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ADSORPTION
ISOTHERMS
1
Adsorption
Mechanism of adsorption
Types of adsorption
Applications of adsorption
Adsorption isotherms
Different types of isotherms
Applications of isotherms
Summary
References
2
Adsorption
3
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.
Some Important Terms
4
Adsorbent-The solid
that takes up a gas,
vapour or a solute from
a solution, e.g. silica
gel, charcoal, clay, etc.
Adsorbate-The
gas, vapour or the
solute, which is
held to surface of
the solid. e.g.
poisonous gases
Desorption-The
process of removal
of adsorbed
substances from
the surface on
which it is
absorbed.
silica
Activated
charcoal
Alumina
Bentonite clay Zeolites Bagasse
Some commonly used adsorbents
5
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.
Examples of adsorption
6
Difference between adsorption and
absorption
7
 It is the phenomenon in
which the higher conc. of
particles of gas or liquid on
surface than in bulk.
 Surface phenomenon
 Rapid in beginning but
slowly decreases.
 Silica gel absorbs water
vapour.
 It is the phenomenon in
which the particles of gas or
liquid uniformly distributed
throughout.
 Bulk phenomenon
 Occurs at uniform rate
 Anhydrous CaCl2 absorbs
water.
Adsorption
Absorption
continued……
8
Absorption Adsorption
Mechanism of Adsorption
9
 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
contact with them.
Continued…..
10
Exothermic
process
Spontaneous
∆𝐺
= ∆𝐻 − 𝑇∆𝑆
Types of Adsorption
Physisorption Chemisorption
11
continued……
PROPERTIES PHYSISORPTION CHEMISORPTION
Bonding Weak, long range forces,
van der Waals interactions.
Strong, short range
forces, Chemical bonding
involving orbital overlap
and charge transfer.
Enthalpy 20-40 kJ mol-1 80-240 kJ mol-1
Saturation Multi-layer Mono-layer
Nature reversible irreversible
Effect of temperature Occurs at low temperature
and decreases with increase
in temperature.
Occurs at high
temperature and
increases with increase in
temperature.
Effect of pressure Increases with increase in
pressure of adsorbate.
Decreases with increase
of pressure
Activation energy Not needed High activation energy is
needed.
Surface specificity No Yes
12
CONTINUED……
13
Lenard-Jones model for physisorption and
chemisorption of molecules.
Factors affecting adsorption
Nature of gas - easily liquefiable gases easily gets
adsorbed.
Nature of adsorbent- 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
in pressure.
14
APPLICATIONS OF ADSORPTION
Gas masks
Adsorption indicators
Chromatographic separation
Removal of coloring matter
Heterogeneous catalysis
Controlling humidity
Curing diseases
Froth flotation process
Production of high vacuum
Purification
15
Adsorption equilibria
16
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
Continued….
Isobars: m,
T-
diagrams
at constant
Pressure
Isosteres:
In(𝑝 𝑝𝑜),
T-
diagrams
at
constant
m
17
Adsorption isotherm
18
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.
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 equilibrium will be
favored.
19
Basic Adsorption isotherm
20
After saturation pressure Ps, adsorption
does not occur anymore.
Limited numbers of vacancies on the surface
of the adsorbent.
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
of pressure.
Types of isotherms
Langmuir
isotherm
Freundlich
isotherm
BET isotherm
Dubinin–
Radushkevich
isotherm
Temkin isotherm
21
Langmuir Adsorption isotherm
History
In 1916, Dr. Irving
Langmuir presented this
model.
Langmuir was awarded the
Nobel Prize in 1932
Adsorption can be
physisorption or
chemisorption
Estimate the adsorption capacity
of adsorbent used
22
Basic assumptions of Langmuir Model
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
Adsorbate molecules have tendency
to get adsorb and desorb from surface
23
Langmuir Adsorption isotherm
The linear form of the Langmuir isotherm
qe =
bqmax
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)
b = Langmuir adsorption equilibrium constant (lmg-1) 24
Continued….
Plot of original equation
25
Continued….
The rearranged form of the Langmuir isotherm
1
qe
=
1
Cebqmax
+
1
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)
b = Langmuir adsorption equilibrium constant (lmg-1)
26
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.
27
y = 0.2597x + 0.0018
R² = 0.9637
0
0.01
0.02
0.03
0.04
0.05
0.06
0 0.05 0.1 0.15 0.2 0.25
1/qe
1/Ce
Limitations of Langmuir 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
Freundlich Adsorption Isotherm
This isotherm is
an empirical
expression that
accounts for
surface
heterogeneity.
Estimate the
sorption
intensity of
the adsorbent
towards the
adsorbate.
1909, Dr.
Herbert
Freundlich
29
Assumptions of Freundlich Isotherm
30
Surface roughness
Inhomogeneity
Adsorbate-
adsorbate
interactions
Freundlich Adsorption Isotherm
31
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,
k and n are constants.
Continued…
The linear form of Freundlich isotherm is
logqe = log Kf +
1
n
logPe
or
logqe = log Kf +
1
n
logCe
Where
qe = Extent of adsorbate adsorbed per unit weight of
adsorbent at equilibrium (mgg-1)
Pe = Equilibrium pressure of adsorbent in solution after
adsorption
Ce = Equilibrium concentration of adsorbent in solution
after adsorption (mgl-1)
Kf = Freundlich constant indicating adsorption capacity
n = Empirical constant
32
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
with pressure.
33
Continued…
The parameters of the Freundlich isotherm can be
determined by plotting logqe versus logCe.
34
y = 0.9452x + 1.3982
R² = 0.9637
2
2.5
3
3.5
4
4.5
5
1 2 3 4
log
qe
log Ce
Limitations of Freundlich 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 Freundlich and
Langmuir adsorption isotherms
36
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.
LANGMUIR
ADSORPTION
ISOTHERM
• Tells about the number
of active site
undergoing adsorption
and pressure.
• Represented by
formula θ = 𝐾𝑃
1+ KP
• Homogeneity of
adsorption site.
• Based on adsorption
and desorption
equilibrium.
BRUNAUER–EMMETT–TELLER ISOTHERM
In 1938, Stephen
Brunauer, Paul Hugh
Emmett, and Edward
Teller
Applies to
systems of
multilayer
adsorption
Utilizes probing
gases that do not
chemically react
with material
surfaces to
quantify specific
surface area 37
CONTINUED…
38
• the most commonly used
gaseous adsorbate used for
surface probing
Nitrogen
• At boiling temperature of
N2 (77 K)
BET
analysis
conducted
• Argon, carbon dioxide and
water
Other
probing
adsorbents
CONTINUED….
39
 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 applied
to each layer
CONTINUED…
The BET equation
(P/Po)/Q ((P/Po)-1)= 1/kQm + (k-1/Qmk)(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 of BET adsorption theory
42
Drawbacks
• Surface is assumed to be homogenous
Drawbacks
• Interaction between the adsorbed
molecules in neglected
Drawbacks
• Heat of adsorption from second layer
onwards to be equal to subsequent
layers which is not usually true
Applications of BET isotherm
43
The inner surface
of hardened cement
paste determination
solid
catalysis
Specific
surface area
calculation
TYPES OF BET 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
46
Sigmoid type graph
Multilayer adsorption
Pore condensation but
no hysteresis.
Nonporous or
macroporous solids.
(pore diameter > 50
nm).
Described by the BET
equation
Vapors of non-polar
organic substances on
mesoporous activated
carbons.`
TYPE III ADSORPTION ISOTHERM
47
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
TYPE IV BET ADSORPTION ISOTHERM
48
Water vapor from humid air on
special types of activated carbons
and hydrophilic zeolites.
Pore condensation with hysteresis
behavior between the adsorption and
the desorption branch.
Adsorption behavior of special
mesoporous materials
TYPE V BET ADSORPTION ISOTHERM
49
Elongated S shaped graph
Perpendicular middle portions
deviate from Type IV curves
Mesoporous materials
Pore condensation may occur.
Water on special activated
carbons and carbon molecular
sieves.
TYPE VI BET ADSORPTION ISOTHERM
50
Stepwise multilayer adsorption
Pronounced at low
temperatures
Nonpolar, spherical molecules
on planar graphite surfaces
Butanol on aluminum silicate
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
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
slope respectively. 55
CONTINUED…….
y = -0.0076x + 6.5814
R² = 0.8041
4
4.5
5
5.5
6
6.5
7
7.5
0 50 100 150 200 250
ln
qe
Ԑ2 ( x 103)
D-R adsorption isotherm
56
The experimental data is evaluated by plotting lnqe against
2.
CONTINUED…….
The value of Qm and β are estimated from the
intercept and slope respectively.
The mean adsorption energy is calculated with
the equation
E =
1
2β
57
CONTINUED…….
This parameter
tells the nature of
adsorption process
such as chemical
ion exchange or
physical adsorption
The value smaller
than 8 kJmol-1 then
the reaction
continues
physically
The value between
8-16 kJmol-1 then
the process will
proceeds
chemically
58
USES OF D-R ISOTHERMS
Describe
adsorption by
microporous
solids
carbonaceous
sorbents or
activated
carbons
applicable for
microporous
solids with
uniform
microporous
structures
59
DRAWBACKS OF D-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
• At first, Temkin
equation was
proposed to
describe adsorption
of hydrogen on
platinum electrodes
within acidic
solutions
Basic assumptions
• The adsorption heat
of all molecules
decreases linearly
with the increase in
coverage of the
adsorbent surface
• Uniform distribution
of binding energies
• Useful for
chemisorption 61
CONTINUED…….
Tempkin model was:
qe = BTlnKT + BTlnCe
Where
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),
BT =
RT
bT
R is the gas constant (8.314 JK-1mol-1),
T = temperature (K) 62
CONTINUED…….
y = 483.54x - 61.548
R² = 0.8841
0
200
400
600
800
1000
1200
1 1.5 2 2.5 3 3.5
qe
ln Ce
63
Plot of amount adsorbed qe against lnCe
DRAWBACKS OF TEMKIN ISOTHERM
Temkin isotherm
model can’t be used
for complex systems
64
APPLICATIONS OF ADSORPTION ISOTHERMS
65
Spontaneity
Exothermicity
Percentage removal of adsorbate
Langmuir parameters- maximum adsorbent
uptake and affinity between adsorbent and
adsorbate
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,
Temkin isotherm
68
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 adsorbates to
quantify specific surface area.
69
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
REFERENCES
 Alothman Z A (2012) A review: Fundamental aspects of silicate
mesoporous materials. Materials 5: 2874–902.
 Chakrabarty D K (2001) An Introduction to Physical
Chemistry. Pp. 327-30. Narosa Publication House, New
Delhi.
 Dada A O, Olalekan A P, Olatunya A M and Dada O (2012)
Langmuir, freundlich, temkin and dubinin-radushkevich
isotherms studies of equilibrium sorption of Zn2+ unto
phosphoric acid modified rice husk. IOSR J Appl Chem
3: 38–45.
 Davis W M (ed) (2012) Physical Chemistry A Modern
Introduction. Pp. 399-419. CRC Press, New York.
 Erhayem1 M, Al-Tohami F, Mohamed R, Ahmida K (2015)
Isotherm, kinetic and thermodynamic studies for the sorption
of Mercury (II) onto activated carbon from Rosmarinus
officinalis leaves. Am J Analyt Chem 6: 1-10.
 Febrianto J (2009) Equilibrium and kinetic studies in
adsorption of heavy metals using biosorbent: A summary
of recent studies. J Hazard Mater 162(2): 616–45.
71
REFERENCES
 Kyzas G Z and Matis K A (2015) Nanoadsorbents for
pollutants removal: A review. J Mol Liq 203: 159-68.
 Mahmoud M A and El-Halwany M M (2014) Adsorption of
cadmium onto orange peels: Isotherms, kinetics, and
thermodynamics. J Chromatogr Sep Tech 5(5):
1000238-244.
 Mehta V (2016) Wiley Physical Chemistry for JEE (Main &
Advanced). Pp. 911-925. Wiley India Pvt. Ltd., New
Delhi.
 Puri B R, Sharma L R and Pathania M S (2017) Principles of
Physical Chemistry. Pp. 1251-72. Vishal Publications,
India.
 Silbey R J, Alberty R A and Bawendi M G (2011) Physical
Chemistry. Pp. 840-47. Wiley India, New Delhi.
 Thajeel A S (2013) Isotherm, kinetic and thermodynamic of
adsorption of heavy metal ions onto local activated
carbon. Aquat Sci Tech 1(2): 53–77.
72
73

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Adsorptionisotherm.pptx

  • 2. Adsorption Mechanism of adsorption Types of adsorption Applications of adsorption Adsorption isotherms Different types of isotherms Applications of isotherms Summary References 2
  • 3. Adsorption 3 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.
  • 4. Some Important Terms 4 Adsorbent-The solid that takes up a gas, vapour or a solute from a solution, e.g. silica gel, charcoal, clay, etc. Adsorbate-The gas, vapour or the solute, which is held to surface of the solid. e.g. poisonous gases Desorption-The process of removal of adsorbed substances from the surface on which it is absorbed.
  • 5. silica Activated charcoal Alumina Bentonite clay Zeolites Bagasse Some commonly used adsorbents 5
  • 6. 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. Examples of adsorption 6
  • 7. Difference between adsorption and absorption 7  It is the phenomenon in which the higher conc. of particles of gas or liquid on surface than in bulk.  Surface phenomenon  Rapid in beginning but slowly decreases.  Silica gel absorbs water vapour.  It is the phenomenon in which the particles of gas or liquid uniformly distributed throughout.  Bulk phenomenon  Occurs at uniform rate  Anhydrous CaCl2 absorbs water. Adsorption Absorption
  • 9. Mechanism of Adsorption 9  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 contact with them.
  • 12. continued…… PROPERTIES PHYSISORPTION CHEMISORPTION Bonding Weak, long range forces, van der Waals interactions. Strong, short range forces, Chemical bonding involving orbital overlap and charge transfer. Enthalpy 20-40 kJ mol-1 80-240 kJ mol-1 Saturation Multi-layer Mono-layer Nature reversible irreversible Effect of temperature Occurs at low temperature and decreases with increase in temperature. Occurs at high temperature and increases with increase in temperature. Effect of pressure Increases with increase in pressure of adsorbate. Decreases with increase of pressure Activation energy Not needed High activation energy is needed. Surface specificity No Yes 12
  • 13. CONTINUED…… 13 Lenard-Jones model for physisorption and chemisorption of molecules.
  • 14. Factors affecting adsorption Nature of gas - easily liquefiable gases easily gets adsorbed. Nature of adsorbent- 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 in pressure. 14
  • 15. APPLICATIONS OF ADSORPTION Gas masks Adsorption indicators Chromatographic separation Removal of coloring matter Heterogeneous catalysis Controlling humidity Curing diseases Froth flotation process Production of high vacuum Purification 15
  • 16. Adsorption equilibria 16 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
  • 18. Adsorption isotherm 18 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.
  • 19. 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 equilibrium will be favored. 19
  • 20. Basic Adsorption isotherm 20 After saturation pressure Ps, adsorption does not occur anymore. Limited numbers of vacancies on the surface of the adsorbent. 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 of pressure.
  • 21. Types of isotherms Langmuir isotherm Freundlich isotherm BET isotherm Dubinin– Radushkevich isotherm Temkin isotherm 21
  • 22. Langmuir Adsorption isotherm History In 1916, Dr. Irving Langmuir presented this model. Langmuir was awarded the Nobel Prize in 1932 Adsorption can be physisorption or chemisorption Estimate the adsorption capacity of adsorbent used 22
  • 23. Basic assumptions of Langmuir Model 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 Adsorbate molecules have tendency to get adsorb and desorb from surface 23
  • 24. Langmuir Adsorption isotherm The linear form of the Langmuir isotherm qe = bqmax 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) b = Langmuir adsorption equilibrium constant (lmg-1) 24
  • 26. Continued…. The rearranged form of the Langmuir isotherm 1 qe = 1 Cebqmax + 1 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) b = Langmuir adsorption equilibrium constant (lmg-1) 26
  • 27. 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. 27 y = 0.2597x + 0.0018 R² = 0.9637 0 0.01 0.02 0.03 0.04 0.05 0.06 0 0.05 0.1 0.15 0.2 0.25 1/qe 1/Ce
  • 28. Limitations of Langmuir 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
  • 29. Freundlich Adsorption Isotherm This isotherm is an empirical expression that accounts for surface heterogeneity. Estimate the sorption intensity of the adsorbent towards the adsorbate. 1909, Dr. Herbert Freundlich 29
  • 30. Assumptions of Freundlich Isotherm 30 Surface roughness Inhomogeneity Adsorbate- adsorbate interactions
  • 31. Freundlich Adsorption Isotherm 31 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, k and n are constants.
  • 32. Continued… The linear form of Freundlich isotherm is logqe = log Kf + 1 n logPe or logqe = log Kf + 1 n logCe Where qe = Extent of adsorbate adsorbed per unit weight of adsorbent at equilibrium (mgg-1) Pe = Equilibrium pressure of adsorbent in solution after adsorption Ce = Equilibrium concentration of adsorbent in solution after adsorption (mgl-1) Kf = Freundlich constant indicating adsorption capacity n = Empirical constant 32
  • 33. 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 with pressure. 33
  • 34. Continued… The parameters of the Freundlich isotherm can be determined by plotting logqe versus logCe. 34 y = 0.9452x + 1.3982 R² = 0.9637 2 2.5 3 3.5 4 4.5 5 1 2 3 4 log qe log Ce
  • 35. Limitations of Freundlich 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
  • 36. Differences between Freundlich and Langmuir adsorption isotherms 36 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. LANGMUIR ADSORPTION ISOTHERM • Tells about the number of active site undergoing adsorption and pressure. • Represented by formula θ = 𝐾𝑃 1+ KP • Homogeneity of adsorption site. • Based on adsorption and desorption equilibrium.
  • 37. BRUNAUER–EMMETT–TELLER ISOTHERM In 1938, Stephen Brunauer, Paul Hugh Emmett, and Edward Teller Applies to systems of multilayer adsorption Utilizes probing gases that do not chemically react with material surfaces to quantify specific surface area 37
  • 38. CONTINUED… 38 • the most commonly used gaseous adsorbate used for surface probing Nitrogen • At boiling temperature of N2 (77 K) BET analysis conducted • Argon, carbon dioxide and water Other probing adsorbents
  • 39. CONTINUED…. 39  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 applied to each layer
  • 40. CONTINUED… The BET equation (P/Po)/Q ((P/Po)-1)= 1/kQm + (k-1/Qmk)(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
  • 42. Drawbacks of BET adsorption theory 42 Drawbacks • Surface is assumed to be homogenous Drawbacks • Interaction between the adsorbed molecules in neglected Drawbacks • Heat of adsorption from second layer onwards to be equal to subsequent layers which is not usually true
  • 43. Applications of BET isotherm 43 The inner surface of hardened cement paste determination solid catalysis Specific surface area calculation
  • 44. TYPES OF BET 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
  • 45. 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
  • 46. TYPE II ADSORPTION ISOTHERM 46 Sigmoid type graph Multilayer adsorption Pore condensation but no hysteresis. Nonporous or macroporous solids. (pore diameter > 50 nm). Described by the BET equation Vapors of non-polar organic substances on mesoporous activated carbons.`
  • 47. TYPE III ADSORPTION ISOTHERM 47 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
  • 48. TYPE IV BET ADSORPTION ISOTHERM 48 Water vapor from humid air on special types of activated carbons and hydrophilic zeolites. Pore condensation with hysteresis behavior between the adsorption and the desorption branch. Adsorption behavior of special mesoporous materials
  • 49. TYPE V BET ADSORPTION ISOTHERM 49 Elongated S shaped graph Perpendicular middle portions deviate from Type IV curves Mesoporous materials Pore condensation may occur. Water on special activated carbons and carbon molecular sieves.
  • 50. TYPE VI BET ADSORPTION ISOTHERM 50 Stepwise multilayer adsorption Pronounced at low temperatures Nonpolar, spherical molecules on planar graphite surfaces Butanol on aluminum silicate
  • 51. 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
  • 52. BET ADSORPTION ISOTHERM Why is Langmuir surface area always higher than BET surface area? 52
  • 53. 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
  • 54. 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
  • 55. CONTINUED…….  can be acquired from the following relation 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 slope respectively. 55
  • 56. CONTINUED……. y = -0.0076x + 6.5814 R² = 0.8041 4 4.5 5 5.5 6 6.5 7 7.5 0 50 100 150 200 250 ln qe Ԑ2 ( x 103) D-R adsorption isotherm 56 The experimental data is evaluated by plotting lnqe against 2.
  • 57. CONTINUED……. The value of Qm and β are estimated from the intercept and slope respectively. The mean adsorption energy is calculated with the equation E = 1 2β 57
  • 58. CONTINUED……. This parameter tells the nature of adsorption process such as chemical ion exchange or physical adsorption The value smaller than 8 kJmol-1 then the reaction continues physically The value between 8-16 kJmol-1 then the process will proceeds chemically 58
  • 59. USES OF D-R ISOTHERMS Describe adsorption by microporous solids carbonaceous sorbents or activated carbons applicable for microporous solids with uniform microporous structures 59
  • 60. DRAWBACKS OF D-R ISOTHERM The D-R isotherm does not reduce to Henry's law at low pressures Not act as thermodynamically consistent adsorption isotherm 60
  • 61. TEMKIN ADSORPTION ISOTHERM History • At first, Temkin equation was proposed to describe adsorption of hydrogen on platinum electrodes within acidic solutions Basic assumptions • The adsorption heat of all molecules decreases linearly with the increase in coverage of the adsorbent surface • Uniform distribution of binding energies • Useful for chemisorption 61
  • 62. CONTINUED……. Tempkin model was: qe = BTlnKT + BTlnCe Where 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), BT = RT bT R is the gas constant (8.314 JK-1mol-1), T = temperature (K) 62
  • 63. CONTINUED……. y = 483.54x - 61.548 R² = 0.8841 0 200 400 600 800 1000 1200 1 1.5 2 2.5 3 3.5 qe ln Ce 63 Plot of amount adsorbed qe against lnCe
  • 64. DRAWBACKS OF TEMKIN ISOTHERM Temkin isotherm model can’t be used for complex systems 64
  • 65. APPLICATIONS OF ADSORPTION ISOTHERMS 65 Spontaneity Exothermicity Percentage removal of adsorbate Langmuir parameters- maximum adsorbent uptake and affinity between adsorbent and adsorbate
  • 66. 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
  • 67. 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
  • 68. 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, Temkin isotherm 68
  • 69. 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 adsorbates to quantify specific surface area. 69
  • 70. 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
  • 71. REFERENCES  Alothman Z A (2012) A review: Fundamental aspects of silicate mesoporous materials. Materials 5: 2874–902.  Chakrabarty D K (2001) An Introduction to Physical Chemistry. Pp. 327-30. Narosa Publication House, New Delhi.  Dada A O, Olalekan A P, Olatunya A M and Dada O (2012) Langmuir, freundlich, temkin and dubinin-radushkevich isotherms studies of equilibrium sorption of Zn2+ unto phosphoric acid modified rice husk. IOSR J Appl Chem 3: 38–45.  Davis W M (ed) (2012) Physical Chemistry A Modern Introduction. Pp. 399-419. CRC Press, New York.  Erhayem1 M, Al-Tohami F, Mohamed R, Ahmida K (2015) Isotherm, kinetic and thermodynamic studies for the sorption of Mercury (II) onto activated carbon from Rosmarinus officinalis leaves. Am J Analyt Chem 6: 1-10.  Febrianto J (2009) Equilibrium and kinetic studies in adsorption of heavy metals using biosorbent: A summary of recent studies. J Hazard Mater 162(2): 616–45. 71
  • 72. REFERENCES  Kyzas G Z and Matis K A (2015) Nanoadsorbents for pollutants removal: A review. J Mol Liq 203: 159-68.  Mahmoud M A and El-Halwany M M (2014) Adsorption of cadmium onto orange peels: Isotherms, kinetics, and thermodynamics. J Chromatogr Sep Tech 5(5): 1000238-244.  Mehta V (2016) Wiley Physical Chemistry for JEE (Main & Advanced). Pp. 911-925. Wiley India Pvt. Ltd., New Delhi.  Puri B R, Sharma L R and Pathania M S (2017) Principles of Physical Chemistry. Pp. 1251-72. Vishal Publications, India.  Silbey R J, Alberty R A and Bawendi M G (2011) Physical Chemistry. Pp. 840-47. Wiley India, New Delhi.  Thajeel A S (2013) Isotherm, kinetic and thermodynamic of adsorption of heavy metal ions onto local activated carbon. Aquat Sci Tech 1(2): 53–77. 72
  • 73. 73

Editor's Notes

  1. to indicate the condensation of gases on the free surfaces. In contract to gases absorption where the molecules of the gas penetrate into the mass of the adsorbing solid.
  2. This is because the surface particles of adsorbent (solid) are not in same environment as the particles present in bulk.
  3. at given temperature and pressure
  4. According to Le-Chatelier principle, case of application of
  5. From the graph, we can predict that
  6. 1 for the adsorption of gaseous species onto simple surfaces 4, but are held by it in a similar way to groups of molecules in solid bodies.
  7. The surface containing the adsorbing sites is a perfectly flat plane with no folds (assume the surface is homogeneous) . The adsorbing gas adsorbs into an immobile state. All sites are equivalent. Each site can hold at most one molecule of Adsorbent (mono-layer coverage only). There are not any interactions between adsorbate molecules on adjacent sites. Dynamic equilibrium exits between the adsorbed molecules and free molecules.
  8. There are two kinds of adsorbate/adsorbate interactions: direct interaction and indirect interaction. Direct interactions are between adjacent adsorbed molecules, which could make adsorbing near another adsorbate molecule more or less favorable and greatly affects high-coverage behavior. In indirect interactions, the adsorbate changes the surface around the adsorbed site, which in turn affects the adsorption of other adsorbate molecules nearby. The Langmuir adsorption model deviates significantly in many cases, primarily because it fails to account for the surface roughness of the adsorbent Rough inhomogeneous surfaces have multiple site-types available for adsorption
  9. gave an expression known as Freundlich adsorption isotherm or Freundlich adsorption equation. 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.
  10. he modifications in Langmuir try to account for the points mentioned in above section like:
  11. k and n are constants which depend on the nature of the adsorbent and the gas at a particular temperature.
  12. By application of the BET theory it is possible to determine the inner surface of hardened cement paste. If the quantity of adsorbed water vapor is measured at different levels of relative humidity a BET plot is obtained.  In the field of solid catalysis, the surface area of catalysts is an important factor in catalytic activity. Catalysis[edit] In the field of solid catalysis, the surface area of catalysts is an important factor in catalytic activity. Porous inorganic materials such as mesoporous silica and layered clay mineralshave high surface areas of several hundred m2/g calculated by the BET method, indicating the possibility of application for efficient catalytic materials. For example, activated carbon strongly adsorbs many gases and has an adsorption cross section {s} of 0.162 nm2 for nitrogen adsorption at liquid-nitrogen temperature (77 K). BET theory can be applied to estimate the specific surface area of activated carbon from experimental data, demonstrating a large specific surface area, even around 3000 m2/g.
  13. They are characterized by a horizontal plateau, i.e. the asymptotic value the mass adsorbed approaches and maintains for even very high gas pressures. materials showing micropore filling but no multilayer adsorption.
  14. i. e. strongly associating admolecules.
  15. spherical molecules (noble gases)
  16. of the transfer per mole of the adsorbate from infinity to the adsorbent surface
  17. , which is a necessity for a thermodynamically consistent.
  18. and the constants (BT and kT ) were resolved from the slope and intercept of curve.
  19. Since the basis of derivation for Temkin equation are a simple assumption, the complex phenomenon involved in liquid phase adsorption are not taken into account by this equation. As a result, this equation is often not suitable for representation of experimental data in complex systems.