Consider a solution of two species S1/S2 at 25

Example 6.1
o
C such that x
1
1
V =0.4. If =40 x 10
-6
m
3
2
V
/mol,
find . The solution specific gravity is =0.90 and the molecular weights of the species are
32 and 18 respectively.
Molar mass of solution =x
1
M
1
+x
2
M
2
=0.4 x 32 +0.6 x 18
(M =MW)
=23.433 gm/mol =23.6 x 10
-3
Solution molar volume =
kg/mol
Density
mass Molar

=
3
3
23.6 10 /
900 /
x kg mol
kg m

=26.2 x 10
-6
m
3
Now V =x
/mol
1
2 2 1
V x V +


( )
6
2 1 1 2
26.2 - 0.4 40 10
( ) /
0.6
x x
V V xV x

= =

=17.0 x 10
-6
m
3
/mol.
The molar enthalpy of a binary solution is given by:
Example 6.2
V =500 x
1
+1000 x
2
+x
1
x
2
(50 x
1
+40x
2
) cm
3
1 1
, and . V V

/mol. Find the expressions for

Putting x
1
=1- x
2
V =500 +550 x
; it follows:
2
60 x
2
2
+10 x
2
2
2 2
2
550 120 30
dV
x x
dx
= +
3

1 2
2
dV
V V x
dx
=

=500 x
1
+1000 x
2
+x
1
x
2
(500x
1
+40 x
2
) -x
2
[550 120 x
2
+30 x
2
2
Putting x
]
2
=1-x
1

; and simplifying:
3
1 1 1
540 60 x 20 x V = +

1
1 1
0
lim 540 J / mol
x
V V

= =


Alternately one may also use the generic definitions:
2
1
1
, , n T P
nV
V
n

V =500 +550 x
2
60 x
2
2
+10 x
2
Putting x
3

2
=1-x
1
V =1000 460 x
and simplifying:
1
30 x
1
2
10 x
1
V =1000 460
3

3
3
1
2
2
1 1
n
n
10
n
n
30
n
n

Where, n =n
1
+n
2
2
1
1

n
nV
V
n

(moles of mixture)
; note that:
2
1
n
nV
n

=1
2
2 3
1 1 1
1 2 3
1
10
1000 460 30
n
n n n
V n
n n n n
( | |
=
( |

\ .

=
2
2 3
1 1
1 2
1
10
1000 460 30
n
n n
n n
n n n
(

(

=640 60
2 3
1 1
2 3
20
n n
n n
+
=640 60 x
1
2
+20 x
1
3
The same exercises may be carried for obtaining
[same as the earlier expression]
2
. V
What is the change in entropy when 0.6 m
Example 6.3
3
of CO
2
and 0.4 m
3
of N
2
, each at 1 bar and 25
o
For an ideal gas, mole fraction =volume fraction
C
blend to form a gas mixture at the same conditions? Assume ideal gases.
CO
2
(1) / N
2
(2); y
1
=0.6, y
2

=0.4
( ) ln 5.5 /
mix i i
S R y y J molK = =

Estimate the fugacity of ethane at 122.2 K and 5 bar using the truncated virial EOS.
Example 6.4
For ethane T
c
=305.4K, P
c

= 48.84 bar, = 0.099

Now,




Estimate the fugacity of ammonia vapor at 4.0 MPa and 321K assuming that it obeys the RK
equation of state.


Example 6.5
Now,

In the above equation T =321.55K, V is not known.
So solve RK-EOS for V
vapour
V
at the given temperature and pressure, i.e., at P =1.95 MPa, T =
321.55 K (see example 2.3)
vapour
turns out to be 1.1987 * 10
-3
m
3
Thus on substitution in eq. (1) ln =-0.1189 =0.888


/mol

Estimate the fugacity of methane at 32C and 9.28 bar. Use the generalized correlation
approach.
Example 6.6
For methane T
c
=190.7 K, P
c
For given T
= 46.41 bar, = 0.011

r
and P
r
, read off
0
and
1
Then

from figures of fugacity coefficients.
Example 6.7
Estimate the fugacity of cyclopentane at 110 C and 275 bar. At 110 C the vapor pressure of
cyclopentane is 5.267 bar.
For cyclopentane T
c
=511.8 K, P
c
= 45.02 bar, = 0.196, Z
c
=0.273, V
c
=258 cm/mol,
T
n
T =383K, P =275 bar, P
=322.4 K
3
T
(383K) =5.267 bar
r
0.117
sat sat
r C
P P P = = =0.7486,
Calculate f
sat
Virial EOS
at the given Vapour pressure by
ln
sat sat sat sat sat
BP RT f P = =
Here T =383K, B is obtained as in problem 18, by B
0
, B
1
Final
.
S
Now by Rackett equation
=0.9
0.2857
(1- )

nbr
T sat
C C
V V Z =
( )
3
322.4/ 54.8 0.63 97.092
.exp 10.79
sat
nbr
sat sat sat sat sat
cm
T V
mol
f P V P P RT bar
= = =
(
= =


For the following system compute the species fugacity coefficients for an equimolar mixture
at 20 bar and 500K.
Example 6.8

T
c
P (K)
c
V (
bar)
c
X 10
3
(m
3
Z /mol)
c
y
i
Propane (1) 369.9 42.57 0.2 0.271 0.153 0.4
Pentane (2) 469.8 33.75 0.311 0.269 0.269 0.6

P =20 bar, T =500 K, y
1
=y
2

=0.5











Similarly, for pure components
Following the same procedure above (K
11
=K
22
=0), [K
ij
B
=0 if i =j] it may be shown that:
11
=- 1.183310
-4
m
3
/mol, B
22
=- 3.440710
-4
m
3
Thus:




/ mol
Similarly,



Calculate the fugacities of ethylene and propylene in a mixture of 70 mole percent ethylene
and 30 mole percent propylene at 600 K and 60 bar. Assume that the mixture follows the
Redlich-Kwong equation of state.
Example 6.9

T
c
P (K)
c
( bar)
Ethylene (1) 283.1 51.17
Propylene (2) 365.1 46.0

R-K parameters for pure species and mixture are obtained first


Similarly,



Now, solve for Z from cubic EOS,


It follows,



Since one real root only exists,










Methanol (1)-acetone (2) system is described by the Van Laar activity coefficient model. At
60
Example 6.10
0
12 21
0.47; 0.78 A A = = C, the model parameters are . Estimate the activity coefficients for a
solution containing 10mole% of methanol.
12 21
1 2 2 2
12 1 21 2
21 2 12 1
ln ;ln
1 1
A A
A x A x
A x A x
= =
| | | |
+ +
| |
\ . \ .

For x
1
= 0.1,
1
= 1.5219,
2

=1.0032
Use of Regular Solution Model to estimate activity coefficients for an equimolar benzene (1)
/ cyclohexane (2) solution 350
Example 6.11
o
K. The solubility parameters are:
1
=9.2 (cal/cm
3
)
1/2
;
2
=
8.2 (cal/cm
3
)
1/2
. The molar volumes: V
1
L
=88 cm
3
/mol; V
2
L
=107 cm
3
Volume fraction =
/mol
( )
1 1 1 1 1 2 2
/
L L L
xV xV x V = + =88 / (88 +107) =0.45
2 1
1 0.55 = =
| |
2
2 2 2
1 1 2 1 2
ln ( ) 88 0.55 9.2 8.2
L
RT V x = =
R =1.987 cal/mol, T =350
o
Hence ln
K
1
=0.038
1
Similarly RT ln
=1.04
2
=
2 2
2 1 1 2
( )
L
V
Hence
2

=1.03


Use UNIFAC model to estimate activity coefficients for an equimolar n-pentane (1) /acetone
(2) solution 350
Example 6.12
o
( )
( )
3
11 22 12
12 12 11 22
2
11 1 2 12
1
2
22 2 1 12
2
963, 1523, 52 /
2
exp
exp
S
S
B B B cm mol
B B B
B P P Py
RT
B P P Py
RT

= = =
= =
(
+
( =
(

(
+
( =
(

K.

Follow the algorithm provided in the text for bubble pressure calculation.

Final Answer:
1 2
85.14 , 0.812, 0.188
b
P KPa y y = = =