Define catalyst

Catalyst
A substance that affects the rate of a reaction but emerges from the
process unchanged

No catalyst
Slow

H2 + O2 H2 O

Catalyst
Fast

reaction coordinates, which is a measure the progress along the reaction path.
 Development & search
Therefore, the development and use of a catalyst, new catalyst, is a major part
of constant search, particularly for improving yield and selectivity. This is
because the catalyst is known to reduce the activation energy required for
taking reactants into a product stream. It actually enables reducing the
activation energy for converting the reactants into products. Clearly, because it
is reducing the activation energy, it is likely to have a strong impact on the
yield and selectivity of that particular system which may have multiple
reactions occurring simultaneously.

S-882 This catalyst currently used for synthesizing ethylene oxide has a great selectivity

Year Selectivity
1960 70%
2000 80%
2017 theoretically ~93%
Components of catalyst
 Components of catalyst
The active species
The active species have a catalytic activity towards one or more catalytic reactions.
These species are constituted of one or more compounds which either contribute each
one with its own different functional properties, or interact between themselves creating
synergistic effects at their interfaces.

Promoter
Promoter is small amount of additional material which insert in the catalyst composition,
to improve the physical and chemical properties of catalyst. These materials can be
classified in physical and chemical promoters. Physical promoter, it is element or
compounds resulted in enhancement in the thermal stability and mechanical resistance
of catalyst depending upon high melting point such as Al2O3, SiO2, TiO2 and MgO. In
addition, chemical promoter, it is element or compound brought about modifications in
the activity, selectivity and lifetime of the catalyst such as Li and K oxides.

Support
Support is the substance that forms the largest amount of the catalytic component. The
activity of the support varies according to the nature of the catalytic reaction in which
the catalyst is present. Alumina, active carbon, magnesia, silica, titiania, zirconia and
zeolites are the important industrial supports.
Requirements of good catalysts
 Classification of catalysis
There are essentially 2 types of catalysis or 2 classes of catalysis.

Homogeneous catalysis
The catalyst is in a solution that contains at least 1 reactant that is
participating in the reaction.
Oxo process for manufacturing isobutalaldehyde, is a good example
where propylene reacts with CO and H2 in the presence of a cobalt
complex catalyst in the solution phase.
CHO

CH3-CH-CH3
Co
CH3-CH=CH2 + CO + H2
CH3-CH2-CH2-CHO
 Classification of catalysis
Heterogeneous catalysis

It involves more than 1 phase. where the catalyst is typically present in the
solid phase and the reactants and products are actually in, may be in the
gaseous or the liquid phase.

Let us look at an example. Cyclohexane on platinum catalyst, platinum

on impregnated in alumina, will lead to benzene formation.

Pt/Al2O3
+ 3H2

Cyclohexane Benzene
Supported and unsupported catalysts
Zeolite catalyst is selective to xylene formation from toluene and methane. It is
a very good example of such molecular sieve, which is actually very selective to
a particular product formation. It is not that all catalysts actually have such
kind of extended surface.

There are 2 classes of catalysts, supported and unsupported catalyst.

Supported catalysts are those where the catalytic material, typically oxides
of noble metal, will be impregnated in the particle form on the surface of a
supporting material. A supporting material, for instance, could be silicon or
alumina. A good example of such a catalyst is platinum on alumina.

Unsupported catalyst is where such a support is not required and directly the
catalyst particles are used as a catalytic material for facilitating the surface
reaction. For example, Pt wire gauze used for ammonia oxidation.
Supported and unsupported catalysts

For supported catalyst, Platinum on alumina is used for petroleum

reforming. Vanadium pentoxide on silica is used for oxidizing SO2 in H2SO4
production process.

As an example for unsupported catalyst, Pt gauze is typically used for

ammonia oxidation. Promoted iron is used for ammonia synthesis. Silica
alumina is used for dehydrogenation, typically in butadiene manufacturing.
 Reactions and catalyst
Based on the reaction temperature and TOF

Class of reactions Catalyst

Alkyation and dealkylation AlCl3

Isomerization Acid promoted Al2O3

Hydrogenetion and dehydrogenation Co, Pt,Ni, Ru etc.

Oxidation Reaction Ag, Cu, Pt

Hydration and dehydration Al2O3

Halgenation and dehalogenetion Supported copper or silver halide

 How does a catalyst works?
How does a catalyst facilitate acceleration or deceleration depending upon the
situation? Or, in general, how does it facilitate affecting the rate of the reaction?
During a catalytic reaction, the species which needs to react actually goes into
the pores and thereby gets access to the surface of the catalyst. The catalyst
material present in the surface somehow interacts with the species present, that
is, the species which is participating in the reaction. This interaction typically
involves adsorption process which is essentially the adherence of the species to
the material. Adsorption can typically be of 2 types, viz., chemical adsorption
or physical adsorption. Adsorption is the mechanism that involved in the gas
phase reactions catalyzed by solid catalyst.

The typical range for heat of adsorption (∆Hads) for physical adsorption is
~4 – 62 kJ/mol. In a similar fashion, the chemical adsorption is also an
exothermic step and the ∆Hads is in the range ~40 – 400 kJ/mol. Thus, one
needs to supply heat for the species to actually adsorb onto the surface.
 Rate controlling step
Given that multiple steps are involved, there must be a rate controlling step as all steps
will not occur at the same speed. Thus, the slowest step will dictate the overall rate at
which the reaction occurs. This slowest step is the rate controlling step. This is due to
the fact that relative to the speed at which the slowest step occurs, all other steps
actually occur faster. As a result, the overall rate at which the reactant species is
converted to products is essentially controlled by that particular step which is the
slowest. In principle any one of the 7 steps could be the slowest. Next, let’s consider
one-by-one each of these 7 steps being the slowest step and understand what will be
the overall reaction rate in that case.
Selectivity of catalyst
 -

-
 Active sites and TOF
During chemisorption, species actually binds to the active material available on
the catalyst sites. These sites are referred to as active sites. An active site is a
point on the catalyst surface that can form strong chemical bond with an
adsorbed atom or molecule.

In fact, the number of active sites is quantified by turnover frequency or TOF

in short. TOF reflects the number of molecules reacting per active site per
second at a certain experimental condition.

numbers of molecules reacting

TOF =
per site × per second
 Examples of Mathematics
Reaction CO + 3H2 → CH4 + H2 O was studied using a commercial 0.5 wt% Ru on
γ − Al2 O3 . The catalyst dispersion percentage of atoms exposed, determined from
hydrogen chemisorption was found to be 49%. At a pressure of 988 kPa and a
temperature of 475 K, a turnover frequency, 𝑓𝐶𝐻4 , of 0.044 s-1 was reported for
methane. What is the rate of formation of methane, 𝑟 ′ M , in mol/s.g of catalyst (metal
plus support)

Solution 1 % Ru
𝑟′ M = 𝑓𝐶𝐻4 𝐷
MWRu 100

0.044 molecules 1 mol CH4 0.49 surface atoms

= × ×
surface atom Ru ∙ s 6.02 × 1023 molecules total atoms Ru

6.02 × 1023 atoms Ru g atoms Ru 0.005 g Ru

× × ×
g atom mol Ru 101.1 g Ru g total

mol
= 1.07 × 10−6
s ∙ g catalyst