VAPOR/LIQUID EQUILIBRIUM

Review
What is bubble point?
What is dew point?
We have previously go through the 2 simplest
models for solving VLE problems
Raoults Law
Henrys Law

Lecture Overview
1. VLE by modified Raoults Law
2. VLE from K-value correlations
Flash calculation
3. Summary
VLE
Raoults Law Henrys Law
Modified
Raoults Law
K-Values
The 2
nd
assumption of Raoults Law is abandoned,
taking into account the deviation from solution
ideality in L phase.
Thus, activity coefficient is introduced in
Raoults Law
Modified Raoults Law

( ) N i P x P y
sat
i i i i
,..., 2 , 1 = =
Activity coefficients are function of T & liquid
phase composition, x
1 =

i
i
y

=
i
sat
i i i
P x P

=
i
sat
i i i
P y
P

1
For bubble point
For dew point
Since;
Example 10.3
For the system methanol(1)/methyl acetate(2),
the following equations provide a reasonable
correlation for the activity coefficients:
2
2 1
ln Ax =
2
1 2
ln Ax =
Where A=2.771-0.00523T.
In addition, the following Antoine equations
provide vapor pressures;
424 . 53
54 . 665 , 2
2043 . 14 ln
424 . 33
31 . 643 , 3
59158 . 16 ln
0
2
0
1
+
=
+
=
C t
kPa P
C t
kPa P
sat
sat
Find;
a) P and {yi}, for x1=0.25 and T=318.15K
b) P and {xi}, for y1=0.60 and T=318.15K
c) T and {yi}, for x1=0.85 and P=101.33kPa
d) T and {xi}, for y1=0.40 and P=101.33kPa
e) The azeotropic pressure, and the azeotropic
composition, for T=318.15K
a) P and {y
i
}, for x
1
=0.25 and T=318.15K
This is a BUBL P calculation.
For T=318.15K, the Antoine equations yield:
kPa P kPa P
sat sat
54 . 65 51 . 44
2 1
= =
Activity coefficients are calculated from the given
equations;
2
2 1
ln Ax =
2
2 1
ln Ax =
( )( ) | | 864 . 1 75 . 0 107 . 1 exp ) exp(
2
2
2 1
= = = Ax
( )( ) | | 072 . 1 25 . 0 107 . 1 exp ) exp(
2
2
1 2
= = = Ax
) 64 . 65 )( 072 . 1 )( 75 . 0 ( ) 51 . 44 )( 864 . 1 )( 25 . 0 ( + = P
kPa P 50 . 73 =
282 . 0
1 1 1
1
= =
P
P x
y
sat

718 . 0
2 2 2
2
= =
P
P x
y
sat

b) P and {x
i
}, for y
1
=0. 60 and T=318.15K
This is a DEW P calculation.
For T=318.15K, values of P
sat
from Antoine
equations and A are unchanged. However, liquid
composition is unknown, but is needed for
calculation of activity coefficient .
Therefore, an iterative scheme is indicated:
1)First, assume
1
=
2
=1.0 (Ideal solution)
2)Calculate P
DEW
from:


3)Calculate x
1
by x
1
=y
1
P/
1
P
1
sat
and then x
2
from
x
2
=1-x
1
4)Evaluate
1
and
2
.
5)Using these values, go back to step (2) and
repeat the procedure.
6)Iteration to convergence yield:

=
i
sat
i i i
P y
P

1
P = 62.89 kPa x
1
= 0.8169

1
= 1.0378
2
= 2.0935
(c) BUBL T calculation.

1)First, assume system temperature, T using Antoine Eqn
and averaging of T
sat
using mole fraction:
T = x
i
T
i
sat
2)Calculate
1
,
2
and o P
1
sat
/P
2
sat
3)Find a new value for P
1
sat
from:


4)Find new value of T from:
5)Use this T and compute from Step (2) until
Step (4).
6)Compare the T
new
obtained in Step (4) with T
old
.
If not same, repeat procedures till you get T
new

= T
old
.
o /
2 2 1 1
1
x x
P
P
sat
+
=
1
1 1
1
ln
C
P A
B
T
sat

=
BUBL P
BUBL P CALCULATION


Find
sat
i
P
Find
i

Find P from equation 10.6
sat sat
P x P x P
2 2 2 1 1 1
+ =
Find
i
y from equation 10.5
P P x y
sat
i i i i
=
DEW P
DEW P CALCULATION


Find
sat
i
P
Find
1
&
2
. Initial guess is=1
Find P using equation 10.7
sat sat
P y P y
P
2 2 2 1 1 1
1
+
=
Find xi using equation 10.5
sat
i i i i
P P y x =
Evaluate from the given
equation

Converge?
NO
YES
It is the P dew.
Find liquid phase mole fraction
sat
P
P y
x
1 1
1
1

= &
1 2
1 x x =
BUBL T
BUBL T CALCULATION

Find initial T from mole-fraction weighted average
sat sat
T x T x T
2 2 1 1
+ =

Find
sat
i
T
For current T, find A,
1
,
2
,
sat sat
P P
2 1
= o
Find new value for
sat
P
1
from equation 10.6;
( ) o
2 2 1 1
1
x x
P
P
sat
+
=

Find new T from Antoine equation for species 1
1
1 1
1
ln
C
P A
B
T
sat

=


Converge?
NO
YES
It is the T bubble.
Find
sat
i
P , A and
1
&
2

Find vapor phase mole fraction
P P x y
sat
1 1 1 1
= &
1 2
1 y y =
DEW T
DEW T CALCULATION

Find initial T from mole-fraction weighted average
sat sat
T y T y T
2 2 1 1
+ =

Find
sat
i
T
For current T, find A,
sat sat
P P
2 1
,
sat sat
P P
2 1
= o
Find new value for
sat
P
1
from equation 10.7;
|
|
.
|

\
|
+ = o

2
2
1
1
1
y y
P P
sat


Find new T from Antoine equation for species 1
1
1 1
1
ln
C
P A
B
T
sat

=


Converge?
NO
YES
It is the T bubble.
Find
sat
i
P , A and
1
&
2

Find vapor phase mole fraction
P P x y
sat
1 1 1 1
= &
1 2
1 y y =
Find
sat
P P y x
1 1 1 1
= &
1 2
1 x x =
Calculate
2 1
& from given correlation
AZEOTROPE
When x1=y1, the dew
point and bubble point
curves are tangent to
the same horizontal line
A boiling L of this
composition produce a
vapor exactly the same
composition; L does not
change in composition
as it evaporates
) 8 . 10 (
2 2
1 1
12
x y
x y
o
Relative volatility;
( )
sat
sat
x
P
A P
2
1
0
12
exp
1
=
=
o
( )
A P
P
sat
sat
x
exp
2
1
1
12
1
=
=
o
If one limit is >1 &
the other limit is
<1; azeotrope
exists.
VLE from K-Value
i
i
i
x
y
K =
P
P
K
sat
i i
i

=
P
P
K
sat
i
i
=
K
i
: equilibrium ratio i.e. measure of lightness
(tendency to favor vapor phase)
Raoults Law Modified
Raoults Law
Maybe determined from
calculation or DePriester
chart
1
1
=
=
=

i i
i
i i i
x K
y
x K y
Bubble point
Must find the
sets of Ks that
satisfy this
equation
1
1
=
=
=

i i
i
i i i
K y
y
K y x
Dew point
Must find the
sets of Ks that
satisfy this
equation
K-value
from
DePriester
chart
-Low T
range
K-value
from
DePriester
chart
-High T
range
When given a mixture of composition at certain
T or P;
Bubble point
- Insignificant L

-The given mole
fraction is yi

- Need to satisfy
equation 10.14

- Composition of
dew is xi=yi/Ki
Dew point
-System is almost
condensed
-The given mole
fraction is xi

- Need to satisfy
equation 10.13

- Composition of
buble is yi=Kixi
FLASH CALCULATION
V


L
Feed, F
Vapor, V
Liquid, L
Liquid at P > P
bubble

partially evaporates
when P is reduced,
producing 2-phase
system of V & L in
equilibrium
Find; T, P, z
FLASH CALCULATION


Find BUBL P with
i i
x z = ;
bubble
P
Find DEW P with
i i
y z = ;
dew
P

Using equation 10.11, find
i
K
Is the given P
between
dew bubble
P P & ?
NO
No need for flash
calculation
YES
Substitute
i
K in equation 10.17. By trial & error,
solve for V. Then L=1-V
Solve equation 10.16 for each component -
i
y
Solve equation 10.10 for each component -
i
x
Flowchart for
flash
pressure
V


L
Feed, F =1 mol
Acetonitrile 0,2
Nitrometane 0,35
Aceton 0,45
Vapor, V
Liquid, L
T = 80 C
P = 110 kPa
Tentukan fraksi mol difase
Cair dan uap!
TUGAS:
Suatu campuran pengolahan minyak bumi
terdiri dari nC3 10%, nC4 20%, nC5 20%, nC6
30%, sisanya nC7. temperatur campuran 93 F.
tentukan kondisi bubble pointnya!
Suatu campuran terdiri dari Aceton 50%,
Acetonitrile 20%, sisanya Benzene. temperatur
campuran 75 C. tentukan kondisi bubble
pointnya!

Suatu campuran pengolahan minyak bumi
terdiri dari i-C3 20%, nC3 20%, i-C4 20%, n-C4
15%, sisanya I-C5 20%. Tekanan 120 Psia.
tentukan kondisi dew pointnya!

V


L
Feed, F = 100kg/mol
benzen 0,5
Toluen 0,3
Acetonitril 0,2
Vapor, V
Liquid, L
T = 87 C
P = 1 atm
Tentukan fraksi mol difase
Cair dan uap!