Termodinamica de Hidrocarburos: Generalized Phase Equilibria

4/4/2014 1
Termodinamica de
Hidrocarburos
Generalized Phase Equilibria
4/4/2014 2

Phase Equilibrium
Evolution
4/4/2014 3
The Concept of Equilibrium
Equilibrium indicates static conditions,
the absence of change
In thermodynamics is taken to mean
not only the absence of change, but the
absence of any tendency to change.
A system existing in equilibrium is one
in which under such conditions that
there is no tendency for a change to
state to occur.
4/4/2014 4
The Concept of Equilibrium
Tendencies toward a change are
caused by a driving force of any
kind

Equilibrium means the absence of
any driving force, or that all forces
are in exact balance.
4/4/2014 5
Driving Forces
Typical driving forces include:
mechanical forces such as pressure
on a piston tend to cause energy
transfer as work
temperature differences tend to
cause the flow of heat
chemical potentials tend to cause
mass transfer from one phase to
another or cause substances to react
chemically.
4/4/2014 6
Phase Equilibrium and the
Phase Rule
In reservoir engineering applications
we assume that reservoir fluids are at
equilibrium, we do not say how long
the equilibrium will last.
As a reservoir block changes pressure
due to production (injection) we
assume that equilibrium is reached
instantly.
Fluid properties in reservoir cells are
evaluated using a sequence of
connected equilibrium stages.

4/4/2014 7
Phase Rule
It tells us the number of independent
variables required to fully
characterize a system
It does not tell us which variables to
select

4/4/2014 8
Generalization of the phase rule
for N
c
non reacting components
Number of components Number of phases Degrees of Freedom
1 1 2
1 2 1
1 3 0
2 1 3
2 2 2
2 3 1

N
c
N
p
(N
c
-N
p
)+2
4/4/2014 9
Phase Equilibrium and the
Phase Rule
Thus for non-reacting systems

F = # of variables # of Independent
equations relating these variables

2
p c
N N F
4/4/2014 10
First Law and Fundamental
Thermodynamic Relationships
Closed Systems
The system does not exchange
matter with the surroundings, but
it can exchange energy.
The first law is a generalization of
the conservation of energy
dW dQ dU
t
4/4/2014 11
Compression and
expansion work
in a gas container
indicating
the convention
used for heat and
work
Heat and Work Sign Convention
4/4/2014 12
For a reversible process, dQ = TdS
t
thus,

If the work of expansion or
compression is the only kind of
work allowed then:

dW TdS dU
t t
=
t
PdV dW =
4/4/2014 13
Replacing work and heat
expressions

Thus

t t t
PdV TdS dU
t t t t
V S U U ,
4/4/2014 14
Since

Thus one can identify,

T
nS
nU
n nV
=
|
|
.
|
\
|
c
c
,
P
nV
nU
n nS
=
|
|
.
|
\
|
c
c
,
t t t t
V S U U ,
Define:
M
t
= nM with M = U, H, A, G, S
4/4/2014 15
Other Thermodynamic
Functions
The relationship among these
properties is:

t t t
PV U H + =
t t t t t t
TS U TS PV H F = =
t t t
TS H G =
Flow processes
Phase equilibria
4/4/2014 16
Differentials of
Thermodynamic Functions
Expressions similar to

( ) P S H H dP V TdS dH
t t t t t t
, i.e. = + =
( )
t t t t t t
V T F F PdV dT S dF , i.e. = =
( ) T P G G dP V dT S dG
t t t t t
, i.e. = + =
t t t
PdV TdS dU =
The same relationships hold for
the intensive properties (M = M
t
/n)
4/4/2014 17
Key Concept
The (U
t
,H
t
,F
t
,G
t
,S
t
) are STATE
properties which means
independent of path.
4/4/2014 18
State Functions
) , (
1 1 1
T P M
P
r
e
s
s
u
r
e

Temperature
) , (
2 2 2
T P M
4/4/2014 19
Open Systems
For an open system, U
t
, H
t
, F
t
, and G
t
,
will also depend on the concentration
of each of the components.
The number of moles of each specie
may change due to:
Chemical reaction within system
Interchange of matter with surroundings
Interchange and chemical reaction.

4/4/2014 20
Open Systems
The functional form of U
t
, H
t
, F
t
,
and G
t
for open systems are,

c
N t t t t
n n n V S U U ..., , , ,
2 1
=
c
N t t t
n n n P S H H ..., , , ,
2 1
=
c
N t t t
n n n V T F F ..., , , ,
2 1
=
c
N t t
n n n P T G G ..., , , ,
2 1
=
4/4/2014 21
Open Systems
The differential form of the
thermodynamic functions are
i
i n V S
N
i
i
t
t t t
dn
n
U
PdV TdS dU
j t t
c
=
=
|
|
.
|
\
|
c
c
+ =
, ,
1
4/4/2014 22
Open Systems
The differential form of the above
equations are,

i
i n V T
N
i
i
t
t t t
dn
n
F
PdV dT S dF
j t
c
=
=
|
|
.
|
\
|
c
c
+ =
, ,
1
i
i n P T
N
i
i
t
t t t
dn
n
G
dP V dT S dG
j
c
=
=
|
|
.
|
\
|
c
c
+ + =
, ,
1
4/4/2014 23
Open Systems
Define the chemical potential of
component " i " as
i n , P , T
i
t
i
i n , V , T
i
t
i n , P , S
i
t
i n , V , S
i
t
i
j
j t j t j t t
n
G

also and
n
F

n
H

n
U
=
= = =
|
|
.
|
\
|
c
c
=
|
|
.
|
\
|
c
c
=
|
|
.
|
\
|
c
c
=
|
|
.
|
\
|
c
c
=
Most well-known
4/4/2014 24
Second Law and the
Equilibrium Criteria
Equilibrium
dS = 0
Time
E
n
t
r
o
p
y
,

S
4/4/2014 25
Second Law and the
Equilibrium Criteria
The criteria of equilibrium of a system can
also be stated in terms of U
t
, H
t
, F
t
, and G
t
as
follows

The internal energy, U
t
, must be a minimum at
constant S
t
, V
t
, and n
i
.
The enthalpy, H
t
, must be a minimum at constant
S
t
, P, and n
i
.
The Helmholtz free energy, F
t
, must be a
minimum at constant T, V
t
, and n
i
.
The Gibbs free energy, G
t
, must be a minimum at
constant T, P, and n
i
.
4/4/2014 26
Chemical and Phase Equilibria
Criteria for an Open System
Using Intensive Properties

Gas System
Liquid system
open
4/4/2014 27
Open System: Derivation of
Equilibrium Conditions
Variation of internal energy for
liquid system is

Variation of internal energy for gas
system is

v
i
N
i
v
i
v v v
dn nV Pd nS Td nU d
c
=
+ =
1

l
i
N
i
l
i
l l l
dn nV Pd nS Td nU d
c
=
+ =
1

4/4/2014 28
Derivation of Equilibrium
Conditions
Gas + Liquid systems make a closed
system and the total energy is

thus for a closed system at equilibrium
l
i
N
i
l
i
v
i
N
i
v
i
dn dn nV Pd nS Td nU d
c c
= =
+ + =
1 1

0

1 1
= +

= =
l
i
N
i
l
i
v
i
N
i
v
i
dn dn
c c
4/4/2014 29
Derivation of Equilibrium
Conditions
From mass conservation

replace in

Therefore
l
i
v
i
dn dn
0

1 1
= +
= =
l
i
N
i
l
i
v
i
N
i
v
i
dn dn
c c
0

1
=
=
v
i
l
i
N
i
v
i
dn
c
4/4/2014 30
Auxiliary Thermodynamic
Functions
The mole fractions are also
thermodynamic functions
and
1 1
l
l
i
N
i
l
i
l
i
i
v
v
i
N
i
v
i
v
i
i
n
n
n
n
x
n
n
n
n
y
c c
= = = =
= =
4/4/2014 31
Phase Equilibria Models
Can be classified according to:

the type of fluids (hydrocarbons,
alcohols, electrolytes, water and
other non-hydrocarbon species)

pressure and temperature ranges of
interest.
4/4/2014 32
Phase Equilibria Models for
Low-pressure ranges, such as
those of separator and surface
conditions
High-pressures ranges which
apply to the reservoir.
Type of reservoir fluid, whether a
black oil or a volatile oil, also
determines the type of Phase
equilibrium model
4/4/2014 33
Residual Properties
Define the residual properties for
mathematical convenience as the
difference between the actual
(real) property minus the same
property, evaluated at the same
pressure, temperature, and
composition, but evaluated using
the ideal gas equation.
4/4/2014 34
VLE

We will start with the simpler
models first, the ones for lower
pressures

Single Component
&
Multicomponent

4/4/2014 35
Residual Properties
That is
M
R
= M-M
ig
M=U, H, G, S, F (F is A in
American Notation)

M: Real Property @ (T, P) of the system
M
R
: Residual Property
M
ig
: Property @ (T, P) of the system
evaluated as if the fluid were an ideal
gas

Note: there is no T
R
or P
R

4/4/2014 36
Residual Properties
Recall for a constant composition
closed system

SdT VdP dG =
dT S dP V dG
ig ig ig
=
dT S dP V dG
R R R
=
4/4/2014 37
Residual Properties
Note that the properties used in
these equations are intensive
properties, that is the volume is
the molar volume
G and S are expressed in BTU/lb-
mol and BTU/lb-mol-R,
respectively, (or in cal/g-mol,
cal/g-mol K in the SI system of
units).

4/4/2014 38
Gibbs Residual Energy
At constant temperature,

Divide by RT

dP V dG
R R
=
= =
P
R
G
R R R
dP
RT
V
RT
dG
dP
RT
V
RT
dG
R
0 0
4/4/2014 39
Gibbs Residual Energy
From previous lectures we had:

1 ,
RT
PV
z
RT
PV
ig
P
z
RT
V
R
) 1 (

=
=
P
R
P
dP
z-
RT
G
0
1
Thus
4/4/2014 40
Phase Equilibrium of a Single
Component
Recall
l v
l l l
v v v
G G
dT dP-S V dG
dT dP-S V dG
4/4/2014 41
Predicted Isotherms from a
cubic EOS
4/4/2014 42
Phase Equilibrium
Single Component
For constant temperature,

At equilibrium P
1
=P
5
=P
o

0 ) ( = = = PdV PV d VdP dG
= =
5
1
5
1
1 1 5 5
0 dV P V P V P dG
=
o
5
1
1 5
0 ) ( dV P V V P
4/4/2014 43
Phase Equilibrium of a Single
Component
By inspection,

And also,

) 1 7 6 5 3 1 ( ) (
1 5
=
o
Area V V P
) 1 7 6 5 4 3 2 1 (
5
1
=
}
Area PdV
) 3 5 4 3 ( ) 1 2 3 1 ( ) 1 7 6 5 3 1 (
) 1 7 6 5 4 3 2 1 (
+
=
Area Area Area
Area
4/4/2014 44
Maxwell Equal Area Rule
4/4/2014 45
VLE in Dimensionless or
Reduced Form
Write the EOS in dimensionless
form using T
r
=T/T
c
, P
r
=P/P
c
,
V
r
=V/V
c
, and the values for a and b
found from the critical constraints

0 , 0
2
2
=
|
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c
c
T
c
T
V
P
V
P
4/4/2014 46
Reduced Form
For Van der Waals EOS

with

2
V
a
b V
RT
P
=
c c
V RT a
8
9
=
c
c c
P
RT V
b
8 3
= =
4/4/2014 47
Reduced Form
and
c
c c
c
RT
V P
z = =
8
3
c
c
c
P
RT
V
8
3
=
2 2
8
3
r c
c c
c
c r
c r
c r
V V
V RT a
V
V V
T RT
P P
=
4/4/2014 48
Application of Equal Area Rule

At T constant

or

0 dG
0 ) ( dV P PV d VdP dG
=
o
rg
rl
V
V
r r rl rg r
dV P V V P
4/4/2014 49
Reduced Form
Replacing and integrating

Since P is constant,

Thus,

(
(
+
(
=
o
rl rg rl
rg
r
rl rg r
V V V
V
T
V V P
3 3
1 3
1 3
ln
3
8
0 = dP
= 0 dP V
4/4/2014 50
Reduced Form
0
r
rg
rl
r
rg
rl
V
V
r
T
r
r
V
V
r r
dV
V
P
V dP V
(
+ =
rg
rl
V
V
r
r
r
r
dV
V
) - V (
Tr -
V
6
1 3
24

3 2
4/4/2014 51
Reduced Form
From integral tables,

etc.,

(
+
+ + =
+
}
bx a
a
bx a
b bx a
xdx
) ln(
1
) (
2
2
0
1 1
4
9
1 3
1
1 3
1
1 3
1 3
ln =
|
|
.
|
\
|

|
|
.
|
\
|
+
|
|
.
|
\
|
|
|
.
|
\
|
rg rl r rl rg rg
rg
V V T V V V
V
4/4/2014 52
Reduced Form
Have three equations to work with

EOS

Maxwell Equal Area Rule

and

}
= 0 dP V
unknowns P
r
o
, V
rl
, V
rg
.
4/4/2014 53
VLE at low pressures
We will see first
models that apply
ONLY for low
pressures
4/4/2014 54
Systems of Variable
Composition: Ideal Behavior
Applications to low pressures
Simplifications

the gas phase behaves as an Ideal
Gas
the liquid phase exhibits Ideal
Solution Behavior.

4/4/2014 55
Systems of Variable

The equilibrium criteria between 2
phases o and | is,

c i i
N i
T T
P P
,.... 2 , 1 ,

| o
| o
| o
4/4/2014 56
Systems of Variable
Thus, at constant T and P,

=
=
=
=
c
c
n
i
l
i
l
i
l
n
i
v
i
v
i
v
dn nG d
dn nG d
1
1
) (
) (
4/4/2014 57
Systems of Variable

Simplest VLE model (IG+IS) imply that

IG: molecular interactions are zero,
molecules have no volume.

IS: forces of attraction/repulsion
between molecules are the same
regardless of molecular species.
Volumes are additive (Amagats Law).
4/4/2014 58
Forces between molecular
species
A A
B B
A B
AB BB AA
F F F
4/4/2014 59
Ideal Gas Mixture
The pressure in a vessel
containing an ideal gas mixture (n)
or a single gas component (n
k
) is

t
k
k
t
V
RT n
P
V
nRT
P
=
=
4/4/2014 60
Systems of Variable

P
k
is the partial
pressure of
component k, and by
definition
k
k k
y
n
n
P
P
= =
=
c
N
i
k
P P
1
P

p
k
T
1
T
1
n
1
,n
2
,
n
k
, n
k
4/4/2014 61
Systems of Variable
Generalize this principle to any
thermodynamic property for an
ideal gas mixture

=
c
n
k
k
ig
k k
ig
P T M n P T nM
1
) , ( ) , (
4/4/2014 62
A total thermodynamic
property (nU, nG, nS, nH,
nF) of an ideal gas
mixture is the E of the
total properties of the
individual species each
evaluated at the T of the
mixture and at its own
partial pressure.

4/4/2014 63
Derive Equilibrium Relations
Begin with an ideal gas

The enthalpy of an ideal gas is
independent of pressure, thus

ig ig ig
TS H G
) , ( ) , (
k
ig
k
ig
k
P T H P T H
4/4/2014 64

For the entropy, we must express

) , ( P T S S
ig ig
=
dT
T
S
dP
P
S
dS
P T
|
.
|
\
|
c
c
+
|
.
|
\
|
c
c
=
4/4/2014 65
Recall Maxwell Rules

For ideal gas,

dT
T
c
dP
T
V
dS
p
P
+
|
.
|
\
|
c
c
=
dT
T
c
dP
P
R
dS
ig
p
ig
k
+ =
4/4/2014 66
at constant temperature,

=
= =
P
P
P
P
ig
k
ig
k
k k
P d R dS
P Rd dP
P
R
dS
ln
ln
k
k
k
ig
k
ig
k
y ln R
P
P
ln R ) P , T ( S ) P , T ( S =
|
|
.
|
\
|
=
4/4/2014 67
We also know from ideal
averaging applied to entropy,

=
=
c
N
k
k
ig
k k
ig
P T S n P T nS
1
) , ( ) , (
=
=
c
N
k
k
ig
k k
ig
) P , T ( S y ) P , T ( S
1
4/4/2014 68
Substituting,

the entropy change of mixing the ideal
gases is not zero
= =
=
c c
N
k
k k
N
k
k
ig
k k
ig
y y R P T S y P T S
1 1
ln ) , ( ) , (
= =
> =
c c
N
k
k
k
N
k
ig
k k
ig
y
y R S y S
1 1
0
1
ln
4/4/2014 69
Now, we can build the expression
for the Gibbs energy for an ideal
gas.

recall

= = =
+ =
c c c
N
k
k k
N
k
ig
k k
N
k
ig
k k
ig
y y RT P T S y T P T H y P T G
1 1 1
ln ) , ( ) , ( ) , (
i j
n P T
i
i
n
nG
=
|
|
.
|
\
|
c
c
=
, ,
4/4/2014 70
Expressed in terms of n (y
k
=n
k
/n),

= =
+ =
c c
N
k
k k
N
k
ig
k
k
ig
n
n
n
n
RT G
n
n
P T G
1 1
ln ) , (
(
+ =
= = =
c c c
N
i
n
i
k k k
N
i
ig
k k
ig
n n n n RT G n P T nG
1 1 1
ln ) ( ln ) , (
4/4/2014 71
Recall,
=
=
c
N
i
i
n n
1
k j
n
n
k j
n
n
n
n
j
k
j
k
k
= =
c
c
= =
c
c
=
c
c
, 1
, 0
1
4/4/2014 72
Therefore,

(
+ + =
|
|
.
|
\
|
c
c
=
=
n
n
n
n
n
n RT G
n
nG
k
i
i
i
ig
i
n p T
i
ig
ig
i
i j
ln ln
, ,
i
ig
i
ig
i
y RT G ln
4/4/2014 73
Ideal Solution
Following the same reasoning as
for gases, we have that,

=
i i i
id
x R S x S
i i i i
id
x x RT G x G ln + =
i i
id
i
RTx G + =
Here, S
i
and G
i
are the properties of the pure
species in the liquid state at the T and P of the
mixture.
4/4/2014 74
Raoults Law
It is a combination of IG + IS
models. VLE for a mixture of N
c

components

c
id
l
i
ig
v
i
l
i
v
i
N ,..., i
)
( )
(

1 =
= =
4/4/2014 75
Raoults Law
Thus, at T and P,

i
l
i i
ig
i
x RT G y RT G ln ln + = +
) , ( ) , ( ln P T G P T G
x
y
RT
ig
i
l
i
i
i
=
The right hand side of this Eq. indicates pure
species properties evaluated at the equilibrium T
and P of the mixture

4/4/2014 76
Raoults Law

As we seen before for a pure
component,

So, this leads to Raoults Law!

P
P
RT P T G P T G
x
y
RT
i
i
ig
i i
l
i
i
i
o
o o
+ = ln ) , ( ) , ( ln
0 ) , ( ) , ( =
o o
i
ig
i i
l
i
P T G P T G
o
i i i
P x P y
4/4/2014 77
Equilibrium Ratio
Vapor-Liquid Equilibrium ratio is defined as

There are several correlations and models for K
i

From Raults law (ideal model )
i
i
i
x
y
K

i
i
i
i
K
P
P
x
y
= =
o
RECALL LIMITATIONS OF
IDEAL MODEL
4/4/2014 78
Equilibrium Ratio
READ papers placed in module 3
folder for other composition-
independent k-value models (we will
have exercises using them)
Compositional dependence in
considered when using EOS but
K-values become implicit
4/4/2014 79
Bubble Point Evaluation
Under Raoults law, the bubble point
has a linear dependence with the vapor
pressures of the pure components.

Once the bubble point pressure is
found, the equilibrium vapor
compositions are found from Raoults
law.

4/4/2014 80
Deviations from Raoult's law
The dew point curve (lower
black curve) in is always
curved regardless whether
the mixture is ideal or not.
The red curves in indicate
deviations from Raoult's law.
When the bubble point curve
is above the straight line, we
will have positive deviations
from Raoult's Law. When the
bubble point curve is below
the straight line, we will have
negative deviations from
Raoult's Law. This happens
for non-ideal mixtures and
may lead to azeotropy.
P
2
o
P
1
o
T
x
1
,y
1
4/4/2014 81
Dew Point Calculation
At the dew point the overall fluid
composition coincides with the
gas composition. That is.

i i
y z
4/4/2014 82
Statement of Equilibrium
o
=
i i i
P x P y
P
T
1
2
3
o
1
P
IG/IS Raoults law
4/4/2014 83
Bubble Point Evaluation
The bubble point pressure at a
given T is

o
i i
bp
i
P z P y
o
i i bp
P z P
4/4/2014 84
Dew Point Calculation
Find DP pressure and equilibrium
liquid compositions

o
o
=
=
i i i
i i i
P x P z
P x P y
=
o
P
x
P
z
i
i
i
1
1
=
o
(
(
=
c
N
i
i
i
dp
P
z
P
4/4/2014 85
Types of Phase Equilibria
Calculations
Given Variables
(independent)
Unknown Variables
(dependent)
Problem
Type
Example
Application
P, zi = xi T, yi Bubble Point
T, zi = xi P,yi Bubble Point
Gas injection,
production
P, zi = yi T,xi Dew Point
T, zi = yi P,yi Dew Point
Gas
Condensates,
Production
P, T, zi xi, yi, fv Flash
Production
Separation
4/4/2014 86
Bubble Point Temperature
given P
We must follow an iterative
procedure.

i i
x z
Bubble point temperature
enters into the equation non-linearly
4/4/2014 87
Find TB pressure and equilibrium
gas compositions

( )
( ) Tb P z P y
or
Tb P x P y
i i i
i i i
o
o
=
=
4/4/2014 88
The problem is that we do not
know yet at what temperature to
evaluate the pure component
vapor pressures. See the following
diagram

o
) (
bp i i bp
T P z P
4/4/2014 89
For well-behaved systems (no
azeotropes), the searched
temperature will be bounded by
the highest and lowest saturation
temperature of the components in
the mixture at the selected system
pressure.

4/4/2014 90
T
2
o
T
1
o
P
x
1
,y
1
P
4/4/2014 91
Procedure
1. Evaluate and at the given
pressure P, which is a saturation
pressure.

2. Choose your first guess bubble point
temperature as

o
1
T
o
2
T
i i
i
i i
c T
b
a P
+
=
o
o
ln
i
i
i
i
c
P ln a
b
T
=
o
o
=
=
i
n
i
i
o
bp
T z T
c
1
) (
4/4/2014 92
Procedure
3. Define a relative volatility using a
reference substance such that all
relative volatilities are either > 0 or < 0
(i.e. monotonically increasing or
decreasing).

with the saturation pressures evaluated at the
guess temperature evaluated in (2)
o
o
=
j
i
ij
P
P
4/4/2014 93
Procedure
4. Expand the volatility as

with T from step 2.

2
2
1
1
2 1 2 1 12
ln ln ln
c T
b
c T
b
a a P P
+
+
+
= = o
o o
(
+
+
+
= o
2
2
1
1
2 1 12
exp
c T
b
c T
b
a a
4/4/2014 94
Procedure
5. Write the bubble point equation in terms
of volatilities and a reference vapor
pressure (lowest or highest)
For a binary, you would have only one
volatility

| |
2 12 1 2 2
2
1
1 2 2 2 1 1
z z P z
P
P
z P P z P z P + =
(
+ = + = o
o
o
o
o o o
| |
2 12 1
2
z z
P
P
+
=
o
o
Guessed vapor pressure
4/4/2014 95
Procedure
Thus

this is your first guess saturation
pressure for the reference component
(here 2) at the first guess
temperature evaluated in step 1.
From this saturation pressure use the
Antoine equation to find an updated
bubble point temperature (step 1).
2 12 1
2
z z
P
P
+ o
=
o
4/4/2014 96
Procedure

From the saturation pressure
evaluated in use the Antoine
equation to find a new temperature

2
2 2
2
c
P ln a
b
T
b

=
o
| |
2 12 1
2
z z
P
P
+
=
o
o
4/4/2014 97
Procedure
This new T new new
iterate until two successive
temperatures do not change by a
specified tolerance.
The Excel file provided in our WEB site
illustrates this procedure for a ternary
mixture. You can modify it and extend
it to multicomponents.

12
o
2
P
4/4/2014 98
Dew Point Temperature
Procedure
You can follow a very similar
reasoning as the one developed
for the bubble point and devise the
algorithm required to solve this
problem using relative volatilities
4/4/2014 99
Flash Calculations
In this type of calculations, the work-
horse of reservoir simulation packages,
the objective is to:

find fraction of vapor vaporized and
equilibrium gas and liquid compositions
given the overall mixture composition, P
and T.

4/4/2014 100
Flash Calculations
Start with the equilibrium equation

Material balance

o
i i i
P x P y
v i v i v i l i i
f y f x f y f x z 1
4/4/2014 101
Flash Calculations
Now replace either liquid or gas
compositions using equilibrium
equation

v i v
i
i i
f y f
P
P
y z
o
1
|
|
.
|
\
|
=
i
i
i
x
P
P y
o
Here replaced x
i
4/4/2014 102
Flash Calculations
Rearrange and sum over all
compositions

v v
i
i
i
f f
P
P
z
y
+
=
o
1
( )
(
(
(
(
+
=
o
v v
i
i
i
f f
P
P
z
y
1
4/4/2014 103
Separation process
z
i
(T
1
,P
1
)
x
i
(T
1
,P
2
)
y
i
(T
1
,P
2
)
P
1
> P
2

T
1
,P
2

4/4/2014 104
Flash Calculations
Objective function (flash function)
is

0 1
1
=
(
(
(
(
+
=
v v
i
i
v
f f
P
P
z
f F
o
) (
4/4/2014 105
Flash Calculations
There are several equivalent expressions
for the flash function

(a)

(b)

(c)

(c) is the best well behaved for
numerical solution (Rachford- Rice
function)
0 1=
i
y
0 1=
i
x
0 =
i i
x y
4/4/2014 106
Flash Calculations
Once f
v
is found the equilibrium
gas and liquid compositions are
evaluated from
v v
i
i
i
f f
P
P
z
y
+
=
o
1
|
|
.
|
\
|
=
i
i
i
x
P
P y
o
and
) / ( IG IS
i
i
k
p
p
=
o
4/4/2014 107
( )
1
1 1
1

|
|
.
|
\
|
+
=
c
N
i i v
i
k f
z
( )
1
1 1
1

|
|
.
|
\
|
+
=
c
N
i i v
i i
k f
k z
( )
=
+
c
N
i
i v
i i
k f
k z
1
1 1
) 1 (
VLE Examples
Flash Functions and Rachford Rice
Function
-6.00
-4.00
-2.00
0.00
2.00
4.00
6.00
0.00 0.20 0.40 0.60 0.80 1.00
Molar Fraction of vapor (fv)
F
(
f
v
)
Sum Xi
Sum Yi
Rachford Rice
4/4/2014 108
x
1
, y
1
T
a
T
b
T
c
P
1
v
P
2
v
P
r
e
s
s
u
r
e

x
1
, y
1
P
a
P
b
P
c
T
1
v
T
2
v
T
e
m
p
e
r
a
t
u
r
e

But .Raoults model will NOT work well
in these cases
then what ?
4/4/2014 109

Equations of State
(EOS)

Termodinamica de Hidrocarburos: Generalized Phase Equilibria

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