Surface Chemistry and Colloids

1
Adsorption
 Adsorption

the phenomenon of accumulation of large number of

molecular species at the surface of liquid or solid
phase in comparison to the bulk.
 Adsorption

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. Adsorption is essentially a surface
phenomenon.
 uniform distribution of
Adsorption the substance
throughout the bulk

happens at the surface

of the substance
Absorption
 Two Components of Adsorption

Adsorbent Adsorbate

substance on the surface substance which is being

at which adsorption takes adsorbed on the surface
place of adsorbent.
 Facts About Adsorption Process

Adsorption is a Adsorption is an
spontaneous process. exothermic process.
 Types of Adsorption

Physical Adsorption or Physisorption

Chemical Adsorption or Chemisorption

 2
Adsorption
Isotherm
 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
have been Freundlich, Langmuir and BET theory.
Basic Adsorption Isotherm
Freundlich Adsorption Isotherm

Freundlich Isotherm

In 1909, Freundlich gave an empirical

expression representing the isothermal
variation of adsorption of a quantity of
gas adsorbed by a unit mass of solid
adsorbent with pressure.
Langmuir Adsorption Isotherm
BET Adsorption Isotherm
 Types of Adsorption Isotherm

Type 1
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.
 Types of Adsorption Isotherm

Type 2
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.
 Types of Adsorption Isotherm

Type 3
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.
 Types of Adsorption Isotherm

Type 4
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.
 Types of Adsorption Isotherm

Type 5
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.
 3
Chemical
Reactions
on
Surfaces
 Chemical Reactions on Surfaces

Unimolecular
Reaction
reactions involving a single
reacting substance. The
mechanism of the surface
catalyzed ammonia Molecularity
decomposition is usually
unimolecular. number of reactant
Bimolecular molecules that come
Reaction together during the course
reactions involving two reacting of reaction
substances. The kinetics of the
decomposition of acetaldehyde
on various surfaces can only be
interpreted on the hypothesis
that two acetaldehyde
molecules, adsorbed on
neighboring surface sites,
undergo a bimolecular reaction.
 Unimolecular Reactions

[] []
= =
+ + [] []

[] []
= = =
+ [] + +

Equation 1 Equation 2 Equation 3 Equation 4

Michaelis
Menten
equation
Bimolecular Reactions

23
 References:

http://www.chemistrylearning.com/adsorption/

http://www.chemistrylearning.com/adsorption-isotherm/
 ChE - 4102
Lopez, Laurence Troy

Surface Chemistry Lubay, Kathleen Mae

Lusanta, Evita
and Colloids
Magadia, Jesy
Manalo, Krystel Monica