ADSORPTION

Since solids exist because of intermolecular forces between the repeating

units that make up the lattice, those intermolecular forces are unsaturated
or unsatisfied at the surface of the solid.
In the interior of the solid, each molecule (if it is a molecular solid) is
surrounded on all sides by identical molecules. At the surface of such a
solid, however, each molecule is only partially surrounded by identical
molecules; when it is not surrounded by identical molecules, any
available molecule or ion is adsorbed to its surface. The solid phase is
called the adsorbent. The molecules that are absorbed on the absorbent
are collectively called the absorbed phase or absorbate. The absorbate is
either a gas(molecules) or a solute(molecules or ions) in a solution. In
this experiment, we will investigate the adsorption of acetic acid in
aqueous solution on activated charcoal.

Adsorption by a solid is not a very important process unless the solid has
a very large surface compared to its mass. Consequently, charcoal made
from bone, blood, or coconut shells is specially effective because it has a

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highly porous structure. Charcoal is activated by being heated to quite
high temperatures in a vaccum or in a stream of dry air. This stream
desorbes the hydrocarbons that are adsorbed when the charcoal is first
produced. Charcoal , a covalently bonded solid, is more effective at
absorbing molecules than ions.
Silver chloride, on the other hand, forms as a precipitate of nearly
colloidal dimensions if precipitated rapidly; in colloidal form it has a
very high surface-to-mass ratio and readily adsorbes ions from solutions,
often to the dismay of analytical chemists.

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 Introduction of Adsorption

Adsorption is the adhesion of atoms, ions, biomolecules or molecules of

gas, liquid, or dissolved solids to a surface. This process creates a film of
the adsorbate (the molecules or atoms being accumulated) on the surface
of the adsorbent. It differs from absorption, in which a fluid permeates or
is dissolved by a liquid or solid. The term sorption encompasses both
processes, while desorption is the reverse of adsorption. It is a surface
phenomenon.

Similar to surface tension, 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 filled by other
atoms in the material. However, atoms on the surface of the adsorbent are
not wholly surrounded by other adsorbent atoms and therefore can attract
adsorbates. The exact nature of the bonding depends on the details of the
species involved, but the adsorption process is generally classified as
phsiosorption (characteristic of weak van der wall forces) or
chemisorption (characteristic of covalent bonding). It may also occur due
to electrostatic attraction.

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 Freundlich Equation

The first mathematical fit to an isotherm was published by Freundlich

and Küster (1894) and is a purely empirical formula for gaseous
adsorbates,

where x is the quantity adsorbed, m is the mass of the adsorbent, P is the

pressure of adsorbate and k and n are empirical constants for each
adsorbent-adsorbate pair at a given temperature. The function has an
asymptotic maximum as pressure increases without bound. As the
temperature increases, the constants k and n change to reflect the
empirical observation that the quantity adsorbed rises more slowly and
higher pressures are required to saturate the surface.

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Freundlich Adsorption Isotherm

The Freundlich Adsorption Isotherm is mathematically expressed as

It is also written as

or

It is also written as

where

x = mass of adsorbate.
m = mass of adsorbent.
p = Equilibrium pressure of adsorbate.
c = Equilibrium concentration of adsorbate in solution.

K and n are constants for a given adsorbate and adsorbent at

a particular temperature.

At high pressure 1/n = 0 Hence extent of adsorption is

independent of pressure

But at high pressure it is dependent on pressure.

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 Freundlich Adsorption
Isotherm Graph

Example of the Freundlich isotherm, showing the amount adsorbed, q

(e.g., in mol/kg), as a function of equilibrium concentration in the
solution, c (e.g., in mol/L). The graph is for the values of the constants of
K=4 and 1/n=0.

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 Adsorption of Acetic Acid on
Charcoal

The amount of adsorption, given the symbol Y, has units of moles adsorbate per
mass adsorbent.
If the adsorbate is a gas, Y may have units of volume adsorbate per mass adsorbent.
The amount of adsorption Y increases with the concentration c of the adsorbate.
The increase is very rapid at first, when the surface of the adsorbent is relatively
free. As the surface fills with the adsorbate, the rate of adsorption d Y/ d c
decreases.

Eventually the surface of the adsorbent becomes full and further increases in the
concentration cause no further increase in the amount adsorbed as shown in the
figure below. The amount adsorbed when the surface is just covered with a mono
molecular of the adsorbate is called Ymax.
At a given concentration the amount adsorbed decreases with increasing
temperature.

In this purely empirical equation (Y= kc1/n), the units of Y are moles adsorbate per
gram adsorbent, c is the concentration(mole/ L), And k and n are experimentally
determined constants.
Since above equation is valid only for a given adsorbed phase and adsorbent at a
constant temperature, it is sometimes called as feundlich isotherm. To test the
validity of the freundlich isotherm, take the logarithm of both sides of the equation-

Log10Y= Log10k+1/n Log10C

If Log10 Y is plotted against Log10 C, Straight lines results with the slope= 1/n and
the intercept =Log10k.

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 Limitation of Freundlich Equation

Experimentally it was determined that extent of adsorption varies directly with

pressure till saturation pressure Ps is reached. Beyond that point, rate of adsorption
saturates even after applying higher pressure.

Thus freundlich adsorption isotherm failed at higher pressure. To correct this the
following theory was followed.
The postulates of this theory are as follows:-

1. The adsorbed phase forms a layer of molecules, one molecule deep.

2. The system is in a state of equillbrium such that the rate of adsorption equals
the rate of desorption.
3. The rate of adsorption is proportional to the concentration and the fraction of
the surface that is vacant.
4. The rate of desorption is proportional to the fraction of the surface that is
already covered.

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 Applications of Adsorption

Some of the important applications of adsorption are as follows:

(1) In the preparation of gas masks using activated charcoal to avoid poisonous
gases like etc.

(2) Froth floatation method used for concentration of sulphide ores is based on
adsorption.

(3) Silica gel can be used to remove moisture and to control humidity.

(4) Ion exchange method used to soften water is based on adsorption.

(5) Adsorption chromatography is used to purify and separate pigments, harmones

etc.

(6) Charcoal powder can remove coloured impurities from sugar.

(7) Charcoal is used for making high vacuum.

(8) The cleaning action of soaps and detergents.

(9) Formation of stable emulsions in cosmetics and syrups etc.

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 Types of Adsorption
Forces of attraction exist between adsorbate and adsorbent. These forces of
attraction can be due to Vanderwaal forces of attraction which are weak forces or
due to chemical bond which are strong forces of attraction. On the basis of type of
forces of attraction existing between adsorbate and adsorbent, adsorption can be
classified into two types: Physical Adsorption or Chemical Adsorption.

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 has low enthalpy of adsorption i.e. ΔHadsorption is 20-
40KJ/mol.

It takes place at low temperature below boiling point of adsorbate.As the

temperature increases in, process of Physisorption decreases.

Physical Adsorption vs. Temperature graph

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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. 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.

Chemical Adsorption vs. Temperature Graph

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Difference Between Absorption
and Adsorption

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