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ENGINEERING:
Catalysis & Catalytic
Reaction Mechanism
Part B: The Rate
Limiting Step..
Rate Limiting
Step??
When
heterogeneous reactions are carried out at
rA ' rAD rs rD
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)
Cu
CO2
1
N2
2
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
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
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
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)
rAD
C C S
k A PC CV
KC
rAD k A PC CV
K
.(1)
PP C BS .(3
K
S
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
.(6
rD
C BS K B PB CV 0
So,
kD
C BS K B PB CV
.(8)
C C S
K B PB PP CV
KS
.(9)
kD
rAD
C C S
k A PC CV
KC
rAD
rAD
rAD
K B PB CV PP
This terms is simply the
k A PC CV
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
Ct CV
KS
+ CC.S. + CB.S.(12)
K B PB CV
Occupied Site
(cumene &
benzene
adsorb on the
surface)
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)
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)
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 '
initial rate,
rS k S CCS
PP C BS
KS
.(1)
CCS .(2)
PC:CV
rAD k Ais
The adsorption rate expression
K
C
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)
.(5
rD
0 .(6)
kD
rD
C BS K B PB CV 0
So,
kD
C BS K B PB CV .(7)
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
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
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
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
r 'c rCO
k S K C Ct PCO
1 K C PCO
r 'c rCO
kPCO
1 K C PCO
where,
k k S K C Ct
K C PCO 1
r 'c rCO
kPCO
1 K C PCO
K C PCO K C
initial pressure of
cumene.
ERT 208/4 REACTION ENGINEERING
SEM 2 (2009/2010)
rCO '
initial rate,
rD k D C BS K B PB CV
.(1)
CCS .(2)
PC:CV
rAD k Ais
The adsorption rate expression
K
C
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)
rS k S CCS
PP C BS
KS
.(5)
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)
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
equilibri
um
constant
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)
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)
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
k S K C Ct ( PC PP K B / K P )
r 'c rS
1 K P PB K C PC
reaction
between
adsorbed
molecule & a
molecule in the
End of Part B