CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013

1
CHEMICAL REACTION
EQUILIBRIA
Raw materials are transformed into products by chemical reaction.
A chemical equilibrium has been established when a chemical reaction
reaches a state where the concentrations of reactants and products
remain constant.
At equilibrium, the rate of the forward reaction is equal to the rate of the
reverse reaction.
Both the rate and the equilibrium conversion of a chemical reaction
depend on the temperature, pressure and composition of reactants.
The study of thermodynamics give the equilibrium values. The study of
rate gives speed of reaching those values.
The purpose of this chapter is to determine the effect of temperature,
pressure and initial composition on the equilibrium conversion of chemical
reactions.

2
THE REACTION COORDINATE
APPLICATION OF EQUILIBRIUM CRITERIA
TO CHEMICAL REACTIONS
THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT
EFFECT OF TEMPERATURE ON THE
EQUILIBRIUM CONSTANT
EVALUATION OF EQUILIBRIUM
CONSTANTS

3
For general chemical reaction


where is stoichiometric coefficient
A
i
is chemical formula.
v
i
is stoichiometric number, and it is
positive (+) for product negative (-) for reactant
Example:
the stoichiometric numbers are

The stoichiometric number for inert species is zero.
As the reaction in eq. (13.1) progresses, the changes in the numbers of moles of
species present are in direct proportion to the stoichiometric numbers. E.g. If 0.5
mol CH
4
disappears, 0.5 mol H
2
O also disappears; simultaneously 0.5 mol CO and
1.5 mol H
2
are formed.

4
4 2 2
3 CH H O CO H + +
4 2 2
1 1 1 3
CH H O CO H
v v v v = = = =
1 1 2 2 3 3 4 4
A A A A v v v v + + + +
i
v
(13.1)
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
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Applied to differential amount of reaction, this principle provides the equations:


The list continues to include all species. Comparison yields


All terms being equal, they can be identified collectively by a single quantity
representing an amount of reaction. A definition of dc is given by the equation:


The general relation connecting the differential change dn
i
with dc is therefore


c is called the reaction coordinate (also known as degree of reaction or extent of
reaction), characterizes the extent or degree to which a reaction has taken place.

3 1 2 4
1 2 3 4
...
dn dn dn dn
dc
v v v v
= = = =
5
( ) 1, 2, ..., N
i i
dn d i v c = =
(13.2)
(13.3)
3 2 1 1
2 1 3 1
etc.
dn dn dn dn
v v v v
= =
3 1 2 4
1 2 3 4
...
dn dn dn dn
v v v v
= = = =
Integration of eq. (13.3) from an initial unreacted state where c = 0 and n
i
= n
io
to a
state reached after an amount of reaction gives


or
Summation over all species yields


or
where

Thus the mole fractions y
i
of the species present are related to c by
6
0 i i i
i i i
n n n c v = = +

0
n n vc = +
0 0 i i i
i i i
n n n n v v

0
0
i i i
i
n n
y
n n
v c
vc
+
= =
+
(13.5)
0 0
i
i
n
i i
n
dn d
c
v c =
} }
( )
0
1, 2, ...,
i i i
n n i N v c = + = (13.4)
For a system in which the following reaction occurs,


assume there are present initially 2 mol CH
4
, 1 mol H
2
O, 1 mol CO and 4 mol H
2
.
Determine expressions for the mole fractions y
i
as functions of c.












4 2 2
3 CH H O CO H + +
7
Consider a vessel which initially contains only n
0
mol of water vapor. If
decomposition occurs according to the reaction,

find expressions which relate the number of moles and the mole fraction of each
chemical species to the reaction coordinate c.
Solution:
For the reaction,

Application of eq. (13.5) yields


The fractional decomposition of water vapor is


When n
0
= 1, c is directly related to the fractional decomposition of the water vapor.



8
0
0
i i i
i
n n
y
n n
v c
vc
+
= =
+
1
2 2 2 2
H O H O +
v = + + =
1 1
2 2
1 1
2 2 2
1
2 0
1 1 1
2 2 2 0 0 0
H O H O
n
y y y
n n n
c c c
c c c

= = =
+ + +
( )
2 0 0 0
0 0 0
H O
n n n n
n n n
c c
= =
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
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For multireaction, v
i,j
designates the stoichiometric number of species i in reaction j.
The general relation, eq. (13.3) becomes


Integration from n
i
= n
i0
and c
j
= 0 to n
i
and c
j
gives

Summing over all species yields


The definition of a total stoichiometric number v for a single reaction has
its counterpart here in the definition:

Combination of this last equation with eq. (13.6) gives the mole fraction


9
( )
,
1, 2, ...,
i i j j
j
dn d i N v c = =

( )
0 ,
1, 2, ...,
i i i j j
j
n n i N v c = + =
(13.6)
0 , 0 , i i j j i j j
i i j j i
n n n v c v c
| |
= + = +
|
\ .

( ) i i
v

, 0
thus
j i j j j
i j
n n v v v c = +

( )
0 ,
0
1, 2, ...,
i i j j j
i
j j j
n
y i N
n
v c
v c
+
= =
+

(13.7)
i = CH
4
H
2
O CO CO
2
H
2
j v
j
1 -1 -1 1 0 3 2
2 -1 -2 0 1 4 2
10
Consider a system in which the following reactions occur:



where the numbers (1) and (2) indicate the value of j, the reaction index. If there
are present initially 2 mol CH
4
and 3 mol H
2
O, determine expressions for the y
i
as
functions of c
1
and c
2
.

Solution:
The stoichiometric numbers v
i,j
can be arrayed as follows:

( )
( )
4 2 2
4 2 2 2
3 1
2 4 2
CH H O CO H
CH H O CO H
+ +
+ +
Application of eq. (13.7) gives
11
( )
0 ,
0
1, 2, ...,
i i j j j
i
j j j
n
y i N
n
v c
v c
+
= =
+

4
2 2
2
1 2 1
1 2 1 2
1 2 2
1 2 1 2
1 2
1 2
2
5 2 2 5 2 2
3 2
5 2 2 5 2 2
3 4
5 2 2
CH CO
H O CO
H
y y
y y
y
c c c
c c c c
c c c
c c c c
c c
c c

= =
+ + + +

= =
+ + + +
+
=
+ +
The Gibbs function serves as variable that determines whether a given chemical
change is thermodynamically possible.




In a spontaneous change, Gibbs energy always decreases and never increases. The
physical meaning of AG is that it tells how far the free energy of the system has
changed from G
o
of the pure reactants.
Composition of a chemical reaction system will tend to change in a
direction that brings it closer to its equilibrium composition. Once this
equilibrium composition has been attained, no further change in the quantities of
the components will occur.


12
AG<0 Reaction can spontaneously proceed to the right: AB
AG>0 Reaction can spontaneously proceed to the left: AB
AG=0 The reaction is at equilibrium; the quantities of A and B will not change
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
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For a reaction A B, the standard free energy of
the products (point 2) is smaller than that of the
reactants (point 1), so the reaction will take place
spontaneously.
This does not mean that each mole of pure A will
be converted into one mole of pure B. For
reactions in which products and reactants occupy
a single phase (gas or solution), the meaning of
spontaneous is that the equilibrium composition
will correspond to an extent of reaction greater
than 0.5 but smaller than unity.
As the reaction proceeds to the right, the
composition changes, and AG begins to fall.When
the composition reaches point 3, AG reaches its
minimum value and further reaction would
cause it to rise. But because free energy can only
decrease but never decrease, this does not
happen. The composition of the system
remains permanently at its equilibrium
value.
13
Fig. 1 Spontaneous reaction (AG<0)
Fig. 2 Non-spontaneous reaction (AG>0)
Fig. 13.1 shows the relation of G
t
and c. The arrows along the curve indicate the
directions of changes in (G
t
)
T,P
. The reaction coordinate, c has its equilibrium value c
e

at the minimum of the curve.
This figure (also the two previous figure) indicates two distinctive features of
the equilibrium state for given T and P,
Total Gibbs energy G
t
is a minimum.
Its differential is zero


14
(For a single chemical reaction)
( )
,
0
t
T P
dG =
reactants
products
Forward reaction
Equation (11.2) provides an expression for the total differential of the Gibbs energy:


If changes in the mole numbers n
i
occur as the result of a single chemical reaction in
a closed system, then by eq. (13.3) each dn
i
may be replaced by the product v
i
dc. Eq.
(11.2) then becomes


Because nG is a state function, the right side of this equation is an exact differential
expression,


The quantity represents, in general, the rate of change of total Gibbs energy
of the system with respect to the reaction coordinate at constant T and P.
( ) ( ) ( )
i i
i
d nG nV dP nS dT d v c = +

15
( ) ( ) ( )
i i
i
d nG nV dP nS dT dn = +

(11.2)
( ) ( )
,
,
t
i i
i T P
T P
G nG
v
c c
( c c (
= = (
(
c c (

i i
i
v

Fig. 13.1 shows that this quantity is zero at the equilibrium state. A criterion of
chemical reaction equilibrium is therefore


Recall the definition of the fugacity of a species in solution:


In addition, eq. (11.31) may be written for pure species i in its standard state at the
same temperature:


The difference between these two equations is

16
0
i i
i
v =
(13.8)
( )

ln
i i i
T RT f = I + (11.46)
( ) ln
o o
i i i
G T RT f = I +

ln
o i
i i o
i
f
G RT
f
= (13.9)
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
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Combining eq. (13.8) with eq. (13.9) to eliminate
i
gives for the equilibrium state
of a chemical reaction:


or


or

where H
i
signifies the product over all species i.
In exponential form, this equation becomes


where the definition of K and its logarithm are given by

( )

ln 0
i
o o
i i i i
i i
G RT f f
v
v + =

17
( )

ln 0
o o
i i i i
i
G RT f f v
(
+ =

( )

ln
o
i i i i
G
o
RT i i
i
f f
v v

=
[
( )

i
o
i i
i
f f K
v
=
[ (13.10)
exp
ln
o
o
G
K
RT
G
K
RT
| A |

|
\ .
A
=
(13.11a)
(13.11b)
Also by definition,

G
i
o
, AG
o
and K are functions of temperature.




The function AG
o

i
v
i
G
i
o
in eq. (13.12) is the difference between the Gibbs energies
of the products and reactants when each is in its standard state as a pure substance
at the standard state pressure, but at the system temperature.
Other standard property changes of reaction are similarly defined. For general
property M:


The relation between the standard heat of reaction and the standard Gibbs energy
change of reaction is


18
o o
i i i
G G v A

(13.12)
K is called the equilibrium constant for the reaction;
i
v
i
G
i
o
,
represented by AG
o
, is called the standard Gibbs-energy change of
reaction.
o o
i i
i
M M v A

( )
2
o
o
d G RT
H RT
dT
A
A = (13.13)
Because the standard state temperature is that of the equilibrium mixture, the
standard property changes of reaction, such as AG
o
and AH
o
, vary with the
equilibrium temperature.
The dependence of AG
o
on T is given by eq. (13.13), which may be rewritten as



In view of eq. (13.11b), this becomes



If AH
o
is negative, i.e., if the reaction is exothermic, the equilibrium constant
decreases as the temperature increases. K increases with T for endothermic
reaction.
If AH
o
is assumed independent of T, integration of eq. (13.14) from T to T leads to
the simple result:


A plot of ln K vs. the reciprocal of absolute temperature is a
straight line.


19
( )
2
o o
d G RT H
dT RT
A A
=
2
ln
o
d K H
dT RT
A
= (13.14)
' '
1 1
ln
o
K H
K R T T
A | |
=
|
\ .
(13.15)

20
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
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Effect of temperature on equilibrium constant is based on the definition of the
Gibbs energy at standard state:

Multiply by v
i
and summation over all species gives



As a result of the definition of a standard property change of reaction, this reduces
to

The standard heat of reaction is related to temperature:


The temperature dependence of the standard entropy change of reaction is:


Multiply by v
i
and summation over all species gives




21
o o o
G H T S A = A A (13.16)
o o o
i i i
G H TS =
o o o
i i i i i i
i i i
G H T S v v v =

0
0
o
T
p o o
T
C
H H R dT
R
A
A = A +
} (4.18)
i
o o
i P
dT
dS C
T
=
o o
P
dT
d S C
T
A = A
Integration gives


where AS
o
and AS
0
o
are the standard entropy changes of reaction at temperature T
and at reference temperature T
0
.
Eqs. (13.16), (4.18) and (13.17) are combined to yield


However,


Hence,


Finally, division by RT yields




( )
0 0
0 0 0
0
o o
T T
o o o o P P
T T
T C C
G H H G R dT RT dT
T R R
A A
A = A A A +
} }
22
0
0
o
T
o o P
T
C dT
S S R
R T
A
A = A +
}
(13.17)
0
0 0
0 0
0
1
o o o o o o
T T
P P
T T
G H H G C C dT
dT
RT RT RT T R R T
A A A A A A
= + +
} }
0 0
0 0
o o
T T
o o o P P
T T
C C
G H R dT T S RT dT
R R
A A
A = A + A
} }
0 0
0
0
o o
o
H G
S
T
A A
A =
(13.18)
( )
0
2
0 0 2 2
0
1
ln 1
2
o
T
P
T
C dT D
A BT CT
R T T
t
t t
t
( | | A A + | |
= A + A + A +
( | |
\ .
\ .
}
23
The first integral of eq. (13.18) is



where

OR



The second integral of eq. (13.18) is



OR
( ) ( ) ( ) ( )
0
2 2 3 3
0 0 0
0
1
1 1 1
2 3
o
T
P
T
C B C D
dT A T T T
R T
t
t t t
t
A A A A | |
= A + + +
|
\ .
}
(13.19)
0
T
T
t
(4.19)
( ) ( )
0
2 2
0 0 2 2
0
1 1
ln
2 2
T o
P
o T
C dT T C D
A B T T T T
R T T T T
| | | | A A A
= A + A +
| |
\ . \ .
}
( )( ) ( ) ( )
0
2 2 3 3
0 0
1 1
2 3
o
T
P
o
T
o
C B C
dT A T T T T T T D
R T T
| | A A A
= A + + A
|
\ .
}
AG
o
/RT(= - ln K) as given in eq. (13.18) is readily calculated at any temperature from
the standard heat of reaction and the standard Gibbs energy change of reaction at a
reference temperature (usually 298.15 K).
Factor K may be organized into three terms:





24
0 1 2
K K KK =
0
0
0
exp
o
G
K
RT
| | A

|
\ .
(13.21)
0 0
1
0
exp 1
o
H T
K
RT T
( A | |

| (
\ .

0 0
2
1
exp
o o
T T
P P
T T
C C dT
K dT
T R R T
| A A |
+
|
\ .
} }
(13.22)
(13.23)
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
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EXAMPLE 13.4
Calculate the equilibrium constant for the vapor phase hydration of ethylene at
145
o
C (418.15 K) and at 320
o
C (593.15 K) from data given in App. C.

Solution:
The chemical reaction:


From Table C.1 and C.4:









25
( ) ( ) ( )
2 4 2 2 5
C H g H O g C H OH g +
v
i
A B (x10
-3
) C (x10
-6
) D (x10
5
) H
o
298
(J/mol)
G
o
298
(J/mol)
C
2
H
5
OH 1 3.518 21.001 -6.002 - -235100 -168490
C
2
H
4
-1 1.424 14.394 -4.392 - 52510 68460
H
2
O -1 3.470 1.450 - 0.121 -241818 -228572










For T = 418.15 K, values of integrals in eq. (13.18) are


Substitute into eq. (13.18) for a reference temperature of 298.15 K gives:


-1
298 ,298
8378 Jmol
o o
i i
i
G G v A = =

26
-1
298 ,298
45792 Jmol
o o
i i
i
H H v A = =

( ) ( )
0 0
23.121 . 4.19 0.0692 . 13.19
o o
T T
P P
T T
C C dT
dT eqn eqn
R R T
A A
= =
} }
( )( ) ( )( )
418.15
8378 45792 45792 23.121
0.0692 1.9356
8.314 298.15 8.314 418.15 418.15
o
G
RT
A +
= + + + =
-3
-6
5
-1.376
4.157 10
1.610 10
- 0.121 10
i i
i
i i
i
i i
i
i i
i
A A
B B
C C
D D
v
v
v
v
A = =
A = =
A = =
A = =

0
0 0
0 0
0
1
o o o o o o
T T
P P
T T
G H H G C C dT
dT
RT RT RT T R R T
A A A A A A
= + +
} }
(13.18)
For T = 593.15 K,








Finally, by eq. (13.11b)



At 418.15 K, ln K = -1.9356 and K = 1.443 x 10
-1
At 593.15 K, ln K = -5.8286 and K = 2.942 x 10
-3

Alternative solution by using eq. (13.21), (13.22) and (13.23).

0
0
22.632
0.0173
o
T
P
T
o
T
P
T
C
dT
R
C dT
R T
A
=
A
=
}
}
( )( ) ( )( )
593.15
8378 45792 45792 22.632
0.0173 5.8286
8.314 298.15 8.314 593.15 593.15
o
G
RT
A +
= + + =
27
ln
o
G
K
RT
A
=
RELATION OF EQUILIBRIUM
CONSTANTS TO COMPOSITION
EQUILIBRIUM CONVERSIONS FOR
SINGLE REACTIONS

28
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
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Gas phase reactions
The standard state for a gas is the ideal gas state of the pure gas at the standard
state pressure P
o
of 1 bar.
Because the fugacity of ideal gas is equal to its pressure, f
i
o
= P
o
for each species i.
Therefore for gas phase reactions and eq. (13.10) becomes



This eq. relates K to fugacities of the reacting species as they exist in the real
equilibrium mixture. These fugacities reflect the non-idealities of the equilibrium
mixture and are functions of temperature, pressure and composition.
The fugacity is related to the fugacity coefficient by eq. (11.52):
29
o o
i i i
f f f P =

i
i
o
i
f
K
P
v
| |
= |
\ .
[
(13.25)

i i i
f y P | =
( )

i
o
i i
i
f f K
v
=
[ (13.10)
Substitute into eq. (13.25) provides an equilibrium expression displaying the
pressure and the composition:



where and P
o
is the standard state pressure of 1 bar.
The y
i
s may be eliminated in favor of the equilibrium value of the reaction
coordinate c
e
. For fixed temperature eq. (13.26) relates c
e
to P. If P is specify, c
e
can
be solved. can be evaluated by using eq. (11.63 or 11.64).
If the equilibrium mixture is an ideal solution, then each becomes |
i
, then eq.
(13.26) becomes


Each |
i
for a pure species can be evaluated from a generalized correlation.
For pressure sufficiently low or temperatures sufficiently high, the equilibrium
mixture behaves essentially as an ideal gas. Each and eq. (13.26) reduces to:



( )
i
i i o
i
P
y K
P
v
v
|

| |
=
|
\ .
[
30
( )

i
i i o
i
P
y K
P
v
v
|

| |
=
|
\ .
[ (13.26)

i
|
(13.27)

1
i
| =
( )
i
i o
i
P
y K
P
v
v

| |
=
|
\ .
[
(13.28)
v v
i i

i
|
Some conclusions based on eq. (13.28) that are true in general:
According to eq. (13.14), the effect of temperature on the equilibrium constant K
is determined by the sign of AH
o
.



When AH
o
is positive, i.e., when the standard reaction is endothermic, an increase
in T results in an increase in K. Eq. (13.28) shows that an increase in K at constant
P results in an increase in H
i
(y
i
)
vi
; this implies a shift of the reaction to the right
and an increase in c
e
.
When AH
o
is negative, i.e., when the standard reaction is exothermic, an increase
in T causes a decrease in K and a decrease in H
i
(y
i
)
vi
at constant P.This implies a
shift of reaction to the left and a decrease in c
e
.
If the total stoichiometric number v (
i
v
i
) is negative, eq. (13.28) shows that an
increase in P at constant T causes an increase in H
i
(y
i
)
vi
, implying a shift
of the reaction to the right and an increse in c
e
.
If v is positive, an increase in P at constant T causes a decrease in H
i
(y
i
)
vi
,
implying a shift of the reaction to the left and a decrease in c
e
.
31
2
ln
o
d K H
dT RT
A
= (13.14)
( )
i
i o
i
P
y K
P
v
v

| |
=
|
\ .
[
(13.28)
Liquid phase reactions
For a reaction occurring in the liquid phase,


Standard state for liquid f
i
o
is the fugacity of pure liquid i at the temperature of the
system and at 1 bar.
According to eq. (11.90),


The fugacity ratio can be expressed as



Because the fugacities of liquids are weak function of pressure, the ratio f
i
/f
i
o
is often
taken as unity.
For pure liquid i, eq. (11.31) is written for temperature T and pressure P, and for the
same temperature T but for standard state pressure P
o
.




32
( )

i
o
i i
i
f f K
v
=
[ (13.10)

i i i i
f x f =

i i i i i
i i o o o
i i i
f x f f
x
f f f

| |
= =
|
\ .
(13.29)
( )
( )
ln
ln
i i i
o o
i i i
G T RT f
G T RT f
I +
I +

i
i
i i
f
x f
(11.90)
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
9
The difference between these two equations is


Integration of eq. (6.10) at constant T for the change of state of pure liquid i from P
o

to P yields

As a result,


Because V
i
changes little with pressure for liquids (and solids), integration from P
o
to
P gives


With eq. (13.29) and (13.30), eq. (13.10) may be written as

33
ln
o i
i i o
i
f
G G RT
f
=
o
P
o
i i i
P
G G VdP =
}
ln
o
P
i
i o
P
i
f
RT VdP
f
=
}
( )
ln
o
i i
o
i
V P P f
f RT

= (13.30)
( )
( )
( ) exp
i
o
i i i i
i i
P P
x K V
RT
v
v
(
= (
(
[ (13.31)
Except for high pressure, the exponential term is close to unity and may be omitted.
Then,


If the equilibrium mixture is an ideal solution, then
i
is unity and eq. (13.32)
becomes

34
( )
i
i i
i
x K
v
=
[ (13.32)
( )
i
i
i
x K
v
=
[
(13.33)
EXAMPLE 13.5

A water gas shift reaction,


is carried out under the different sets of conditions described below. Calculate the
fraction of steam reacted in each case. Assume the mixture behaves as an ideal gas.

35
( ) ( ) ( ) ( )
2 2 2
CO g H O g CO g H g + +
(a) The reactants consist of 1 mol of H
2
O vapor and 1 mol of CO. The
temperature is 1100 K and the pressure is 1 bar.
For the given reaction at 1100 K, 10
4
/T = 9.05, and from Figure 13.2, ln K = 0
and K = 1.

Because the reaction mixture is an ideal gas, eq. (13.28) applies





By eq. (13.5),



Substitute into eq. (A) gives



Therefore the fraction of the steam that reacts is
36
1 1 1 1 0
i i
v v = = + =

( ) ( ) ( ) ( ) ( )
2 2 2
2 2
2
0
1 1 1 1 1
1
1
1
CO H O CO H
H CO
CO H O
bar
y y y y
bar
y y
y y
| |
= |
\ .
= (A)
2 2 2
1 1
2 2 2 2
e e e e
CO H O CO H
y y y y
c c c c
= = = =
( )
2
e 2
1 or 0.5
1
e
e
c
c
c
= =

( )
i
i o
i
P
y K
P
v
v

| |
= |
\ .
[
0
0
i i i
i
n n
y
n n
v c
vc
+
= =
+
( )
2 2
2
1 1
0.5
1
oH O H O
oH O
n n
n
c
c

= = =
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
10
(b) Same as (a) except that the pressure is 10 bar.
(c) Same as (a) except that 2 mol of N
2
is included in the reactants.
(d) The reactants are 2 mol of H
2
O and 1 mol of CO. Other conditions are the same
as in (a).
(e) The reactants are 1 mol of H
2
O and 2 mol of CO. Other conditions are the same
as in (a).
(f) The initial mixture consists of 1 mol of H
2
O, 1 mol CO and 1 mol of CO
2
. Other
conditions are the same as in (a).
(g) Same as (a) except that the temperature is 1650 K.





37
Estimate the maximum conversion of ethylene to ethanol by vapor-phase hydration
at 250
o
C (523.15 K) and 35 bar for an initial steam to ethylene ratio of 5. Assume
the reaction mixture is an ideal solution.

Solution:
The calculation of K for this reaction is treated in Example 13.4.
At T = 523.15 K, K = 10.02 x 10
-3
For ideal solution,


Because this equation becomes





38
( )
i
i i o
i
P
y K
P
v
v
|

| |
=
|
\ .
[
v v = =

1 1 1 1
i i
(13.27)
( ) ( )
2 4 2 4 2 2
3
10.02 10
EtOH EtOH
o
C H C H H O H O
y P
A
y y P
|
| |
| |
=
|
\ .
Fugacity coefficients are evaluated by eq. (11.68).





The results are summarized in the following table:





Substitute values of |
i
and P = 35 bar into eqn. (A) gives:
39
T
c
/K P
c
/bar e
i
Tr
i
Pr
i
B
0
B
1
|
i
C
2
H
4
282.3 50.40 0.087 1.853 0.694 -0.074 0.126 0.977
H
2
O 647.1 220.55 0.345 0.808 0.159 -0.511 -0.281 0.887
EtOH 513.9 61.48 0.645 1.018 0.569 -0.327 -0.021 0.827
( ) ( )
0 1 0 1
ln or exp
r r
r r
P P
B B B B
T T
| e | e
(
= + = +
(

0 1
1.6 4.2
0.422 0.172
0.083 and 0.139
r r
B B
T T
= =
( ) ( )
( )
( ) ( )
2 4 2
3
0.997 0.887 35
10.02 10 0.367
0.827 1
EtOH
C H H O
y
B
y y
| |
= =
|
\ .
( ) ( )
2 4 2 4 2 2
3
10.02 10
EtOH EtOH
o
C H C H H O H O
y P
A
y y P
|
| |
| |
=
|
\ .
By eqn. (13.5),


Substitute these into eqn. (B) yields:



The solution for the smaller root is c
e
= 0.233. Therefore the maximum conversion
of ethylene to ethanol is

40
2 4 2
1 5
6 6 6
e e e
C H H O EtOH
e e e
y y y
c c c
c c c

= = =

( )
( ) ( )
2
6
0.367 6 1.342 0
5 1
e e
e e
e e
or
c c
c c
c c

= + =

( )
2 4 2 4
2 4
1 1
0.233 23.3%
1
oC H C H
oC H
n n
n
c
c

= = = =
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
11
In a laboratory investigation, acetylene is catalytically hydrogenated to ethylene at
1120
o
C (1393.15 K) and 1 bar. If the feed is an equimolar mixture of acetylene and
hydrogen, what is the composition of the product stream at equilibrium?

Solution:
The required reaction is obtained by addition of the two formation reactions
written as follows:



The sum of reactions (I) and (II) is the hydrogenation reaction:


Also,
By eq. (13.11b),


41
( )
( )
2 2 2
2 2 4
2 I
2 2 II
C H C H
C H C H
+
+
2 2 2 2 4
C H H C H +
o o
o
I II
G G G A = A + A
ln ln ln
I II I II
RT K RT K RT K or K K K = =
Data for both reactions (I) and (II) are given by Fig. 13.2. For 1120
o
C (1393.15 K),
10
4
/T = 7.18, the following values are read from the graph:



Therefore, K = K
I
K
II
= 1.0
At this temperature and pressure of 1 bar, assume ideal gases.
By eq. (13.28),



On the basis of one mole initially of each reactant, eq. (13.5) gives


Therefore,


The smaller root of this quadratic expression is c
e
= 0.293.



42
5
6
ln 12.9 4.0 10
ln 12.9 2.5 10
I I
II II
K K
K K

= =
= =
2 4
2 2 2
1
C H
H C H
y
y y
=
2 2 2 2 4
1
and
2 2
e e
H C H C H
e e
y y y
c c
c c

= = =

( )
( )
2
2
1
1
e e
e
c c
c

( )
i
i o
i
P
y K
P
v
v

| |
=
|
\ .
[
The equilibrium composition of the product gas is then
43
2 2 2 2 4
1 0.293 0.293
0.414 and 0.172
2 0.293 2 0.293
H C H C H
y y y

= = = = =
Acetic acid is esterified in the liquid phase with ethanol at 100
o
C (373.15 K) and
atmospheric pressure to produce ethyl acetate and water according to the
reaction:


If initially there is one mole each of acetic acid and ethanol, estimate the mole
fraction of ethyl acetate in the reacting mixture at equilibrium.

Solution:
44
( ) ( ) ( ) ( )
3 2 5 3 2 5 2
CH COOH l C H OH l CH COOC H l H O l + +
AH
o
298
(J)

AG
o
298
(J)

CH
3
COOC
2
H
5
-480 000 -332 000
H
2
O -285 830 -237 130
CH
3
COOH -484 500 -389 900
C
2
H
5
OH -277 690 -174 780
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/16/2013
12
By eq. (13.11b),





For small temperature change from 298.15 K to 373.15 K, eq. (13.15) is adequate
for estimation of K. Therefore,




or

and

45
( )( ) ( )( ) ( )( ) ( )( )
( )( ) ( )( ) ( )( ) ( )( )
298
298
1 480000 1 285830 1 484500 1 277690 3640 J
1 332200 1 237130 1 389900 1 174780 4650 J
o o
i i i
o o
i i i
H H
G G
v
v
A =
= + + + =
A =
= + + + =

( )( )
298
298 298
4650
ln 1.8759 or 6.5266
8.314 298.15
o
G
K K
RT
A
= = = =
373 298
298
1 1
ln
373.15 298.15
o
K H
K R
A | |
=
|
\ .
373
3640 1 1
ln 0.2951
6.5266 8.314 373.15 298.15
K | |
= =
|
\ .
( )( )
373
6.5266 0.7444 4.8586 K = =
For the given reaction, eq. (13.5), with x replacing y, yields


Because the pressure is low, eq. (13.32) is applicable. In the absence of data for
activity coefficients, assume the reacting species form an ideal solution. In this case
eq. (13.33) is employed, giving





Solution yields
46
2
1
2 2
e e
AcH EtOH EtAc H O
x x x x
c c
= = = =
2
2
4.8586
1
EtAc H O
AcH EtOH
e
e
x x
K
x x
c
c
=
| |
=
|

\ .
0.6879 and 0.6879/ 2 0.344
e EtAc
x c = = =
( )
i
i
i
x K
v
=
[ (13.33)
Smith, J.M., Van Ness, H.C., and Abbott, M.M. 2005. Introduction to Chemical
Engineering Thermodynamics. Seventh Edition. Mc Graw-Hill.
http://www.chem1.com/acad/webtext/chemeq/Eq-01.html#SEC1
http://www.chem1.com/acad/webtext/thermeq/TE4.html
http://www.chem1.com/acad/webtext/thermeq/TE5.html


47
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303