ADSORPTION

Dr RASHA ELMHEIDI ELBAKUSH

ADSORPTION
• The phenomenon of attracting and retaining the
molecules of a substance on the surface of a liquid or
solid resulting in to higher concentration of the
molecules on the surface is called adsorption.
• The material which is
adsorbed is called the
adsorbate, and that which
does the adsoption is the
adsorbent.
Different between adsorption and
absorption
Type of adsorptions
• 1- physisorption; physical bonding between adsorbent and
adsorbate.
• 2- chemisorption; chemical bonding between adsorbent and
adsorbate.
• The differences between physisorption and chemisorption are
that physisorption is by weak bonds ( such as hydrogen bonding
, with energies up to 40 kj /mol) whilst chemisorption is due to
strong bonding (greater than 80 kj /mol). Physisorption is
reversible, whilst chemisorption is seldom ; physisorption may
progress beyond a single layer coverage of molecules on the
surface ( monolayer formation to multilayer formation ), whilst
chemisorption can only proceed to monolayer coverage.
 Solid/vapour interfaces
• There are many process at the solid/vapour
interface which are of pharmaceutical
interest, but the most important are water
vapour/solid interaction.

Adsorption isotherm
 Adsorption isotherms
• The process of Adsorption is usually studied
through graphs know as adsorption isotherm.
It is the graph between the amounts of
adsorbate (x) adsorbed on the surface of
adsorbent (m) and pressure at constant
temperature. Different adsorption isotherms
have been Freundlich, Langmuir and BET
theory.
A-Freundlich adsorption isotherm
 Frendlich adsorption isotherm
• From the graph, we can predict that after
saturation pressure Ps, adsorption does not
occur anymore. This can be explained by the
fact that there are limited numbers of
vacancies on the surface of the adsorbent.
 Freundlich adsorption isoterm:
• Freundlich gave an empirical expression representing the
isothermal variation of adsorption of a quantity of gas
adsorbed by unit mass of solid adsorbent with pressure. This
equation is known as Freundlich Adsorption Isotherm or
Freundlich Adsorption equation or simply Freundlich Isotherm.

at constant temperatur
• Where x is the mass of the gas adsorbed on mass m of the
adsorbent at pressure p and k, n are constants whose values
depend upon adsorbent and gas at particular temperature.
• The equation when written in the logarithmic
form yield a straight line.
• Log k, is the intercept on the ordinate, and 1/n
is the slope of the line
1/n can have any value between 0 and 1.
When 1/n(slop)=0 x/m = constant which show that adsorption is independent of
pressure
When 1/n(slop)=1 x/m=kp so x/m α p the adsorption various directly as per
pressure.
Limitation ………………………………………………….
1-The freundlich equation is empirical relationship between the quantity
of a gas adsorbed into a solid surface and the gas pressure and has no
theoretical basis.
2-The constant k change with change temperature.
3-It can not determine maximum adsorption capacity.
4-The equation is valid only at low pressure at high pressure it becomes
not linear(plot of log x/m against log p shows slight curvature at higher
pressures)
• The freundlich adsorption is valid as the plot
of log x/m versus p is straight line

• The freundlich adsorption isotherm followed

by another two isotherms, Langmuir and BET
theory.
 B-Langmuir Adsorption Isotherm

• Langmuir proposed another Adsorption Isotherm known as

Langmuir Adsorption isotherm. This isotherm was based on
different assumptions one of which is that dynamic equilibrium
exists between adsorbed gaseous molecules and the free
gaseous molecules.(rate of adsorption =rate of desorption)

• where A(g) is unadsorbed gaseous molecule, B(s) is unoccupied

metal surface and AB is Adsorbed gaseous molecule.
• Based on his theory, he derived Langmuir Equation which
depicted a relationship between the number of active sites of
the surface undergoing adsorption and pressure.
 Langmuir Adsorption Isotherm

• Where θ the number of sites of the surface which are

covered with gaseous molecule, P represents pressure
and K is the equilibrium constant for distribution of
adsorbate between the surface and the gas
phase .The basic limitation of Langmuir adsorption
equation is that it is valid at low pressure only. For
monolayer adsorption and homogeneous sites
• Limitation ………………………………………………….
• Langmuir assumes a homogenous surface with
specific adsorption site
• Applied for monolayer adsorption (freundlich
isotherm applied to multilayer adsorption on
heterogeneous sites confirmed by calorimetry)
• Interaction between adsorbed molecules is assumed
to be negligible
• The heat of adsorption is therefor independ of
coverage (∆H independent on θ)
C-BET EQUATION
• BET Theory put forward by Brunauer, Emmett and Teller
explained that multilayer formation is the true picture of
physical Adsorption.
• One of the basic assumptions of Langmuir Adsorption
Isotherm was that adsorption is monolayer in nature.
Langmuir adsorption equation is applicable under the
conditions of low pressure. Under the condition of high
pressure and low temperature, thermal energy of gaseous
molecules decreases and more and more gaseous molecules
would be available per unit surface area. Due to this
multilayer adsorption would occur. The multilayer formation
was explained by BET Theory. The BET equation is given as
Type of adsorption isoterms
Comparison between different isotherms
• Langmuir Type I adsorption isotherm(chemosorption)
• )non-porous). This isotherm shows that the extent
of adsorption increases with pressure until it
reaches saturation, at which point no further
adsorption occurs ( only monolayer).
• Type II adsorption Isotherm. )non-porous)
• It is obtained when the bilayer is formed only after
the monolayer has been fully formed, and the
trilayer is formed only after the bilayer has been
fully formed.
 Comparison between different isotherms
• Type III adsorption Isotherm )non-porous)
• It is obtained when the formation of monolayers, bilayers,
trilayers, and other layers all take place at the same time, resulting
in an almost exponential increase in the amount of adsorption.
• Type IV adsorption isotherm (porous)
• Type IV isotherm predicts the formation of two surface layers on
the plane surface or on the wall of a pore much wider than
mesoporous.
• Type V adsorption isotherm (porous)
• This type of adsorption isotherm is obtained only when
intermolecular attraction effects are large, and adsorption takes
place in pores and capillaries (capillary condensation).
Comparison between different isotherms
SOLID/LIQUID INTERFACES
• The usual pharmaceutical situation is to have a liquid (solvent),
particles of a solid dispersed in that liquid and another
component dissolved into the liquid (solute). To help stabilize the
suspension (keep the solid particles from joining together) there
may be a surface active agent dissolved in the water . The
surface active agent will adsorb on the surface of the powder
particles and help to keep them separated from each other. It is
also possible to use this surface interaction in the treatment of
drug overdose, where charcoal of high surface area can be
administered and the excess of drug in the patient's
gastrointestinal tract can be adsorbed from solution onto the
surface of the charcoal, which is then cleared from the patient.
 Factors Affecting Adsorption

Adsorption occurs on the surface of almost all

solids. However, the extent of adsorption of a
gas on the surface of a solid depends upon the
following factors:
• Nature and surface area of the adsorbent
• Nature of the adsorbed gas
• Temperature
• Pressure of the gas
• Nature and Surface Area of the Adsorbent
• Different solids would adsorb different amounts of
the same gas even under similar conditions.
Substances like charcoal and silica gel are excellent
adsorbents. The substances that are porous in nature
and have rough surfaces are better adsorbents.
• The extent of adsorption also depends upon the
surface area of the solid. Greater the surface area,
more is the surface available for adsorption and
greater is the adsorption.
• Nature of the Adsorbed Gas
• The gases which are more easily liquifiable or
are more soluble in water are more readily
adsorbed than others.
• Temperature………………………………….
• The extent of adsorption decreases with rise in
temperature. Adsorption is an exothermic process it would
be favored at low temperature. Therefore, the extent
of adsorption would increase on decreasing the temperature
and would decrease on increasing the temperature.
• The adsorption process is similar to the condensation
process. The reverse process is called desorption and
is endothermic in nature. It is similar to the evaporation
process.
• When a gas is kept in contact with a solid
adsorbent in a closed container, a dynamic
equilibrium is established in due course of time.
• gas (adsorbate) + solid (adsorbent) ⇌ gas
adsorbed on the solid + heat
Pressure of the gas…………………………….
• At a constant temperature the extent of
adsorption increases with increase in the
pressure of the gas (adsorbate).
 Application of adsorption
• Gas masks
• Production of vaccum
• Removal of moisture
• Removal of colour
• As catalysts
Electro kinetic properties of interfaces
• Most surfaces acquire a surface electric charge
when brought into contact with an aqueous
medium, in which charged particles (ions
and/or electrons)cross the interface between
two phases of matter such as the interface
between a solid and a liquid.
 electrical double layer EDL
• A double layer (DL, also called an electrical double
layer, EDL) is a structure that appears on the surface of
an object when it is exposed to a fluid. The object might
be a solid particle, a gas bubble, a liquid droplet , or a
porous body . The DL refers to two parallel layers of
charge surrounding the object. The first layer, the
surface charge (either positive or negative) comprises
ions adsorbed onto the object due to chemical
interactions (fixed layer). The second layer is composed
of ions attracted to the surface charge, electrically
screening the first layer.
• This second layer is loosely associated with
the object. It is made of free ions that move in
the fluid under the influence of electric
attraction and thermal motion rather than
being firmly anchored. It is thus called the
"diffuse layer".
• The figure illustrate a single solid particle in water showing a
negatively charged surface. The innermost layer or ‘halo’
around the particle has a predominance of positively-charged
ions. The outer layer or halo also has a predominance of
positively-charged ions, but to a lesser extent than the inner
layer. Finally the bulk vehicle has no overall net charge.
Charges in the inner layer are held tightly to the particle and
this is therefore known as the fixed layer, whereas charges
within the outer layer are more mobile and can move away
from the solid surface and hence this is denoted the ‘diffuse
layer’. The two layers, fixed and diffuse, are also known as the
Stern and Gouy-Chapman layers, respectively.
• The two parts of the double layer are separated by a plane,
the stern plane, at about a hydrated ion radius from the
surface; thus counter-ions may be held at the surface by
electrostatic attraction and the centre of these hydrated
ions forms the stern plane. The surface of loosely surround
layer named slipping plane .
• The electric potential decreases linearly from ψ0 (the
surface potential) to the Stern potential ψδ and then it
decays exponentially to zero in the diffuse layer.
• The potential at the slipping plane is termed the zeta ζ-
potential.
• The zeta potential is caused by the net
electrical charge contained within the region
bounded by the slipping plane, and also
depends on the location of that plane.
However, zeta potential is not equal to the
Stern potential or electric surface potential in
the double layer.
• The zeta potential is a key indicator of the stability of
colloidal dispersions. The magnitude of the zeta potential
indicates the degree of electrostatic repulsion between
adjacent, similarly charged particles in a dispersion. For
molecules and particles that are small enough, a high zeta
potential will confer stability, i.e., the solution or
dispersion will resist aggregation. When the potential is
small, attractive forces may exceed this repulsion and the
dispersion may break and flocculate. So, colloids with high
zeta potential (negative or positive) are electrically stabilized
while colloids with low zeta potentials tend to coagulate or
flocculate.