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Catalysis

Speeding up the approach to


equilibrium
History
Kirchoff in 1814 noted that acids aid hydrolysis of starch to glucose
Faraday (and Davy) studied oxidation catalysts in the 1820s
Catalyst defined by Berzelius in 1836

A compound, which increases the rate of a chemical reaction,
but which is not consumed by the reaction

Deacon, Messel, Mond, Ostwald, Sebatier processes (HCl, SO
2

oxidation, water gas shift, ammonia oxidation, ethene
hydrogenation)
20
th
C: ammonia production, cracking reactions, hydrocarbon
production, catalytic converters etc.
Catalysis science developed by Langmuir, Emmett, Rideal and
others.
http://dept.chem.polimi.it/~citterio/SilsisMI/Introduction.pdf
Catalysis
When we consider a catalytic reaction, we
may imagine that the reaction mechanism
consists of many different steps. Catalyst
must be a reactant in one of the first steps
in the mechanism and a product in one of
the last steps.
Heterogeneous catalysis
Chemisorption and catalysis
Diffusion of reactants
Adsorption
Surface diffusion
Reaction
Desorption
Diffusion of products
2 main mechanisms
Langmuir-Hinshelwood
Reaction between adsorbates
Eley-Rideal
Reaction between adsorbate and incoming
molecule
LH model for unimolecular reaction
B (ads) A (g) A
Decomposition occurs uniformly across the surface.
Products are weakly bound and rapidly desorbed.
The rate determining step (rds) is the surface
decomposition step.

Rate = k u
A

For Langmuir adsorption
p
p k
K 1
K
Rate
+
=
p
A
O
A
fast
fast
RDS
k
het
A
B
LH model for unimolecular reaction
Two limiting cases
High pressures/
Strong binding
Kp>>1
Rate k
Rate independent
of gas pressure
Zero order reaction
Surface coverage
almost unity

Low pressures/
Weak binding
Kp<<1
Rate kKp
Rate linearly
dependent on gas
pressure
First order reaction
Surface coverage
very low

LH model for bimolecular reaction
Langmuir-Hinshelwood reaction with surface reaction as rds
(g) AB (ads) AB (ads) B (ads) A
(ads) B (g) B
(ads) A (g) A
fast
+

rds
Rate = k u
A
u
B

p
A
O
A
fast
fast
RDS
k
het
A
AB
B
p
B
O
B
Langmuir adsorption of mixed
components
{ }
{ }
B d
B
B A B a
B
A d
A
B A A a
A
surface
d
a
surface g
surface
d
a
surface g
k
dt
d
p k
dt
d
k
dt
d
p k
dt
d
S B
k
k
S B
S A
k
k
S A
u
u
u u
u
u
u
u u
u
= =
+ = =
= =
+ = =
+
+
rate desorption
) 1 ( B of rate adsorption
rate desorption
) 1 ( A of rate adsorption
Langmuir adsorption of mixed
components
B
d
B
a
S B B
B
B
d S B
B
a
A
d
A
a
S A A
A
A
d S A
A
a
k
k
p
k p k
k
k
p
k p k
= =
=
= =
=
B B
A A
K , K
K , K
m equilibriu At
u u
u u
u u
u u
1
1
= + +
+ =
B A S
B A S
u u u
u u u
Langmuir adsorption of mixed
components
B B A A
B B
B
B B A A
A A
A
B B A A
S
B B A A S
S B B S A A S
p K p K
p K
p K p K
p K
p K p K
p K p K
p K p K
+ +
=
+ +
=
+ +
=
= + +
= + +
1
1
1
1
1 1
1
u
u
u
u
u u u
LH model for bimolecular reaction
Rate = k u
A
u
B

2
1
Rate
B B A A
B B A A
p K p K
p K p kK
+ +
=
LH model for bimolecular reaction
p
A
r
a
t
e

For constant P
B
O
B
>> O
A
Rate limited by
surface concentration of A
O
B
<< O
A
Rate limited by
surface concentration of B
Eley-Rideal
bimolecular surface reactions

p
A
O
A
fast
RDS
k
het
A
AB
B
p
B An adsorbed molecule may
react directly with an
impinging gas molecule by a
collisional mechanism
Eley-Rideal
bimolecular surface reactions

rate = k O
A
p
B
= k K
A
p
A
p
B
/ (1+K
A
p
A
)
O
A
= 1
p
A
r
a
t
e

For constant P
B

Low pressure
Weak binding

K
A
p
A
<< 1

rate = k
het
K
A
p
A
p
B
.. first order in A
k
exp


High pressure
Strong binding

K
A
p
A
>> 1

rate = k

p
B
.. zero order in A
k
exp

Note: For constant p
A
, the
rate is always first order
wrt p
B

Diagnosis of mechanism
If we measure the reaction rate as a function of the
coverage by A, the rate will initially increase for both
mechanisms.
Eley-Rideal: rate increases until surface is covered by A.
Langmuir-Hinshelwood: rate passes a maximum and
ends up at zero, when surface covered by A.

B + S B-S
cannot proceed when A blocks all sites.

Transition State Model of Catalyst Activity

reactants
products
AE
hom

p
o
t
e
n
t
i
a
l

e
n
e
r
g
y

AE
ads

AE
des

AE
het

reaction co-ordinate
Langmuir-Hinshelwood Kinetics
Adsorption of reactants and desorption of products
are very fast. AE
ads
and AE
des
very small.

Surface Reaction is RDS: AE
het

transition state
#
hom
adsorbed reactants
adsorbed products
#
het
Principle of Sabatier
When different metals are used to catalyse the same reaction, it is generally
observed that the reaction rate can be correlated with the position of the metal in the
periodic table:
A volcano
curve
Catalyst Preparation
For a catalyst the desired properties are
high and stable activity
high and stable selectivity
controlled surface area and porosity
good resistance to poisons
good resistance to high temperatures and temperature fluctuations.
high mechanical strength
no uncontrollable hazards

Once a catalyst system has been identified, the parameters in the
manufacture of the catalyst are
If the catalyst should be supported or unsupported.
The shape of the catalyst pellets. The shape (cylinders, rings, spheres,
monoliths) influence the void fraction, the flow and diffusion phenomena and
the mechanical strength.
The size of the catalyst pellets. For a given shape the size influences only
the flow and diffusion phenomena, but small pellets are often much easier
to prepare.
Catalyst based on oxides are usually activated by reduction in H
2
in the
reactor.
Case studies
Ammonia synthesis (Haber-Bosch)
Hydrogenation of CO (Fischer-Tropsch)

http://www.uyseg.org/greener_industry/index.htm

Ammonia synthesis
A: Steam reforming
B: High temperature water-gas shift
C: Low temperature water-gas shift
D: CO
2
absorption
E: Methanation
F: Ammonia synthesis
G: NH
3
separation.
Ammonia reactants
Steam reforming
CH
4
(g) + H
2
O(g) CO(g) + 3 H
2
(g)
15-40% NiO/low SiO
2
/Al
2
O
3
catalyst (760-816C)
products often called synthesis gas or syngas



Water gas shift
CO(g) + H
2
O(g) CO
2
(g) + H
2
(g)
Cr
2
O
3
and Fe
2
O
3
as catalyst
carbon dioxide removed by passing through sodium hydroxide.
CO
2
(g) + 2 OH
-
(aq) CO
3
2-
(aq) + H
2
O(l)

Ammonia Synthesis
Fe/K catalyst

exothermic
Mechanism
1 N
2
(g) + * N
2
*
2 N
2
* + * 2N*
3 N* + H* NH* + *
4 NH* + H* NH
2
* + *
5 NH
2
* + H* NH
3
* + *
6 NH
3
* NH
3
(g) + *
7 H
2
(g) + 2* 2H*
Step 2 is generally rate-limiting. Volcano curve is
therefore apparent with d-block metals as catalysts.
Ru and Os are more active catalysts, but iron is used.
Hydrogenation of CO
Hydrogenation of CO is thermodynamically favourable; the first example,
methanation catalysed by nickel was reported by Sabatier and Senderens in
1902

CO+3H
2
CH
4
+H
2
O ( AG
298
, -140 kJ/mol)
In their classic 1926 papers Fischer and Tropsch showed that linear alkenes
and alkanes (as well as some oxygenates) are formed at 200300C and
atmospheric pressure over Co or Fe catalysts

nCO+(2n+1)H
2
C
n
H
2n+2
+nH
2
O


2nCO+(n+1)H
2
=C
n
H
2n+2
+nCO
2

Since syngas (CO + H
2
) is readily available from a variety of fossil fuels,
including coal, the FischerTropsch process became industrially important
for economies which had good supplies of cheap coal but which lacked oil
Fischer-Tropsch
Iron catalysts give mainly linear alkenes and
oxygenates, while cobalt gives mostly linear
alkanes. Ruthenium, one of the most active
catalysts but one which, owing to its expense is
little used industrially, can give high molecular
weight hydrocarbons; rhodium catalysts make
significant amounts of oxygenates in addition to
hydrocarbons, while nickel gives mainly
methane. Catalyst can be immobilised on
Kieselguhr (diatomaceous silicate earth),
alumina, active carbon, clays and zeolites.
FT mechanism
adsorption and cleavage of CO and the stepwise hydrogenation of surface
carbide giving methylene and other species
Maitlis, P. M.; Quyoum, R.; Long, H. C.; Turner, M. L. Appl. Catal. A:
General 1999, 186, 363-374. Towards a Chemical Understanding of the
Fischer-Tropsch Reaction: Alkene Formation
Other mechanisms?
Boudouard reaction. Important in methanation
(over Nickel).
2CO C + CO
2
Some evidence that hydrogenation of adsorbed
carbon leads to formation of hydrocarbons.
Also an important side (undesired) reaction in
some hydrocarbon conversion reactions (coking)