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ADSORPTION

SUBMITTED BY
BHANU CHAUDHARY
SID : 17201020
ADSORPTION DEFINITION
• It is a surface phenomenon
• It is the adhesion of atoms, ions, or molecules from a
gas, liquid, or dissolved solid to a surface.
• This process creates a film of the adsorbate on the
surface of the adsorbent.
DEFINITIONS
• ADSORBATE – the substance which is adsorbed on the surface
• ADSORBENT – the substance on which surface the adsorbate
is adsorbed
• Adsorption is a spontaneous process i.e. ΔG is negative
• Adsorption is an exothermic process i.e. ΔH is negative
PRINCIPLE
• Adsorption is a surface phenomenon and consequence of
surface energy
• The surface of a solid or liquid is in a state of strain or
unsaturation which results in unbalanced residual force
at the surface
• These unbalanced residual force results in higher surface
energy. Consequently, the surface of a solid/liquids have
a tendency to attract and retain the molecular species
with which it comes in contact
• This tendency is responsible for the phenomenon of
adsorption
ADSORPTION IN LIQUIDS
• LIQUID- A molecule in the interior of a liquid is
completely surrounded by other molecules so on an
average it is equally attracted in all directions. On a
molecule, in the surface however there is a net attraction
inwards.
• Hence particles at surface and particles at the bulk are in
different environment thus giving rise to difference in
free energy at the surface and in the bulk.
ADSORPTION IN SOLIDS
• SOLID- The cleavage of a big crystal of solid into
smaller units is done to increase the surface area.
• Due to cleavage of a big crystal into smaller unit,
residual forces or vacancies gets generated on the
surface of the solid.
• Occupancy of these vacancies by some other
molecular species results into adsorption
PHYSIOSORPTION
• When the force of attraction existing between adsorbate
and adsorbent are weak Vanderwaal forces of attraction,
the process is called Physical Adsorption or Physisorption
• Physical Adsorption takes place with formation of
multilayer of adsorbate on adsorbent.
• It takes place at low temperature below boiling point of
adsorbate. As the temperature increases in, process of
Physisorption decreases.
CHEMISORPTION
When the force of attraction existing between adsorbate and
adsorbent are chemical forces of attraction or chemical bond,
the process is called Chemical Adsorption or Chemisorption.
Chemisorption takes place with formation of unilayer of
adsorbate on adsorbent.
It can take place at all temperature. With the increases in
temperature, Chemisorption first increases and then
decreases.
FACTORS AFFECTING ADSORPTION
Temperature:
Adsorption increases at low temperature conditions.
A + B ↔ AB + Heat
Adsorption process is exothermic in nature. According to
Le Chatleir principle, low temperature conditions would
favour the forward direction.
Pressure:
As depicted by Adsorption Isotherm, with the increases
in pressure, adsorption increases up to a certain extent
till saturation level is achieved. After saturation level is
achieved no more adsorption takes place no matter how
high the pressure is applied.
Surface Area:
Adsorption is a surface phenomenon therefore it
increases with increase in surface area.

Activation of Adsorbent:
Activation of adsorbent surface is done so as to
provide more number of vacant sites on surface of
adsorbent. This can be done by breaking solid
crystal in small pieces, heating charcoal at high
temperature, breaking lump of solid into powder or
other methods suitable for particular adsorbent.
ADSORPTION ISOTHERMS
• The process of Adsorption is usually studied through graphs
know as adsorption isotherm. It is the graph between the
amounts of adsorbate (x) adsorbed on the surface of
adsorbent (m) and pressure at constant temperature.

Adsorbate + Adsorbent ↔ Adsorption

• According to Le-Chatelier principle, the direction of


equilibrium would shift in that direction where no of
molecules decreases.
• Different adsorption isotherms:
1. Freundlich
2. Langmuir
3. BET theory.
Freundlich Isotherm
Freundlich gave an empirical expression representing the
isothermal variation of adsorption of a quantity of gas
adsorbed by unit mass of solid adsorbent with pressure.
• This equation is known as Freundlich Adsorption Isotherm or
Freundlich Adsorption equation or simply Freundlich
Isotherm.
x/m = kPˆ(1/n)

• Where; x is the mass of the gas adsorbed on mass m of the


adsorbent at pressure p and k, n are constants whose values
depend upon adsorbent and gas at particular temperature.
Langmuir Adsorption Isotherm:
•In 1916 Langmuir proposed another Adsorption Isotherm known
as Langmuir Adsorption isotherm. This isotherm was based on
different assumptions one of which is that dynamic equilibrium
exists between adsorbed gaseous molecules and the free gaseous
molecules.
A(g) + B(s) ↔ AB
•Where A(g) is unadsorbed gaseous molecule, B(s) is unoccupied
metal surface and AB is Adsorbed gaseous molecule.
θ = KP/(1+KP)
•Based on his theory, he derived Langmuir Equation which
depicted a relationship between the number of active sites of the
surface undergoing adsorption and pressure.
•Where θ the number of sites of the surface which are covered
with gaseous molecule, P represents pressure and K is the
equilibrium constant for distribution of adsorbate between the
surface and the gas phase .
BET ADSORPTION ISOTHERM
• BET Theory put forward by Brunauer, Emmett and
Teller explained that multilayer formation is the true
picture of physical Adsorption.
• Under the condition of high pressure and low
temperature, thermal energy of gaseous molecules
decreases and more and more gaseous molecules
would be available per unit surface area. Due to this
multilayer adsorption would occur. The multilayer
formation was explained by BET Theory. The BET
equation is given as
TYPES OF ADSORBENTS
• Oxygen containing compounds: Typically hydrophilic and polar
e.g. silica gel & zeolites

• Carbon based compounds: typically hydrophobic and non-


polar .e.g. activated carbon & graphite

• Polymer based compounds: polar or non polar functional


groups in a porous polymer matrix. e.g. polymers & resins

• Another classification is based on the pore size of adsorbents:


1. Microporous adsorbents: Pore size range 2Å to 20Å
2. Mesoporous adsorbents: Pore size range 20Å to 500Å
3. Macroporous adsorbents: Pore size range >500Å
COMMERCIAL ADSORBENTS
Silica gel
Applications:
Drying of gases, refrigerants, organic solvents, transformer oils
Desiccant in packings and double glazing
Dew point control of natural gas

Activated alumina
Applications:
Drying of gases, organic solvents, transformer oils
Removal of HCl from hydrogen
Removal of fluorine in alkylation process
• Activated carbon

• Applications:
1. Nitrogen from air
2. Hydrogen from syngas
3. Ethene from methane and hydrogen
4. Vinyl chloride monomer (VCM) from air
5. Removal of odours from gases
6. Recovery of solvent vapours
7. Removal of SOX and NOX
8. Purification of helium
9. Clean-up of nuclear off-gases
10. Water purification
• Clay
Applications:
1. Treatment of edible oils
2. Removal of organic pigments
3. Refining of mineral oils
4. Removal of polychlorinated biphenyls (PCBs)

• Polymer And Resins


Applications:
1. Water purification
2. Recovery and purification of steroids, amino acids
3. Separation of fatty acids from water and toluene
4. Separation of aromatics from aliphatics
5. Recovery of proteins and enzymes
6. Removal of colours from syrups
7. Removal of organics from Hydrogen peroxide
APPLICATIONS OF ADSORPTION
• Charcoal is used as a decoloriser as it adsorbs the
coloring matter from the colored solution of
sugar.
• Separation and purification of liquid and gas
mixtures, bulk chemicals, isomers and air
• Drying gases and liquids before loading them in
industrial systems
• Removal of impurities from liquid and gas media
• Removal of chemicals from industrial and vent
gases
• Water purification