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Physical Adsorption
Chemical 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)
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.
x /m px /m=k p
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
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
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)
x
=K 3
m
(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
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
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)
( 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 .
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
Do not diffuse
Very little or no
Tyndall effect.
Sr. No.
1.
Lyophillic colloids
Ths are easily prepared and are self stabilised.
2.
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.
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.
3.
4.
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
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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.
As 2 O3 +3 H 2 S As 2 S3 +3 H 2 O
(Colloidal sol .)
ii) By reduction:
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iii) By oxidation:
Br 2 + H 2 S 2 HBr+
(Colloidal sol)
iv) By hydrolysis:
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
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
and the decreasing order of flocculation value of electrolytes for a +ve sol is
Fe
KCl> Na2 SO 4 > Na3 PO 4 > K 4
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
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.
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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
H 2 O2 in presenc of MnO2 .
H 2 O2
2 SO 2 ( g )+O2 ( g) NO ( g ) 2 SO 3 (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
Theory:
9
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)
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)
10
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
KMnO 4 discharges slowly in the beginning during the reaction with oxalic acid but fasterns
A.
CH 4 >CO 2> NH 3
B.
NH 3 >CH 4 >CO 2
C.
NH 3 >CO 2 >CH 4
D.
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
C2 H 6
B. Ne
C.
H2O
D.
H2
+
Ag
B.
+
Na
C.
2+
Mg
D.
2+
Ca
11
A.
x
po when point A is reached
m
x
p1/ n along OA
m
( T 1000 K )
12
C. Some of the
SiO 4
9
5 AlO6
units are replaced by
ions in zeolites
AlO 4
k p E/ RT
=e
wherek p= Rate constant for reaction with catalyst.
ka
Na 2 SO 3 Na 2 SO 4 .
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
EXAMPLE:44 Combination of
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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