Catalysts

Explaining what catalysts do and how they work

The two types of catalysts

HETEROGENEOUS CATALYSTS
The catalyst and the reactants are in different phases

HOMOGENEOUS CATALYSTS
The catalyst and the reactants are in the same phase

Remember the use of the term PHASE for catalysts; as opposed to state. Two immiscible liquids are both in the same state but can only benefit from a catalyst if it can enter both phases or be in the same phase as the reactants.

Most catalysts used in industry are heterogeneous why?

1. Better for most processes can orientate molecules 2. Easier to separate from the products

What do catalysts do?

The Activation Energy required for the catalysed route is lower. The rate is therefore increased with the catalyst present

Catalysis does not alter the quantity of product formed.

Remember these from the MaxwellBoltzmann distribution work?

How do they do it?

HETEROGENEOUS CATALYSTS
In heterogeneous catalysis the catalyst is nearly always in the solid phase and the reactants are in a liquid or gaseous phase. If we consider two reacting phases A and B in the presence of a solid catalyst C Reactant A can adsorb to the surface of C resulting in bond-breaking or re-arrangement. The adsorption process may also weaken bonds within a molecule. Activation energy decreases

Molecule weakened or damaged

Reactant A, being adsorbed to the surface, is now more accessible to favourable reactions with B rather than in random collisions in the gas phase. Successful collision frequency increases

Molecule captured prior to collision Reactant A is adsorbed onto the surface of C in a particularly favourable And highly reactive configuration. Unadsorbed B collides with adsorbed A.

Successful collision frequency increases

Molecule preferentially orientated prior to collision

Heterogeneous Catalyst Efficiency

The efficiency of the catalyst depends on the adsorption strength to the surface.

Too strong and while reactions may increase, the surface becomes concentrated with product that cannot desorb.
Too weak and the reaction rate is not increased sufficiently.

Weak adsorption, such as with metals like silver, can be used to advantage for selective and specific catalysis. This occurs when the catalyst can adsorb one reactant out of several possible reactants (it is selective). It is specific to a few adsorbing reactants.

Transition metal catalysts

Transition metals position in the periodic table LEFT Metals MIDDLE Iron (Fe), Nickel (Ni) Platinum (Pt), Palladium(Pd), Rhodium (Rh) etc Ideal RIGHT Silver (Ag)

Tungsten (W)

Adsorption Metal oxides

Too strong Manganese dioxide (MnO 2) Vanadium V oxide (V 2O5 ) Ideal

Too weak (unless specific)

How do we make catalysts more efficient?

Heterogeneous catalysts work by surface reactions therefore any method of increasing the surface area will improve their performance. Method 1: Spread very thin as a foil Method 2: Attach to an INERT SUPPORT MEDIUM. These are solids which have a high surface area to mass (volume) ratio, typically: a. fibres (like silica or asbestos); b. porous solids (like some ceramics or zeolites); c. or powders. The use of high surface area leads to effective catalysis and an efficient use of high cost catalysts. It is important that the catalyst is well adhered, attached or contained by the inert support medium or loss can affect process efficiency and cost of replacement.

How can the support medium help catalysis?

Most surfaces can adsorb to varying degrees, so it should not be surprising that the support medium can also help in catalysis as long as the adsorption is not too strong.

A catalyst that comprises both a catalytic material and a support medium that helps catalysis is called a MIXED CATALYST.

Can catalysts be damaged CATALYST POISONS

An unusual use of the word poison! Any chemical that affects the way the catalyst can function in a process is known as a poison.

The main ways in which poisoning occurs are when contaminants or products become too strongly attached to the surface. Largely, this applies to contamination.
Example 1: Sulphur contamination Sulphur reacts with metal catalysts to form inactive metal sulphides. This builds up until the catalyst fails to function. What could you use as a catalyst when sulphur is present? Ans: An oxide like V2 O5

Example 2: Lead additives in petrol Lead is used as an anti-knock agent (ensures the petrol ignites at the correct point in the engine cycle). Modern catalytic converters used to convert CO and NOx gases to CO 2 and N 2 are poisoned by lead.

Examples of heterogeneous catalysis

There are five examples that you should be aware of, but this does not mean these are the only examples you will be aware of from the AS ad A2 courses.

1. 2. 3. 4. 5.

Catalytic converters in cars Haber Process Contact Process Nitric Acid manufacture Hydrogenation of oils

The three highlighted examples are dealt with on the next page.

< The Haber Process N2 + 3H2 Fe catalyst 200 atm 450 degC 2NH 3

Fe is used primarily because it is effective and cheap. It cannot corrode in this atmosphere or be poisoned.

1st stage in Nitric Acid Manufacture (making NO gas) > 4NH3 + 5O 2 4NO + 6H 2O Fe cannot be used because it would Red hot corrode and oxides would be too Pt/Rh reactive with the reagents. Hence the catalyst use of expensive noble metals. < The Contact Process Fe would corrode and other metals, though unreactive, would still suffer from sulphur poisoning. Oxides are more ideal catalysts. Vanadium V oxide is also involved in the reaction.

SO 2 +

O2

2SO 3

V 2 O5 catalyst 1-2 atm 450 degC

Homogeneous Catalysis
Both the catalyst and the reactant are in the same phase

What do you need to know:

Be aware of one liquid phase example and how it works; Be aware of one gas phase example and how it works; And know the principles of autocatalysis.

Remember, autocatalysis does NOT occur in a car exhaust !!!!

Oxidation of iodide ions with peroxodisulphate VI ions

S 2O8 2- + 2I I2 + 2SO 4 2-

Liquid phase homogeneous catalysis:

Slow reaction Repulsion of negative ions Low possibility of successful reactions Fe II is used as a catalysts and intermediary (although equally, Fe III could be used for this reaction). 2Fe 2+ 2Fe3+ + + S 2O8 22I 2Fe 3+ + 2Fe 2+ + 2SO 4 2I2

Overall this gives the reaction above, but the two reactants do not have to meet !

Interactions in the ozone layer of the atmosphere

Ozone is constantly being formed and destroyed by the action of UV light in the upper atmosphere. UV light is absorbed. O2 O2 O3 uv => + uv => O O O2 + + O => O (radicals unpaired electrons) O3

Gas phase homogeneous catalysis:

However, chlorofluorocarbons interfere in a homogeneous catalysis process to destroy ozone without a UV step. This is the main cause of polar ozone holes and is shown simply below. Cl ClO + + O 3 ClO Cl + + O2 O2

Autocatalysis
Autocatalysis occurs when a product in a reaction also becomes the catalyst. Typically, these reactions start slow and then the rate accelerates as more catalyst is added as a product. Example: The reaction of manganate VII ions with ethanedioic acid 2MnO4 + 6H+ + COOH => 2Mn 2+ + 10CO COOH Catalyst production + 8H2 O

Catalysed route 4Mn 2+ + 2Mn 3+ + MnO 4 COOH COOH + => 8H + => 2Mn 2+ + 5Mn 3+ + 2CO 2 4H2 O