PETE 310

Lectures # 32 to 34
Cubic Equations of State

Last Lectures

Instructional Objectives
Know the data needed in the EOS to evaluate
fluid properties
Know how to use the EOS for single and
multicomponent systems
Evaluate the volume (density, or z-factor)
roots from a cubic equation of state for
Gas phase (when two phases exist)
Liquid Phase (when two phases exist)
Single phase when only one phase exists

Equations of State (EOS)

Single Component Systems
Equations of State (EOS) are mathematical
relations between pressure (P) temperature
(T), and molar volume (V).

Multicomponent Systems
For multicomponent mixtures in addition to
(P, T & V) , the overall molar composition
and a set of mixing rules are needed.

Uses of Equations of State

(EOS)
Evaluation of gas injection processes
(miscible and immiscible)
Evaluation of properties of a reservoir oil
(liquid) coexisting with a gas cap (gas)
Simulation of volatile and gas condensate
production through constant volume
depletion evaluations
Recombination tests using separator oil
and gas streams

Equations of State (EOS)

One of the most used EOS is the PengRobinson EOS (1975). This is a threeparameter corresponding states model.

P Prep Pattr

PV Phase Behavior
Pressurevolume
behavior
indicating
isotherms for
a pure
component
system

Tc

Pres sure

CP

T2

v
P
1
T1
L
2 - P has es
V
L

Mo lar V olum e

Equations of State (EOS)

The critical point conditions are used
to determine the EOS parameters

0
Tc

2
V
2

0
Tc

Equations of State (EOS)

Solving these two equations
simultaneously for the Peng-Robinson
EOS provides
2

2
c

RT
a a
Pc

and

RTc
b b
Pc

Equations of State (EOS)

Where
and

a 0.45724
b 0.07780

1 m 1 Tr

with

m 0.37464 1.54226 0.2699

EOS for a Pure Component

Pres sur e

CP

T2
4
v

P
1

1
L

A1

10
0

A2
P
~
V

2 - P has
hases

1
2

Mo la r V o lum e

T1

Equations of State (EOS)

PR equation can be expressed as a
cubic polynomial in V, density, or Z.

Z ( B 1) Z
3

( A 3B 2 B ) Z
2

( AB B B ) 0
2

with

aP
A
2
RT
bP
B
RT

Equations of State (EOS)

When working with mixtures (a )
and (b) are evaluated using a set of
mixing rules
The most common mixing rules are:
Quadratic for a
Linear for b

Quadratic MR for a
Nc Nc

a m xi x j ai a j i j
i 1 j 1

0.5

1 k

where the kijs are called interaction

parameters and by definition

kij k ji
kii 0

ij

Linear MR for b

Nc

bm xibi
i 1

Example
For a three-component mixture (Nc
= 3) the attraction (a) and the
repulsion constant (b) are given by

a m 2 x1x2 a1a21 2 (1 k12 ) 2 x2 x3 a2a3 2 3 (1 k23 )

0.5
2 x1 x3 a1a31 3 (1 k13 ) x 2 a11 x22 a2 2
x32 a3 3
0.5

0.5

bm x1b1 x2b2 x3b3

Equations of State (EOS)

The constants a and b can be
evaluated using
Overall compositions zi with i = 1, 2Nc
Liquid compositions xi with i = 1, 2Nc
Vapor compositions yi with i = 1, 2Nc

Equations of State (EOS)

The cubic expression for a mixture is
then evaluated using

a m P
Am
2
RT

bm P
Bm
RT

Analytical Solution of Cubic

Equations
The cubic EOS can be arranged
into a polynomial and be solved
analytically as follows.

Z ( B 1) Z
3

( A 3B 2 B ) Z
2

( AB B B ) 0
2

Analytical Solution of Cubic

Equations
Lets write the polynomial in the
following way

x a1 x a2 x a 0
3

Note: x could be either the molar

volume, or the density, or the zfactor

Analytical Solution of Cubic

Equations
When the equation is expressed in
terms of the z factor, the
coefficients a1 to a3 are:

a1 ( B 1)

a2 ( A 3B 2 B)
2

a3 ( AB B B )
2

Procedure to Evaluate the Roots

of a Cubic Equation Analytically
Let

3a2 a
Q
9
3
9a1a2 27 a3 2a1
R
54
2
1

S R Q R

T R Q R

Procedure to Evaluate the Roots

of a Cubic Equation Analytically
The solutions are,

1
x1 S T a1
3
1
1
1
x2 S T a1 i 3 S T
2
3
2
1
1
1
x3 S T a1 i 3 S T
2
3
2

Procedure to Evaluate the Roots

of a Cubic Equation Analytically
If a1, a2 and a3 are real and if D =
Q3 + R2 is the discriminant, then
One root is real and two complex
conjugate if D > 0;
All roots are real and at least two are
equal if D = 0;
All roots are real and unequal if D < 0.

Procedure to Evaluate the Roots

of a Cubic Equation Analytically
1
1
x1 2 Q cos a1
3
3
If D 0

1
1

o
x2 2 Q cos 120 a1
3
3

1
1

o
x3 2 Q cos 240 a1
3
3

where

cos

R
Q 3

Procedure to Evaluate the Roots

of a Cubic Equation Analytically

x1 x2 x3 a1
x1 x2 x2 x3 x3 x1 a2
x1 x2 x3 a3
where x1, x2 and x3 are the three
roots.

Procedure to Evaluate the Roots

of a Cubic Equation Analytically
The range of solutions that are
used for the engineer are those for
positive volumes and pressures, we
are not concerned about imaginary
numbers.

Solutions of a Cubic Polynomial

From the shape
of the
polynomial we
are only
interested in
the first
quadrant.

Solutions of a Cubic Polynomial

http://www.uni-koeln.de/math-natfak/phchem/deiters/quartic/quartic
.html contains Fortran codes to
solve the roots of polynomials up to
fifth degree.

Web site to download Fortran source

codes to solve polynomials up to fifth
degree

EOS for a Pure Component

Pres sur e

CP

T2
4
v

P
1

1
L

A1

10
0

A2
P
~
V

2 - P has
hases

1
2

Mo la r V o lum e

T1

Parameters needed to solve

EOS
Tc, Pc, (acentric factor for some
equations I.e Peng Robinson)
Compositions (when dealing with
mixtures)
Specify P and T determine Vm
Specify P and Vm determine T
Specify T and Vm determine P

Tartaglia: the solver of cubic

equations

http://es.rice.edu/ES/humsoc/Galileo/Catalog/Files/tartalia.html

Cubic Equation Solver

http://www.1728.com/cubic.htm

Equations of State (EOS)

Phase equilibrium for a single
component at a given temperature
can be graphically determined by
selecting the saturation pressure
such that the areas above and
below the loop are equal, these are
known as the van der Waals loops.

Two-phase VLE
The phase equilibria equations are
expressed in terms of the
equilibrium ratios, the K-values.
l

yi i
Ki v
xi i

Dew Point Calculations

Equilibrium is always stated as:
l
v

xii P yii P

(i = 1, 2, 3 ,Nc)

with the following material balance

constrains
Nc

x
i 1

1,

Nc

y
i 1

1,

Nc

z
i 1

Dew Point Calculations

At the dew-point
l
v

xii zii

xi K i zi

(i = 1, 2, 3 ,Nc)

Dew Point Calculations

Rearranging, we obtain the DewPoint objective function
Nc

zi
1 0

i 1 K i

Bubble Point Equilibrium

Calculations
For a Bubble-point
Nc

z K
i 1

1 0

Flash Equilibrium Calculations

Flash calculations are the work-horse
of any compositional reservoir
simulation package.
The objective is to find the fv in a
VL mixture at a specified T and P
such that

zi ( K i 1)
0

i 1 1 f v ( K i 1)
Nc

Evaluation of Fugacity Coefficients

and K-values from an EOS
The general expression to evaluate
the fugacity coefficient for
component i is

RT

RT
ln

Vi
dP

P
0

v
i

T fixed

Evaluation of Fugacity Coefficients

and K-values from an EOS
The final expression to evaluate
the fugacity coefficient using an
EOS is.
V tv

P
RT
v
v

RT ln i
v dVt RT ln Z v
v
n

Vt

i T ,nv i