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 1820’s
• 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, SO2

oxidation, water gas shift, ammonia oxidation, ethene
hydrogenation)
• 20th 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
A (g)  A (ads) 
 B
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 qA pA
B
A
fast RDS
For Langmuir adsorption fast
QA khet

kKp
Rate 
1  Kp
 LH model for unimolecular reaction
Two limiting cases

Low pressures/
High pressures/
Weak binding
Strong binding
Kp<<1
Kp>>1
Rate ≈ kKp
Rate ≈ k
Rate linearly
Rate independent
dependent on gas
of gas pressure
pressure
Zero order reaction
First order reaction
Surface coverage
Surface coverage
almost unity
very low
 LH model for bimolecular reaction
Langmuir-Hinshelwood reaction with surface reaction as rds

A (g)  A (ads)
B (g)  B (ads)
A (ads)  B (ads)  AB (ads)  AB (g)
rds fast

pA B
pB AB

Rate = k qA qB A
fast RDS
QB fast
khet
QA
Langmuir adsorption of mixed
components
ka
Ag  S surface A  S surface
kd
ka
Bg  S surface B  S surface
kd
dq A
adsorption rate of A   k a p A (1  q A  q B )
dt
dq A
desorption rate   k dq A
dt
dq B
adsorption rate of B   k a pB (1  q A  q B )
dt
dq B
desorption rate   k dq B
dt
 Langmuir adsorption of mixed
components
At equilibriu m
k a A p Aq S  k d Aq A
ka A q S  1  q A  q B 
q A  K A p Aq S , K A  qS q A qB  1
kd A
k a B p Bq S  k d Bq B
ka B
q B  K B p Bq S , K B 
kd B
Langmuir adsorption of mixed
components
q S  K A p Aq S  K B pBq S  1
q S 1  K A p A  K B pB   1
1
qS 
1  K A p A  K B pB 
K A pA
qA 
1  K A p A  K B pB 
K B pB
qB 
1  K A p A  K B pB 
LH model for bimolecular reaction
Rate = k qA qB

kKA p A K B pB
Rate 
1  K A pA  K B pB 2
 LH model for bimolecular reaction

For constant PB
rate

Rate limited by
surface concentration of A
Rate limited by
surface concentration of B

pA

QB >> QA QB << QA
 Eley-Rideal
bimolecular surface reactions

pA
A
AB
An adsorbed molecule may pB
B
react directly with an RDS
khet
impinging gas molecule by a QA
fast

collisional mechanism
 Eley-Rideal
bimolecular surface reactions
rate = k QA pB  k KApA pB / (1+KApA)

QA = 1

Note: For constant pA, the

rate is always first order
rate

wrt pB
For constant PB

Low pressure
High pressure
Weak binding pA Strong binding
KApA << 1
KApA >> 1
rate = khet KA pA pB …….. first order in A
rate = k pB …….. zero order in A

kexp
kexp
 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

transition state
#hom Langmuir-Hinshelwood Kinetics
Adsorption of reactants and desorption of products
are very fast. DEads and DEdes very small.

Surface Reaction is RDS: DEhet

DEhom #het
potential energy

DEads
reactants DEhet

products
adsorbed reactants DEdes

adsorbed products
reaction co-ordinate
 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 H2 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: CO2 absorption
E: Methanation
F: Ammonia synthesis
G: NH3 separation.
 Ammonia reactants
Steam reforming
CH4(g) + H2O(g)  CO(g) + 3 H2(g)
15-40% NiO/low SiO2/Al2O3 catalyst (760-816C)
products often called synthesis gas or syngas

Water gas shift

CO(g) + H2O(g)  CO2(g) + H2(g)
Cr2O3 and Fe2O3 as catalyst
carbon dioxide removed by passing through sodium hydroxide.
CO2(g) + 2 OH-(aq)  CO32-(aq) + H2O(l)
Ammonia Synthesis

Fe/K catalyst

exothermic
 Mechanism

1 N2(g) + * N2*
2 N2* + * 2N*
3 N* + H* NH* + *
4 NH* + H* NH2* + *
5 NH2* + H* NH3* + *
6 NH3* NH3(g) + *
7 H2(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+3H2CH4+H2O ( DG298, -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 200–300°C and
atmospheric pressure over Co or Fe catalysts

nCO+(2n+1)H2CnH2n+2+nH2O

2nCO+(n+1)H2=CnH2n+2+nCO2
Since syngas (CO + H2) is readily available from a variety of fossil fuels,
including coal, the Fischer–Tropsch 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 + CO2
Some evidence that hydrogenation of adsorbed
carbon leads to formation of hydrocarbons.
Also an important side (undesired) reaction in
some hydrocarbon conversion reactions (coking)