ADSORPTION

• The phenomena of higher concentration of any molecular

species at the surface than in the bulk of a solid is known
as adsorption.

• As a result of residual forces the surface of a solid has a

tendency to attract and retain molecules of other species
with which it is brought into contact.

• As these molecules remain only at the surface and do not

go deeper into the bulk, their concentration is more at
the surface than in the bulk of the solid.

• The solid that takes up a gas or vapour from a solution is

called as adsorbent, while gas which is held to the surface
of the solid is called adsorbate.
 ADSORPTION Vs ABSORPTION
• The phenomenon of adsorption implies that a substrate is
uniformly distributed throughout the body of the solid.
• Adsorption is a surface phenomenon, while absorption is
a bulk phenomenon.
• In adsorption, the concentration of the adsorbed
molecules is always greater in the immediate vicinity of
the surface than in the free phase. Absorption involves
the bulk penetration of molecules into structure of solid
or liquid.
• Adsorption is rapid process and equilibrium is attained in
a short time. In absorption the equilibrium takes place
slowly.
Examples:

• Water vapour  Anhydrous CaCl2

(Absorption)
Silica gel (Adsorption)

• Ammonia  Water (Absorption)

Charcoal (Adsorption)

• Decolorization of sugar by charcoal is an example

for adsorption.
• TYPES OF ADSORPTION

• Physical Adsorption:

• In this type adsorbate molecules and adsorbent

molecules are held together by week vanderWaal
attractive force.

• Heat of adsorption is less than 10 kcal mol-1.

• The process is relatively fast and thru equilibrium

is attained quickly.
• Multilayer adsorption is possible.

• It is not specific in nature.

• The process is appreciable at low temperature

and high pressure.

• No activation energy is required in this process.

• Eg: Accumulation of various gases on the surface

of the charcoal.
• Chemical Adsorption:

• In this type adsorbate molecules are held by

adsorbent molecules by very strong attractive
chemical forces.

• Large amount of activation energy is needed for

the process.

• Energy of activation is more than 10-50 k cal

mol-1.
• Only monolayer adsorption is possible in this
situation.

• The adsorption is highly specific and takes place

at any desired temperature.

• Eg; Adsorption of nitrogen and hydrogen gas on

pt catalyst in the Haber process of manufacture
of ammonia gas.
• CHARACTERISTICS OF ADSORPTION

• The phenomenon of adsorption strictly refers to

the existence of higher concentration of any
particular component at the surface of the liquid
or a solid phase than is present in the bulk or the
interior.

• Adsorption is specific and selective phenomena.

Extent of adsorption depends on the physical and
chemical nature of both adsorbent as well as
adsorbate.

•
• Colloids on account of extremely small size
possess enormous surface area per unit mass and
are good adsorbents. Eg charcoal, silica gel,
alumina gel, clay etc.,

• Adsorption is accompanied by decrease in the

enthalpy of the system.

• Adsorption is exothermic in nature and

accompanied by decrease in entropy of the
system.
• FACTORS AFFECTING ADSORPTION

• Temperature: Since adsorption is exothermic in

nature, higher the temperature lower will be the
rate of adsorption.

• Amount of nitrogen adsorbed on charcoal

increases from 10cc to 45 cc as the temperature
decreases from 0oC to -78oC
• Effect of adsorbate:
It has been found that easily liquefiable gases such as
NH3, HCl, Cl2, SO2 are more easily adsorbed than
permanent gases such as O2, N2, H2. This is because
molecules of the former type of gases have greater
Vander Waal force of attraction.

• Effect of adsorbent:
Greater the surface area per unit volume of the
adsorbent, the greater will be its power of adsorption.
For effective adsorption adsorbent should act as a very
good catalyst. For eg; Hydrogen is strongly adsorbed on
Ni, where as it is weakly adsorbed on alumina
 Pressure/ Concentration:
It has been found that adsorption is reversible and an
increased pressure of a gas or vapour or an increase in the
concentration of solute cause increased rate of adsorption

• The relation between the amount of substance adsorbed

by an adsorbent and the equilibrium pressure or
concentration at constant temperature is called as
adsorption isotherm,

• In general, during chemical adsorption the amount of gas

adsorbed per given quantity of adsorbent increases
relatively rapidly with pressure, and the much more
slowly as the surface covered with gas molecules.
• TypeI: Unimolecular adsorption (Chemical) eg:
Adsorption of H2/N2 on charcoal at temperature
app -180oC. Amount of gas adsorbed reaches the
saturated value.

• TypeII and TypeIII: Multilayer adsorption

(Physical) Here, the amount of gas adsorbed
keeps on increasing with increase with pressure.
II Adsorption of N2 on Fe/Pt at -195oC.
• III Adsorption of Br2 on silica or alumina
at 80oC
• Type IV and Type V: Formation of multilayers of
gas molecules but also condensation of some of
gas molecules within narrow capillary pores i.e
capillary condensation.

• Eg: IV Adsorption of benzene on silica gel at

50oC
• V Adsorption of water vapour on activated
carbon at 100oC
• FREUNDLICH’S ADSORPTION ISOTHERM
• Emperical relationship
• According to Freundlich’s
• x/m = k P 1/n ---------(1)
•y = k P 1/n --------(2)
where,
• x = Mass of the adsorbate.
• M= Mass of the adsorbent.
• [y = Mass of the adsorbate adsorbed per unit
area /unit mass of adsorbent.]
• P= Equilibrium pressure.
• k, n = constants.(depending upon the nature of
gas, solid and temperature.

• log x/m = log k + 1/n log P--------- (3)

• If log y is plotted against log P a straight line

should be obtained with the slope=1/n and
intercept = k.

• Eg: Adsorption of nitrogen on mica at 90oK.

• Limitations:

• Mainly applicable at lower pressure ranges.

• Values of k, n vary with temperature.

• Purely empherical formula without any

theoretical foundation.

• Can not explain mechanism of adsorption.

 Langmuir theory
• Assumptions:
• The adsorbed gas behaves ideally in the vapour phase-
holds at low pressure
• Only one monolayer is formed by the adsorbed gas –
breaks when P of the gas is increased.
• The surface of the solid is homogeneous –each binding
site has the same affinity for the gas molecules.-not
strictly true. Real surfaces are heterogeneous hence
affnity varies.
• There is no interaction between the adsorbate molecules
The adsorbed gas molecules are localised.
• LANGMUIR’S ADSORPTION ISOTHERM

• Langmuir suggested that the gases adsorbed on

the surface of a solid cannot form a layer of
more than one molecule in thickness.
• According to him, magnitude of adsorption of a
gas on the solid at a given temperature, goes on
increasing with pressure, till the entire surface of
the solid gets completely covered by a
unimolecular layer of gases.
• The thickness cannot exceed a single molecule in
depth hence no further adsorption will take place
• The process of adsorption can be visualized as
follows:

• Condesation of molecules from the gas phase

into the surface, to form a layer with a depth not
more than a single molecule.

• Evaporation of molecules from the surface back

into the body of the gas.
In the beginning, every molecule colloding with
the surface may condense on it.

As the adsorption proceeds only those molecules may be

expected to be adsorbed, which strike a part of the
surface not already covered by adsorbed molecule.

Initial rate of condensation of molecules on the surface is

highest and falls off as the area of surface available for
adsorption decreased. The rate of evaporation increases,
as the surface becomes more fully saturated.
• A(g) + M (surface) ↔AM
• Ka – rate constant for adsorption
• Kd –rate constant for desorption
• Rate of adsorption α to pressure of A;pA and no. of vacant sites on
• the surface;
N(1-θ);
• Θ –fraction occupied by gas molecules.
• Rate of desorption α no. Of adsorbed molecules N θ
• At eqbm. Rate of adsorption = rate of desorption
• Ka pA N(1- θ) = kd N θ
• Ka pAN(1- θ) ∕ kd N θ
• K pA (1- θ) = θ where K = Ka/Kd
•K pA (1- θ) = θ
•(1- θ) / θ = 1/ K pA
•1/ ϴ - 1 = 1 / K pA
•1/ ϴ = 1 / K pA + 1
= 1 + K pA / K pA
ϴ = K pA / 1 + K pA
Langmuir adsorption isotherm.

At low pressure K pA << 1

At high pressures K pA >> 1
At low pressure θ= KpA this means, adsorption
increases with increase in pressure. The reaction is
1st order.

At high pressure θ =1 The entire surface is

covered by monolayer of the gas. The reaction
becomes zero order

At intermediate pressure θ = kP 1/n The system

follows Freundlich’s adsorption isotherm.
• Merits of the Langmuir adsorption isotherm:

Explains clearly chemical adsorption by monolayer

formation.
Offers theoretical explanation to chemical adsorption.

• Limitations:
Cannot explain physical adsorption.
Cannot explain all 5 types of adsorption isotherm.
Tells that adsorption is independent of temperature. But
in fact, it falls off with temperauture
• B.E.T. ADSORPTION ISOTHERM

Brunauer, Emmett and Teller described 4 out of

the 5 different adsorption isotherms. It clearly
explains the mechanism of the physical adsorption.

• The adsorbed layers are of multilayer thickness.

• Langmuir’s assumptions holds good for every layer.
• There is a dynamic equilibrium between successive layers.
• Heat of adsorption in each layer other than first layer is
equal to heat of liquefaction of gas.
• Condensation forces are the principal forces
of adsorption.
B.E. T Equation is given by

P/ V ( Po – P) = 1/ Vm C + ( P/ Po) (C− 1)/VmC

P = Relative pressure of the adsorbate.

Po = Saturated vapour pressure of the adsorbate
at temperaute T.

V = Volume of gas adsorbed at pressure P.

Vm = Volume of gas adsorbed when the surface of solid

is covered with monolayer of adsorbed gas.
C is a constsnt for a given gas.

C = e(E1-EL) / RT
E1= Heat of adsorption of first layer.
EL =Heat of liquefaction of the gas.

If E1 > EL , so that c is considerably greater than unity gives a

curve of II type.
E1 < EL it is of form of III type curve.

IV and V differ from II and III, respectively in so far as the adsorption in

the former cases reaches a limit at pressures well below the vap.
Pressure.
By extending the multi-molecular layer theory so as to allow for the
possibility that the capillary pores of the surface become filled,
possibly as a result of condensation, at pressures appreciably below
the saturation values, types IV and V can be explained.
Under capillary condensation,
If E1 > EL IV type curve .

E1 < E L V type curve.

 Validity of the equation.

Since C is a constant for a given

gas,
Vm is a constant for a given gas-
solid
System.

The plot of p/ v(po –p) vs p/po

should give a straight line with
slope = C -1/ Vm C and intercept
1/ Vm C.

From the slope and the intercept

both vm and c can be calculated.
• Limitations:

Fails below the pressure P/Po < 0.05 and above

0.35.

The assumption that gas has liquid properties is

not correct
• DETERMINATION OF SURFACE AREA:

Knowing Vm ( the volume of gas required to give a

complete unimolecular layer) the surface area of the
adsorbent can be easily calculated since the number of
molecules of gas in this volume is known, and the area of
cross section per single molecule is available.
According to B.E.T equation the area of the solid per
definite weight of the adsorbent given by
∑ = [ Po Vm] N.S / RTo. where
∑ = denotes the area in Ao ,
Po = the pressure in atmospheres,
R = gas constant.
To = absolute temperature
Vm = the volume of gas for monolayer adsorption.,
N= Avogadro’s number
S= area occupied on the surface by a single molecule.
 Considering the inert nature usually nitrogen
gas is best utilized as the adsorbed gas for the
determination of the surface area of the
adsorbent.
The area occupied by nitrogen gas is 0.162 (nm)2
Problem
At 0oC and 1 atm pressure, the volume of nitrogen
gas required to cover a sample of silica gel,
assuming Langmuir monolayer adsorption is
found to be 130cm3g-1 of the gel. Calculate the
surface area per gram of silica gel. Given the area
occupied by a nitrogen molecule is 0.162(nm)2 .
• no of molecules required to cover a unit mass of the adsorbent

with monolayer = Nmono = (Vm X NA )/ V

• (0.130 dm3g-1 x 6.022x1023 mol-1 ) / 22.414dm3mol-1
• = 3.49 x 10 21

• Area covered by 3.49 x 10 21 molecules

• = 3.49 x 10 21 x area covered by a single
molecule
• 3.49 x 10 21 x 0.162 x 10 -18 m2
= 565.821 m2g-1
 ADSOPTION FROM SOLUTION

In solution either solute or the solvent may be

adsorbed.

Due to the tendency of the free energy of the surface to

decrease, the concentration of a solute on the surface
may differ from that in the bulk of the solution.

The component with lower surface tension will tend to

concentrate on the surface.

In this manner the free energy of the system is reduced.

 Area of cross section of the
molecule.
• ρ = Mm / V = Mm / NA v
• v = Mm / NA ρ
• Assuming molecule to be spherical with radius r
• v = 4/3 πr3 = Mm / NA ρ
• r = {3 Mm / 4 π NA ρ}1/3

• a= πr
2
=π {3 Mm / 4 N
π A ρ}2/3
 TYPES OF ADSORPTION FROM SOLUTION
i) Positive adsorption: In this type of adsorption, the
solute alone is adsorbed and the concentration of the
solution decreases.
Eg: when the activated charcoal is added into the
solution of acetic acid, in water a part of the acid is
removed by the charcoal and the solution will become
dilute.
ii) Negative Adsorption: Here solvent is adsorbed and not
the solute, with the result the concentration of the
solution increases.
Eg: when charcoal is added to KCl solution the
concentration of the solution increases.
 GIBBS ADSORPTION ISOTHERM
It is the relationship between adsorption and change in
surface tension of a solvent due to the presence of the
solute.

For a system containing two components the Gibbs free

energy can be written as

G = n1 μ1 + n2 μ2 ----( 1)

Where, n1 and n2 are the amounts (number of moles)

and μ1 and μ2 are the chemical potential of the two
components respectively.

Since we are dealing with the adsorption of one of the

components on the surface which results in changing the
surface energy ,

Equation 1 can be written as

G = n1 μ1 + n2 μ2 + γ σ ----- ( 2)

Where, γ is the surface tension and σ is the surface area.

The complete differential of the above equation is given

by

dG = n1d μ1 + μ1 d n1 + n2dμ2 + μ2 d n2 + γd σ + σ dγ
-------- (3)

Thus, G now depends upon five independent variables

viz T, P, n1, n2 and σ

G = f (T, P, n1, n2 , σ) -------(4)

The total differential of G is given by
dG =

( δG/ δT) P, n1, n2 , σ dT + ( δG/ δP) T, n1, n2 , σ dP

+ ( δG/ δn1)T n2 , σ,P dn1 + ( δG/ δn2) P.T, n1, σ dn2

+ ( δG/ δσ)T n2 , n1,P dσ --------(5)

• According to thermodynamics, the terms

( δG/ δT) P, n1, n2 , σ , ( δG/ δP) T, n1, n2 , σ, ( δG/ δn1)T n2 , σ,P ,

( δG/ δn2) P.T, n1, σ ( δG/ δσ)T n2 , n1,P stand

respectively, for S, V, μ1 μ2 and γ.

dG = − S dT + V dP + μ1 d n1 + μ2 d n2 + γd σ
------( 6)
At constant temperature dT = 0 and at constant pressure
dP = 0

dG = μ1 d n1 + μ2 d n2 + γd σ
----- (7)
 From eqn (7) in eqn ( 3) we will obtain
n1d μ1 + n2dμ2 + σ dγ = o
----- ( 8)
We can imagine the system under consideration made of
two portion
• Surface phase- portion of the system that is affected by
the surface process and therefore eq. (8) holds true only
for it.
• Bulk phase- The remainder of the solution which is not
affected by the surface process is bulk and
The corresponding expression for the bulk of the liquid
is given by
no1d μ1 + no2dμ2 = 0 ---- ( 9)
• d μ1 = - ( no2/ no1) dμ2 ----- ( *)
• where no1 and no2 amounts (number of moles) of the
liquid and the solute respectively, in the bulk phase.
Since the system is in equilibrium the chemical potential
of each component in the bulk and the surface must be
same.

The system on being disturbed attains a new equilibrium

so that the changes in the chemical potentials must be
identical in both the phases.

Thus d μ1 and d μ2 in the equation( 8) and (9) must be

identical. Elimination of dμ2 from these equations gives

n1 [ − ( no2/ no1) dμ2 ] + n2dμ2 + σ dγ = 0 --

------ ( 10)
(n2 − n1 no2 / no1) dμ2 + σ dγ = 0 -------(11)
 Rearranging the terms we will get
- dγ/ dμ2 = [n2 − (n1 no2 / no1)] / σ ------- (12)

The quantity within the brackets of the above equation

gives the amount of solute associated with the amount
no1 of the liquid in the bulk phase.

On the other hand, n2 is the amount of the solute

associated with the amount n1 of the liquid at the surface.

Thus numerator on the R.H.S gives the excess amount of

the solute present in the surface of the solid.

Thus R.H.S gives the excess concentration of the solute

per unit area of the surface, designated as Γ.
 Γ = − dγ/ dμ2
-------( 13)

The chemical potential of solute 2 is given by

μ2 = μ2* (l) + RT ln a2 --------( 14)

where μ2* (l) is the chemical potential of the pure

solute in the liquid phase. Hence

dμ2 = RT d ln a2 ( d μ2* (l)) =0

Substituting for dμ2 in equation 13 we get

 Γ = − 1/RT ( dγ/d ln a2 )T

------( 15)
= − a2 /RT ( dγ/d a2 )T
------ ( 16)

When the solution is very dilute, it behaves ideally so that

the activity a2 of the solute can be replaced by
concentration C2 Thus

Γ = − C2 /RT ( dγ/d C2 )T
------ ( 17)
• Conclusion

For a solute that lowers the surface

tension, the surface excess concentration Γ
is positive and for the solute that increases
the surface tension the Γ is negative.
The surface tension of water is quite high viz 0.772.8 N
m-1 at room temperature and most of the solutes tend to
reduce this value.

Therefore most of the solutes are positively adsorbed

from aqueous solutions by adsorbents such as charcoal
and silica gel.

On the other hand, surface tension of alcohol is low.

(0.0223 N m-1) . So most of the solutes fails to decrease
the surface tension of this to considerable extent.

This makes us to conclude that a given solute would be

more readily adsorbed from aqueous solution than from
alcoholic solutions.
Applications Of Adsorption
• Industrial applications
Animal charcoal is used in removing the colour in
the manufacture of cane sugar.
Removal of odours from refrigerators and in general
air condition procedures
Activated charcoal is used in gas masks in which all
toxic gases vapours are adsorbed by charcoal and pure air
passes through the pores unchanged.
Adsorption plays an important role in the
heterogeneous catalysis.
Example: In Haber’s process of ammonia the finely divided
iron acts as heterogeneous catalyst.
Colloidal silica and aluminium gels are used as
adsorbents for removing moisture and for controlling
humidities of rooms.
• General Applications:
• Softening and deionization of water.
• Colloidal silica is used to adsorb impurities
from petroleoum oils.
• Process of adsorption is used in case of
detergents,paints,and other fields.
 Analytical Applications
• Chromatographic analysis ; important application of
adsorption from solution.
- used in separating a mixture of substances into its
various components by passing through the column of
suitable adsorbent. In this the most strongly adsorbed
substance is at the top, while successive layers contain
other solutes in the order of their ease of adsorption.
Adsorbing material consists of finely powdered alumina,
magnesium oxide, charcoal etc.
Solutes are generally organic compounds dissolved in
acetone, petroleum ether or suitable solvent.
• Adsorption indicators: certain dye stuffs
are used as adsorption indicators and are
generally used in the silver titration based
on adsorption.
• AgNO3 vs KBr AgBr
• If eosin(pinkish yellow) is used as the
indicator, then the colour of the ppt.
changes from yellow to brick red, the
moment there is any Ag+ ion. The silver
ions are adsorbed only when no more
bromide ions are
DERIVATION OF B.E.T EQUATION.

Let,

S0, S1, S2, S3 ………..Si : reactive site of the total surface of

the adsorbent.

0, 1, 2, 4 ……………i : Layers of the adsorbed molecule

.
E1, E2, E3 ………….Ei : Average heat of adsorption of the
gases in the I,II and ith layer
respectively.
Rate of adsorption ά PS0

Rate of adsorption = a1 PS0

The rate at which the molecules leave the surface = k2 S1
According to Boltzman k2 = b1e –E1/RT

Rate of evaporation = b1S1 e –E1/RT

a1 PS0 = b1S1 e –E1/RT

a2 PSo = b2S2 e –E2/RT

• .
• .
• .
• .
• .
• ai PSo = biSi e –Ei/RT
 The total surface area = A = Σ Si
V = V0 Σ i Si

Where, Vo Volume of the gas adsorbed on one sq.cm of

the adsorbent, when it is covered with a complete uni
molecular layer of the adsorbed gas Then,

• V/ A Vo = V/V m = Σ iSi/ Σ Si where Vm

is the volume of the gas adsorbed when the adsorbent
surface A is covered with the complete monolayer.

• Average heat of adsorption of each layer is given by

E2 = E 3 = E4 = E5 …….Ei = EL

b2/a = b3/a3 = b4/a4 = b5/a5 = bi/ai = k

The heat of liquefaction is equivalent in saying that

evaporation and condensation properties of second
and higher adsorbed layers are the same as those of
liquid state.
• B.E. T Equation is given by
• P/ V ( Po – P) = 1/ Vm C + ( P/ Po) C− 1/ Vm C