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Dr.S.Alexandar,M.Pharm,Ph.D,
Associate Professor
Vinayaka Missions College of Pharmacy,
Yercaud main road,
Kondappanaickanpatty,
Salem,Tamilnadu,
Pin:636008
AdsorptionAdsorption
Adsorption EquilibriumAdsorption Equilibrium
Adsorption vs. Absorption
◦ Adsorption is accumulation of molecules on a surface
(a surface layer of molecules) in contact with an air
or water phase
◦ Absorption is dissolution of molecules within a phase,
e.g., within an organic phase in contact with an air or
water phase
 adsorbate: material being adsorbed
 adsorbent: material doing the adsorbing. (examples
are activated carbon or ion exchange resin).
Adsorption
Absorption (“partitioning”)
PHASE I
PHASE 2
PHASE I
‘PHASE’ 2
gas H aqP K c=
Henry’s Law
Physisorption or physical adsorption is a type of
adsorption in which the adsorbate adheres to the surface
only through Van der Waals (weak intermolecular)
interactions, which are also responsible for the non-ideal
behaviour of real gases.
Chemisorption in this kind of adsorption, the gas
molecules or atoms are held to the solid by chemical
bonds. For example hydrogen is chemisorbed on nickel.
Factors influencing adsorption
Adsorption of gases by solids
1.Adsorption and surface area
2.Nature of gas
3.Heats of adsorption
4.Reversible character
5.Effect of temperature
6.Effect of pressure
7.Thickness of adsorbed layer of gas
Factors influencing adsorption
Adsorption of gases by solids
1.Adsorption and surface area
Adsorption being a surface phenomenon, the extent of adsorption depends on the
surface area. Increase in the surface area of the adsorbent, increase the total
amount of the gas adsorbed.
2. Nature of gas
The amount of gas adsorbed by a solid depends on the nature of the gas. In
general, more Easily liquefiable gas is more readily adsorbed.
3. Heats of adsorption
Heat of adsorption is defined as the energy liberated when 1gm mole of a gas is
adsorbed on the solid surface. In physical adsorption, gas molecules concentrate
on the solid surface. Thus it is similar to the condensation of a gas to liquid.
Therefore, adsorption like condensation is an exothermic process.
4. Reversible character
Physical adsorption is reversible process. The gas adsorbed onto a solid can be removed under
reverse conditions of temperature and pressure.
5. Effect of temperature
Physical adsorption occurs rapidly at low temperature and decreases with increasing temperature.
Chemisorption, like most chemical changes, generally increases with temperature. Thus a rise of
temperature can often cause physical adsorption to change to Chemisorption.
6. Effect of pressure
Pressure leads to increase of adsorption and decrease of pressure causes desorption.
7. Thickness of adsorbed layer of gas
The physically adsorbed gas forms only one molecular thick layer. However, above a certain
pressure, multimolecular thick layer is formed.
S.No Physical adsorption Chemical adsorption
1.
Caused by intermolecular forces Caused by chemical bond formation
2.
Heat of adsorption is small Heat of adsorption is large
3.
Reversible Irreversible
4.
Forms multimolecular layer Forms unimolecular layer
5.
Decreases with increasing temperature Increases with increasing of temperature
6.
Depends on nature of gas Much more specific than physical
adsorption
7.
Increase of pressure increases adsorption,
decrease of pressure causes of desorption
Change of pressure has no such effects
Some common examples of adsorption are silica gel packets to adsorb
moisture from packaged electronic or optical equipment, and carbon "filter" to
deodorize drinking water. In pharmacy, activated charcoal is considered to be
the most effective single agent available as an emergency decontaminant in the
gastrointestinal tract. It is used after a person swallows or absorbs almost any
toxic drug or chemical.
Adsorption is usually described through isotherms, that is, functions which
connect the amount of adsorbate on the adsorbent, with its pressure (if gas) or
concentration (if liquid). One can find in literature several models describing
process of adsorption, namely Freundlich isotherm, Langmuir isotherm, BET
isotherm, etc.
Isotherm models:
The figures below show that there are four
common models for isotherms.
Typical isotherm
solid-phase concentration (y-axis) vs liquid phase concentration (x-
axis)
This is a favorable isotherm:
higher solid-phase
concentration at low liquid
concentrations
Commonly Reported Adsorption Isotherms
max
1
L
L
K c
q q
K c
=
+linq k c=
n
fq k c=
Linear: Langmuir:
Freundlich:
Langmuir isotherm
In 1916, Irving Langmuir published an isotherm for gases adsorbed on
solids, which retained his name. It is an empirical isotherm derived
from a proposed kinetic mechanism. It is based on four hypotheses:
1. The surface of the adsorbent is uniform, that is, all the adsorption
sites are equal.
2. Adsorbed molecules do not interact.
3. All adsorption occurs through the same mechanism.
4. At the maximum adsorption, only a monolayer is formed: molecules
of adsorbate do not deposit on other, already adsorbed, molecules of
adsorbate, only on the free surface of the adsorbent.
Shape of Langmuir IsothermShape of Langmuir Isotherm
Shape of Freundlich Isotherm
n
fq k c=
The Freundlich (or Classical) adsorption isotherm
The variation of adsorption with pressure can often be
represented (especially at moderately low pressures) by the
equation
where k and n are constants, n usually being greater than unity.
Taking logarithms,
a plot of log V versus log p should give a straight line
Freundlich equation of an adsorption from solution
where x –quantity of the adsorbed substance, m-adsorbent’s
mass, p and c-equilibrium pressure and concentration
n
kc
m
x
Г /1
==
Applications of adsorption
1. Production of high vacuum
If a partially evacuated vessel is connected to a container of activated
charcoal cooled with liquid air, the charcoal adsorbs all the gas
molecules in the vessel. This results in a very vacuum.
2. Gas mask
Gas masks are devices contain an adsorbent (activated charcoal) or a
series of adsorbents; these adsorbents remove poisonous gases by
adsorption and purify the air for breathing.
3. Heterogeneous catalysis
In a heterogeneous catalysis, the molecules of the reactant are adsorbed
at the catalyst surface, where they form an “adsorption complex”. This
decomposes to form the product molecules which then take off from the
surface.
4. Removal of coloring matter from solutions
Animal charcoal removes colours of solution by adsorbing coloured
impurities thus in the manufacture of cane-sugar, the coloured solution is
clarified by treating with animal charcoal or activated charcoal.
5. Chromatographic analysis
Mixtures of small quantities of organic substances can be separated with
the help of chromatography which involves the principles of selective
adsorption.

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Adsorption

  • 1. Dr.S.Alexandar,M.Pharm,Ph.D, Associate Professor Vinayaka Missions College of Pharmacy, Yercaud main road, Kondappanaickanpatty, Salem,Tamilnadu, Pin:636008 AdsorptionAdsorption
  • 2. Adsorption EquilibriumAdsorption Equilibrium Adsorption vs. Absorption ◦ Adsorption is accumulation of molecules on a surface (a surface layer of molecules) in contact with an air or water phase ◦ Absorption is dissolution of molecules within a phase, e.g., within an organic phase in contact with an air or water phase  adsorbate: material being adsorbed  adsorbent: material doing the adsorbing. (examples are activated carbon or ion exchange resin).
  • 3. Adsorption Absorption (“partitioning”) PHASE I PHASE 2 PHASE I ‘PHASE’ 2 gas H aqP K c= Henry’s Law
  • 4.
  • 5. Physisorption or physical adsorption is a type of adsorption in which the adsorbate adheres to the surface only through Van der Waals (weak intermolecular) interactions, which are also responsible for the non-ideal behaviour of real gases. Chemisorption in this kind of adsorption, the gas molecules or atoms are held to the solid by chemical bonds. For example hydrogen is chemisorbed on nickel.
  • 6. Factors influencing adsorption Adsorption of gases by solids 1.Adsorption and surface area 2.Nature of gas 3.Heats of adsorption 4.Reversible character 5.Effect of temperature 6.Effect of pressure 7.Thickness of adsorbed layer of gas
  • 7. Factors influencing adsorption Adsorption of gases by solids 1.Adsorption and surface area Adsorption being a surface phenomenon, the extent of adsorption depends on the surface area. Increase in the surface area of the adsorbent, increase the total amount of the gas adsorbed. 2. Nature of gas The amount of gas adsorbed by a solid depends on the nature of the gas. In general, more Easily liquefiable gas is more readily adsorbed. 3. Heats of adsorption Heat of adsorption is defined as the energy liberated when 1gm mole of a gas is adsorbed on the solid surface. In physical adsorption, gas molecules concentrate on the solid surface. Thus it is similar to the condensation of a gas to liquid. Therefore, adsorption like condensation is an exothermic process.
  • 8. 4. Reversible character Physical adsorption is reversible process. The gas adsorbed onto a solid can be removed under reverse conditions of temperature and pressure. 5. Effect of temperature Physical adsorption occurs rapidly at low temperature and decreases with increasing temperature. Chemisorption, like most chemical changes, generally increases with temperature. Thus a rise of temperature can often cause physical adsorption to change to Chemisorption. 6. Effect of pressure Pressure leads to increase of adsorption and decrease of pressure causes desorption. 7. Thickness of adsorbed layer of gas The physically adsorbed gas forms only one molecular thick layer. However, above a certain pressure, multimolecular thick layer is formed.
  • 9. S.No Physical adsorption Chemical adsorption 1. Caused by intermolecular forces Caused by chemical bond formation 2. Heat of adsorption is small Heat of adsorption is large 3. Reversible Irreversible 4. Forms multimolecular layer Forms unimolecular layer 5. Decreases with increasing temperature Increases with increasing of temperature 6. Depends on nature of gas Much more specific than physical adsorption 7. Increase of pressure increases adsorption, decrease of pressure causes of desorption Change of pressure has no such effects
  • 10. Some common examples of adsorption are silica gel packets to adsorb moisture from packaged electronic or optical equipment, and carbon "filter" to deodorize drinking water. In pharmacy, activated charcoal is considered to be the most effective single agent available as an emergency decontaminant in the gastrointestinal tract. It is used after a person swallows or absorbs almost any toxic drug or chemical. Adsorption is usually described through isotherms, that is, functions which connect the amount of adsorbate on the adsorbent, with its pressure (if gas) or concentration (if liquid). One can find in literature several models describing process of adsorption, namely Freundlich isotherm, Langmuir isotherm, BET isotherm, etc.
  • 11. Isotherm models: The figures below show that there are four common models for isotherms.
  • 12.
  • 13. Typical isotherm solid-phase concentration (y-axis) vs liquid phase concentration (x- axis) This is a favorable isotherm: higher solid-phase concentration at low liquid concentrations
  • 14. Commonly Reported Adsorption Isotherms max 1 L L K c q q K c = +linq k c= n fq k c= Linear: Langmuir: Freundlich:
  • 15. Langmuir isotherm In 1916, Irving Langmuir published an isotherm for gases adsorbed on solids, which retained his name. It is an empirical isotherm derived from a proposed kinetic mechanism. It is based on four hypotheses: 1. The surface of the adsorbent is uniform, that is, all the adsorption sites are equal. 2. Adsorbed molecules do not interact. 3. All adsorption occurs through the same mechanism. 4. At the maximum adsorption, only a monolayer is formed: molecules of adsorbate do not deposit on other, already adsorbed, molecules of adsorbate, only on the free surface of the adsorbent.
  • 16. Shape of Langmuir IsothermShape of Langmuir Isotherm
  • 17. Shape of Freundlich Isotherm n fq k c=
  • 18. The Freundlich (or Classical) adsorption isotherm The variation of adsorption with pressure can often be represented (especially at moderately low pressures) by the equation where k and n are constants, n usually being greater than unity. Taking logarithms, a plot of log V versus log p should give a straight line Freundlich equation of an adsorption from solution where x –quantity of the adsorbed substance, m-adsorbent’s mass, p and c-equilibrium pressure and concentration n kc m x Г /1 ==
  • 19. Applications of adsorption 1. Production of high vacuum If a partially evacuated vessel is connected to a container of activated charcoal cooled with liquid air, the charcoal adsorbs all the gas molecules in the vessel. This results in a very vacuum. 2. Gas mask Gas masks are devices contain an adsorbent (activated charcoal) or a series of adsorbents; these adsorbents remove poisonous gases by adsorption and purify the air for breathing. 3. Heterogeneous catalysis In a heterogeneous catalysis, the molecules of the reactant are adsorbed at the catalyst surface, where they form an “adsorption complex”. This decomposes to form the product molecules which then take off from the surface.
  • 20. 4. Removal of coloring matter from solutions Animal charcoal removes colours of solution by adsorbing coloured impurities thus in the manufacture of cane-sugar, the coloured solution is clarified by treating with animal charcoal or activated charcoal. 5. Chromatographic analysis Mixtures of small quantities of organic substances can be separated with the help of chromatography which involves the principles of selective adsorption.