# 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.
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.

# What is absorption?
Absorption means uniform distribution of the substance throughout the bulk.

# What is sorption?
When both Adsorption and Absorption processes take place simultaneously, the process is called
sorption.

Adsorption process involves two components Adsorbent and Adsorbate.

Adsorbent: Adsorbent is the substance on the surface of which adsorption takes place.
Adsorbate: Adsorbate is the substance which is being adsorbed on the surface of adsorbent.
ADSORPTION IN SOLIDS
In case of solid state these residual forces arise because of an unbalanced valence forces of atoms
at the surface. 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. It can be explained diagrammatically as follows:

ADSORPTION IN LIQUIDS
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.

# TYPES OF ADSORPTION
1. Physical Adsorption or Physisorption
2. Chemical Adsorption or Chemisorption
1. 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 takes place at
low temperature below boiling point of adsorbate. As the temperature increases in, process of
Physisorption decreases (see below). It has low enthalpy of adsorption i.e. ΔHadsorption is 20-40
KJ/mol.

2. 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 can take
place at all temperature. With the increases in temperature, Chemisorption first increases and
then decreases (see below). It has high enthalpy of adsorption i.e. ΔHadsorptionç is 200-400 KJ/mol.
# FACTS ABOUT ADSORPTION PROCESS
A. Adsorption is a spontaneous process
B. Adsorption is an exothermic process

A. 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.
Also we know, ΔG = ΔH – TΔS
And during this process of adsorption, randomness of the molecule decreases which ΔS is
negative. We can rewrite above equation as
ΔG = ΔH + TΔS
Therefore, for a reaction to be spontaneous ΔH has to be negative and
IΔH I> ITΔSI
B. 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.
# ADSORPTION ISOTHERM
The process of Adsorption is usually studied through graphs called as adsorption isotherm. It is
the graph between the amounts of adsorbate adsorbed on the surface of adsorbent and pressure
at constant temperature.

# FACTORS ON WHICH ADSORPTION DEPENDS

1. Temperature
Adsorption increases at low temperature conditions. Adsorption process is exothermic in nature.
A+B AB + Heat
According to LeChatleir 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. 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.
4. Surface area
Adsorption is a surface phenomenon therefore it increases with increase in surface area.

# LANGMUIR ADSORPTION ISOTHERM

In 1916, Irving Langmuir proposed another Adsorption Isotherm which explained the variation of
Adsorption with pressure. 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.
Assumptions of Langmuir Isotherm
Langmuir proposed his theory by making following assumptions.
1. Fixed number of vacant or adsorption sites are available on the surface of solid.
2. All the vacant sites are of equal size and shape on the surface of adsorbent.
3. Each site can hold maximum of one gaseous molecule and a constant amount of heat energy
is released during this process.
4. 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.
5. Adsorption is monolayer or unilayer.

# Derivations of the Langmuir Adsorption Equation

Calculation of Equilibrium Constant
Langmuir proposed that dynamic equilibrium exists between adsorbed gaseous molecules and
the free gaseous molecules. Using the equilibrium equation, equilibrium constant can be
calculated.

A(g) + B (s) AB

Where Ka represents equilibrium constant for forward reaction and Kd represents equilibrium
constant for backward direction.
According to Kinetic theory,
Rate of forward reaction = Ka [A] [B]
Rate of backward reaction = Kd [AB]
At equilibrium, Rate of forward reaction is equal to Rate of backward reaction
Ka [A] [B] = Kd [AB]
Ka/Kd = [AB]/[A][B] =K
The above equation represents the equilibrium constant for distribution of adsorbate between
the surface and the gas phase.
Derivation
Langmuir Equation which depicts a relationship between the number of active sites of the surface
undergoing adsorption (i.e. extent of adsorption) and pressure.

A(g) + B(s) AB

Rate of adsorption PA
No of vacant sites
N(1-θ)
Where, N = total no. of sites
θ = Fraction of surface covered by gas molecules
= No. of adsorption sites occupied/No. of adsorption sites available
Rate of adsorption = Ka PA N(1- θ)
Rate of desorption = Kd Nθ [Rate of desorption No. of adsorbed molecules]

At equilibrium,
Rate of adsorption = Rate of desorption
Ka PA N(1- θ) = Kd Nθ or Ka/Kd PA (1- θ) = θ or K PA (1- θ) = θ or 1/θ = (1 + KPA)/KPA
θ = KPA/(1 + KPA)

At intermediate pressure θ = K(PA)n (Where n = 0-1)

Amount of gas adsorbed per unit mass (assuming monolayer is forming)
a θ (a = adsorbent)
a = K 1θ
a = K1K(PA)n
a = K’PAn

# LIMITATIONS OF LANGMUIR ADSORPTION EQUATION

1. The adsorbed gas has to behave ideally in the vapor phase. This condition can be fulfilled
at low pressure conditions only. Thus Langmuir Equation is valid under low pressure only.

2. Langmuir Equation assumes that adsorption is monolayer. But, monolayer formation is

possible only under low pressure condition. Under high pressure condition the assumption
breaks down as gas molecules attract more and more molecules towards each other. BET theory
proposed by Brunauer, Emmett and Teller explained more realistic multilayer adsorption
process.

3. Another assumption was that all the sites on the solid surface are equal in size and shape and
have equal affinity for adsorbate molecules i.e. the surface of solid if homogeneous. But we all
know that in real solid surfaces are heterogeneous.

4. Langmuir Equation assumed that molecules do not interact with each other. This is impossible
as weak force of attraction exists even between molecules of same type.
5. The adsorbed molecules have to be localized i.e. decrease in randomness is zero (ΔS = 0). This
is not possible because on adsorption liquefaction of gases taking place, which results into
decrease in randomness but the value is not zero.

@Langmuir equation is valid under low pressure Conditions

# APPLICATION OF ADSORPTION
The process of adsorption is very important as it has many applications in domestic as well as in
industrial processes. Some of them are as follows:

1. In heterogeneous catalysis: Surface active materials are widely used as catalysts mostly
due to adsorption processes. If the surface active materials (adsorbents) have a different
phase from that of substrates, then the catalysis is called heterogeneous catalysis. A
system where both the catalyst and the substrate are in same phase is called
homogeneous (catalysis).

2. In removal of colouring material: Many coloured materials or impurities are removed

through adsorption by suitable surface active materials like charcoal. Activated charcoal
has been extensively used for this purpose.

3. In ion exchange resins: Several polymeric materials are used for the separation of ionic
substances in chromatography through ion-exchange.

4. In gas masks: Activated charcoal is used to remove toxic gases in gas masks.

5. In the humidizers: Many substances, when they adsorb water, change their colour.
Silica and alumina gels are used as adsorbents for removing moisture. Silica is colourless
but after adsorbing water becomes blue.
6. In dyeing of cloth: Many substances work as mordants for dyeing of cloths. Several
metal cyanogen complexes and alums work as efficient mordants in dyeing cloths.
What is Chromatography?

Chromatography is a physical method of separation in which the components to be separated

are distributed between two phases, one of which is stationary (stationary phase) while the other
(the mobile phase) moves in a definite direction.

• Types of Chromatographic Techniques:

Technique: Stationary/Mobile Phase

Column/Adsorption Chromatography: solid/Liquid
Partition Chromatography: Liquid/Liquid
Paper Chromatography: Liquid/Liquid
Thin Layer Chromatography (TLC): Liquid/Solid
Liquid Gas – Liquid chromatography (GLC): Liquid/gas
Gas – Solid Chromatography (GSC): Solid/gas
Ion Exchange Chromatography: Solid/Liquid

What Is Thin Layer Chromatography?

Thin Layer Chromatography can be defined as a method of separation or identification of a

mixture of components into individual components by using finely divided adsorbent solid /
(liquid) spread over a glass plate and liquid as a mobile phase. • Synonyms: Drop, strip, spread
layer, surface chromatography and open column chromatography - Adsorption or retention or
partition or both or any other principle of a substance (s) on the stationary phase - Separation of
the adsorbed substances by the mobile phase - Recovery of the separated substances by a
continuous flow of the mobile phase (elution) - Qualitative and quantitative analysis of the eluted
substances.

Thin Layer Chromatography is a technique used to isolate non-volatile mixtures. The experiment
is conducted on a sheet of aluminium foil, plastic, or glass which is coated with a thin layer of
adsorbent material. The material usually used is aluminium oxide, cellulose, or silica gel.
On completion of the separation, each component appears as spots separated vertically. Each
spot has a retention factor (Rf) expressed as:

Rf = dist. travelled by sample / dist. travelled by solvent

The factors affecting retardation factor are the solvent system, amount of material spotted,
absorbent and temperature. TLC is one of the fastest, least expensive, simplest and easiest
chromatography technique.

Thin Layer Chromatography Principle

Like other chromatographic techniques, thin layer chromatography (TLC) depends on the
separation principle. The separation relies on the relative affinity of compounds towards both
the phases. The compounds in the mobile phase move over the surface of the stationary phase.
The movement occurs in such a way that the compounds which have a higher affinity to the
stationary phase move slowly while the other compounds travel fast. Therefore, the separation
of the mixture is attained. On completion of the separation process, the individual components
from the mixture appear as spots at respective levels on the plates. Their character and nature
are identified by suitable detection techniques.

Thin Layer Chromatography Procedure

Before starting with the Thin Layer Chromatography Experiment let us understand the different
components required to conduct the procedure along with the phases involved.
 1. Thin Layer Chromatography Plates – ready-made plates are used which are chemically
inert and stable. The stationary phase is applied on its surface in the form of a thin layer.
The stationary phase on the plate has a fine particle size and also has a uniform thickness.
2. Thin Layer Chromatography Mobile phase – Mobile phase is the one that moves and
consists of a solvent mixture or a solvent. This phase should be particulate-free. The
higher the quality of purity the development of spots is better.
3. Thin Layer Chromatography Chamber – Chamber is used to develop plates. It is
responsible to keep a steady environment inside which will help in developing spots. Also,
it prevents the solvent evaporation and keeps the entire process dust-free.

Thin Layer Chromatography Experiment

The stationary phase that is applied to the plate is made to dry and stabilize.

 To apply sample spots, thin marks are made at the bottom of the plate with the help of a
pencil.

 Apply sample solutions to the marked spots.

 Pour the mobile phase into the TLC chamber and to maintain equal humidity, place a
moistened filter paper in the mobile phase.

 Place the plate in the TLC chamber and close it with a lid. It is kept in such a way that the
sample faces the mobile phase.

 Immerse the plate for development. Remember to keep the sample spots well above the
level of the mobile phase. Do not immerse it in the solvent.

 Wait till the development of spots. Once the spots are developed, take out the plates and
dry them. The sample spots can be observed under a UV light chamber.

Thin Layer Chromatography Applications

 It is used to study if a reaction is complete.

  The qualitative testing of Various medicines such as sedatives, local anaesthetics,
anticonvulsant tranquilisers, analgesics, antihistamines, steroids, hypnotics is done by
TLC.

 TLC is extremely useful in Biochemical analysis such as separation or isolation of

biochemical metabolites from its blood plasma, urine, body fluids, serum, etc.

 Thin layer chromatography can be used to identify natural products like essential oils or
volatile oil, fixed oil, glycosides, waxes, alkaloids, etc

 It is widely used in separating multicomponent pharmaceutical formulations.

 It is used to purify of any sample and direct comparison is done between the sample and
the authentic sample

 It is used in the food industry, to separate and identify colours, sweetening agent, and
preservatives

 It is used in the cosmetic industry.

Disadvantages of Thin Layer Chromatography:

1. It is only a qualitative analysis technique and not quantitative.

2. The results generated from TLC are difficult to reproduce.
3. Thin Layer Chromatography plates do not have longer stationary phase.
4. When compared to other chromatographic techniques the length of separation is limited.
5. Since TLC operates as an open system, some factors such as humidity and temperature
can be consequences to the final outcome of the chromatogram.
6. The detection limit is high and therefore if you want a lower detection limit, you cannot
use TLC.

What Is Paper Chromatography?

Chromatography technique that uses paper sheets or strips as the adsorbent being the stationary
phase through which a solution is made to pass is called paper chromatography. It is an
inexpensive method of separating dissolved chemical substances by their different migration
rates across the sheets of paper. It is a powerful analytical tool that uses very small quantities of
material. Paper chromatography was discovered by Synge and Martin in the year 1943.

Paper Chromatography Principle

The principle involved can be partition chromatography or adsorption chromatography. Partition

chromatography because the substances are partitioned or distributed between liquid phases.
The two phases are water held in pores of the filter paper and the other phase is a mobile phase
which passes through the paper. When the mobile phase moves, the separation of mixture takes
place. The compounds in the mixture separate themselves based on the differences in their
affinity towards stationary and mobile phase solvents under the capillary action of pores in the
paper. Adsorption chromatography between solid and liquid phases, wherein the solid surface of
the paper is the stationary phase and the liquid phase is the mobile phase.

Paper Chromatography Procedure

Below we have explained the procedure to conduct Paper Chromatography Experiment for easy
understanding of students.
 1. Selecting a suitable type of development: It is decided based on the complexity of the
solvent, paper, mixture, etc. Usually ascending type or radial paper chromatography is
used as they are easy to perform. Also, it is easy to handle, the chromatogram obtained
is faster and the process is less time-consuming.
2. Selecting a suitable filter paper: Selection of filter paper is done based on the size of the
pores, and the sample quality.
3. Prepare the sample: Sample preparation includes the dissolution of the sample in a
suitable solvent (inert with the sample under analysis) used in making the mobile phase.
4. Spot the sample on the paper: Samples should be spotted at a proper position on the
paper by using a capillary tube.
5. Chromatogram development: Chromatogram development is spotted by immersing the
paper in the mobile phase. Due to the capillary action of paper, the mobile phase moves
over the sample on the paper.
6. Paper drying and compound detection: Once the chromatogram is developed, the paper
is dried using an air drier. Also, detecting solution can be sprayed on the chromatogram
developed paper and dried to identify the sample chromatogram spots.

Paper Chromatography Applications

There are various applications of paper chromatography. Some of the uses of Paper
Chromatography in different fields are discussed below:

 To study the process of fermentation and ripening.

 To check the purity of pharmaceuticals.

 To inspect cosmetics.

 To detect the adulterants.

 To detect the contaminants in drinks and foods.

 To examine the reaction mixtures in biochemical laboratories.

 To determine dopes and drugs in humans and animals.

Types of paper chromatography:

1. Ascending Paper Chromatography – The techniques goes with its name as the solvent
moves in an upward direction.
2. Descending Paper Chromatography – The movement of the flow of solvent due to
gravitational pull and capillary action is downwards hence the name descending paper
chromatography.
3. Ascending – Descending Paper Chromatography – In this version of paper
chromatography movement of solvent occurs in two directions after a particular point.
Initially, the solvent travels upwards on the paper which is folded over a rod and after
crossing the rod it continues with its travel in the downward direction.
4. Radial or Circular Paper Chromatography – The sample is deposited at the center of the
circular filter paper. Once the spot is dried, the filter paper is tied horizontally on a Petri
dish which contains the solvent.
5. Two Dimensional Paper Chromatography – Substances which have the same rf values can
be resolved with the help of two-dimensional paper chromatography.

# What Is Column Chromatography?

Column chromatography in chemistry is a chromatography method used to isolate a single

chemical compound from a mixture. Chromatography is able to separate substances based on
differential adsorption of compounds to the adsorbent; compounds move through the column
at different rates, allowing them to be separated into fractions. The technique is widely
applicable, as many different adsorbents (normal phase, reversed phase, or otherwise) can be
used with a wide range of solvents.

# Column Chromatography Principle

When the mobile phase along with the mixture that needs to be separated is introduced from
the top of the column, the movement of the individual components of the mixture is at different
rates. The components with lower adsorption and affinity to stationary phase travel faster when
compared to the greater adsorption and affinity with the stationary phase. The components that
move fast are removed first whereas the components that move slow are eluted out last.

Column Chromatography Procedure

Stationary phase – It is a solid material which should have good adsorption property and meet
the conditions given below:

1. Shape and size of particle: Particles should have uniform shape and size in the range of
60 – 200μ in diameter.
2. Stability and inertness of particles: high mechanical stability and chemically inert. Also, no
reaction with acids or bases or any other solvents used during the experiment.
3. It should be colourless, inexpensive and readily available.
4. Should allow free flow of mobile phase
5. It should be suitable for the separation of mixtures of various compounds.

Mobile phase – This phase is made up of solvents and it performs the following functions:

1. It acts as a solvent – sample mixture can be introduced in the column.

2. It acts as a developing agent – helps in the separation of components in the sample to
form bands.
 3. It acts as an eluting agent – the components that are separated during the experiment
are removed from the column
4. Some examples of solvents used as mobile phase based on their polarity are – ethanol,
acetone, water, acetic acid, pyridine, etc.

Column Chromatography Experiment

 The stationary phase is made wet with the help of solvent as the upper level of the mobile
phase and the stationary phase should match. The mobile phase or eluent is either solvent
or mixture of solvents. In the first step the compound mixture that needs to be separated,
is added from the top of the column without disturbing the top level. The tap is turned
on and the adsorption process on the surface of silica begins.

 Without disturbing the stationary phase solvent mixture is added slowly by touching the
sides of the glass column. The solvent is added throughout the experiment as per the
requirement.

 The tap is turned on to initiate the movement of compounds in the mixture. The
movement is based on the polarity of molecules in the sample. The non-polar
components move at a greater speed when compared to the polar components.

 For example, a compound mixture consists of three different compounds viz red, blue,
green then their order based on polarity will be as follows blue>red>green

 As the polarity of the green compound is less, it will move first. When it arrives at the end
of the column it is collected in a clean test tube. After this, the red compound is collected
and at last blue compound is collected. All these are collected in separate test tubes.

# Advantages of Column Chromatography

 All different kinds of complex mixtures can be separated by column chromatography.

 Mobile phase is on a wide range.
 No limit for quantity as any amount of mixture can be separated by this technique.
 It is a robust method.
 The separated analytes can be reused.
  This process can be automated.

# Disadvantages of Column Chromatography

 It is a time-consuming process for the separation of compounds.

 It is expensive as higher quantities of solvents are required.
 The automated process becomes complicated and therefore costly.
 It has a low separation power.
# Column Chromatography Applications

 Column Chromatography is used to isolate active ingredients.

 It is very helpful in separating compound mixtures.
 It is used to determine drug estimation from drug formulations
 It is used to remove impurities.
 Used to isolation metabolites from biological fluids.