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ERT 208/4 REACTION

ENGINEERING:
Catalysis & Catalytic
Reaction Mechanism
Part B: The Rate
Limiting Step..

By; Mrs Hafiza Binti Shu

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Rate Limiting
Step??
When
heterogeneous reactions are carried out at

STEADY STATE.the rate of each of the 3 reaction


step in series (adsorption, surface reaction &
desorption) are equal to one another.

rA ' rAD rs rD

only ONE particular step in the series is usually


found to be RATE LIMITING @ RATE CONTROLLING
If we could make this particular step GO FASTER,
the entire reaction would proceed at accelerated
rate.
It consist of first assuming a sequence of steps in
the reaction.
In writing sequence choice, must made some;
ERT 208/4
ENGINEERING
a)mechanism (molecular
@REACTION
atomic)
SEM 2 (2009/2010)

Rate Limiting Step??.....cont.


ASSUMPTION..
All the steps are reversible reaction.
Activity of the surface towards adsorption,
desorption @ surface reaction is INDEPENDENT of
coverage.
The surface is essentially uniform as far as the
various steps in the reaction are concerned.

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Rate Limiting Step??......cont

EXAMPLE 1: ADSORPTION LIMITED REACTION


Synthesis of Ammonia
3H 2 N 2 2 NH 3

Over an iron catalyst that proceeds by the following m

H 2 2S 2 H S

Rapid

N2 S N2 S
N 2 S S 2N S
N S H S HN S S
NH S H S H 2 N S S
H 2 N S H S NH 3 S S

Rate-Limiting
(adsorption of
N2 molecules as
an N atom)
Rapid

NH 3 S NH 3 S
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)

Rate Limiting Step??......cont

EXAMPLE 2: SURFACE- LIMITED REACTION


Reactions between 2 noxious automobile
products, CO & NO
CO NO

Cu

CO2

1
N2
2

Over an Copper catalyst that proceeds by the following

CO S CO S

Rapid

NO S NO S
NO S CO S CO2 N S S
N S N S N2 S
N2 S N2 S

Rate-Limiting
(CO2 & N2 are
weakly adsorbed)
Rapid

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Rate Limiting Step??......cont

Synthesizing a Rate Law, Mechanism, and Rat


EXAMPLE 3:
FORM
PLATINUM

DECOMPOSITION OF CUMENE TO
BENZENE & PROPYLENE USING
CATALYZED
C 6 H 5 CH CH 3 2 C 3 H 6 C 3 H 6
C

3 STEPS REPRESENT THE MECHANISME FOR CUMENE


DECOMPOSITION
CS BS P
C

C S CS

P
B

catalyst

catalyst

Adsorption of
cumene on the
surface

BS BS

catalyst

Surface reaction to
form adsorbed
benzene & propylene
in the gas phase

catalyst

Desorption of
benzene from
surface

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Which step is Rate Limiting Step???


Adsorption r k P C k C
AD
A C V
A C S
C S CS

C C S
kA
rAD k A PC CV
Kc
KC
kA

rS k S CCS k S PP C BS
Surface Reaction
CS BS P

Desorption

BS BS

kS
KS
k S

rS k S CCS

PP C BS

KS

rD k D PBS k D PB CV
1
KB
rD k D C BS K B PB CV
K DB
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)

1) Is the ADSORPTION of cumene is Rate Limi


C S CS

The rate of adsorption :

rAD

C C S
k A PC CV
KC

Assumption For Adsorption Limited Reaction ;


Rate constant for this step (kA) is SMALL with
respect to the specific
rates of other steps (kS and kD).
Ratio rS/kS and rD/kD very SMALL (approximately
0)
Ratio rAD/kA is LARGE
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)

Is the ADSORPTION of cumene is Rate Limitin


C C S
The rate of adsorption :

rAD k A PC CV
K

.(1)

For steady state operation


rC ' rAD : rS rD .(2)

PP C BS .(3

The surface reaction rate expression


rS k S CCis
:
S

K
S

For adsorption limited reaction, kS is large..so,


we
rS
0 .(4)
kS

So, rS
PP C BS
0
CCS
kS
K S
PP C BS
.(5) We evaluate CB.S to
C C S
express CC.S in term of
KS
partial pressure

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Is the ADSORPTION of cumene is Rate Limitin


The desorption rate expression
C:BS K B PB CV
rD k Dis

.(6

For adsorption limited reaction, kD is large..so,


we
rD
0 .(7)

rD
C BS K B PB CV 0
So,
kD
C BS K B PB CV

.(8)

Combine (5) and (8),

C C S

K B PB PP CV

KS

.(9)

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

kD

Is the ADSORPTION of cumene is Rate Limitin


We know that ,,

rAD

C C S
k A PC CV
KC

Put (9) in above


equation;

rAD
rAD
rAD

K B PB CV PP
This terms is simply the

k A PC CV

overall partial pressure


K
K
S
C

equilibrium constant for


C BP
this
reaction.

K B PB PP

k A CV PC

K
K
S
C

Where
KS KC

PB PP
.(11)
.(10) K P

k A CV PC
KB
K
P

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Is the ADSORPTION of cumene is Rate Limitin


To eliminate Cv, we use SITE
BALANCE,
Total sites ,Ct
Cv
=
Vaca
nt
Site

Put (8) and (9) in (12)


..
K B PB CV PP

Ct CV

KS

+ CC.S. + CB.S.(12)

K B PB CV

Occupied Site
(cumene &
benzene
adsorb on the
surface)

Solving for Cv,

K B PB PP
Ct CV 1
K B PB
KS
Ct
So CV
K B P B PP
1
K B PB
KS

.(13)

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Is the ADSORPTION of cumene is Rate Limitin


Now, we put (13) in
(10)..

rAD

rAD

PB PP

k A CV PC
KP

Ct

kA

K B PB PP
K B PB
1
KS

P PB PP
C
KP

So

rc ' rAD

k A Ct ( PC PS PP / K P )

1 K B PB PP / K S K B PB

.(14)

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Is the ADSORPTION of cumene is Rate Limitin


Now, we wish to sketch a plot of the initial rate as
a function of partial pressure of cumene,Pco

Pp PBso
0
Initially, no product are present,
Sothe initial rate,

rc ' rAD

k A Ct ( PC PS PP / K P )

1 K B PB PP / K S K B PB

rCO ' k A Ct PCO kPCO


If the cumene
decomposition is
ADSORPTION
LIMITED, then the
initial rate will be
linear with the
initial partial

rCO '
initial rate,

initial partial pressure of cum

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

2) Is the SURFACE REACTION of cumene is


Rate Limiting Step???
CS BS P
The rate of SURFACE REACTION :

rS k S CCS

PP C BS

KS

.(1)

Since we cannot readily measure the conc of the adsorbed species,


we must utilize the adsorption & desorption step to eliminate C C.S
and CB.S from this equation.

Assumption For SURFACE REACTION Limited


Reaction ;
Rate constant for kA is LARGE (rAD)
Rate constant for kD is LARGE (rD)
Rate constant for kS is SMALL (rAD)
Ratio rAD/kA and rD/kD very SMALL
ERT 208/4 REACTION ENGINEERING
(approximately 0)
SEM 2 (2009/2010)

Is the SURFACE REACTION of cumene is Rate


Limiting Step???..cont..

CCS .(2)
PC:CV

rAD k Ais
The adsorption rate expression

K
C

For adsorption limited reaction, kA isrADlarge..so,;


0 .(3)
kA
So,

CC . S
rAD
PC CV
kA
KC
CC . S
0 PC CV
KC
CC . S K C PC CV .(4)
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)

Is the SURFACE REACTION of cumene is Rate


Limiting Step???..cont..
The desorption rate expression
C:BS K B PB CV
rD k Dis

.(5

For SURFACE REACTION limited reaction, kD is large

rD
0 .(6)
kD

rD
C BS K B PB CV 0
So,
kD
C BS K B PB CV .(7)

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Is the SURFACE REACTION of cumene is Rate


Limiting Step???..cont..
Now, put (4) and (7) in (1).

PP C BS

KS

rS k S CCS

PP K B PB CV

rS k S K C PC CV

K
S

PP K B PB

rS k S CV K C PC

K
S

PP PB
.(8)
rS k S K C CV PC
KP

We know that,,

KS KC
K P .(9)
KB

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Is the SURFACE REACTION of cumene is Rate


Limiting Step???..cont..
Site Balance.

Ct CV C BS CCS .(10)
Ct CV K P PB CV K C PC CV
Ct CV (1 K B PB K C PC )
Ct
.(11)
CV
1 K B PB K C PC

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Is the SURFACE REACTION of cumene is Rate


Limiting Step???..cont..
Put (11) in (8).

Ct
rS k S K C
1 K B PB K C PC

PP PB
PC

KP

k S K C Ct ( PC PP PB / K P )
r 'c rS
1 K B PB K C PC

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Is the SURFACE REACTION of cumene is Rate


Limiting Step???..cont..
Now, we wish to sketch a plot of the initial rate as
a function of partial pressure of cumene,Pco

Pp PBso
0
Initially, no product are present,
k S K C Ct ( PC PP K B / K P )
r 'c rS
1 K B PB K C PC

Sothe initial rate,

r 'c rCO

k S K C Ct PCO

1 K C PCO

r 'c rCO

kPCO

1 K C PCO

where,

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

k k S K C Ct

Is the SURFACE REACTION of cumene is Rate


Limiting Step???..cont..
At low partial pressure
of cumene,
We observed that the
initial rate will increase
linearly with the initial
pressure of cumene.

K C PCO 1
r 'c rCO

kPCO

1 K C PCO

rCO ' kPCO

At high partial pressure of K C PCO 1


kPCO
cumene,
r 'c rCO
We observed that the
1 K C PCO
initial rate will
kPCO
k
independent with the
r 'c rCO

K C PCO K C
initial pressure of
cumene.
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)

Is the SURFACE REACTION of cumene is Rate


Limiting Step???..cont..
Figure show that the initial rate of reaction as a
function of initial partial pressure of cumene for
the case of surface reaction controlling..

rCO '
initial rate,

initial partial pressure of cumene,Pco

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

3) Is the DESORPTIONof cumene is Rate


Limiting Step???
BS BS
The rate of DESORPTION:

rD k D C BS K B PB CV

.(1)

Assumption For DESORPTION Limited Reaction ;


Rate constant for kA is LARGE (rAD)
Rate constant for kS is LARGE (rS)
Rate constant for kD is SMALL (rD)
Ratio rAD/kA and rS/kS very SMALL
(approximately 0)
Ratio rD/kD is LARGE
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)

Is the DESORPTIONof cumene is Rate


Limiting Step???..cont..

CCS .(2)
PC:CV

rAD k Ais
The adsorption rate expression

K
C

For adsorption limited reaction, kA isrADlarge..so,;


0 .(3)
kA
So,

CC . S
rAD
PC CV
kA
KC
CC . S
0 PC CV
KC
CC . S K C PC CV .(4)
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)

Is the DESORPTION of cumene is Rate


Limiting Step???..cont..
The SURFACE REACTION rate expression is :

rS k S CCS

PP C BS

KS

.(5)

For DESORPTION limited reaction, kS is large..so, w

rS
0 .(6)
kS

So,

rS
PP C BS
CCS
KS
KS
C B S

K S C C S

PP

.(7)
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)

Is the DESORPTION of cumene is Rate


Limiting Step???..cont..
Now, put (4) and (7) in (1).

rD k D C BS K B PB CV
K S C C S

rD k D
K B PB CV
PP

K S K C Pc CV

rD k D
K B PB CV
PP

We know that,,

Pc PB
CV .(8)
rD k D K S K C

PP K P

K S KC
K P Gas
phase
KB

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

equilibri
um
constant

Is the DESORPTION of cumene is Rate


Limiting Step???..cont..
Site Balance.

Ct CV C BS CCS .(9)
K S C C S
Ct CV K c Pc CV
PP
K S K C PC
Ct CV (1 K C PC
)
PP
CV

Ct
K S K C PC
1 K C PC
PP

.(10)

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

Is the DESORPTION of cumene is Rate


Limiting Step???..cont..
Put (10) in (8).

PC PB
Ct

rD k D K C K S

K
K
P
P
K
C
S
C
P
P
1 K C PC

PP

PC PB
K C K S PC
/ 1 K C PC
rD k D Ct K C K S

PP
PP K P

PB PP

k D Ct K C K S PC
KP

.(11)
rC ' rD
PP K C PC PP K C K S PC
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)

Is the DESORPTION of cumene is Rate


Limiting Step???..cont..

To determine the dependence of the initial rate on


partial pressure of cumene, we again set:

Pp PBso
0
Initially, no product are present,

PB PP

k D Ct K C K S PC
Sothe initial rate,
KP

rCO ' rD
PP K C PC PP K C K S PC
initial rate,

rCO '

rCO ' rD k D Ct
Initial rate
independent of the
initial partial pressure
of cumene

ERT 208/4 REACTION ENGINEERING


initial partial pressure of cumene,Pco
SEM 2 (2009/2010)

SUMMARY OF THE CUMENE


DECOMPOSITION

The experimental observation of rco as a function


of Pco are shown in figure..from that, we clearly can
see that either adsorption
desorption
CH 3 2 Cis
C 6 nor
H 5 CH
HRATE
C3 H 6
3
6
rCO '
C
B
P
initial rate,
LIMITING

initial partial pressure of cumene,Pco

The rate law derived by assuming that SURFACE


REACTION is RATE LIMITING agrees with
Eley-Rideal
experimental data.
Mechanism-

k S K C Ct ( PC PP K B / K P )
r 'c rS
1 K P PB K C PC

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)

reaction
between
adsorbed
molecule & a
molecule in the

ALGORITHM FOR DETERMINING REACTION


MECHANISM & RATE LIMITING STEP
1) Select a mechanism for adsorption, surface
reaction & desorption (treat each reaction step
as an elementary reaction when writing rate
law)
2) Assume a rate limiting step. Choose the
SURFACE REACTION first since >than 75% of all
heterogeneous reactions that are not diffusion
limited are surface reaction limited.
3) Write down the rate law for surface reaction
step
4) Solve concentration of adsorbed species using
other step that are not limiting reaction.
(expression for adsorption & desorption rate
law)
5) Assume, ratio rAD/kA and rD/kD very SMALL
208/4 REACTION ENGINEERING
(approximately 0) ERT
SEM 2 (2009/2010)

End of Part B

ERT 208/4 REACTION ENGINEERING


SEM 2 (2009/2010)