V.

ADSORPTION

 Adsorption is the process in which molecules from gas (or liquid) phase land on, interact
withand attach to solid surfaces:
 Adsorption is the adhesion of atoms, ions, or molecules from gas, liquid, or dissolved
solid to a surface. This process creates a film of absorbate on the surface of the
adsorbate.
 Adsorbate – adsorbed phase – substance attached on the surface
 Adsorbent – adsorbing medium – medium through which the substance settles

 Absorption: Gas or liquid penetrates in to the capillary spaces of adsorbing medium

 The reverse process of adsorption, i.e. the process in which adsorbed molecules escape
from solid surfaces, is called Desorption.
 Molecules can attach to surfaces in two different ways because of the different forces
involved. These are Physisorption (Physical adsorption) and Chemisorption (Chemical
adsorption)
 Adsorption of gases by solids depends on:
1. Nature of adsorbent
2. Nature of gas being adsorbed
3. Area of adsorbent
4. Pressure of the gas

Types of Adsorption:
Depending upon the nature of forces existing between adsorbate molecules and
adsorbent, the adsorption can be classified into two types:
1. Physical adsorption (Physisorption): if the force of attraction existing between
adsorbate and adsorbent are Vander-Waal’s forces, the adsorption is called
physical adsorption. It is also known as Vander-Waals’s adsorption. In physical
adsorption, the force of attraction can be easily reversed by heating or by
decreasing the pressure.
2. Chemical adsorption (Chemisorption): If the force of attraction between
adsorbate and adsorbent are almost same strength as chemical bonds, the
adsorption is called chemical adsorption. It is also known as Langmuir adsorption.
In chemisorption, the force of attraction is very strong; therefore adsorption
cannot be easily reversed.

Comparison between Physisorption and Chemisorption

 Physisorption
1. Low heat of adsorption usually in
the range of 20-40 KJ/mol
2. Force of attraction are Vander-
Waal’s forces
3. It usually takes place at low
temperature and decreases with
increasing pressure.
4. It is reversible
5. It is related to the ease of
liquefacation of the gas
6. It is very specific
7. It forms multi-molecular layers
8. It does not require activation
energy
Chemisorption
1. High heat of adsorption. In the
range of 40-400 KJ/mol
2. Forces of attraction are chemical
bonds
3. It takes place at high temperature
4. It is irreversible
5. The extent of adsorption is
generally not related to
liquefaction of the gas
6. It is highly specific
7. It forms monomolecular layers
8. It requires activation energy

 Adsorption process is usually studied through graphs known as adsorption isotherm.

That is the amount of adsorbate on the adsorbent as a function if its pressure or
concentration at constant temperature. The quantity adsorbed is nearly always
normalized by the mass of the adsorbent to allow comparison of different materials.

Adsorption Isotherm

x
m

Saturation Pressure

P Ps

Types of Adsorption Isotherm

Type I: Monolayer
Type II: Multilayer
Type III: Multilayer
Type IV: Multilayer
A A A
6

a III
I II

P, C P, C P, C

A IV A
a V
6

P, C P, C
5. Type V: Multilayer

BET Adsorption Isotherm

The explanation proposed for type II and type III isotherm is that in these the adsorption
is multimolecular, i.e, the adsorption involves the formation of many molecular layers on
surface rather than a single one. On this postulate Brunauer, Emmett and Teller derived for
these types of isotherms the relation:

P 1 c−1 P
= +( )
v (P −P) v m C v m C Po
o

P-equilibrium pressure of the gas

v - volume of gas adsorbed/unit weight adsorbent (corrected to STP)
v m- volume of gas adsorbed/unit weight adsorbent when 1 layer of molecules covers
the surface (corrected to STP)
Po- saturated vapour pressure of adsorbate
E 1−E L
c – constant, c=e RT

Where: E1- heat of adsorption of the first layer of vas molecules

E L- heat of liquefaction of the gas
 The isotherms of type II follows when E1 > E L and those of type III E1 < E L
P P
 v m and c can be found by plotting o vs o . The plot should be a straight line
v (P −P) P
c−1 1
with slope given by
vm C
and intercept by
vm C
.

To explain types IV and V isotherms, it has been suggested that substances

exhibiting such behaviour undergo not only multilayer adsorption but also condensation of
 gas in the pores and capillaries of the adsorbent. The two types arise from the relative
magnitude of E1∧E L. When E1 > E L isotherms of type IV are obtained , whereas when
E1 < E L isotherms of type V follows.

Although these theories have fairly proved successful in explaining the more
complex types of isotherms, they are still insufficient account quantitatively for all
phenomena observed.
Determination of surface area of adsorbents:
1. BET method – Type II isotherm exhibits a point B (corresponds to the adsorbed volume
necessary to yield a monolayer of gas on the surface, this point is equal to v m).

Po v B
Ʃ =( )
RTo

Where:
 Ʃ = surface area/weight of adsorbent
 Po - 1 atm
 T – 273.15K
 v B- volume corresponding to point B
 R – gas constant
 N – Avogadro’s number
 S – area occupied on the surface by a single gas molecule

2. Harkins-Jura Method
P 1
Involves plotting log 10 vs 2
Po v
Where:
k – constant for a given gas and temperature
A – slope

Ʃ =k √− A
Adsorption isotherm – relation between the amount of substance adsorbent and the
equilibrium pressure on concentration at constant temperature

A. Type 1 – First order

 The amount of gas adsorbed per given quantity of adsorbent increases
relatively rapidly with pressure and then much more slowly as the surface
become covered with gas molecules. To represent the variation of the amount
of adsorption per unit area of unit mass with pressure, Freundlich proposed the
equation:

1
y=k P n
 Where:
y - weight or volume of gas adsorbed per unit area or unit mass of adsorbent
P – equilibrium pressure
K, n – empirical constants dependent on the nature of solid and gas and on the
temperature

Linear form:
1
lny = lnk + n lnP
B. The Langmuir Adsorption Equation

 A much better equation for Type 1 isotherm was deduced by Irving Langmuir
from theoretical considerations. Langmuir postulated that gases are being
absorbed by solid surface cannot form a layer more than a single molecule in
depth. Further, he visualized the adsorption process as consisting of two
opposing actions, a condensation of molecules form the gas phase onto the
surface and an evaporation of molecules from the surface back onto the
body of the gas.

aP
Y= 1+ bP
Linear form:
P 1 b
= + P
Y a a
Where: a and b – Langmuir constants

Sample Problem
1. The following data are data from the adsorption of CO on wood charcoal at 0 ⁰C. The
pressure P is in mmHg, while x is the volume of gas in cc, measured at standard conditions,
adsorbed by 2.964g of charcoal:
P X
73 7.5
180 16.5
309 25.1
540 38.1
882 52.3
Find graphically the constants k and the n of the Freundlich equation

2. Find graphically the constants a and b in the Langmuir equation that will fir the data given in
problem 1

3. The following data were obtained for the adsorption of acetone and charcoal from an
aqueous solution at 18 ⁰C

Y(millimole/g) C(millimoles/L)
0.208 2.34
0.618 14.65
1.075 41.03
1.5 88.62
2.08 117.69
2.88 268.97

Evaluate the constants k and n of the Freundlich equation