Topic 4

Catalysis and catalytic reactors

 Outline
Nonelementary Reactions
Reaction Mechanism and Rate Eqn
Active intermediates
Rate equation derivation by PSSH
Catalytic Reactions
Adsorption and Reactions
Rate limiting step
Rate equation derivation

Ref.: Chap.9 and 10 (Foglers)

Nature has the best example of catalytic
reaction
Catalysis is the foundation of chemical
engineering (>90%)
Catalysis design by molecular engineering
 Design Eqn of using Conversion

Take BR design eqn as an example:

Design eqn from mole balance
- used for reactant ,
rA V
dNA because RHS is positive.
dt
Step 1: Rate Law, rA gCi
NA = NAo (1 - XA) Step 2: Stoichiometry, Ci hX
Step 3: Combine to get rA f X (Ch.3)

rA V
dX A
NAo
dt

Design eqn in terms of conversion
 Design Eqn of catalytic Reactor
using Conversion
Take BR design eqn as an example:
Design eqn from mole balance
- used for reactant ,
rA V
dNA because RHS is positive.
dt
Step 1: Rate Law, rA gCi
NA = NAo (1 - XA) Step 2: Stoichiometry, Ci hX
Step 3: Combine to get rA f X (Ch.3)

Step 4: Consider nonelementary rA
rA V
dX A
NAo
dt

Design eqn in terms of conversion
 Enzyme Reaction ch9.2

What is enzyme: a high-

molecular-weight protein or
protein-like substance that acts
on a substrate (reactant) to
transform it.
How fast the rate: The rate
of enzyme reaction can be 103
to 1017 times faster than that in
the absence of enzyme.
increase yield. Overall Reaction : S P
Why it is unique: An Role of Enzyme : S E E S E P
important property of enzymes
is that they are specific, i.e.,
one enzyme can usually
catalyze only one reaction.--
enhance selectivity
Enzyme Reaction
Examples of enzyme and its reaction:
 Active intermediate (ch. 9,1)

Active intermediate () A*: has a higher

probability to transform into the product but may also
transform back to the reactant.
A+MA*+MProduct
Active intermediates are high-energy molecules that react virtually
as fast as they are formed.
Consequently, the net rate of formation is almost zero. the key of
PSSH (Pseudo-Steady-State Hypothesis), the core concept of ch.9.

Overall Reaction : S P
Role of Enzyme : S E E S E P
 PSSH (Pseudo steady state hypothesis) p343
PSSH (Pseudo steady state hypothesis): Because a
reactive intermediate reacts virtually as fast as it is
formed, the net rate of formation of an active
intermediate is zero. r r 0
A * ,net i , A*
i

S1. Propose an active intermediate.

S2. Propose a mechanism
S3. Write the rate law
S4. Write the net rate of formation of A* by PSSH
S5. Evaluate the rate law.
S6. Compare with experimental data.
 Enzyme Reaction
(important)

Mechanism of enzyme reaction, e.g., urease ()

The rxn:
S E P E
H 2O

The corresponding mechanism

(1) NH2CONH2 Urease
k1
[NH2CONH2 Urease] * S E
k1
E S
(2) [NH2CONH2 Urease] *
k2
Urease NH2CONH2 E S
SE
k2

(3) [NH2CONH2 Urease] * H2O

k3
2NH3 CO2 Urease E S W
P E
k3
 Enzyme Reaction
(Ch.9.2 important)

The enzyme reaction S E P E

H 2O

S1. Propose an active intermediate E.S

S E
k1
E S
S2. Propose a mechanism:
E S
SE
k2

E S W
P E
k3

S3. Write the rate law:

rS k1[ E ][ S ] k2 [ E S ]
rE S k1[ E ][ S ] k2 [ E S ] k3[W ][ E S ] 0
S4. Write the net rate of formation of A* by PSSH:
k1[ E ][ S ]
[ E S ] k2k1[ E ][ S ]
k2 k3[W ] rS k1[ E ][ S ]
k2 k3[W ]
Key with [ Etotal ] [ E ] [ E S ] [ E ] k1[ E ][ S ]
k2 k3[W ] k1k3[ E ][ S ][W ] k1k3[ Etotal ][ S ][W ]

[ Etotal ]( k2 k3[W ]) k2 k3[W ] k1[ S ] k2 k3[W ]
[E ]
k1[ S ] k2 k3[W ]
 Michaelis-Menten Equation
S E
k1
E S
The enzyme reaction:
E S
SE
k2

S E P E
H 2O

E S W
P E
k3

S5. Evaluate the rate law. From S4: k2k1[ E ][ S ]

rS k1[ E ][ S ]
k2 k3[W ]
k1k3[ Etotal ][ S ][W ]
rP rS k1k3[ E ][ S ][W ] k1k3[ Etotal ][ S ][W ]
k1[ S ] k2 k3[W ]
k2 k3[W ] k1[ S ] k2 k3[W ]
[ Etotal ] constant and [W ] constant
k1k "3 [ S ] k [ E ][ S ] k3 [W ] k 2
rP rS cat total KM
k1[ S ] k2 k '3 [S ] KM k1
Michaelis-Menten Eqn Michaelis constant
Vmax [S ] Independent on enzyme concentration
rP rS
KM [S ]
Vmax = kcat [Etotal ], the maximum rate of rxn
(in aqueous soln) Depended on the enzyme concentration
 Michaelis-Menten Equation
Michaelis-Menten Eqn
S E
k1
E S Vmax [S ] k3 [W ] k 2
rP rS KM
E S
SE
k2
KM [S ] k1
E S W
P E
k3
Vmax = kcat [Etotal ], the maximum rate of rxn

When [S]>>KM

rP rS Vmax 0th order

When KM =[S]

1
rP rS Vmax
2
Michaelis constant
When [S]<<KM
Vmax [ S ]
rP rS 1st order
KM
Michaelis-Menten Equation ex9-2
Michaelis-Menten Eqn
S E E S
k1
Vmax [S ] k3 [W ] k 2
E S
SE
k2
rP rS KM
KM [S ] k1
E S W
P E
k3

Vmax = kcat [Etotal ], the maximum rate of rxn

 Batch Rxs for Enzyme Rxns
BR design eqn dNS
rSV
dCS V C
rS max S
dt dt K M CS
Liquid-phase ran, V ~ Vo,

With Michaelis-Menten rate eqn,

Integrate
K 1 C X
t M ln So
Vmax 1 X Vmax
Rearrange
1 1 V C X
ln max So
t 1 X KM KM t

or
1 CSo Vmax CSo CS
ln
t CS KM KMt
 Catalysts and Reactions
ch10.1

Solid catalysts:
Metal catalysts
Oxide catalysts
x
 Catalytic Reactions
ch10.1

How catalyst works:

Increase the reaction rate

Decrease the activation energy
 Catalytic Reactions
ch10.2

3 major steps in a catalytic reaction:

Diffusion, external/internal (1,2)
Reaction, adsorption/surface rxn/desorption (3,4,5)
Diffusion, internal/external (6,7)

Bulk fluid
Outside the catalysts

Catalyst external surface

Inside the catalysts

Internal catalytic surface

Activation site
 Catalytic Reactions (step 3~5)
Steps in the mechanism of catalytic reaction:
S3. Adsorption,

A S A S

S4. Surface reaction,

A S B S
S5. Desorption.
B B
B S B S
 Adsorption ()
ch10.2.3

Adsorption:
the accumulation of atoms or molecules on the surface of
a material (the interface between two phases). This
process creates a film of the adsorbate (the molecules or
atoms being accumulated) on the adsorbent's surface
Types of adsorption:
Criterion Chemisorption Physisorption
Enthalpy of 40-800 kJ/mol 8-20 kJ/mol Exothermic !
adsorption, -DHads
Activation energy, E Usually small Zero

Temperature of Usually low Usually low

occurrence
Number of layers Not more than 1 More than one
adsorbed possible
 Adsorption
(ch10.2.3)

At equilibrium, the forward rate = the

backward rate
k A PACv k AC AS
Chemisorption
described by Langmuir C AS k A PA
K A PA
model Cv k A
Combine with Site Balance:
A + S A-S
1
Assumptions: CT Cv C AS CT C AS C AS
K A PA
(i) uniformly energetic
adsorption sites. C AS

K A PA
q
(ii) Adsorption can only occur CT 1 K A PA
on sites which are vacant.
Langmuir isotherm
(iii) Adsorbed species do not
interact with one another. (Nobel Prize in Chemistry(1932))
q: Surface coverage
KA = equilibrium constant of adsorption
Langmuirs Model
(optional)

Possible Langmuir model equations:

Competitive adsorption,
A + S A-S
B + S B-S

CAS K APA
qA
CT 1 K APA K BPB
CBS K BPB
qB
CT 1 K APA K BPB
 Rate eqn of Catalytic Reaction (ch10.2.4)

rAD k A PACv k AC AS
A catalytic rxn, A B:
C AS
S1 Adsorption: k A [ PACv ]
A + S A-S KA

S2 Duel site surface reaction: rS k sC AS k sCBS

A-S B-S C BS
k s [C As ]
KS
S3 Desorption:
B-S B + S rDC k D C BS k D PB Cv
PB Cv
k D [C BS ]
K DC
 Rate eqn of Catalytic Reaction
dC AS
A catalytic rxn, A B: 0 k1C ACv k1C AS k2C AS
dt
S1 Adsorption: C AS
k1
C ACv
A + S A-S k1 k2
S2 Duel site surface reaction: dCB S
0 k2C AS k3CBS k3CBCv
dt
A-S B-S
k2k1 k
S3 Desorption: C BS C ACv 3 CBCv
k3 (k1 k2 ) k3
B-S B + S

CT C AS CBS Cv ( K AC A K BCB 1)Cv

We can derive the rate
eqn of the above k1
rA k1C ACv k 1C AS k1C ACv k 1
mechanism by PSSH,
C ACv
k 1 k2
taking A-S and B-S as ( k1
k 1k1 kk
)C ACv ( 1 2 )
1
C ACT
active intermediates. k 1 k2 k 1 k2 ( K AC A K BCB 1)
 Rate determining/liminting step (RDS)

Catalytic reaction:
AB
A + S A-S (adsorption)
rAD
A-S B-S (surface reaction)
Rtotal RAD RS RD
rS E E
I
B-S B + S (desorption) Rtotal RAD RS RD
rD
 Surface reaction RDS
C AS
KA C AS K AC ACv
Catalytic reaction C ACv
C B S
KA C B S K B C B Cv
AB C B Cv

rrds k C AS
when surface rxn is the r.d.s. CT C AS CBS Cv
( K AC A K BCB 1)Cv
A + S A-S
A-S B-S rA ~ rrds k C AS
B-S B + S k K AC ACT
k K AC ACv
1 K AC A K BCB
 Summary
Nonelementary rate equation is usually associated with
elementary steps involve in the process of reaction.

Verification of a mechanism by rate equation

Propose a mechanism

Derive the rate equation associated with the

proposed mechanism by, e.g., PSSH
Check the consistency of the derived rate eqn and
the expt rate eqn.

Enzyme rxns
Possible mechanisms.

Michaelis-Menten eqn.