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Chemistry

Session

Surface Chemistry - 1

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

Adsorbent Materials

Activated Carbon

Activated Alumina

Silica Gel

Molecular Sieves (Zeolites)

Polar and Non-polar adsorbents

Activated carbon

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 CO2.

Activated carbon attracts non-polar molecules such as


hydrocarbons.

Typical surface areas are 300 to 1500 m2/g.

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
1.

Physical adsorption

2.

Chemical adsorption

Comparison between physisorption and chemisorption


S. No. Physical adsorption
Chemical adsorption
1
Caused by intermolecular van der
Caused by chemical bond formation
Waals' forces
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
6

Low temperature is favourable


Results multilayer adsorption

Increases with high temperature


Results unimolecular layer

Factors affecting adsorption


Effect of adsorbate: The easily liquifiable gases like NH 3,
HCl, CO2 etc. are adsorbed to a greater extent than the
permanent gases such as H2 ,O2, N2, 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.

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

x
p1
m
At high pressure x/m becomes
independent of p

x
p0
m
Over a narrow range of p

x
K p1/ n
m

log

X
1
logK logp
M
n

Freundlich Isotherm

Langmuir isotherm
f: fraction of surface area covered
p: partial pressure of the adsorbate

m: mass of adsorbate adsorbed per


unit mass of adsorbent

1-f

Rate of adsorption ra =k ap(1- f)


Rate of desorption rd =k df
At equilibrium, ra = rd; f =
Mono-layer coverage

k ap
.........(i)
k ap+k d

x
=k 'af .........(2)
m

Langmuir adsorption isotherm:


Combining equations (1) and (2):

x/m

ap
1 bp

a = ka x ka/kd
b = ka/kd
The values of constants a and b depend
upon the nature of adsorbate, nature of solid
adsorbent and temperature.

Summary of adsorption isotherms


Name

Isotherm
equation

Application

Note
Useful in analysis of
reaction mechanism

Langmuir

x
ap
=
m 1+bp

Chemisorption and
physisorption

Freundlich

x
=Kp1/n
m

Chemisorptions and Easy to fit


physisorption
adsorption data

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


Temperature
Disadvantage--Too hot!

Add other Chemicals


Disadvantage--Separate chemicals

Pressure
Disadvantage--Cause Explosions

Catalysts!!!!
Disadvantage--Costly

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

2KClO3

MnO2

270 C

2KCl 3O2

Negative catalysis

2CHCl3 O2

Alcohol

2COCl2

2HCl

Auto catalysis
CH3 COOC2H5 H2O

CH3 COOH

C2H5OH

Catalysis
Types of catalysis
Homogeneous catalysis

Process
1. Hydrolysis of an ester.
2. Oxidation of SO2 to SO3
in lead chamber process

Products
Acid and Alcohol H+
SO3

Heterogeneous catalysis
Process

Products

Catalyst

1. Ammonia synthesis

NH3

Fe with Al2O3

2. Methanol synthesis

MeOH

ZnO/Cr2O3

Catalyst
NO

Catalysis
Enzyme catalysis
Reaction

Catalyst

1. C12H22O11 H2 O C6H12O6 C6H12O6


Sucrose

Glucos e

2. C6H12O6 2C2H5 OH CO2


Glucos e

Invertase

Fructose

Zymase

Ethanol

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
CHx + O2 CO2 + H2O
CO + O2 CO2
NOx +CHx N2 + H2O + CO2
This is achieved by the use of a
supported precious metal catalyst like
platinum, palladium etc.
Catalyst needs O2 to operate, CeO2 acts
as a temporary regenerable source of O 2.
CeO2 Ce2O3 + 1/2O2

Thank you