Introduction To Heterogeneous Catalysis: Letcture-1

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Introduction to Heterogeneous

Catalysis
Letcture-1
Introduction
Heterogeneous Catalysis
Introduction to Catalysis
 Catalysts are workhorse of chemical transformations in the
industry. Approximately 85-90 % of the products of chemical
industry are made in catalytic processes. Catalysts are
indispensable in
 Production of transportation fuels in one of the approximately 440 oil
refineries all over the world
 Production of bulk and fine chemicals in all branches of chemical
industry
 Prevention of pollution by avoiding formation of waste
 Abatement of pollution in end-of-pipe solutions (automotive and
industrial exhaust)
A catalyst offers an alternative, energetically favorable mechanism to the
non-catalytic reaction, thus enabling process to be carried out under
industrially feasible conditions of pressure and tempearture.
Catalyst Definitions

Berzelius (1836)
“Catalysts are materials that evoke chemical reactions that would
otherwise not take place”

Ostwald (1902)
“Catalyst is a substance that changes the velocity of a chemical
reaction without itself appearing in the product”

A catalyst is substance that increases the rate at which a chemical


reaction approaches equilibrium without itself becoming
permanently involved in the reaction.
What is a Catalyst ?
Potential energy diagram of a
heterogeneous catalytic reaction
Potential Energy (Contd.)

 The catalyst offers an alternative path for the reaction, which is


obviously more complex, but energetically much more favorable.
 The activation energy of the catalytic reaction is significantly smaller
than that of the uncatalyzed reaction. Hence, the rate of the catalytic
reaction is much larger.
 The overall change in free energy for the catalytic reaction equals
that of the uncatalyzed reaction. Hence, the catalyst does not affect
the equilibrium constant for the overall reaction A + B to P. Thus, if a
reaction is thermodynamically unfavorable, a catalyst cannot change
this situation. A catalyst changes the kinetics but not the
thermodynamics.
 The catalyst accelerates both the forward and the reverse reaction
to the same extent. In other words, if a catalyst accelerates the
formation of the product P from A and B, it will do the same for the
decomposition of P into A and B.
Classifications

 Homogeneous Catalysts

 Heterogeneous Catalysts

 Enzymes
Homogeneous Catalysis
 The catalyst and the reactants are in the same phase, i.e., all are molecules in
the gas phase or more commonly, in the liquid phase.
 Examples:
 Ozone decomposition in atmosphere via a reaction with chlorine atoms:
Cl + O3 ClO3
ClO3 ClO + O2
ClO + O Cl + O2
or overall
O3 + O 2O2

 The catalytic carbonylation of methanol to acetic acid:

CH3 OH + CO CH3COOH

By [Rh(CO)2I2]- complexes in solution.


Biocatalysis (Enzymes)
 Enzymes are nature’s catalysts. Usually
these are large protein molecules,
having shape-specific active site.

 Having shapes that are optimally


suited to guide reactant molecules
(substrates) in the optimum
configuration for reaction,
enzymes are highly specific and
efficient catalysts.
 Example: The enzyme catalase
catalyzes the decomposition of
hydrogen peroxide into water and
oxygen
2H2O 2 2H2O + O2
catalase

@ of up to 107 H2O2 molecules/sec!


Heterogeneous Catalysis
 The reactants and catalyst exist in
different phases. Most commonly, solid
catalysts are used with gaseous or liquid
reactants, some time both. Other
permutations are possible but less
often encountered.
 Catalysts are usually nanometer-sized
particles, supported on an inert, porous
structure.
 Interfacial phenomena.  Heterogeneous catalysts are convenient
 Diffusion, absorption, and adsorption to use commercially.
play critical role in establishing the rate.
 Easily prepared solid catalyst pellets,
 Ammonia synthesis was the first
important catalytic process, emerging packed in tubes through which
over 70 years ago – yet the nature of reactants flow, satisfy process
the catalytic surface is still debated. requirements for simple construction
and dependable operation.
 Control is good, product quality high.
Applications of Heterogeneous catalysts

• Synthesis of chemicals: NH3 (85% for fertilizer)


Synthesis gas,
Polymers, etc.

• Environmental Cat.: HDS (removal of sulfur)


DeNOx (cleaning of flue gas)
SO2 oxidation (H2SO4)

• Energy Production: Fuel Cells


Cleaning of flue gasses
Commercial Catalysts
Catalyst – Important properties

 Arrhenius Rate constant:


k = Ao exp (-Ea/RT)
Small change in Ea leads to big
change in rate.

Example:

Ea non-catalytic = 40 Kcal/mol
Ea Catalytic = 30 Kcal/mol

Ratecatalytic = Rate non-catalytic. e10


= 2.2 x 104 . (rate, non-
catalytic)

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