ADSORPTION

Adsorption
It is a surface phenomenon and refers to the uniform distribution of a
substance through another at the surface.
It is the phenomenon in which a layer of ions, molecules or aggregates of
molecules condense upon the surface with which they come in contact.
It is defined as the concentration of a substance at the interface or
boundary between heterogeneous phases e.g. solid/ gas or two immiscible
liquids
Adsorption vs. Absorption
Adsorption is accumulation of molecules on a surface (a surface layer of
molecules) in contact with an air or water phase
Absorption is dissolution of molecules within a phase, e.g., within an
organic phase in contact with an air or water phase
 Adsorption

PHASE I

‘PHASE’ 2

Absorption (“partitioning”)

PHASE I

PHASE 2
Adsorbate and Adsorbant
Adsorbate is the substance which is adsorbed at the surface of another
substance
Examples: gases, dyes, water vapors etc.
Adsorbant is the substance which adsorbs the other substance at its
surface.
Examples are: activated charcoal, bone charcoal, alumina, silica gel,
kaolin and filler’s earth.
Types of Adsorption
Vander Walls or Physical Adsorption
Physical adsorption is a type of adsorption in which the adsorbate adheres
to the surface only through Van der Waals (weak intermolecular)
interactions, which are also responsible for the non-ideal behaviour of real
gases.

Chemisorption or Chemical Adsorption

In this kind of adsorption, the gas molecules or atoms are held to the solid
by chemical bonds.
For example hydrogen is chemisorbed on nickel.
Comparison:Physical & Chemical Adsorption
Physical Adsorption Chemical Adsorption
Intermolecular van der Waal’s Chemical bond formation.
forces. Much more specific than physical
Nature of gas: Easily liquefiable adsorption.
gases are adsorbed readily.
Heat of adsorption is small Heat of adsorption is large (20-
(about 5 Kcal /mol) 100 Kcal /mol)
Reversible.
Rapid at ↓temp.; ↓ with ↑temp. Irreversible.
↑ with ↑ of temp.
Comparison:Physical & Chemical Adsorption
Physical Adsorption Chemical Adsorption
↑ of pressure ↑ adsorption; Change of pressure has no
↓ of pressure causes such effects.
desorption.
Forms multimolecular
layers on adsorbent surface. Forms unimolecular layer.
Adsorption may be
Positive adsorption
Negative adsorption
Sorption
Positive adsorption
In case of adsorption by solids from the solutions, mostly the solute is
adsorbed on the surface of the solid adsorbent so that the concentration of
solute on the surface of the adsorbent is greater than in the bulk. This is
known as positive adsorption.
Hence when the concentration of the adsorbate is more on the surface of
the adsorbent than in the bulk, it is known as positive adsorption.
Negative adsorption
In some cases, the solvent from the solution may be adsorbed by the
adsorbent so that the concentration of the solution increases than the initial
concentration. This is called negative adsorption.
Hence if the concentration of the adsorbate is less on the surface of the
adsorbent than in the bulk, it is known as negative adsorption
Factors affecting adsorption
Solubility of adsorbate
Nature of Adsorbate
Nature of adsorbent
Surface area of absorbant
Affinity between adsorbent and adsorbate
Concentration of both adsorbate and adsorbent
Pressure
Temperature
pH
Factors influencing adsorption of gases by solids

1. Adsorption and surface area

Adsorption being a surface phenomenon, the extent of adsorption depends
on the surface area. Increase in the surface area of the adsorbent increases
the total amount of the gas adsorbed.

2. Nature of gas
The amount of gas adsorbed by a solid depends on the nature of the gas. In
general, more Easily liquefiable gas is more readily adsorbed.
Factors influencing adsorption of gases by solids

3. Heats of adsorption
Heat of adsorption is defined as the energy liberated when 1gm mole of a
gas is adsorbed on the solid surface. In physical adsorption, gas molecules
concentrate on the solid surface. Thus it is similar to the condensation of a
gas to liquid. Therefore, adsorption like condensation is an exothermic
process

4. Reversible character
Physical adsorption is reversible process. The gas adsorbed onto a solid
can be removed under reverse conditions of temperature and pressure.
Factors influencing adsorption of gases by solids
5. Effect of temperature
Physical adsorption occurs rapidly at low temperature and decreases with
increasing temperature.
Chemisorption, like most chemical changes, generally increases with
temperature. Thus a rise of temperature can often cause physical
adsorption to change to Chemisorption.
6. Effect of pressure
Pressure leads to increase of adsorption and decrease of pressure causes
desorption.
Factors influencing adsorption of gases by solids
7. Thickness of adsorbed layer of gas
The physically adsorbed gas forms only one molecular thick layer.
However, above a certain pressure, multimolecular thick layer is formed.
Process of Adsorption
 A simple experimental method of studying adsorption is as follows:

 Shake a known mass of the adsorbent material with a solution of known

concentration at a fixed temperature
 Shake it until there is no further change in the concentration of the supernatant
is observed
 This condition may be called as equilibrium conditions
 This data may be analyzed by
Adsorption Isotherms.
 ADSORPTION ISOTHERMS
Adsorption process is usually studied through graphs known as Adsorption Isotherm. (The amount of
adsorbate on the adsorbent as a function of its pressure (gas) or concentration (liquid) at constant
(T)
Adsorption ADSORPTION
A D S O RB A T E + ADS ⇌
Desorption (product)
O RBENT
 According to Le Chatlier’s principle, on application of excess pressure , the equilibrium will shift
in the direction where number of molecules decreases.

 Since no. of molecules (of reactants) decreases in forward direction

i.e. direction of Adsorption , and number of product molecules increases
with increase of pressure , forward direction equilibrium will be
achieved

 In the given Adsorption Isotherm , after saturation pressure,

Ps ,adsorption does not increase
 Vacancies on the surface of the adsorbent are limited, at Ps ,
Graph between the amounts of adsorbate (x)
a stage is reached when all the sites are occupied and adsorbed on the surface of adsorbent (m) and
further increase in pressure does not increase adsorption pressure at constant temperature
extent.
Types of Adsorption Isotherms : (A) FREUNDLICH
ISOTHERM
 Empirical equation for representing the isothermal variation of adsorption of a quantity of gas
(adorbate) adsorbed by unit mass of solid adsorbent with pressure is Freundlich Adsorption
Isotherm

…………. FREUNDLICH ISOTHERM

x/m = kP1/n OR x/m =
kC1/n
 x/m = adsorption per gram of adsorbent which is obtained by dividing the amount of adsorbate (x)
by the weight of the adsorbent (m).

 P is Pressure, k and n are constants whose values depend upon adsorbent and gas at particular
temperature .

 Taking the logarithms of Freundlich Isotherm : Log x/m = log k + 1/n log P

 Freundlich Isotherm correctly

establishes the relationship of
adsorption with pressure at lower
values,

Limitation : Failed to predict

adsorption capacity at higher
pressure
Freundlich Isotherm curve Log x/m versus log P
 Types of Adsorption Isotherms: (B) LANGMUIR ISOTHERM
In 1916, Langmuir proposed another Isotherm : Langmuir Adsorption isotherm

 Based on different assumptions one of which is that dynamic equilibrium exists between
adsorbed gaseous molecules and the free gaseous molecule. A(g) = unadsorbed gaseous
molecules
....................... M(surface) = unoccupied adsorbent
A(g) + M (surface) ⇌ AM (surface) surface
AM(surface ) = Adsorbed gaseous
molecules
 The extent of surface coverage is normally expressed as the fractional coverage, θ

θ =number of adsorption sites occupied / number of adsorption sites available

 The rate of change of surface coverage due to adsorption is proportional to the partial pressure p of
gas & the number of vacant sites N(1 − θ ), where N is the total number of sites, ka & kd rate
constants for adsorption & desorption

dθ/dt = ka pN (1- θ ) ………………………. Rate of Adsorption

 The rate of change of θ due to desorption is proportional to the number of adsorbed species, Nθ

dθ/dt = -kd Nθ .......................... Rate of Desorption

 CONTINUED.....
 At equilibrium there is no net change (the sum of these two rates is zero), and solving for θ
gives the Langmuir Isotherm, where K = (ka / kd)

θ = Kp / ( 1 + Kp) .............. LANGMUIR ISOTHERM

 At lower pressure, Kp is so small that factor (1 + Kp ) in denominator can almost be ignored &
Langmuir equation reduces to :
θ = Kp

 At higher pressure , Kp is so large that factor ( 1 + Kp) in denominator is nearly

equal to Kp &
Langmuir equation reduces to :
θ = Kp / Kp = 1

Limitation : Valid at low Pressures only

Langmuir isotherm for different values of K

 Types of Adsorption Isotherms: (C) TEMKIN ISOTHERM

 An assumption of the Langmuir isotherm is the independence and equivalence of the adsorption
sites.

 Deviations from the isotherm can often be traced to the failure of these assumptions

 The enthalpy of adsorption often becomes less negative as θ increases, which suggests that
the energetically most favourable sites are occupied first.

 Temkin Isotherm takes into account all the indirect adsorbate-adsorbate interactions on
adsorption isotherms

θ = c₁ ln (c₂ p) ………………….. TEMKIN ISOTHERM

where c1 and c2 are constants, corresponds to supposing that the adsorption enthalpy
changes linearly with pressure
 BET ISOTHERM

 Most widely used isotherm dealing with multilayer adsorption is BET Isotherm

 In physical adsorption , if initial adsorbed layer can act as substrate, then instead of the isotherm
levelling off to some saturated value at high pressures, it can be expected to rise indefinitely

 Under the condition of high P & low T , thermal energy of gaseous molecules decreases & more &
more gaseous molecules would be available per unit surface area of adsorbent and this leads to
multilayer adsorption
BET ISOTHERM

V / Vmon = cz / (1 − z){1 − (1 − c)z} with z = p / p*

p* is the vapour pressure above a layer of adsorbate that is more

than one molecule thick & which resembles a pure bulk liquid,
V mon , is the monolayer coverage vol., c is a constant

BET Isotherm for different values of c

TYPES OF ADSORBENTS
Oxygen Containing Compounds Carbon Based Compounds

Typically Hydrophilic & Polar Typically Hydrophobic & Non Polar Examples :
Examples : Silica Gel & Zeolites Activated Carbon & Graphite

Polymer Based Compounds

Polar or Non polar functional
groups in a porous polymer matrix
Examples : Polymers & Resins

Another Classification is based on diameter of pore sizes of Adsorbents

Microporous Mesoporous Macroporous

Adsorbents Adsorbents Adsorbents
Another
Pore Size Range Pore Size Range 20 Pore Size Range
2 Aº to 20 Aº Aº to 500 Aº > 500 Aº
COMMERCIAL ADSORBENTS

• Drying of refrigerants , • Drying of gases, organic • Removal of odours from gases

organic solvents, transformer solvents, transformer oils • Recovery of solvent
oils • Removal of HCl from vapours
• Desiccants in packing & Hydrogen • Nitrogen from air
double glazing • Removal of fluorine in • Water purification
• Dew Point Control of Alkylation process • Purification of He
natural Gas

SILICA ACTIVATED ACTIVATED

GEL ALUMINA CARBON

• Oxygen from air

• Water Purification • Treatment of edible oils
• Drying of gases
• Recovery & purification of • Removal of organic
pigments • Drying of refrigerants &
steroids & amino acids organic liquids
• Separation of fatty acids from • Refining of mineral oils
• Pollution control including
water & toulene • Removal of poly chlorinated
biphenyls (PCBs) removal of Hg
• Recovery of proteins & • Recovery of fructose from Cor n
enzymes Syrup

POLYMERS CLAY ZEOLITES

& RESINS
APPLICATIONS OF ADSORPTION
 Separation and purification of liquid and gas mixtures, bulk
chemicals, isomers and air

 Drying gases and liquids before loading them in industrial

systems

 Removal of impurities from liquid and gas media

 Recovery of chemicals from industrial and vent gases &

Water Purification
