Tutorial Sheet No.

3: Answers
Engineering Design of Chemical Reactors Using
Chemical Reaction Equilibrium Calculations

Overview
In chemical reaction equilibria problems, the reaction equilibrium constant K
P
is related to
the operating conditions in the reactor vessel by the design performance equation, which for
the stoichiometric balance of:

D d C c B b A a + +

is:

| | P
P
f

P
f
P
f

P
f

) (y ) (y
) (y ) (y

) ( ) (
) ( ) (
K
b - a - d c
T b
T
o
a
T
o
d
T
o
c
T
o
b
B
a
A
d
D
c
C
b
B
a
A
d
D
c
C
p
B A
D C
+
(
(
(
(
(

|
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
(

=

There is very little data on the activity coefficients,
i
, in a gas phase, so that these are taken
as unity,
i
= 1.0, even in real, non-ideal systems. The design performance equation reduces
to:

| | P
P
f

P
f
P
f

P
f

) (y ) (y
) (y ) (y
K
b - a - d c
T b
T
o
a
T
o
d
T
o
c
T
o
b
B
a
A
d
D
c
C
p
B A
D C
+
(
(
(
(
(

|
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
(

=

When the chemical reaction is ideal, then the fugacity-pressure coefficients become unity,
f
i
/P
T
= 1.0, the mathematical model simplifies to:

| | P
) (y ) (y
) (y ) (y
K
b - a - d c
T b
B
a
A
d
D
c
C
p
+
(

=

Whether pressure affects the condition of this reaction equilibrium and hence the fractional
conversion of the limiting reactant hidden in the mole fraction, y
i
, depends on the indicie in
the pressure function, namely:

c+d-a-b is +ve reduces effective value of K
P

c+d-a-b is zero no pressure effect
c+d-a-b is -ve increases effective value of K
P


However, before the design performance equation can be used, the magnitude of the reaction
equilibrium constant, K
P
, has to be available from experimental measurement or calculated as
a function of temperature.
2
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
).
Answer:
a)

A A = A
f
298 i REACTANT i
f
298 i PRODUCT i 298 REACTION
H n - H n H

235000) - (1 - 242000)] - (1 52340) [(1 H
298 REACTION
+ + = A

3
kJ 45340 H
298 REACTION
+ = A


A A = A
f
298 i REACTANT i
f
298 i PRODUCT i 298 REACTION
G n - G n G

168400) - (1 - 228800)] - (1 68160) [(1 G
298 REACTION
+ + = A

kJ 7760 G
298 REACTION
+ = A

298 REACTION 298 REACTION 298 REACTION
S T - H G A A = A

) S (298 - 45340 kJ 7760
298 REACTION
A + = +

K kmol kJ / 126.1 S
298 REACTION
= A

As AG is +ve the reaction is not spontaneous.

b)
}
A + A = A
T
298
P 298 REACTION T REACTION
dT C H H

}
A + A = A
650
298
P 298 REACTION 650 REACTION
dT C H H

Now,


A = A
i REACTANT P i i PRODUCT P i P
C n - C n C

Therefore,

} ) T 10 1.373 T 10 8.39 - T 0.2141 (9.014 1 {
- } )] T 10 3.596 - T 10 1.055 T 0.001924 (32.24 [1
)] T 10 17.55 T 10 8.348 - T 0.1566 (3.806 [1 { C
3 9 - 2 5 -
3 9 - 2 5 -
3 -9 2 -5
P
+ +
+ +
+ + + = A


3 -9 2 -5
P
T 10 12.581 T 10 1.097 T 0.05558 - 27.032 C + + = A

} }
+ + = A
650
298
3 9 - 2 5 -
650
298
P
dT ) T 10 12.581 T 10 1.097 T 0.05558 - (27.032 dT C

| |
(

+
(

+
(

= A
}
) 298 - (650
4
10 12.581
) 298 - (650
3
10 1.097

) 298 - (650
2
0.05558
- 298) - (650 27.032 dT C
4 4
9 -
3 3
5 -
2 2
650
298
P

4
kmol kJ / 1686.61 dT C
650
298
P
= A
}


kmol kJ / 47026.61 1686.61 5340 4 H
650 REACTION
= + = A

}
A
+ A = A
650
298
P
298 REACTION 650 REACTION
dT
T
C
S S

} }
+ +
=
A
650
298
3 -9 2 -5
650
298
P
dT
T
) T 10 12.581 T 10 1.097 T 0.05558 - (27.032
dT
T
C


} }
|
.
|

\
|
+ + =
A
650
298
2 -9 -5
650
298
P
dT T 10 12.581 T 10 1.097 0.05558 -
T
27.032
dT
T
C


| |
(

+
(

+
(

|
.
|

\
|
=
A
}
) 298 - (650
3
10 12.581
) 298 - (650
2
10 1.097

298) - (650 0.05558 -
298
650
ln 27.032 dT
T
C
3 3
9 -
2 2
5 -
650
298
P


K kmol kJ / 4.39 dT
T
C
650
298
P
=
A
}


K kmol kJ / 130.49 4.39 26.1 1 S
650 REACTION
= + = A

650 REACTION 650 REACTION 650 REACTION
S T - H G A A = A

kmol kJ / 37791.89 - (130.49) 650 - 47026.61 G
650 REACTION
= = A

Reaction is now spontaneous as AG is negative.

c) For ideal gas,

| |
P
K ln T R - G = A

|
.
|

\
| A
=
T R
G
exp K
P


atm 1089
650 8.314
) 89 . 37791 - (
exp K
P
=
|
.
|

\
|

=





5
d) DIAGRAM



At T = 650 K, K
P
= 1089 atm

STOICHIOMETRY:

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

ASSUMPTIONS:
Ideal gas phase reaction system / steady state / equilibrium is reached / no inert or dilutant
molecular species present.

BASIS OF CALCULATION:
1.0 kmols of ethanol which is the limiting reactant as it is the only reactant.

Let the fractional conversion of the limiting reactant at equilibrium be o kmols.

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


Component kmols mole fraction
y
i

C
2
H
5
OH (1 - o)
|
.
|

\
|
o +
o
1
- 1

C
2
H
4
(o)
|
.
|

\
|
o +
o
1

H
2
O (o)
|
.
|

\
|
o +
o
1

TOTAL (1 + o) y
i
= 1.0

For an ideal gas system, the design performance equation for reaction becomes:

| | P
) (y
) (y ) (y
K
1 - 1 1
T 1
OH H C
1
O H
1
H C
p
5 2
2 4 2
+
(
(

=

CATALYTIC
REACTOR
Feedstock
Gas
Product
Gas
1 kmol
C
2
H
5
OH
C
2
H
4
?
H
2
O ?
C
2
H
5
OH ?
T = 650 K
P
T
= 2 atm
6
using the information in the table gives:

| | P
1
- 1
1 1
K
1
T 1
1 1
p
(
(
(
(

|
.
|

\
|
o +
o
|
.
|

\
|
o +
o
|
.
|

\
|
o +
o
=

substitute for the available data on K
P
and o to give:

| | atm 2
) (1 ) - (1
atm 1089
2
(

o + o
o
=

(

o
o
=
) - (1
2
1089
2
2


2 2
2 ) - (1 1089 o = o

1091
1089

2
= o

0.999 = o

e)

Compound T
C

K
P
C

MPa
T
r

(=650 / T
C
)
P
r

(=200 atm / P
C
in atm)
C
2
H
5
OH (g) 516 6.38 1.26 3.18
C
2
H
4
(g) 282.4 5.12 2.30 3.96
H
2
O (g) 647.1 22.06 1.00 0.92



7
From the correlation chart we get:

0.69 ) / P (f 0.96 ) / P (f 0.62 ) / P (f
T O H T H C T OH H C
2 4 2 5 2
= = =

( ) ( )
( )
| | P
/ P f
/ P f / P f

) (y
) (y ) (y
K
1 - 1 1
T
1
T OH H C
1
T O H
1
T H C
1
OH H C
1
O H
1
H C
p
5 2
2 4 2
5 2
2 4 2 +
(
(

(
(

=

using the information from before gives:

| | atm 200
0.62
0.96 0.69

1
- 1
1 1
atm 1089
1
1 1
(

(
(
(
(

|
.
|

\
|
o +
o
|
.
|

\
|
o +
o
|
.
|

\
|
o +
o
=

| || | atm 200 1.068
) (1 ) - (1
atm 1089
2
(

o + o
o
=

| | atm 200
) (1 ) - (1
atm 1019.66
2
(

o + o
o
=

(

o
o
=
) - (1
200
1019.66
2
2


1219.66
1019.66

2
= o

0.9143 = o


















8
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]

Data Supplied:

Data Sheet No. (2): General Thermodynamic Formula.


Answer
i) If AG is positive, the proposed process change (chemical reaction) will not occur.
If AG is zero, the system is at a stable/equilibrium condition.
If AG is negative, a spontaneous change (chemical reaction) will occur.

ii) BASIS OF CALCULATION: 2 kmols of SO
3



A A = A
f
298 i REACTANT i
f
298 i PRODUCT i 298 REACTION
H n - H n H

( ) ( ) ] H [n - ] H [n ] H [n H
f
SO SO
f
O O
f
SO SO 298 REACTION
3 3 2 2 2 2
A A + A = A

( ) ( ) (-395700)] [2 - (0)] [1 (-296800)] [2 H
298 REACTION
+ = A

3 298 REACTION
SO kmol 2 / kJ 197800 H = A

9
iii)

A A = A
o
298 i REACTANT i
o
298 i PRODUCT i 298 REACTION
S n - S n S

( ) ( ) ] S [n - ] S [n ] S [n S
o
SO SO
o
O O
o
SO SO 298 REACTION
3 3 2 2 2 2
A A + A = A

( ) ( ) (256.7)] [2 - (205)] [1 (248.1)] [2 S
298 REACTION
+ = A

3 298 REACTION
SO kmol 2 / kJ 187.8 S = A

iv)
T REACTION T REACTION T REACTION
S T - H G A A = A

187.8) (298 - 197800 G
298 REACTION
= A

3 298 REACTION
SO kmol 2 / kJ 141835.6 G = A

v) From the answer to question (iv) given here we can see that;

3 298 REACTION
SO kmol 2 / kJ 141835.6 G = A

This is positive which means we dont have a spontaneous reaction.

For a spontaneous reaction to occur
3 T REACTION
SO kmol 2 / kJ 0 G < A , so we need to calculate
the temperature, T, at which 0 G
T REACTION
= A . If the enthalpy and entropy dont change with
temperature we can use:

0 S T - H
T REACTION T REACTION
< A A

T REACTION
T REACTION
S
H
T
A
A
>

K 2 . 1053 T >
187.8
197800
>

vi) If the enthalpy and entropy do change with temperature then the enthalpy of reaction at
any given temperature can be calculated from,

}
A + A = A
T
298
P 298 REACTION T REACTION
dT C H H

298] - [T C H H
P 298 REACTION T REACTION
A + A = A

and the entropy of reaction at any given temperature is:

10
}
A
+ A = A
T
298
P
298 REACTION T REACTION
dT
T
C
S S

|
.
|

\
|
A + A = A
298
T
ln C S S
P 298 REACTION T REACTION


Knowing the entropy and enthalpy, the Gibbs Free Energy at the new temperature can be
calculated from:

T REACTION T REACTION T REACTION
S T - H G A A = A

In order to calculate these values we need to know
P
C A . This can again be calculated via:


A = A
i REACTANT P i i PRODUCT P i P
C n - C n C

( ) ( ) ] C [n - ] C [n ] C [n C
3 3 2 2 2 2
SO P SO O P O SO P SO P
+ = A

( ) ( ) (68.76)] [2 - (32.96)] [1 (50.15)] [2 C
P
+ = A

K) SO kmol (2 / kJ 4.26 - C
3 P
= A

Using the answer to part (v) as an initial guess and the data at 298 K we get::

Guess
Temp
K
298] - [T C
P
A
kJ / 2 kmol
SO
3

298] / [T ln C
P
A
kJ / 2 kmol SO
3

AH
REACT T

kJ / 2 kmol
SO
3

AS
REACT T

kJ / (2 kmol
SO
3
K)
AG
REACT T

kJ / 2 kmol
SO
3

298 0 0 197800 187.8 141835.6
1053.2 -3217.2 -5.38 194582.8 182.42 2458.1

Interpolating to AG = 0

K 1066.5 141835.6) - 0 (
141835.6) - (2458.1
298) - (1053.2
298 T = + =

Guess
Temp
K
298] - [T C
P
A
kJ / 2 kmol
SO
3

298] / [T ln C
P
A
kJ / 2 kmol SO
3

AH
REACT T

kJ / 2 kmol
SO
3

AS
REACT T

kJ / (2 kmol
SO
3
K)
AG
REACT T

kJ / 2 kmol
SO
3

298 0 0 197800 187.8 141835.6
1066.5 -3273.8 -5.43 194526.2 182.37 28.6

This is good enough, therefore, the sublimation temperature is 1066.5 K.

Note: We could interpolate further using the data at 1053.2 K and 1066.5 K which would
give 1066.7 K and a AG of -6.1 kJ / 2 kmol SO
3
, so the actual temperature is between 1066.5
and 1066.7 K.

11
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 an 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]


Answer:
(a) Factors affecting the equilibrium yield of a chemical reaction are:
(i) Temperature and the Vant Hoff Isochore
P
K RT G ln = A
(ii) Pressure. This is particularly important if the number of moles produced are less
than the initial number of moles and the pressure is high. If the pressure is high we
also have to consider the real behaviour of gases and the use of fugacity.
(iii) The concentration or number of moles of reactants.
(iv) The presence of an inert compound.

(b)

STOICHIOMETRY:

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

ASSUMPTIONS:
Ideal gas phase reaction system / steady state / equilibrium is reached / no inert or dilutant
molecular species present in gas phase / carbon black as the product is present in a separate
solid phase and so does not contribute to the gas phase equilibrium balance.

REACTOR

Feedstock
Gas
Product
Gas
1 kmol CH
4
CH
4
?
H
2
?
T = 650C,
P = 1.0 atm
C (s)
12
BASIS OF CALCULATION:
1.0 kmol of methane. As this is the only component in the gas phase to the reactor this is also
the limiting reactant.

Let the fractional conversion of the limiting reactant at equilibrium be o kmols CH
4
(again
note from the basis of the calculation o s 1.0).

The mole fractions and partial pressures in the gas phase in the reactor vessel at equilibrium
are then given in the following table from the stoichiometric molar mass balance at
equilibrium of:

) (2 ) ( ) - (1
(g) H 2 (s) C (g) CH
2 4
o o o
+


Component kmols mole fraction
y
i

CH
4
(1 o) |
.
|

\
|
+

o
o
1
1

H
2
2o |
.
|

\
|
+o
o
1
2

C(s)
Discounted
as solid phase
-
TOTAL 1 + o y
i
= 1.0

The design performance equation for an ideal gas phase reaction system at equilibrium for the
methane reaction is:

| |
1 2
1
2
) (
) (
4
2

(
(

= P
y
y
K
CH
H
P


For ideal gas,

| |
P
K RT G ln = A

atm 243 . 4
) 273 650 ( 314 . 8
10 109 . 1
exp exp
4
=
|
|
.
|

\
|
+

=
|
.
|

\
| A
=
RT
G
K
P


Using the value of K
P
and the information in the table gives:

| | atm 1.0
1
1
1
2
atm 4.243
1
1
2
(
(
(
(

|
.
|

\
|
+

|
.
|

\
|
+
=
o
o
o
o


Note the pressure units must cancel as o is dimensionless.
13

2
2 2
1
4
) 1 )( 1 (
4
243 4
o
o
o o
o

=
+
= .

7175 . 0
243 . 4 4
243 . 4
=
+
= o

This is the fraction decomposed.

Substituting this value of o back into the functions in the table gives:

Component mole fraction
y
i

CH
4
164 . 0
1
1
=
|
.
|

\
|
+

o
o

H
2
836 . 0
1
2
=
|
.
|

\
|
+o
o

TOTAL y
i
= 1.0

c) Allowing for the inert nitrogen in the balance at equilibrium gives:

(1) ) (2 ) ( (1) ) - (1
(g) N (g) H 2 (s) C (g) N (g) CH
2 2 2 4
o o o
+ + +


Component kmols mole fraction
y
i

CH
4
(1 o) |
.
|

\
|
+

o
o
2
1

H
2
2o |
.
|

\
|
+o
o
2
2

N
2
1 |
.
|

\
|
+o 2
1

C(s)
Discounted
as solid phase
-
TOTAL 2 + o y
i
= 1.0

The design performance equation for an ideal gas phase reaction system at equilibrium for the
methane reaction is:

| |
1 2
1
2
) (
) (
4
2

(
(

= P
y
y
K
CH
H
P


Remember the N
2
is just an inert component and plays no part in the reaction.

Using the value of K
P
from before and the information in the table gives:
14

| | atm 1.0
2
1
2
2
atm 4.243
1
1
2
(
(
(
(

|
.
|

\
|
+

|
.
|

\
|
+
=
o
o
o
o


Note the pressure units must cancel as o is dimensionless.

2
2 2
2
4
) 1 )( 2 (
4
243 4
o o
o
o o
o

=
+
= .

2 2
4 ) 2 ( 243 4 o o o = .

2 2
9427 . 0 2 o o o =

0 2 9427 . 1
2
= +o o

7894 . 0 or 3041 . 1
9427 . 1 2
) 2 9427 . 1 4 ( 1 1
2
=

= o

Therefore the fraction decomposed is: 0.7894

Substituting this value of o back into the functions in the table gives:


Component kmols mole fraction
y
i

CH
4
(1 o)
076 . 0
2
1
=
|
.
|

\
|
+

o
o

H
2
2o
566 . 0
2
2
=
|
.
|

\
|
+o
o

N
2
1 359 . 0
2
1
=
|
.
|

\
|
+o

TOTAL 2 + o y
i
= 1.0











15
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
T
1

R
H -
K ln
o
p
+
|
.
|

\
|
(

A
=

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

R
S
constant
o
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

Answer:
a) Starting with | | constant
T
1

R
H -
K ln
o
p
+
|
.
|

\
|
(

A
= (1)
16
using
o o o
S T - H G A A = A (2)

and | |
P
o
K ln T R - G = A (3)

therefore from Eq (3):

| |
T R
G
- K ln
o
P
A
=

substituting into Eq. (1)

constant
T
1

R
H -

T R
G
-
o o
+
|
.
|

\
|
(

A
=
A


T R
H G -
constant
o o
A + A
=

but from Eq. (2):

o o o
H G - S T A + A = A

therefore:

T R
S T
constant
o
A
=

R
S
constant
o
A
=

and

| |
|
|
.
|

\
| A
+
|
.
|

\
|
(

A
=
R
S

T
1

R
H -
K ln
o o
p


b) Now need to calculate the magnitude of the reaction equilibrium constant K
P
at T = 600 K
from the Vant Hoff Isochore, namely:

| |
|
|
.
|

\
| A
+
|
.
|

\
|
(

A
=
R
S

T
1

R
H -
K ln
o o
p


Note the
o
f
H A and
o
f
S A data are given for T = 600 K.

Hence at T = 600 K for stoichiometric amounts in kmols:


A A = A
o
T at REACTANTS f
o
T at PRODUCTS f
o
T R
H - H H
17
(-242200)] (1) (52280) [(1) - (-235300)] [(1) H
o
K 600 R
+ = A

kmol / kJ 45380 - H
o
K 600 R
= A

and


A A = A
o
T at REACTANTS f
o
T at PRODUCTS f
o
T R
S - S S

(188.7)] (1) (219.5) [(1) - (282.0)] [(1) S
o
K 600 R
+ = A

K) kmol /( kJ 126.2 - S
o
K 600 R
= A

Then the reaction equilibrium constant is (note units):

| |
|
|
.
|

\
|
+
|
.
|

\
|
(

+
=
K) (kmol / kJ 8.314
K) (kmol / kJ 126.2 -

K 600
1

K) (kmol / kJ 8.314
kmol / kJ 45380
K ln
p


| | 6.082 - 15.179 - 9.097 K ln
p
= =

-1 -3 082 . 6
p
atm 10 2.283 e K = =



As convert K
P
to m
2
N
-1
:

1 - 2 8 -
2 - 5
-3
p
N m 10 2.254
m N 10 1.013
atm 1

atm 1
10 2.283
K =
|
.
|

\
|

|
|
.
|

\
|
=

c) To report the value of the Gibbs Free Energy change of the reaction (see notes Section 1)
the Vant Hoff Isotherm is used (as AG = 0 at equilibrium):

| |
P
o
K ln T R - G = A

then,
| | atm 10 2.283 ln K) (600
K kmol
kJ 8.314
- G
3 - o

|
.
|

\
|
= A

kmol / kJ 340 30 G
o
+ = A

d) For the gas phase hydration of ethylene to ethanol, transfer the information to a diagram.
DIAGRAM






18


STOICHIOMETRY:

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

ASSUMPTIONS:
Ideal gas phase reaction system / steady state / equilibrium is reached / no inert or dilutant
molecular species present in gas phase / liquid phase phosphoric acid catalyst.

BASIS OF CALCULATION:
1.0 kmol of ethylene as limiting reactant.

In this system, an equimolar composition of the two reactants in the feedstock gas stream is
equivalent to the stoichiometric amounts or ratio, and so either the steam or the ethylene is a
limiting reactant. In this case, the equilibrium conversion yield is to be specified in terms of
the ethylene hence C
2
H
4
is used as the basis of calculation.

Let the fractional conversion of the ethylene limiting reactant at equilibrium, o kmols C
2
H
4

(again note from the basis of the calculation o s 1.0).

The mole fractions and partial pressures in the gas phase in the reactor vessel at equilibrium
are then given in the following table using the stoichiometric molar mass balance at
equilibrium of:

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


Component kmols mole fraction
y
i

partial pressure
p
i

C
2
H
4
(1 - o)
|
.
|

\
|
o
o
- 2
- 1

T
P
- 2
- 1
|
.
|

\
|
o
o

H
2
O (1 - o)
|
.
|

\
|
o
o
- 2
- 1

T
P
- 2
- 1
|
.
|

\
|
o
o

C
2
H
5
OH (o)
|
.
|

\
|
o
o
- 2

T
P
- 2
|
.
|

\
|
o
o

TOTAL (2 - o) y
i
= 1.0 p
i
= P
T


The design performance equation for an ideal gas phase reaction system at equilibrium is for
the ethylene hydration reaction system:
GAS PHASE
CATALYTIC
REACTOR
Feedstock
Gas
Product
Gas
C
2
H
4
1.0 kmol
H
2
O 1.0 kmol
mole %
C
2
H
5
OH
C2H
4

H
2
O
T
S
= 600 K
P
T
= 70.0 atm
19
| |
1 - 1 1
T 1
O H
1
H C
1
OH H C
p
P
) (y ) (y
) (y
K
2 4 2
5 2

(
(

=

Using the information in the diagram, the calculated value of K
P
and the functions in the table
to find the value of the equilibrium fractional conversion, o, giving:

(

(
(
(
(

|
.
|

\
|
o
o
|
.
|

\
|
o
o
|
.
|

\
|
o
o
=
atm 70.0
1

- 2
- 1

- 2
- 1
- 2
atm 10 2.283
1 1
1
1 - 3 -


Again check the pressure units cancel, as function must be dimensionless:

(

o
o o
=
2
3 -
) - (1
) - (2
70 10 2.283

) - (2 ) - (1 (0.160)
2
o o = o

2 2
- 2 1) 2 - ( (0.160) o o = + o o

0 0.160 2.320 - 1.160
2
= + o o

The roots to the quadratic function a x
2
+ bx + c = 0 are:

a 2
ac 4 - b b -
x
2

=

(1.160) 2
(0.160) (1.160) 4 - 2.320 2.320

2

= o

2.320
2.1541 2.320

= o

Then

solution Valid root Invalid
0715 . 0 or 928 . 1 + = o + = o


Therefore the yield of ethanol from ethylene is:

4 2 5 2
H C kmol / OH H C kmols 0.0715
1.00
0.0715

feed in ethylene
product in ethanol
= =


20
e) Using the results of this analysis of the gas phase ethylene hydration reaction system to
determine how the system operational temperature T and pressure P
T
affect the magnitude of
the reaction equilibrium constant K
P
and hence yield of ethanol on ethylene. The enthalpy
change AH
R
of this reaction system in part (b) is -45 380 kJ / kmol C
2
H
4
and so the reaction is
exothermic. Consequently, the magnitude of K
P
decreases with increasing temperature (see
Le Chateliers Principle in Section 1 of notes) and the equilibrium conversion yield decreases
with increasing temperature at constant pressure (note: do not forget effect of temperature on
kinetic rates).

From the design performance equation for the reaction equilibrium, namely:

(

(
(

=
T
1
O H
1
H C
1
OH H C
p
P
1

) (y ) (y
) (y
K
2 4 2
5 2


then,

| || |
(
(

=
1
O H
1
H C
1
OH H C
T p
) (y ) (y
) (y
P K
2 4 2
5 2


Hence, increasing the system operational pressure increases the effective magnitude of K
P

and the equilibrium conversion yield increases with pressure at constant temperature.