Adsorption

BY- SANCHIT DHANKHAR

 Contents

 Adsorption
 Adsorption versus absorption, Desorption
 Types of adsorption: Physisorption and Chemisorption
 Factors affecting adsorption
 Adsorption isotherms: Freundlich and Langmuir
 Gibbs adsorption isotherm
 Bet equation and its use in surface area determination
 Applications

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ADSORPTION

Adsorption is the process in which matter is extracted from one phase

and concentrated at the surface of a second phase. (Interface
accumulation). This is a surface phenomenon as opposed to absorption
where matter changes solution phase, e.g. gas transfer. This is
demonstrated in the following schematic.

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d

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Adsorption
The phenomenon of higher concentration of any molecular
species at the surface than in the bulk

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Adsorbent
The substance on the surface of which adsorption takes place is called
adsorbent

Adsorbate
The substance which is being adsorbed on the surface of another
substance.

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Adsorbent Materials

• Activated Carbon

• Activated Alumina

• Silica Gel

• Molecular Sieves (Zeolites)

• Polar and Non-polar adsorbents

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Activated carbon

• Made from nutshells, wood, and petroleum, bituminous coal by

heating in the absence of oxygen to dehydrate and carbonize (remove
volatile components),

• "Activation" is the process that produces the porous structure essential

for effective adsorption by oxidation of carbon with water vapor or
CO2.

• Activated carbon attracts non-polar molecules such as hydrocarbons.

• Typical surface areas are 300 to 1500 m2/g.

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Adsorption vs Absorption

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 Types of Adsorption
Positive adsorption occurs when the concentration of adsorbate is higher on
the surface of adsorbent than in the bulk.

Negative adsorption occurs when the concentration of adsorbate is less on

the surface of adsorbent than in the bulk.

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Types of Adsorption
1. Physical adsorption

2. Chemical adsorption

Comparison between physisorption and chemisorption

S. No. Physical adsorption Chemical adsorption
1 Caused by intermolecular van der Caused by chemical bond formation
Waals' forces
2 It is not specific It is highly specific
3 It is reversible It is irreversible
4 Heat of adsorption is low (20-40 kJ/mol) High heat of adsorption (80-240 kJ/mol)
5 Low temperature is favourable Increases with high temperature
6 Results multilayer adsorption Results unimolecular layer

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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 specific area of the absorbent: The greater the

specific area of the solid, the greater would be its adsorbing
capacity.

Effect of temperature:adsorption decreases with increase in

temperature.

Effect of pressure: An increase in pressure causes an increase

in the magnitude of adsorption of an adsorbent.

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 Adsorption On Solid Surface
 Five types of physisorption isotherms are found over all solids
I
 Type I is found for porous materials with small pores e.g.
charcoal. It is clearly Langmuir monolayer type, but the other
are not
II

 Type II for non-porous materials

amount adsorbed

III
 Type III porous materials with cohesive force between adsorbate
molecules greater than the adhesive force between
adsorbate molecules and adsorbent
IV

 Type IV staged adsorption (first monolayer then build up of

additional layers)
V

 Type V porous materials with cohesive force between adsorbate

1.0 molecules and adsorbent being greater
13 than that between

relative pres. P/P0 adsorbate molecules

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
m
 K  p1/ n
x
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Freundlich Isotherm

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Langmuir Adsorption Isotherm
f: fraction of surface area covered
p: partial pressure of the adsorbate
f
m: mass of adsorbate adsorbed per
1-f
unit mass of adsorbent

Rate of adsorption ra =k ap(1- f)

Rate of desorption rd = k df

k ap
At equilibrium, ra = rd; f= .........(i)
k ap+k d

x
Mono-layer coverage =k 'af .........(2)
m
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Langmuir adsorption isotherm:
Combining equations (1) and (2):

ap
x /m 
1  bp

a = ka x ka’/kd
b = ka/kd

The values of constants ‘a’ and ‘b’ depend upon

the nature of adsorbate, nature of solid
adsorbent and temperature.

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 Summary of adsorption isotherms
Name Isotherm Application Note
equation
Langmuir x ap Chemisorption and Useful in analysis of
=
m 1+bp physisorption reaction mechanism
Freundlich x Chemisorptions and Easy to fit
=Kp1/n physisorption adsorption data
m

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Adsorption Isobar
Graph between the amount adsorbed(x/m) and temperature at a
constant equilibrium pressure of adsorbate gas is known as
adsorption isobar

Chemisorption isobar shows an initial increase with temperature and

then expected decrease .The initial increase is because of the fact that
the heat supplied acts as activation energy required in chemisorption.
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 Adsorption On Solid Surface
 BET (Brunauer-Emmett-Teller) isotherm
 Many physical adsorption isotherms were found, such as the types II and III, that
the adsorption does not complete the first layer (monolayer) before it continues
to stack on the subsequent layer (thus the S-shape of types II and III isotherms)
 Basic assumptions
 the same assumptions as that of Langmuir but allow multi-layer adsorption
 the heat of ads. of additional layer equals to the latent heat of condensation
 based on the rate of adsorption=the rate of desorption for each layer of ads.
the following BET equation was derived

P / P0 1 c 1
  ( P / P0 )
V ( 1  P / P0 ) cVm cVm
Where P - equilibrium pressure
P0 - saturate vapour pressure of the adsorbed gas at the temperature
P/P0 is called relative pressure
V - volume of adsorbed gas per kg adsorbent
Vm - volume of monolayer adsorbed gas per kg adsorbent
c - constant associated with adsorption heat and condensation heat
Note: for many adsorption systems c=exp[(H1-HL)/RT], where H1 is adsorption heat of 1st
layer & HL is liquefaction heat, so that the adsorption heat can be determined from
constant c. 20
 Adsorption On Solid Surface
 Comment on the BET isotherm
 BET equation fits reasonably well all known adsorption isotherms observed so far
(types I to V) for various types of solid, although there is fundamental defect in
the theory because of the assumptions made (no interaction between adsorbed
molecules, surface homogeneity and liquefaction heat for all subsequent layers
being equal).

 BET isotherm, as well as all other isotherms, gives accurate account of

adsorption isotherm only within restricted pressure range. At very low
(P/P0<0.05) and high relative pressure (P/P0>0.35) it becomes less applicable.

 The most significant contribution of BET isotherm to the surface science is that
the theory provided the first applicable means of accurate determination of the
surface area of a solid (since in 1945).

 Many new development in relation to the theory of adsorption isotherm, most of

them are accurate for a specific system under specific conditions.

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 Adsorption On Solid Surface
 Use of BET isotherm to determine the surface area of a solid
 At low relative pressure P/P0 = 0.05~0.35 it is found that
P / P0
P / P0 1 c 1 V (1 P / P0 )
  ( P / P0 )  ( P / P0 )
V ( 1  P / P0 ) cVm cVm
P/P0
Y = a + b X
 The principle of surface area determination by BET method:
P / P0
A plot ofV (1 P / P0 )
against P/P0 will yield a straight line with slope of equal to (c-
1)/(cVm) and intersect 1/(cVm).
For a given adsorption system, c and Vm are constant values, the surface area of a
solid material can be determined by measuring the amount of a particular gas
adsorbed on the surface with known molecular cross-section area Am,
V Vm - volume of monolayer adsorbed gas molecules calculated from the
As  Am N m  Am m  6.022  1023 plot, L
VT , P VT,P - molar volume of the adsorbed gas, L/mol
Am - cross-section area of a single gas molecule, m2
* In practice, measurement of BET surface area of a solid is carried out by N2
physisorption at liquid N2 temperature; for N2, Am = 16.2 x 10-2022m2
Application of Adsorption
 In clarification of sugar

 In gas masks

 In catalysis

 In adsorption indicators

 In chromatographic analysis

 In softening of hard water

 In preserving vacuum

 In paint industry

 In removing moisture from air in the storage of delicate

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instruments
Summary

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THANKYOU

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