What is Adsorption Isotherm?
The process of Adsorption is usually studied through
graphs known 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 such as
Freundlich, Langmuir and BET theory.
Adsorption Isotherm Graph
BET adsorption Isotherm
BET Theory put forward by Brunauer, Emmett and
Teller explained that multilayer formation is the true
picture of physical Adsorption.
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.
MATHEMATICAL EXPRESSION
The BET equation is normally applied in its linear form
Va is the amount adsorbed at P/P0
Vm is the monolayer capacity
C is the emprical constant
PRINCIPLE
In a BET measurement, the sample are dried
with nitrogen purging, or in a vaccum applying
elevated temperatures.
The specific surface area of a powder is
determined by physical adsorption of a gas on
the surface of the solid and by calculating the
amount of adsorbate gas corresponding to a
monomolecular layer on the surface.
..continuing
This physical adsorption results from relating
weak forces between the adsorbate gas
molecules and the adsorbent surface area of the
test powder.
In a BET measurement the amount of nitrogen
absorbed to the surface of the material is
determined and this amount is translated into a
total surface area.
BET APPARATUS
TYPES OF NITROGEN ADSORPTION ISOTHERM
Type I Adsorption Isotherm
The above graph depicts Monolayer
adsorption.
This graph can be easily explained using
Langmuir Adsorption Isotherm.
If BET equation, when P/P0<<1 and
c>>1, then it leads to monolayer
formation and Type I Adsorption
Isotherm is obtained.
Examples of Type-I adsorption are
Adsorption of Nitrogen (N2) or Hydrogen
(H) on charcoal at temperature near to -
1800C.
Type II Adsorption Isotherm
Type II Adsorption Isotherm shows large
deviation from Langmuir model of
adsorption.
The intermediate flat region in the
isotherm corresponds to monolayer
formation.
In BET equation, value of C has to be
very large in comparison to 1.
Examples of Type-II adsorption are Nitrogen (N2
(g)) adsorbed at -1950C on Iron (Fe) catalyst and
Nitrogen (N2 (g)) adsorbed at -1950C on silica gel.
Type III Adsorption Isotherm
Type III Adsorption Isotherm also shows
large deviation from Langmuir model.
In BET equation value if C <<< 1 Type III
Adsorption Isotherm obtained.
This isotherm explains the formation of
multilayer.
There is no flattish portion in the curve
which indicates that monolayer formation
is missing.
Examples of Type III Adsorption
Isotherm are Bromine (Br2) at 790C on
silica gel or Iodine (I2) at 790C on silica
gel.
Type IV Adsorption Isotherm
At lower pressure region of graph is quite
similar to Type II. This explains formation of
monolayer followed by multilayer.
The saturation level reaches at a pressure
below the saturation vapor pressure .This
can be explained on the basis of a
possibility of gases getting condensed in the
tiny capillary pores of adsorbent at pressure
below the saturation pressure (PS) of the
gas.
Examples of Type IV Adsorption Isotherm
are of adsorption of Benzene on Iron Oxide
(Fe2O3) at 500C and adsorption of Benzene
on silica gel at 500C.
Type V Adsorption Isotherm
Explanation of Type V graph is similar
to Type IV.
Example of Type V Adsorption
Isotherm is adsorption of Water
(vapors) at 1000C on charcoal.
Type IV and V shows phenomenon of
capillary condensation of gas.
CONCLUSION
Therefore, BET measurements can be helpful in
characterizing the porosity of a metal powder.
Incase of irregularly-shaped powders, surface area
will be generally high. As a generalization, it can be
said that larger the specific surface lower will be
its apparent density.
