Equations of State

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

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

The critical point conditions are used
to determine the EOS parameters
0
Tc
2
V
2
0
Tc

Solving these two equations
simultaneously for the Peng-Robinson
EOS provides
2
2
c
RT
a a
Pc
and
RTc
b b
Pc

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

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

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

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

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

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

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

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

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.

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

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

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

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

At the dew-point
l
v
xii zii
xi K i zi
(i = 1, 2, 3 ,Nc)

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

Equations of State

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PETE 310

Equations of State (EOS)

Uses of Equations of State

Equations of State (EOS)

Equations of State (EOS)

Equations of State (EOS)

Equations of State (EOS)

m 0.37464 1.54226 0.2699

EOS for a Pure Component

Equations of State (EOS)

Equations of State (EOS)

where the kijs are called interaction

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

bm x1b1 x2b2 x3b3

Equations of State (EOS)

Equations of State (EOS)

Analytical Solution of Cubic

Analytical Solution of Cubic

Note: x could be either the molar

Analytical Solution of Cubic

Procedure to Evaluate the Roots

Procedure to Evaluate the Roots

Procedure to Evaluate the Roots

Procedure to Evaluate the Roots

Procedure to Evaluate the Roots

Procedure to Evaluate the Roots

Solutions of a Cubic Polynomial

Solutions of a Cubic Polynomial

Web site to download Fortran source

EOS for a Pure Component

Parameters needed to solve

Tartaglia: the solver of cubic

Cubic Equation Solver

Equations of State (EOS)

Dew Point Calculations

with the following material balance

Dew Point Calculations

Dew Point Calculations

Bubble Point Equilibrium

Flash Equilibrium Calculations

Evaluation of Fugacity Coefficients

Evaluation of Fugacity Coefficients

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