Surface chemistry

Adsorption
Freundlich, Langmuir adsorption and BET isotherm
Application of adsorption

Some common observations

1. If a gas like O2, H2, CO, Cl2, NH3 or SO2 is taken in a closed vessel
containing powdered charcoal,
Observation: It is observed that the P in the enclosed vessel decreases.
What really happens? The gas molecules concentrate at the surface of the
charcoal, i.e., gases are adsorbed at the surface.
2. Aqueous solution of raw sugar, when passed over beds of animal charcoal,
Observation: the sugar solution becomes colourless
Why? the colouring substances are adsorbed by the charcoal
3. Many hygroscopic samples/highly water vapor (moisture) reactive substance are kept
with silica gel (in desiccators with silica gel)
Because: The air becomes dry in the presence of silica gel because the water
molecules get adsorbed on the surface of the gel.

What is adsorption?
Adsorption is the phenomenon of accumulation of large number of molecular species
at the surface of solid in comparison to the bulk.
Adsorbent ----is the
substance on the surface
of which adsorption
takes place.
Adsorbate -------is the
substance which is being
adsorbed on the surface
of adsorbent.
How Adsorption occurs?
Atoms of adsorbent at the surface are not in the same environment as those in the
bulk.
In the inner side/bulk, all atoms of the adsorbent all the forces acting between the
particles are mutually balanced, but on the surface the particles are not surrounded by
atoms or molecules of their kind on all sides.
Therefore, the atoms at the surface possess unbalanced forces
These unbalanced residual forces have tendency to attract and retain the molecular
species with which it comes in contact with the surface.

Oxygen molecules (red) adsorb on a

bimetallic surface of platinum (purple) and
cobalt (green).
from Balbuena et al., J. Phys. Chem. B.

Thermodynamics of Adsorption
----is a spontaneous process
----is a exothermic process
Also we know, G = H TS
And during this process of
adsorption, randomness of the
molecule decreases, therefore
S is negative.

Therefore for a reaction to be spontaneous

G has to be ve, for which H has to be
negative and greater than T S.
H has to be ve for the
adsorption to take place

At equilibrium, H has to be equal to T S

Adsorption is a term which is completely different from Absorption. While absorption

means uniform distribution of the substance throughout the bulk, adsorption
essentially happens at the surface of the substance.
Example: Water is absorbed by a sponge but adsorbed by anhydrous calcium chloride
Water vapors are adsorbed by silica gel
Adsorption of gases by solids
All gases adsorbed to soilds to some measurable extent
Magnitude depends on (i) nature of solid and gas being adsorbed (ii) the state of
subdivision of the solid and (iii) T and pressure
Solids with largest possible surface areas are good adsorbing agents------larger surface
Areas means more amount of gases adsorbed.
(Examples: charcoal, alumina, clay minerals and aluminosilicates)
The adsorption power (capacity) of a solid can be increased by a process, activation,
by heating the solid to higher temperatures in a stream of air.
This removes/drives out all the impurities and makes the surface free for adsorption of
the gases of interest.
To illustrate: At 24 deg C, activate charcoal adsorbs 1.48 gm of CCl4/gm of charcoal
whereas, before activation, it could adsorb only 0.011 gm CCl4/gm of charcoal.

During adsorption, there is always a decrease in residual forces of the surface, i.e.,
there is decrease in surface energy which appears as heat.
Adsorption, therefore, is invariably an exothermic process, accompanied by heat of
adsorption
Types of adsorption

Physical

Chemical

Vander Waals forces of attraction

Chemical bond formation

Non-Specific

Specific

Hads= 20-40 kJ/mol

Hads= 80-240 kJ/mol

Low temperature is favourable for

adsorption. It decreases with increase of
temperature

High temperature is favourable for

adsorption. It increases with the increase
of temperature.

It depends on the nature of gas. More

easily liquefiable gases are adsorbed
readily

Gases which can react with the adsorbent

show chemisorption.

Sometimes, these two processes occur simultaneously. A physical adsorption

at low temperature may pass into chemisorption as the temperature is
increased.
For example, dihydrogen is first adsorbed on Ni by van
der Waals forces. Molecules of hydrogen then dissociate to form hydrogen
atoms which are held on the surface by chemisorption.

Adsorption isotherm: At a constant T, the variation of the mass of gas adsorbed

(per unit mass of adsorbent) to the pressure (P) of the gas is expressed in terms
of curves known as adsorption isotherm.
In 1909, Freundlich gave an empirical expression representing the isothermal
variation of Adsorption of a quantity of gas adsorbed by unit mass of solid
adsorbent with pressure.
This equation is known as Freundlich Adsorption Isotherm or Freundlich
Adsorption equation.

x
= kp1 n
m

log

x
= log k + (1 / n) log p
m

where x is the mass of the gas adsorbed on mass m of the adsorbent at

pressure p and
k, n are constants whose values depend upon adsorbent and gas at particular
temperature.
n>1.
1/n generally is between 0.1 to 0.5

x
m

= kp

1 n

log

x
= log k + (1 / n ) log p
m

Limitation: It fails to explain adsorption phenomena at higher pressures

Langmuir adsorption isotherm

In 1916, Irving Langmuir proposed another Adsorption Isotherm which explained the
variation of Adsorption with pressure.
He derived a relationship between the number of active sites undergoing adsorption,
and the pressure.
Assumptions:
1. Adsorption is monolayer or uni-layer.
2. Dynamic equilibrium exists between adsorbed gaseous molecules and the free
gaseous molecules.
Where A (g) is unadsorbed gaseous molecule, B(s) is unoccupied metal surface
and AB is Adsorbed gaseous molecule.
A(g) +B(s) AB
3. Each site can hold maximum of one gaseous molecule and a constant amount
of heat energy is released during this process.
4. All the vacant sites are identical and there is no interaction between adsorbed
molecules
At equlibrium rates of adsorption and desorption are equal

 fraction of sites of the surface which are covered with gaseous molecules.
Fraction unoccupied by gaseous molecules will be (1 ).
Rate of forward direction (adsorption) depends upon two factors: Number of sites
available on the surface of adsorbent, (1 ) and Pressure, P.
Rate of forward reaction is directly proportional to both mentioned factors.
Rateads= Kads p (1- )..(1)
Rate of Desorption depends upon number of sites occupied by the gaseous
molecules on the surface of adsorbent.
Ratedes= Kdes
At equilibrium

--------(2)

Kads p (1- ) = Kdes

=>Kp - Kp =
=> = Kp/(1+Kp)

 = Kp/(1+Kp)
Two cases:
(1) at very low p, 1>>kp
Therefore, is proportional to pressure.
At higher p, Kp>>1, so 1+Kp Kp
So, is independent of pressure and very close to 1
(Almost all the sites are occupied by adsorbate, so that change in p has little
effect in further adsorption)

What is the physical significance of the ratio /(1-)?

Langmuir adsorption isotherm (alternate forms)

= Kp/(1+Kp)
can be expressed in terms of easily measurable parameters such as the volume
of gas adsorbed.
The QUANTITY of adsorbate is usually expressed as the volume of the gas (at a
standard pres.) by the solid.
Therefore, at a given P = V/Vs (where Vs is the volume adsorbed at saturation p)

V
Vs

1
1
=
V
KPV

KP
=
( 1 + KP )

+
S

1
Vs

From the following data of Kr adsorption by 1 gm. of charcoal; establish

whether the system obeys Langmuir adsorption isotherm.
From the data, calculate (1) the equilibrium constant for the adsorption process
(2) the no. of active sites on charcoal
(3) volume adsorbed at saturation pressure.

P (Kr) Torr

2.45

3.5

5.2

7.2

V(Kr) mL at 273K and 1 atm)

5.98

7.76

10.10

12.35

Problem:The adsorption of a gas follows Langmuir isotherm with K=0.85 kPa-1.

Find the pressure at which the surface coverage is 15%. (0.21kPa)

Problem: Calculate the fractions of area covered at a temperature (T) when the
amounts of gas adsorbed on a solid at pressures of 34 kPa and 5 kPa are 0.52 mg
and 0.21 mg, respectively. Assume that Langmuir adsorption is valid for the gas.
(0.75; 0.30)

Langmuir adsorption: (For a mixture of two gases)

Rate of adsorption: (For A )

Rateads= Kads p (1- )..(1)

RateAads= kAads pA (1- A-B)..(1)

(For B)

Rate of desorption: (For A )

RateAads= kBads pB (1- A-B)..(1)

Ratedes= KAdes (A + B)..(2)

kAdes (A)..(2)

(For B)

Ratedes= kBdes (B)..(2)

At adsorption equilibrium
kAads pA (1- A-
B) =

kBads pB (1- A-
B) =

kAdes (A)

kBdes (B)

Formulate the two equations with A,B as the unknowns

Solve the two equations for A,B in terms of KA,B and pA,B

A=KApA/(1+KApA+KBpB)

BET Isotherm
Brunauer, Emmett & Teller extends the Langmuir isotherm model to
multilayer adsorption
When adsorption of a gas can occur over a previously adsorbed monolayer
of the gas

Assumptions:
1.Adsorption of 1st layer takes place on a surface of uniform energy
2. 2nd layer only adsorbs on 1st, 3rd on 2nd, etc
3. At equilibrium, rates of condensation & evaporation are same for each
individual layer
For layers 2, H0AD = - H0VAP

n = number of molecules adsorbed at all sites

n = jS j
j =0

n = 0 S o + 1 S 1 + 2 S 2 + ....... where Sj = number of SITES with j molecules

n0 = number of molecules in first layer at saturation

no = S j
j =0

n0 = S 0 + S1 + S 2 + ...........
For the vacant layer (zero layer)

k 1 P 0 = k 1' 1

1 k1

= ' P = K P
0 k1
S 1 / S j
S 0 / S j

S1
S0

= KP

Formation terms= desorprtion from monolayer layer

Destruction term= adsorprtion to form mono layer

For the monolayer

k 1 P 0 + k 2' 2 = k 2 P 1 + k 1' 1
k 1 P 0 + k 2' 2 = k 2 P 1 + k 1' 1
S2

= K 'P
S1
S
similarly, 3 = K ' P
S2

Formation terms= adsorprtion on zero layer

+
Desorprtion from double layer

Destruction terms= adsorprtion on first layer to form

double layer
+
Desorprtion to form Zero layer

S 2 = S 1 K ' P = S 0 ( KP )( K ' P )
S 3 = S 2 K ' P = S 0 ( KP )( K ' P ) 2
.
S j = S j 1 K ' P = S 0 ( KP )( K ' P ) j 1
K = cK '
K 'P = x
j

S j = cS 0 x ; j 1

How to find n and n0?

n = jS j

n = 0 S 0 + jCS 0 x j
j =1

n = CS 0 (1 x 1 + 2 x 2 + 3 x 3 ......
n = CS 0

x
(1 x ) 2

n0 = S j
j =0

n0 = S 0 + S j
j =1

n 0 = S 0 + CS 0 x j
j =1

(1 x + Cx )
n0 = S 0
(1 x )

n / n 0 = total no. of molecules adsorbed at all sites

no. of molecules required for saturation monolayer adsorption

n
Cx
=
n 0 (1 x )(1 x + cx )
V
Cx
=
V m (1 x )(1 x + cx )
How to get the value of x?

k ' = 1 / PS
x = K 'P =

P
PS

P
1
1
C 1 P
=
+(
)
( PS P ) V CV m
CV m PS

V
Cx
=
V m (1 x )(1 x + cx )

c=e

( H ads H des ) / RT

P
1
1
C 1 P
=
+(
)
( PS P ) V CV m
CV m PS

Q. If each atom occupies 0.16 nm2 area, what is the total area?