EP318 Surface Chemistry and Catalysis

Chapter 3: Part I

Adsorption & Desorption

Prepared by Dr. Tan, M.C.

 Adsorption vs. Absorption
Sorption
The phenomenon in which adsorption and absorption occur
simultaneously.
Adsorption
Accumulation of molecules on a surface
(a surface layer of molecules) in contact
with an air or water phase.

Absorption
The process in which atoms, molecules
or ions enter some bulk phase of gas,
liquid or solid material.

Example: In the drying of dishes, a film of water adsorbed on a

plate is absorbed into a towel.
 Adsorption vs. Absorption

Adsorption Absorption
Phenomenon A surface phenomenon A bulk phenomenon

Heat exchange Exothermic process Endothermic process

Temperature Favoured by low Not affected by

temperature temperature
Rate of reaction Steadily increases and Occurs at uniform rate
reach to equilibrium
Concentration Concentration on the It is same throughout
surface of absorbent is the material
different from that in
the bulk
 Adsorption
Adsorption is a spontaneous process
• For reaction or process to be spontaneous, there must be
decreases in free energy of the system, i.e. ∆𝐺 of the
system must have negative value.
• In general, ∆𝐺 = ∆𝐻 − 𝑇∆𝑆
• During the process of adsorption, randomness of the
molecule decreases, which ∆𝑆 is negative.
• Rewrite the equation, ∆𝐺 = ∆𝐻 + 𝑇∆𝑆
• Therefore for a reaction to be spontaneous, ∆𝐻 has to be
negative, hence | ∆𝐻 |>|𝑇∆𝑆|

Where ∆𝐺 = Gibbs free energy

∆𝐻 = enthalpy change total heat content in a system
∆𝑆 = entropy change degree of disorder or randomness
 Adsorption

Adsorption is an exothermic process

• Adsorption process takes place by adsorbate getting
adsorbed on adsorbent.
• Forces of attraction exist between adsorbate and
adsorbent and due to these forces of attraction, heat
energy is released. So, adsorption is an exothermic
process.
 Adsorption on Solid Surface
Adsorptive

Adsorbate
Adsorbent

• Adsorption is a process in which molecules from gas (or liquid)

phase land on, interact with and attach to solid surfaces.
• Adsorpt or adsorptive: the substance to be adsorbed before it
is on the surface.
• Adsorbate: the material being adsorbed .
• Adsorbent: the solid material being used as the adsorbing
phase.
• Desorption: the reverse process of adsorption, where the
process of adsorbed molecules escape from solid surfaces.
Adsorption Absorption

Desorption
 Adsorption on Solid Surface
• The phenomenon of adsorption is essentially an attraction of
adsorbate molecules to an adsorbent surface.
• The preferential concentration of molecules in the proximity
of a surface arises because the surface forces of an adsorbent
solid are unsaturated.
• Both repulsive and attractive forces become balanced when
adsorption occurs.
• Adsorption is nearly always an exothermic process.
• We can distinguish between 2 types of adsorption process
depending on which of these 2 force types plays the bigger
role in the process.
• Adsorption processes can be classified as either physisorption
(van der Waals adsorption) or chemisorptioninvolves (activated
activation energy
adsorption) depending on the type of forces between the
adsorbate and adsorbent.
 Physisorption
• In physisorption, the individuality of the adsorbate and adsorbent
are preserved.
• Physical adsorption from a gas occurs when the inter-molecular
attractive forces between molecules of the solid adsorbent and the
gas are greater than those between molecules of the gas itself.
• In effect, the resulting adsorption is like condensation, which is
exothermic and thus is accompanied by the release of heat.
• Physical adsorption occurs quickly and may be mono-molecular
(unimolecular) layer (monolayer), or multi-molecular layer
(multilayer).
• As physical adsorption takes place, it begins as a monolayer.
• It can then become multi-layer, and then, if the pores are close to
the size of the molecules, more adsorption occurs until the pores
are filled with adsorbate.
• Accordingly, the maximum capacity of a porous adsorbent can be
more related to the pore volume than to the surface area.
 Chemisorption
• Chemisorption is a kind of adsorption which involves a
chemical reaction between the surface and the adsorbate.
• New chemical bonds are generated at the adsorbent surface.
• Example: corrosion, heterogeneous catalysis.
• The strong interaction between the adsorbate and the
substrate surface creates new types of electronic bonds.
• The nature of chemisorption depending on the chemical
identity and the surface structure.
• In chemisorption, there is a transfer or sharing of electron, or
breakage of the adsorbate into atoms or radicals which are
bound separately.
• In contrast, chemisorption involves the formation of chemical
bonds between the adsorbate and adsorbent in a monolayer,
often with a release of heat much larger than the heat of
condensation.
Physisorption Chemisorption
 Types of Adsorption
Types of adsorption Characteristics

1. Physical adsorption Unselective. Low energy of adsorption. Extent

(physisorption) of adsorption related to boiling point of gas, not
nature of solid surface. No breaking of bonds in
molecules and negligible changes in bond
energies.
2. Associative chemical adsorption Selective, strongly dependent on both gas and
(chemisorption) solid surface. Higher energies of adsorption
than those of physisorption. Bonds in the
adsorbed molecules are changed in strength
but not broken, i.e. molecule adsorbed whole.

3. Dissociative chemical adsorption Selective, strongly dependent on both gas and

(chemisorption) solid surface. Higher energies of adsorption
than those of physisorption. Bonds in the
adsorbed molecules are broken, i.e. molecule
adsorbed as two or more molecular fragments.
 Types of Adsorption

Schematic representation of the adsorption, and possible subsequent reaction, of

carbon monoxide on various solid surfaces.
 Adsorption and Reaction at Surfaces
PHYSISORPTION
WEAK, LONG RANGE BONDING
Van der Waals interactions (e.g. London
dispersion, dipole-dipole)
NOT SURFACE SPECIFIC
Physisorption takes place between all molecules
on any surface providing the temperature is low
enough
LOW HEAT OF ADSORPTION
-DHads = 20 - 40 kJ mol-1
Does not require any activation energy
It is reversible
No surface reactions.
Takes place at low temperature and decreases
with increasing temperature
It is related to ease of liquefaction of the gas
MULTILAYER ADSORPTION
BET Isotherm used to model adsorption
equilibrium
CHEMISORPTION
STRONG, SHORT RANGE BONDING
Chemical bonding involving orbital overlap and
charge transfer
SURFACE SPECIFIC
E.g. Chemisorption of hydrogen takes place on
transition metals but not on gold or mercury
HIGH HEAT OF ADSORPTION
-DHads = 35 ….. 500 kJ mol-1
Require activation energy
It is irreversible
Surface reactions may take place:- Dissociation,
reconstruction, catalysis.
Takes place at high temperature
The extent of adsorption is generally not related
to liquefaction of the gas
MONOLAYER ADSORPTION
Langmuir Isotherm used to model adsorption
equilibrium
 How Adsorption occurs?

• The process of adsorption arises due to presence of

unbalanced or residual forces at the surface of liquid
or solid phase.
• 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).
 Applications of Adsorption

• Some of the industrial applications for adsorption are

air-conditioning, adsorption chillers, synthetic resin
and water purification.
• In pharmaceutical industry applications, adsorption
is used as a means to prolong neurological exposure
to specific drugs or parts thereof.
• Adsorption of molecules onto polymer surfaces is
used in various applications such as in the
development of non-stick coatings and in various
biomedical devices.
Applications of Adsorption in Wastewater Treatment

Many industrial wastewaters contain substances that:

• Are difficult to remove via conventionally secondary
treatment
• Are toxic or hazardous
• Are volatile and cannot be transferred to the
atmosphere
• Have the potential for creating noxious vapors or
odors, or for imparting color to the wastewater
• Are present in very small concentrations that make
their removal via other methods difficult
Applications of Adsorption in Wastewater Treatment

• Adsorption is typically used in wastewater treatment

to remove toxic or recalcitrant organic pollutants
(especially halogenated but also non-halogenated),
and to a lesser extent, inorganic contaminants, from
the wastewater.
• Adsorption finds applications in tertiary wastewater
treatment as a polishing step before final discharge.
• Adsorption is commonly used in the treatment of
industrial wastewaters containing organic
compounds not easily biodegraded during secondary
(biological) treatment or toxic.
 Common Adsorbents

• Activated carbon – a char-like material

with high surface area.
• Silica gel – hard, granular, porous material
made by precipitation from sodium
silicate solutions treated with an acid.
• Activated alumina – aluminum oxide
activated at high temperature and used
primarily for moisture adsorption.
• Aluminosilicates (molecular sieves) –
porous synthetic zeolites used primarily in
separation processes.
 Common Adsorbents

• Activated carbon is by far the most common

adsorbent used in wastewater treatment.
• Since, during adsorption, the pollutant is removed by
accumulation at the interface between the activated
carbon (absorbent) and the wastewater (liquid
phase), the adsorbing capacity of activated carbon is
always associated with very high surface area per
unit volume.
 Causes of Adsorption

• Dislike of water phase – hydrophobicity

• Attraction to the sorbent surface
van der Waals forces – physical attraction
electrostatic forces (surface charge interaction)
chemical forces (e.g. hydrogen bonding)
 Factors Affecting Adsorption
i. The surface area of adsorbent – larger sizes imply a greater
adsorption capacity.
ii. Particle size of adsorbent – smaller particle sizes reduce
internal diffusional and mass transfer limitation to the
penetration of the adsorbate inside the adsorbent (
equilibrium is more easily achieved and nearly full adsorption
capability can be attained).
iii. Contact time or residence time – the longer the time the more
complete the adsorption will be.
iv. Solubility of solute (adsorbate) in liquid (wastewater) –
substances slightly soluble in water will be more easily
removed from water (adsorbed) than substances with high
solubility.
v. Size of the molecule with respect to size of the pores – large
molecules may be too large to enter small pores.
 Factors Affecting Adsorption

vi. Degree of ionization of the adsorbate molecule – more highly

ionized molecules are adsorbed to a smaller degree than
neutral molecules.
vii. pH – the degree of ionization of a species is affected by pH.
viii. Affinity of the solute for the adsorbent (carbon) – the surface
of activated carbon is only slightly polar. Hence, non-polar
substances will be more easily picked up by the carbon than
polar ones.
ix. Number of carbon atoms – for substances in the same
homologous series a larger number of carbon atoms is
generally associated with a lower polarity and hence a greater
potential for being adsorbed.
 Adsorption Equilibrium
• Adsorption will continue until equilibrium
established between the substance in solution and
the same substance in the adsorbed state.
• At equilibrium, a relationship exists between the
concentration of the species in solution and the
concentration of the same species in the adsorbed
state (i.e. the amount of species adsorbed per unit
mass of adsorbent).
 Accommodation Coefficient
• Accommodation coefficient, α is a measure of how
much energy is exchanged before a molecule leaves
the adsorbent again.
Treflected molecules − Tmolecules before impact
• α=
Tsurface − Tmolecules before impact

• For elastic reflection, the mean velocity of the

molecules before and after hitting the surface are
identical, so Treflected molecules = Tmolecules before impact ,
then α = 0.
• If the molecules reside a long time on the surface
they have the same temperature, after desorption,
Treflected molecules = Tsurface , then α = 1.
 How to Measure Sorption
• If the adsorbent and adsorbate are contacted long
enough, an equilibrium will be establish between the
amount of adsorbate adsorbed and the amount of
adsorbate in solution.
• The results of the experiment are plotted on a graph,
called an isotherm.
Equilibrium sorption isotherm
can be used when sorption process is rapid
compared to the flow velocity
Kinetic sorption isotherm
needed when the sorption process is slow
compared with the rate of fluid flow
 Adsorption Isotherm
• The adsorption equilibrium relates q to C. The
equilibrium is a function of the temperature.
Therefore, the adsorption equilibrium relationship at
a given temperature is typically referred to as
adsorption isotherm, i.e.:
q = f(C)
where:
q = mass of species adsorbed/ mass of adsorbent
(i.e. equilibrium concentration of adsorbable
species in solid adsorbent)
C = equilibrium concentration of adsorbable species
in solution
 Adsorption Isotherm
• Different adsorbates-adsorbents exhibit different
types of equilibrium relationships.
• It has been found that for most of the cases of
importance in wastewater treatment the function
q = f(C) takes the form of one the following
isotherms:
- Langmuir isotherm
- Brauner-Emmet-Teller (BET) isotherm
- Freundlich isotherm
Classification of Adsorption Isotherm
 Langmuir Isotherm
• An isotherm for gases adsorbed on solids.
• It is an empirical isotherm derived from a proposed kinetic
mechanism.
• The assumptions made in the derivation of the Langmuir
model are:
1. Adsorption is a reversible process.
2. The adsorbed layer is made up of a single layer of
molecules (monolayer).
3. The adsorbed molecules do not move on the surface of
the adsorbent. However, they can be lost back to the
solution.
4. The enthalpy of adsorption is the same for all molecules
independently of how many have been adsorbed.
 Langmuir Isotherm
5. Fixed number of vacant or adsorption sites are available
on the surface of solid.
6. All the vacant sites are of equal size and shape on the
surface of adsorbent.
7. Each site can hold maximum of one gaseous molecule
and a constant amount of heat energy is released
during this process.
8. 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.
 Derivation of Langmuir Isotherm
• In the Langmuir model (1918) adsorption is assumed to be a
dynamic process.
• At equilibrium the number of molecules being adsorbed will be
equal to the number of molecules leaving the adsorbed state, i.e.:
rate of adsorption
= (conc. in solution)·(available area for absorption)
= C (Atotal − Aoccupied )
= C (k1 qm − k1 q)
= k1 C (qm − q)
where C = concentration
A = area
k = constant
q= amount of solute adsorbed (x) by a definite mass (m)
of adsorbent = x/m
 Derivation of Langmuir Isotherm

Similarly:
rate of desorption ∝ (amount already adsorbed)
∝ Aoccupied
= k2q

At equilibrium it is:
rate of adsorption = rate of desorption
𝒌𝟏 C (𝒒𝒎 − 𝐪) = 𝒌𝟐 𝐪
 Derivation of Langmuir Isotherm

The previous equation can be rewritten as:

𝑞𝑚 𝑘1 𝐶
𝑞=
𝑘2 + 𝑘1 𝐶
Which, with the substitution : 𝐾𝐴 = 𝑘1 /𝑘2 , becomes
the final expression for
𝒒𝒎 𝑲𝑨 𝑪
𝒒=
𝟏 + 𝑲𝑨 𝑪
Where:
𝑞𝑚 = maximum adsorbable value of q
𝐾𝐴 = constant (function of enthalpy of adsorption and
temperature)
Langmuir Isotherm

𝒒𝒎 𝑲𝑨 𝑪
𝒒=
𝟏 + 𝑲𝑨 𝑪
 Langmuir Isotherm
The Langmuir isotherm can be rearranged to give:
𝑪 𝟏 𝟏
= + 𝑪
𝒒 𝑲𝑨 𝒒𝒎 𝒒𝒎

Accordingly, a plot of C/q vs. C should produce a

straight line with:
1
𝑆𝑙𝑜𝑝𝑒 =
𝑞𝑚
1
𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 =
𝐾𝐴 𝑞𝑚
Langmuir Isotherm

𝑪 𝟏 𝟏
= + 𝑪
𝒒 𝑲𝑨 𝒒𝒎 𝒒𝒎
 Langmuir Isotherm
The Langmuir isotherm can also be rearranged to give:
𝟏 𝟏 𝟏 𝟏
= +
𝒒 𝒒𝒎 𝑲𝑨 𝒒𝒎 𝑪

from which a plot of 1/q vs. 1/C gives:

1
𝑠𝑙𝑜𝑝𝑒 =
𝐾𝐴 𝑞𝑚
1
𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 =
𝑞𝑚
Langmuir Isotherm

𝟏 𝟏 𝟏 𝟏
= +
𝒒 𝒒𝒎 𝑲𝑨 𝒒𝒎 𝑪
 Langmuir Isotherm
Limitations of Langmuir Equation:
1. The adsorbed gas has to behave ideally in the vapor
phase. This condition can be fulfilled at low pressure
condition only. Thus Langmuir equation is valid
under low pressure only.
2. Langmuir equation assumes that adsorption is
monolayer. But, monolayer formation is possible
only under low pressure condition. Under high
pressure condition the assumption breaks down as
gas molecules attract more and more molecules
towards each other. BET theory explained more
realistic multilayer adsorption process.
 Langmuir Isotherm
3. Another assumption was that all the sites on the
solid surface are equal in size and shape and have
equal affinity for adsorbate molecules, i.e. the
surface of solid if homogeneous. But in real, solid
surfaces are heterogeneous.
4. Langmuir equation assumed that molecules do not
interact with each other. This is impossible as weak
force of attraction exists even between molecules of
same type.
 Langmuir Isotherm: Problem 1
An adsorption study is set up in laboratory by adding a known amount
of activated carbon to six flasks which contain 200 mL of an industrial
remove any chemical that can be oxidised
waste. An additional flask containing 200 mL of waste but no carbon is
run as a blank. Plot the Langmuir isotherm and determine the values
of the constants.

=C
Langmuir Isotherm: Problem 1

=q
 Langmuir Isotherm: Problem 1
q

C
 Langmuir Isotherm: Problem 1
Langmuir Isotherm
𝒒𝒎 𝑲𝑨 𝑪
𝒒=
𝟏 + 𝑲𝑨 𝑪

𝟏 𝟏 𝟏 𝟏
= +
𝒒 𝒒𝒎 𝑲𝑨 𝒒𝒎 𝑪

Determine the constants from a plot of 1/q to 1/C.

Langmuir Isotherm: Problem 1

1/C 1/q
1/q

1/C
 Langmuir Isotherm: Problem 1
1/q

1/C
 Langmuir Isotherm: Problem 1
𝟏 𝟏 𝟏 𝟏
= +
𝒒 𝒒𝒎 𝑲𝑨 𝒒𝒎 𝑪

𝟏
Intercept = = 5.3 𝒒𝒎 = 0.189
𝒒𝒎

16.39 −7.19 𝟏
Slope = = 51.11 = 51.11 𝑲𝑨 = 0.104
0.21 −0.03 𝑲𝑨 𝒒𝒎

𝟏 𝟏 𝟏 𝟏
The Langmuir Equation: = +
𝒒 𝟎.𝟏𝟖𝟗 𝟎.𝟏𝟎𝟒 𝒙 𝟎.𝟏𝟖𝟗 𝑪

amount of solute adsorbed (x) by Concentration of adsorbate

a definite mass (m) of adsorbent
 Langmuir isotherm: Problem 2

A known amount of activated carbon were added to the flasks to

treat the organic contaminants (COD) in 300 mL of an industrial
wastewater. Plot the Langmuir isotherm and determine the
values of the constants.
Flask No. Mass of activated Volume in Final COD
carbon (mg) flask (mL) (mg/L)
1 1035 300 2.5
2 765 300 4.6
3 610 300 8.4
4 430 300 19.5
5 280 300 56.4
6 210 300 78.3
7 0 300 150
 Answer
25

20
y = 35.537x + 9.488
R² = 0.9946
15
1/q

10

0
0 0.1 0.2 0.3 0.4 0.5
1/C
 Answer

intercept 1/Qm = 9.488

Qm = 0.1054

slope 1/KaQm = 35.54

KaQm = 0.02814
Ka = 0.2670

𝟏 𝟏 𝟏 𝟏
= +
𝒒 𝒒𝒎 𝑲𝑨 𝒒𝒎 𝑪

𝟏 𝟏 𝟏 𝟏
The Langmuir Equation: = +
𝒒 𝟎.𝟏𝟎𝟓𝟒 𝟎.𝟐𝟔𝟕𝟎 𝒙 𝟎.𝟏𝟎𝟓𝟒 𝑪