Welcome to surface
Mukesh Sharma
The surface of a solid has the tendency to attract
and retain the molecules of the phase with which
it comes into contact.
These molecules remain only at the surface and do
not go deeper into the bulk.
The accumulation of moleculaes
at the surface rather than in the bulk of a solid
or liquid is termed
Adsorption.
This is anhydrous calcium chloride,which is
an absorbant - not an adsorbent.
It can absorb moisture from the
atmosphere while silica gel adsorb moisture
from the atmosphere
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Adsorption
The binding and accumulation of molecules at the
surface
Adsorbate :- The substance, accumulates at the
surface
Adsorbent :- the material on the surface of
which the adsorption takes place is called
Adsorbent
sajeevan
Distinction between Adsorption and
Absorption
In adsorption, the substance is concentrated
only at the surface
while in absorption, the substance is
uniformly distributed throughout the bulk of
the solid.
For example, when a chalk stick is dipped in
ink,
The term sorption is used to describe both
Both adsorption and absorption
simultaneously
Distinction between Adsorption and
Absorption
Adsorption in action
(i) If a gas like O2, H2, CO, Cl2, NH3 or SO2 is
taken in a closed vessel containing powdered
charcoal, it is observed that the pressure of
the gas in the enclosed vessel decreases. The
gas molecules concentrate at the surface of the
charcoal, i.e., gases are adsorbed at the
surface.
How adsorption take palce
Surface has unbalanced or residual attractive
forces.
These forces of the adsorbent are responsible for
attracting the adsorbate particles on its surface
During adsorption, there is always a decrease in
residual forces of the surface,
Thermodynamics of adsorptions
new bond and attraction forces between
adsorbent and adsorbate , are formed,hence
H of adsorption is always negative.
When a gas is adsorbed, the freedom of
movement of its molecules become
restricted.
This leads to decrease in the entropy of the
gas after adsorption, i.e., S is negative
Thermodynamics of adsorptions
Adsorption is accompanied by decrease in
enthalpy as well as decrease in entropy of the
system.
For a process to be spontaneous, the
thermodynamic requirement is that, at constant
temperature and pressure, G must be
negative,
, G = H TS, G can be negative
if H has sufficiently high negative value as
TS is positive.
Types of Adsorption
Physisorption
Chemisorption
1. It arises because of van der Waals
1. It is caused by chemical bond
forces.
formation.
2. It is not specific in nature.
2. It is highly specific in nature.
3. It is reversible in nature.
3. It is irreversible.
4. It results into multimolecular layers
on adsorbent surface under high
pressure.
4. It results into unimolecular layer.
5. Enthalpy of adsorption is low (20-40
5. Enthalpy of adsorption is high (80-
kJ mol )in this case.
240 kJ mol ) in this case.
6. Low temperature is favourable for
6. High temperature is favouable for
adsorption. It decreases with increase
absorption. It increases with the
of temperature
increase of temperature.
7. No appreciable activation energy is
7. High activation energy is sometimes
needed.
needed.
-1
-1
Desorption.
The process of removing
an adsorbed substance
from a surface on which
it is adsorbed is called
desorption.
Adsorbent
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Characteristics ofphysisorption
Nature of adsorbate /adsorbent : The amount of gas adsorbed by a solid depends on
the nature of gas.
In general, easily liquefiable gases (i.e., with higher
critical temperatures) are readily adsorbed as van der
Waals forces are stronger near the critical
temperatures
(iv) Surface area of adsorbent: x/m increases with
the increase of surface area of the adsorbent.
Thus, finely divided metals and porous substances
having large surface areas are good adsorbents.
Factors affecting adsorption
Effect of adsorbate:
The easily liquifiable gases like NH3, HCl, CO2 etc. are
adsorbed to a greater extent than the permanent gases
such as H2 ,O2, N2, etc.
Effect of surface area [specific area] of the
absorbent:
The greater the surface area of the solid, the greater
would be its adsorbing capacity.
Effect of temperature:
Physical adsorption decreases with increase in
temperature.
Effect of pressure:
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Adsorption Isotherms
x/m = k.p1/n(n>1)(5.1)
where x is the mass of the gas adsorbed on
mass m of the adsorbent at pressure P, k and n
are constants which depend on the nature of
the adsorbent and the gas at a particular
temperature. The relationship 16is
Freundlich Isotherm
A graph between the amount (x/m) adsorbed by an adsorbent
and the equilibrium pressure of the adsorbate at constant
temperature is called adsorption isotherm
At low pressure the graph is nearly straight line
x
p1
m
At high pressure x/m becomes
independent of p
x
p0
m
Over a narrow range of p
x/m = k.p1/n(n>1
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Langmuir isotherm
f: fraction of surface area covered
p: partial pressure of the adsorbate
m: mass of adsorbate adsorbed per
unit mass of adsorbent
1-f
Rate of adsorption
Rate of desorption
ra = k ap(1- f)
rd = k df
At equilibrium, ra = frd=
;
k ap
.........(i)
k ap+k d
x
=k 'af .........(2)
m
Mono-layer coverage
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Activationof adsorbent
increasing the surface area of solid adsorbent by
converting into fine powder
To make it more efficient in adsorbing the molecules
Activated charcoal is used in gas masks as it adsorbs all
the toxic gases and vapours and purifies the air for
breathing.
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Adsorption from Solution Phase
Solids can adsorb solutes from solutions also
When a solution of acetic acid in water is shaken
with charcoal,
a part of the acid is adsorbed by the charcoal
and the concentration of the acid decreases in the
solution
(i) x/m decreases with an increase in temperature.
(ii) x/m increases with an increase of surface area of the
adsorbent.
(iii) x/m depends on the concentration of the solute in
solution.
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(iv) x/m adsorption depends on the nature of the
Applications of Adsorption
(i) Production of high vacuum
(ii) Gas masks
(iii) Control of humidity
(iv) Removal of colouring matter from solutions
(v) Heterogeneous catalysis
(vi) Froth floatation process
(vii) Chromatographic analysis
(ix) Separation of inert gases
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