UNIT IV

SURFACE CHEMISTRY:
 Adsorption- Types
 Freundlich adsorption isotherms (Derivation)
 Langmuir adsorption isotherms (Derivation)
 BET isotherm: applications (derivation not required).
CO: Recognize the
 Applications of adsorption
 Abatement of air (anti-pollution mask) and water pollution (ion-
principles and industrial
exchange resin)
applications of surface
 Automobile catalytic converter chemistry and adsorption
 Surface active agents: Surfactants- types, examples. Detergents, phenomena.
emulsifiers, properties- critical micelle concentration

 Contact angle
 Wetting and Water repellency
 Superhydrophobic surfaces- Coatings

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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.
 Adsorption is essentially a surface phenomenon.

 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.

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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.

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Desorption
The adsorbed molecular species can be removed from the surface of the adsorbent
and the process of removing an adsorbed substance from a surface on which it is
adsorbed is called desorption.

E.g. for adsorbents

Solids, particularly in finely divided state, have large surface area and therefore,
charcoal, silica gel, alumina gel, clay, colloids, metals in finely divided state, etc. act
as good adsorbents.
E.g. for adsorbates
NH3, HCl, Cl2 and SO2

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Surface area
Materials made up of smaller sizes have a relative larger surface area when
compared to the same volume of material made up of bigger particles.

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Adsorption in liquids
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.
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

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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. 7
THERMODYNAMIC FACTS ABOUT ADSORPTION
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.

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.

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Types of Adsorption
Physical Adsorption or Physisorption
 When the force of attraction existing between adsorbate and adsorbent are weak
van der Waal’s 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 – 40 kJ/mol.
 It takes place at low temperature below boiling point of adsorbate. As the
temperature increases in, process of physisorption decreases.
Example: Adsorption of hydrogen or oxygen on charcoal

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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.
E.g. H2 on Ni surface
 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.

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S. Physisorption Chemisorption
No.
1 Caused by intermolecular van der Caused by chemical bond formation
Waal’s forces
2 Depends on the nature of gas. Much more specific than Physisorption
Easily liquefiable gas adsorbed
readily
3 Heat of adsorption is small, 20 – 40 Heat of adsorption is large, 80 to 240
kJ/mol kJ/mol
4 Reversible Irreversible
5 Occurs rapidly at low temperature; With the increases in temperature,
decreases with increasing chemisorption first increases and then
temperature decreases
6 Increase of pressure increases Change of pressure has no significant
physisorption effect
7 Forms multimolecular layer on Forms unimolecular layer
adsorbent surface 11
Influencing Factors
Temperature: Adsorption is high at low temperature conditions.
Adsorption process is exothermic in nature. According to LeChatleir principle, low
temperature conditions would favour the forward direction
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.
Surface Area: Adsorption is a surface phenomenon therefore it increases with increase
in surface area.
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.
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Adsorption isotherm
It is the graph between the amounts of adsorbate (x) adsorbed on the surface of adsorbent
(m) and pressure at constant temperature.

Freundlich Adsorption Isotherm

In 1909, Freundlich gave an empirical expression representing the isothermal variation of
adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent with pressure. This
equation is known as Freundlich Adsorption Isotherm or Freundlich Adsorption equation.

Where Ɵ is the amount of gas adsorbed per unit mass of the adsorbent at pressure P.
K and n are constants depending on the nature of the gas and nature of the adsorbent.
The value of n is less than 1, i.e., it should be in fraction.
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Taking log on both sides of equation (1) we have
log Ɵ = log K + n log P
According to the above equation a plot of log Ɵ Vs log P will give a straight line whose
slope will be equal to “n” and intercept is equal to log K.

The above equation shows that as pressure increases Ɵ also increases and there is no limit to
this increase. But experimental values show deviations from linearity, especially at high
pressure it reaches a saturation limit and Ɵ becomes constant as shown in the 2nd graph

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Limitation of Freundlich Adsorption Isotherm

1. Freudlich’s equation is purely empirical without any theoretical foundation.

2. The equation is valid only upto a certain range of pressure and is invalid at higher pressure.
3. Freudlich adsorption isotherm fails, when the concentration of adsorbate is very high.
4. The constants “k” and “n” are not temperature independents, they vary with temperature.

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Langmuir Adsorption Isotherm
In 1916, Irving Langmuir proposed another adsorption Isotherm which explained the variation
of adsorption with pressure based on some theoretical consideration. This theory is based on
the following assumptions
Assumptions of Langmuir Isotherm
1. The adsorbed gas behaves ideally in the gas phase
2. Only a monolayer is formed by the adsorbed gas
3. The surface of the solid is homogenous so that each binding site has the same affinity for the
gas molecules.
4. There is no lateral interaction between the adsorbed molecules.
5. The adsorbed gas molecules are localized, i.e., they do not move around the surface.
6. Each site can hold maximum of one gaseous molecule and a constant amount of heat energy
is released during this process.
7. Dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous
molecules. Here A is unadsorbed gaseous molecule, M is unoccupied metal surface and AM
is Adsorbed gaseous molecule.
A(g) + M(surface) AM
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Derivation

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This equation is called as Langmuir adsorption isotherm. This equation could be subjected to various
pressure conditions

1. At low pressure: When the pressure is low KP << 1, so 1 + KP ≈ 1. Substituting this in Langmuir
adsorption isotherm, θ = KP/1; θ = KP. The fraction of the surface covered is directly proportional to
the pressure of the gas. It could also be seen that the adsorption process follow first order reaction,
which is responsible for steep rise in the θ vs. P graph.
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2. At high pressure: When the pressure is high KP >> 1, so 1 + KP ≈ KP. Substituting this in
Langmuir adsorption isotherm, θ = KP/KP; θ = 1. Thus, at high pressures, the value of Ɵ tends to
become unity. i.e., the entire surface gets covered by a monomolecular layer of gas thereby
making the reaction rate independent of the pressure. In other words, the reaction becomes
zero-order. Thus the magnitude of adsorption should first increase in proportion to increase of
pressure and finally tend to attain a certain limiting value. This is exactly indicated by
experimental curve.
3. At intermediate pressure: When the pressure is intermediate
θ takes the form θ = KPn, where n lies between 0 and 1.
This equation is similar to Freundlich adsorption isotherm.

Merits of Langmuir Adsorption Equation

Langmuir’s model is based on a theoretical construct,
unlike Freundlich model.
It established a logic picture of adsorption process
It fits well for many adsorption system
Langmuir adsorption isotherm is mainly used in the analysis of reaction mechanism. 19
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. From above facts we can conclude that,
Langmuir equation is valid under low pressure conditions.
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