ADSORPTION

ADSORPTION
▪ The accumulation of molecular species at the surface
rather than in bulk of a solid or liquid
▪ The molecular species which concentrates or
accumulates at the surface is termed ADSORBATE &
the material on whose surface the adsorption has taken
place is called ADSORBENTS.
▪ If the concentration of a substance is at the surface of
another substance is more than in the bulk of adjoining
phases then it is +ve adsorption , otherwise -ve
adsorption
 Related Terms
▪ Desorption :- Process of removing an adsorbed
substance from a surface on which it is adsorbed.
▪ Sorption:- The process which involves both adsorption &
absorption .Substances undergoing sorption are said to
be sorped.
▪ Occlusion:-Adsorption of gas on metal surface
 Adsorption Absorption
▪ Surface phenomenon (i.e. ▪ Bulk Phenomenon (i.e.
adsorbate are distributed
over surface of adsorbent. ) uniform distribution of
absorbate throughout the
▪ Involves unequal but fast bulk of absorbent.)
distribution of molecular
species.
▪ Occurs at uniform rate but
▪ Rapid in beginning & gradually slowly
slows down at equilibrium.
▪ Forces involved are either
weak Vander Waal's forces or
chemical bond.

Water vapors are absorbed by anhydrous 𝐶𝑎𝐶𝑙2

to form 𝐶𝑎𝐶𝑙2 . 2𝐻2 𝑂but adsorbed by silica gel.
 Types of ADSORPTION
PHYSISORPTION
▪ Physical adsorption
▪ Caused by intermolecular
Vander Waal's forces
▪ Reversible process
▪ Depends on nature of gas
.Easily liquefiable gases
(whose critical temperature
is high) are easily adsorbed
CHEMISORPTION
▪ Activated/Chemical adsorption
▪ Caused by chemical bond
formation which may be
ionic/covalent
▪ Irreversible
▪ Highly specific , shown by
those gases only which can
react with adsorbent.
 Contd….
PHYSISORPTION
▪ Small heat of adsorption (20 −
40 𝐾𝐽𝑚𝑜𝑙 −1 )
▪ Forms multi molecular layer on
surface.
▪ Equilibrium is attained readily.
▪ Occurs at low temperature;
decreases with increase in
temperature.
▪ Adsorption increases with pressure.
CHEMISORPTION
▪ High heat of adsorption (80 −
240 𝐾𝐽𝑚𝑜𝑙 −1 )
▪ Forms unimolecular layer on surface
▪ Equilibrium is attained slowly
▪ Initially increases with temperature,
attains a maxima & decreases with
further increase in temperature.
▪ High pressure is favored .Decrease
of pressure doesn’t cause desorption.
▪ Sometimes both type of adsorption
occur simultaneously e.g. 𝐻2 is 1st
adsorbed on Nickel by Vander
Waal's forces (i.e. Physisorption),
molecules oh Hydrogen then
dissociate to form H-atom which
are held on surface by
Chemisorption.
 Enthalpy of Adsorption
▪ The adsorption of one substance on the surface
of the surface of another leads to the existence
of new types of forces between them , hence is
exothermic.
▪ It is accompanied by decrease in entropy as well
as decrease in enthalpy.
▪ In the adsorption process ∆𝐻 becomes less &
less negative ultimately ∆𝐻 becomes equal to T
∆𝑆 & ∆𝐺 becomes 0 .At this state equilibrium is
attained.
 Nature Of Gas
▪ Easily liquefiable gases (whose critical
temperature is high) (e.g. HCl , N𝑯𝟑 , C𝒍𝟐 ) are
more easily adsorbed than permanent gases (
e.g. 𝑯𝟐 , 𝑵𝟐 , 𝑶𝟐 )
▪ Critical Temperature/Liquifieability trends ( in
Kelvin)
𝑯𝟐 𝑶 𝟔𝟒𝟕 𝐊 > 𝐒𝑶𝟐 𝟔𝟑𝟎 𝑲 > 𝑪𝟐 𝑯𝟒 𝟒𝟏𝟕 𝑲 >
𝑵𝑯𝟑 𝟒𝟎𝟕 𝑲 > 𝑯𝑪𝒍 𝟑𝟐𝟒 𝑲 > 𝑪𝟐 𝑯𝟔 𝟑𝟎𝟓 𝑲 >
𝑪𝑶𝟐 𝟑𝟎𝟒 𝑲 > 𝑪𝑯𝟒 𝟏𝟗𝟏 𝑲 > 𝑶𝟐 𝟏𝟓𝟓 𝑲 >
𝑪𝑶 𝟏𝟑𝟒 𝑲 > 𝑵𝟐 𝟏𝟐𝟔 𝑲 > 𝑵𝒆 𝟒𝟒 𝑲 > 𝑯𝟐 𝟑𝟑 𝑲 >
𝑯𝒆(𝟓 𝑲)
 Nature Of Solid/adsorbent
▪ Larger the surface area greater will be adsorption
▪ If adsorbent is in very fine powdered form then
adsorption is very low
▪ Activate charcoal is preferred for 𝑪𝑯𝟒 & 𝑪𝑶 whereas,
Ni , Pd , Pt is preferred for 𝑶𝟐 , 𝑯𝟐 , 𝑵𝟐
▪ Preferential/competing Adsorption:-A strongly
adsorbable substance can easily displace a weakly
adsorbed substance irrespective of its amount present.
▪ E.g. 𝑶𝟐 & 𝑵𝟐 gets displaced from charcoal surface when
they come in contact with 𝑪𝑯𝟒 /𝑪𝑶𝟐 .
 Effect Of Pressure
▪ Adsorption isotherm is a graph plotted between
magnitude of adsorption & pressure , at constant
temperature . Extent of adsorption increases with
increasing pressure and becomes maximum at some
pressure called Saturation Pressure (𝑷𝒔 ). At 𝑷𝒔 the
rate of adsorption become equal to rate of
desorption (i.e. dynamic equilibrium reached) &
further increase of pressure doesn’t alter the
equilibrium.
 Freundlich Adsorption Isotherm
▪ Applicable only for physisorption as it considers multi
molecular layer of adsorption.
▪ In 1909, by Herbert Freundlich
▪ Fails at high temperature
𝟏
𝒙
▪ = 𝑲𝒑 𝒏 (empirical formula)
𝒎

x= mass of adsorbate
m = mass of adsorbent
p = Equilibrium pressure of adsorbate
K and n are constants for a given adsorbate
and adsorbent at a particular temperature
Freundlich Adsorption Isotherm

Variation of Isotherm @ 𝑥 𝟏
different temperature log 𝑚 = log 𝒑 + log 𝑲
𝒏
 Langmuir Adsorption Isotherm
▪ By Irving Langmuir in 1916
▪ Assumptions
Gases form unimolecular layer of adsorption on surface of
adsorbate.
Gases undergoing adsorption behave ideally.
Adsorption sites are homogeneous & equivalent.
Dynamic equilibrium exists on the surface of adsorbent i.e.
two opposite process (adsorption & desorption) takes place
simultaneously @ same rate.
Adjacent adsorbed molecule don’t interact .
 Langmuir Adsorption Isotherm
𝐊𝐩 𝐚𝐦 𝐊𝐩
𝛉= 𝐚=
𝟏 + 𝐊𝐩 𝟏 + 𝐊𝐩
𝜽=fractional coverage of the surface
K=constant
p=pressure of adsorbate over surface of adsorbent

Case-I (At very low pressure)

i.e. Kp<<1 then, 𝜽 = 𝑲𝒑
Case-II (At very high pressure)
i.e. Kp>>1 then, 𝜽 = 𝟏 & 𝒂 = 𝒂𝒎 (constant @ saturation pressure)
Langmuir Adsorption Isotherm

𝒂𝒎 𝑲𝒑 𝒑 𝟏 𝟏
𝒂= = 𝒑+
𝟏 + 𝑲𝒑 𝒂 𝒂𝒎 𝒂𝒎 𝑲
Effect Of Temperature
Physisorption Isobar Chemisorption Isobar

Le Chatelier’s Principle Activation Energy Required

▪ Nature of adsorption of nitrogen on the surface of
iron depends on temperature. At 83 K 𝑵𝟐 is
physisorbed on Fe as 𝑵𝟐 molecules . The degree of
adsorption decreases rapidly as temperature increase
. At Room te3mperature there is no adsorption of 𝑵𝟐
on Fe , When temperature is further increased to
773 K & above then Nitrogen is chemisorbed on Fe
surface as N atoms.
 Activation Of adsorbent
▪ Metallic adsorbents are activated by rubbing the
surface.
▪ Increasing specific area by making the surface
rough or granulating it.
▪ By heating adsorbent with super heated steam
(e.g. Charcoal is activated by heating b/w 650 K –
1330 K in vacuum / superheated air
 Activation Of adsorbent
▪ Metallic adsorbents are activated by rubbing the
surface.
▪ Increasing specific area by making the surface
rough or granulating it.
▪ By heating adsorbent with super heated steam
(e.g. Charcoal is activated by heating b/w 650 K –
1330 K in vacuum / superheated air
 Application Of Adsorption
▪ Silica/Aluminum Gel is used for controlling humidity.
▪ Activated charcoal is used in used in gas mask , it can also adsorb
acetic acid , can decolorize litmus solution
▪ Several organic compounds are purified by Chromatographic adsorption
▪ Separation of inert gases – Due to difference in degree of adsorption
of gases by charcoal , A mixture of noble gases can be separated by
adsorption of coconut charcoal at different temperature.
▪ Adsorption indicators:-Surface of certain precipitate such as AgX
(Silver halide) have property of adsorbing some dyes like eosin ,
fluorescein etc. thereby producing characteristic color at end point.
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