Tutorial Sheet No.

4: Answers

Process Equipment Design for Phase-Equilibria Systems.

1) a) Calculate the bubble point pressure and composition of the vapour in equilibrium with a
liquid at 40 C containing:

5 mole % methane (CH
4
)
20 mole % ethane (C
2
H
6
)
25 mole % propane (C
3
H
8
)
20 mole % isobutane (C
4
H
10
)
30 mole % n-butane (C
4
H
10
)

Use an initial guess of 1000 kPa.
[12.5 marks]

b) Calculate the dew point pressure and composition of the liquid in equilibrium with a
vapour at 40 C containing:

5 mole % methane (CH
4
)
20 mole % ethane (C
2
H
6
)
25 mole % propane (C
3
H
8
)
20 mole % isobutane (C
4
H
10
)
30 mole % n-butane (C
4
H
10
)

Use an initial guess of 1000 kPa.
[12.5 marks]

Answer:
a) Use high temperature nomograph with: K
i
= y
i
/ x
i


Therefore y
i
= x
i
K
i


Guess P until y
i
= 1.0

P = 1000 kPa P = 2500 kPa P = 2700 kPa
Component x
i
K
i
y
i
K
i
y
i
K
i
y
i

methane 0.05 18 0.90 7.8 0.39 7.2 0.36
ethane 0.20 3.9 0.78 1.9 0.38 1.8 0.36
propane 0.25 1.35 0.34 0.68 0.17 0.64 0.16
isobutane 0.20 0.60 0.12 0.32 0.064 0.31 0.062
nbutane 0.30 0.43 0.13 0.23 0.069 0.22 0.066
1.00 2.27 1.07 1.01

The bubble point pressure is ~ 2700 kPa and the composition of the vapour is:

36 mole % methane, 36 mole % ethane, 16 mole % propane, 6.2 mole % isobutane
and 6.6 mole % n-butane
[12.5 marks]
2







b) Use high temperature nomograph with: K
i
= y
i
/ x
i


Therefore x
i
= y
i
/ K
i


Guess P until x
i
= 1.0


3
P = 1000 kPa P = 820 kPa P = 760 kPa
y
i
K
i
x
i
K
i
x
i
K
i
x
i

methane 0.05 18 0.00278 21.5 0.00233 23 0.00217
ethane 0.20 3.9 0.05128 4.6 0.04348 5 0.04000
propane 0.25 1.35 0.18519 1.6 0.15625 1.7 0.14706
isobutane 0.20 0.60 0.33333 0.72 0.27778 0.76 0.26316
nbutane 0.30 0.43 0.69767 0.52 0.57692 0.56 0.53571
1.00 1.27 1.06 0.99

The dew point pressure is ~ 760 kPa and the composition of the liquid is:

0.2 mole % methane, 4 mole % ethane, 14.7 mole % propane, 26.3 mole % isobutane
and 53.6 mole % n-butane
[12.5 marks]




4
2) Many thermodynamic process engineering design problems consider a system in which
either a vapour phase is just being formed from a boiling liquid phase, or a liquid phase is just
being formed from a saturated vapour phase. In order to take into account molecular
interactions in real systems, the liquid-vapour equilibrium constant, K
i
, can be used in some
hydrocarbon systems.

a) For a non-ideal system, show that the Design Performance Equation to predict the
component mole fraction x
i
in the liquid stream from a flash vessel processing a liquid
feed stream of component mole fraction x
Fi
is:

L) - (1 K L
x
x
i
Fi
i
+
=

where L is the product liquor molar flow from the flash vessel operating at a system
pressure P and a system temperature T. Identify the assumptions used in the
derivation.
[5 marks]

b) A liquid stream containing 15 mol% ethane (C
2
H
6
), 35 mol% propane (C
3
H
8
) and 50
mol% n-butane (C
4
H
10
) enters a flash vessel at 40 C. If 40% of the stream remains as
a liquid (based on the molar flow), calculate the pressure of the vessel and the
composition of the exit streams.
[10 marks]

c) The vapour stream from a gas well is a mixture containing 50 mol% methane, 10
mol% ethane, 20 mol% propane and 20 mol% n-butane. The stream is fed to a partial
condenser at a pressure of 17.25 bar and a temperature of 27 C. Determine the mole
fraction of the gas which condenses and the composition of the liquid and gas phases
leaving the condenser.
[10 marks]

Data supplied:
Data Sheet No. (1): De Priester Nomogram for Phase Equilibrium Constants for
Hydrocarbons (High Temperature Range).




5
Answer:
DIAGRAM


Assumptions: No chemical reaction only physical division between binary phases. Steady
state system at constant temperature, T, and pressure, P. System is at phase equilibrium.

Basis of calculation: F = 1.0 kmol feedstock.

Mass Balance:

0) ( 0) (
ON ACCUMULATI REACTION OUT - IN
= =
=

IN = OUT

Overall Balance:

F = V + L
1.0 = V + L
then V = 1 L (1)

Component Balance:

L x V y F x
i i Fi
+ =

Substitute for basis, F = 1.0 and for V from Eq. (1) to give:

L x L y x
i i Fi
) - (1 + = (2)

At phase equilibrium,
i i i
x K y =

Substitute for y
i
in Eq. (2) to give:

L x L K x x
i i i Fi
) - (1 + =


) - (1 L K L
x
x
i
Fi
i
+
= (3)
[5 marks]
Feedstock
F kmol
Liquid Feed
x
Fi

EQUILBRIUM
UNIT
OR STAGE
V kmol
y
i

L kmol
x
i

6
b) Now we know L = 0.4, so guess P and use;

) 1 ( L K L
x
x
i
Fi
i
+
=

To calculate x
i
and then check for Ex
i
= 1.

P =600 kPa P =820 kPa
Component x
Fi
K
i
x
i
K
i
x
i
y
i

ethane 0.15 6 0.0375 4.7 0.0466 0.2190
propane 0.35 2.1 0.2108 1.6 0.2574 0.4118
n-butane 0.5 0.67 0.6234 0.54 0.6906 0.3729
0.8717 0.9946 1.0037

Iteration can be done from first guess on component contributing largest amount to x
i
using:

K
i new
= K
i old
x
i


Using data P = 600 kPa K
n-butane
= 0.6234 0.8717 = 0.54

Drawing a line through 40C and K
n-butane
= 0.54, gives the second set of data at P = 820 kPa
and the required result.


7
c) We know that: T = 27 C and P = 17.25 bar (= 17.25 10
5
Pa = 1725 kPa).

Therefore we can draw a line on the nomograph to get the K
i
values.



We know y
Fi
values coming in therefore we need to guess L and iterate until Ex
i
= 1.

L = 0.5 L = 0.2 L = 0.1 L = 0.142
Component y
Fi
K
i
x
i
x
i
x
i
x
i
y
i

methane 0.5 10.3 0.0885 0.0592 0.0534 0.0557 0.5737
ethane 0.1 2.1 0.0645 0.0532 0.0503 0.0514 0.1079
propane 0.2 0.69 0.2367 0.2660 0.2774 0.2725 0.1880
n-butane 0.2 0.21 0.3306 0.5435 0.6920 0.6208 0.1304
1.0 0.7203 0.9219 1.0731 1.0004 1.0000

We know L is between 0 and 1 so iteration is straight forward (final result L = 0.142 and V =
0.858 with compositions given in the table).




8
3) For a non-ideal system, show that the Design Performance Equation to predict the
component mole fraction x
i
in the liquid stream from a flash vessel processing a liquid feed
stream of component mole fraction x
Fi
is:

L) - (1 K L
x
x
i
Fi
i
+
=

where L is the product liquor molar flow from the flash vessel operating at a system pressure
P and a system temperature T. Identify the assumptions used in the derivation.
[5 marks]

A liquid of composition 25 mole % ethane, 15 mole % n-butane and a third unknown
component enters a separation vessel which operates at a pressure of 750 kPa and
temperature of 6 C. If 87% of the solution leaves the vessel as the liquid stream, calculate:

a) The equilibrium constant, K
i
, for the unknown component.
[10 marks]
b) The composition of the vapour and liquid leaving the separation unit.
[7 marks]
c) Determine the chemical name of the third remaining component in the liquid mixture.
[3 marks]

Answer:
DIAGRAM


Assumptions: No chemical reaction only physical division between binary phases. Steady
state system at constant temperature, T, and pressure, P. System is at phase equilibrium.

Basis of calculation: F = 1.0 kmol feedstock.

Mass Balance:

0) ( 0) (
ON ACCUMULATI REACTION OUT - IN
= =
=


IN = OUT

Overall Balance:

Feedstock
F kmol
Liquid Feed
x
Fi

EQUILBRIUM
UNIT
OR STAGE
V kmol
y
i

L kmol
x
i

9
F = V + L
1.0 = V + L
then V = 1 L (1)

Component Balance:

L x V y F x
i i Fi
+ =

Substitute for basis, F = 1.0 and for V from Eq. (1) to give:

L x L y x
i i Fi
) - (1 + = (2)

At phase equilibrium,
i i i
x K y =

Substitute for y
i
in Eq. (2) to give:

L x L K x x
i i i Fi
) - (1 + =


) - (1 L K L
x
x
i
Fi
i
+
= (3)
[5 marks]

a) The mole fraction of the unknown component in the feed stream is:

x
Fi
of unknown component = 1 0.25 0.15 = 0.6

Next, draw a tie line on the De Priester Chart between P = 750 kPa and T = 6 C. Read off the
K
i
values for ethane and n- butane. Knowing the K
i
values and that L = 0.87 we can calculate
the mole fractions of ethane and n-butane in the output liquid stream using:

i
Fi
i
Fi
i
K .
x
. - K .
x
x
0.13 87 0 ) 87 0 1 ( 87 0 +
=
+
=

Component x
Fi
K
i
x
i

ethane 0.25 2.6 0.207
n-butane 0.15 0.18 0.168
unknown 0.6 - -

We know that:
Ex
i
= 1

Therefore
x
ethane
+ x
n-butane
+ x
unknown
= 1

0.207 + 0.168 + x
unknown
= 1

x
unknown
= 0.625
10



We can now calculate K
i
as:

i
K .
.
0.13 87 0
6 . 0
625 0
+
=

0.87 + 0.13 K
i
= 0.6/0.625


11
K
i
= [(0.6/0.625) 0.87]/0.13 = 0.69
[10 marks]

b) Using the calculated data we get:

Component x
Fi
K
i
x
i
y
i

ethane 0.25 2.60 0.207 0.538
n-butane 0.15 0.18 0.168 0.030
unknown 0.6 0.69 0.625 0.431
Total 1.00 - 1.000 0.999

Remember y
i
= K
i
x
i


Therefore, the stream compositions are:

Liquid: 20.7 mole % ethane, 16.8 mole % n- butane, 62.5 mole % of the unknown compound
Vapour: 53.8 mole % ethane, 3.0 mole % n- butane, 43.1 mole % of the unknown compound
[7 marks]

c) Looking on the De Priester chart, the compound which has a K
i
of 0.69 when P = 750 kPa
and T = 6 C is propane.

Therefore, the unknown compound is most likely propane.
[3 marks]



12
4) Acetone (1) and methanol (2) form an azeotrope boiling at 55.7 C and 760 mmHg
pressure, with a mole fraction of 80% acetone. Given the following Antoine equations, where
o
i
p is in mmHg and T is in C:

Acetone:
229.664
1210.595
- 7.11714 log
1 10
+
=
T
p
o

Methanol:
239.726
1582.271
- 8.08097 log
2 10
+
=
T
p
o


a) Determine the Van Laar coefficients from the azeotrope data and the following
equations;

1
2
1 1
2 2
12
ln
ln
ln
1
x
x
A
|
|
.
|

\
|
+ =
2
2
2 2
1 1
21
ln
ln
ln
1
x
x
A
|
|
.
|

\
|
+ =
[5 marks]

b) Calculate the azeotropic boiling point and composition at P = 1520 mmHg. Use A
12

and A
21
as calculated above and:

2
2
1
21
12
12
1
1
ln
|
|
.
|

\
|
+
=
x
x
A
A
A

2
1
2
12
21
21
2
1
ln
|
|
.
|

\
|
+
=
x
x
A
A
A

[15 marks]

c) Calculate the lowest pressure at which an azeotrope exists.
[5 marks]

Answer:
a) When T = 55.7 C and P = 1 atm, we are at the azeotrope and
o
i i
P/p = , therefore:

Acetone:
229.664 55.7
1210.595
- 7.11714 p log
o
1 10
+
=

mmHg 749.65 p
o
1
=

1.0138
mmHg 749.65
mmHg 760

p
P

o
1
1
= = =

Methanol:
239.726 55.7
1582.271
- 8.08097 p log
o
2 10
+
=

mmHg 530.97 p
o
2
=

1.4313
mmHg 530.97
mmHg 760

p
P

o
1
1
= = =
13
We know x
1
= 0.8, x
2
= 0.2,
1
= 1.0138 and
2
= 1.4313, therefore:

2
1 1
2 2
1 12
ln x
ln x
1 ln A
|
|
.
|

\
|

+ =

0.7790
1.0138 ln 0.8
1.4313 ln 0.2
1 1.0138 ln A
2
12
=
|
.
|

\
|
+ =

2
2 2
1 1
2 21
ln x
ln x
1 ln A
|
|
.
|

\
|

+ =

0.4767
1.4313 ln 0.2
1.0138 ln 0.8
1 1.4313 ln A
2
21
=
|
.
|

\
|
+ =
[5 marks]

b) At the azeotrope:

o
1
o
2
o
2
o
1
2
1
p
p
P/p
P/p
= =

Therefore:

2
1
2
12
21
21
2
2
1
21
12
12
2 1
2
1
o
1
o
2
1 1
ln ln ln
p
p
ln
|
|
.
|

\
|
+

|
|
.
|

\
|
+
= =
|
|
.
|

\
|

=
|
|
.
|

\
|
x
x
A
A
A
x
x
A
A
A


Let:
2
1
21
12
x
x
A
A
= |

Therefore:

( ) ( ) ( )
2
2
21 12
2
21
2
12
o
1
o
2
1 1 1 1 p
p
ln
| +
|
=
| +

| +
=
|
|
.
|

\
| A A A A


Need to guess T, calculate
o
1
p ,
o
2
p and solve for |. Then calculate x
1
and
1
and P =
1

o
1
p .
Iterate until P = 1520 mmHg

1
st
guess: When T = 55.7 C, we know that mmHg 749.65 p
o
1
= and P = 760 mmHg, therefore

old
o
1
old
new
new
o
1
) (p
P
P
) (p =

14
mmHg 1499.3 749.65
760
1520
) (p
new
o
1
= =

C 77.50
7.11714 - 1499.3 log
1210.595
- 229.664 - T
10
new
= =

mmHg 1239.00 p
o
2
=

( )
2
2
1
4767 . 0 7790 . 0
1499.3
1239.00
ln
| +
|
=
|
.
|

\
|


0 96966 . 0 38138 . 0 286042 . 0
2
= | |

Giving: | = 2.624803 which results in
1
= 1.0611

mmHg 87 . 1590 0611 . 1 3 . 1499 p P
1
o
1
= = =

This is too high, therefore we need to iterate.

1
st
iteration:
mmHg 1432.51 29 . 1499
1590.87
1520
) (p
new
o
1
= =

C 75.96
7.11714 - 1432.51 log
1210.595
- 229.664 - T
10
new
= =

mmHg 1171.72 p
o
2
=

( )
2
2
1
4767 . 0 7790 . 0
1432.51
1171.72
ln
| +
|
=
|
.
|

\
|


0 97992 . 0 40191 . 0 275779 . 0
2
= | |

Giving: | = 2.749636 which results in
1
= 1.0570

mmHg 11 . 1514 0570 . 1 51 . 1432 p P
1
o
1
= = =

This is slightly too low so can iterate again:

2
nd
iteration:
mmHg 1438.08 51 . 1432
1514.11
1520
) (p
new
o
1
= =

C 76.09
7.11714 - 1438.08 log
1210.595
- 229.664 - T
10
new
= =
15

mmHg 1177.31 p
o
2
=

( )
2
2
1
4767 . 0 7790 . 0
1438.08
1177.31
ln
| +
|
=
|
.
|

\
|


0 97905 . 0 40016 . 0 276652 . 0
2
= | |

Giving: | = 2.738652 which results in
1
= 1.0573

mmHg 50 . 1520 0573 . 1 08 . 1438 p P
1
o
1
= = =

Close enough, so T = 76.09 C.

===============================================================
We could also have interpolated this value using the first 2 points we had already i.e.:

C 08 . 76
) 11 . 1514 87 . 1590 (
) 96 . 75 5 . 77 (
) 11 . 1514 1520 ( 96 . 75
o
=

+ = T
===============================================================

Composition:

) 1 (
1
1
21
12
2
1
21
12
x
x
A
A
x
x
A
A

= = |

Rearranging, gives:

6263 . 0
) 1 (
1
) 1 (
1
4767 . 0 738652 . 2
7790 . 0
1
21
12
=
+
=
+
=
|A
A
x

Therefore, the azeotrope at 1520 mmHg is at 62.63% Acetone.
[15 marks]


c) Since x
1
decreases as P rises, it will increase as P falls and eventually reach a value of 1.0
for P < 760 mmHg. When x
1
= 1.0 then:

= = |
2
1
21
12
x
x
A
A

Therefore:

( ) ( )
21 2
21
2
12
o
1
o
2
1 1 1 p
p
ln A
A A
=
| +

| +
=
|
|
.
|

\
|


This equation can be solved either by trial and error or analytically:
16

( ) ( )
o
i
o
i
p log 30258 . 2 p ln =

Therefore,

( ) ( ) ( ) ( ) ( )
21
o
1
o
2
o
1
o
2 o
1
o
2
p log p log 30258 . 2 p ln p ln
p
p
ln A = = =
|
|
.
|

\
|


30258 . 2 229.664
1210.595
- 7.11714
239.726
1582.271
- 8.08097
21
A
T T

=
(

+


| | | |
229.664
1210.595

239.726
1582.271
30258 . 2
7.11714 8.08097
21
+

+
= +
T T
A


A
21
= 0.4767, so:

229.664
1210.595

239.726
1582.271
170873 . 1
+

+
=
T T


239.726) 1210.595( ) 229.664 ( 271 . 1582 ) 229.664 )( 239.726 ( 170873 . 1 + + = + + T T T T

1 . 290211 1210.595 7 . 363390 271 . 1582 ) 55056.43 469.39 ( 170873 . 1
2
+ = + + T T T T

59 . 73179 676 . 371 64464.07 549.60 170873 . 1
2
+ = + + T T T

0 8715.52 - 92 . 177 170873 . 1
2
= + T T

Therefore: T = 38.98 C (or -190.94 C which is invalid)

When T = 38.98 C;

Acetone:
229.664 38.98
1210.595
- 7.11714 p log
o
1 10
+
=

mmHg 408.15 p
o
1
=

So mmHg 15 . 408 1 15 . 408 p P
1
o
1
= = =
[5 marks]


17
5) Acetone (1) and Hexane (2) form an azeotrope containing 41 wt% of Hexane, boiling at
49.8 C at a pressure of 760 mmHg. Pure component vapour pressures may be calculated
using the following equation and Antoine coefficients:

) (
log
*
10
C T
B
A p
i
+
=

Antoine Coefficients RMM
kg / kmol A B C
Acetone (1) 7.1327 1219.97 230.653 58.08
Hexane (2) 7.01051 1246.33 232.988 86.18

with
*
i
p in mmHg and T in C.

a) Calculate the normal boiling points for Acetone and Hexane at 1 atm.
[4 marks]

b) Use the azeotropic data and the following equations to estimate the van Laar constants
A
12
and A
21
.

2
1 1
2 2
1 12
ln
ln
1 ln
|
|
.
|

\
|

+ =
x
x
A
2
2 2
1 1
2 21
ln
ln
1 ln
|
|
.
|

\
|

+ =
x
x
A
[7 marks]

c) Using the Antoine equations and Van Laar coefficients calculated in part (b), estimate
the boiling point and vapour composition at 760 mmHg of a liquid containing 20 %
by mole of Acetone.

2
1 12 2 21
2
2
2
21 12
1
] [
ln
x A x A
x A A
+
=
2
2 21 1 12
2
1
2
12 21
2
] [
ln
x A x A
x A A
+
=
[8 marks]

d) Find the dew point of a vapour containing 50 % by mole of Acetone.
[6 marks]

Answer:
a) To find the boiling point substitute a pressure of 1 atm (=760 mmHg) into the Antoine
equations:

18
For Acetone:

) 653 . 230 (
97 . 1219
1327 . 7 760 log
+
=
T


760 log 1327 . 7
) 653 . 230 (
97 . 1219
=
+ T


760 log 1327 . 7
97 . 1219
653 . 230

= + T

C 3 . 56 653 . 230
760 log 1327 . 7
97 . 1219
=

= T
[2 marks]

For Hexane:

) 988 . 232 (
33 . 1246
01051 . 7 760 log
+
=
T


760 log 01051 . 7
) 988 . 232 (
33 . 1246
=
+ T


760 log 01051 . 7
33 . 1246
988 . 232

= + T

C 8 . 68 988 . 232
760 log 01051 . 7
33 . 1246
=

= T
[2 marks]

b) When T = 49.8 C and P = 760 mmHg, we are at the azeotrope and
*
/
i i
p P = , therefore:

Acetone: 7827 . 2
) 653 . 230 8 . 49 (
97 . 1219
1327 . 7 log
*
1
=
+
= p

mmHg 32 . 606
*
1
= p

2535 . 1
32 . 606
760
1
= =

Hexane: 6032 . 2
) 988 . 232 8 . 49 (
33 . 1246
01051 . 7 log
*
2
=
+
= p

mmHg 05 . 401
*
2
= p

19
8950 . 1
05 . 401
760
2
= =

Need to work out mole fractions at azeotrope, therefore taking a basis of 100 kg of the
mixture:

Mass of Hexane = (41/100) 100 = 41 kg
Mass of Acetone = 100 41 = 59 kg

Moles of Hexane = 41 / 86.18 = 0.4757 kmols
Moles of Acetone = 59 / 58.08 = 1.0158 kmols

Mole fraction of Acetone (x
1
) = 1.0158 / (0.4757 + 1.0158) = 0.681
Mole fraction of Hexane (x
2
) = 1 x
1
= 1 0.681 = 0.319

2
1 1
2
1 12
ln
ln
1 ln
(

+ =
2
x
x
A

2216 . 1
2535 . 1 ln 681 . 0
8950 . 1 ln 319 . 0
1 2535 . 1 ln
2
12
=
(

+ = A

2
2 2
1
2 21
ln
ln
1 ln
(

+ =
1
x
x
A

9678 . 1
8950 . 1 ln 319 . 0
2535 . 1 ln 681 . 0
1 8950 . 1 ln
2
21
=
(

+ = A
[7 marks]

c) x
1
= 0.2, x
2
= 0.8 and P = 760 mmHg.

2
1 12 2 21
2
2
2
21 12
1
] [
ln
x A x A
x A A
+
=

9154 . 0
)] 2 . 0 2216 . 1 ( ) 8 . 0 9678 . 1 [(
8 . 0 9678 . 1 2216 . 1
ln
2
2 2
1
=
+

=

4978 . 2
1
=

2
2 21 1 12
2
1
2
12 21
2
] [
ln
x A x A
x A A
+
=

0355 . 0
)] 2 . 0 2216 . 1 ( ) 8 . 0 9678 . 1 [(
2 . 0 2216 . 1 9678 . 1
ln
2
2 2
2
=
+

=

20
0361 . 1
2
=

Now we need to guess T, so as a first guess use the average boiling point, T = 62.6 C.

Acetone: 9726 . 2
) 653 . 230 6 . 62 (
97 . 1219
1327 . 7 log
*
1
=
+
= p

mmHg 86 . 938
*
1
= p

Hexane: 7941 . 2
) 988 . 232 6 . 62 (
33 . 1246
01051 . 7 log
*
2
=
+
= p

mmHg 44 . 622
*
2
= p

i i i i
p x p =
*
and

=
i
p P

So

mmHg 02 . 469 4978 . 2 86 . 938 2 . 0
1
= = p

mmHg 93 . 515 0361 . 1 44 . 622 8 . 0
2
= = p

mmHg 95 . 984 93 . 515 02 . 469 = + = =
i
p P

This value is too high as we need P = 760 mmHg, so iterate temperature value as follows:

=
i
old new
p
p p
760
) ( ) (
*
1
*
1


mmHg 44 . 724
95 . 984
760
86 . 938 ) (
*
1
= =
new
p

From Antoine equation for Acetone: C 87 . 54 =
new
T .

Hexane: 6808 . 2
) 988 . 232 87 . 54 (
33 . 1246
01051 . 7 log
*
2
=
+
= p

mmHg 51 . 479
*
2
= p

i i i i
p x p =
*
and

=
i
p P

So

mmHg 90 . 361 4978 . 2 44 . 724 2 . 0
1
= = p
21

mmHg 46 . 397 0361 . 1 51 . 479 8 . 0
2
= = p

mmHg 36 . 759 46 . 397 90 . 361 = + = =
i
p P

This value is slightly too low as we need P = 760 mmHg, so iterate again:

=
i
old new
p
p p
760
) ( ) (
*
1
*
1


mmHg 725.05
36 . 759
760
44 . 724 ) (
*
1
= =
new
p

From Antoine equation for Acetone: C 90 . 54 =
new
T .

Hexane: 6813 . 2
) 988 . 232 90 . 54 (
33 . 1246
01051 . 7 log
*
2
=
+
= p

mmHg 06 . 480
*
2
= p

i i i i
p x p =
*
and

=
i
p P

So

mmHg 21 . 362 4978 . 2 05 . 725 2 . 0
1
= = p

mmHg 91 . 397 0361 . 1 06 . 480 8 . 0
2
= = p

mmHg 12 . 760 91 . 397 21 . 362 = + = =
i
p P

Therefore: T = 54.90 C and the vapour composition is found from:

P
p x
y
i i i
i
*

=

477 . 0
760
05 . 725 4978 . 2 2 . 0
1
=

= y

523 . 0
760
06 . 480 0361 . 1 8 . 0
2
=

= y
[8 marks]

d) y
1
= 0.5, y
2
= 0.5, P = 760 mmHg, 2216 . 1
12
= A and 9678 . 1
21
= A .

Again guess T = 62.6 C.
22

Therefore mmHg 86 . 938
*
1
= p and mmHg 44 . 622
*
2
= p

Also assume
1
=
2
= 1 then

*
i i
i
i
p
P y
x

=

4047 . 0
86 . 938
760 5 . 0
1
=
1

= x

6105 . 0
44 . 622
760 5 . 0
2
=
1

= x

Recalculate
i
values using Van Laar equations:

8462 . 1
)] 4047 . 0 2216 . 1 ( ) 6105 . 0 9678 . 1 [(
6105 . 0 9678 . 1 2216 . 1
exp
2
2 2
1
=
|
|
.
|

\
|
+

=

1821 . 1
)] 6105 . 0 9678 . 1 ( ) 4047 . 0 2216 . 1 [(
4047 . 0 2216 . 1 9678 . 1
exp
2
2 2
2
=
|
|
.
|

\
|
+

=

Recalculate x
i
values:

2192 . 0
938 8462 1
760 5 0
1
=
.86 .

=
.
x

5165 . 0
44 . 622
760 5 . 0
2
=
1.1821

= x

7357 . 0 =
i
x

Therefore: mmHg 72 . 690
0 . 1
7357 . 0
86 . 938 ) (
*
1
= =
new
p

From Antoine equation: C 5 . 53 =
new
T

mmHg 23 . 457 ) (
*
2
=
new
p

Recalculate
i
values using Van Laar equations:

1495 . 2
)] 2192 . 0 2216 . 1 ( ) 5165 . 0 9678 . 1 [(
5165 . 0 9678 . 1 2216 . 1
exp
2
2 2
1
=
|
|
.
|

\
|
+

=

23
0893 . 1
)] 5165 . 0 9678 . 1 ( ) 2192 . 0 2216 . 1 [(
2192 . 0 2216 . 1 9678 . 1
exp
2
2 2
2
=
|
|
.
|

\
|
+

=

Recalculate x
i
values:

2559 . 0
72 . 690
760 5 . 0
1
=
2.1495

= x

7630 . 0
23 . 457
760 5 . 0
2
=
1.0893

= x

0189 . 1 =
i
x

Therefore: mmHg 77 . 703
0 . 1
0189 . 1
72 . 690 ) (
*
1
= =
new
p

From Antoine equation: C 04 . 54 =
new
T

mmHg 93 . 465 ) (
*
2
=
new
p

Again recalculate
i
values using Van Laar equations:

3091 . 2
)] 2559 . 0 2216 . 1 ( ) 7630 . 0 9678 . 1 [(
7630 . 0 9678 . 1 2216 . 1
exp
2
2 2
1
=
|
|
.
|

\
|
+

=

0602 . 1
)] 7630 . 0 9678 . 1 ( ) 2559 . 0 2216 . 1 [(
2559 . 0 2216 . 1 9678 . 1
exp
2
2 2
2
=
|
|
.
|

\
|
+

=

Recalculate x
i
values:

2338 . 0
77 . 703
760 5 . 0
1
=
2.3091

= x

7693 . 0
93 . 465
760 5 . 0
2
=
1.0602

= x

0031 . 1 =
i
x

Could recheck final values with another iteration.
[6 marks]