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Mohammad Ali Fanaei, Ferdowsi University of Mashhad
EOS Method
1 VaporLiquid Equilibrium
At Equilibrium:
Where
Therefore
l
i
v
i
f f =
t i
l
i
l
i t i
v
i
v
i
P x f P y f o o = = ,
v
i
l
i
i
i
vl
i
x
y
k
o
o
= =
EOS Method
2 LiquidLiquid Equilibrium
At Equilibrium:
Where
Therefore
2 1
l
i
l
i
f f =
t
l
i
l
i
l
i t
l
i
l
i
l
i
P x f P x f
2 2 2 1 1 1
, o o = =
1
2
2
1
2 1
l
i
l
i
l
i
l
i
l l
i
x
x
k
o
o
= =
EOS Method
3 VaporLiquidLiquid Equilibrium
At Equilibrium:
Where
Therefore
v
i
l
i
l
i
f f f = =
2 1
t i
v
i
v
i
t
l
i
l
i
l
i t
l
i
l
i
l
i
P y f
P x f P x f
o
o o
=
= =
2 2 2 1 1 1
,
v
i
l
i
l
i
i
vl
i
v
i
l
i
l
i
i
vl
i
x
y
k
x
y
k
o
o
o
o
2
2
2
1
1
1
, = = = =
EOS Method
4 Fugacity Coefficient Formula
o o
o
o
m
V
n V T
i
i
Z dV
V
RT
n
P
RT
j
ln
1
ln
, ,
÷
÷


.

\

c
c
÷ =
í
·
Cubic Equations of State in the Aspen Physical Property System
RedlichKwong(Soave) based PengRobinson based
RedlichKwong (RK) Standard PengRobinson(PENGROB)
Standard RedlichKwongSoave(RKSOAVE ) PengRobinson(PRBM)
RedlichKwongSoave (RKSBM) PengRobinsonMHV2
RedlichKwongASPEN(RKASPEN) PengRobinsonWS
SchwartzentruberRenon
RedlichKwongSoaveMHV2
Predictive SRK (PSRK)
RedlichKwongSoaveWS
EOS Method
5 Standard RKSOAVE
) ( b V V
a
b V
RT
P
m m m
+
÷
÷
=
Where
¯ ¯¯
= ÷ =
i
i i
i j
ij j i j i
b x b k a a x x a , ) 1 ( ) (
5 . 0
ci
ci
i
ci
ci
i i
P
RT
b
P
T R
a 08664 . 0 , 42747 . 0
2 2
= =o
2 2 5 . 0
176 . 0 57 . 1 48 . 0 , )] 1 ( 1 [ ) (
i i i ri i i
m T m T e e o ÷ + = ÷ + =
EOS Method
6 Standard PENGROB
) ( ) ( b V b b V V
a
b V
RT
P
m m m m
÷ + +
÷
÷
=
Where
¯ ¯¯
= ÷ =
i
i i
i j
ij j i j i
b x b k a a x x a , ) 1 ( ) (
5 . 0
ci
ci
i
ci
ci
i i
P
RT
b
P
T R
a 07780 . 0 , 45724 . 0
2 2
= =o
2 2 5 . 0
26992 . 0 54226 . 1 37464 . 0 , )] 1 ( 1 [ ) (
i i i ri i i
m T m T e e o ÷ + = ÷ + =
EOS Method
7 Advantages and Disadvantages
Equations of state can be used over wide ranges of
temperature and pressure, including subcritical and
supercritical regions.
Thermodynamic properties for both the vapor and liquid
phases can be computed with a minimum amount of
component data.
For the best representation of nonideal systems, you must
obtain binary interaction parameters from regression of
experimental VLE data. Binary parameters for many
component pairs are available in the Aspen databanks.
EOS Method
7 Advantages and Disadvantages…
Equations of state are suitable for modeling
hydrocarbon systems with light gases such as CO
2
, N
2
and H
2
S .
The assumptions in the simpler equations of state
(SRK, PR, LeeKesler , … ) are not capable of
representing highly nonideal chemical systems, such
as alcoholwater systems. Use the activitycoefficient
options sets for these systems at low pressures. At high
pressures, use the predictive equations of state.
Activity Coefficient Method
1 VaporLiquid Equilibrium
At Equilibrium:
Where
Therefore
F0r ideal gas and liquid
l
i
v
i
f f =
l
i i i
l
i t i
v
i
v
i
f x f P y f
*,
, ¸ o = =
t
v
i
l
i i
i
i
vl
i
P
f
x
y
k
o
¸
*,
= =
Law s Raoult
P
P
x
y
k
t
i
i
i
vl
i
v
i i
' 1 , 1
*
= = ¬ = = o ¸
Activity Coefficient Method
2 LiquidLiquid Equilibrium
At Equilibrium:
Where
Therefore
2 1
l
i
l
i
f f =
l
i
l
i
l
i
l
i
l
i
l
i
l
i
l
i
f x f f x f
*, *,
2 2 2 1 1 1
, ¸ ¸ = =
1
2
2
1
2 1
l
i
l
i
l
i
l
i
l l
i
x
x
k
¸
¸
= =
Activity Coefficient Method
3 VaporLiquidLiquid Equilibrium
At Equilibrium:
Where
Therefore
v
i
l
i
l
i
f f f = =
2 1
t i
v
i
v
i
l
i
l
i
l
i
l
i
l
i
l
i
l
i
l
i
P y f
f x f f x f
o
¸ ¸
=
= =
*, *,
2 2 2 1 1 1
,
t
v
i
l
i
l
i
l
i
i
vl
i
t
v
i
l
i
l
i
l
i
i
vl
i
P
f
x
y
k
P
f
x
y
k
o
¸
o
¸
*, *,
2
2
2
1
1
1
, = = = =
Activity Coefficient Method
4 Liquid Phase Reference Fugacity
For solvents: The reference state for a solvent is defined as
pure component in the liquid state, at the temperature and
pressure of the system.
o
i
*,v
= Fugacity coefficient of pure component i at the system
temperature and vapor pressures, as calculated from the vapor phase
equation of state
u
i
*,l
= Poynting factor
) 1 1 ( , ) , (
*, *, *, *, *,
÷ ÷ =
i i
l
i
l
i
l
i
v
i
l
i
x as P P T f ¸ u o

.

\

=
í
P
P
l
i
l
i l
i
dP V
RT
*,
*, *,
1
exp u
Activity Coefficient Method
4 Liquid Phase Reference Fugacity
For dissolved gases: Light gases (such as O
2
and N
2
) are
usually supercritical at the temperature and pressure of the
solution. In that case pure component vapor pressure is
meaningless and therefore it cannot serve as the reference
fugacity.
0 1
* *,
*, *
÷ ÷ =
=
i i i
l
i
l
i i i
l
i
x as and H f where
f x f
¸
¸
Activity Coefficient Method
5 NRTL (NonRandom TwoLiquid)
The NRTL model calculates liquid activity coefficients for the
following property methods: NRTL, NRTL2, NRTLHOC,
NRTLNTH, and NRTLRK. It is recommended for highly
nonideal chemical systems, and can be used for VLE, LLE and
VLLE applications.
¯
¯
¯
¯ ¯
¯



.

\




.

\

÷ + =
j
k
kj k
m
mj mj m
ij
k
kj k
ij j
k
ki k
j
ji ji j
i
G x
G x
G x
G x
G x
G x
t
t
t
¸ ln
Activity Coefficient Method
5 NRTL (NonRandom TwoLiquid)
Where
The binary parameters a
ij
, b
ij
, c
ij
, d
ij
, e
ij
and f
ij
can be determined
from VLE and/or LLE data regression. The Aspen Physical Property
System has a large number of builtin binary parameters for the
NRTL model.
¯
¯
¯
¯ ¯
¯



.

\




.

\

÷ + =
j
k
kj k
m
mj mj m
ij
k
kj k
ij j
k
ki k
j
ji ji j
i
G x
G x
G x
G x
G x
G x
t
t
t
¸ ln
) 15 . 273 (
0 , ln
1 , ) exp(
÷ + =
= + + + =
= ÷ =
T d c
T f T e T b a
G G
ij ij ij
ii ij ij ij ij ij
ii ij ij ij
o
t t
t o
Activity Coefficient Method
6 Advantages and Disadvantages
The activity coefficient method is the best way to represent
highly nonideal liquid mixtures at low pressures.
You must estimate or obtain binary parameters from
experimental data, such as phase equilibrium data.
Binary parameters are valid only over the temperature and
pressure ranges of the data.
The activity coefficient approach should be used only at low
pressures (below 10 atm).
1. Choosing the most suitable model/thermo method.
2. Comparing the obtained predictions with data from
the literature.
3. Estimate or obtain binary parameters from
experimental data if necessary.
4. Generation of lab data if necessary to check the
thermo model.
Principle Steps in Selecting the Appropriate
Thermodynamics Package
Eric Carlson’s Recommendations
E?
R?
P?
Polar
Real
Electrolyte
Pseudo & Real
Vacuum
Nonelectrolyte
Braun K10 or ideal
ChaoSeader,
GraysonStreed or
Braun K10
PengRobinson,
RedlichKwongSoave,
LeeKeslerPlocker
Electrolyte NRTL
Or Pizer
See Figure 2
Figure 1
Polarity
R?
Real or
pseudocomponents
P?
Pressure
E?
Electrolytes
All
Nonpolar
P?
ij?
ij?
LL?
(See also
Figure 3)
P < 10 bar
P > 10 bar
PSRK
PR or SRK with MHV2
SchwartentruberRenon
PR or SRK with WS
PR or SRK with MHV2
UNIFAC and its
extensions
UNIFAC LLE
Polar
Nonelectrolytes
No
Yes
Yes
LL?
No
No
Yes
Yes
No
WILSON, NRTL,
UNIQUAC and
their variances
NRTL, UNIQUAC
and their variances
LL?
Liquid/Liquid
P?
Pressure
ij?
Interaction Parameters
Available
Figure 2
VAP?
DP?
Yes
No
Wilson, NRTL,
UNIQUAC, or UNIFAC*
with ideal Gas or RK EOS
Wilson
NRTL
UNIQUAC
UNIFAC
Hexamers
Dimers
Wilson, NRTL, UNIQUAC,
UNIFAC with Hayden O’Connell
or Northnagel EOS
Wilson, NRTL, UNIQUAC,
or UNIFAC with special EOS
for Hexamers
VAP? Vapor Phase Association
Degrees of Polymerizatiom DP?
UNIFAC* and its Extensions
Figure 3
Eric Carlson’s Recommendations
for 1Propanol ,H
2
O mixture
E?
Polar
Nonelectrolyte
See Figure 2
Figure 1
Polarity
R?
Real or
pseudocomponents
P?
Pressure
E?
Electrolytes
P?
ij?
LL?
(See also
Figure 3)
P < 10 bar
UNIFAC and its
extensions
Polar
Nonelectrolytes
Yes
LL?
No
No
No
WILSON, NRTL,
UNIQUAC and
their variances
LL?
Liquid/Liquid
P?
Pressure
ij?
Interaction Parameters
Available
Figure 2
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