Catalytic Reactions

Catalyst
Is a substance that affects the rate of a reaction but emerges from the
process unchanged.
Usually changes the reaction rate by promoting a different molecular
path (mechanism) for the reaction.

A catalyst changes only the rate of a reaction; it does not affect the
equilibrium.
Homogeneous Catalyzed Reactions
The rate of reaction for a homogeneous catalyzed system is the sum of the rates of both the
uncatalyzed and the catalyzed reactions,

1

2
+ +
 With reaction rates given as

= 1 , = 2
1 2

The overall rate of disappearance of substance A is then,

= 1 + 2 = (1 + 2 )

Rearranging we have,

= 1 + 2

Integrating the equation we get,


= 1 + 2
0

ln = 1 + 2 =

Where k= k1+k2CC
Autocatalytic Reaction
Autocatalytic reaction is a reaction in which one of the products of
reaction acts as a catalyst.
The simplest of such reaction is

+ +
The rate of reaction becomes

= =

Because the total number of moles of A and R remains unchanged as A is

consumed, we may write that at any time
0 = + = 0 + 0 =
Thus, CR=C0+CA and the rate equation becomes,

= (0 )

Rearranging,

=
(0 )
 1
= +
0 0

1 + + 0
= =
0 0 (0 )
Equating coefficients of every power of CA.
1 = 0
1
=
0
 0=
1
==
0
Substituting A and B to the equation,
1
+ =
0 0
Integrating
1 0
ln ln =
0 0 0 0
 1 (0 0 )
ln =
0 0 (0 )

1 0 (0 )
ln =
0 (0 0 )
Since CR=C0-CA and CR0= C0-CA0, the equation becomes

/0
ln = 0 = 0 + 0
/0
Example Problem:
Example Leyes and Othmer(Ind. Eng. Chem.,37; 968(1946)) present the
following batch homogenous data for the esterification reaction of
butanol(B) and acetic acid(A).
T=100C = 0.2332 = 1.16
Time,h

0 0
1 .01636
2 .02732
3 .03662
4 .04525
5 .05405
6 .06086
7 .06833
8 .07398

.
SOLUTION:
The reaction is

FIRST ORDER
1
+
2
+ + +
Corresponding reaction rates:

1 = = 1
1

2 = = 2
2
Overall rate of disappearance of A:

= 1 + 2 = (1 + 2 )

Assuming that the concentration of the catalyst does not change and
does not relatively change, we can say that = (`1 + 2 ).
Substituting:

=

Integrating:

- =


=


Since : = 1


= 1

Substituting, the equation becomes:

ln 1 =

y m x
Linearizing data:
-ln(1-Xa) vs. t
0.45

From the equation of the line, 0.4

We get 0.35
y = 0.0466x + 0.0222
R = 0.9926

K= 0.0492 0.3

2 = 0.9931 0.25

-ln(1-Xa)
0.2

0.15

0.1

0.05

0
0 1 2 3 4 5 6 7 8 9
t(h)
Second Order
1
+
1
+ + +

*Corresponding reaction rates:

dCA
1 = = k1 CA CB
dt 1
dCA
2 = = k 2 CA CB Cc
dt 2
*Overall rate of disappearance of A
dCA
= k1 CA CB + k 2 CA CB Cc = CA CB k1 + k 2 Cc
dt
*Assumption
is constant; = 1 + 2

=

*Expressing in terms of :

= =

= 1 = 1
= =
At any time t, amount of A and B reacted is equal
=
Then: =
=

=


= 1


= 2 1 ( )

*Integration (partial fractions)

Since =

= 2 1 ( )

*breaking into partial fractions
1
= + 1 (1 )
1 1 ( )
1 = + 1

Let =M Let = 1
1=0+ 1 1= 1 +0
1 1 1
= = =
1 1 1
 1 1

= 1 + 1 =
1 ( ) ( ) ( )

1
= =
1 (1 ( )

= = ( 1)
0 1 0 ( )

Let = 1 let =
= =


+ = 1
0 0
1
ln + ln = 1
1

ln = ln
1 1

= 1 = 1 =

ln =
1
 2 = 0.9941
= 0.0386

ln((_))/((1_)) vs t
0.35
y = 0.0386x + 0.0166
R = 0.9941
0.3

0.25

ln((_))/((1_))
0.2

0.15

0.1

0.05

0
0 1 2 3 4 5 6 7 8 9
t(h)