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 Peng-

Robinson EOS (1975). This is a three-
parameter corresponding states model.

RT a
P
V b V (V b) b(V b)

P Prep Pattr
 PV Phase Behavior
Pressure-
Tc volume
CP
behavior
indicating
Pres sure

isotherms for
T2 a pure
component
v
P
1 system
T1

L
2 - P has es
V

L V

Mo lar V olum e
 Equations of State (EOS)

The critical point conditions are used

to determine the EOS parameters

P
0
V Tc
P
2
2 0
V Tc
 Equations of State (EOS)

Solving these two equations

simultaneously for the Peng-Robinson
EOS provides

RT 2 2 RTc
a a c and b b
Pc Pc
 Equations of State (EOS)

Where a 0.45724
b 0.07780
and

1 m 1 Tr
2

with

m 0.37464 1.54226 0.2699 2

EOS for a Pure Component

CP
Pres sur e

T2

4
T1
v 3 A2 5
P 1
1 -
L A1 1
10 P
~ >0 2 V
0 V T

2 - P has
hases
2

L V

7
Mo la r V o lum e 6
 Equations of State (EOS)

PR equation can be expressed as a

cubic polynomial in V, density, or Z.

Z ( B 1) Z
3 2

( A 3B 2 B ) Z
2

( AB B B ) 0
2 3
a P
A
RT 2

with
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
0.5

a m xi x j ai a ji j 1 k
Nc Nc

ij
i 1 j 1

where the kijs are called interaction

parameters and by definition

kij k ji
kii 0
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 0.5

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

0.5
1

x32 a3 3

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 bm P
Am Bm
RT
2
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 2

( A 3B 2 B ) Z
2

( AB B B ) 0
2 3
 Analytical Solution of Cubic
Equations
Lets write the polynomial in the
following way

x a1x a2 x a 0
3 2 3

Note: x could be either the molar

volume, or the density, or the z-
factor
 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 3
Procedure to Evaluate the Roots
of a Cubic Equation Analytically

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

T R Q R
3 3 2
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
1 1
If D 0 x2 2 Q cos 120 a1
3 3
1 1
x3 2 Q cos 240 a1
3 3

where R
cos
Q3
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-nat-
fak/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

CP
Pres sur e

T2

4
T1
v 3 A2 5
P 1
1 -
L A1 1
10 P
~ >0 2 V
0 V T

2 - P has
hases
2

L V

7
Mo la r V o lum e 6
 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.

yi i l
Ki v
xi i
 Dew Point Calculations

Equilibrium is always stated as:

l
xii P yii P
v
(i = 1, 2, 3 ,Nc)

with the following material balance

constrains
Nc Nc Nc

x
i 1
i 1, y
i 1
i 1, z
i 1
i 1
 Dew Point Calculations

At the dew-point

xii zii
l v

xi K i zi (i = 1, 2, 3 ,Nc)
 Dew Point Calculations

Rearranging, we obtain the Dew-

Point objective function
Nc
zi

i 1 K i
1 0
 Bubble Point Equilibrium
Calculations
For a Bubble-point

Nc

z K
i 1
i i 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
Nc
zi ( Ki 1)

i 1 1 f v ( K i 1)
0
Evaluation of Fugacity Coefficients
and K-values from an EOS

The general expression to evaluate

the fugacity coefficient for
component i is

P
RT
i Vi
v
RT ln dP
0
P T fixed
Evaluation of Fugacity Coefficients
and K-values from an EOS

The final expression to evaluate

the fugacity coefficient using an
EOS is.
Vtv
P RT v

RT ln i
v v dVt RT ln Z v
n
v
V

i T ,n j i
v t