Universidad Simn Bolvar

Departamento de Termodinmica y Fenmenos de Transferencia

Termodinmica II (TF-2323)
Profesor: Freddy Figueira
1/4


ECUACIONES DE ESTADO CBICAS

MODELO DE VAN DER WAALS (van der Waals, 1873)

Ecuacin:

2
RT a
P
v b v
=

Parmetros:

2 2
27
64
c
c
R T
a
P
=
1
8
c
c
RT
b
P
=
3
8
c
c
c
RT
v
P
=


Forma Polinmica:

3 2
0
RT a ab
v b v v
P P P
| |
+ + =
|
\ .


Criterio de Maxwell:

( )
1 1
ln
g
g f
f g f
v b
P v v RT a
v b v v
| | | |
= +
| |
| |

\ . \ .


Propiedades residuales

( )
0
0
2
,
( , ) ln 1
r
r
a b
h T v h h RT
RT v v b
b
s T v s s R Z
v
| |
= =
|

\ .
( | |
= =
| (
\ .


Reglas de Mezclado

i j i j
i j
a x x a a =

,
i i
i
b x b =

Universidad Simn Bolvar
Departamento de Termodinmica y Fenmenos de Transferencia
Termodinmica II (TF-2323)
Profesor: Freddy Figueira
2/4


MODELO DE REDLICH-KWONG (Redlich y Kwong, 1949)

Ecuacin:

( )
1/ 2
RT a
P
v b T v v b
=
+


Parmetros:

( )
2 2,5
3
1
9 2 1
c
c
R T
a
P
=

3
2 1
3
c
c
RT
b
P

=
1
3
c
c
c
RT
v
P
=


Forma Polinmica:

3 2 2
1
0
RT a ab
v v b RT Pb v
P P T P T
| |
+ =
|
\ .


Criterio de Maxwell:

( )
( )
( )
ln ln
g f g
g f
f f g
v v b v b
a
P v v RT
v b v v b b T
(
+ | |
= (
|
|
+
(
\ .



Propiedades residuales

( )
0
1,5
0
1,5
1, 5
, 1 ln 1
( , ) ln 1 ln 1
2
r
r
a b
h T v h h RT Z
bRT v
b a b
s T v s s R Z
v bRT v
( | |
= = + +
| (
\ .
( ( | | | |
= = +
( | | (
\ . \ .


Regla de Mezclado

( )
1
i j i j ij
i j
a x x a a k =

,
i i
i
b x b =

Donde el parmetro de interaccin binaria viene dado por:
0
0
ij
ij ji
parai j
k
k k parai j
=
=

=

Universidad Simn Bolvar
Departamento de Termodinmica y Fenmenos de Transferencia
Termodinmica II (TF-2323)
Profesor: Freddy Figueira
3/4


MODELO DE SOAVE-REDLICH-KWONG (Soave, 1972)
Ecuacin:
( )
c
a RT
P
v b v v b

=
+

Parmetros:
( )
2 2
3
1
9 2 1
c
c
c
R T
a
P
=

3
2 1
3
c
c
RT
b
P

=
1
3
c
c
c
RT
v
P
=

Funcin de Cohesin Soave
2
1 1
c
T
m
T

( | |
= +
( |
|
(
\ .
, con:
2
0, 48508 1, 55171 0,15613 m = +

Forma Polinmica:
( )
3 2 2
1
0
c
c
a b RT
v v a b RT Pb v
P P P

+ =

Criterio de Maxwell:
( )
( )
( )
ln ln
g f g
c
g f
f f g
v v b v b
a
P v v RT
v b b v v b

(
+ | |
= (
|
|
+
(
\ .


Propiedades residuales:
( )
0
0
'
, 1 ln 1
'
( , ) ln 1 ln 1
r c c
r c
a Ta b
h T v h h RT Z
bRT v
a b b
s T v s s R Z
v bR v

( | |
= = + +
| (
\ .
( ( | | | |
= = +
( | | (
\ . \ .

Donde:
'
c
d
m
dT T T

= =

Regla de mezclado:
( ) ( ) ( )
1
c i j c c ij
i j
i j
a x x a a k =

,
i i
i
b x b =

( )
( )
( )
( )
( )
( )
( )
1
' ' ' 1
2
c
c j
i
c i j c c ij
j i
i j
c c
j i
a
a
a x x a a k
a a

| |
|
= +
|
\ .

Donde el parmetro de interaccin binaria viene dado por:
0
0
ij
ij ji
parai j
k
k k parai j
=
=

=

Universidad Simn Bolvar
Departamento de Termodinmica y Fenmenos de Transferencia
Termodinmica II (TF-2323)
Profesor: Freddy Figueira
4/4


MODELO DE PENG-ROBINSON (Peng y Robinson, 1976)
Ecuacin:
2 2
2
c
a RT
P
v b v b vb

=
+

Parmetros:
2 2
0, 45724
c
c
c
R T
a
P
= 0, 07780
c
c
RT
b
P
= 0, 307
c
c
c
RT
v
P
=
Funcin de Cohesin
2
1 1
c
T
T

( | |
= +
( |
|
(
\ .
, con:
2
0, 37464 1, 54226 0, 26992 = +
Forma Polinmica:
( )
2
3 2 2 3
1
2 3 0
c
c
a b RTb RT
v b v a b RT Pb v b
P P P

| |
| |
+ =
| |
\ .
\ .

Criterio de Maxwell:
( )
( ) ( )
( ) ( )
1 2 1 2
ln ln
2 2
1 2 1 2
g f
g
c
g f
f
g f
v b v b
v b
a
P v v RT
v b b
v b v b

( ( (
+ + +
| |
(
=
|
| (
( (
+ + +
\ .
(


Propiedades residuales
( )
( )
( )
( )
( )
0
0
1 2
'
, 1 ln
2 2
1 2
1 2
'
( , ) ln 1 ln
2 2
1 2
r c c
r c
v b
a Ta
h T v h h RT Z
bRT
v b
v b
a b
s T v s s R Z
v bR
v b

( ( (
+ +

( (
= = +
( (
(
+
( (

( ( (
+ +
( | |
( (
= = +
| (
( (
(
\ . +
( (


Donde:
'
c
d
dT T T

= =
Regla de mezclado:
( ) ( ) ( )
1
c i j c c ij
i j
i j
a x x a a k =

,
i i
i
b x b =

( )
( )
( )
( )
( )
( )
( )
1
' ' ' 1
2
c
c j
i
c i j c c ij
j i
i j
c c
j i
a
a
a x x a a k
a a

| |
|
= +
|
\ .

Donde el parmetro de interaccin binaria viene dado por:
0
0
ij
ij ji
parai j
k
k k parai j
=
=

=