Adsorption

- The accumulation of molecular species on the surface of a solid own liquid

resulting in a higher concentration of the molecules on the surface is known as
adsorption.

2 TYPES
1. Physical Adsorption
- When gas molecules or atoms are held to the surface of a solid by weak van der
Waals forces.
- Also known Vander Waals adsorption or Physisorption.
- There is no chemical bonding between the absorbent and the adsorbate
- Physical adsorption occurs when a gas accumulates on the surface of a sonnet
by Van der Waals forces without the formation of a chemical bond between the
adsorbate and the adsorbent.
o Ex. In the adoption of dihydrogen on the is a finely divided platinum
hydrogen molecules are first attracted towards the surface of platinum by
weak van der Waals forces And then adsorbed due to the presence of
unbalanced attractive forces or free valences on the metal surface
o Platinum is the adsorbent and dihydrogen molecules the adsorbate

2. Chemical Adsorption
- The phenomenon that occurs when gas molecules or atoms are held to the
surface of a solid by chemical bonds.
o In the example of dihydrogen and platinum on increasing the temperature
the adult dihydrogen molecules on the surface of platinum dissociate into
hydrogen atoms.
o These hydrogen atoms are held strongly by platinum through chemical
bonds (ionic / covalent).

Some cases both physical and chemical absorption may take place at the same time
and it may not be possible to identify the types of absorption. (They can occur
simultaneously).
Basic Characteristics Of Adsorption
1. Specificity Of the Absorbent 5. Activation Energy
2. Nature Of the Adsorbate 6. Layers Of Adsorption
3. Reversibility Of the Process 7. Surface Area of Adsorbent
4. Enthalpy Of Absorption

1. Specificity of the Adsorbent

- In physical absorption of the solid or the absorbent has no specific preference for
any type of gas molecules or the adsorbate because the Van der Waals forces the
act on the absorbent and the adsorbate are universal.
- However chemical absorption is highly specific and will occur only when an ionic or
covalent bonding is possible between the absorbent and the adsorbate.
- Therefore, we can infer that while physical adsorption is not specific in nature
chemical absorption is highly specific.

2. Nature of Adsorbate
- The amount of gas adsorbed by the adsorbent also depends on the nature of the
gas or the adsorbate.
- Different gases are absorbed to different extents by the same adsorbent at the
same temperature.
 o Ex. at 288 K ,one gram of charcoal adsorbs 380 CC of sulfur dioxide ,16.2
CC of methane and only 4.5 CC of hydrogen..
- It may be seen from the critical temperature values that higher the critical
temperature of the gas the greater is the extent of adsorption.
o This is because gases that can be easily liquefied have high critical
temperatures and are more easily absorbed.
o This can be attributed to the fact that the van der Waals forces are strong in
the range closer to the critical temperature of that gas.

Critical Temperature of a Gas - defined as the temperature above which the gas
cannot be liquefied however high the pressure applied .

- It can be seen that the volume of the absorbed gas increases as the critical
temperature increases.
- In chemical absorption no correlation is seen between the amount of gas
absorbed and the critical temperature of the gas, but adsorption depends on the
chemical nature of the gas.
- The greater the reactivity of the adsorbate the greater is the amount of absorption.
Therefore, we can inform that both physical and chemical adsorption depend on the
nature of the adsorbate.

3. Reversibility of the Process

- Like any other equilibrium, absorption is the process involving through equilibrium.
- With adsorption on one site and desorption on the other.
o The two opposite processes include the absorption of gas molecules on the
surface of a solid and desorption of gas molecules from the surface of a
solid into the gaseous phase.
- Adsorption is an exothermic process, the equilibrium can be represented by:

- On applying Le Chatelier’s principle, it can be seen that when we increase the

pressure or decrease the temperature the equilibrium shifts forward, that is
adsorption increases.
- Similarly, when we decrease the pressure or increase the temperature the
equilibrium shifts backwards that is adsorption decreases/desorption.
- Physical adsorption is a reversible process due to the presence of weak van der
Waals forces of attraction.
- Chemical absorption chemical bonds are formed between the adsorbate and the
absorbent molecules.
o Ex. when oxygen is chemically absorbed on carbon to reverse this process
there is a need to free the absorbed gas however the diverse process
releases carbon monoxide or carbon dioxide instead of oxygen hence
chemical absorption is irreversible in nature.

Therefore, we can conclude that physical observes the reversible process , while
chemical adsorption is irreversible.
4. Enthalpy of Absorption
- In physical adsorption since the van der Waals forces of attraction are weak , the
heat evolved or the enthalpy of adsorption is very little .
 - Chemical adsorption is on exothermic process ,however, in chemical adsorption
surface compounds form and the forces involved are similar to chemical
bonds ,does a relatively high amount of heat .
Therefore we see that the enthalpy of adsorption of physical adsorption is low,
whereas the enthalpy of chemical adsorption is very high.
5.Activation Energy
- Activation energy is the minimum energy required to convert reactants into the
respective products.
- Physical absorption involves only weak van der Waals forces and does not involve
the formation of surface compound or any chemical bonds, therefore it does not
require activation energy.
- However, a chemical adsorption in formation of surface compound ,activation
energy is required for the formation of chemical bonds between the adsorbent and
the adsorbate.
- A gas may be physically adsorbed at low temperature but chemically adsorbed at
high temperature.
o Ex. During the absorption of hydrogen only nickel at low temperatures,
hydrogen is physically adsorbed on nickel.
o However, at high temperatures, hydrogen gets chemically adsorbed on the
surface of nickel.
- In other words, an increase in the temperature supplies the necessary activation
energy for the formation of surface compounds and the process is called
activated adsorption.
We can therefore conclude that physical adsorption requires no appreciable activation
energy, while chemical adsorption requires high activation energy

6. Layers of Adsorption
- Layers of gas molecules are adsorbed one over another by van der Waals forces
in physical adsorption, that is why multi molecular layers are formed under high
pressure in physical absorption.
- In chemical adsorption a chemical bond is formed with the molecules that come in
direct contact with the surface of the absorbent, and only a unimolecular layer is
formed in chemical absorption.
Therefore, multi molecular layers are formed in physical absorption but only a
unimolecular layer is formed during chemical assumption
7. Surface Area of Adsorbent
- The greater surface area the greeter the adsorption.
- Therefore, substances with porous structures are good adsorbent.
- Charcoal is a good absorbent as it has a porous structure
For both physical and chemical adsorption the extent of adsorption increases with an
increase in the surface area of the adsorbent.