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# Tutorial Sheet No.

4 (2014):

Process Equipment Design for Phase-Equilibria Systems.

Please complete and hand-in Questions 2 & 5 by 3pm Monday 7
th
April 2014.

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]

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

2
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).

3
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]

Supplied Data : Data Sheet No. (2): De Priester Nomogram for Phase-Equilibrium
Constants for Hydrocarbons (Low Temperature Range).

4
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]

Supplied Data: 1 atm = 760 mmHg

5
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]

Supplied Data: 1 atm = 760 mmHg

6
Data Sheet No. (1): De Priester Nomogram for Phase Equilibrium Constants for
Hydrocarbons (High Temperature Range)

7
Data Sheet No. (2): De Priester Nomogram for Phase Equilibrium Constants for
Hydrocarbons (Low Temperature Range)