ADSORPTION

Adsorption is a process that involves the accumulation of a substance in molecular species in

higher concentrations on the surface. If we look at Hydrogen, Nitrogen and Oxygen, these gases
adsorb on activated charcoal.

Note that adsorption is different from absorption. The two processes involve totally different
mechanisms.

For the adsorption process, two components are required:

 Adsorbate: Substance that is deposited on the surface of another substance. For

example, H2, N2 and O2 gases.
 Adsorbent: Surface of a substance on which adsorbate adsorbs. For example, Charcoal,
Silica gel, and Alumina.
Types of Adsorption
On the basis of interaction forces between adsorbate and adsorbent, adsorption is of two types.

1. Physical adsorption
This type of adsorption is also known as physisorption. It is due to weak Van der Waals
forces between adsorbate and adsorbent.

For example, H2 and N2 gases adsorb on coconut charcoal.

2. Chemical adsorption
This type of adsorption is also known as chemisorption. It is due to strong chemical forces of
bonding type between adsorbate and adsorbent. We can take the example involving the
formation of iron nitride on the surface when the iron is heated in N2 gas at 623 K.

The adsorption of a gas on a solid is a spontaneous exothermic reaction. The amount of heat
liberated when a unit mass of a gas is adsorbed on the surface is called heat of adsorption.

Characteristics of physical adsorption:

1. This type of adsorption is caused by physical forces.

2. Physisorption is a weak phenomenon.
3. This adsorption is a multi-layered process.
4. Physical adsorption is not specific and takes place all over the adsorbent.
5. Surface area, temperature, pressure, and nature of adsorbate effects physisorption.
6. Energy for activation is low (20 – 40 kJ/mol).
Characteristics of chemical adsorption:

1. This type of adsorption is caused by chemical forces.

2. It is a very strong process.
3. This type of adsorption is almost a single-layered phenomenon.
4. Chemisorption is highly specific and takes place at reaction centres on the adsorbent.
5. Surface area, temperature, and nature of adsorbate effects chemisorption.
6. The energy of activation is very high, 40 – 400 kJ/mol.

Adsorption Isotherms

An adsorption isotherm is a graph that represents the variation in the amount of adsorbate(x)
adsorbed on the surface of the adsorbent with the change in pressure at a constant temperature.
The adsorption isotherm is used for predicting the adsorption capacity of a given material.

Freundlich Adsorption Isotherm

According to Le Chatelier’s principle, the direction of equilibrium in a reaction shifts in the

direction in which stress is relieved. So, here we can see that upon application of excess pressure
on the system, the equilibrium shifts in the direction where the number of molecules decreases so
that the pressure in the system decreases.

After attaining a pressure Ps, that is the saturation pressure, the variation in the amount of
adsorbent adhering to the adsorbate becomes zero. This happens because the surface area
available for adsorption is limited and as all the sites are occupied, a further increase in pressure
does not cause any difference.
Freundlich adsorption gives the variation in the quantity of gas adsorbed by a unit mass of
solid adsorbent with the change in pressure of the system for a given temperature. The
expression for the Freundlich isotherm can be represented by the following equation:

where n>1

Where x is the mass of the gas adsorbed, m is the mass of the adsorbent, P is the pressure and n
is a constant which depends upon the nature of the adsorbent and the gas at a given temperature.
Taking the logarithm on both the sides of the equation, we get,

To test the validity of Freundlich isotherm, we can plot log x/m on the y-axis and log P on the x-
axis. If the plot shows a straight line, then the Freundlich isotherm is valid, otherwise, it is not.
The slope of the straight line gives the value of 1/n, while the intercept on the y-axis gives the
value of log k.

Limitations of Freundlich Isotherm

Freundlich isotherm only approximately explains the behaviour of adsorption. The value of 1/n
can be between 0 and 1, therefore the equation holds good only over a limited range of pressure.

 When 1/n = 0, x/m is constant, the adsorption is independent of pressure.

 When 1/n =1, x/m = k P, i.e. x/m ∝ P, adsorption is directly proportional to pressure.
Experimental results support both of the above mentioned conditions. At high pressure, the
experimental isotherms always seem to approach saturation. Freundlich isotherm does not
explain this observation and therefore, fails at high pressure.

The Freundlich isotherm was followed by two other isotherms – Langmuir adsorption isotherm
and BET adsorption isotherm. Langmuir isotherm assumed that adsorption is monolayer in
nature whereas BET isotherm assumed that it is multi-layer.

Langmuir Adsorption Isotherms

The Langmuir adsorption isotherms predict linear adsorption at low adsorption densities and a
maximum surface coverage at higher solute metal concentrations.
The Langmuir adsorption isotherm has the form:
Kp
Ꝋ=
(1+ Kp)
Where
 θ is the fraction of the surface covered by the adsorbed molecule.
 K is an equilibrium constant known as the adsorption coefficient.
 K= (ka/kd) = rate constant for adsorption/ rate constant for desorption}
 p is the pressure.
The Langmuir adsorption is applicable for monolayer adsorption onto a homogeneous surface
when no interaction occurs between adsorbed species.
It is the most common isotherm equation to use due to its simplicity and its ability to fit a variety
of adsorption data. It is based on four assumptions:

1. The gas adsorbed behaves ideally in a vapour phase.

2. Only monolayer adsorption takes place.
3. The surface of the solid is homogeneous.
4. There is no lateral interactive force between the adsorbate molecule.
5. The adsorbed gas molecules are localised.
BET Adsorption Isotherm

The theory of multilayer adsorption proposed by Brunauer, Emmett and Teller in 1938 (BET
Theory) assumes that physisorption results in the formation of multilayer adsorption. The theory
also assumes that the solid surface has uniform sites of adsorption and that adsorption at one site
does not affect adsorption at neighbouring sites.
After the formation of the monolayer, the adsorption process can continue with the formation of
the multilayer involving the second layer, third layer and so on. They modified Langmuir's
mechanism as follows:

A(g) + S ⇌ AS,
A(g) + AS ⇌ A2S,
A(g) + A2S ⇌ A3S and so on.

Note: The Langmuir isotherm is usually better for chemisorption, and the BET isotherm
works better for physisorption for non-microporous surfaces.

Characteristics of Adsorbents

A good adsorbent material possesses several key properties and characteristics that enhance its
ability to attract and hold molecules on its surface. Here are the main properties:

1. High Surface Area: A large surface area allows for more adsorption sites, increasing
the material's capacity to hold adsorbates. Materials like activated carbon, zeolites, and
metal-organic frameworks (MOFs) are known for their high surface areas.
2. Porosity: The presence of pores in the material facilitates the penetration of molecules,
allowing for greater interaction and adsorption. Microporous and mesoporous
structures are particularly effective.
3. Chemical Affinity: The adsorbent should have a strong interaction with the target
adsorbates. This can be achieved through various types of bonding, such as van der
Waals forces, hydrogen bonding, ionic interactions, or covalent bonding.
4. Selectivity: A good adsorbent selectively binds specific molecules, which is crucial for
applications like gas separation or pollutant removal. This selectivity can be influenced
by the adsorbent's functional groups or surface chemistry.
5. Stability: The material should be chemically and thermally stable under the conditions
of use. This ensures that the adsorbent maintains its structural integrity and
performance over time.
6. Regenerability: A good adsorbent can be easily regenerated after saturation, allowing
it to be reused multiple times without significant loss of performance.
7. Low Density: A lower density allows for easier handling and reduces the overall
weight of adsorbent systems, which can be beneficial in various applications.
 8. Ease of Modification: The ability to modify the surface properties of the adsorbent
(e.g., through chemical treatments or functionalization) can enhance its adsorption
characteristics for specific applications.

Types of Adsorbents
The majority of industrial adsorbents are divided into three categories:
Oxygen-containing compounds — These include materials like silica gel and zeolites, which are
often hydrophilic and polar.
Carbon-based compounds — These include materials like activated carbon and graphite, which
are typically hydrophobic and nonpolar.
Polymer-based chemicals — Depending on the functional groups in the polymer matrix, they can
be polar or nonpolar.

Some of the commonly used adsorbents are:

Silica gel:
Silica gel is an amorphous form of SiO 2 that is chemically inert, non-toxic, polar, and
dimensionally stable (400 °C or 750 °F). It is formed by reacting sodium silicate with
acetic acid, then going through a variety of post-processing steps like aging, pickling, and so on.
The pore size distributions produced by these post-treatment procedures are diverse. Silica has
been used in drying of process air (such as oxygen and natural gas) as well as adsorb heavy
(polar) hydrocarbons from natural gas.

Zeolites:

Zeolites are crystalline aluminosilicates with a repeating pore network that release water at high
temperatures. They can be natural or manmade. In nature, zeolites are polar. They're made via
ion exchange with particular cations (Na+, Li+, Ca2+, K+, NH4+) after hydrothermal synthesis
of sodium aluminosilicate or another silica source in an autoclave. Zeolite cages typically have a
channel diameter of 2 to 9 mm. The crystals are dried after the ion exchange process, and then
pelletized with a binder to make macroporous pellets. Drying of process air, CO 2 removal from
natural gas, CO removal from reforming gas, air separation, catalytic cracking, and catalytic
synthesis and reforming are all applications for zeolites. Aluminum-free silica sources or
deallumination of aluminum-containing zeolites are used to make non-polar (siliceous) zeolites.
Delayumination is accomplished by processing zeolite with steam at high temperatures, often
above 500 °C (930 °F). The aluminum-oxygen connections are broken by the high temperature
heat treatment, and the aluminium atom is ejected from the zeolite framework.
Activated carbon:

Activated carbon is a porous, amorphous material made up of microcrystallites with a

graphite lattice that is typically sold as small pellets or powder. It's non-polar and inexpensive.
One of its most significant disadvantages is that it interacts with oxygen at moderate
temperatures (over 300 °C). Microporous type I behaviour in an activated carbon nitrogen
isotherm. Carbonaceous materials such as coal (bituminous, subbituminous, and lignite), peat,
wood, and nutshells can be used to make activated carbon (e.g., coconut). Carbonization and
activation are the two processes of the manufacturing process. Activated carbon is commonly
used for waste gas (and wastewater) treatment, as well as the adsorption of organic compounds
and non-polar adsorbates.

Applications of Adsorption
1) Air pollution masks

These consist of silica gel or activated charcoal powder; when dust or smoke are paused through
them, these particles get adsorbed on the surface of these materials.

Gas masks are also used during airborne epidemics and also by coal miners, where poisonous
gases get adsorbed at the surface of the mask and prevent its encounter when used.

2) Separation of noble gases by Dewar’s flask process

A mixture of noble gases of Ne, Ar, and Kr is passed through Dewar’s flask in the presence of
heated coconut charcoal. Argon and Krypton get adsorbed, leaving Neon.

Adsorption of air is also used for production of vacuum: Traces of air are adsorbed on charcoal
and removed from devices undergoing the process of evacuation.

3) Purification of water

By the addition of alum stone to the water, impurities get adsorbed on the alum, and the water
gets purified.

4) Removal of moisture and humidity

 Moisture in the air is removed by placing silica gel on which water molecules gets
adsorbed in medicines and new plastic bottles in order to control humidity.
5) Adsorption chromatography

 It is used to separate pigments and hormones. For example, the juice extracted from cane
is treated with animal charcoal for the removal of the colouring agent in order to get a
clear liquid solution.

6) Ion exchange method

In this method of removing the hardness of water, calcium and magnesium ions get adsorbed on
the surface of the ion exchange resin.

7) In metallurgy

In the froth floatation process of concentration of ore, the particle gets adsorbed on the froth.

8) In chemical reactions involving use of catalysts

Suitable materials are used as a catalyst such that reactants get adhered to its surface, thus
enabling the reaction to proceed at a faster rate and increasing the rate of reaction.

9)Polymer Adsorption

Adsorption of molecules is found on the surfaces of the polymer. This characteristic is important
in a number of use-case applications. For example, it is important in the development of non-
stick coatings and in several biomedical devices. Using the process of polyelectrolyte adsorption,
polymers can also be adsorbed to surfaces.

Differences between Absorption and Adsorption

Absorption Adsorption

Complete deposition of a substance in The deposition of a substance on the

another substance is absorption surface is known as adsorption.

It is not a surface phenomenon. It is a surface process.

It is not spontaneous. The adsorption of a gas on a solid is

spontaneous.

It takes place uniformly throughout. It does not take place uniformly.

Greater molecular interaction. Less molecular interaction.

It involves the application of potential in There is no involvement of

the absorption of water by root hairs. potentials during adsorption.

It is not subdivided. Surface absorption is adsorption,

and it is subdivided.