Chemistry

Surface Chemistry - 1
Session
Session Objectives
Adsorption
Adsorption versus absorption
Types of adsorption: physisorption and chemisorption
Desorption
Adsorption isotherms: Freundlich and Langmuir
Adsorption isobar
Catalysis
Adsorption
The phenomenon of higher concentration of any
molecular species at the surface than in the bulk
Adsorbent
The substance on the surface of which adsorption takes
place is called adsorbent
Adsorbate
The substance which is being adsorbed on the
surface of another substance.
Desorption
The process of removal of an adsorbed substance from
the surface on which it is absorbed
Activated Carbon
Activated Alumina
Silica Gel
Molecular Sieves (Zeolites)
Polar and Non-polar adsorbents
Adsorbent Materials
Made from nutshells, wood, and petroleum, bituminous
coal by heating in the absence of oxygen to dehydrate
and carbonize (remove volatile components),

"Activation" is the process that produces the porous
structure essential for effective adsorption by oxidation
of carbon with water vapor or CO
2
.

Activated carbon attracts non-polar molecules such as
hydrocarbons.

Typical surface areas are 300 to 1500 m
2
/g.
Activated carbon
Adsorption vs absorption
Types of Adsorption
Positive adsorption occurs when the
concentration of adsorbate is higher on the
surface of adsorbent than in the bulk.

Negative adsorption occurs when the
concentration of adsorbate is less on the
surface of adsorbent than in the bulk.
Types of adsorption
S. No. Physical adsorption Chemical adsorption
1 Caused by intermolecular van der
Waals' forces
Caused by chemical bond formation
2 It is not specific It is highly specific
3 It is reversible It is irreversible
4 Heat of adsorption is low (20-40 kJ/mol) High heat of adsorption (80-240 kJ/mol)
5 Low temperature is favourable Increases with high temperature
6 Results multilayer adsorption Results unimolecular layer
Comparison between physisorption and chemisorption
1. Physical adsorption

2. Chemical adsorption
Factors affecting adsorption
Effect of adsorbate: The easily liquifiable gases like NH
3
,
HCl, CO
2
etc. are adsorbed to a greater extent than the
permanent gases such as H
2 ,
O
2
, N
2
, etc.

Effect of specific area of the absorbent: The greater
the specific area of the solid, the greater would be its
adsorbing capacity.

Effect of temperature:adsorption decreases with increase
in temperature.

Effect of pressure: An increase in pressure causes an
increase in the magnitude of adsorption of an adsorbent.
1/ n
x
K p
m

Over a narrow range of p
Freundlich Isotherm
A graph between the amount (x/m) adsorbed by an
adsorbent and the equilibrium pressure of the adsorbate
at constant temperature is called adsorption isotherm
At low pressure the graph is nearly straight line
At high pressure x/m becomes
independent of p
0
x
p
m

1
x
p
m

Freundlich Isotherm
X 1
log logK logp
M n

Rate of adsorption
a a
r =k p(1- f)
Rate of desorption
d d
r =k f
At equilibrium, r
a
= r
d
;
a
a d
k p
f = .........(i)
k p+k
Mono-layer coverage
'
a
x
=k f .........(2)
m
m: mass of adsorbate adsorbed per
unit mass of adsorbent
f: fraction of surface area covered
f
1-f
p: partial pressure of the adsorbate
Langmuir isotherm
Langmuir adsorption isotherm:
ap
x / m
1 bp

The values of constants a and b depend

upon the nature of adsorbate, nature of solid
adsorbent and temperature.
a = k
a
x k
a
/k
d
b = k
a
/k
d
Combining equations (1) and (2):
Summary of adsorption isotherms
Easy to fit
adsorption data

Chemisorptions and
physisorption

Freundlich

Useful in analysis of
reaction mechanism
Chemisorption and
physisorption
Langmuir
Note Application Isotherm
equation
Name
1/n
x
=Kp
m
x ap
=
m 1+bp
Adsorption isobar
Graph between the amount adsorbed(x/m) and temperature
at a constant equilibrium pressure of adsorbate gas is known
as adsorption isobar
Chemisorption isobar shows an initial increase with temperature and
then expected decrease .The initial increase is because of the fact that
the heat supplied acts as activation energy required in chemisorption.
Application of Adsorption
In clarification of sugar

In gas masks

In catalysis

In adsorption indicators

In chromatographic analysis

In softening of hard water

In preserving vacuum

In paint industry

In removing moisture from air in the storage of
delicate instruments
Need to make chemicals faster
Most Reactions are too slow to be useful...
Ways to Make Chemicals Faster
Pressure
Disadvantage--Cause Explosions
Catalysts!!!!
Disadvantage--Costly
Disadvantage--Too hot!
Temperature
Add other Chemicals
Disadvantage--Separate chemicals
The Story of Catalysis
Why Catalysis ?

What is a Catalyst ?

How Catalysts Work ?
Role of a Catalyst
Catalysts speed up a chemical reaction
without being used up...
Catalyst + Reactants
Catalyst-Reactants
Catalyst + Products
Hydrogenation of alkene
Important properties of catalyst
Activity: A reasonable rate of reaction
is needed.
Selectivity: Byproducts should be
minimized.
Cost: The acceptable cost depends upon
the catalyst lifetime and product value.
Catalysis
Positive catalysis
Negative catalysis
Auto catalysis

2
MnO
3 2
270 C
2KClO 2KCl 3O

Alcohol
3 2 2
2CHCl O 2COCl 2HCl

3 2 5 2 3 2 5
CH COOC H H O CH COOH C H OH
Catalysis
Types of catalysis
Homogeneous catalysis
Process Products Catalyst
1. Hydrolysis of an ester. Acid and Alcohol H
+

2. Oxidation of SO
2
to SO
3
SO
3
NO
in lead chamber process
Heterogeneous catalysis
Process Products Catalyst
1. Ammonia synthesis NH
3

Fe with Al
2
O
3

2. Methanol synthesis MeOH ZnO/Cr
2
O
3
Catalysis
Enzyme catalysis
Reaction Catalyst
1. Invertase

2. Zymase
12 22 11 2 6 12 6 6 12 6
Sucrose Glucose Fructose
C H O H O C H O C H O
6 12 6 2 5 2
Glucose Ethanol
C H O 2C H OH CO
A coenzyme is an organic non-protein molecule that
is a functional part of an enzyme. Coenzymes are not
used up in the reactions in which they assist
Do Catalysts Live Forever?
NO!!!
They can die from:

-- poisons which contaminate the catalyst
-- large molecules which cover the catalyst
-- over heating, over pressurizing
-- crumbling/crushing
Automotive Emission Control
Automobile catalytic converters need to
catalyze several reactions
CH
x
+ O
2
CO
2
+ H
2
O
CO + O
2
CO
2
NO
x
+CH
x
N
2
+ H
2
O + CO
2
This is achieved by the use of a
supported precious metal catalyst like
platinum, palladium etc.
Catalyst needs O
2
to operate, CeO
2
acts
as a temporary regenerable source of O
2
.
CeO
2
Ce
2
O
3
+ 1/2O
2
Thank you