Heterogeneous Catalysis

Lecturer – 5

Adsorption
 Adsorption
• Physical Adsorption – secondary (van
der Walls) attractive forces such as dipole-
dipole interaction and induced dipoles
• Chemisorption – involves chemical
bonding, similar to chemical reaction, and
involves transfer of electrons between
adsorbent and adsorbate.
• Border line cases
 Differing characteristics between physical and chemical
adsorption

Physisorption Chemisorption
1. No electron transfer – no bonding, Electron transfer – chemical bonds formed,
van der Waals forces, weak interaction strong interaction
2. Heat of adsorption, Qp, low – similar Heat of adsorption, Qc, high,
to heat of liquefaction Typically ≥ 10 kcal/mole
3. Occurs near or below boiling point Occurs at temperatures far above
of adsorbate boiling point
4. Non-activated May be activated May be activated
5. Non-specific Very specific, depends on Very specific, depends on surface
surface
6. Multilayer Monolayer
 Physisorption, Chemisorption and Dissociation

4
• Overall picture Metal +2X
3
– Physisorption 2

Energy (arb. units)

– Chemisorption 1
Ea Metal +X2
0
– Reaction -1 Ed
Physisorption (exaggerated)
-2
-3 Associativ chemisorption

-4 Metal-X2
Metal-X
-5
Dissociativ chemisorption
-6
Reaction coordinate (arb. units)
 Physisorption

Remember: 1 
r = (x,y,z),
q e  e,   
1
Physisorption is only
polarization, there is No + - (x,y,z)
exchange of electrons.
r
Energetics of Adsorption d (0,0,d)
- +
U = Ud +Ur + Up + Ufd + Ufq + Usp

Where U is the interaction potential

Ud is the attractive (dispersion) potential,
Ur is the close-range repulsion term,
Up is the polarization energy,
Ufd is the field-dipole interaction,
Ufq is the field-gradient-dipole-quadrupole interaction, and
Usp is the self-potential which takes into account
adsorbate-adsorbate interaction
 Physisorption

• Lennar-Jones potential
illustrating the activation
energy needed to transfer from 8
the physically adsorbed to the

Potential Energy [kJmol-1]

VR(d) = CR*exp(-d/)

chemisorbed state. 4
• deBoer considered adsorption
from the viewpoint of an 0
adsorption time.
-4
Eint Tres V(d) = VR(d) + VW(d)

Typical heats of physisorption for -8

VW(d) = -CW*d-3
a number of small molecules.
0 2 4 6 8 10
Molecule Enthalpy kJmol-1 Distance from surface d [Å]

CH4 -21

CO -25

CO2 -25

N2 -21

O2 -21
 Catalysis must always be preceded by
Adsorption

Langmuir-Hinshelwood Eley-Rideal mechanism

mechanism
 Adsorption Isothemrs and Isobars
• Adsorption isotherm: the amount adsorbed depends upon the
equilibrium pressure of the gas at constant temperature

• Adsorption isobar: the amount adsorbed varies with

temperature at constant pressure.
 Adsorption Equilibrium on Uniform (Ideal)
Surfaces – Langmuir Isotherms
• The Langmuir isotherm is obtained based on the assumptions
associated with an ideal uniform surface on which all sites are
identical, i.e.,
1. Localized adsorption occurs only on vacant sites,
2. Only one adsorbed species can exist per site, that is, saturation coverage is
achieved at one monolayer, and
3. The heat of adsorption is constant and independent of coverage, which
assumes that no interaction occurs between adsorbed species.

• At equilibrium, the rates of adsorption and desorption must be equal

 Mathematical Derivation
• At equilibrium, the rates of adsorption and desorption must be equal
and, with the above assumptions, equations 2.5 and 2.6 can be
used as written. [θA is the occupied fraction of possible adsorption
sites]
 Chemisorption
• Interesting aspects of chemisorption in catalysis

1. The rates of chemical adsorption of reactants or desorption of products,

studied individually, may indicate the slow, and therefore rate-limiting, step
in the catalytic reaction. They may also help characterize surface
heterogeneities.

2. The heat of chemisorption is a measure of the strength of the bonds formed

between adsorbent and adsorbate. The variation of heat of adsorption with
surface coverage is a measure of surface heterogeneity.

3. The nature of the actual chemisorbed species as revealed, for example, by

infrared adsorption gives direct evidence of possible chemical interaction in
the reaction.
 Types of Chemisorption
• Nondissociative chemisorption or
associative chemisorption

• Dissociative chemisorption