Surface Chemistry

Surface Chemistry
Introduction:
From the surface,we mean the boundary or interface separating the two bulk phases
and the chemistry at the boundary or interface of the two bulk phases is known as
Surface Chemistry.
For example ,the interface between a solid and a liquid may be represented by solid-
liquid interface.
There is no interface between gases because they are miscible
Adsorption: The accumulation of molecular species at the surface rather than in the bulk of a solid or
liquid is termed as adsorption.

Adsorbate: The substance which is being adsorbed on the surface of another substance is called
adsorbate.

Adsorbent: The substance present in bulk, on the surface of which adsorption is taking place is called
adsorbent.

Example:If some powdered charcoal is placed in contact

with a gas like NH2,CO2, Cl2 etc.taken is a closed
vessel ,pressure of the gas falls.This indicates that the gas
has been adsorbed on the surface of charcoal.Here,gas is
adsorbate and charcoal is the adsorbent
Desorption: It is the reverse of adsorption ,i.e., it is the process which involves the removal of
adsorbate from the surface of the adsorbent.

Absorption: When the molecules of a substance are uniformly distributed throughout the body
of another substance ,the phenomenon is called absorption. Example: Ammonia(g) dissolved in
water.

Sorption: The process of simultaneous adsorption and absorption is called sorption. Example:
Dyes gets adsorbed as well as absorbed in cotton fibres, i.e., sorption takes place.
 Difference between adsorption and absorption
Adsorption Absorption
• Adsorption is a surface phenomenon. • Absorption is a bulk phenomenon.
• Rapidly starts and slowly decreases. • Absorption occurs at a uniform state.
• Exothermic process. • Endothermic process.
Types of Adsorption:
(a)Physical adsorption(or Physisorption)
(b)Chemisorption (or Langmuir adsorption)

Physisorption : In this type of adsorption, the molecules of the adsorbate are

being held to the solid surface by weak attractive forces called van der Walls’
forces. Therefore, physical adsorption is also called van der Walls’ adsorption.
Adsorption of gases like hydrogen or oxygen on charcoal is an example of physical
adsorption.

Chemisorption: In this type of adsorption, molecules or atoms of adsorbate are

held to the solid surface by chemical bonds. These bonds may be covalent or ionic
in nature.
Example: Hydrogen is chemisorbed on nickel.
Chemisorption is also called activated adsorption.
 Physisorption Chemisorption

• Molecules are held due to chemical bonds.

• Molecules are held due to van der Walls’ forces.
• Heat of adsorption are in the range , 80-
• Heat of adsorption are in the range, 20-40kJmol-1
240kJmol-1
• Usually completely reversible.
• Often irreversible.
• Increases with increase in pressure.
• Change of pressure has no such effect.
• Usually occurs rapidly at low temperature and
• Can occur at high temperature.
decreases with increase in temperature.
• Activation energies are small.
• It requires high energies of activation.
 Factors affecting the adsorption of a gas by
solid
1. Nature of the gas (adsorbate): In general if a gas is more liquefiable it will be more easily
adsorbed. For example: gases like NH3,HCl,CL2,CO2,which can be liquefied easily are more
readily adsorbed on the solid surface rather than permanent gases like O2,H2,etc.
2. Surface area: The volume of gas adsorbed increases with increase in surface area of the
adsorbent. Finely divided substance have larger adsorption power that when they are
present in the compact form. This is again due to the larger surface area of the finely
divided substance.
3. Pressure: At constant temperature the adsorption of gas increases with increase in
pressure till it reaches equilibrium.
4. Temperature: The magnitude of adsorption increases with decrease in temperature.
However, the chemisorption first increases with rise in temperature and then starts
decreasing .The initial increase id due to the fact that heat supplied acts as activation
energy. The decrease afterward is due to the exothermic nature of adsorption equilibrium.