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Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Sorption
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Absorption, in chemistry, is a physical or


chemical phenomenon or a process in which
atoms, molecules, or ions enter some bulk
phase - gas, liquid or solid material.
This is a different process from adsorption,
since the molecules are taken up by the volume,
not by surface.
A more general term is sorption which covers
adsorption, absorption, and ion exchange.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

If absorption is a physical process not


accompanied by any other physical or chemical
process, it usually follows the Nernst partition
law:
"the ratio of concentrations of some solute species
in two bulk phases in contact is constant for a
given solute and bulk phases";

The value of constant KN depends on temperature and is called partition


coefficient.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

This equation is valid if concentrations are not


too large and if the species "x" does not change
its form in any of the two phases "1" or "2".
If such molecule undergoes association or
dissociation then this equation still describes the
equilibrium between "x" in both phases, but only
for the same form - concentrations of all
remaining forms must be calculated by taking
into account all the other equlilibria.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

In the case of gas absorption, one may calculate


its concentration by using e.g. the Ideal gas law,
c = p/RT. R = 8.314472Jmol K
Alternatively, one may use partial pressures
instead of concentrations.
1

In many technologically important processes,


the chemical absorption is used in place of the
physical process, e.g. absorption of carbon
dioxide by sodium hydroxide - such processes
do not follow the Nernst partition law.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

For some examples of this effect see liquidliquid extraction, it is possible to extract from
one liquid phase to another a solute without a
chemical reaction.
Examples of such solutes are noble gases and
osmium tetroxide.
In pharmacology (and more specifically
pharmacokinetics), absorption is the movement
of a drug into the bloodstream.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Absorption involves several phases. First, the drug


needs to be administered via some route of
administration (oral, via the skin, etc.) and in a
specific dosage form such as a tablet, capsule,
and so on.
In other situations, such as intravenous therapy,
intramuscular injection, enteral nutrition and
others, absorption is even more straight-forward
and there is less variability in absorption and
bioavailability is often near 100%.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Absorption is a primary focus in drug


development and medicinal chemistry, since
the drug must be absorbed before any
medicinal effects can take place.

Moreover, the drug's pharmacokinetic profile


can be easily and significantly changed by
adjusting factors that affect absorption.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Dissolution

In the most standard situation, a tablet is ingested


and passes through the gullet to the stomach.
Because the stomach is an aqueous environment,
this is the first place where a tablet will dissolve.
The rate of dissolution is a key target for
controlling the duration of a drug's effect, and as
such, several dosage forms that contain the same
active ingredient may be available, differing only
in the rate of dissolution.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

If a drug is supplied in a form that is not readily


dissolved, the drug may be released more
gradually over time with a longer duration of
action. Having a longer duration of action may
improve compliance since the medication will
not have to be taken as often. Additionally, slowrelease
dosage
forms
may
maintain
concentrations within an acceptable therapeutic
range over a long period of time, as opposed to
quick-release dosage forms which may result in
sharper peaks and troughs in serum
concentrations.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

The rate of dissolution is described by the


Noyes-Whitney equation as shown below:
Where:

is the rate of dissolution.


A is the surface area of the solid.
C is the concentration of the solid in the
bulk dissolution medium.
Cs is the concentration of the solid in the
diffusion layer surrounding the solid.
D is the diffusion coefficient.
L is the diffusion layer thickness.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

As can be inferred by the Noyes-Whitney


equation, the rate of dissolution may be
modified primarily by altering the surface
area of the solid.
The surface area may be adjusted by altering
the particle size (e.g. micronization).
The rate of dissolution may also be altered by
choosing a suitable polymorph of a
compound.
Specifically, cystalline forms dissolve slower
than amorphous forms.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Also, coatings on a tablet may act a barrier to


reduce the rate of dissolution. Coating may also
be used to modify where dissolution takes place.
For example, enteric coatings may be applied to a
drug, so that the coating only dissolves in the
basic environment of the intestines. This will
prevent release of the drug before reaching the
intestines.
Since solutions are already dissolved, they do not
need to undergo dissolution before being
absorbed.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Ionization
The gastrointestinal tract is lined with epithelial
cells. Drugs must pass through these cells in order
to be absorbed into the circulatory system. One
particular cellular barrier that may prevent
absorption of a given drug is the cell membrane.
Cell membranes are essentially lipid bilayers which
form a semipermeable membrane. Pure lipid
bilayers are generally permeable only to small,
uncharged solutes. Hence, whether or not a
molecule is ionized will affect its absorption, since
ionic molecules are considered charged molecules
by definition.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Due to the Henderson-Hasselbalch equation,


drugs that are weak acids (such as aspirin) will
be present mainly in their non-ionic form, and
weak bases will be in their ionic form. Since
non-ionic species diffuse more readily through
cell membranes, weak acids will have a higher
absorption in the highly-acidic stomach.
However, the reverse is true in the basic
environment of the intestines-- weak bases
(such as caffeine) will diffuse more readily
since they will be non-ionic.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

This aspect of absorption has been targeted by


medicinal chemistry. For example, a suitable
analog may be chosen so that the drug is more
likely to be in a non-ionic form. Also, prodrugs of
a compound may be developed by medicinal
chemists-- these chemical variants may be more
readily absorbed and then metabolized by the body
into the active compound. However, changing the
structure of a molecule is less predictable than
altering dissolution properties, since changes in
chemical
structure
may
affect
the
pharmacodynamic properties of a drug.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Adsorption
Adsorption is a process that occurs when a gas
or liquid solute accumulates on the surface of a
solid or, more rarely, a liquid (adsorbent),
forming a molecular or atomic film (the
adsorbate).
It is different from absorption, in which a
substance diffuses into a liquid or solid to form a
solution.
The term sorption encompasses both processes,
while desorption is the reverse process.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Adsorption is operative in most natural physical,


biological, and chemical systems, and is widely
used in industrial applications such as activated
charcoal, synthetic resins and water purification.

Adsorption, ion exchange and chromatography


are sorption processes in which certain
adsorptives are selectively transferred from the
fluid phase to the surface of insoluble, rigid
particles suspended in a vessel or packed in a
column.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Similar to surface tension, adsorption is a


consequence of surface energy. In a bulk
material, all the bonding requirements (be they
ionic, covalent or metallic) of the constituent
atoms of the material are filled. But atoms on the
(clean) surface experience a bond deficiency,
because they are not wholly surrounded by other
atoms. Thus it is energetically favourable for
them to bond with whatever happens to be
available. The exact nature of the bonding
depends on the details of the species involved,
but the adsorbed material is generally classified
as exhibiting physisorption or chemisorption
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Adsorption isotherms
Adsorption is usually described through
isotherms, that is, functions which connect the
amount of adsorbate on the adsorbent, with its
pressure (if gas) or concentration (if liquid).
The first isotherm is due to Freundlich and Kster
(1894) and it is a purely empirical formula valid
for gaseous adsorbates:

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

where
x is the adsorbed quantity,
m is the mass of adsorbent,
P is the pressure of adsorbate and
k and n are empirical constants for each
adsorbant-adsorbate pair at each temperature.
The function has an asymtotic maximum.
As the temperature increases, the adsorbed
quantity rises more slowly and more pressure is
required to achieve the maximum.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Langmuir isotherm

In 1916, Irving Langmuir published a new


isotherm for gases adsorbed on solids,
which retained his name. It is an empirical
isotherm derived from a proposed kinetic
mechanism.
It is based on four hypotheses:

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

1. The surface of the adsorbent is uniform, that is,


all the adsorption sites are equal.
2. Adsorbed molecules do not interact.
3. All adsorption occurs through the same
mechanism.
4. 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.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

These four points are seldom true: there are always


imperfections on the surface, adsorbed molecules
are not necessarily inert, the mechanism is clearly
not the same for the very first molecules as for the
last to adsorb.
The fourth condition is the most troublesome, as
often more molecules can adsorb on the
monolayer, but this problem is solved by the BET
isotherm.
Langmuir suggests that adsorption takes place
through this mechanism: A(g) + S AS, where A
is a gas molecule and S is an adsorption site.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

The direct and inverse rate constants are k and


k-1. If we define surface coverage, , as the
fraction of the adsorption sites occupied, in the
equilibrium we have
or

For very low pressures


and for high pressures

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

is difficult to measure experimentally;


usually, the adsorbate is a gas and the adsorbed
quantity is given at standard temperature and
pressure (STP) volume per gram of adsorbent.
Therefore, if we call vmon the STP volume of
adsorbate required to form a monolayer on the
adsorbant (per gram of adsorbent too)
and we obtain an expression for a

straight line:

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Through its slope and y-intercept we can obtain


vmon and K, which are constants for each
adsorbent/adsorbate pair at a given temperature.
vmon is related to the number of adsorption sites
through the ideal gas law. If we assume that the
number of sites is just the whole area of the solid
divided into the cross section of the adsorbate
molecules, we can easily calculate the surface area
of the adsorbent. Surface area of adsorbents
depends on their structure, the more pores they
have, the greater the area, which has a big
influence on reactions on surfaces.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

If more than one gas adsorbs on the surface, we


call E the fraction of empty sites and we have

and

where i is each one of the gases that adsorb.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Frumkin isotherm
Frumkin isotherm is an extension of Langmuir
isotherm. It states that adsorbed molecules do
interact and affect further adsorption by either
repulsion or attraction of molecules.
GFrumkin = GLangmuir 2gi
BET isotherm
Often molecules do form multilayers, that is,
some are adsorbed on already adsorbed
molecules and the Langmuir isotherm is not
valid.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

In 1938 Stephan Brunauer, Paul Emmett and Edward


Teller developed an isotherm that takes into account that
possibility. The proposed mechanism is now:
A(g) + S AS A(g) + AS A2S A(g) + A2S A3S
and so on

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Langmuir isotherm (red) and BET isotherm


(green). The derivation of the formula is more
complicated than Langmuir's. We obtain:

x is the pressure divided into the vapour pressure for the


adsorbate at that temperature, v is the STP volume of
adsorbed adsorbate, vmon is the STP volume of the amount
of adsorbate required to form a monolayer and c is the
equilibrium constant K we used in Langmuir isotherm
multiplied by the vapour pressure of the adsorbate.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

The biggest step in BET isotherm is to consider


that the successive equilibria for all the layers
except for the first are equal to the liquefaction of
the adsorbate.

Langmuir isotherm is usually better for


chemisorption and BET isotherm works better
for physisorption.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Adsorption enthalpy
Adsorption is an exothermic process because
energy is liberated, therefore enthalpy is always
negative. Adsorption constants are equilibrium
constants, therefore they obey van't Hoff's
equation:

As can be seen in the formula, the variation of K


must be isosteric, that is, at constant coverage.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

If we start from BET isotherm and assume that the


entropy change is the same for liquefaction and
adsorption we obtain Hads = Hliq RTlnc, that is
to say, adsorption is more exothermic than
liquefaction.

Adsorbents
Characteristics and general requirements
The adsorbents are used usually in the form of
spherical pellets, rods, moldings or monoliths with
hydrodynamic diameter between 0.5 and 10 mm.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

They must have high abrasion resistance, high


thermal stability and small micropore diameter,
which results in higher exposed surface area and
hence high capacity of adsorption. The adsorbents
must also have a distinct macropore structure
which enables fast transport of the gaseous
vapours.
Different types of industrial adsorbents used are:
Oxygen-containing compounds hydrophilic /
polar such as silica gel and hydrophilic zeolites
Carbon-based compounds hydrophobic / nonpolar such as activated carbon
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Polymer-based compounds-polar / non-polar


functional groups in porous polymer matrix.
Silica Gel
Silica gel is a chemically inert, nontoxic, polar
and dimensionally stable (< 400C) amorphous
form of SiO2. It is prepared by the reaction
between sodium silicate and sulphuric acid,
which is followed by a series of after-treatment
processes such as aging, pickling, etc. These after
treatment methods results in various pore size
distributions on its surface.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Silica is also used for drying of process air (e.g.


Oxygen, natural gas etc) and adsorption of higher
(polar) hydrocarbons from natural gas.
Zeolites
Zeolites are natural or synthetic aluminum
silicates which form a regular crystal lattice and
release water at high temperature. Zeolites are
polar in nature.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

They are manufactured by hydrothermal synthesis


of sodium aluminosilicate in an autoclave
followed by ion exchange with certain cations
(Na+, Li+, Ca++, K+). The channel diameter of
zeolite cages usually ranges from 2-9 . This
process is followed by drying of microcrystals,
which are palletized with a binder, to form
macropores and thermally activated at a
temperature of 6500C.
Zeolites are applied in drying of process air (only
traces), CO2 removal from natural gas, CO
removal from reforming gas and air separation.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Non-polar zeolites are synthesized by


dealumination of polar zeolites.
This is done by treating the zeolite with steam at
elevated temperatures, greater than 500 C (1000
F).
This high temperature heat treatment breaks the
aluminum-oxygen bonds and the aluminum atom
is expelled from the zeolite framework.
Non-polar zeolites are used in non-polar organics
removal.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Activated carbon
They are highly porous, amorphous solids
consisting of microcrystallites with a graphite
lattice. They are non-polar and cheap. One of their
main drawbacks is that they are combustible
Activated carbon can be manufactured from
carbonaceous
material,
including
coal
(bituminous, subbituminous, and lignite), peat,
wood, or nutshells (i.e., coconut). The
manufacturing process consists of
two phases, carbonization and activation.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

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 carbonization process is completed by
heating the material at 400600 C in an oxygendeficient atmosphere that cannot support
combustion.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

The carbonized particles are activated by


exposing them to an activating agent, such as
steam at high temperature. The steam burns off
the decomposition products from the
carbonization phase to develop a porous, threedimensional graphite lattice structure. The size
of the pores developed during activation is a
function of the time that they are exposed to the
steam. Longer exposure times result in larger pore
sizes.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

The most popular aqueous phase carbons are


bituminous based because of their hardness,
abrasion resistance, pore size distribution, and low
cost, but their effectiveness needs to be tested in
each application to determine the optimal product.
Activated carbon is used for adsorption of
organic substances and non-polar adsorptives
and it is also usually used for waste gas (and waste
water) treatment. It is the most widely used
adsorbent. Its usefulness derives mainly from its
large micropore and mesopore volumes and the
resulting high surface area.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Adsorption and Absorption

Adsorption in viruses
Adsorption is the first step in the viral infection
cycle. The next steps are penetration,
uncoating, synthesis (transcription if needed,
and translation), and release. The virus
replication cycle is similar, if not the same, for all
types of viruses. Factors such as transcription may
or may not be needed if the virus is able to
integrate its genomic information in the cell's
nucleus, or if the virus can replicate itself directly
within the cell's cytoplasm.
Lecturer N.Muthukrishnan, CARISM, SASTRA University