Use the van Laar activity coefficient expression to predict the compositions of co-existing
liquid phases (I and II) comprised of two partially miscible liquids (1) and (2) at 50
Example 9.1
o
12 21
1 2 12 21
2 2
12 1 21 2
21 2 12 1
ln ;ln ; 2.5; 3.5
[1 ] [1 ]
A A
A A
A x A x
A x A x
= = = =
+ +
C and 4
bar. At these conditions the van Laar equations are given by:
Solution:
This system is a binary; however, there are 2 phases since 1 and 2 are partially miscible.
One of the phases (I) is rich in component 1 (with some 2 dissolved in it); while the
second phase (II) is rich in component 2 (with some 1 dissolved in it). Estimates of the
composition of both phases are required. We use two equations of type 9.34 as there are 2
components.
For component 1:
1 1 1 1 1 1
2 2
1 1
1 1
exp( ) exp( )
[1 ] [1 ]
(1 ) (1 )
I I I II II II
I II
I II
x x x x
x x
x x
= = =
+ +
..(a)
For component 2:
2 2 2 2 2 2
2 2
2 2
2 2
exp( ) exp( )
[1 ] [1 ]
(1 ) (1 )
I I I II II II
I II
I II
x x x x
x x
x x
= = =
+ +
..(b)
Lastly
1 2
1
I I
x x + = ..(c)
And:
1 2
1
II II
x x + = ..(d)
Equations I IV need to be solved simultaneously using a suitable algorithm to obtain the
final solution:
1 1
0.12, 0.85
I II
x x = = ; and
2 2
0.88, 0.15
I II
x x = =
Example 9.2
Estimate solubility of a solid A in a liquid B at 300
o
( ) ( )
1/2 1/2
3 3
100 / ; 125 / ; 9.5 cal / cc ; 7.5 cal / cc .
L L
A B A B
V cm mol V cm mol = = = =
K, using (i) ideal solution
assumption, (ii) regular solution model for liquid-phase. The following data are
available:
Heat of fusion for A: 17.5 kJ/mol. Melting point for A = 350
o
K.
Assuming that solid-phase is pure naphthalene (which is in equilibrium with
solution of naphthalene in hexane), z
1
= 1,
1
S
,
,
1 1
ln ln
m
fus
T A
A A
m A
H
x
R T T
(
| |
= ( |
|
(
\ .
= 1, we start with the simplified
equation:
For ideal solution the above equation reduces to:
,
,
1 1
ln
m A
fus
T
A
m A
H
x
R T T
( | |
= ( |
|
(
\ .
Using the data provided:
17500 1 1
ln
8.314 300 350
A
x
(
| |
=
| (
\ .
Thus, the ideal solubility x
A
By Regular solution theory:
= 0.38.
2 2
ln ( )
L
A A A A B
RT V =
( )
2
2
ln 1
A
L
fus
A B A B
A
m
V
H T
x
RT RT T
(
=
(
(
..(1)
Also
L
B b
B L L
A A B B
x V
x V x V
=
+
..(2)
T = 300 K,
1
m
T = 350
o
( ) ( )
1/2 1/2
3 3
100 / ; 125 / ; 9.5 cal / cc ; 7.5 cal / cc .
L L
A B A B
V cm mol V cm mol = = = =
K
Solution
algorithm:
(1) Assume x
A
(to start with assume x
A
(2) Calculate
= 0)
B
(3) Use equation (1) to calculate new x
from eqn 2
(4) If x
A
A
,
i+1
x
A,i
< 0.01, x
A,i+1
is the solution or else, return to step 1.
The final converged value for 0.08
A
x
Note that the result differs significantly from that obtained by assuming ideal
solution behaviour for the liquid phase.
Example 9.3
Compute the eutectic composition and temperature for a mixture of two substances A and B
using the following data:
Property A B
Normal T
m
(
o
180 K) 181
fus
H (J /mol)
6600 9075
We use the ideal solution behaviour for the liquid phase. The following equation then holds at
the eutectic point:
, ,
, ,
exp exp 1
fus fus
m A m B
A B
m A m B
T T T T
H H
RT T RT T
( (
| | | |
+ =
( (
| |
( ( \ . \ .
On substituting all relevant data:
6600 180 9075 180
exp exp 1
8.314 180 8.314 181
T T
x T x T
( (
| | | |
+ =
| | ( (
\ . \ .
On solving by trial and error, ( )
0
150 T eutectic K
The eutectic composition is found from the following equation:
exp
A
A
fus
m
A
A
m
T T
H
x
RT T
(
| |
=
(
|
( \ .
Substituting all the available data with T =150
0
0.5.
A
x
K, the eutectic composition is found to be:
Example 9.4
A certain solid A has a vapour pressure of 0.01 bar at 300
0
We start with the following equation:
K. Compute its solubility at the
same temperature in a gas B at a pressure of 1.0bar. The molar volume of the solid is
125cc/mol.
( )
exp
S sat
A A
sat sat
A A A A
V P P
P y P
RT
(
( =
(
Since
2
10 , 1.0
sat sat
A A
P bar
=
Further as the total system pressure is 1.0bar, it follows that
1.0
A
Thus the solubility of the solid at the system pressure is given by:
( )
( / )exp
S sat
A A
sat
A A
V P P
y P P
RT
(
( =
(
Substituting all relevant data the solubility is:
2
1.05 10 .
A
y x
=
