Adsorption

“The phenomenon of higher concentration of molecular species (gases or liquid) at the

surface of a solid than in bulk is called Adsorption”. The solid substance on the surface of
which adsorption occurs is called Adsorbentwhile the substance which gets adsorbed on the solid
surface is called Adsorbate. The adsorbent may be a solid or a liquid and the adsorbate may be
gas or a solute in some solutions. For example, activated charcoal (Finely divided charcoal)
adsorbs a number of gases like ammonia, phosgene etc. Here, charcoal is adsorbent and the gases
are adsorbate. Water vapours are adsorbed by silica gel. In this case silica gel is adsorbent and
water vapours are adsorbate.

Differences between adsorption and absorption

Adsorption Absorption
Substance is assimilated on the surface of a Substance is uniformly distributed throughout
solid or liquid the body
Surface phenomenon Bulk phenomenon
Fast process slow process
Attains easily Equilibrium attains slowly
Depends upon the surface area of the No such effect
adsorbent.
Adsorption of Litmus on charcoal Absorption of water by chalk

Distinguish between physical adsorption and chemical adsorption

Physical Adsorption Chemical adsorption

1. The forces of attraction holding the The forces of attraction holding the adsorbate
adsorbate are Vander Waal’s forces. are chemical bond forces.

2. The enthalpy of adsorption is low and
ranges from 20 to 40 kcal/ mol.
3. This adsorption occurs at low temperature
and decrease with rise in temperature.
4. Multilayer adsorption occurs.
5. It is completely reversible.
6. It is not specific in nature.
7. Equilibrium is established rapidly.
8. It does not require any activation energy.
9. Not specific
10. As pressure increases physical adsorption
increases.
The enthalpy of adsorption is high and ranges
from 40 to 400 kcal/mol.
This adsorption occurs at relatively high
temperature.
Adsorption leads to mono layer.
It is completely irreversible.
It is highly specific in nature.
Establishment of equilibrium requires time.
It requires activation energy.
Specific
As pressure increases chemical adsorption
decreased because it is confined to single layer

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2. Explain about Langmuir’s theory of adsorption.

According to Langmuir’s adsorption, the phenomenon can be explained on the following

assumptions:

1. Adsorbent has fixed number of active sites. [Valencies at the surface of the adsorbent
atoms are not fully satisfied. Therefore, they can form a weak physical adsorption or a
strong chemical adsorption]
2. Each active site holds one molecule only
3. There is no interaction between adsorbed molecules
4. The thickness of the adsorbed layer is equal to size of molecule.
5. Generally adsorption proceeds by condensation and evaporation processes.
6. Initially the rate of adsorption is high and desorption is small.

Consider a surface on which the molecules are adsorbing.

Rate of adsorption, r1 = k1 (1- θ) P --------------------(1)

Where k1 is the adsorption constant and P is the pressure

Rate of desorption, r2 = k2 (θ) --------------------(2)

Therefore, at equilibrium; r1 = r2

k1 (1- θ) P = k2 (θ)

k1 P – k1θ P = k2 θ

k1θ P + k2 θ = k1 P

(k1 P + k2 ) θ = k1 P

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 k1 p

(k1p/k2)
Dividing both numerator and denominator with k2

k1 p
  k2
k1 p  k 2
k2 k2
Since k1/k2=K1

K1 p

K1 p  1

K1 p

K1 p  1
But, the quantity of gas adsorbed per unit mass of the adsorbent, ‘w’ is proportional to the
surface covered,

w = x/m=K2 

Substituting  value in above equation

K 2 K1 p
x/m 
K1 p  1
Therefore,

p
x/m 
p  1
Here α = K2K1 and K1 = β

This equation is called Langmuir adsorption equation.

Case I: At very low pressure, ‘βP’ is becomes negligible and hence, w = α P

Therefore, adsorption is directly proportional to pressure.

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Case II: At high pressure, ‘βP’ is very high as compared with 1 and

Hence, w = αP/βP = α/β = constant.

Therefore, it is independent of pressure.

Case III: At intermediate pressure follow Freundlich adsorption theory

3. Explain about Freundlich’s adsorption theory.

The variation in the amount of gas adsorbed by the adsorbent with pressure at constant
temperature can be expressed by means of a curve termed as adsorption isotherm. Freundlich
adsorption isotherm: Freundlich, in 1909, gave an empirical relationship between the quantity of
gas adsorbed by unit mass of solid adsorbent and pressure at a particular temperature. The
relationship can be expressed by the following equation:

Where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure P, k and n are
constants depend on the nature of the adsorbent and the gas at a particular temperature.

From the adsorption, the following observation can be made:

(i) At very low pressure, the graph is almost straight line indicating linear relation-

(ii) At very high pressure, the graph is almost parallel to X-axis indicating extent of adsorption
does not depend on pressure-

(iii) At intermediate pressure, extent of adsorption (x/m) depends on 0 to 1 power of pressure

(i.e. fractional power of pressure)-

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4. Write the various applications of adsorption.

The phenomenon of adsorption finds a number of applications.

Important ones are listed here:
1. Production of high vacuum: The remaining traces of air can be absorbed by charcoal
from a vessel evacuated by a vacuum pump to give a very high vacuum.
2. Gas masks: Gas mask (a device which consists of activated charcoal or mixture of
adsorbents) is usually used for breathing in coal mines to adsorb poisonous gases.
3. Purification of water: Activated charcoal is used to remove the toxic metals due to
adsorption of metals on charcoal.
4. Control of humidity: Silica and aluminium gels are used as adsorbents for removing
moisture and controlling humidity.
5. Refining of petroleum: Fullers earth is used to remove the unwanted matter present in
crude oil during the refining.
6. Removal of colouring matter from solutions: Animal charcoal removes colours of
solutions by adsorbing coloured impurities.
7. Heterogeneous catalysis: Adsorption of reactants on the solid surface of the catalysts
increases the rate of reaction. There are many gaseous reactions of industrial importance
involving solid catalysts. Manufacture of ammonia using iron as a catalyst, manufacture
of H2SO4 by contact process and use of finely divided nickel in the hydrogenation of oils
are excellent examples of heterogeneous catalysis.
8. Separation of inert gases: Due to the difference in degree of adsorption of gases by
charcoal, a mixture of noble gases can be separated by adsorption on coconut charcoal at
different temperatures.
9. In curing diseases: A number of drugs are used to kill the germs by getting adsorbed on
them.
10. Arsenic poisoning: Colloidal Ferric hydroxides are used for the treatment of of arsenic
poisoning
11. Adsorption indicators: Surfaces of certain precipitates such as silver halides have the
property of adsorbing some dyes like eosin, fluorescein, etc. and thereby producing a
characteristic colour at the end point.
12. Chromatographic analysis: Chromatographic analysis based on the phenomenon of
adsorption finds a number of applications in analytical and industrial fields.

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FACTORS AFFECTING ADSORPTION OF GASES ON SOLIDS

Nature of adsorbate: Physical adsorption is non – specific in nature and therefore every gas gets
adsorbed on the surface of any solid to a lesser or greater exetent. However, easily liquefiable
gases like NH3, HCl, CO2 etc are adsorbed to greater extent whereas H2, O2, N2 etc are adsorbed
to lesser extent.
Nature of Adsorbent: Activated carbon, metal oxides like aluminum oxide, silica gel and clay
are commonly used adsorbents. They have their specific adsorption properties depending upon
pores.
Activation of the adsorbent: Increasing the surface area of the adsorbent is called as activation,
which can be done by
Mechanical rubbing of metallic surface
Subjecting to chemical reaction- chemical itching
Sub dividing the particles
Treating in superheated steam, in case of charcoal

The greater the specific area, more will be the extent of adsorption. That is why porous or finely
divided forms of adsorbents adsorb larger quantities of adsorbate.
Effect of temperature (Isobar): As adsorption is exothermic, temperature increases adsorption
should decrease. This is applicable in case of physical adsorption. Whereas in chemical
adsorption, initially adsorption increases (because it requires activation energy) then decreases.

Effect of pressure of the gas (Isotherm): Physical adsorption increases with increase in
pressure. The extent of adsorption is expressed as x/m where ‘x’ is amount of adsorbate. ‘m’ is
mass of adsorbent when the dynamic equilibrium is established between free gas and the
adsorbed gas.

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Adsorption from Solutions

Here adsorbent adsorbs solute from solution.

Ex. Activated Charcoal adsorbs colour from sugar solution, also adsorbs acid from solutions,
adsorbs ammonia from ammonium chloride solutions, An adsorbent adsorbs certain solute from
solutions in preference to other solutes. For example charcoal adsorbs non electrolytes more
readily than electrolytes. Alumina adsorbs electrolytes than non electrolytes. This is also affected
by concentration and temperature. Adsorption from solution decreases with increasing the
temperature and decreasing the concentration.

Positive adsorption – Activated charcoal in Con. KCl decreases the concentration of KCl
solution due to more adsorption of KCl than water (Positive adsorption)

Negative adsorption - Activated charcoal in Dil. KCl increases the concentration of KCl solution
due to more adsorption of water than KCl (Negative adsorption)

Effect of Concentration adsorption from solutions can be expressed as given below

x / m  KC1 / n