Lecture 1

1. Introduction to Catalysis
Catalysts are substances added to a chemical process that do not
enter into the stoichiometry of the reaction but that cause the reaction to
proceed faster or make one reaction procees faster than others.

Mechanism of increasing rate reaction by catalysts

In terms of the transition-state theory, the catalyst reduces the potential

energy barrier (activation energy) over which the reactants must pass to
form products. This lowering in energy barrier is shown in Figure.

2. Catalyst materials

We distinguish between homogeneous and heterogeneous catalysts.

Homogeneous catalysts are molecules in the same phase as the reactants
(usually a liquid solution( and heterogeneous catalysts in another phase
(usually solids whose surfaces catalyze the desired reaction). Acids,
bases, and organometallic complexes are examples of homogeneous
catalysts, while solid powders, pellets, reactor walls, silica, Zeolites, and
noble metal (Pt, Pd, Ag, Rh, Ni, ) are examples of heterogeneous
catalysts.

3. Structure of catalytic pellets

Most catalysts consist of porous catalyst pellets that may be spherical,

cylindrical, or planar and have a microporous stracture with pores ranging
in diameter from a few angstroms to a few microns. In most situations
reaction occurs throughout the porous pellet, not just on its external
surface.

Kinetic Models for Heterogeneous Reactions

For a solid-catalyzed reaction, the rate depends on the reactant

concentrations at the catalyst surface, but these are not the same as the
bulk concentrations, because some driving force is needed for mass
transfer to the surface.

Models For Surface Reaction

The concentrations of reactants and products on the surface are given in

terms of adsorption isotherms, where the amount adsorbed is expressed as
the fraction of surface (or sites) covered.

Adsorption Phenomena

Adsorption is the adhesion in an extremely thin layer of molecules

(as of gases, solutes, or liquids) to the surfaces of solid bodies or
liquids with which they are in contact.

There are two types of adsorption:

1. Physical adsorption: involves vander Waals or secondary valence

forces.It is akin to condensation.
 2. Chemisorption: involves a chemical interaction with attendant
transfer of electrons between the adsorbent and the adsorbing
species (adsorbate).

Adsorption Isotherm

Plots of an amount of material adsorbed versus pressure at a fixed

temperature.

Langmuir Isotherm

The Langmuir isotherm corresponds to a highly idealized type of

adsorption and the maximum amount of adsorption that is possible is that
which corresponds to a monolayer.

The process is described as a reaction between a molecule from the gas

phase and an unoccupide site, S:

𝐴 + 𝑆 → 𝐴𝑆 (1)

𝑟𝑎𝑑𝑠,𝐴 = 𝑘1𝐴 𝑃𝐴 (1 − 𝜃𝐴 ) (2)

𝑘1𝐴 = 𝑎𝑒 −𝐸𝑎𝑑𝑠/𝑅𝑇

where θ, is the fraction of the surface covered by adsorbed species A.

The rate of desorption of A is proportional to the amount of A on the

surface:

𝑟𝑑𝑒𝑠,𝐴 = 𝑘2𝐴 𝜃𝐴 (3)

𝑘2𝐴 = 𝑑𝑒 −𝐸𝑑𝑒𝑠/𝑅𝑇

At equilibrium the rates of adsorption and desorption are equal:

𝑘1𝐴 𝑃𝐴 (1 − 𝜃𝐴 ) = 𝑘2𝐴 𝜃𝐴 (4)

𝑘1𝐴 𝑃𝐴
𝜃𝐴= (5)
𝑘2𝐴 +𝑘1𝐴 𝑃𝐴

Or,
𝑏𝑃𝐴
𝜃𝐴 = (6)
1+𝑏𝑃𝐴
 𝑘1𝐴
𝑏=
𝑘2𝐴

Equation 6 is the Langmuir isotherm for adsorption of a single species.

If adsorption follows the Langmir isotherm, an arithmatic plot of the

amount adsorbed versus the pressure will have the shape shown in
Figure:

Where Vm is the volume corresponding to a monolayer on the surface or

to all sites occupied.

To test the fit of data to a Langmuir isotherm, a rearranged form of the

equation is used. From equation 6 and the definition of Vm :
𝑏𝑃𝐴
𝑉 = 𝑉𝑚 (7)
1+𝑏𝑃𝐴

1 1+𝑏𝑃𝐴 1 1 1
= = ( )+𝑉 (8)
𝑉 𝑉𝑚 𝑏𝑃𝐴 𝑉𝑚 𝑏 𝑃
𝐴 𝑚

Ploting 1/V against 1/PA should give a straight line with intercept 1/Vm

and slope 1/Vmb: