Surface Chemistry, Kinetics & Catalysis

UNIT 3: Surface Chemistry, Kinetics & Catalysis

Adsorption - Characteristics, Classification, Application, Adsorption isotherms
- Freundlich, Langmuir & BET

Reference books: Atkins' Physical Chemistry &

Essentials of Physical Chemistry by Arun Bahl
1
 Adsorption - Characteristics, Classification, Application,
Adsorption isotherms - Freundlich, Langmuir & BET

INTRODUCTION TO ADSORPTION
Definition: Adsorption is a process whereby a substance (adsorbate or
sorbate) is accumulated on the surface of a solid (adsorbent, or sorbent). The
adsorbate can be in a gas or liquid phase.

Adsorption refers to the existence of a higher concentration of any particular

component at the surface of a liquid or a solid phase.

An example of an excellent adsorbent is the charcoal used in gas masks to

remove poisons or impurities from a stream of air.

2
Dr Busupalli
 Adsorbate

Adsorbent

Solids that are used to adsorb gases or dissolved substances are called
adsorbents; examples: charcoal, alumina, silica gel

The adsorbed molecules are usually referred to collectively as the adsorbate;

examples: gases like oxygen, nitrogen etc.
3
Dr Busupalli
 Difference between adsorption & absorption

Adsorption is a surface phenomenon Absorption is a bulk phenomenon

The word "adsorption" was coined in 1881 by German physicist Heinrich Kayser
4
Dr Busupalli
 Surfaces for adsorption

Source: Atkin’s Physical chemistry Dr Busupalli

5
 CHARACTERISTICS OF ADSORPTION
Adsorption is accompanied by decrease in the free energy change of the
system when, adsorption equilibrium is said to be established.

If a material has a very high surface area, then lots of molecules

(adsorbate) can stick/adsorb to the surface.

Adsorption process is exothermic which means evolution of heat is

accompanied in adsorption process i.e., ∆H (enthalpy) is negative.

When adsorbate molecules are adsorbed on the surface, freedom of

movement of molecules become restricted and this results in a decrease
in entropy.

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 fulfilled by other atoms in the
material.
But atoms on the surface of the adsorbent are not wholly surrounded by
other adsorbent atoms and therefore can attract adsorbates. 6
Dr Busupalli
Factors affecting adsorption

The extent of adsorption depends upon the following main factors:

1. Nature of adsorbate and adsorbent.

Greater the surface area of the adsorbent, greater is the volume of the
gas adsorbed. Different gases (adsorbates) are adsorbed differently by the
same adsorbent at same temperature.

2. Activation of adsorbent.
This is performed to increase the surface area of the adsorbent via
making the surface of the adsorbent rough or subdividing the adsorbent
to smaller grains.

3. Experimental conditions. ex: temperature, pressure, etc.

Temperature - generally adsorption decreases with increase in
temperature.
Pressure – at constant temperature the adsorption increases with
increase in pressure.

7
Dr Busupalli
 CLASSIFICATION OF ADSORPTION

Types of adsorption

Physical adsorption Chemical adsorption

(Physisorption) (Chemisorption)

Force of attraction existing Force of attraction existing between

between adsorbate and adsorbent
are Van der Waal’s forces.
In physical adsorption the force of
attraction between the adsorbate
and adsorbent are very weak,
therefore this type of adsorption
can be easily reversed by heating or
by decreasing the pressure.
Dr Busupalli
adsorbate and adsorbent are almost
same strength as the chemical bonds,
the adsorption is called chemical
adsorption.
In chemisorption the force of
attraction is very strong, therefore
adsorption cannot be easily reversed.
8
 Differences between Physisorption & Chemisorption
Physisorption Chemisorption
1. Force of attraction are Van der 1. Forces of attraction are chemical
Waal's forces. bond forces (usually covalent bonds).

2. Low heat of adsorption usually in the 2. High heat of adsorption in the range of
range of 20-40 kJ/mol. 40-400 kJ/mol.
3. It usually takes place at low 3. It takes place at high temperature.
temperature and decreases with
increasing temperature.
4. It is reversible. 4. It is irreversible.

5. It is related to the ease of liquefaction 5. The extent of adsorption is generally

of the gas. not related to liquefaction of the gas.
6. It is not very specific. 6. It is highly specific.
7. It does not require any activation 7. It requires activation energy.
energy.
9
Dr Busupalli
 APPLICATIONS OF ADSORPTION

1. Silica gel packets are kept in most products that we purchase, have you
ever wondered why?

Because of this application

The silica gel packets keep the moisture out by allowing the moisture vapours
to get adsorbed over the surface of silica or alumina gel particles. So next time,
you may consider saving those tiny packets to use later as drying agents!

10
Dr Busupalli
2. Pollution Masks

Amid this pandemic, masks have become an extended part of our body. If
you ever try to cut open a pollution mask, you shall find it consists of two
or more layers of fabric, and between the layers exists activated carbon
granules or a filter sheet, which serves as a purifier. It allows clean air to
reach our nostrils by adsorbing the dust and smoke particles. The
activated carbon element or the filter sheet is the adsorbent, while the
dust and smoke particles are adsorbates.

11
Dr Busupalli
3. In curing the diseases

It should not be surprising at all to tell that adsorption is used in curing

many diseases. The disease-causing germs get deposited on the surface
of the drug taken against it, which later gets ejected from the body
through natural processes.

12
Dr Busupalli
4. Charcoal gas masks

The masks used in mining or other related activities are required to be

designed with the utmost efficiency and care because the personnel
working there have to deal with toxic and poisonous gases. In such
applications, the manufacturers make use of adsorption properties of the
substance like charcoal to filter out the unwanted gases or hazardous
fumes to avoid any dangerous outcomes.

13
Dr Busupalli
5. Purification of water

Another common example of adsorption is when you purify water using

alum. During this process, a small piece of alum is inserted in water and is
allowed to rest. A little later, you can observe the impurities getting
combined to form a large cluster. Now, one can easily remove it by
various separation methods, such as sedimentation, sieving, etc.

Water Purification - Why is alum added to water-adsorption.mp4

14
Dr Busupalli
6. Removing hardness from water

Removing hardness from water signifies removing elements like calcium

and magnesium for they make water hard. Usually, these elements can
easily be removed by the process of ion exchange in which the
cation/anion resins are added to water, the hardness causing elements
get stuck to the resins and can be filtered out easily. Finally, providing us
with softened water.

15
Dr Busupalli
7. Misty windows

Every night a layer of water vapour gets deposited on the surface of

windows, which is more prominently visible during cold weather. This is
yet another example of adsorption from daily life. Therefore, the next
time you write your name on the fog deposited on your windowpane,
give thanks to the wonderful phenomenon of adsorption. And, this
phenomenon can be applied in cleaning delicate surfaces such as glass
etc.

16
Dr Busupalli
8. Decoloring of matter

A lot of entities get contaminated due to the presence of impurities

around them. This contamination leads to a color change that may be
compensated by placing them in a decolorizing solution, such as fuller’s
earth (clay material) or charcoal solution. The impurities get deposited or
dissolved in the solution, leaving the entities decolored.

17
Dr Busupalli
9. In heterogeneous catalysis

Adsorption plays a very important role in the heterogeneous catalysis

processes. Reactants get adsorbed onto the surface of the catalyst in the
first step. After the reaction is completed on the catalysts surface the
products are then desorbed from the catalyst surface. As the entire
process of adsorption and reaction and desorption occurs on the surface
of the heterogeneous catalyst and not in the bulk of the catalyst, this
signifies the role of adsorption in heterogeneous catalysis.

18
Dr Busupalli
10. Other applications of adsorption

Adsorption in metallurgy: during the process of concentration of ore, for

example in froth floatation process, adsorption of particles onto the froth
occurs facilitating the concentration of the ore.

Adsorption in chromatography: to separate pigments.

Adsorption in virology: viruses first adsorb onto the hosts and then
colonize the host machinery to replicate and to cause disease.

Adsorption in polymer science: to produce polymer products such as non-

stick coatings and biomedical devices.

Polyelectrolytes adsorption (non-covalent layer-by-layer adsorption) onto

solid surfaces is extremely useful in industries dedicated to oil recovery,
nutrition, concrete etc.

19
Dr Busupalli
 ADSORPTION ISOTHERMS
The free gas and the adsorbed gas are in dynamic equilibrium, and the
fractional coverage (θ) of the surface depends on the pressure of the
overlying gas. The variation of θ with pressure at a chosen temperature is
called the adsorption isotherm.

In simpler terms

Adsorption isotherm describes the amount of adsorbate on the

adsorbent as a function of its pressure (if gas) or concentration (for liquid
phase solutes) at constant temperature.

Different adsorption isotherms:

1) Langmuir adsorption isotherm

2) Freundlich adsorption isotherm

3) BET adsorption isotherm

20
Dr Busupalli
Langmuir adsorption isotherm

This simplest physically plausible isotherm is based on three assumptions:

1. Adsorption cannot proceed beyond monolayer coverage.

2. All sites are equivalent and the surface is uniform (that is, the surface is
perfectly flat on a microscopic scale).

3. The ability of a molecule to adsorb at a given site is independent of the

occupation of neighbouring sites (that is, there are no interactions between
adsorbed molecules).

21
Dr Busupalli
The dynamic equilibrium is given as:

A(g) + M(surface) AM(surface)

A(g) is gaseous adsorbate

M(surface) is solid adsorbent

AM (surface) is the material where the gaseous adsobate is adsorbed

onto the solid adsorbent surface.

with rate constants ka for adsorption and kd for desorption. The rate of
change of surface coverage due to adsorption is proportional to the
partial pressure p of A and the number of vacant sites N(1 − θ ), where N
is the total number of sites:

22
Dr Busupalli
The rate of change of θ due to desorption is proportional to the number
of adsorbed species, Nθ :

At equilibrium there is no net change (that is, the sum of these two rates
is zero), and solving (via kinetic derivation) for θ gives the Langmuir
isotherm:
p

23
Dr Busupalli
In other words, at equilibrium, the rate of desorption is equal to the rate of
adsorption. So,
Where, the rate of adsorption depends on available
sites on the adsorbent for adsorption i.e., (1-θ) at
K1(1-θ)P = K2θ
partial pressure of the adsorbate P

K1P – K1θP = K2θ R1 = K1(1-θ)P………………….(i)

K1P = θ(K2 + K1P) And the rate of desorption depends on the fraction
covered θ

R2 = K2θ……………………..(ii)

where K1 and K2 are adsorptions and desorption

constants respectively.
……………………..(iii)

24
Dr Busupalli
 25
Dr Busupalli
Limitations of Langmuir adsorption isotherm

1) It assumes monomolecular adsorption onto the surface of the adsorbent,

but in reality many layers of molecules could get adsorbed onto adsorbent.

2) It assumes no interaction between the adsorbed molecules, whereas in

certain reactions there are noticeable interaction observed.

3) The Langmuir equation works reasonably well at low pressure but fails to
provide adsorption information at high pressures.

4) The effect of temperature is not well considered.

5) Relation between heat of adsorption and surface area not explained.

Thus these limitations of the Langmuir adsorption isotherm led to proposal of

Several other isotherms such as Freundlich and BET among others.

26
Dr Busupalli
Freundlich adsorption isotherm

27
Dr Busupalli
The Langmuir isotherm is applied to monolayer adsorption on homogeneous sites, whereas
the Freundlich isotherm suites are applied to multilayer adsorption on heterogeneous sites.
28
Dr Busupalli
 Limitations of Freundlich adsorption isotherm

Freundlich adsorption isotherm is based on assumption that every adsorption site is

equivalent. It is applicable to physical adsorption.

29
Dr Busupalli
BET adsorption isotherm
If the initial adsorbed layer can act as a substrate for further (for example,
physical) adsorption, then, instead of the isotherm levelling off to some
saturated value at high pressures, it can be expected to rise indefinitely. The
most widely used isotherm dealing with multilayer adsorption was derived
by Stephen Brunauer, Paul Emmett, and Edward Teller, and is called the BET
isotherm:

Salient features of BET isotherm:

1) Gas molecules physically adsorb on a solid in layers infinitely
2) gas molecules only interact with adjacent layers; and the Langmuir theory
can be applied to each layer.
3) the enthalpy of adsorption for the first layer is constant and greater than
the second (and higher).
4) the enthalpy of adsorption for the second (and higher) layers is the same
as the enthalpy of liquefaction.

30
Dr Busupalli
The BET Equation uses the information from the isotherm to determine the
surface area of the sample, where X is the weight of nitrogen adsorbed at a
given relative pressure (P/Po), Xm is monolayer capacity, which is the volume
of gas adsorbed at standard temperature and pressure (STP), and C is constant.

(STP is defined as 273 K and 1 atm)

a BET isotherm plots the amount of gas adsorbed as a function of the

relative pressure. There are five types of adsorption isotherms possible from
the surface adsorption analyses of materials using BET.

31
Dr Busupalli
 BET Type I isotherm
When P/Po < 1 and C > 1

Volume or

Type I is a pseudo-Langmuir isotherm because it depicts monolayer adsorption.

A type I isotherm is obtained when P/Po < 1 and C > 1 in the BET equation, where
P/Po is the partial pressure value and c is the BET constant, which is related to
the adsorption energy of the first monolayer and varies from solid to solid.
The characterization of microporous materials, those with pore diameters
less than 2 nm, gives this type of isotherm. This isotherm shows that the extent of
adsorption increases with pressure until it reaches saturation, at which point no
32
further adsorption occurs. Dr Busupalli
 BET Type II isotherm
When C > 1

A type II isotherm is very different than the Langmuir model. The flatter region in
the middle represents the formation of a monolayer. A type II isotherm is obtained
when C > 1 in the BET equation. This is the most common isotherm obtained when
using the BET technique. It is obtained when the bilayer is formed only after the
monolayer has been fully formed, and the trilayer is formed only after the bilayer
has been fully formed. 33
Dr Busupalli
BET Type III isotherm
When C < 1

A type III isotherm is obtained when the C < 1 and shows the formation of a
multilayer. It is obtained when the formation of monolayers, bilayers, trilayers,
and other layers all take place at the same time, resulting in an almost exponential
increase in the amount of adsorption.
34
Dr Busupalli
BET Type IV isotherm

At the lower pressure regions, it shows the formation of a monolayer

followed by a formation of multilayers. BET surface area characterization of
mesoporous materials, which are materials with pore diameters between
2 - 50 nm, gives this type of isotherm.
35
Dr Busupalli
BET Type V isotherm

This type of adsorption isotherm is obtained only when intermolecular attraction

effects are large, and adsorption takes place in pores and capillaries. Type V
isotherms are very similar to type IV isotherms.

36
Dr Busupalli