CE 6301 DR Hasan - Adsorption L3

Md. Mahmudul HASAN, Engr.
, PhD
Assistant Professor
Dept. of Civil Engg.
UAP
(Former Head of Civil Engg. Dept., UITS)
Lecture 04
Water Treatment
-- Adsorption
Dr. Engr. Md. Mahmudul HASAN
Adsorption
• Adsorption: The physical and/or chemical process in which a
substance/material is accumulated at the interface between the phases
which may be solid-liquid, liquid-liquid, gas-liquid or gas-solid.
• It is a surface phenomenon. It is the adhesion of atoms, ions,
biomolecules or molecules of gas, liquid, or dissolved solids to a surface.
• This process creates a film of the adsorbate on the surface of
the adsorbent.
• Adsorbate: the substance/material which is adsorbed at the surface of
another substance i.e. the substance being adsorbed (and so removed);
Examples: gases, dyes, water vapors etc.
• Adsorbent: the substance/material which adsorbs the other substance at
its surface i.e. the substance doing the adsorbing; Examples: activated
charcoal/carbon, bone charcoal, alumina, silica gel, kaolin and filler’s
earth.
• Adsorption is generally accompanied by release of energy, that is, most
adsorption processes are exothermic in nature.
2
Adsorption
Adsorption systems treat water by adding a substance to the water
supply.
The most commonly-used adsorbent is activated carbon
•Powdered activated carbon is often used when temporary quality
problems arise; it can simply be added to the water and discarded with
waste sludge.
•Granular activated carbon is often arranged in a bed through which
source water is slowly passed or percolated.
•Activated alumina treatment is used to attract and remove
contaminants, like arsenic treatment is used to attract and remove
contaminants, like arsenic and fluoride, which have negatively charged
3
Adsorption Vs Absorption
– Adsorption essentially happens at the surface of the substance.
– Absorption is dissolution of molecules within a phase, e.g., within
an organic phase in contact with an air or water phase. It means
uniform distribution of the substances throughout the bulk.
– Adsorption + Absorption = Sorption
4
4
Adsorption Vs Absorption
Adsorption
PHASE I
‘PHASE’ 2
Absorption (“partitioning”)
PHASE I
Henry’s Law
PHASE 2
5
Adsorption
6
Adsorption
7
Order of Adsorption
I. Liquid/ Solid adsorption

II. Solid/ Gas adsorption
III. Liquid/ Gas adsorption
IV. Liquid/ Liquid adsorption
8
Types/Mechanisms of Adsorption
Depending on the nature of the forces between adsorbate &

adsorbent, Adsorption is of two types:
1.Physical Adsorption or physisorption

2.Chemical Adsorption or chemisorption
Besides these, another type called Adsorption of Electrolytes is also
observed.
9
Physical adsorption (Physisorption)
• The forces of attraction between the molecules of the adsorbate and
the adsorbent are of the weak van der Waals' type.
• van der Waals forcesvan der Waals forces is the sum of the attractive or
repulsive forces between moleculesvan der Waals forces is the sum of
the attractive or repulsive forces between molecules (or between parts
of the same molecule) other than those due to covalent bondsvan der
Waals forces is the sum of the attractive or repulsive forces
between molecules (or between parts of the same molecule) other than
those due to covalent bonds or to the electrostatic interactionvan der
Waals forces is the sum of the attractive or repulsive forces
between molecules (or between parts of the same molecule) other than
those due to covalent bonds or to the electrostatic interaction of ions
with one another or with neutral molecules
• A van der Waals bonding already illustrates the difference in bonding
between two molecules and one molecule with a solid.
10
Chemical adsorption (Chemisorption)
• The forces of attraction between the adsorbate and the adsorbent are
very strong.
• the molecules of adsorbate form electrostatic chemical bonds with the
molecules of the adsorbent present in the surface.
ROH (aq) + SOH = SOR + H2O (aq)
R is metal ion adsorbate and S is metal oxide adsorbent
Adsorption of Electrolytes
• Adsorption of ionic species to surfaces by electrostatic attraction.
• Highly depends on pH and ionic strength. pH governs the stability of acids
and bases in polar water.
11
Physisorption Vs Chemisorption
Enthalpy is a measure of the total energyEnthalpy is a measure of the total energy of

a thermodynamic systemEnthalpy is a measure of the total energy of
a thermodynamic system. It includes the internal energyEnthalpy is a measure of the
total energy of a thermodynamic system. It includes the internal energy, which is the
energy required to create a system, and the amount of energy required to make
room for it by displacing its environment and establishing its volume and pressure.
Enthalpy of Physisorption, which is the enthalpy change for the adsorption of one 12
Surface Polarity and Adsorption
Adsorbents having affinity for non-polar substances such as fats,

oil, petrol/gasoline called as “hydrophobic” adsorbents.
13
Kinetics of Adsorption
14
Factors affecting Adsorption
15
16
17
18
Adsorption equilibria/ isotherm
• Adsorption is usually described through
isotherms
• If 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. The
equilibrium relationship is described by
isotherms.
• Adsorption equilibrium is a dynamic concept achieved when the rate
at which molecules adsorb onto a surface is equal to the rate at which
they desorb.
• isotherms is the amount of adsorbate on the adsorbent as a function
of its pressure (if gas) or concentration (if liquid) at constant
temperature.
• The quantity adsorbed is nearly always normalized by the mass of the
adsorbent to allow comparison of different materials. 19
Adsorption isotherm
• Most of the adsorption theories have been developed for gas solid
systems because the gaseous state is better understood than the liquid.
• Till now the statistical theories developed for gas – solid systems were
applied for liquid solid systems with little confidence for designing of
the equipment.
20
Adsorption isotherm
21
Adsorption isotherm models
• The figures below show that there are four common models for isotherms.
22
Some general isotherms
23
23
Freundlich: K Freundlich isotherm coefficient and n
• The amount of adsorbate adsorbed is a function of the liquid-
phase concentration and called adsorption equilibrium isotherm.
• Different functions can be used to describe the adsorption
equilibrium.
• Freundlich isotherm data can be used.
• This adsorption isotherm empirical equation is. 1.
0
0. n = 0.1
9
0.
8
n = 0.2
0.
n = 0.5
Mass Sorption
7
0.
• in which: 6
0.
5
• qmax = loading capacity (g/kg) 0.
4
n=1
0.
3
• cs = equilibrium concentration (g/m3) 0. n=2
2
0. n=5
• x = adsorbed amount of compound (g) 1
0.
0 0. 0.1 0. 0. 0. 0. 0. 0.7 0. 0. 1.
• m = mass of activated carbon (kg) 0 2 3Concentration
4 5 6 8 9 0
• K = Freundlich constant ((g/kg).(m3/g)n)

• n = Freundlich constant (-) 24
• The Freundlich constants K and n are influenced by water temperature, pH,
type of carbon and the concentration of other organic compounds.
• Using laboratory experiments the Freundlich constants can be determined
for a single substance with a specific type of activated carbon.
• Taking logs and rearranging:
log q = log K + n log Cs.
• When these graphs are plotted on a logarithmic scale the Freundlich
constant K can be determined from the intersection of the graph with the y-
axis.
• The slope of the line is equal to the Freundlich constant n.
• The higher the K-value, the better the adsorption.
25
26
Langmuir
• In 1916, Irving Langmuir published a new model isotherm for gases
adsorbed to solids. It is a semi-empirical isotherm derived from a proposed
kinetic mechanism.
It is based on four assumptions:
– The surface of the adsorbent is uniform, that is, all the adsorption sites are
equivalent.
– Adsorbed molecules do not interact.
– All adsorption occurs through the same mechanism.
– At the maximum adsorption, only a monolayer is formed: molecules of
adsorbate do not deposit on other, already adsorbed, molecules of adsorbate,
only on the free surface of the adsorbent.
• These four assumptions are seldom all true
27
Langmuir
• Langmuir suggested that adsorption takes place through this mechanism:
where Ag is a gas molecule and S is an adsorption site.

• Letting xo represent the total concentration of available sites on a given amount
of fresh solid substrate, we can define a fractional coverage (θ) as
(1)
where x is the concentration of occupied sites.
• The rate of adsorption va will be proportional to the concentration of gas or
liquid (c) above the surface and the fraction of the surface that is not covered
(1- θ), yielding a rate equation

(2)
where ka is the rate constant for adsorption. 28

Langmuir
• The rate of desorption is simply proportional to the fraction of the surface that
is already occupied, so the rate equation is
• (3)
• and kd is the rate constant for desorption. Setting equations (2) and (3) equal
yields an equilibrium statement that can be written as
(4)
•
The ratio of rate constants in equation (4) is equal to an equilibrium constant
(K = ka/kd).
• Upon substitution and further rearrangement, the fractional coverage is given
by
(5)

29

Langmuir
• Equation (5) is plotted for an arbitrary value of K, (is often called a Langmuir
absorption isotherm)
• The surface sites becomes saturated as the concentration rises.
• The magnitude of K quantifies the relative affinity that a given solute has for
surface adsorption.
• Like all equilibrium constants, K is temperature dependent.
fractional
coverage
30
BET Isotherm
• Often molecules do form multilayers, that is, some are adsorbed on already
adsorbed molecules and the Langmuir isotherm is not valid.
• In 1938 Stephen Brunauer, Paul Emmett, and Edward Teller developed a
model isotherm that takes that possibility into account. Their theory is
called BET theory, after the initials in their last names.
• They modified Langmuir's mechanism as follows:
• A(g) + S ⇌ AS
• A(g) + AS ⇌ A2S
• A(g) + A2S ⇌ A3S and so on
31
Adsorbent: Characteristics & Classes

• Adsorbents are used in the form of spherical pellets, rods, moldings, or
monoliths with hydrodynamic diameters between 0.5 and 10 mm.
• They must have high abrasion resistance, high thermal stability and
small pore diameters, which results in higher exposed surface area and
hence high surface capacity for adsorption.
• The adsorbents must also have a distinct pore structure which enables
fast transport of the gaseous vapors.
Most industrial adsorbents fall into one of three classes:
• Oxygen-containing compounds – Are typically hydrophilic and polar,
including materials such as silica gel and zeolites.
• Carbon-based compounds – Are typically hydrophobic and non-polar,
including materials such as activated carbon and graphite.
• Polymer-based compounds - Are polar or non-polar functional groups in
a porous polymer matrix. 32
Silica gel
• a chemically inert, nontoxic, polar and dimensionally stable (< 400 °C)

amorphous form of SiO2.
• Prepared by the reaction between sodium silicate and acetic acid,
which is followed by a series of after-treatment processes such as
aging, pickling.
• After treatment methods results in various pore size distributions.
• Silica is used for drying of process air (e.g. oxygen, natural gas) and
adsorption of heavy (polar) hydrocarbons from natural gas
• silica gel is a solid
• it has an average pore size of 2.4
nanometers and has a strong
affinity for water molecules .
33
Zeolites
• Natural or synthetic crystalline aluminosilicates.
• Having a repeating pore network and release water at high temperature.
• Zeolites are polar in nature. They are manufactured by hydrothermal synthesis
of sodium aluminosilicate or another silica source in an autoclave followed by
ion exchange with certain cations (Na+, Li+, Ca2+, K+, NH4+).
• The channel diameter of zeolite cages usually ranges from 2 to 9 Å.
• The ion exchange process is followed by drying of the crystals, which can be
pelletized with a binder to form macroporous pellets.
• applied in drying of process air, CO2 removal from natural gas, CO removal from
reforming gas, air separation
• Non-polar (siliceous) zeolites are synthesized from aluminum-free silica sources
or by dealumination of aluminum-containing zeolites. The dealumination
process is done by treating the zeolite with steam at elevated temperatures,
typically greater than 500 °C. This high temperature heat treatment breaks the
aluminum-oxygen bonds and the aluminum atom is expelled from the zeolite
framework.
34
Activated Carbon (AC)
35
Activated Carbon
• non-polar and cheap, highly porous, amorphous solid consisting of
microcrystallites with a graphite lattice
• Usually prepared in small pellets or a powder.
• Main drawbacks : reacts with oxygen at moderate temp (over 300 °C).
• manufactured from carbonaceous material, including coal, peat, wood, or
nutshells (e.g., coconut).
• The manufacturing process consists of two phases, carbonization and
activation.
• The carbonization process includes drying and then heating to separate
by-products, including tars and other hydrocarbons from the raw
material, as well as to drive off any gases generated.
• The process is completed by heating the material over 400 °C in an
oxygen-free atmosphere that cannot support combustion. 36
Activated Carbon
• The carbonized particles are then "activated" by exposing them to an
oxidizing agent, usually steam or carbon dioxide at high temperature.
• This agent burns off the pore blocking structures created during the
carbonization phase and so, they develop a porous, three-dimensional
graphite lattice structure.
• The size of the pores developed during activation is a function of the
time that they spend in this stage.
• Longer exposure times result in larger pore sizes.
• Activated carbon is used for adsorption of organic substances and non-
polar adsorbates and it is also usually used for waste gas (and waste
water) treatment.
• It is the most widely used adsorbent??? most of its chemical (eg.
surface groups) and physical properties (eg. pore size distribution and
surface area) can be tuned according to what is needed.
37
Activated Carbon
Activated Carbon Granular Activated Carbon Powder 38

Activated Carbon
39
Characteristics of Different Adsorbents
Table. Characteristics of Different Adsorbents
Type Characteristics Use Disadvantages
Activated Hydrophobic, favors Removal of organic Difficult to

Carbon organics over water pollutants regenerate
Zeolites Hydrophillic, polar, Air separation, Low total

regular channels dehydration capacity
Silica gel High capacity, Drying gas streams Trace removal
hydrophilic not effective
Activated High capacity, Drying gas streams Trace removal
alumina hydrophilic not effective
40
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Md. Mahmudul HASAN, Engr.

I. Liquid/ Solid adsorption

Depending on the nature of the forces between adsorbate &

1.Physical Adsorption or physisorption

Enthalpy is a measure of the total energyEnthalpy is a measure of the total energy of

Adsorbents having affinity for non-polar substances such as fats,

• K = Freundlich constant ((g/kg).(m3/g)n)

• These four assumptions are seldom all true

where Ag is a gas molecule and S is an adsorption site.

where ka is the rate constant for adsorption. 28

(5)

Adsorbent: Characteristics & Classes

• a chemically inert, nontoxic, polar and dimensionally stable (< 400 °C)

Activated Carbon Granular Activated Carbon Powder 38

Table. Characteristics of Different Adsorbents

Type Characteristics Use Disadvantages

Activated Hydrophobic, favors Removal of organic Difficult to

Zeolites Hydrophillic, polar, Air separation, Low total

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