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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 Low temperature is favourable Increases with high temperature
6 Results multilayer adsorption Results unimolecular layer
Factors affecting adsorption
Effect of adsorbate: The easily liquifiable gases like NH3,
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
m
K p1/ n
x
Freundlich Isotherm
M n
log logK logp
X 1
Langmuir isotherm

f: fraction of surface area covered

p: partial pressure of the adsorbate


f
m: mass of adsorbate adsorbed per
1-f
unit mass of adsorbent

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

Rate of desorption rd =k df

k ap
At equilibrium, ra = rd; f = .........(i)
k ap+k d

x
Mono-layer coverage =k 'af .........(2)
m
Langmuir adsorption isotherm:
Combining equations (1) and (2):

ap
x /m
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 Application Note


equation
Langmuir x ap Chemisorption and Useful in analysis of
=
m 1+bp physisorption reaction mechanism
Freundlich x Chemisorptions and Easy to fit
=Kp1/n physisorption adsorption data
m
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 Pressure

Disadvantage--Too hot! Disadvantage--Cause Explosions

Catalysts!!!!
Add other Chemicals

Disadvantage--Separate chemicals 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

MnO
2KClO3
2 2KCl 3O
2
270 C

Negative catalysis

Alcohol
2CHCl3 O2 2COCl2 2HCl

Auto catalysis

CH3COOC2H5 H2O CH3COOH C2H5OH


Catalysis
Types of catalysis

Homogeneous catalysis

Process Products Catalyst


1. Hydrolysis of an ester. Acid and Alcohol H+
2. Oxidation of SO2 to SO3 SO3 NO
in lead chamber process

Heterogeneous catalysis

Process Products Catalyst


1. Ammonia synthesis NH3 Fe with Al2O3
2. Methanol synthesis MeOH ZnO/Cr2O3
Catalysis

Enzyme catalysis

Reaction Catalyst
1. C12H22O11 H2O C6H12O6 C6H12O6 Invertase
Sucrose Glucose Fructose

2. C6H12O6 2C2H5OH CO2 Zymase


Glucose 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 O2.
CeO2 Ce2O3 + 1/2O2
Thank you