Adsorption of gases on

solids

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 Adsorption of gases on solids
• When the gas molecules come in contact to a solid surface they are attached or bonded
by chemical or physical reactions.
• Chemical adsorption (e.g. chemisorption) is when the gas molecules are bound to the
surface by chemical bond.
• Physical adsorption (e.g. physisorption) is when the gas molecules are bound by the sum
of attractive or repulsive forces between molecules and electrostatic forces.
• The extent of adsorption of a gas on the surface of a solid depends on the following
factors: 
Nature of gas 
Nature of solid 
Specific area of solid 
Pressure of gas 
Temperature 
Activation of solid 
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Nature of Gas
• Since physical adsorption is non-specific in nature, any gas will be adsorbed
on the surface of a solid to some extent or other.
• However, under any given conditions of temperature and pressure, easily
liquefiable gases such as NH3, CH4, HCI, CI2, SO2, CO etc. are adsorbed more
than permanent gases like H2, O2, N2 etc.
• Chemisorption is specific in nature.
• Therefore, only those gases will be adsorbed which form chemical bonds with
it. 

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Nature of Solid 
• Activated charcoal is the most common adsorbent for easily liquefiable
gases. Poisonous gases such as CH4 and CO fall in this group. Therefore, it is
used in gas masks.
• Other gases such as O2, H2 and N2 adsorb more on metals such as Ni, Pt and
Pd. 
Specific Area of Solid
• Specific area of an adsorbent is the surface area available for adsorption per
gm of adsorbent. Greater the specific area of an adsorbent, greater will be the
adsorption.
• The specific area of an adsorbent can be increased by making the surface
rough. The pores must be large enough to allow penetrations of gas
molecules.
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Pressure of a Gas
• As physical adsorption is reversible, it is accompanied by decrease in
pressure. Therefore, it is expected that at a given temperature the extent of
adsorption will increase with the increase of pressure of the gas.
• The extent of adsorption is measured as x/m where m is the mass of
adsorbent and x that of adsorbate.

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 Adsorption Isotherm
• The process of Adsorption is usually studied through graphs know as
adsorption isotherm. It is the graph between the amounts of adsorbate (x)
adsorbed on the surface of adsorbent (m) and pressure at constant
temperature. The common types adsorption isotherms have been Freundlich,
Langmuir and BET (Brunauer – Emmett – Teller) theory.
Basic Adsorption Isotherm
• In the process of adsorption, adsorbate gets adsorbed on adsorbent.

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• According to Le-Chatelier principle, the direction of equilibrium would shift
in that direction where the stress can be relieved. In case of application of
excess of pressure to the equilibrium system, the equilibrium will shift in the
direction where the number of molecules decreases. Since number of
molecules decreases in forward direction, with the increases in pressure,
forward direction of equilibrium will be favored.
• From the graph, we can predict that after saturation pressure Ps, adsorption
does not occur anymore.
• This can be explained by the fact that there are limited numbers of vacancies
on the surface of the adsorbent. At high pressure a stage is reached when all
the sites are occupied and further increase in pressure does not cause any
difference in adsorption process. At high pressure, Adsorption is independent
of pressure.

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• Hence, if the physical adsorption is limited to unimolecular layer, the plot of
x/m vs. equilibrium pressure at a constant temperature is as shown.        

• It is evident from the graph that at a certain pressure the adsorption reaches a
maximum value i.e. the adsorption becomes saturated and the corresponding
pressure is called saturation pressure (Ps). Beyond this pressure the adsorption
remains constant. 
At low pressures : x/m varies linearly with p 

or

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• At high pressures :  x/m is independent of p 

• At intermediate pressures:  The variation of x/m vs p can be expressed as

• Where n > 1
or

• Comparing the above given equation with equation of straight line 

y = mx + c
• we know that, if we plot log p vs log x/m, we would get a straight line with
slope equal to 1/n and intercept log k.
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 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 or simply Freundlich Isotherm.

• Where x is the mass of the gas adsorbed on mass m of the adsorbent at

pressure p and k, n are constants whose values depend upon adsorbent and gas
at particular temperature. Though Freundlich Isotherm correctly established
the relationship of adsorption with pressure at lower values, it failed to predict
value of adsorption at higher pressure.

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• Graph representing a Freundlich adsorption isotherm.

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 Langmuir Adsorption Isotherm

• In 1916 Langmuir proposed another Adsorption Isotherm known as Langmuir

Adsorption isotherm. This isotherm was based on different assumptions one of
which is that dynamic equilibrium exists between adsorbed gaseous molecules
and the free gaseous molecules.

Where A(g) is unadsorbed gaseous molecule, B(s) is unoccupied metal surface

and AB is Adsorbed gaseous molecule.
The release of adsorbed gas is commonly described by a pressure relationship
called the Langmuir Isotherm. The Langmuir adsorption isotherm assumes that
the gas attaches to the surface of the coal or shale, and covers the surface as a
single layer of gas (a monolayer). At low pressures, this dense state allows
greater volumes to be stored by sorption than is possible by compression.
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 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.

• 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

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• The above equation represents the equilibrium constant for
distribution of adsorbate between the surface and the gas phase.

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 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.
• To derive Langmuir Equation and new parameter ‘ θ ’ is introduced. Let θ the
number of sites of the surface which are covered with gaseous molecules.
Therefore, the fraction of surface which are unoccupied by gaseous
molecules will be (1 – θ).
• Now, Rate of forward direction depends upon two factors: Number of sited
available on the surface of adsorbent, (1 – θ) and Pressure, P. Therefore rate
of forward reaction is directly proportional to both mentioned factors.

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• Similarly, Rate of backward reaction or Rate of Desorption depends upon
number of sites occupied by the gaseous molecules on the surface of
adsorbent.

• At equilibrium, rate of adsorption is equal to rate of desorption

Ka P (1 – θ) = Kd θ
• We can solve the above equation to write it in terms of θ
KaP – KaP θ = Kd θ
KaP = KaP θ + Kd θ
KaP = (Kd + KaP) θ

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• Divide numerator and denominator on RHS by Kd, we get

• Now put in above equation we get

This is known as Langmuir Adsorption Equation.

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• The typical formulation of Langmuir isotherm is:

where V(P) is the gas content measured in scf/ton of coal or shale.

The mathematical expression of the Langmuir adsorption isotherm involving only

one sorbing species can be demonstrated in different ways: the kinetics approach,
the thermodynamics approach, and the statistical mechanics approach respectively.
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 BET adsorption Isotherm

• BET Theory put forward by Brunauer, Emmett and Teller explained that
multilayer formation is the true picture of physical Adsorption.
• One of the basic assumptions of Langmuir Adsorption Isotherm was that
adsorption is monolayer in nature. Langmuir adsorption equation is applicable
under the conditions of low pressure.
• Under these conditions, gaseous molecules would possess high thermal energy
and high escape velocity. As a result of this less number of gaseous molecules
would be available near the surface of adsorbent.
• Under the condition of high pressure and low temperature, thermal energy of
gaseous molecules decreases and more and more gaseous molecules would be
available per unit surface area. Due to this multilayer adsorption would occur.
The multilayer formation was explained by BET Theory. The BET equation is
given as
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• The another form of BET equation is

• Where Vmono be the adsorbed volume of gas at high pressure conditions so

as to cover the surface with a unilayer of gaseous molecules,

• the ratio is designated C. K1 is the equilibrium constant when single molecule

adsorbed per vacant site and KL is the equilibrium constant to the saturated
vapor liquid equilibrium.
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• Temperature
• As adsorption is accompanied by release of heat energy, so in accordance with
Le-Chatelier’s principle, the increase of temperature should decrease the
extent of adsorption. This has indeed been found to be so. A plot of x/m vs.
temperature at constant pressure is called adsorption isobar. 
• In the case of physical adsorption x/m decreases with increase of temperature.
However, in the case of chemisorption x/m initially increases with
temperature and then decreases as shown below.
• The initial increase is due to the fact that chemisorptions require activation
energy. 

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Activation of Solid 
• Activation of adsorbent means increasing its adsorbing power. This is
increased by increasing specific area either by making the surface rough or by
breaking the solid into smaller particles. But care must be taken so that
particles do not become very small, otherwise the inter-particle spaces will be
too small to allow penetration of gas molecules. 
Competing Adsorption 
• There is always a competition between different adsorbates to adsorb on the
adsorbent.
• A strongly adsorbable substance can easily displace a weakly adsorbed
substance. For example, on the surface of activated charcoal, gases such as O2,
N2 etc. are already adsorbed. But when charcoal comes in contact with
poisonous gases such as CH4, CO which are strongly adsorbable, O2 and N2 get
displaced.
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• If a mix of gases is allowed to adsorb on a particular adsorbent, the
strongly adsorbable adsorbate adsorbs.
• For example, moisture though present in small proportion in air is
strongly adsorbed by silica gel. Charcoal adsorbs poisonous gases
even though they are present in small concentration in air.

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 Adsorption from the Solutions
• Some solids are capable of adsorbing certain solutes from the solution. This property
is made use of in adsorbing colouring matter from solutions of organic substances.
• Raw cane juice is decolourised by activated charcoal. Similarly, charcoal adsorbs
oxalic and acetic acid dyes from their aqueous solutions. 
• Freundlich adsorption isotherm is also applicable to solutions by replacing the
pressure term by the concentration (C) of adsorbates in solutions. The relationship is
modified as follows .

• Taking logarithm, it becomes 

log x/m = logk + 1/n logC 

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• A graph between log (x/m) and log C is a straight line for small ranges of
 concentrations.
• Another isotherm derived by Langmuir considers the formation of a mono-
molecular layer of adsorbate on adsorbent. It is known as Lamuir
adsorption isotherm and is based on the following points : 
• It takes place on the surface of solids till a unimolecular layer is formed.
• Adsorption is result of condensation of adsorbent molecules on solid surface
and their evaporation.
• At equilibrium, the rate of condensation of adsorbate molecules on solid
surface and the rate of  their evaporation becomes equal.
• Based on these aspects, Lagmuir derived the expression given below:

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• The values of constants “a” and “b” depends upon the nature of
adsorbate, nature of solid adsorbent, and temperature. “p” is
equilibrium pressure
• Lagmuir theory has limitations. This theory of unimolecular
adsorption is valid only at low pressure and high temperature.
• As the pressure is increases or temperature is lowered, additional layer
starts forming . This leads to multilayer adsorption.

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 Applications of Adsorption

Following are the applications of adsorption:

• Gas masks: Poisonous gases get adsorbed to at the surface of the mask and
prevent its encounter when used by coal miners.
• Production of vacuum: Traces of air are adsorbed on charcoal and removed
from devices undergoing the process of evacuation.
• Removal of moisture: Silica gel pellets are used for the adsorption of moisture
in medicines and new plastic bottles in order to control humidity.
• Removal of colour: 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.
• As 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.
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