PURPOSE

OF THIS CHAPTER
To determine the effect of of temperature, pressure and initial composition on the
equilibrium conversions of chemical reaction.

Example
The rate of oxidation of sulfur dioxide to sulfur trioxide catalyzed by vanadium pentoxide
increases at higher temperature.
However, the equilibrium conversion falls as temperature rises, decreasing from 90% at
520oC to 50% at 680oC
These values represent maximum possible conversion regardless of catalyst or reaction
rate.

CONCLUSION
Both the equilibrium and rate must be considered in the exploitation of chemical
reactions for commercial purposes.

Reaction is from where Chemical Engineers get
Derived Chemicals from Feed Stock (raw
material)
Examples of reactions:
Why is chemical reaction so important to
chemical engineers ?
1. Production of Methanol from Carbon Monoxide and Hydrogen
CO (g) + 2H
2
(g) = CH
3
OH (g)
2. Fischer Tropsch Synthesis
x CO (g) + y H
2
(g) = Hydrocarbons
Chemical Reaction
Kinetics - reaction rate
Equilibria - extent of reaction
Composition
Catalyst
Temperature Pressure
we will focus here !
parameters
The difference between chemical reaction kinetics and the
chemical reaction equilibrium
To sum it all .
Reaction Equilibrium
A measure to indicate the extent of reaction
especially for reversible reaction.
Combining both concept (reaction kinetic and equlibrium).
Indicate the speed of a reaction system achieving
its equilibrium which will be the end state.
It is worth looking at the thermodynamics of chemical equilibrium before
moving over to look at its kinetics.
Forward Reaction
Reverse Reaction
CO (g) + H
2
O (g) CO
2
(g) + H
2
(g)
On a macroscopic view, the reaction will be seemed as if it has
achieved a final static condition.

In actual fact, at microscopic level, the reaction still proceeds but the
forward and the reverse reaction have balanced each other in term of
the speed and therefore no net change could be viewed.
The reaction coordinate
Consider the following reaction equation .
........ ..... + + + + nN mM bB aA
The equation can be written in general form as
u
a
A + u
b
B + .. u
m
M + u
n
N +
where u is known as stoichiometric coefficient. It has a positive value for
product but negative value for reactant.
Iu
1
I A
1
+ Iu
2
I A
2
+ Iu
3
I A
3
+ ..... -----> Iu
n
I A
n
+ Iu
n+1
I A
n+1
+......
Reactant
Product
Applied to a differential amount of reaction, the equation below is derived:
dn
i
= u
i
dc
ui - stoichiometry numbers
An - chemical species
+ve for products
-ve for reactants
dn
1
= dn
2
= dn
3
= ......... = dc
Reaction coordinate-
Characterizes extent or degree
of reaction
as a general form (the differential change dn
i with
dc;
The general form of reaction structure could be written in the following equation;
u
1
u
2
u
3
(i = 1,2,..N)
by integrating the equation,
dn = u
i
dc
n
i
= n
io
+ u
i
c (i = 1,2,3 ...., n)
Summation over all species ;
n = E n
i
= E n
io
+ c E u
i
note : here c is expressed in mol
n
i
n
io
c
0
i i i
The mole fraction for each component at any time can be calculated using

vc
c v
+
+
= =
0
0
n
n
n
n
x or y
i i i
i i
where

=
i
i
v v
No. of moles initially for
component i
FOR SINGLE REACTION
SEE EXAMPLE 13.1
Consider a fuel cell based on the direct conversion of methanol to form hydrogen:
H
2
O(g) + CH
3
OH(g) CO
2
(g) + 3 H
2
(g)
The reaction is carried out at 60 C and low pressure, with a feed of twice as
much water as methanol. The equilibrium extent of reaction (c) is 0.87. How
many moles of H
2
can be produced per mole of CH
3
OH in the feed. What is the
mole fraction of H
2
.
Taking a basis of 1 mole CH
3
OH, the initial composition can be written as:
n
0

CH3OH
= 1 and n
0

H2O
= 2 with the number of moles of product = 0
Using the equation:
n
i
= n
io
+ u
i
c
n (CH3OH) = 1 - c
n (H2O) = 2 - c
n (CO2) = c
n (H2) = 3c
n (total) = 3 + 2c
Example
For a given c = 0.87,
n (H
2
) could be calculated i.e.,
n(H2) = 0.87 X 3 = 2.61 moles

The others can be calculated as well,

n(CH3OH) = 1 - 0.87 = 0.13 moles
n(H2O) = 2 - 0.87 = 1.13 moles
n(CO2) = 0.87 X 1 = 0.87 moles
The mole fraction of H
2
is calculated by ;
y (H2) = 2.61 / (3 + 2(0.87))
= 0.55
FOR MULTIPLE REACTION
See Example 13.3
dG = 0
T,P
Similar to physical equilibrium, the criteria for chemical reaction equilibrium from
thermodynamics point of view;
G
c
c
e
dG = 0
T,P
The total Gibbs Free Energy is at minimum
possible value at equilibrium condition
d(nG) = nV dP - nS dT + E
i
dn
i
i
Now, for physical equilibrium we can write ;
d(nG) = nV dP - nS dT + E v
i

i
dc
i
[ oG
T,P
/ oc ] E v = 0
i
i
i
= 0 at const. T,P
Equilibrium Criteria for Chemical Reaction
i
Similarly, for chemical reaction, the equation can be written as;
At equilibrium

= =
|
.
|

\
|
c
c
i
i i
P T
G
0
,
v
c
At equilibrium, we can write
Substituting for chemical potential,
0
0
ln
i
i
i i
f
f
RT + =

= + =
|
.
|

\
|
c
c
i
i
i
i i
P T
f
f
RT
G
0 ) ln (
0
0
,
v
c
We know that:
Simplify;

=
(

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

=
(

0
ln
Where signifies the product over all species i.
G
o
= standard Gibbs-energy change of reaction
- fixed for a given reaction once the temperature is established and is
independent of the equilibrium pressure and composition.

K = equilibrium constant
EFFECT OF TEMPERATURE ON THE
EQUILIBRIUM CONSTANT
Relation of K and enthalpy of reaction (Ah
R
)
From the following equation,
Equilibrium Constant
-RT ln K(T) = E v
i

i
o
= A g
R
o
We can derive,
dT
RT g d
dT
K d
R
) / ( ln
0
A
=
2
0 0 0
1 ) / (
RT
g
dT
g d
RT dT
RT g d
R R R
A
+
A
=
A
Since,
2
0 0
1 ln
RT
g
dT
g d
RT dT
K d
R R
A
+
A
=
Therefore,
From earlier developed relation,
0
0
R
P
R
s
T
g
A =
(

c
A c
Recall,

dG = (dG/dT)
P
dT + (dG/dP)
T
dP

= - s dT + v dP
Equilibrium Constant
From the definition;
0 0 0
R R R
s T h g A A = A
2
0 0
1 ln
RT
g
dT
g d
RT dT
K d
R R
A
+
A
=
0
0
r
P
r
s
T
g
A =
(

c
A c
We will obtain;
2
0
ln
RT
h
dT
K d
R
A
=
And the enthalpy of reaction can be calculated in similar manner to the Gibbs Free
energy for reaction but enthalpy of formation for the individual component is used.
E v
i
h
i
o
= E v
i
(Ah
f
o
)
i
= A h
R
o
Effect of Temperature on Equilibrium Constant
From the following equation,
we can develop the relation that give the temperature dependence
of the equilibrium constant by integrating the above relation.
Equilibrium Constant
2
0
ln
RT
h
dT
K d
R
A
=
=
If H
o
is independent of T
(constant)

If H
o
is varies with T
(dependent on T)

See example 13.4

Problem 13.3 and 13.11
Consider the following reaction equation,
Find the equilibrium constant at room temperature.
CH
4
O
(g)
H
2
CO
(g)
+ H
2

(g)


Ag
R
o
= E v
i
Ag
f
o
298
= - (-162.0 kJ/mol) + (-110 kJ/mol) + (0 kJ/mol)

i
o
= 52 kJ/mol
Refer to appendix data
K
298
= exp ( - Ag
f
o
298
/ RT ) = exp ( - 52,000 / 8.314 . 298.15)
K
298
= 7.64 X 10
-10
Equilibrium Constant
formaldehyde
To demonstrate the effect of temperature on K, consider the reaction system ;
H
2
O
(g)
+ CH
3
OH
(g)
CO
2(g)
+ 3 H
2(g)
Given K
298(25 C)
= 4.69
Similarly to Gibbs Free Energy, the enthalpy of reaction could be determined from
the enthalpy of formation,
Ah
0
rxn
= E v
i
(Ah
0
f

)
i
= 1 (Ah
0
f

)
CO2
+ 3 (Ah
0
f

)
H2
- 1 (Ah
0
f

)
H2O
-

1 (Ah
0
f

)
CH3OH

Ah
0
rxn
= (-393.51) + 3 (0) (-241.82) (- 200.66) = 48.97 (kJ/mol)
ln (K
2
/K
1
) = - ( Ah
R
/ R ) [ 1/T
2
- 1/T
1
]
From equation :
ln (K
333
/K
298
) = - ( Ah
R
/ R ) [ 1/333 - 1/298 ]
ln (K
333
/4.69) = - ( Ah
R
/ 8.314 ) [ 1/333 - 1/298 ]
K
333
= 37.44
Find the K value at 60
o
C
Equilibrium Constant
and C
pi
= [a
i
+ b
i
T + c
i
T
2
+ d
i
T
-2
]R
Therefore, enthalpy of reaction at temp T is ;
integrate the above relation and substitute in the equation below,
In actual fact, the heat capacity is a function of temperature.
yielding the eqn. in the next slide
Equilibrium Constant
i
P
P
i
C
dT
dh
=
(

}
+ A = A
T
T
P i
T
T
dT C v h h
i
0
0
0 0
} }
A
=
(

A
T
T
T
T
dT
T
T h
R RT
g
d
0 0
2
0 0
) ( 1
the constants a
i
, b
i
and c
i
are determined from Appendix 2,
Text Chem. Eng. Thermo. by J. Winnick.
Equilibrium Constant
( ) ( )
|
|
.
|

\
|

(

2
0
2
2
0
2
0
0 0
0
1 1
2 6 2
ln
1 1
T T
d v
T T
c v
T T
b v
T
T
a v
T T
F
i i i i i i
i i

+ + +
(

A
=
i i
i i i i
i i
T
d v
T
c v
T
b v
T a v T
R
h
F
0
3
0
2
0 0 0
1
3 2
0
and
This will give
) ln ln (
0
0
0
0
T
T
T T
K K
RT
g
RT
g
=
A

A
Equilibrium Constant
Example : We wish to produce formaldehyde, CH
2
O by the gas phase pyrolysis of
methanol, CH
3
OH according to;
CH
3
OH
(g)
CH
2
O
(g)
+ H
2(g)
a. What is the equilibrium constant at room temperature? Would you expect
an appreciable amount of product?
b. Consider the reaction at 600 C and 1 bar. What is the equilibrium
constant?
i. Assuming enthalpy of reaction is constant
ii. If enthalpy of reaction varies with temperature
Data : CH
3
OH CH
2
O H
2

Gibbs Free Energy at 298 -162 -110 0
(Formation)

Enthalpy of Formation at 298 -200.7 -116 0

V
i
-1 1 1

a
i
2.211 2.264 3.249
b
i
1.222X10
-2
7.022X10
-3
0.422X10
-3
c
i
-3.450X10
-6
-1.877X10
-6
-
d
i
- - 0.083X10
5
Equilibrium Constant
a. The equilibrium constant can be calculated from the Gibbs Free Energy of Reaction
Ag
R
o
= E v
i
Ag
f
o
298
= 1 ( -110) + 1 (0) 1 (-162.0) = 52 kJ/mol
-RT ln K(T) = E v
i

i
o
= A g
R
o
ln K = - 52,000 / RT = -52,000 / (8.314 X 298.15) = 7.64 X 10
-10
too small !
b. (i) To calculate K at 600 C, we need the enthalpy of reaction.
Ah
R
o
= E v
i
Ah
f
o
298
= 1 ( -116) + 1 (0) 1 (-200.7) = 84.7 kJ/mol
(

A
=
|
|
.
|

\
|
1 2
0
1
2
1 1
ln
T T R
h
K
K
R
K at 873 K = 4.63 produce noticeable amount of product
K = 2.07 x 10
-7
Equilibrium Constant
b. (ii) To calculate K at 600 C while accounting for changes in enthalpy of reaction.
( ) ( )
|
|
.
|

\
|

(

2
0
2
2
0
2
0
0 0
0
1 1
2 6 2
ln
1 1
T T
d v
T T
c v
T T
b v
T
T
a v
T T
F
i i i i i i
i i

+ + +
(

A
=
i i
i i i i
i i
T
d v
T
c v
T
b v
T a v T
R
h
F
0
3
0
2
0 0 0
1
3 2
0
and
Substitute all the value for the constants and taking T
0
= 298 and T = 873, the value
of - ln K at 873 could be obtained
) ln ln (
0
0
0
0
T
T
T T
K K
RT
g
RT
g
=
A

A
K (873 K) = 8.67
The assumption of constant enthalpy has caused significant error !
=
A

A
RT
g
RT
g
T T
0
0
0

RELATION OF EQUILIBRIUM CONSTANTS TO COMPOSITION
Gas-phase Reactions

The standard state for the gas is ideal gas state of the pure gas at the standard-state pressure
(P
o
) of 1 bar. Since



For ideal solution,
Each for a pure species can be evaluated from a generalized correlation once the equilibrium T and P
are specified .

For pressures sufficiently low or temperatures sufficiently high, the equilibrium mixture behaves essentially
as an ideal gas. In this case, = 1, so above equation becomes;


EXAMPLES
LIQUID-PHASE REACTIONS




Where, is the fugacity of pure liquid i at the temperature of system and at 1 bar.



The fugacity ratio can be expressed as:




By using equation 13.29 and 13.30, equation 13.10 can be written as;





At high pressure, the equation is reduced to;




If the equilibrium mixture is an ideal solution, = 1, therefore,















=
=
Some reactions of industrial importance are carried out at high pressure therefore
the impact causing from the non ideality behaviour becomes more apparent.
H ( a
i
)
v
i
= exp [ - E v
i

i
O

/ RT ] = K (T)
Recall the equation
The modification required here is to account for the | term.
a
i
= y
i
|
i
P instead of = y
i
P as used previously
Therefore,
K = H yi |i P
vi vi v
In order to determine |i, use method as given in earlier section on real gas.
= (z - 1)/P dP
P
ln |
P*
For high density region, use generalised compressibility chart
For low density region, use virial equation of lowest order
Equilibrium for Non-Ideal Gases Reaction System
i i
For our earlier example
in mol
fraction
x/(2x+1)
2x/(2x+1) (1-x)/(2x+1)
CO(g) + 2H2(g) <===> CH3OH(g)
Equilibrium composition x
2x
1-x
will now become
( )( )
v
P
y y
y
K
H CO
OH CH
(
(

=
2
2
3
( )( )
2
2
2 2
3 3
P
y y
y
K
H H CO CO
OH CH OH CH
(
(

=
| |
|
Example : Consider reaction to produce ammonia as below;
N2 + 3 H2 2 NH3 High pressure reaction and exothermic
( ) ( )
i
i
v
i i
v
i
P y a K
[ [
= = |
( )
( )( )
2
3
2
2 2 2 2
3 3
(
(

= P
y y
y
K
H H N N
NH NH
| |
|
Using the free energy data, calculation on equilibrium constant give K = 8.93 X 10
-6
Knowing K value then the composition could be calculated. However for non ideal
gas case the fugacity coefficient (|) has to be additionally determined.
One way of doing so is by calculating it based on pure component basis (Lewis
and Randall Rule)
(

=
RT
BP
i
e |
B = B
R
RT
c
/ P
c

B
R
= B
0
+ e B
1
|for ammonia calculated is 0.975
| for other components nearly 1
To calculate the equilibrium concentrations,
N2 + 3 H2 2 NH3
At equilibrium
x 3x 2(1-x) N total = 2 + 2x
( )
( )( )
2
3
2
2 2 2 2
3 3
(
(

= P
y y
y
K
H H N N
NH NH
| |
|
Substitute in
( )
( )( )
( ) ( )
( )( )
2
2 3
2
2
2 3
2
1 . 3 1 .
975 . 0 ). 2 2 (
. 3 .
). 2 2 (
2 2
3

=
(
(

= P
n x x
x
P
n x x
x
K
T T H N
NH
| |
|
( ) ( )
( )( )
2
2 3
2
6
1 . 3 1 .
975 . 0 ). 2 2 (
10 93 . 8

= P
n x x
x
T
y
(NH3)
= 0.144
y
(H2)
= 0.642
y
(N2)
= 0.214
Answer :
EQUILIBRIUM CONVERSIONS FOR
SINGLE REACTIONS
SINGLE-PHASE REACTIONS
For homogeneous system, and K is known, the calculation for phase composition at equilibrium is straightforward if the gas phase is assumed an ideal gas and liquid mixture is ideal solution.
For non-ideal solution, activity coefficient must be determined first.
See example 13.5 to 13.9.