Construction of Global

Phase Equilibrium Diagrams

Martn Cismondi
Universidad Nacional de Crdoba - CONICET
Introduction
A real binary system show one of 5 (or 6)
different types of phase behaviour.
EOS modelling leads to the same possible
types (+ other) .
Correspondence between real and predicted
type depends on the model and parameters.

Type I: Unique Critical Line (LV)
0
20
40
60
80
100
120
220 270 320 370 420
Temperature [K]
P
r
e
s
s
u
r
e

[
B
a
r
]
Pv2
A
Pv1
Type II: Also a LL critical line and LLV
0
50
100
150
200
250
200 250 300 350 400 450 500 550
Temperature [K]
P
r
e
s
s
u
r
e

[
B
a
r
]
B
A
LLV
Ps2
Ps1
Type IV: Discontinuity in the LV
critical line and second LLV region
0
50
100
150
200
250
300
350
400
200 250 300 350 400 450 500 550
Temperature [K]
P
r
e
s
s
u
r
e

[
B
a
r
]
B
D
E
D
E
UCEP
LCEP
LLV
LLV
LLV
Type IV: T-x projection
220
270
320
370
420
470
520
0.4 0.5 0.6 0.7 0.8 0.9 1
Composition
T
e
m
p
e
r
a
t
u
r
e

[
K
]
B D
E
UCEP
LCEP
UCEP
Type III: rearrangement of critical lines
0
50
100
150
200
250
300
350
400
200 250 300 350 400 450 500 550
Temperature [K]
P
r
e
s
s
u
r
e

[
B
a
r
]
C
D
UCEP
Type III: T-x projection
220
270
320
370
420
470
520
0.4 0.5 0.6 0.7 0.8 0.9 1
Composition
T
e
m
p
e
r
a
t
u
r
e

[
K
]
C
D
UCEP
Type V: Just like type IV but
without LL immiscibility at low T
0
50
100
150
200
250
300
120 170 220 270 320 370 420 470
Temperature [K]
P
r
e
s
s
u
r
e

[
B
a
r
]
30
35
40
45
50
55
60
65
70
180 182 184 186 188 190 192 194 196 198
Temperature [K]
P
r
e
s
s
u
r
e
[ B
a
r
]
D
E
D
E
UCEP
LCEP
LLV
Azeotropic lines and
Azeotropic End Points (AEP)
PAEP (Pure, meeting a vapour pressure line)
CAEP (Critical, meeting a critical line)
HAEP (Heterogeneous, meeting a LLV line)
One example of azeotropic line (P-T)
0
20
40
60
80
100
200 220 240 260 280 300 320 340 360 380
Temperature [K]
P
r
e
s
s
u
r
e

[
B
a
r
]
CAEP
HAEP
The same example in T-x
150
200
250
300
350
400
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Molar Fraction of CO2 DNN
T
e
m
p
e
r
a
t
u
r
e

[
K
]
CAEP
HAEP
System: Ethanol - n-Hexane
120
170
220
270
320
370
420
470
520
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Molar Fraction of Ethanol
T
e
m
p
e
r
a
t
u
r
e

[
K
]
Cases with two azeotropic lines!
P
H
C
H
Objectives
Identification of predicted type
Automated calculation of global phase
equilibrium diagrams
Automated calculation of Pxy, Txy and
isoplethic diagrams from limiting points
What do we need?
Strategy for construction of a GPED
without knowing the type in advance.
General method for CRIT lines calculation.
Location of isolated LL critical lines.
General methods for LLV and AZE lines.
Detection of CEPs and AEPs (critical
and azeotropic end points).
Classifications of Pxy, Txy and isoplethic
diagrams in terms of limiting points.
Methods for calculation of Pxy, Txy and
isoplethic segments.
Algorithm:

Basic
Structure
Critical line from C2 to
Critical line D
from CP1 to UCEP
Critical Line B
until UCEP
type I or II type III
LCEP
type I or V
not
found
High Pressure C1
E C A
Search for a high
pressure critical point
found
type II or IV
type IV or V
Critical line from C2 to
Critical line D
from CP1 to UCEP
Critical Line B
until UCEP
type I or II type III
LCEP
type I or V
not
found
High Pressure C1
E C A
Search for a high
pressure critical point
found
type II or IV
type IV or V

Some remarks about the methods
Formulation in T, v and x, y, w
Solve using Newton J X = -F ; F
n
= X
S
- S
Michelsens procedure for tracing lines
J (dX/dS) = (dF/dS) X
new
= X
old
+ (dX/dS) S
S
new
= min (4 S
old
/ N
iter
, S
max
)
The variable to be specified depends on dX/dS
Calculation of critical points:
Criticality conditions
tpd
2
=0 b = smallest eigenvalue
1
=0

tpd
3
=0 c = = 0
( ) ( )
q
q q
2
1 1
0
1
= =
~ |
.
|

\
|
c
c
=
s s
s
s
V T
j
i
j i ij
n
f
z z B
,

ln
|
|
.
|

\
|
c
c
=
n1 = z1 + s u1; n2 = z2 + s u2
1
2
2
2
1
= + u u
1
z
2
z
How to locate an
isolated LL critical line?


T
c









T
e
m
p
e
r
a
t
u
r
e
Xc Composition
P = 2000 bar
P = 2000 bar
0

200 K T


300 K
Composition Xc
P T
n
,
2
1

ln
1
|
|
.
|

\
|
c
c
=

Must be 0 and min at (T, P)

LLV equilibrium and CEPs
Use of stability analysis in the search
for a Critical End Point (CEP)
0.0 0.2 0.4 0.6 0.8 1.0
-0.04
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
t
p
d


Reduced tangent plane distance (tpd) curves
at four consecutive critical points
at conditions close to an UCEP
Molar fraction of component 1
Calculation of a Critical End Point
Calculation of LLV lines
Examples: type II
100
120
140
160
180
200
220
240
260
280
300
320
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
A
B


Critical lines
LLVE lines
CH
4
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
100 120 140 160 180 200 220 240 260 280 300 320
0
20
40
60
80
100
120
140
160
180
200
A
B
Critical lines
LLVE lines
Vapour pressure
CH
4
+ CO
2
SRK EOS
k
ij
= 0.120
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


100
120
140
160
180
200
220
240
260
280
300
320
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
A
B


Critical lines
LLVE lines
CH
4
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
100 120 140 160 180 200 220 240 260 280 300 320
0
20
40
60
80
100
120
140
160
180
200
A
B
Critical lines
LLVE lines
Vapour pressure
CH
4
+ CO
2
SRK EOS
k
ij
= 0.120
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


minimum composition
Split of LV critical line in type IV or V
140 150 160 170 180 190 200 210 220
-80
-60
-40
-20
0
20
40
60
80
100
LCEP
UCEP
unstable
critical line
E
D
Critical lines
LLVE lines
Vapour pressure
CH
4
+ C
6
H
14
SRK EOS
k
ij
= 0.00
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


140
160
180
200
220
240
0.90 0.92 0.94 0.96 0.98 1.00
unstable
critical
line
UCEP
LCEP
E


Critical lines
LLVE lines
CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
140 150 160 170 180 190 200 210 220
-80
-60
-40
-20
0
20
40
60
80
100
LCEP
UCEP
unstable
critical line
E
D
Critical lines
LLVE lines
Vapour pressure
CH
4
+ C
6
H
14
SRK EOS
k
ij
= 0.00
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


140
160
180
200
220
240
0.90 0.92 0.94 0.96 0.98 1.00
unstable
critical
line
UCEP
LCEP
E


Critical lines
LLVE lines
CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
Transition

III


IV


II
200 300 400 500 600 700
0
100
200
300
400
500
600
A
B
Critical lines
LLVE lines
Vapour pressure
k
ij
= 0.078
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


240
260
280
300
320
340
360
380
400
420
440
0.85 0.90 0.95 1.00
A
B
k
ij
= 0.078


Critical lines
LLVE lines
CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
200 300 400 500 600 700
0
100
200
300
400
500
600
300 305 310 315 320
70
75
80
85
90
95
100
E
B
k
ij
= 0.084
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


D
E



240
260
280
300
320
340
360
380
400
420
440
0.85 0.90 0.95 1.00
B
E
D
E
B
k
ij
= 0.084


CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
200 300 400 500 600 700
0
100
200
300
400
500
600
300 305 310 315 320
70
75
80
85
90
95
100
C
C
k
ij
= 0.090
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


D
C



240
260
280
300
320
340
360
380
400
420
440
0.85 0.90 0.95 1.00
C
D
C
k
ij
= 0.090


CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
200 300 400 500 600 700
0
100
200
300
400
500
600
A
B
Critical lines
LLVE lines
Vapour pressure
k
ij
= 0.078
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


240
260
280
300
320
340
360
380
400
420
440
0.85 0.90 0.95 1.00
A
B
k
ij
= 0.078


Critical lines
LLVE lines
CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
200 300 400 500 600 700
0
100
200
300
400
500
600
A
B
Critical lines
LLVE lines
Vapour pressure
k
ij
= 0.078
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


240
260
280
300
320
340
360
380
400
420
440
0.85 0.90 0.95 1.00
A
B
k
ij
= 0.078


Critical lines
LLVE lines
CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
200 300 400 500 600 700
0
100
200
300
400
500
600
300 305 310 315 320
70
75
80
85
90
95
100
E
B
k
ij
= 0.084
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


D
E



240
260
280
300
320
340
360
380
400
420
440
0.85 0.90 0.95 1.00
B
E
D
E
B
k
ij
= 0.084


CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
200 300 400 500 600 700
0
100
200
300
400
500
600
300 305 310 315 320
70
75
80
85
90
95
100
E
B
k
ij
= 0.084
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


D
E



240
260
280
300
320
340
360
380
400
420
440
0.85 0.90 0.95 1.00
B
E
D
E
B
k
ij
= 0.084


CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
200 300 400 500 600 700
0
100
200
300
400
500
600
300 305 310 315 320
70
75
80
85
90
95
100
C
C
k
ij
= 0.090
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


D
C



240
260
280
300
320
340
360
380
400
420
440
0.85 0.90 0.95 1.00
C
D
C
k
ij
= 0.090


CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
200 300 400 500 600 700
0
100
200
300
400
500
600
300 305 310 315 320
70
75
80
85
90
95
100
C
C
k
ij
= 0.090
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


D
C



240
260
280
300
320
340
360
380
400
420
440
0.85 0.90 0.95 1.00
C
D
C
k
ij
= 0.090


CO
2
Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
Our Classification for Adding Azeotropy
Line
(a)
Azeotropy
(b)
Usual Types
0 to P P, N or D I, II, V
0 to C N V
P to P P, N or D I, II, V
P to C P, N or D I
H to P P II, IV
H to C P II, IV
C to C P or D I, II
P to H
H to P
P II
P to H
H to C
P II

Detection of AEPs
PAEP: compute
along each vapour pressure line
CAEP: Pseudocritical point
compute 1
st
derivative along the LV critical line
HAEP: crossing between L and V composition
compute y
1
x
1
along LLV line
) 0 (

ln ) 0 (

ln = =
i
V
i i
L
i
z z
0
,
,
2
2
=
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
T z
T z
v
P
v
P
Calculation of azeotropic lines:
variables and equations
Illustration: Negative Azeotropy
0
10
20
30
40
50
60
70
80
140 160 180 200 220 240 260 280 300 320
Temperature [K]
P
r
e
s
s
u
r
e

[
B
a
r
]
Double Azeotropy:
Minimum T in the azeotropic line
70
120
170
220
270
320
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Molar Fraction of CO2
T
e
m
p
e
r
a
t
u
r
e

[
K
]
0
5
10
15
20
25
30
190 200 210 220 230 240 250 260 270
Temperature [K]
P
r
e
s
s
u
r
e

[
B
a
r
]
PAEP
PAEP
Tmin
Bancroft point
(Pv
1
= Pv
2
)
Automated construction of complete
Pxy and Txy diagrams
Reading and storing the lines and points of the Global
Phase Equilibrium Diagram. Identification of type.
Detection of local temperature and pressure minima
or maxima in critical lines.
Determination of the pressures (or temperatures) at
which the different lines intersect at the specified
temperature (or pressure).
Deduction, from the points obtained, of how many
and which zones there will be.
Calculation of each zone or two-phase region.
T specified (NVP=2, NC=2, NLLV=1)


Composition
P
r
e
s
s
u
r
e

Translating from limiting points to diagrams
variables and equations
0
20
40
60
80
100
120
140
160
0.0 0.2 0.4 0.6 0.8 1.0
300 K


Ethane molar fraction
P
r
e
s
s
u
r
e

(
b
a
r
)
150
200
250
300
350
400
450
500
0.0 0.2 0.4 0.6 0.8 1.0
50 bar


Ethane molar fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
0
20
40
60
80
100
120
140
160
0.0 0.2 0.4 0.6 0.8 1.0
330 K


Ethane molar fraction
P
r
e
s
s
u
r
e

(
b
a
r
)
150
200
250
300
350
400
450
500
0.0 0.2 0.4 0.6 0.8 1.0
120 bar


Ethane molar fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
0
20
40
60
80
100
120
140
160
0.0 0.2 0.4 0.6 0.8 1.0
300 K


Ethane molar fraction
P
r
e
s
s
u
r
e

(
b
a
r
)
150
200
250
300
350
400
450
500
0.0 0.2 0.4 0.6 0.8 1.0
50 bar


Ethane molar fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
0
20
40
60
80
100
120
140
160
0.0 0.2 0.4 0.6 0.8 1.0
330 K


Ethane molar fraction
P
r
e
s
s
u
r
e

(
b
a
r
)
150
200
250
300
350
400
450
500
0.0 0.2 0.4 0.6 0.8 1.0
120 bar


Ethane molar fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
Examples: Closed loops in Pxy diagrams
200 300 400 500 600 700 800
0
100
200
300
400
500
600
700
800
900
770 775 780 785 790
0
50
100
150
CO
2
+ n-Docosane
RK-PR EOS (k
ij
=0.10)


P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


0
20
40
60
80
100
120
140
160
0.0 0.2 0.4 0.6 0.8 1.0
10
20
30
0.0 0.1 0.2 0.3
CO
2
+ n-Docosane
RK-PR EOS (k
ij
=0.10)


CO
2
Molar Fraction
P
r
e
s
s
u
r
e

(
b
a
r
)
774 K
776 K
778 K
780 K


200 300 400 500 600 700 800
0
100
200
300
400
500
600
700
800
900
770 775 780 785 790
0
50
100
150
CO
2
+ n-Docosane
RK-PR EOS (k
ij
=0.10)


P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


0
20
40
60
80
100
120
140
160
0.0 0.2 0.4 0.6 0.8 1.0
10
20
30
0.0 0.1 0.2 0.3
CO
2
+ n-Docosane
RK-PR EOS (k
ij
=0.10)


CO
2
Molar Fraction
P
r
e
s
s
u
r
e

(
b
a
r
)
774 K
776 K
778 K
780 K


Detection of composition local minima or
maxima in critical lines, as well as in vapour
or liquid branches of LLV lines.
Location of intersection points at specified
composition.
Deduction of the number and nature of the
segments the isopleth will be constituted of.
Calculation of each segment of the isopleth.
Generation of Complete Isopleths
Location of intersection points

100
200
300
400
500
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ethane + Methanol
RK-PR EOS k
ij
= 0.02
l
ij
= 0.20


Critical lines
LLVE lines
Ethane Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
z
=
0
.
4
5
z
=
0
.
7
1
z
=
0
.
9
4
z
=
0
.
9
7
C
L
C
L
2
L
1
L
V
100
200
300
400
500
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ethane + Methanol
RK-PR EOS k
ij
= 0.02
l
ij
= 0.20


Critical lines
LLVE lines
Ethane Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
z
=
0
.
4
5
z
=
0
.
7
1
z
=
0
.
9
4
z
=
0
.
9
7
C
L
C
L
2
L
1
L
V
Number and nature of segments
N
V

N
L

N
C
R
I

Phase
Behav.
Type
Segments of the isopleth homogeneity
boundary
Portions of
LLV line
to print
Isopleth
Case
0 0 1 III ( C | LTDP)
y
( C | HPLP)
x
All 3
0 1 1 II/III/IV ( C | LTDP)
y
( L | C)
x
( L | HPLP)
x/y
T
min
to L 7
0 2 0 III/IV ( L
1
| LTDP)
y
( L
2
| L
1
)
x
( L
2
| HPLP)
y

T
min
to L
2

L
1
to K
11
1 1 1 II/III (V | LTDP)
y
(C | V)
y
(L | C)
x
(L | HPLP)
y
T
min
to V 17

Calculation of each segment
Numerical continuation method
Sensitivities are used to
Choose which variable to specify for next point
Estimate values for all variables

(
(
(
(
(
(
(

=
P
T
v
v
y
x
X
y
x
ln
ln
ln
ln
ln
ln
2
1

0
) (
ln ) (
) , , (

ln ) , , (

ln
) , , (

ln ) , , (

ln
ln ) , , ( ln
ln ) , , ( ln
2 2
1 1
=
(
(
(
(
(
(
(
(

=
S X g
z X g
v T y f v T x f
v T y f v T x f
P v T y P
P v T x P
F
spec
i phase
y
y
x
x
y
y
x
x
y y
x x
Global Diagram: P-T projection
200 250 300 350 400 450 500
0
20
40
60
80
100
120
140
160
180
200
Ethane + Methanol
D
C
Critical lines
LLVE lines
Vapour pressure
RK-PR EOS k
ij
= 0.02
l
ij
= 0.20
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)


100
200
300
400
500
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ethane + Methanol
RK-PR EOS k
ij
= 0.02
l
ij
= 0.20


Critical lines
LLVE lines
Ethane Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
z
=
0
.
4
5
z
=
0
.
7
1
z
=
0
.
9
4
z
=
0
.
9
7
C
L
C
L
2
L
1
L
V
100
200
300
400
500
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ethane + Methanol
RK-PR EOS k
ij
= 0.02
l
ij
= 0.20


Critical lines
LLVE lines
Ethane Molar Fraction
T
e
m
p
e
r
a
t
u
r
e

(
K
)
z
=
0
.
4
5
z
=
0
.
7
1
z
=
0
.
9
4
z
=
0
.
9
7
C
L
C
L
2
L
1
L
V

Global Diagram: T-x projection

200 250 300 350 400 450
0
50
100
150
200
250
Critical
point
Isopleth for z = 0.45
(case 7 in Table 1)
LLVE
LLE
LVE
Vapour
phase
Liquid phase


P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)
(
L

|

H
P
L
P
)
x
/
y
(
L

|

C
)
x
(
C

|

L
T
D
P
)
y
200 250 300 350 400 450
0
50
100
150
200
250
Critical
point
Isopleth for z = 0.45
(case 7 in Table 1)
LLVE
LLE
LVE
Vapour
phase
Liquid phase


P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)
(
L

|

H
P
L
P
)
x
/
y
(
L

|

C
)
x
(
C

|

L
T
D
P
)
y

Ethane-Methanol. RK-PR EOS.

200 250 300 350 400 450
0
50
100
150
200
250
300
Critical point
LLVE
LLE
LVE
Vapour
phase
Dense phase


P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)
Isopleth for z = 0.71
(case 3 in Table 1)
( C | LTDP)
y
( C | HPLP)
x
200 250 300 350 400 450
0
50
100
150
200
250
300
Critical point
LLVE
LLE
LVE
Vapour
phase
Dense phase


P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)
Isopleth for z = 0.71
(case 3 in Table 1)
( C | LTDP)
y
( C | HPLP)
x

Ethane-Methanol. RK-PR EOS.
200 250 300 350
0
50
100
150
200
320 321 322 323 324 325 326
56
57
58
59
60
61
62
LLE
LVE
Vapour
phase
Liquid phase


P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)
Isopleth for z = 0.94
(case 11 in Table 1)
LVE
LLVE
LLVE
LLE
LVE
Vapour
phase
Liquid phase



Ethane-Methanol. RK-PR EOS.
200 250 300
0
50
100
150
314 315 316 317 318 319 320 321 322 323
52
53
54
55
56
57
58
LLE


P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)
Isopleth for z = 0.97
(case 17 in Table 1)
Critical point
L
II
VE
L
I
VE
LLVE
LLE
LVE
Vapour
phase
Liquid phase



Ethane-Methanol. RK-PR EOS.
Modular Approach
One general subroutine for calculation of
P, and derivatives wrt T, V and n
(given T, V and n)

Model specific subroutines for calculation
of A
r
and derivatives wrt T, V and n
i
f

ln
Conclusions
We have provided strategies for constructing
GPEDs from scratch.
Types I to V, with or without azeotropy.
Pxy, Txy and Isopleths can be derived.
Strength: based on the GPED
Weakness: everything is based on the GPED
www.gpec.plapiqui.edu.ar
www.gpec.efn.uncor.edu
References
Global phase equilibrium calculations
Cismondi, M., Michelsen, M. Global Phase Equilibrium Calculations: Critical Lines,
Critical End Points and Liquid-Liquid-Vapour Equilibrium in Binary Mixtures. The
Journal of Supercritical Fluids, Vol. 39, 287-295. 2007.
Cismondi, M., Michelsen, M. Automated Calculation of Complete Pxy and Txy
Diagrams for Binary Systems. Fluid Phase Equilibria, Vol. 259, 228-234. 2007.
Cismondi, M., Michelsen, M. L., Zabaloy, M.S. Automated generation of phase
diagrams for binary systems with azeotropic behavior. Industrial and Engineering
Chemistry Research, Vol. 47 Issue 23, 97289743. 2008.
GPEC (the program)
Cismondi, M., Nuez, D. N., Zabaloy, M. S., Brignole, E. A., Michelsen, M. L.,
Mollerup, J. M. GPEC: A Program for Global Phase Equilibrium Calculations in
Binary Systems (Oral Presentation). EQUIFASE 2006. Morelia, Michoacn, Mxico.
October 21-25, 2006.
Models and their pure compound parameters
Cismondi, M., Mollerup, J. Development and Application of a Three-Parameter RK-PR
Equation of State. Fluid Phase Equilibria, Vol. 232, 74-89. 2005.
Cismondi, M., Brignole, E. A., Mollerup, J. Rescaling of Three-Parameter Equations
of State: PC-SAFT and SPHCT. Fluid Phase Equilibria, Vol. 234, 108-121. 2005.