Tutorial Sheet No.

3 (2014)

Engineering Design of Chemical Reactors Using Chemical Reaction
Equilibrium Calculations

Please complete and hand-in Question 3 by 3pm Monday 24
th
March 2014.

1) Ethanol decomposes in the vapour phase over a catalyst according to the gas phase
reaction:
(g) O H (g) H C (g) OH H C
2 4 2 5 2
+

a) Using the following data calculate the heat, Gibbs Free energy and entropy of the reaction
at 298 K. Is this reaction spontaneous at 298 K?

Compound
o
298 f
H A
kJ / kmol
o
298 f
G A
kJ / kmol
C
2
H
5
OH (g) -235000 -168400
C
2
H
4
(g) +52340 +68160
H
2
O (g) -242000 -228800
[5 marks]

b) Using the following data calculate the heat, Gibbs Free Energy and entropy of the reaction
at 650 K. Is this reaction spontaneous now?

3
i
2
i i i P
T d T c T b a C
i
+ + + = (units kJ kmol
-1
K
-1
)

Compound a
i
b
i
c
i
d
i

C
2
H
5
OH (g) 9.014 0.2141 -8.39 10
-5
1.373 10
-9

C
2
H
4
(g) 3.806 0.1566 -8.348 10
-5
17.55 10
-9

H
2
O (g) 32.24 0.001924 1.055 10
-5
-3.596 10
-9

[5 marks]

c) What is the equilibrium constant, K
P
, for this reaction at 650 K?
[5 marks]

d) Assuming that the gas phase system is ideal, calculate the equilibrium conversion of pure
ethanol feed at 2 atm pressure and 650K?
[5 marks]

e) Repeat the above calculation but now we are at 200 atm and 650 K (so the system is not
ideal).
[5 marks]

Supplied Data: Universal Gas Constant R = 8.314 kJ kmol
-1
K
-1

Data Sheet No. 1 Table of Critical Constants of Gases.
Data Sheet No. 2 Dimensionless Plot of the Fugacity Coefficient (f
i
/ P
T
)
versus Reduced Pressure (P
r
) and Reduced Temperature (T
r
).
1 atm = 1.013 10
5
Pa
2
2) Sulphur trioxide, SO
3
(g), decomposes when heated, by undergoing the reversible reaction:

2SO
3
(g) 2SO
2
(g) + O
2
(g)

Using the following data:

Compound
f
298
H A
kJ kmol
-1

0
298
S
kJ kmol
-1
K
-1

P
C
kJ kmol
-1
K
-1

SO
3
(g) -395700 256.7 68.76
SO
2
(g) -296800 248.1 50.15
O
2
(g) 0 205.0 32.96

(i) For a closed system, operating at constant temperature and pressure, state the
conditions in terms of AG which give rise to an equilibrium/no change system,
and spontaneous change system.
(ii) Calculate the standard enthalpy change (heat of reaction, AH
R
) for the
decomposition of sulphur trioxide at 298 K.
(iii) Calculate the standard entropy change (AS) for the decomposition of sulphur
trioxide at 298 K.
(iv) Calculate the free energy change (AG) of the reaction at 298 K.
(v) Is this reaction spontaneous at 298 K? If it isnt and assuming the enthalpy and
entropy changes do not vary with temperature, estimate the temperature at which
the reaction becomes spontaneous.
(vi) Allowing for changes in enthalpy and entropy with temperature, calculate the
temperature at which the reaction becomes spontaneous.
[25 marks]























3
3) Carbon black is produced by the decomposition of methane at 650 C and 1 atm by
undergoing the reaction:

CH
4
(g) C (s) + 2H
2
(g)

For equilibrium at 650 C and 1 atm, the Gibbs Free Energy Change (AG) for the reaction is
1.109 10
4
kJ kmol
-1
.

a) What factors affect the equilibrium yield of a chemical reaction?
[5 marks]

b) What is the gas phase composition of gases exiting the reactor if pure methane only
enters the reactor, and what fraction of methane decomposes? State any assumptions
you make.
[10 marks]

c) Repeat the same calculation as for part (b) when the feed to the reactor is now an
equimolar mixture of methane and nitrogen.
[10 marks]































4
4) The gas phase hydration of ethylene for the production of ethanol is described by the
stoichiometric balance equation of:

(g) OH H C 1 (g) O H 1 (g) H C 1
5 2 2 4 2
+

This gas phase catalysed reaction takes place in a reactor vessel operated at a system pressure
of 70.0 atm and a system temperature of 600 K over a phosphoric acid catalyst. The feedstock
gas contains an equimolar concentration of steam and ethylene. The reacting gas phase can be
assumed to be ideal.

a) Starting with the Vant Hoff Isochore equation, namely:

| | constant
1

-
ln
o
+
|
.
|

\
|
(

A
=
T R
H
K
p


and using appropriate thermodynamic relationships show that the constant is equal to:

R
S
o
constant
A
=
[5 marks]

b) Using the Vant Hoff Isochore calculate the magnitude of the equilibrium constant (K
P
in
m
2
N
-1
) for the gas phase reaction at 600 K.
[5 marks]

c) Report the value of the Gibbs Free Energy at 600 K (
-1 o
600
(kmol) kJ , G A )
[5 marks]

d) Using the calculated value of K
P
at 600 K, determine the magnitude of the molar yield of
ethanol on ethylene at the system pressure of 70.0 atm ab.
[5 marks]

e) With reference to the results of the analysis of this reaction system, comment on how
product yield is affected by the operational temperature and pressure of the reactor vessel.
[5 marks]

Supplied Data: Enthalpy and Entropy of Formation Data at 600 K:

Components
o
f
H A
kJ / kmol
o
f
S A
kJ / (kmol K)
C
2
H
4
(g) + 52 280 219.5
H
2
O (g) -242 200 188.7
C
2
H
5
OH (g) -235 300 282.0





5
Data Sheet No. 1: Table of Critical Constants of Gases.

Substance Formula Molar Mass
kg/kmol
T
C

K
P
C

MPa
Air - 28.97 132.5 3.77
Ammonia NH
3
17.03 405.5 11.28
Argon Ar 39.948 151 4.86
Benzene C
6
H
6
78.115 562 4.92
Bromine Br
2
159.808 584 10.34
n-Butane C
4
H
10
58.124 425.2 3.80
Carbon dioxide CO
2
44.01 304.2 7.39
Carbon monoxide CO 28.011 133 3.50
Carbon tetrachloride CCl
4
153.82 556.4 4.56
Chlorine Cl
2
70.906 417 7.71
Chloroform CHCl
3
119.38 536.6 5.47
Dichlorodifluoromethane (R-12) CCl
2
F
2
120.91 384.7 4.01
Dichlorofluoromethane (R-21) CHCl
2
F 102.92 451.7 5.17
Ethane C
2
H
6
30.070 305.5 4.48
Ethanol C
2
H
5
OH 46.07 516 6.38
Ethylene C
2
H
4
28.054 282.4 5.12
Helium He 4.003 5.3 0.23
n-Hexane C
6
H
14
86.179 507.9 3.03
Hydrogen (normal) H
2
2.016 33.3 1.30
Krypton Kr 83.80 209.4 5.50
Methane CH
4
16.043 191.1 4.64
Methyl alcohol CH
3
OH 32.042 513.2 7.95
Methyl chloride CH
3
Cl 50.488 416.3 6.68
Neon Ne 20.183 44.5 2.73
Nitrogen N
2
28.013 126.2 3.39
Nitrous oxide N
2
O 44.013 309.7 7.27
Oxygen O
2
31.999 154.8 5.08
Propane C
3
H
8
44.097 370 4.26
Propylene C
3
H
6
42.081 365 4.62
Sulfur dioxide SO
2
64.063 430.7 7.88
Tetrafluoroethane (R-34a) CF
3
CH
2
F 102.03 374.2 4.059
Trichlorofluoromethane (R-11) CCl
3
F 137.37 471.2 4.38
Water H
2
O 18.015 647.1 22.06
Xenon Xe 131.30 289.8 5.88












6
Data Sheet No. 2: Dimensionless Plot of the Fugacity Coefficient (f
i
/ P
T
) versus Reduced
Pressure (P
r
) and Reduced Temperature (T
r
).