CATALYSIS

The presence of even 1mg of fine platinum powder is enough to catalyse the combination of 2.5
litresof a mixture of H2 and O2 to form H2O.
Types of catalytic reactions

Catalysts can be divided into two main types - heterogeneous and homogeneous. In a heterogeneous
reaction, the catalyst is in a different phase from the reactants. In a homogeneous reaction, the
catalyst is in the same phase as the reactants.

Homogeneous catalysis

This has the catalyst in the same phase as the reactants. Typically everything will be present as a
gas or contained in a single liquid phase. The examples contain one of each of these . . .
Other examples of homogeneous catalysis
The reaction between persulphate ions and iodide ions
This is a solution reaction that you may well only meet in the context of catalysis, but it is a lovely
example!
Persulphate ions (peroxodisulphate ions), S2O82-, are very powerful oxidising agents. Iodide ions are
very easily oxidised to iodine. And yet the reaction between them in solution in water is very
slow.
If you look at the equation, it is easy to see why that is:

The reaction needs a collision between two negative ions. Repulsion is going to get seriously in the
way of that!

The catalysed reaction avoids that problem completely. The catalyst can be either iron(II) or iron(III)
ions which are added to the same solution. This is another good example of the use of transition
metal compounds as catalysts because of their ability to change oxidation state.

For the sake of argument, we'll take the catalyst to be iron(II) ions. As you will see shortly, it doesn't
actually matter whether you use iron(II) or iron(III) ions.

The persulphate ions oxidise the iron(II) ions to iron(III) ions. In the process the persulphate ions are
reduced to sulphate ions.

The iron(III) ions are strong enough oxidising agents to oxidise iodide ions to iodine. In the process,
they are reduced back to iron(II) ions again.

Both of these individual stages in the overall reaction involve collision between positive and negative
ions. This will be much more likely to be successful than collision between two negative ions in the
uncatalysed reaction.

Example of homogeneous catalysis in gas phase

In lead chamber process

SO2 + O2 = SO3( in presence of NO)
Sulphur dioxide is introduced with steam & oxides of nitrogen into large lead chambers lined with
sheet lead.

NO + ½ O2 = NO2

2. Iodine vapour acts as catalyst for pyrolysis of acetaldehyde.

Thus Heterogeneous catalysis- involves the use of a catalyst in a different phase from the
reactants. Typical examples involve a solid catalyst with the reactants as either liquids or gases.

How the heterogeneous catalyst works (in general terms)

Most examples of heterogeneous catalysis go through the same stages:

One or more of the reactants are adsorbed on to the surface of the catalyst at active sites.

An active site is a part of the surface which is particularly good at adsorbing things and helping
them to react.

There is some sort of interaction between the surface of the catalyst and the reactant molecules
which makes them more reactive.

This might involve an actual reaction with the surface, or some weakening of the bonds in the
attached molecules.

The reaction happens.

 At this stage, both of the reactant molecules might be attached to the surface, or one might be
attached and hit by the other one moving freely in the gas or liquid.

The product molecules are desorbed.

This leaves the active site available for a new set of molecules to attach to and react.

A good catalyst needs to adsorb the reactant molecules strongly enough for them to react, but not so
strongly that the product molecules stick more or less permanently to the surface. Silver, for example,
isn't a good catalyst because it doesn't form strong enough attachments with reactant molecules.
Tungsten, on the other hand, isn't a good catalyst because it adsorbs too strongly. Metals like
platinum and nickel make good catalysts because they adsorb strongly enough to hold and activate
the reactants, but not so strongly that the products can't break away.

Examples of heterogeneous catalysis

(1) The hydrogenation of a carbon-carbon double bond

The simplest example of this is the reaction between ethene and hydrogen in the presence of a
nickel catalyst.

In practice, this is a pointless reaction, because you are converting the extremely useful ethene into
the relatively useless ethane. However, the same reaction will happen with any compound containing
a carbon-carbon double bond.

One important industrial use is in the hydrogenation of vegetable oils to make margarine, which also
involves reacting a carbon-carbon double bond in the vegetable oil with hydrogen in the presence of a
nickel catalyst.

Ethene molecules are adsorbed on the surface of the nickel. The double bond between the carbon
atoms breaks and the electrons are used to bond it to the nickel surface.

Hydrogen molecules are also adsorbed on to the surface of the nickel. When this happens, the
hydrogen molecules are broken into atoms. These can move around on the surface of the nickel.

If a hydrogen atom diffuses close to one of the bonded carbons, the bond between the carbon and
the nickel is replaced by one between the carbon and hydrogen.
That end of the original ethene now breaks free of the surface, and eventually the same thing will
happen at the other end.

As before, one of the hydrogen atoms forms a bond with the carbon, and that end also breaks free.
There is now space on the surface of the nickel for new reactant molecules to go through the whole
process again.

(2) Decomposition of potassium chlorate:Potassium chlorate is often used in high school and college
laboratories to generate oxygen gas[citation needed]; it is a far cheaper source than a pressurized or cryogenic oxygen
tank. Potassium chlorate will readily decompose if heated in contact with a catalyst, typically manganese (IV)
dioxide (MnO2).

When heated strongly, potassium chlorate decomposes into potassium chloride and oxygen. This
reaction is used for the preparation of oxygen.

If the decomposition is carried out in the presence of manganese dioxide (MnO2), it takes place at a lower
temperature. In this case, MnO2 is used as a catalyst.

(3) In the manufacture of sulfuric acid by contact Process

Reaction of sulfurdioxide and oxygen using finely divided platinum or vanadium pentoxide as
catalyst.

Sulphur dioxide and oxygen then react as follows:

2 SO2(g) + O2(g)⇌ 2 SO3(g) : ΔH = −197 kJ mol−1

According to the Le Chatelier's principle, a lower temperature should be used to shift the chemical equilibrium
towards the right, hence increasing the percentage yield. However too low of a temperature will lower the
formation rate to an uneconomical level. Hence to increase the reaction rate, high temperatures (450 °C),
medium pressures (1-2 atm), and vanadium(V) oxide (V2O5) are used to ensure a 96% conversion. Platinum
would be a more effective catalyst, but it is very costly and easily poisoned.[citation needed] The catalyst only serves
to increase the rate of reaction as it does not change the position of the thermodynamic equilibrium. The
mechanism for the action of the catalyst comprises two steps:

1. Oxidation of SO2 into SO3 by V5+:

2 SO2 + 4V5+ + 2 O2- → 2 SO3 + 4V4+

2. Oxidation of V4+ back into V5+ by oxygen (catalyst regeneration):

4 V4+ + O2 → 4 V5+ + 2 O2-

(4) Manufacture of nitric acid -Oxidation of ammonia in presence of platinum gauze

4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g) (ΔH = −905.2 kJ)

Nitric oxide is then reacted with oxygen in air to form nitrogen dioxide.

2 NO (g) + O2 (g) → 2 NO2 (g) (ΔH = −114 kJ/mol)

This is subsequently absorbed in water to form nitric acid and nitric oxide.

3 NO2 (g) + H2O (l) → 2 HNO3 (aq) + NO (g) (ΔH = −117 kJ/mol)

(5)Synthesis of ammonia by Haber Process

The Haber process, also called the Haber–Bosch process, It is the main industrial route to ammonia:[1]
N2 + 3 H2⇌ 2 NH3 (ΔH = −92.22 kJ·mol−1)
The most popular catalysts are based on iron promoted with K2O, CaO, SiO2, and Al2O3. The original
Haber–Bosch reaction chambers used osmium as catalysts. However, under Bosch's direction in 1909, the
BASF researcher AlwinMittasch discovered a much less expensive iron-based catalyst, which is still used.

The reaction mechanism, involving the heterogeneous catalyst, is believed to involve the following steps:

1. N2 (g) → N2 (adsorbed)
2. N2 (adsorbed) → 2 N (adsorbed)
3. H2(g) → H2 (adsorbed)
4. H2 (adsorbed) → 2 H (adsorbed)
5. N (adsorbed) + 3 H(adsorbed)→ NH3 (adsorbed)
6. NH3 (adsorbed) → NH3 (g)
The poisoning of the catalyst is probably due to the preferential adsorption of poison on the surface of the catalyst thus
reducing the space available for adsorption of reacting molecules.
Enzyme catalysis
Enzymes are macromolecules, usually proteins, produced in living systems, which act as catalysts in
physiological reactions. The striking characteristics of enzymes are their catalytic power and specificity.
Enzymes have immense catalytic power. They accelerate reactions by factors of at least a million. Most
reactions in living systems do not occur at perceptible rates in the absence of enzymes.

A simple reaction like the hydration of CO2 is catalyzed by the enzyme carbonic anhydrase and is called
as enzyme catalyzed reaction.The transfer of CO2 from tissues into the blood and then to the alveolar air
would be very slow in the absence of this enzyme. The enzyme can hydrate 105 molecules of CO2 per second,
which is 107 times faster than the uncatalyzed one.

This example illustrates the fact that enzymes have immense catalytic power.Enzymes increase at the rate of
106 to 1020 times. The catalytic power of proteins comes from their capacity to bind substrates (reactant)
molecules in precise orientations and to stabilize transition states in the making and breaking of bonds.

Enzymes are highly specific. An enzyme usually catalyses a single chemical reaction or a set of closely related
reactions.

For e.g., urease catalyses the hydrolysis of urea only.

Characteristics of Enzymes
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Given below are some of the characteristics of enzymes :

 Enzymes are proteins involved in all the biochemical conversions in the plant and animal cells. Enzymes act as
biochemical catalysts and accelerate the chemical conversion but remain unmodified themselves. The enzymes
work by decreasing the activation energy required for the reaction.
 The reactant in a biochemical conversion is called a substrate. The site in the enzyme molecule where the
substrate binds and the reaction takes place is called the active site. It is usually a small pocket like cleft found
deep inside the enzyme molecule.
  Enzymes are selective in terms of the substrate and act upon closely related molecules. On one hand, certain
enzymes act on only one substrate thus displaying absolute selectivity while others recognize only the bond that
they act on and are not affected by the type of the molecule containing the bond.
 Being protein in nature, enzymes require specific conditions of pH and temperature for optimal activity. At high
temperatures and non-optimal pH the enzymes lose their tertiary structure (are denatured) which is critical for
its activity.

Each enzyme has a specific active site

The active site of an enzyme binds the substrate and contains the residues that directly participate in the making
and breaking of bonds. Some features of the active site are :

1. The active site takes up a relatively small part of the total volume of an enzyme.
2. The active site is a three dimensional entity formed by groups that come from different parts of the linear amino
acid sequence.
3. Enzymes bind the substrate by multiple weak interactions. These weak interactions are electrostatic bonds,
hydrogen bonds, van der Waals' forces and hydrophobic interactions. van der Waals' forces become significant
in binding only when many substrate species can come simultaneously close to many enzymes species. Hence,
the enzyme and substrate should have complementary shapes. The directional nature of hydrogen bonds
between substrate and enzyme brings about a high degree of specificity.
4. Active sites are clefts and crevices. Substrate molecules bind to the clefts or crevices.
5. The specificity of binding of a substrate depends on the precisely defined arrangement of atoms in the active
site. To fit into the active site the substrate must have a matching shape, just like how a key fits into a lock.