.0019 0.0018 0.0016 0.0092 0.0072 0.0455
n-Butane 0.0219 0.0279 0.0127 0.1025 0.1773 0.2405 0.0367 0.0456 0.0389
I-Pentane 0.01 0.0124 0.0106 0.0096 0.0088 0.0082 0.0064 0.0249
n-Pentane 0.0096 0.008 0.0099 0.009 0.0082 0.0076 0.018 0.0186 0.0182
Hexane 0.0132 0.0237 0.0215 0.0197 0.0182 0.0217 0.0255 0.0394
Heptanes + 0.1126 0.0878 .1125a .1023a .0937a .0865a 0.0907 0.1201 0.0897
Avg. Mol. Wt.

Mol. Wt. 155 172 118 118 118 118 173 166 133
Specific Gravity or API 0.7994 38 59.27 59.27 59.27 59.27 41.2 0.8126 51.9
SG 0.7994 0.83 0.74 0.74 0.74 0.74 0.82 0.81 0.77
Tb 831.8 885.4 718.0 718.0 718.0 718.0 880.6 862.3 768.0
C 3.1322 3.1818 3.0072 3.0072 3.0072 3.0072 3.1838 3.1643 3.0616
Pc,psia 371.3 365.5 420.2 420.2 420.2 420.2 349.1 358.0 403.6
Tc, oR 1175.2 1237.2 1052.4 1052.4 1052.4 1052.4 1224.4 1206.4 1109.2
ω 0.3947 0.4213 0.3238 0.3238 0.3238 0.3238 0.4291 0.4156 0.3516
Zc 0.2552 0.2530 0.2613 0.2613 0.2613 0.2613 0.2524 0.2535 0.2589
Ωω 0.3571 0.3569 0.3578 0.3578 0.3578 0.3578 0.3568 0.3569 0.3576
155
Mixture No. 47 - 1 26 - 1 26 - 2 26 - 3 47 - 2 26 - 4 26 - 5 26 - 6 26 - 7 26 - 8
Nitrogen 0.0884 0.1611 0.2441 0.113 0.24 0.1146 0.135 0.0705

Carbon Dioxide 0.012 0.0109 0.01 0.0091 0.0044 0.003 0.002 0.0013 0.002 0.0025
Methane 0.9089 0.8286 0.7625 0.887 0.858 0.7364 0.7364 0.7665 0.7515 0.8532
Ethane 0.044 0.0401 0.0369 0.0333 0.016 0.015 0.012 0.0551 0.061 0.0411
Propane 0.0191 0.0174 0.016 0.0144 0.007 0.006 0.0053 0.0335 0.0327 0.0198
I-Butane 0.0033 0.003 0.0028 0.003 0.0014 0.0012 0.001 0.0035 0.0038 0.0037
n-Butane 0.006 0.0055 0.0051 0.004 0.002 0.0018 0.0015 0.009 0.006 0.0039
I-Pentane 0.0021 0.0019 0.0018 0.0016 0.0007 0.0006 0.0005 0.0017
n-Pentane 0.0013 0.0012 0.0011 0.001 0.0005 0.0004 0.0004 0.0015 .0020c .0022c
Hexane 0.0015 0.0014 0.0012 0.0011 0.0005 0.0004 0.0004
Heptanes + 0.0018 0.0016 0.0015 0.0014 0.0007 0.0006 0.0005 .0033d
Helium 0.01 0.006 0.0031
Avg. Mol. Wt. 18.4 19.25 19.94 20.75 16.9 18.11 19.56 20.02 19.98 18.6
Mol. Wt. 115 115 115 115 115 115 115 100
Gravity (API) 60.58 60.58 60.58 60.58 60.58 60.58 60.58 68.35 #DIV/0! #DIV/0!
SG 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.71 #DIV/0! #DIV/0!
Tb 708.1 708.1 708.1 708.1 708.1 708.1 708.1 656.3 #DIV/0!
C 2.9956 2.9956 2.9956 2.9956 2.9956 2.9956 2.9956 2.9337 #DIV/0!
Pc,psia 425.3 425.3 425.3 425.3 425.3 425.3 425.3 452.0 #DIV/0!
Tc, oR 1041.6 1041.6 1041.6 1041.6 1041.6 1041.6 1041.6 983.5 #DIV/0!
ω 0.3178 0.3178 0.3178 0.3178 0.3178 0.3178 0.3178 0.2874 #DIV/0!
Zc 0.2618 0.2618 0.2618 0.2618 0.2618 0.2618 0.2618 0.2645 #DIV/0!
Ωω 0.3579 0.3579 0.3579 0.3579 0.3579 0.3579 0.3579 0.3582 #DIV/0!
156
CRITICAL PRESSURE PREDICTIONS FOR COMPLEX MIXTURES
BY FOUR METHODS
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This work
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Figure C. 1. Critical Pressure Prediction for Complex Mixtures – All Data.
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Figure C. 2. Critical Pressure Prediction for Complex Mixtures -Mixture 145-1.
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Figure C. 3. Critical Pressure Prediction for Complex Mixtures – Mixture 145 – 10.
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Figure C. 4. Critical Pressure Prediction for Complex Mixtures – Mixture 4 – 6.
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This work
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Figure C.5. Critical Pressure Prediction for a Complex Mixture 75 – 5.
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This work
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Figure C. 6. Critical Pressure Prediction for a Complex Mixture 141 – 7.
162
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Simon-Yarborough
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163
5900
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CRITICAL TEMPERATURE PREDICTION FOR COMPLEX MIXTURES
BY LLS EOS METHOD
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This work
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Experimental Critical Temperature (oR)

Figure C. 11. Critical Temperature Prediction for Complex Mixtures – All Data.
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Figure C. 12. Critical Temperature Prediction for a Complex Mixture 145 - 1

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Figure C. 13. Critical Temperature Prediction for a Complex Mixture 145 – 10

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Figure C.14. Critical Temperature Prediction for a Complex Mixture 4 – 6.
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Experimental Critical Temperature (oR)

Figure C. 15. Critical Temperature Prediction for a Complex Mixture 75 – 6.
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CLOSED-FORM VAN DER WAALS CRITICAL POINT

FOR PETROLEUM RESERVOIR FLUIDS

TALAL HUSSEIN HASSOUN, B.S., M.S.

Submitted to the Graduate Faculty

discussion contributed to this dissertation. I would like to acknowledge the Petroleum

This Dissertation is dedicated to my father, my mother, my wife, Majida, my

inspiration and confidence.

LIST OF TABLES vii

1.1 Importance of Critical State 7

1.2 Approaches to Critical State Prediction 12

1.3 Retrograde Reservoir Fluids 14

1.4 Objectives of Work 16

II. CRITICAL PROPERTY CORRELATION METHODS 18

2.1 Criteria of the Critical State 19

2.2 Empirical Models 22

2.3 Corresponding States 25

2.4 Convergence Pressure 31

2.5 Equation of State Models 45

III. CLOSED-FORM VAN DER WAALS EXPRESSIONS 54

3.1 Van der Waals Equations of State Theory 54

3.2 Closed-Form Equations for Fluid Critical Point 61

IV. CRITICAL PROPERTIES FOR RESERVOIR FLUIDS 74

4.1 Critical Pressure Data for Complex Hydrocarbon Mixtures 74

4.2 Calculation of Critical Properties

4.3 Results and Discussion 75

4.4 Comparison Between Calculated and Experimental Data 80

V. CONCLUSIONS AND RECOMMENDATIONS 86

A. ANALYTICAL SOLUTION FOR CUBIC EQUATIONS 99

B. VAN DER WAALS EXPRESSIONS FOR FLUID CRITICAL POINT 112

C. PREDICTION RESULTS OF CRITICAL PRESSURE, CRITICAL 130

TEMPERATURE, AND HEPTANE PLUS PROPERTIES

The prediction of critical points is of great practical importance because the

properties of reservoir fluids and designing supercritical fluid processes.

applied to predicting critical properties of reservoir fluids.

of complex reservoir fluids by using the Lawal-Lake-Silberberg (LLS) equation of state

terms of molecular weight ratios of the binary constituent of reservoir fluids.

are within average absolute percent deviation of 3% to 5% of the measured critical

3.1 Parameter of Selected Equations of State ..................................................................62

3.2 Relationship of EOS Constants to Critical Parameters..............................................64

4.1 Sample of Experimental Data Used in Calculations of Mixture 1.............................76

4.2 Calculated Critical Data of Heptane-plus Fraction Correlation.................................77

4.4 Calculated Results for Pure Component parameters .................................................78

4.5 Calculated Results for Mixtures Parameters..............................................................79

C.1 Critical Pressure Prediction for Complex Mixtures………………………………130

C.2 Critical Pressure Prediction for Complex Mixtures ……………………………...131

C.3 Critical Pressure Prediction for Complex Mixtures...….…………………………132

C.4 Critical Pressure Prediction for Complex Mixtures...… …………………………133

C.5 Critical Pressure Prediction for Complex Mixtures……………………………....134

C.6 Critical Pressure Prediction for ComplexMixture………………………………...135

C.7 Critical Pressure Prediction for Complex Mixtures ……………………………...136

C.8 Critical Pressure Prediction for Complex Mixtures ……………………………137

C.9 Critical Pressure Prediction for Complex Mixtures ……………………………138

C.10 Critical Temperature Prediction for Complex Mixtures ……………………….139

C.12 Critical Temperature Prediction for Complex Mixtures………………………..141

C.13 Critical Temperature Prediction for Complex Mixtures…………………….….142

C.14 Critical Temperature Prediction for Complex Mixtures ……………………….143

C.15 Critical Temperature Prediction for Complex Mixtures ……………………….144

C.16 Critical Temperature Prediction for Complex Mixtures ……………………….145

C.17 Critical Temperature Prediction for Complex Mixtures ……………………….146

C.18 Critical Temperature Prediction for Complex Mixtures ……………………….147

C.19 Critical Pressure, Temperature, and Properties Prediction

C.20 Critical Pressure, Temperature, and Properties Prediction

C.21 Critical Pressure, Temperature, and Properties Prediction