ADSORPTION

By MD SAJID ALI
 ADSORPTION
What is Adsorption?
Adsorption is the phenomenon of
accumulation of large number of molecular
species at the surface of liquid or solid
phase in comparison to the bulk.
 How Adsorption occurs?

The process of adsorption arises due to presence

of unbalanced or residual forces at the surface of
liquid or solid phase.

These unbalanced residual forces have tendency

to attract and retain the molecular species with
which it comes in contact with the surface.
Adsorption is essentially a surface phenomenon.
Adsorption Vs Absorption
Adsorption is a term which is completely different from
Absorption .While absorption means uniform distribution of the
substance throughout the bulk, adsorption essentially happens at the
surface of the substance. When both Adsorption and Absorption
processes take place simultaneously, the process is called sorption.

Adsorption process involves two components Adsorbent and

Adsorbate. Adsorbent is the substance on the surface of which
adsorption takes place.Adsorbate is the substance which is being
adsorbed on the surface of adsorbent. Adsorbate gets adsorbed.

Adsorbate + Adsorbent gives rise to Adsorption

 Adsorbents
Natural or synthetic
Amorphous or microcrystalline structure
Very high specific surface area
Examples:
•Synthetic Polymers (vinyl based, absorb polar and or non-polar
org.)
•Bentonite (clay adbsorbent, adsorbs proteins readily for
winemaking)
•Activated carbon (organics, microcrystalline, 300 to 1200 m2/g)
•Silica gel (dry gas and liq., fractionate hydrocarbons, 600 to 800
m2/g)
•Activated alumina (dry gas and liq., 200 to 500 m2/g)
•Zeolite (molecular sieves with specific pore sizes, separation,
drying)
Adsorption in liquids
Adsorption can be understood by considering a simple
example. In case of liquid state, water molecule present on the
surface is attracted inwards by the molecules of water present
in the bulk. This gives rise to surface tension. While the
molecule of water present within the bulk is equally attracted
from all the sides and the net force experienced by the water
molecule in bulk is zero. This clearly shows that particles at
surface and particles at the bulk are in different environment.
Water molecule on surface
experiencing unbalanced
forces as compared to
molecule inside which
experiences forces from all
direction.
Adsorption in solids
In case of solid state these residual forces arises because a
of unbalanced valence forces of atoms at the surface. The
generation of these forces on solid surface can be explained
diagrammatically as follows:

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.
Facts about Adsorption Process
•Adsorption is a spontaneous process

For reaction or process to be spontaneous, there must be

decreases in free energy of the system i.e. ΔG of the system
must have negative value.

•Adsorption is an exothermic process

Adsorption process takes place by adsorbate getting adsorbed

on adsorbent .Forces of attraction exist between adsorbate
and adsorbent and due to these forces of attraction, heat
energy is released. So adsorption is an exothermic process.
Types of Adsorption

Forces of attraction exist between adsorbate and

adsorbent. These forces of attraction can be due to Van
der waal forces of attraction which are weak forces or due
to chemical bond which are strong forces of attraction. On
the basis of type of forces of attraction existing between
adsorbate and adsorbent, adsorption can be classified into
two types:
1.Physical Adsorption
2.Chemical Adsorption.
Physical Adsorption or Physisorption
• 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 has low enthalpy of
adsorption i.e. ΔHadsorption is 20-
40KJ/mol.
• It takes place at low temperature
below boiling point of adsorbate.As the
temperature increases in, process of
Physisorption decreases. Physical Adsorption vs.
Temperature graph
Chemical Adsorption or 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 has high enthalpy of adsorption. i.e.

It can take place at all

temperature. With the
increases in temperature,
Chemisorption first
increases and then
decreases. Chemical Adsorption vs. Temperature Graph
Applications of Adsorption
1. Charcoal is used as a
decoloriser as it adsorbs the
coloring matter from the
coloured solution of sugar.

2. Silica gel adsorbs moisture from

the desiccators.
3. Silica and alumina gels are used
as adsorbents for removing
moisture and for controlling
humidity of rooms.
4. Activated charcoal is used in gas masks as it
adsorbs all the toxic gases and vapours and purifies
the air for breathing.

5. Adsorption processes are

useful in carrying out
heterogeneous catalysis.
6. Adsorption of drugs and toxins on finely divided
substance is considered as a useful interaction
when these substances are used as:
1. Antidote for toxins (Charcoal).
2. Antidiarrheal mixtures (Kaolin, Pectin,
Attapulgite).
3. Antacids (Magnesium trisilicate, Al (OH)3 ,
Mg(OH)2 ).

However when antidiarrheal mixtures, Charcoal, antacids

possessing adsorptive properties are concurrently
administered with other drugs, possible adsorption
leads to decreased bioavailability of these drugs.
Factors on which Adsorption Depends
1. Temperature
Adsorption increases at low temperature conditions.
Adsorption process is exothermic in nature. According to
Le Chatleir principle, low temperature conditions would
favour the forward direction.

2. 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.
3. Surface Area
Adsorption is a surface phenomenon therefore it
increases with increase in surface area.

4. 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.

5. Surface Area of Adsorbent

Adsorption Isotherm

The process of Adsorption is usually studied through

graphs called 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.
From the graph, we can predict that after
saturation pressure Ps, adsorption does not occur
anymore. This can be explained by the fact that
there are limited numbers of vacancies on the
surface of the adsorbent. At high pressure a stage
is reached when all the sites are occupied and
further increase in pressure does not cause any
difference in adsorption process. At high
pressure, Adsorption is independent of pressure.
 ADSORPTION EQUILIBRIA
If the adsorbent and adsorbate are contacted
long enough an equilibrium will be established
between the amount of adsorbate adsorbed
and the amount of adsorbate in solution. The
equilibrium relationship is described by
isotherms.
Define the following:
qe = mass of material adsorbed (at equilibrium)
per mass of adsorbent.

Ce = equilibrium concentration in solution

when amount adsorbed equals qe.

qe/Ce relationships depend on the type of

adsorption that occurs, multi-layer, chemical,
physical adsorption, etc.
Langmuir Isotherm:
This model assumes monolayer coverage and
constant binding energy between surface and
adsorbate. The model is:

0
K  Q a  Ce
qe 
1  K  Ce
 0
Q arepresents the maximum adsorption
capacity (monolayer coverage) (g solute/g
adsorbent).

Ce has units of mg/L.

K has units of L/mg

BET (Brunauer, Emmett and Teller) isotherm:
This is a more general, multi-layer model. It
assumes that a Langmuir isotherm applies to each
layer and that no transmigration occurs between
layers. It also assumes that there is equal energy
of adsorption for each layer except for the first
layer.
K B  Ce  Qa 0
qe 
(C S  C e ){1  (K B  1)(C e / C S )}
CS =saturation (solubility limit) concentration of
the solute. (mg/liter)

KB = a parameter related to the binding intensity

for all layers.

Note: when Ce << CS and KB >> 1 and K =

KB/Cs BET isotherm approaches Langmuir
isotherm.
 Freundlich Isotherm:
For the special case of heterogeneous surface
energies (particularly good for mixed wastes) in
which the energy term, “KF”, varies as a function
of surface coverage we use the Freundlich
model.
1
q K C
e F e
n

n and KF are system specific constants.

Type of Adsorption Isotherm
Type I Adsorption Isotherm

The above graph depicts Monolayer adsorption.

This graph can be easily explained using Langmuir Adsorption
Isotherm.
If BET equation, when P/P0<<1 and c>>1, then it leads to
monolayer formation and Type I Adsorption Isotherm is
obtained.
Examples of Type-I adsorption are Adsorption of Nitrogen
(N2) or Hydrogen (H) on charcoal at temperature near to
-1800C.
Type II Adsorption Isotherm

Type II Adsorption Isotherm shows large deviation

from Langmuir model of adsorption.
The intermediate flat region in the isotherm
corresponds to monolayer formation.
In BET equation, value of C has to be very large in
comparison to 1.
Examples of Type-II adsorption are Nitrogen (N2 (g))
adsorbed at -1950C on Iron (Fe) catalyst and Nitrogen
(N2 (g)) adsorbed at -1950C on silica gel.
Type III Adsorption Isotherm

Type III Adsorption Isotherm also shows large deviation

from Langmuir model.
In BET equation value if C <<< 1 Type III Adsorption
Isotherm obtained.
This isotherm explains the formation of multilayer.
There is no flattish portion in the curve which indicates
that monolayer formation is missing.
Examples of Type III Adsorption Isotherm are Bromine
(Br2) at 790C on silica gel or Iodine (I2) at 790C on silica
gel.
Type IV Adsorption Isotherm

At lower pressure region of graph is quite similar to Type II. This

explains formation of monolayer followed by multilayer.
The saturation level reaches at a pressure below the saturation vapor
pressure .This can be explained on the basis of a possibility of gases
getting condensed in the tiny capillary pores of adsorbent at pressure
below the saturation pressure (PS) of the gas.
Examples of Type IV Adsorption Isotherm are of adsorption of
Benzene on Iron Oxide (Fe2O3) at 500C and adsorption of Benzene
on silica gel at 500C.
Type V Adsorption Isotherm

Explanation of Type V graph is similar to Type IV.

Example of Type V Adsorption Isotherm is adsorption of
Water (vapors) at 1000C on charcoal.
Type IV and V shows phenomenon of capillary
condensation of gas.