ADSORPTION

Adsorption 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. This process differs from absorption, in which
a fluid (the absorbate) permeates or is dissolved by a liquid or solid
(the absorbent). Note that adsorption is a surface-based process while
absorption involves the whole volume of the material. The
term sorptionencompasses both processes, while desorption is the reverse of
adsorption. It is a surface phenomenon.
Similar to surface tension, adsorption is a consequence of surface energy. In
a bulk material, all the bonding requirements (be they ionic, covalent,
or metallic) of the constituent atoms of the material are filled by other atoms
in the material. However, atoms on the surface of the adsorbent are not
wholly surrounded by other adsorbent atoms and therefore can attract
adsorbates. The exact nature of the bonding depends on the details of the
species involved, but the adsorption process is generally classified
as physisorption (characteristic of weak van der Waals forces)
or chemisorption (characteristic of covalent bonding). It may also occur due
to electrostatic attraction.
Adsorption is present in many natural physical, biological, and chemical
systems, and is widely used in industrial applications such as activated
charcoal, capturing and using waste heat to provide cold water for air
conditioning and other process requirements (adsorption chillers), synthetic
resins, increase storage capacity of carbide-derived carbons for tunable
nanoporous carbon, and water purification. Adsorption, ion exchange,
and chromatography are sorption processes in which certain adsorbates are
selectively transferred from the fluid phase to the surface of insoluble, rigid
particles suspended in a vessel or packed in a column. Lesser known, are the
pharmaceutical industry applications as a means to prolong neurological
exposure to specific drugs or parts thereof.

Adsorption:
The phenomenon of attracting and retaining the molecules of a substance on
the surface of a liquid or a solid resulting into a higher concentration of the
molecules on the surface is called adsorption. The substance thus adsorbed on
the surface is called the adsorbate and the substance on which it is absorbed
is known as adsorbent. The reverse process i.e. removal of the adsorbed
substance from the surface is called desorption. The adsorption of gases on
the surface of metals is called occlusion.
 Difference between Adsorption and Absorption:

ADSORPTION ABSORPTION

It is surface phenomenon i.e. it occurs It is bulk phenomenon i.e. it occurs

only at the surface of the adsorbent. throughout the body of the material.

In this phenomenon, the concentration In this phenomenon, the concentration

on the surface of adsorbent is different is same throughout the material.
from that in the bulk.

Its rate is high in the beginning and Its rate remains same throughout the
then decreases till equilibrium is process.
attained.
 TYPES OF ADSORPTION

Adsorption can be classified into two categories as described below,

(1) Depending upon the concentration : In adsorption the concentration of
one substance is different at the surface of the other substance as compared to
adjoining bulk or interior phase.
(i) Positive adsorption : If the concentration of adsorbate is more on the
surface as compared to its concentration in the bulk phase then it is called
positive adsorption.
Example :When a concentrated solution of KCl is shaken with blood
charcoal, it shows positive adsorption.
(ii) Negative adsorption : If the concentration of the adsorbate is less than its
concentration in the bulk then it is called negative adsorption.
Example :When a dilute solution of KCl is shaken with blood charcoal, it
shows negative adsorption.
(2) Depending upon the nature of force existing between adsorbate
molecule and adsorbent
(i) Physical adsorption : If the forces of attraction existing between
adsorbate and adsorbent are Vander Waal’s forces, the adsorption is called
physical adsorption. This type of adsorption is also known as physisorption
or Vander Waal’s adsorption. It can be easily reversed by heating or
decreasing the pressure.
(ii) Chemical adsorption :If the forces of attraction existing between
adsorbate particles and adsorbent are almost of the same strength as chemical
bonds, the adsorption is called chemical adsorption. This type of adsorption is
also called as chemisorption or Langmuir adsorption. This type of adsorption
cannot be easily reversed.
Comparison between physisorption and chemisorption
Physisorption Chemisorption
(Vander Waal's (Langmuir adsorption)
adsorption)
Low heat of adsorptionHigh heat of adsorption
usually in range of 20-in the range of 50-
40kJ/mol 400 kJ/mol
Force of attraction Forces of attraction
areVander Waal's arechemical bond
forces. forces.
It is reversible It is irreversible
It is usually takes place It takes place at high
atlow temperature and temperature.
decreases with increasing
temperature.
It is related to the case of It is not related.
liquefication of the gas.
It forms multimolecular It forms monomolecular
layers. layers.
It does not require any It requires high activation
activation energy. energy.
High pressure is High pressure is
favourable. Decrease of favourable. Decrease of
pressure pressure does not cause
causesdesorption desorption.
It is not very specific. It is highly specific.

Factors which affect the extent of adsorption : The following are the
factors which affect the adsorption,

(1) Nature of the adsorbate (gas) and adsorbent (solid)

(i) In general, easily liquefiable gases e.g., CO 2, NH3, Cl2 and SO2 etc. are
adsorbed to a greater extent than the elemental gases e.g. H 2, O2, N2, He etc.
(while chemisorption is specific in nature.)
(ii) Porous and finely powdered solid e.g. charcoal, fullers earth, adsorb more
as compared to the hard non-porous materials. Due to this property powdered
charcoal is used in gas masks.

(2) Surface area of the solid adsorbent

(i) The extent of adsorption depends directly upon the surface area of the
adsorbent, i.e. larger the surface area of the adsorbent, greater is the extent of
adsorption.
(ii) Surface area of a powdered solid adsorbent depends upon its particle size.
Smaller the particle size, greater is its surface area.
(3) Effect of pressure on the adsorbate gas
(i) An increase in the pressure of the adsorbate gas increases the extent of
adsorption.
(ii) At low temperature, the extent of adsorption increases rapidly with
pressure.

Positive adsorption:
In case of adsorption by solids from thesolutions, mostly the solute is
adsorbed on the surface of the solid adsorbent so that the concentration of
solute on the surface of theadsorbent is greater than in the bulk. This is
known as positive adsorption. Hence when the concentration of the adsorbate
is more on the surface of the adsorbent than in the bulk, it is known
as positive adsorption.
Negative adsorption:
In some cases, the solvent from the solution may be adsorbed by
the adsorbent so that the concentration of the solution increases than the
initial concentration. This is called negativeadsorption. Hence if the
concentration of the adsorbate is less on the surface of the adsorbentthan in
the bulk, it is known as negative adsorption.
 ADSORPTION OF GASES ON SOLIDS

The magnitude of adsorption of gases by solids depends on the following

factors.
1. Nature of the adsorbent
2. The surface area of the adsorbent
3. Nature of the gases
4. Pressure of the gas
5. Temperature of the gas
6. Reversible character of the adsorbed gases
7. Activation of the adsorbent
8. Enthalpy of adsorption

Factors infleunce adsorption of gases on solids

1. Nature of the adsorbent
The adsorption depends upon the type of adsorbent used. The excellent
adsorbents are highly porous in nature. The larger the pores, the greater is the
adsorption.
Ex : porous substances are silica gel, aluminia and charcoal.
The adsorption power of these substances can further be enhanced by a pores
called activation. During activation, the adsorbent is heated in steam to about
1500°c. Heating drives out all impurities and leads to a lager free surface for
adsorption.
Ex. Charcoal adsorbs 0.011 gms of CCl4 at 24°C.
Activated charcoal adsorbs 1.48 gm of at 24°C.
The surface area of adsorbent
The extent of adsorption depends on the surface area.
1. The greater the surface area, the greater is the adsorption.
2. Larger pores on the adsorbent, larger is the adsorption.
Ex. Charcoal and silica gel ( excellent adsorbents).

Nature of gases
The amount of gas adsorbed by a solid depends on the nature of the gas.
Easily liquefiable gases like Hl, NH3, Cl2, SO2 etc., are adsorbed more
easily then the permanent gases like H2, N2, O2 etc.,
This is due to the following reasons :

i. Critical temperature
The ease of liquifications depends on its critical temperature (i.e, the
maximum temperature above which a gas cannot be liquefied). Thus if the
critical temperature of the gas is more, it will be liquefied and adsorbed more
readily.
Ex. Adsorption of various gases on 1g of activated charcoal.
 APPLICATION OF ADSORPTION

Adsorption finds extensive applications both in research laboratory and in

industry. A fewapplications are discussed below:
In preserving vacuum:
In Dewar flasks activated charcoal is placed between the walls of the flask so
that any gas which enters into the annular space either due to glass
imperfection or diffusion though glass is adsorbed.

In glass masks:
All gas masks are devices containing suitable adsorbent so that the poisonous
gases present in the atmosphere are preferentially adsorbed and the air for
breathing is purified.

In clarification of sugar:
Sugar is decolorized by treating sugar solution with charcoal powder. The
latter adsorbs the undesirable colors present.

In paint industry:
The paint should not contain dissolved gases as otherwise the paint does not
adhere well to the surface to be painted and thus will have a poor covering
power. The dissolved gases are therefore, removed by suitable adsorbents
during manufacture. Further, all surfaces are covered with layers of gaseous,
liquid or solid films. These have to be removed before the paint is applied.
This is done by suitable liquids which adsorbs these films. Such liquids are
called wetting agents. The use of spirit as wetting agent in furniture painting
is well known.

In chromatographic analysis:
The selective adsorbent of certain substances from a solution by a particular
solid adsorbenthas helped to develop technique for the separation of the
components of the mixture. This technique is called chromatographic
analysis. For example: in column chromatography a long and wide vertical
tube is filled with a suitable adsorbent and the solution of the mixture poured
from the top and then collected one by one from the bottom.

In catalysis:
The action of certain solids as catalysts is best explained in terms
of adsorption. The theory is called adsorption theory. According to this
theory, the gaseous reactants are adsorbed on the surface of the solid catalyst.
As a result, the concentration of the reactants increases on the surface and
hence the rate of reaction increases. The theory is also able to explain the
greater efficiency of the catalyst in the finely divided state, the action of
catalyst promoters and poisons.
In adsorption indicators:
Various dyes which owe their use to adsorption have been introduced as
indicators particularly in precipitation titrations. For example: KBr is easily
titrated with AgNO3 using eosin as an indicator.

In softening of hard water:

The use of ion exchangers for softening of hard water is based upon the
principle of competingadsorption just as in chromatography.
In removing moisture from air in the storage of delicate instruments:
Such instruments which may be harmed by contact with the moist air are kept
out of contact with moisture using silica gel.