4/4/2014 1

Termodinamica de Hidrocarburos

Generalized Phase Equilibria
Models
4/4/2014 2

Generalized Phase Equilibria Models

The Principle of Corresponding States. Correlations and
Models.
Extension of Corresponding States to Mixtures.
Phase equilibrium. Phase rule.
Thermodynamic Properties of Homogeneous and
Heterogeneous Systems.
Phase Equilibrium: Vapor-Liquid-Equilibrium (VLE), Liquid-
Liquid Equilibrium (LLE), Solid-Liquid-Equilibrium (SLE).
Phase Equilibrium Models: Single Components. Reduced
Equations of State (EOS). Multicomponents. Mixing Rules.
Whats on it ?
4/4/2014 3



Types of VLE Computations: Dew Point and Bubble Point
Calculations. Multiphase Flash.
Low Pressure Phase Equilibria Computations (Surface
Separators).
Ideal Systems.
K-value correlations. Empirical methods to determine
equilibrium ratios (K-values).



Whats on it?
4/4/2014 4
Learning Objectives

After completing this module you will be able to:
Understand the Principle of Corresponding States.
Calculate the compressibility factor using different
correlations and models.
Understand phase equilibrium.
Determine the number of variables required to define
a system in equilibrium (Phase Rule).

4/4/2014 5
Learning Objectives

After completing this module you will be able
to:
Evaluate energy relationships using the First
and Second Law of Thermodynamics.
Evaluate dew and bubble points given
pressure or temperature as independent
variables.
Evaluate flash separation processes.


4/4/2014 6
The Principle 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
The Principle of Corresponding states (POC)
originated with single component fluids.
4/4/2014 7
Material properties are usually
expressed in terms of reduced
parameters such as:

Reduced Temperature:

Typical Reduced Parameters

c r
T T T /
4/4/2014 8

Reduced Pressure:



Reduced Molar Volume:


c r
P P P /
c r
V V V
~
/
~ ~
Typical Reduced Parameters
4/4/2014 9
Reduced Parameters
Usually T
r
and P
r
V
r
obtained as a
function of T
r
and P
r
These are called two-parameter
Corresponding States models
Three-parameter corresponding states
models improve predictions but third
parameter is not V
r
(not independent
variable)

4/4/2014 10
This third parameter is called the acentric
factor.
It takes into account the non-spherical nature
of molecules
Peng Robinson and the Soave Redlich
Kwong equations of state (EOS) are
examples of three parameter corresponding
states models.
Generalized Corresponding
States Three-Parameter
4/4/2014 11

The acentric factor e is tabulated for
most pure components and is defined
as

Acentric Factor
7 . 0
log 1
=
r
T
sat
r
P
4/4/2014 12
Acentric Factor Definition
1/T
r
log(P
r
Sat
)
-1
1.43
1.0
Slope = -2.3 ( Ar, Kr, Xe)
4/4/2014 13
Compressibility Factor Charts
Following the POC only one
compressibility factor chart can be used
to determine volumetric properties of
any pure fluid by using its reduced
properties. The shape of this chart is in
general.

4/4/2014 14
Compressibility Factor Charts
T
r
P
r
Z
1
4/4/2014 15
Corresponding States
Correlations & Models
The objective is then to find a model
(models) to predict the Z factor.
Ideal gas behavior is described from the
ideal gas Equation of State (EOS) with a
compressibility factor of 1.

4/4/2014 16
1 =
RT
V P
id
~
Z
RT
V P
=
~
Equations of State for Gases
Ideal gas

Real gas
Z
Z
V P
RT
RT
V P
id
= =
|
|
.
|

\
|
|
|
.
|

\
|
1
~
~
Z is the ratio of the real molar volume
over the ideal molar volume
of a substance measured at the same
pressure and temperature.
4/4/2014 17
Virial Equations of State
Pressure Virial Equation


Density Virial Equation
... ' ' ' 1
~
3 2
+ + + + = P D P C P B
RT
V P
...
~ ~ ~
1
~
3 2
+ + + + =
V
D
V
C
V
B
RT
V P
4/4/2014 18
Evaluation of the Compressibility
Factor (Z-factor)
The simplest correlation for the
compressibility factor is expressed in
terms of the second virial coefficient.

r
r
c
c
T
P
RT
BP
RT
BP
Z
|
|
.
|

\
|
+ = + = 1 1
4/4/2014 19
Evaluation of the Compressibility
Factor (Z-factor)
And the term (BP
c
/RT
c
) is determined using
Pitzers Correlation as follows,



with

1 0
B B
RT
BP
c
c
e + =
|
|
.
|

\
|
6 1
0
422 0
083 0
.
r
T
.
. B =
2 4
1
0172
139 0
.
r
T
. B =
4/4/2014 20
Evaluation of the Compressibility
Factor (Z-factor)
Therefore the compressibility factor is
expressed as:




Note the use of reduced properties and
the acentric factor

r
r
r
r
T
P
B
T
P
B Z
1 0
1
4/4/2014 21
Evaluation of the Compressibility
Factor (Z-factor)
Virial expansion is not adequate for
high pressures (P > 500 psia)
Cubic Equations of State are more
appropriate
4/4/2014 22
Johannes Diderik van der Waals
The Nobel Prize in
Physics 1910
"for his work on the
equation of state for
gases and liquids"
Amsterdam University
Amsterdam, the
Netherlands
1837 - 1923
4/4/2014 23
Cubic Equations of State
The most well-known and older EOS is
the Van der Waals equation, which is
2
~ ~
V
a
b V
RT
P
(two-parameter corresponding states)
4/4/2014 24
Cubic Equations of State
Probable the most widely used EOS in
the gas and petroleum industry is the
Peng-Robinson EOS

V b V b V V
a
b V
RT
P
~
)
~
( )
~
(
~ ~
(three-parameter corresponding states)
4/4/2014 25
Mathematical Foundation of
Cubic Equations of State
The critical point for a single component
in a (PV) diagram is an inflection point
on the critical isotherm (Tc)
The critical point for a single component
on a (PT) diagram is a maximum in P
and T
4/4/2014 26
PV Phase Behavior
Pressure-
volume
behavior
indicating
isotherms for a
pure
component
system
P
r
e
s

s
u
r
e

Mo la r V o lu m e
T
c
T
2
T
1
P
1
v
L
2 - P has es
CP
V
L
V
P
r
e
s

s
u
r
e

Mo la r V o lu m e
T
c
4/4/2014 27
Application of Constraints at the
Critical Point Van der Waals EOS
Example
2
~ ~
V
a
b V
RT
P

=
3 2
~
2
)
~
(
~
V
a
b V
RT
V
P
T
+

=
|
.
|

\
|
c
c
4 3 2
2
~
6
)
~
(
2
~
V
a
b V
RT
V
P
T

=
|
|
.
|

\
|
c
c
4/4/2014 28
Application of Constraints at the
Critical Point
These two derivatives must vanish at
the critical point

3 2
~
2
)
~
(
0
~
c
c
c
T
T
V
a
b V
RT
V
P
c
+

= =
|
.
|

\
|
c
c
3 2
~
2
)
~
(
0
~
c
c
c
T
T
V
a
b V
RT
V
P
c
+

= =
|
.
|

\
|
c
c
4/4/2014 29
Evaluation of a and b Parameters
Parameter b is found from




Next a is
3
~

~
)
~
( 3
2
)
~
(

~
2 ~
)
~
( 3
2
~
2

)
~
(
3 2
3 3
3 2
c
c
c
c
c
c
c
c
c
c
c
c
c
V
b V
b V
RT
b V
RT
V
a
V
b V
RT
V
a
b V
RT
=

8
~
9
~
8
~
9
3 /
~ ~
2
~
~
)
~
( 2
2
3
2
3
3
2
c c
c
c c
c c
c c
c
c
c
V RT
V
V RT
V V
V RT
V
b V
RT
a = =

=
4/4/2014 30
Determination of a and b
Parameters
The critical compressibility factor is


Replace a and b in VdW EOS and
evaluate the critical compressibility
c
c
c
Z
RT
V P
=
~
c
c
c
c
c
c
c
c c
c c
c
c
V
RT
V
RT
V
RT
V
V RT
V V
RT
P
~
8
3
~
8
9
~
2
3
~
8
~
9
3
~ ~
2
= =

=
4/4/2014 31
Critical Compressibility Factor
And the critical compressibility
calculated from VdW EOS is




A unique value for all substances

375 . 0
8
3
~
= = =
c
c
c
Z
RT
V P
4/4/2014 32
Parameters a and b as a
Function of Tc and Pc
Using this we can express the a and b
constants as

( ) ( )
c
c
c
c
c
c
c c c c
P
RT
P
RT
Z
P
RT RT V RT
a
64
27
8
3
8
9
8
9
8
~
9
2 2
= =
|
|
.
|

\
|
= =
c
c
c
c
c
c
c c
P
RT
P
RT
Z
P
RT V
b
8 8
3
3 3 3
~
=
|
.
|

\
|
= = =
4/4/2014 33
Cubic Equations of State
The Z factor is then evaluated as

RT V
a
b V
V
RT
V P
Z
~ ~
~ ~

= =
4/4/2014 34
Solution of Cubic Equations
To solve cubic equations there are
analytical techniques and free software
in the WEB

http://www.uni-koeln.de/math-nat-
fak/phchem/deiters/quartic/quartic.html

4/4/2014 35
Solutions of Cubic Equations
4/4/2014 36
Tartaglia: the solver of cubic
equations

http://es.rice.edu/ES/humsoc/Galileo/Catalog/Files/tartalia.html
4/4/2014 37
Cubic Equation Solver
http://www.1728.com/cubic.htm
4/4/2014 38
Single vs Multicomponent Mixtures
So far have evaluated Z-factors for
single components only
For hydrocarbon mixtures we use the
SAME models with mixing rules
4/4/2014 39
Example Problem
Mr. Jones wants to use some 30 liter cans to ship
ethane from College Station to Conroe. He would
like to fill each of these cylinders with 10 kg of
ethane, but he does not know the pressure at
which he needs to fill these tanks or if the walls of
the tanks will be able to withstand that kind of
pressure. The shipping should be done at an
average temperature of 25
o
C.
4/4/2014 40
Example Problem
Use three different methods:
Ideal gas EOS

Z factor compressibility correlations given in class
Z factor charts using chart given in class notes
(you will do this one)
Z factor from a cubic EOS (you will do this)
Z factor using properties evaluated from NIST
website (you will do this)
4/4/2014 41
Example Problem
The Critical properties and acentric
factor for ethane are:
Mw = 30 g / mol
Tc = 305.5 K
Pc = 48.8 bar
w = 0.098
4/4/2014 42
Example Problem
(a) Ideal Gas EOS






.. (about 4,000 psia)
( )
( )
) K . (
mol K
bar cm .
g/mol
g ,
Mw
mRT
nRT PV 25 15 273
14 83
30
000 10
3
+
|
|
.
|

\
|
= = =
bar .
cm
bar cm
,
.
MwV
mRT
P 424 275
000 30
10 26273 8
3
3 6
=
|
|
.
|

\
|

= =
4/4/2014 43
Example Problem
(b) Z-factor Correlations

To use Pitzer correlation we must
calculate the reduced temperature which
is


9755 . 0
5 . 305
15 . 273 25
=
|
.
|

\
|
+
= =
c
r
T
T
T
4/4/2014 44
Example Problem
The correlation is

(A)

we also know that

(B)


r
r
c
c
T
P
RT
BP
Z
|
|
.
|

\
|
+ = 1
r
r
P
P
Z 177181 . 0
) 25 15 . 273 )( 14 . 83 )( 000 , 10 (
) 30 )( 000 , 30 )( 8 . 48 (
=
+
=
mRT
VMw P P
nRT
PV
Z
c r
= =
4/4/2014 45
Example Problem
with

The acentric factor for ethane can be
obtained from the tables provided with
properties for pure components.

1 0
B B
RT
BP
c
c
e + =
|
|
.
|

\
|
( )
3561 0
9755 0
422 0
083 0
422 0
083 0
6 1 6 1
0
.
.
.
.
T
.
. B
. .
r
= = =
4/4/2014 46
Example Problem
and
( )
0519 . 0
9755 . 0
0172
139 . 0
0172
139 . 0
2 . 4 2 . 4
1
= = =
r
T
B
( ) 3612 . 0 0519 . 0 098 . 0 3561 . 0
1 0
= + = e + =
|
|
.
|

\
|
B B
RT
BP
c
c
|
.
|

\
|
=
|
|
.
|

\
|
+ =
9755 . 0
3612 . 0 1 1
r
r
r
c
c
P
T
P
RT
BP
Z
4/4/2014 47
Example Problem
Combining the 2 equations A and B, we
have


and


r
P Z 37027 . 0 1
r
P Z 177181 . 0
4/4/2014 48
Example Problem
Equating these two equations (A) & (B) we
solve for the reduced pressure, and then for
the pressure P.



There is a substantial difference from the
ideal gas model!

bar . . . P P P
. P
c r
r
12 89 8 48 8263 1
8263 1
= = =
=
4/4/2014 49
Example Problem
(c), (d) and (f) are part of your
homework assignment
4/4/2014 50
Extension of Corresponding
States to Mixtures
Z factor charts (all built from EOS) are
also used for multicomponent systems
in this case the coordinates used are
pseudo-reduced properties
For a mixture you can use the same
charts as for a pure component.
4/4/2014 51
Pseudoreduced Properties
For mixtures the same type of charts apply
but using pseudoreduced properties which
are defined similarly as the ratio of pressure
(or temperature) with pseudoreduced critical
pressure" (or temperature).
These pseudocritical properties are an
average of the critical properties of the
components in the mixture. Charts for
mixtures can also be used for single
component fluids.
4/4/2014 52
Compressibility
factor Z as a
function or
pseudoreduced
pressure
4/4/2014 53
Pseudocritical Properties of
Natural Gases
Pseudoreduced Pressure



Pseudoreduced Temperature

pc
pr
P
P
P =
pc
pr
T
T
T =
4/4/2014 54
Pseudocritical Properties of
Natural Gases
If only the specific gravity of the gases
is known then charts/equations are
available to estimate these
pseudocritical properties (SPE paper
26668)
4/4/2014 55
Pseudocritical Properties of
Natural Gases
Naturally the degree of accuracy is
reduced substantially. We well see
methods when compositional
information is available, in this case:

ci i
N
i
pc
P y P
c
=1
ci i
N
i
pc
T y T
c
=1
4/4/2014 56
Pseudocritical Properties of
Natural Gases
Once Z is evaluated you can find the
gas density as

3
/ ft lbm
V
M
g
4/4/2014 57
So far we were just determining properties
either for a gas or a highly compressed fluid
(liquid like density) in the SINGLE PHASE
REGION.

Notice that Z- factor charts DO NOT
HELP AT ALL IN DETERMINING
PROPERTIES OF GAS AND
LIQUID COEXISTING PHASES.
4/4/2014 58
Z-factor
chart for low
reduced
pressures
4/4/2014 59
SPE Paper 26668

Real Gas Equation
Evaluation of Ppc & Tpc when
composition is known
Evaluation of Ppc & Tpc when gas
specific gravity is known
Corrections for N
2
, CO
2
, H
2
S
4/4/2014 60
Pseudocritical Properties
When all gas compositions are known
4/4/2014 61
Pseudocritical Properties
Compositions known including corrections for
H
2
S, N
2
and CO
2
and
4/4/2014 62
Pseudocritical Properties
Compositions known including corrections for
H
2
S, N
2
and CO
2
And
In this order
4/4/2014 63
Coefficients in Equation 4
4/4/2014 64
Pseudocritical Properties
Specific gas gravity & composition of
impurities is known
i = H
2
S, N
2
and CO
2
- 3 major impurities)
4/4/2014 65
Coefficients in Equation 6
4/4/2014 66
R
2
- Statistical Evaluation of
Goodness of Fit (How well you fit the
data)
2
n
1 i
i
) Y Y

( SSR =

=
2
n
1 i
i i
) Y

Y ( SSE

=
=
SYY
SSR
R ion Determinat of t Coefficien
2
= =
SSE SSR SSY + =
sum of squares of (predicted average)
sum of errors squared
(true value predicted value)
When R
2
is close to 1 SSE is close to zero!
sum of errors squared is nearly zero
4/4/2014 67
Appreciate Estimates
4/4/2014 68
A Faster Procedure (but less
accurate)
Given gas specific gravity read J
Given compositions of N
2
, CO
2
, H
2
S
correct J using charts
J = J + sum(Correction_i)
Note the corrections are negative

4/4/2014 69
A Faster Procedure (but less
accurate)
Given gas specific gravity read K
Given compositions of N
2
, CO
2
, H
2
S
correct K using charts
K = K + sum(Correction_i)
Note the corrections are negative

4/4/2014 70
The Chart for J
4/4/2014 71
The Corrections for J
4/4/2014 72
The Chart & Corrections for K
4/4/2014 73
Procedure
Determine Tpc and Ppc
Given gas composition
Given gas gravity & compositions of
impurities
At given p and T determine Tpr and Ppr
Determine z for the gas requested
4/4/2014 74
Evaluate z-factor
4/4/2014 75
Exercise in Class
Determine the density of an acid gas at
3,500 psia and 220
o
F
The gas contains 5% CO
2
and 15%
H
2
S and has a specific gravity of 1.4
4/4/2014 76
Questions & Assignment
What errors could you have in your
predictions if the corrections for
impurities are neglected?
How good are these new correlations
compared with the existing ones?
READ the paper SPE 26668 for
additional details