1. Speeding up the approach to equilibrium
Catalysis
Speeding up the approach to equilibrium

2. 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.

3. 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.

4. Heterogeneous catalysis
Chemisorption and catalysis
Diffusion of reactants
Adsorption
Surface diffusion
Reaction
Desorption
Diffusion of products

5. 2 main mechanisms Langmuir-Hinshelwood Reaction between adsorbates
Eley-Rideal
Reaction between adsorbate and incoming molecule

8. LH model for unimolecular reaction
Decomposition occurs uniformly across the surface.
Products are weakly bound and rapidly desorbed.
The rate determining step (rds) is the surface decomposition step. pA QA
fast
RDS
khet A B
Rate = k qA
For Langmuir adsorption

9. LH model for unimolecular reaction
Two limiting cases
Low pressures/
Weak binding
Kp<<1
Rate ≈ kKp
Rate linearly dependent on gas pressure
First order reaction
Surface coverage very low
High pressures/
Strong binding
Kp>>1
Rate ≈ k
Rate independent of gas pressure
Zero order reaction
Surface coverage almost unity

10. LH model for bimolecular reaction
Langmuir-Hinshelwood reaction with surface reaction as rds pA QA
fast
RDS
khet A AB B pB QB
Rate = k qA qB

11. Langmuir adsorption of mixed components

12. Langmuir adsorption of mixed components

13. Langmuir adsorption of mixed components

14. LH model for bimolecular reaction
Rate = k qA qB

15. LH model for bimolecular reactionpA
rate
For constant PB
QB >> QA
Rate limited by
surface concentration of A
QB << QA
Rate limited by
surface concentration of B

16. Eley-Rideal bimolecular surface reactionspA QA
fast
RDS
khet A AB B pB
An adsorbed molecule may react directly with an impinging gas molecule by a collisional mechanism

17. Eley-Rideal bimolecular surface reactions
rate = k QA pB
= k KApA pB / (1+KApA)
QA = 1 pA
rate
For constant PB
High pressure
Strong binding
KApA >> 1
rate = k pB …….. zero order in A
kexp
Note: For constant pA, the rate is always first order wrt pB
Low pressure
Weak binding
KApA << 1
rate = khet KA pA pB …….. first order in A
kexp

18. 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.

19. Transition State Model of Catalyst Activity
#hom
adsorbed reactants
adsorbed products
#het
Langmuir-Hinshelwood Kinetics
Adsorption of reactants and desorption of products are very fast. DEads and DEdes very small.
Surface Reaction is RDS: DEhet
DEhom
DEads
DEdes
DEhet
potential energy
reactants
products
reaction co-ordinate

20. Principle of Sabatier A “volcano” curve
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

21. 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.

22. Case studies Ammonia synthesis (Haber-Bosch)
Hydrogenation of CO (Fischer-Tropsch)

23. 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.

24. Ammonia reactants Steam reforming CH4(g) + H2O(g)  CO(g) + 3 H2(g)
15-40% NiO/low SiO2/Al2O3 catalyst ( C)
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)

25. Ammonia Synthesis
Fe/K catalyst
exothermic

26. Mechanism 1 N2(g) + * N2* 2 N2* + * 2N* 3 N* + H* NH* + * 4 NH* + H*
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.

27. CO+3H2CH4+H2O ( DG298, -140 kJ/mol)
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

28. 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.

29. 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, Towards a Chemical Understanding of the Fischer-Tropsch Reaction: Alkene Formation

30. 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)