Adsorption

isotherms

1
Contents
Adsorption

Mechanism of adsorption

Types of adsorption

Applications of adsorption

Adsorption isotherms

Different types of isotherms

Applications of isotherms

Summary 2

References
 Adsorption

The term adsorption

was introduced by
Kayser in 1881.

The phenomenon of
higher concentration of
any species of solid,
liquid or gas at the
surface than in the bulk
of a material, is known
as adsorption. 3
 Some Important Terms

Adsorbent-The solid
that takes up a gas,
vapour or a solute from
a solution, e.g. silica
gel, charcoal, clay, etc.

Desorption-The
Adsorbate-The
process of removal gas, vapour or the
of adsorbed solute, which is
substances from held to surface of
the surface on the solid. e.g.
which it is poisonous gases
absorbed.
4
Some commonl
yused adsorbents

silica Activated Alumina

charcoal

5
Bentonite clay Zeolites Bagasse
Exampl
es of adsorption
Accumulation of dust on our skin when we
travel in regions of heavy traffic

Adsorption of dyes like methylene blue by

charcoal

Protection from poisonous gases

Solution of raw sugar become colorless when

passed over bed of animal charcoal.

Air becomes dry in the presence of silica gel.

6
Difference between adsorption and
absorption
Absorption Adsorption

 It is the phenomenon in  It is the phenomenon in

which the particles of gas or which the higher conc. of
liquid uniformly distributed particles of gas or liquid on
throughout. surface than in bulk.
 Bulk phenomenon  Surface phenomenon
 Occurs at uniform rate  Rapid in beginning but
 Anhydrous CaCl2 absorbs slowly decreases.
water.  Silica gel absorbs water
vapour.

7
 continued… …

8
Absorption Adsorption
 M echanism ofAdsorption
 Adsorption is surface
phenomenon.
 It arises because of unbalanced
forces on the surface of solids
and liquids.
 The surface is under tension
due to unbalanced forces.
 The surface of the solid or
liquid tends to satisfy their
residual forces by attracting
and retaining the molecules of
other species when brought in 9

contact with them.

Continued… .
.

10
Types ofAdsorption

Physisorption Chemisorption

11
 continued… …
PROPERTIES PHYSISORPTION CHEM ISORPTION
Bonding W eak,longrange forces, Strong,short range
van der W aals interactions. forces,Chemicalbonding
involvingorbitaloverlap
and charge transfer.

Enthalpy 20-40kJmol-1 80-240kJmol-1

Saturation M ulti-layer M ono-layer

Nature reversible irreversible
Effect oftemperature Occurs at low temperature Occurs at high
and decreases with increase temperature and
in temperature. increases with increase in
temperature.
Effect ofpressure Increases with increase in Decreases with increase
pressure ofadsorbate. ofpressure

Activation energy Not needed High activation energyis

needed. 12

Surface specificity No Yes

 CONTINUED… …
Lenard-Jones model for physisorption and
chemisorption of molecules.

13
 Factors affectingadsorption

Nature ofgas - easily liquefiable gases easily gets

adsorbed.

Nature ofadsorbent-More the surface area per unit mass

of the adsorbent, more will be the adsorption

Temperature- adsorption increases as temperature

decreases.

Pressure-magnitude of adsorption increases with increase 14

in pressure.
Appl
ications ofAdsorption
Gas masks
Adsorption indicators
Chromatographic separation
Removal of coloring matter
Heterogeneous catalysis
Controlling humidity
Curing diseases
Froth flotation process
Production of high vacuum
15
Purification
Adsorption equil
ibria
The adsorbent and adsorbate are
contacted long enough, an equilibrium
will be established between the
amount of adsorbate adsorbed and the
amount of adsorbate in solution.

Isotherms:
m, P-
diagrams at
constant
temperature 16
Continued… .

17
 Adsorption isotherm
The process of adsorption
is studied through graphs
know as adsorption
isotherms.

Graph between the

amounts of adsorbate (x)
adsorbed on the surface of
adsorbent (m) and
pressure (P) at constant
temperature. 18
 Continued…
 In adsorption, adsorbate gets adsorbed on adsorbent.
 The direction of equilibrium would shift in that
direction where the tension can be relieved.

 In excess of pressure to the equilibrium system, the

equilibrium will shift in the direction where the
number of molecules decreases.
 Number of molecules decreases in forward
direction. Therefore, forward direction of 19

equilibrium will be favored.

 BasicAdsorption isotherm
Limited numbers of vacancies on the surface
of the adsorbent.

After saturation pressure Ps, adsorption

does not occur anymore.

At high pressure a stage is reached when all

the sites are occupied and further increase in
pressure does not cause any difference in
adsorption process.

At high pressure, Adsorption is independent 20

of pressure.
Types ofisotherms

Langmuir
Temkin isotherm
isotherm

Dubinin–Rad Freundlich
ushkevich isotherm
isotherm

BET isotherm
21
Langmuir Adsorption isotherm
In 1916, Dr. Irving
Langmuir presented this
History model.

Langmuir was awarded the

Nobel Prize in 1932

Adsorption can be
physisorption or
chemisorption

Estimate the adsorption capacity 22

of adsorbent used
Basicassumptions ofLangmuir M odel
The surface is homogeneous

All sites are equivalent

Mono-layer adsorption only

No interactions between adsorbate

molecules on adjacent sites

Heat of adsorption is constant and

equivalent for all sites
23
Adsorbate molecules have tendency
to get adsorb and desorb from surface
Langmuir Adsorption isotherm
The linear form of the Langmuir isotherm

bqmax
qe =
1 + bCe

Where
qe= Quantity of adsorbate adsorbed per unit weight of
adsorbent at equilibrium (mgg-1)
Ce = Concentration of adsorbate at equilibrium in
solution after adsorption (mgl-1)
qmax = Maximum adsorption capacity(mgg-1) 24
b = Langmuir adsorption equilibrium constant (lmg-1)
 Continued… .
Plot of original equation

25
 Continued… .
The rearranged form of the Langmuir isotherm

1 1 1
= +
qe Cebqmax qmax

Where
qe= Quantity of adsorbate adsorbed per unit weight of
adsorbent at equilibrium (mgg-1)
Ce = Concentration of adsorbate at equilibrium in
solution after adsorption (mgl-1)
qmax = Maximum adsorption capacity(mgg-1) 26

b = Langmuir adsorption equilibrium constant (lmg-1)

 Continued… .

Isotherm is plotted between 1/qe versus 1/Ce and the slope

of the graph gives the value of qmax and intercept gives the
value of b.

0.06
0.05
0.04
0.03 y = 0.2597x + 0.0018
1/qe

0.02 R² = 0.9637

0.01
0
0 0.05 0.1 0.15 0.2 0.25
1/Ce 27
 Limitations ofLangmuir isotherm
Holds only at low pressure.

Multilayer adsorption is possible.

Ignores adsorbate-adsorbate interactions.

Fails to account for the surface roughness of the

adsorbent.

Saturation value of adsorption depends upon temperature.

28
Freundl
ich Adsorption Isotherm

1909, Dr.
Herbert
Freundlich

Estimate the
sorption
intensity of
the adsorbent
towards the
adsorbate. This isotherm is
an empirical
expression that
accounts for
surface
heterogeneity. 29
Assumptions ofFreundl
ich Isotherm

Surface roughness

Adsorbate-
adsorbate Inhomogeneity
interactions

30
 Freundl
ich Adsorption Isotherm
The linear equation

x/m = k.P1/n (n > 1)

Or
x/m = k.C1/n (n > 1)

where
x is the mass of the gas adsorbed
on mass m of the adsorbent
P is pressure,
C is equilibrium concentration of
adsorbate in solution, 31

k and n are constants.

 Continued…
The linear form of Freundlich isotherm is
1
logqe = log Kf + logPe
n
or
1
logqe = log Kf + logCe
n
Where
qe = Extent of adsorbate adsorbed per unit weight of
adsorbent at equilibrium (mgg-1 )
P e = Equilibrium pressure of adsorbent in solution after
adsorption
C e = Equilibrium concentration of adsorbent in solution
after adsorption (mgl-1 ) 32
K f = Freundlich constant indicating adsorption capacity
n = Empirical constant
 Continued… .
Kf approximately indicates adsorption capacity

1/n is a function of the strength of adsorption

n = 1, the boundary between the two phases is

independent of the concentration.

1/n below 1 indicates a normal adsorption.

n varies with the heterogeneity of the adsorbent and

range for favorable adsorption is of 1-10.

1/ n = 0, x/m = constant, the adsorption is independent of

pressure.

1/ n = 1, x/m = k P, i.e. x/m ∝ P, the adsorption varies directly 33

with pressure.
 Continued…
The parameters of the Freundlich isotherm can be
determined by plotting logqe versus logCe.

4.5

4
log qe

3.5

3
y = 0.9452x + 1.3982
2.5
R² = 0.9637
2 34
1 1.5 2 2.5 3 3.5
log Ce
Limitations ofFreundl
ich Isotherm
Freundlich equation is purely empirical and
has no theoretical basis.

The equation is valid only upto a certain

pressure and invalid at higher pressure.

The constants K and n vary with

temperature.

Frendilich’s adsorption isotherm fails at high

concentration of the adsorbate. 35
Differences between Freundl
ich and
Langmuir adsorption isotherms
FRENDLICH
ADSORPTION
ISOTHERM
• Tells about the
quantity of gas
adsorbed by unit mass
of solid adsorbent with
pressure.
• Represented by
formula
x/m = KP1/n
• Heterogeneity of
adsorption site.
• No information about
adsorption and
desorption. 36
Brunauer–Emmett–Teller isotherm

In 1938, Stephen
Brunauer, Paul Hugh
Emmett, and Edward
Teller

Utilizes probing
gases that do not
chemically react Applies to systems
with material of multilayer
surfaces to adsorption
quantify specific
surface area 37
 Continued…

• the most commonly used

Nitrogen gaseous adsorbate used for
surface probing

BET • At boiling temperature of

analysis N2 (77 K)
conducted
Other • Argon, carbon dioxide and
probing water
adsorbents 38
 Continued… .
 The concept of the theory is
an extension of the Langmuir
theory, which is a theory
for monolayer molecular
adsorption, to multilayer
adsorption with the following
hypotheses
 Gas molecules physically
adsorb on a solid in layers
infinitely
 Gas molecules only interact
with adjacent layers
 Langmuir theory can be 39
applied to each layer
 Continued…
The BET equation

(P/Po )/Q ((P/Po )-1)= 1/kQm + (k-1/Qm k)(P/Po )

Where
P and Po are the equilibrium and the saturation
pressure of adsorbates at the temperature of
adsorption,
Q (in moles) is the amount adsorbed on 1g of adsorbent
and Qm is the monolayer adsorption capacity.
k is the BET constant.
40
Continued…
Plot of BET isotherm

41
Drawbacks ofBET adsorption theory

• Surface is assumed to be homogenous

Drawbacks

• Interaction between the adsorbed

Drawbacks molecules in neglected

• Heat of adsorption from second layer

onwards to be equal to subsequent
Drawbacks layers which is not usually true
42
Appl
ications ofBET isotherm

Specific
surface area
calculation

solid
catalysis

The inner surface

of hardened cement
paste determination

43
Types ofBET adsorption isotherms

Six types of isotherm are

characteristic of adsorbents

Microporous (type I)

Nonporous or macroporous
(types II, III, and VI)

Mesoporous (types IV and V)

44
 Type I BET Adsorption Isotherm
Described by Langmuir
equation
Horizontal plateau

Microporous materials

Organic vapors on zeolites and

molecular sieves
Chemisorption systems often
also show AIs of Type I
No multilayer adsorption 45
 Type II Adsorption Isotherm
Sigmoid type graph

Vapors of non-polar
organic substances Multilayer
on mesoporous adsorption
activated carbons.`

Described by the BET Pore condensation

equation but no hysteresis.

Nonporous or
macroporous solids.
(pore diameter > 50
nm). 46
Type III Adsorption Isotherm

Hyperbolic graph

Occur in systems where the

adsorbate-sorbent (a-s)
interaction is small
compared to the adsorbate-
adsorbate (a-a) interaction

Water on activated carbon

and hydrophobic zeolites
47
 Type IV BET Adsorption Isotherm

Adsorption behavior of special

mesoporous materials

Pore condensation with hysteresis

behavior between the adsorption
and the desorption branch.

Water vapor from humid air on

special types of activated carbons
and hydrophilic zeolites.
48
 Type V BET Adsorption Isotherm

Elongated S shaped graph

Perpendicular middle portions

deviate from Type IV curves

Mesoporous materials

Pore condensation may occur.

Water on special activated 49

carbons and carbon molecular
sieves.
 Type VI BET Adsorption Isotherm

Stepwise multilayer
adsorption
Pronounced at low
temperatures
Nonpolar, spherical molecules
on planar graphite surfaces

Butanol on aluminum silicate

50
Differences between Langmuir and
BET adsorption isotherm
Langmuir
• monolayer
• More surface area
• (P/Po)/Q = 1/kQm +
(1/Qm)(P/Po)

BET
• Monolayer +Multilayer
• Less surface area
• (P/Po)/Q ((P/Po)-1)=
1/kQm + (k-1/Qmk)(P/Po) 51
BET adsorption isotherm

Why is
Langmuir
surface area
always higher
than BET
surface area?
52
Dubinin Raduhkevitch (D-R)
adsorption isotherm:

Dubinin and his co-workers conceived this

equation for micropore solids
Langmuir and Freundlich isotherm constant
do not suggest anything regarding
adsorption mechanism
D-R isotherm helps to determine the
adsorption mechanism

Distinguishing between the chemical

adsorption and physical adsorption
53
 Continued… … .

The linear form of D-R model

lnQe = lnQm − β 2

Where
Qe=amount of adsorbate adsorbed per unit weight of
adsorbent at equilibrium (mgg-1)
Qm = Maximum adsorption capacity of adsorbent (mgg1)
β = constant related to adsorption energy
 = polanyi potential (kJ2mol-2)
54
 Continued… … .

 can be acquired from the following relation

1
å =RTln (1+ )
Ce

Where,
R is gas constant
T is the temperature in (K)
Ce is the concentration of adsorbate at equilibrium in solution
after adsorption(mgl-1).
The experimental data can be evaluated by plotting lnQe against
2.
The value of Qm and β are estimated from the intercept and
55
slope respectively.
 Continued… … .

The experimental data is evaluated by plotting lnqe

against 2 .
D-R adsorption isotherm
7.5
7
6.5 y = -0.0076x + 6.5814
R² = 0.8041
6
ln qe

5.5
5
4.5
4
0 50 100 150 200 250 56
Ԑ2 ( x 103)
Continued… … .

57
 Continued… … .

This parameter
tells the nature of The value smaller The value
adsorption than 8 kJmol-1 between 8-16
process such as then the reaction kJmol-1 then the
chemical ion continues process will
exchange or physically proceeds
physical chemically
adsorption

58
 Uses ofD-R isotherms

applicable for
Describe carbonaceous microporous
adsorption by sorbents or solids with
microporous activated uniform
solids carbons microporous
structures

59
Drawbacks ofD-R Isotherm

The D-R isotherm does not

reduce to Henry's law at low
pressures

Not act as thermodynamically

consistent adsorption isotherm
60
 Temkin Adsorption Isotherm

History Basic assumptions

• At first, Temkin • The adsorption heat
equation was of all molecules
proposed to describe decreases linearly
adsorption of with the increase in
hydrogen on coverage of the
platinum electrodes adsorbent surface
within acidic • Uniform distribution
solutions of binding energies
• Useful for
chemisorption 61
 Continued… … .
Tempkin model was:
qe = BTlnKT + BTlnCe
W here
KT= equilibrium binding constant (lmg-1 )
BT = heat of adsorption (Tempkin constant) (Jmol-1 )
bT= Tempkin isotherm constant related to variation of
adsorption energy (Jmol-1 ),

RT
BT =
bT
R is the gas constant (8.314 JK-1 mol -1 ), 62
T= temperature (K)
 Continued… … .
Plot of amount adsorbed qe against lnCe

1200

1000
= 483.54x - 61.548
.8841 800

600
qe

400

200

0
1 1.5 2 2.5 3 3.5
ln Ce
63
Drawbacks ofTemkin Isotherm

Temkin isotherm
model can’t be used
for complex systems

64
Appl
ications ofAdsorption Isotherms

Spontaneity

Exothermicity

Percentage removal of adsorbate

Langmuir parameters- maximum adsorbent

uptake and affinity between adsorbent and
adsorbate
65
 Continued… … .

Fruendlich parameters-
adsorption capacity of adsobents.
BET isotherms- specific surface
area, pore size distribution curves
D-R parameters- adsorption
mechanism
Temkin parameters- adsorbent-
adsobate interactions
66
 Summary
 Adsorption-The phenomenon of higher concentration
of any species of solid or liquid or gas at the surface
than in the bulk of a material is known as
adsorption.
 Desorption-The process of removal of adsorbed
substances from the surface on which it is absorbed.
 Some commonly used adsorbents- Silica, Activated
charcoal, Alumina, Bentonite clay, Zeolites, Bagasse
 Absorption is the phenomenon in which the particles
of gas or liquid uniformly distributed throughout the
bulk and it occurs at uniform rate.
 While, adsorption is surface phenomenon. It arises
because of unbalanced forces on the surface of solids
and liquids. 67
 Continued… … .
 The extent of adsorption increases with the increase
of surface area per unit mass of adsorbent at given
temperature and pressure.
 Types of adsorption physisorption and chemisorption
 Factors affecting adsorption temperature, pressure,
nature of adsorbent and adsorbate
 Adsorption isotherm- It is the graph between the
amounts of adsorbate (x) adsorbed on the surface of
adsorbent (m) and pressure (P) at constant
temperature.
 Types of adsorption isotherms-Langmuir isotherm,
Freundlich isotherm, BET isotherm, DR isotherm, 68
Temkin isotherm
 Continued… … .
 The Langmuir adsorption assumed that fix number
of accessible sites are available on the adsorbent
surface, with same energy. Surface is homogeneous
and monolayer adsorption takes place.
 Fruendlich isotherm- This isotherm was an empirical
expression that accounts for surface heterogeneity by
multilayer adsorption, exponential distribution of
active sites of adsorbent and their energies towards
adsorbate.
 Freundlich adsorption isotherm failed at higher
pressure.
 The BET theory applies to systems of multilayer
adsorption and usually utilizes probing gases that do
not chemically react with material surfaces as 69
adsorbates to quantify specific surface area.
 Continued… … .
 The concept of the theory is an extension of
the Langmuir theory, which is a theory for monolayer
molecular adsorption, to multilayer adsorption.
 Surface is assumed to be homogenous which the case
is not always. Lateral interaction between the
adsorbed molecules in neglected.
 The D-R equation is an adaptation of the earlier
Polanyi potential theory of adsorption.
 D-R isotherm helps to determine the adsorption
mechanism i.e. helps in distinguishing between the
chemical adsorption and physical adsorption
 The D-R isotherm does not reduce to Henry's law at
low pressures, which is a necessity for a
thermodynamically consistent. 70
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73