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C-05:- Surface Chemistry & Catalysis


1.ADSORPTION
The phenomenon of increase in concentration of the species on the surface of the solid than in the bulk is called adsorption. The
solid substance on the surface of which adsorption occurs is caled adsorbent and the molecuar species that get adsorbed on the
solid surface due to intermoecular attraction are called adsorbate.
The process of removal of an adsorbed substance from the surface is known as desorption.
Cause of adsorption: Adsorptin arises at the surface of solids as a result of the presence of unbalanced forces at the surface.
1.1 Types of adsorption
i) Physisorption: A process in which the particles of the adsorbate are held to the surface of the adsorbent physical forces such as van
der Waa forces.
ii) Chemisorption: A process in which the molecules of the adsorbate are held to the surface of the adsorbant by chemical forces.
1.1.1
Sr.
No.
1.
2.
3.
4.
5.
6.
7.

Physical Adsorption

Chemical Adsorption

The forces of attraction are weak van der Waal forces.


H is 20-40 kJ mol1
It is non-specific.
It is a reversible process.
It is multi-molecular in nature.
No appreciable activation energy is required.
It is also called van der Waal adsorption.

The forces of attracation are chemical forces.


H is 40400 kJ mol1.
He is specific in nature.
It is irreversibe process.
It is unimolecular in nature. i.e., it can form only one layer.
Activation energy is involved in this process.
It is also called Langmuir adsorption.

1.2 Enthalpy of Adsorption: The amount of heat evolved when one mole of an adsorable is adsorbed on the surface of an adsorbet is
called enthalpy of adsorption.
1.3 Factors on Which Extent Of Adsorption Depends
i) Nature of adsorbent .
ii) Natur of the adsorbate.
iii) Surface area of adsorbent. Greater the surface area greater is the adsorption.
iv) Nature of the gas adsorbed. The gas with higher critical temperature, has stronger van der Waals forces of attraction and hence is
adsorbed to a greater extent.
v) Temperature. Adsorption is an exothermic process involving equilibrium.
Gas (adsorbate) + Solid (adsorbent)

Gas adsorbed on solid + Heat.

According to Le-chatelier principle, increase in temperature decreases adsorption and vice versa.
vi) Pressure. Increase in pressure at constant temperatrue increases adsorption.
vii) Activation of the solid adsorbant i.e increasing the adsorbing power of the solid adsorbent. This is achieved by subdividing the
solid adsorbent or by removing the adsorbed gases on passing superheated steam.
The plots of extent of adsorption (x/m) versus prssure at constant temperature is called as adsorption isotherms.

i) At low pressures, the graph is a straight sloping ine and

x /m px /m=k p

ii) At high pressurs, the graph becomes independent of pressure,

x /m p0 x /m=kp0

iii) At intermediate pressure, x/m varies with the power of the pressure lying between 0 and 1,
1 /n

1 /n

x /m p x /m=kp

where n is an integer and k is a constant .

1.4 Langmuir Adsorption Isotherm: The main points of this theory are:i) The solid surface consists of a fixed number of adsorption sites where only adsorption of gaseous molecules can take place.
ii) Each site can hold only one gaseous molecules. Thus a gas on being adsorbed by solid surface cannot form a layer ore than one
molecule of thickness i.e. adsorption is unimolecular.
iii) Adsorption is localised and takes place only when gas molecules collide with vacant solid surfaces. Magnitude of adsorption of a
gas on a solid goes on increasing with increase in pressure until the entire surface of the solid gets completely covered by a
unimolecular layer of tha gas.
iv) Thickness of the adsorbed layer is the same as the thickness of the molecule of the adsorbate
v) The gaseous molecules adsorbed at different sites do not interact with each other.
vi) Heat of adsorption is the same for all the sites and is independent of pressure and fraction of the adsorbent surface covered.
vii) The phenomenon of adsorption involves a dynamic equillibrium and can be represented as:

G+S GS

Where, G,S and GS represent the unadsorbed gaseous molecule, the vacant site on the surface of adsorbent and the adsorbed
gaseous molecule respectively.
1.5 Derivation of Langmuir Adsorption Isotherm: Consider the dynamic equillibrium between free molecules and those adsorbed
on the fraction of the solid surface.
The concentration of adsorbed molecules G-S depends only on one factor, namely the number of occupied adsorption sites which in
turn is proportional to fraction
proportional to the fraction

of the surface covered with gaseous molecules. The rate of description or evaporation is

of the surface that is covered with gaseous molecules.

The concentration of vacant sites on the surface of an adsorbent will be directly proportional to fraction of the surface that remains
uncovered, i.e.

(1) . Therefore, the rate of adsorption or condensation will be proportional to ( 1 ) , i.e. the fraction of

surface covered. It also depends upon the pressure of the gas as according to the kinetic theory, the number of moecules striking per
unit area is prportional to the gas pressure, p.
Rate of adsorption or condensation
Rate of evaporation

( 1 ) p=k 1 ( 1 ) p

=K 2

(i)
A equilibrium

K 1 ( 1 ) p=k 2
K
( 2+ K 1 P )=K 1 P

K
( 1/ K 2) P
bP
=
1+ bP
K
1+ 1 P
K2
K1 P
=
=
K2+ K1 P

Where
Since

.(ii)

K 1 / K 2=b which is another constant.


is proportional to the amount of gas adsorbed per unit mass of the adsorbent

x
=K 3
m

(iii)

From (ii) and (iii)

x
bP
=K 3
m
1+ bP

This is known as Langmuir adsorption isotherm in which constant a and b depends upon the nature of the gas adsorbed, nature of
solid adsorbents and the temperature
As K3 and b are constant, so their product is also equal to constant say (a)

x
aP
=
m 1+bP

This is known as Langmuir adsorptin isotherm

For adsorption of solutes from solutions by solid adsobents. Freundlich equation is

x /m=KC 1/ n , where C is the

equilibrium concentration.
1.6 Adsorption isobar: Plots of extent of adsorption (x/m) versus temperature at constant pressure are called as adsorption isobars.

1.7 Adsorption
characterstics
adsorption:
i) The extent of adsorption (x/m) depends on the concentration (C) of the solute in solution.
ii) It is a reversible process.
iii) The adsorbed solute can be eluted by prolonged washings.
iv) Freundlich isotherm equation is also applicable to this type of adsorption Mathematically,

x /m=kC

for solutions: The following


are observed in this type of

1/ n

v) If there is more than one solute in solution, these compete with each other.
1.8 COLLOIDAL STATE
Substances have been classified into three types depending upon their particle size.
i) True solutions

( 1 nm)

ii) Colloidal solution


iii) Suspensions

( 100 nm )
nm

( 100 nm) .

2.1 Colloids: A heterogeneous system of two immiscible phases is called colloidal state. Among the two phases, one is a continuous
phase, called Dispersion Medium while the other is a discontinuous phase, called Dispersed Phase. The particle size of dispersed
phase ranges from

1 nm100 nm .

Some characteristic differences between them are listed below:

S.No.
1.
2
3.

Property
Particle size
Appearance
Settling

True solution
Less than 1 nm
Clear and transparent
Do not settle

Colloidal solution
Between 1-100 nm
Translucent
Do not settle under gravity,
but can be made to settle
under ultra-centifugation.

Suspension
More than 100 nm.
Opaque
Settle on standing under
gravity.

4.
5.
6.

Filtrability
Diffusion
Tyndall effect

Filterable through filter paper, parchment


membrane.
Diffuse quickly
No Tyndall effect

Not literable at all.


Pass through filter paper, non
filterable through parchment
membrane.
Diffuse slowly
Show Tyndall effect

Do not diffuse
Very little or no
Tyndall effect.

3. THE CLASSIFICATION OF COLLOIDS IS BASED ON


3.1 State of appearance i.e., rigid appearance (called gels) or fluid like appearance (called sols).
3.2 Classification based on affinity: The colloidal solutions in which the praticles of dispresed phase have a great affinity for the
dispersion medium are called lyophillic colloids whereas, the colloidal solutions in which the particles of the dispersed phase have
no affinity (rather have hatred) for the dispersion medium are called lyophobic colloids.
3.2.1 Characteristics of yophillic and lyophobic colloids.
3.2.1 Characteristics of lyophillic and lyophobic colloids

Sr. No.
1.

Lyophillic colloids
Ths are easily prepared and are self stabilised.

2.

Large quantities of electrolytes cause precipitation, smal


quantities have little effect.
Reversible
Surface tension is usually lower than that of dispersion
medium.
Viscosity is higher than that of dispersion medium.
Have higher concentration of dispersed phase.
Cannot be easily detected even with ultramicroscpe.
Do not exhibit Tyndal effect.
Highly solvated.
May or may not migrate in electric field.

3.
4.
5.
6.
7.
8.
9.
10.

Lyophobic colloids
These are difficult to prepare and need small quantities of other
substances for stabilisation.
Small quantities of electrolytes cause precipitation.
Irreversible
Surface tension is usually same as that of medium.
Almost same as that of dispersion phase.
Have lower concentration of dispersed phase.
Can be easily detected with utramicroscope.
Exhibit Tyndall effect
Not solvated.
Migrate in electric field.

3.3 Classification on the basis of size of dispresed phase particles


1.

Multimolecular Colloids
The consist of aggregates of a large number of atoms
of molecules with diameter less than 1 nm e.g. sols of
gold, sulphur

2.

Their molecular masses are not very high

3.

The atoms or molecules in them are held by weak Van


der Waals forces

4.

They are usually lyophilic in nature

Macromolecular Colloids
The particles of dispersed
phase themselves are of large
size e.g. polymers like nylon,
strach, protein, rubber etc.
They have high molecular
masses
The Van der Waals forces
holding the particles are
comparitively stronger due to
the presence of long chain.
They are usually lyophobic in
nature
They are usualy lyophobic in
nature

Associated Colloids
Behave as normal electrolytes at
low concentrations and as colloids
at higher concentrations due to the
aggregation of a large number of
ions in concentrated solutions
Their molecular masses are
generally high.
The Van der Waals forces depend
upon the concentration. Higher th
concentration, greater are the Van
der Waals forces.
Their molecules contain both
lyophilic and lyophobic groups

3.4 Charge on colloidal particles i.e., positive or negative colloids.


3.5 Types of Colloids: Since gases are miscible in all proportions, they do not form colloidal solutions. All other types of
combinations, gases, liquids and solids may exist as colloidal solutions. One phases acts as the dispersion medium while the other as
dispersed phase.
Various types of colloidal solutions

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S.No.
1.
2.

Dispersal Phase
Gas
Gas

Dispersion medium
Liquid
Solid

Designation
Foam
Solid foam

3.
4.
5.
6.
7.

Liquid
Liquid
Liquid
Solid
Solid

Gas
Liquid
Solids
Gas
Solid

Aerosol
Emulsion
Gel
Solid foam
Solid sol

Example
Whipped cream, soap-suds
Pumice stone, bread, foam rubber, styrene
foam.
Clouds, mists, fogs.
Milk, creams and other emulsions.
Cheese, jellies, curd, boot polish.
Smoke, volcanic dust, duststorm.
Coloured glass, precious stones, alloys,
minerals, pearls.

When dispersion medium is a gas, the colloidal system is called aerosol.


4. PROPERTIES OF COLLOIDS
Some characterstics properties shown by colloids are:
i) Sols ar heterogeneous.
ii) Colloidal particles have slow rate of diffusion through semipermeable membrance e.g., parachment paper.
iii) Colloidal particles pass through ordinary filter papers. S
iv) Colloidal particles do not settle down under the influence of gravity.
v) The colloidal particles cannot be seen even with a most powerful microscope as clear image formation of a particle smaller in size
than the wavelength of light used is not possible. However, zones of scattered light can be seen by microscope and sometimes with
naked eye also.
vi) Colligative properties: Like true solutions, colloidal solutions also exhibit coligative properties. These propertis depend upon the
number of particles present. Since colloidal particles have very large average moecular weights, the number of particles present in
solution for a given weight of the solute will be very low. Hence, the value of any colligative property for a substance in colloidal
solution will be very low as compared to its value if it forms a true solution.
vii) Tyndall effect(Optional property): The colloidal particles absorb light, became self luminous and thn scatter light in all possible
directions. Some examples of Tyndall effect are:
A. Blue colour of sky and sea water.
B. Visibility of tails of comets and twinking os stars.
C. Visibility f projector path and circus light.
D. Visibility of sharp ray of sunlight passing through a slit in dark room.
viii) Electrophoresis (Electrical property): The migration of colloidal particles towards the oppositely charged electrodes under the
influence of applied electric field is called electrophoresis. The electrical properties of colloids can also be explained by electrical
double layer theory. According to this theory, a double layer of ions appear at the surface of solid. The ion preferentially adsorbed
is held in fixed part and imparts charge to colloidal particles. The second part consists of both the types of charges.
A. This second layer consists of both the types of charges.
B. The net charge on the second layer is exactly equal to that on the fixed part.
The existence of opposite sign on fixed and diffuse parts of double layr leads to appearance of a difference of potential, known as
Zeta potential or electrokinetic potential. Now when electric field is employed the particles move and we have electrophoresis.
ix) Electro-osmosis: In it the movement of the dispersed partices are prevented from moving by semipermeable membrane. Electroosmosis is a phenomenon in which dispersion medium is allowed to move under the influence of an electrical field, whereas
colloidal particles are not allowed to move.
x) Borwnian Movement (Mechanical or Kinetic property): When a colloidal solution is examined under an ultramicroscope, the
colloidal particles are seen to be in a state of continuous, rapid, random motion. This phenomenon is known as Brownian
movement as it is more rapid in case of particles of smaller size and in less viscous dispersion medium. This movement is due to
the bombardment of solvent or medium particles over dispersed phase particles. Further this movement does not change with time
and exist till last. It offers explanation for the stability of colloidal solutions.
5. PREPARATION OF COLLOIDAL SOLUTIONS
The method of preparation depends on the nature of colloidal solution to be prepared. Some methods are:
i) By double decomposition:

As 2 O3 +3 H 2 S As 2 S3 +3 H 2 O
(Colloidal sol .)

ii) By reduction:

2 AuCl3 +3 SnCl2 2 Au+3 SnCl 4


(Gold sol)

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iii) By oxidation:

Br 2 + H 2 S 2 HBr+

(Colloidal sol)
iv) By hydrolysis:

FeCl3 +3 H 2 O Fe( OH )3+ 3 HCl


(Ferric hydroxide sol)

v) Exchange of solvent and Excessive cooling are other physical methods that can be employed to prepare colloidal solutions.
vi) Mechanical disintergration: It is carried with the help of colloidal mill. The substance is grinded virtually to the size of colloidal
particles.
vii) Ultrasonic dispersion: In this method the utrasonic vibrations having frequncy larger than audible range can change the coarse
suspension or liquids like oi, mercury etc., to colloida range.
viii) Bredigs arc method: This methode is employed to prepare colloidal solutions of metals. The method involves passing electric
current through electrodes made of metals whose solutions are to be prepared. A direct current is passed when an electric arc is
formed and the metal passed into solution is colloidal form. Purple of cassius a colloidal solution of gold is obtained by this
method.
ix) Peptisation: This method involves changing freshly prepared precipitates into colloidal form. Peptisation can be achieved as
follows:
A. By adding another colloid. For example, Lamp black is peptised by adding gums.
B. By washing precipitate. For example CuS and

BaSO 4 on washing continuously pass into colloidal form.

C. By adding organic solvents. For example, a colloidal solution of cellulose nitrate is prepared in ethyl alcohol and ether. The product
so obtained is commercially known as colloidion.
6. PURIFICATION COLLOIDAL SOLUTIONS
i) Dialysis: The separation of soluble impurities form a colloidal soution on the basis of their different rates of diffusion through a
parchemnt paper (semipermeable membrane) is known as dialysis. The small molecular or ionic species pass (diffuse) through the
membrane pores.
ii) Electrodialysis: in case of ionic nature of impurities, dialysis can be accelerated by taking advantage of electricity and the process
is known as electrodialysis.
iii) Ultrafiltration: These are specially prepared filters of uniform pore sizes obtained by dropping filters in collodion solution (4%
nitrocellulose in alcohol + ethers). The pore sizes of ultrafilters depend upon percentage of alcohol, ether as well as rate of drying.
By using ultrafilters colloidal particles can be retained on these while solvent along with the soluble impurities filter out.
iv) Ultracentrifuge is based on sedimentation technique.
7. COAGULATION OR FLOCCULATION
The phenomenon of the precipitaion of a colloidal solution by the addition of electrolyte is called coagulation or flocculation.
The minimum concentration of an electrolyte in millimoles per litre of the electrolyte solution which is required to cause the
coagulation or flocculation of colloidal sol is called Flocculation value.
Greater the coagulation power of effective ion, lower will be the flocculaiton value o the electrolyte containing the effective ion.
Therefore, Flocculation value

1
Coagulating power

Different electrolytes are known to have different coagulation values. The coagulation behaviour is governed by Hardy Schulze
rule according the which:
i) The ion having opposite charge to sol particles cause coagulation and
ii) Coagulation power of an electrolyte depend on the valency of ion i.e., greater the valency more is the coagulating power.
The decreasing order of flocculation vaue of electrolytes for a ve sol is

NaCl>BaCl 2> AlCl 3 > SnCl4

and the decreasing order of flocculation value of electrolytes for a +ve sol is

Fe
KCl> Na2 SO 4 > Na3 PO 4 > K 4

In addition, the colloids can be coagulated by many other ways.


i) Increase in temperature
ii) addition of dehydration agents
iv) Centrifugal fields
v) Presence of impurities.

iii) Agitation

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8. GOLD NUMBER
In order to measure the protective powers of hydrophilic colloids, term gold number is used. It is defined as the number of
milligrams of the protective colloid requird to just prevent the coagulation of 10 mL of red gold sol when 1 mL of 10% solution of
sodium chloride is added to it. Lower is the value of gold numbr greater is the protective power.
The gold numbers of a few protective colloids are given below
Gelatin

0.0050.01

Casein

0.010.02

Egg albumin

0.100.2

Gum Arabic

0.150.25

9. CONGO RUBIN NUMBER


Ostwald introduced Congo rubin number to account for protective nature of colloids. It is defined as the amount of protective
colloid in miligrams which prevents colour change in 100 mL of 0.01% Congo rubin dye to which 0.16 g equivalent of KCl is
added.
10. EMULSIONS
Emulsion is a colloidal soution o two immiscible liqui in which one liqui acats as the dispersed phase while the other iqui acts as the
disperse phase while the other liquid acts as the dispersion medium. There are two types of emulsions i.e.,
i) oil in water, (O in W)
ii) water in oil (W in O) emulsions
An oil in water emulsion consists of droplets of oil dispersed in water. In water in oil emulsions water is present as dispersed phase
with oil as dipersion (or continuous) medium. Which type of emulsion will form on mixing oil and water along with an emulsifying
agent will depend on the composition of the and water (usually the liquid with higher percentage becomes dispersion medium),
nature of emulsifying agent (usually a water soluble substance) stabilise (W) in (O) emulsion while oil soluble substance favours the
formation of (W) in (O) emulsions. For example, () in milk, emulsifying agent are albumin and caesin (ii) In code liver oil
emulsion, egg yolk + caesin + gums are emulsifying agents.
10.1 Properties of emulsions
S.No.
i)
ii)
iii)
iv)
v)
vi)
vii)
viii)
ix)

Property
Dispersed phase
Dispersion medium
Examples
Viscosity
Appearance
Electrical conductivity
Dilution Test
Spreading test
Dye test:Adding of oil soluble dye
like methylene blue

Water in oil
Water
Oil
Butter, cold cream, cod liver oil
More than water
Oily, opaque and translucent
Very low
More oil added is soluble but not water
Spreads easily on an oily layer.
Dye dissolved giving a bright coulor

Oil in water
Oil
Water
Milk, face creams, butter
creams
Slightly more than water
Watey, opaque and
tanslucent
Nearly equal to water.
More water added is soluble but not
oil
Spreads readily on watery layer
Dye remains insoluble in the orm of
coloured droplets.

10.2 Detection of type of emulsion. These can be detected by


i) Diffusion test
ii) Dye test
iii) Electrical conductivity
iv) Spreading test
v) Viscosity test
10.3 Role of Emulsions
i) Cleaning acation of soaps and detergents.
ii) Milk, cream, butter are all emulsions and are important constituents of our food
iii) Various cosmetics as cold cream, body lotions are emulsions.
iv) Digestion of fats in intestine is through emulsification.
v) Various oily drugs are administered as emuslsions for fast assimilation.
11. Gels are colloidal systems in which liquids are dispersed phase and solids act as dispersion medium. Gels may shrink by losing some
liquid held by them. This is known as Synereises or Weeping. Some gels are known to liquify on shaking and reset on being
allowed to stand. This reversible sol-get transformation is calel thixotropy. Gels are of two types
i) Non elastic. The are irreversible i.e., when dehydrate these change into powder which cannot be change back by addition of water.
ii) Elastic. These are reversibe i.e. these can be changed back into origina form even after dehydration.
12. CATALYSIS

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The process of enhancing the rate of chemical reaction by addition of a foreign substance (catalyst) is called catalysis. The catalyst
is specific in nature and enhance the rate of a particular reaction by providing an alternate path o low acativation energy.
12.1 Catalytic poisoning or inhibitor for catalyst: The phenomenon in which presence of a small amount of a certain substance
decreases or stops the activity of a catalyst.
For example:
i) Sulphur or quinoline acts as poison for Pd in Rosenmunds reduction.
ii) Arsenic acts as poison for Pt in correct process for

H 2 SO 4 .

iii) The precious metals present in the catalytic converters of automobiles are poisoned by the lead present in the leaded petrol. As such
only unleaded petrol is used in such automobiles.
The catalytic poisoning is specific in nature. In most of the cases substances poisonous for humans also act as poison for catalyst.
The catalytic poisoners are preferentially adsorbed on the surface of the catalyst to make it inert.
12.2 Catalytic Poisoning is of Two Types
S.No.

Permanent poisoning
The poisoners are held in active sites of
the catalyst by strong forces.
ii)
Catalyst surface is regenerated by scratching the surface.
Catalyst surface is regenerated only by
chemical treatment.
12.3 Promotor for catalyst: Catalytic promotion is the phenomenon in which the presence of a small amount of a certain substance
increases the activity of a catalyst.
For example
i)

Temporary poisoning
The poisoners are held in active sites of the catalyst by weak forces.

i) In the manufacture of

NH 3 by Haber process, Mo acts as a promotor of Fe used as catalyst in the fraction.

ii) In the Bosch process for

H 2 , Cr 2 O3 acts as a promotor for the catalyst

which help in increasing the rate of the reaciton.


13. TYPES OF CATALYST
i) Positive Catalyst:- increase the speed of reaction e.g Decomposition of

Fe2 O3 . The action of a promotor is probably due to

H 2 O2 in presenc of MnO2 .

ii) Negative Catalyst :- decreases the speed of reaction.


e.g Decomposition of

H 2 O2 in presence of Phosphoric acid.

(Phosphoric acid is used for preservation of

H 2 O2

14. TYPES OF CATALYSIS


14.1 Homogeneous Catalysis: When reactant, product as well as catalyst are in same phas, it is called homogeneous catayst and type of
catalysis is homogeneous catalysis. e.g.

2 SO 2 ( g )+O2 ( g) NO ( g ) 2 SO 3 (g)

2CO ( g )+ O2( g) NO ( g ) 2CO 2 (g)

+ ( aq )

CH 3 COOH ( l )+ C2 H 5 OH (l)

CH 3 COOC 2 H 5 ( l ) + H 2 O(l)
14.1.1 Theory o Homogeneous Catalysis:
i) Catalyst enters into chemical reactin and combine with one of the reactant to form intermediate comp.
ii) Intermediate comp decomposes with other reactants to produce product and catalyst is regenerated

A + B Product ( very slow )


A + BC Product (fast )

Theory:

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Step I :
Step II :

A +C AC ( Intermediate comp)
AC +B Product+ C

14.2 Heterogeneous Catalysis: When the catalyst is present in different phase than that of the reactant, it is calle a Heterogeneous
catalyst and is type of catalysis is called Heterogeneous catalysis (Surface catalysis) e.g.
i) Oxidation of sulphur dioxide to Sulphur triocide in presence of

V 2 O5 .

2 SO 2 ( g )+O2 ( g)
ii) Cracking of hydrocarbon in the presence of hydrogen to get lower alkane in presence of Zeolite catalyst.

iii) Stereospecific polymerization of ethylene on titanium IV chloride and Trialkyl aluminium (Zeigler Natta Catalyst)

14.2.1 Theory of Heterogeneous Catalysis


i) Chemisorption: Chemisorption of gaseous reactants on the catalyst surface.
ii) Diffusion and Chemical reaction on the surface.
iii) Description: Products formed on the solid surface are desorbed.
14.2.2 Aspects of Heterogeneous Catalysis
i) Activity: Activity of a catalyst to accelerate the chemical reaction.
ii) Selectivity: Activity to direct the reaction to get a yield of particular product excluding others.
15. ZEOLITES

Zeolites are the naturally occuring or synthetic microporous aluminosilicates of general formula

Mx
n

AlO

SiO
. xH 2 O where n is

the valency of metal ion. They are used as catalyst in peterochemical industry for cracking of hydrocarbons. The remarkable feature of
zeollite is shape selectivity which depend upon para size of the catalyst.
Zeolites have three-dimensional network silicates in which some silicon atoms are replaced by aluminium atoms generate one
negative charge on the alumino silicate frame work, substitution of x atoms generate x negative charge on alumino silicate frame
work, substitution of X atoms generate X negative charge on alumino silicate frame work. This charge is neutralized by exchangeable
cation M of valency n. The void space which cvan be greater than 50% of the volume is occupied by in molecules of water in the unit
cell.
Use of Zeolites
i)

Alcohols ZSM 5 hydrocarbons

( ZSM ' 5 Zeolites Sieve of Molecular Porosity 5 )


ii) Hydrated Zeolites are used in ion-exchangers in softening of hard water.
ILLUSTRATIVE EXAMPLES
i. SUBJECTIVE
EXAMPLE:1 When the rivers meet the ocean, they generally from delta.
EXAMPLE:2 Smoke is passed through charged plates before it is allowed to come out of chimeneys in factories.
EXAMPLE:3 Colloidal particles cannot be seen
EXAMPLE:4 Dust particles become visible when a strong beam of light passes through a cinema hall.
EXAMPLE:5 The coagulation of 10 mL of gold sol is just prevented by addition of 0.025 g of starch to it before adding 1 mL of
10% NaCl solution. Find the gold number of starch.
EXAMPLE:6 Why heat of chemisorption is more than heat of physisorption? ?
EXAMPLE:7 Why activated charocoal is a better adsorbent than ordinary charcoal?
EXAMPLE:8 Which colloidal sol is administered to a patient suffering from arsenic poisoning?

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EXAMPLE:9 On passing

H 2 S in cold, dilute solution during || gp analysis, some times yellow turbid solution is obtained

instead of precipitate.
EXAMPLE:10 During || gp analysis, passage of
EXAMPLE:11 The colour of

H 2 S some times brings in white turbidity in solution.

KMnO 4 discharges slowly in the beginning during the reaction with oxalic acid but fasterns

after some time. Why?


II. MULTIPLE CHOICE QUESTIONS (with only one correct choice)
EXAMPLE:12 The volume of gases

NH 3, CO 2CH 4 adsorbed by one gramof charcoal at 298 K are

A.

CH 4 >CO 2> NH 3

B.

NH 3 >CH 4 >CO 2

C.

NH 3 >CO 2 >CH 4

D.

CO2 > NH 3 >CH 4

EXAMPLE:13 Which of the following reaction gives a colloidal sol?


A.

MgCO 3 MgO+CO2

B.

2 Na+2 H 2 O 2 NaOH + H 2

C.

2 HNO3 +3 H 2 S 3 S +4 H 2 O+2 NO

D.

Cu+ CuCl2 Cu 2 Cl 2

EXAMPLE:14. Which of the following gases is adsorbed to maximum extent?


A. He
B. Ne
C. Ar
D. Xe
EXAMPLE:15 Clouds are colloidal solution of
A. liquid in gas
B. gas in liquid
C. liquid in liquid
D. solid in liquid
EXAMPLE:16 Gas mask contains:
A. charcoal granules
B. powdered charcoal
C. calcium carbonate
D. Fullers earth
EXAMPLE:17 Which of the following gas molecules have maximum value of enthalpy of physi-sorption in a gas mask?
A.

C2 H 6

B. Ne

C.

H2O

D.

H2

EXAMPLE:18 Milk can be preserved by adding a few drops of:


A. Formic acid solution
B. Formaldehyde solution
C. Acetic acid solution
D. Acetaldehyde solution.
EXAMPLE:19 Which of the following can cause coagulation of proteins?
A.

+
Ag

B.

+
Na

C.

2+
Mg

D.

2+
Ca

EXAMPLE:20 Action of catalyst depends upon:


A. mass
B. solubility
C. particle size
D. none of these.
EXAMPLE:21 Movement of dispersion medium under the influence of electric field is known as
A. electrodialysis
B. electrophoresis
C. electro-osmosis
D. cataphoresis.
EXAMPLE:22 Gold number of haemoglobin is 0.03. Hence, 100 mL of gold sol will require haemoglobin so that gold is not
coagulated by 10 mL of 10% NaCl solution
A. 0.03 mg
B. 30 mg
C. 0.30 mg
D. 3 mg
EXAMPLE:23 In the following isotherm

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A.

x
po when point A is reached
m

B. desorption may start alon AB


C.

x
p1/ n along OA
m

D. all of the above


EXAMPLE:24 Oil soluble due is mixed with emulsion and emulsion remains colourless. Then it is
A. O-in-W
B. W-in-O
C. O-in-O
D. W-in-W
EXAMPLE:25 Gold number of a lyophilic sol is such property that
A. the larger its vale, the greater is the peptising power
B. the lower its value, the greater is the peptising power
C. the lower its value, the greater is the protecting power
D. the larger its value, the greater is the protecting power.
EXAMPLE:26 Which of the following statements regarding adsorption is not correct?
A. Extent of adsorption of gases on charcoal increases with increase in pressure of the gas
B. Extent of adsorption is independent of temperature
C. Extent of adsorption by a given mass of adsorbent has an upper limit
D. Extent of adsorption is dependent on the nature of adsorbate and adsorbent
EXAMPLE:27 Which of the following represents a macromolecular colloidal particles?
A. Sol of gol
B. Cellulose
C. Soaps
D. Synthetic detergents
EXAMPLE:28 Which of the following statements is not correct?
A. Peptization is the process by which certain substances are converted into the colloidal state
B. Metals sols of gold, silver and platinum can be prepared by Bredigs arc method
C. Impurities present in a sol makes it more stable
D. Dialysis is a process to remove impurities of ions and molecules from a sol.
III. MULTIPLE CHOICE QUESTIONS (with more than one correct choice)
EXAMPLE:29 When gases are brought in contact with solid absorbents, in most cases
A. absorption involves multimolecular layer formation
B. the amount of absorption increases with the increase of the gas pressure
C. the amount of absorption increases with increase in temperature
D. the larger is the heat of condensation of the gas, greater would be its extent of adsorption
EXAMPLE: 30 Which is/are true statements
A. ammonia is absorbed by water
B. water vapour is absorbed by silica gel
C. chromatographic separation of organic compounds is based on the phenomenon of adsorption
D. oxygen is chemisorbed by charcoal
EXAMPLE:31 Which is/are correct statements about heterogeneous catalysis
A. The reactants molecules form an intermediate compound with the catalyst
B. The reactants get absorbed side by side on the catalyst surface and react
C. The products remain adhered to the catallyst
D. The products formed immediately leave the furface of the catalyst
EXAMPLE:32 Identify the incorrect statement regarding enzymes.
A. Enzymes are specifice biological catalysis that can normally function at very high temperature
B. Enzymes are normally heterogeneous catalysts that are very specific in action
C. Enzymes are specific biological catalysts that cannot be poisoned
D. Enzymes are specific biological catalysis that possess well defined active sites.
EXAMPLE:33 Which of the following statement (s) about zeolites is/are true?
A. They have open structure which enables them to take upo small molecules
B. Zeollites are alumina silicates having three dimensional network

( T 1000 K )

12

C. Some of the

SiO 4

9
5 AlO6
units are replaced by
ions in zeolites
AlO 4

D. They are used as cation exchangers


EXAMPLE:34 Which of the following statements are correct?
A.

k p E/ RT
=e
wherek p= Rate constant for reaction with catalyst.
ka

K a= Rate constant for reaction without catalyst


E= Difference in activation energy for the two ways of reactions.
B. Alcohol acts as a negative catalyst for the conversion of

Na 2 SO 3 Na 2 SO 4 .

C. TEL acts as a negative catalyst in the knocking of petrol


D. Dilute

H 2 SO 4 acts as a positive catalyst in the hydrolysis of esters to carboxylic acids and alcohols.

TRUE/FALSE
EXAMPLE:35 Catalyst makes the reaction more exothermic
EXAMPLE:36 Thermal decomposition of

KClO3 ( s) is presence of MnO2 ( s) is homogeneous catalysis.

EXAMPLE:37 Transition metals are more efficient catalyst.


EXAMPLE:38 The activity of catalyst increases in finely divided state or colloidal state.
EXAMPLE:39 Chemisorption is unilayer and more stronger.
EXAMPLE:40 The shape selective catalysts depend upon pore sizes.
EXAMPLE:41 Zymase is used to catalysed the hydrolysis of glucose.
EXAMPLE:42 Adsorption is a surface phenomenon.
EXAMPLE:43 Granular

V 2 O5 is used as catalyst for conversionof S into SO 2 in manufacature of H 2 SO 4 .

EXAMPLE:44 Combination of

N 2 and H 2 in presence of Fe as catalyst is an example of homogeneous catalysis

EXAMPLE: 45 A catalyst increases the rate of forward reaction without influencing that of reverse reactions.
FILL IN THE BLANKS
EXAMPLE:46 Butter is an example of .whereas milk is..emulsion.
EXAMPLE:47 Smoke is colloidal system of.dispersed in .
EXAMPLE:48 Ice cream is an example of..
EXAMPLE:49 Blood is..charged sol.
EXAMPLE:50 Gelatin is best protective colloid because its gold number is..
EXAMPLE:51 Lower is the critical micelle concentration of surfactant,.is the detergency.
EXAMPLE:52 Migration of sol particle under influence of electrical field is known as.
EXAMPLE:53 Purple of cassius is a colloidal solution of..in water.
EXAMPLE:54 Brownian motion is noticed upto particle size of..in solution.
EXAMPLE:55 More is the coagulation value of electrolyte, lesser it its

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