ADSORPTIONS

When a gas is adsorbed, the freedom of

movement of its molecules become restricted.
This leads to decrease in the entropy of the gas
after adsorption, i.e., S is negative
Adsorption is accompanied by decrease in
enthalpy as well as decrease in entropy of the
system.
For a process to be spontaneous, the
thermodynamic requirement is that, at constant
temperature and pressure, G must be
negative,
, G = H TS, G can be negative if H has
sufficiently high negative value as TS is
positive.
Types of Adsorption

Adsorption :- The binding and accumulation

of molecules at the surface more than bulk
Adsorbate :- The substance, accumulates at
the surface
Adsorbent :- the material on the surface of
which the adsorption takes place

Distinction between Adsorption and

Absorption
In adsorption, the substance is concentrated
only at the surface
while in absorption, the substance is uniformly
distributed throughout the bulk of the solid
SORPTION is used to describe both Both
adsorption and absorption simultaneously
Adsorption in action
(i) If a gas like O2, H2, CO, Cl2, NH3 or SO2 is
taken in a closed vessel containing powdered
charcoal, it is observed that the pressure of the
gas in the enclosed vessel decreases. The gas
molecules concentrate at the surface of the
charcoal, i.e., gases are adsorbed at the surface.

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Desorption.
The process of removing an adsorbed substance
from a surface on which it is adsorbed is called
desorption.

How adsorption take palce

Factors affecting adsorption
Effect of adsorbate: The amount of gas
adsorbed by a solid depends upon the nature of
gas.
In general, more easily liquefiable a gas is
(i.e. higher its critical temperature), the more
readily will it be adsorbed. Thus 1gm of
activated charcoal adsorbs 380 ml of sulphur
dioxide (critical temperature 157C), 16 ml of
methane (critical temperature 83C) and 4.5
ml of hydrogen (critical temperature 240C).
This is valid for physical adsorption only.

Surface has unbalanced or residual attractive

forces. These forces of the adsorbent are
responsible for attracting the adsorbate
particles on its surface
During adsorption, there is always a decrease in
residual forces of the surface, which make
surface most stable
Thermodynamics of adsorptions
new bonds and attraction forces between
adsorbent and adsorbate , are formed,which
relase energy hence adsorption is Exothermic
H of adsorption is always negative.

Since Chemical Adsorption is

Specific in nature, it occurs only if the gas can
form a chemical bond with the solid.

 Effect of surface area [specific area] of

the absorbent: The greater the surface area
of the solid, the greater would be its adsorbing
capacity.
Effect of temperature: Physical adsorption
decreases with increase in temperature.
Effect of Pressure
as physical adsorption is reversible in nature and is
accompanied by decrease in pressure. Therefore, it
is expected that extent of adsorption increases with
increase in pressure and decrease in pressure
causes desorption.
The extent of adsorption is generally
expressed as x/m where m is mass of adsorbent
and x is mass of adsorbate when equilibrium has
attained.
The graph between extent of adsorption
(x/m) and the pressure P of gas at constant
temperature is calledAdsorption Isotherm.
This is a simple type of adsorption isotherm in
which at equilibrium pressure Ps, reaches its
maximum value and no more adsorption takes
place even if the pressure is further increased.
This state is also called SaturationState
and the corresponding pressure (Ps) is
called Saturation Pressure.

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The following adsorption isotherms are at

different temperature

Such isotherms are obtained in cases where

adsorbing gases forms unimolecular layers on
the surface of adsorbent and adsorbing gas
behaves ideally in vapour phase.

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Activationof adsorbent
increasing the surface area of solid adsorbent
by converting into fine powder
To make it more efficient in adsorbing the
molecules
Activated charcoal is used in gas masks as it
adsorbs all the toxic gases and vapours and
purifies the air for breathing.

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x/m = k.p1/n(n>1)(i)
x/m= extent of adsorbtion
where x is the mass of the gas adsorbed on mass
m of the adsorbent at pressure P, k and n are
constants which depend on the nature of the
adsorbent and the gas at a particular
temperature. The relationship is
log x/m = log k+ 1/n log (ii)

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Adsorption from Solution Phase

Solids can adsorb solutes from solutions also
When a solution of acetic acid in water is shaken
with charcoal, a part of the acid is adsorbed by the
charcoal
and the concentration of the acid decreases in the
solution
(i) x/m decreases with an increase in temperature.
(ii) x/m increases with an increase of surface area
of the adsorbent.
(iii) x/m depends on the concentration of the
solute in solution.
(iv) x/m adsorption depends on the nature of the
adsorbent and the
Applications of Adsorption
(i) Production of high vacuum
(ii) Gas masks
(iii) Control of humidity
(iv) Removal of colouring matter from
solutions
(v) Heterogeneous catalysis
(vi) Froth floatation process
(vii) Chromatographic analysis
(ix) Separation of inert gases

Adsorptions

COLLOIDS

Colloids :-It is a heterogenous mixture with

Size of
particles between 1nm to 1000 nm

Solute and solvent are replaced by dispersed

phase & dispersion medium
Its not a type of substance but a state of
substance

DISPERSED DISPERSION

PHASE

MEDIUM

TYPE OF

COLLIDE

EXAMPLES

Solid

Solid

Solid Sol

Some colored
glasses and
gem stones

Solid

Liquid

Sol

paints , cell
fluids

Solid

Gas

Aerosol

Smoke, dust

LiQuid

Solid

Gel

Liquid

ch

Milk , hair
Emulsion cream

Liquid

Gas

Aerosol

Fog, Mist,
Cloud,
insecticide
sprays

Gas

Solid

Solid Sol

Pumice Stone,
Foam Rubber

Foam

Froth,
whipped
cream, soap
lather

Gas

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Liquid

Liquid

self-stabilizing
reversible sols
example, gums, gelatin, starch, albumin in water
Lyophobic colloids (solvent hating colloids )
Can not be formed on simply mixing with a
suitable liquid
e.g. When metals and their sulphides simply
dispersion medium, they dont form colloids.
need stabilizer to preserve them.
Irreversible i.e easy separation but difficult to re
formation .
colloidal solutions of gold,silver, Fe(OH)3, As2S3,
etc.
Classification based on type of particles of
the dispersed phase
Macromolecular colloids:
the single molecules is large enough to have sizes
of a colloidal particles.e.g,proteins, starch,
cellulose
Multimolecular colloids : ,
a large number of atoms or smaller molecules of a
substance aggregate together to form species
having size in the colloidal range Consists of
a gold sol , Sulphur sol consists of particles of S8
sulphur molecules.
Associated colloids: At low concentrations, behave as normal, strong
electrolytes solutions But At higher
concentrations exhibit colloidal state properties
due to the formation of aggregated particles
(micelles)

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Cheese,
butter, jellies

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Classification based on nature of

interaction
Lyophilic colloids (solvent attracting)
Directly formed by on mixing with a suitable
liquid
like gum, gelatine rubber etc.).

Critical Micelle Concentration

The formation of micelles takes place only
and above a particular conc. called CMC

 formation of micelles takes place only

at a particular temperature called
Kraft temperature (Tk)
Properties of colloids
Brownian movement: Zig- zag movement of
colloidal particles in a colloidal sol
(1)
Tyndall effect:When a beam of light is allowed
to pass through a colloidal solution, the path of
light is visible and illuminated due to scattering
of light by colloids
Electrical properties of Colloidals
Electrophoresis The movement of colloidal
particles under an applied electric potential is
called electrophoresis

The existence of charge on colloidal particles is

confirmed by electrophoresis experiment
Electroosmosis movement of the dispersion
medium in an electric field.
Theory of charge formation on colloids
particles
(i) Due to the dissociation of the surface
molecules
C15H31COONa C15H31COO + Na+
Sodium palmitate
(ii) Due to selective adsorption of ions
particles adsorb the ions ..
common with their own lattice ions and
present in excess
e.g colloid of AgI can adsorb either Ag+ or Iwhich ever is in excess

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(+)ve colloid particles :- Metal hydroxides:

Al(OH)3, Fe(OH)3 Metal oxide : TiO2
Stability of lyophobic colloidal system
The stability of the lyophobic sols is due to the
presence of charge on colloidal particles.
(dispersed phase) because this charge do not let
the particles come closer and aggregates to settle
down to form ppt
Coagulation or precipitation: it is
aggregation of colloidal particle which leads to
settle down as Ppt
If, somehow, the charge is removed, the particles
will come nearer to each other to form aggregates
(or coagulate) and settle down under the force of
gravity
Methods of coagulations
All methods help in removing or neutralize the
charge from colloidal particle so they can come
together and form Ppt
1) By electrophoresis
(2) By mixing two oppositely charged sols
(3) By addition of electrolytes
(4) By persistent dialysis
The ions carrying the charge opposite to that of
sol neutralise the charge of colloid particles and
causes coagulation of the sol
Hardy-Schultz Rule The coagulation of a
colloidal solution by an electrolyte does not
take place until the added electrolyte has
certain minimum concentration in the solution.
The minimum amount of an electrolyte
(millimoles) that must be added to one litre of a
colloidal solution so as to bring about complete
coagulation or flocculation is called
the Coagulation or Flocculation Value of
the Electrolyte. Thus smaller is the
flocculation value of electrolyte, greater is its
coagulation or precipitating power.
Different electrolytes have different coagulation
values. The coagulation behaviour of various
electrolytes was studied
by Hardy and Schultz. They gave a
generalisation known as Hardy Schultz
Law, which states,
Greater the valency of oppositely
charged ions of the electrolyte being
added, the faster is coagulation.
So, for coagulation of sols carrying negative
charge Al3+ ion is more effective than Ba2+ions
or Na+ ions. Similarly for coagulation of
positively charged sols ion is more effective
than or ions.

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Examples of charged colloidal particles

(-)ve collod particles :-Metal sulphides: As2S3,
CdS
Metal dispersions : Ag, Au, P

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7. Formation of delta
8. Photography
9. Artificial rain

Thus in case of positively charged sol the

coagulating power of anions is in the order of

and in case of negatively charged sols, the

coagulating power of cations is in the order
of Al3+ > Ba2+ > Na+
Coagulation or flocculation value
The number of millimoles of an electrolyte
required to bring about the coagulation of one
litre of a colloidal solution is called its flocculation
value.
Coagulation value or flocculating value
1/Coagulating power
Peptization : Process of converting a precipitate
into colloidal particles on adding suitable
electrolyte is known as peptisation
e.g. Fe(OH)3 solution is formed from FeCl3.
Electrol-disintegration (Bredigs arc
method)
Preparation of colloid , when alternating
current passed through a metal( gold) electrode
,it gives Electrical disintegration to form colloids
of metals like gold
Dialysis :- It is a Purification method of
colloids
The process of separating the colloidal particles
from those of crystalloids by diffusion of mixture
through a parchment or animal membrane is

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EMULSION
An Emulsion is a colloidal solution in
which both dispersion medium as well as
dispersed phase are liquids. (The liquids
should be Immiscible).
Preparation
The substances thus to stabilize the emulsions are
calledEmulsifiers or Emulsifying Agents
The commonly used emulsifying agents are soaps,
proteins, long chain sulphonic acids,
Types of Emulsion
Emulsion is colloidal solution of two immiscible
liquids. So there are two types of Emulsions.
i). Oil-in-water type (o/w type)
ii). Water-in-oil type (w/o type)
i).
Oil-In-Water Emulsions
In this emulsions, oil acts as disperse phase and
water acts as dispersion medium. Eg . are milk,
vanishing cream etc.
ii). Water-In-Oil Emulsions
In this water acts as dispersed phase and oil acts
as dispersion medium. For example, butter, cod
liver oil, cold cream etc.
Identification of Emulsions
The following tests may be employed to
distinguish between two types of emulsions;
(i). Dye Test
To the emulsion some oil soluble dye is added. If
the background becomes coloured, the emulsion
is water-in-oil type and if the droplets becomes
coloured the emulsion is oil-in-water type.
(ii). Dilution Test
If the emulsion can be diluted with water, this
indicates that water is dispersion medium and the
emulsion is of oil-in-water type. In case the water
added forms a separate layer than emulsion is
water-in-oil type

known as dialysis.

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Electrodialysis
This is a special type of dialysis process, which is
accelerated by the application of a potential
difference across the membrane. So ions
migrate faster than the colloids .
Applications of colloids
1. Rubber plating
(2)
2. Sewage disposal
3. Smoke screen
4. Purification of water
5. Cleaning action of soap
6. In medicine

The styptic action of alum and ferric chloride solution

is due to coagulation of blood forming a clot which
stops further bleeding
River water is a colloidal solution of clay. Sea water
contains a number of electrolytes. When river water
meets the sea water, the electrolytes present in sea
water coagulate the colloidal solution of clay resulting
in its deposition with the formation of delta
Dust particles along with water suspended in air
scatter blue light which reaches our eyes and the sky
looks blue to you

 Applications of emulsions
(i) Cleansing action of soaps.
(ii) Milk, which is an important constituent of our
diet an emulsion of fat in water.
(iii)Digestion of fats in intestine is through
emulsification
Demulsification :-The process of
decomposition of an emulsion into its constituent
liquids is called demulsification. Examples of
demulsifiers are surfactants, ethylene oxide, etc.
Protective collloids
Covering up of lyophobic particles by lyophilic
particles is known as its protective action and
such colloids are called protective colloids
Protection of lyophobic colloids increase their
stability
Gold Number
The lyophilic colloids differ widely in their power
of protection. The protective action of different
colloids is measured in terms of the Gold number
introduced by Zsigmondy. The gold number is
defined as:
The number of milligrams of a lyophilic
colloid that will just prevent the
precipitation of 10ml of standard gold sol
(containing 0.5 to 0.6gm of gold per litre)
when 1 ml of 10% sodium chloride solution
is added.
Smaller the gold number,higher is protective
power
The gold number of few protective colloids is as
follows Geletine = 0.005 0.01
Haemoglobin = 0.03 0.07
Egg Albumin = 0.08 0.10
Gum Arabic = 0.10 0.15
Potato Starch = 25
Casein = 0.01 0.02

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this method between dilute solutions of sodium

silicate and HCl.
a.
Oxidation:
SO2 + 2H2S-------->3S + 2H2O
H2S + (O)-------->S + H2O
b.
Reduction:
2AuCl3 + 3SnCl2----->2Au(Gold sol.)+ 3 SnCl4
or AuCl3 + Tannic acid-------->Au (Sol.)
c.
Hydrolysis:
The method is used to prepare hydroxides and
oxides of weakly electropositive metals like
Fe, Al or Sn.
FeCl3 + 3H2O------>Fe(OH)3(Red Sol.)+ 3HCl.
The important physical methods for
preparing lyophobic sols are:
d.
By Exchange of Solvent:
For Example, when a solution of sulphur in alcohol
(ethanol) is added to an excess of water, a colloidal
solution of sulphur is obtained due to decrease in
solubility.
Dispersion Methods
In this method large particles of the substances are
broken, into particles of colloidal dimensions in
presence of dispersion medium. Since the sols
formed are highly unstable. They are stabilized by

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Column I

Column II

(i)

Protective colloid

(a)

FeCl3 + NaOH

(ii)

Liquid liquid
colloid

(b) Lyophilic colloids

(iii)

Positively charged
colloid

(c)

(iv)

Negatively charged
colloid

(d) FeCl3 + hot water

Emulsion

adding some suitable stabilizer. Some of the methods

employed for carrying out dispersion are as follows:
e.
Bredigs Arc Method:
This process involves dispersion as well as
aggregation. Colloidal solutions of metals such as
gold, silver, platinum etc. can be prepared by this
method. In this method electric arc is struck between
electrodes of metal immersed in the dispersion
medium. The intense heat produced vapourises some
of metal, which then condenses to form particles of
colloidal size.

Method of Preparation of Colloids

1.
Condensation or Aggregation Methods.
2.
Dispersion Methods.
1.
Condensation or Aggregation Methods
These methods consists of chemical reactions
or change of solvent whereby the atoms or
molecules of the dispersed phase appearing
first, aggregate to form colloidal particles. The
important chemical methods for preparing
lyophobic sols are as follows;
2. Double Decomposition:
AS2O3 + 3 H2S-------->AS2S3(Yellow Sol) + 3H2O
Sols of silver halide are obtained by mixing dilute
solutions of silver salts and alkali halides in
equivalent amounts. Silica gel sol is prepared by

CATALYSIS
Catalysts :- . Substances, which increase the rate of
a chemical reaction and themselves remain
chemically and quantitatively unchanged after the
reaction

f.
Peptisation:
Peptisation may be defined as the process of
converting a precipitate into colloidal form by
shaking it with dispersion medium in the presence of
small amount of electrolyte. The electrolyte used for
this purpose is called Peptizing Agent. This method is
applied, generally, to convert fresh precipitate into
colloidal solution because such precipitates are
simply clusters of particles of colloidal size held by
weak forces.
IMP Question:
1 . Explain what is observed
(i) When a beam of light is passed through a colloidal
sol.
(ii) An electrolyte, NaCl is added to hydrated ferric
oxide sol.
(iii) Electric current is passed through a colloidal sol?
Answer
(i) When a beam of light is passed through a colloidal
solution, then scattering of light is observed. This is
known as the Tyndall effect. This scattering of light
illuminates the path of the beam in the colloidal
solution.
(ii) When NaCl is added to ferric oxide sol, it
dissociates to give Na+ and Cl- ions. Particles of ferric
oxide sol are positively charged. Thus, they get
coagulated in the presence of negatively charged Clions.
(iii) The colloidal particles are charged and carry
either a positive or negative charge. The dispersion
medium carries an equal and opposite charge. This
makes the whole system neutral. Under the influence
of an electric current, the colloidal particles move
towards the oppositely charged electrode. When they
come in contact with the electrode, they lose their
charge and coagulate.
2. A colloidal solution of AgI is prepared by 2
different methods as shown: (i) What is the
charge of AgI colloidal particles in the two test
tubes (A) and (B)? (ii) Give reasons for the origin

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Catalysts increase the rate of a reaction by

decreasing the activation energy
Catalysts change the mechanism
Catalysts do not change the equilibrium constant
Catalysts are not consumed
A small quantity of catalyst should be able to
affect
Heterogeneous catalysisthe reactants and the catalyst are in
different phases.
catalyst = solid
reactants = li quid/gas

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Homogeneous catalysiscatalyst and reactants are in the same

phase, usually liquid.

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Shape- Selective Catalyst Zeolites

The catalytic reaction that depends upon the pore
,structure of the catalyst and the size of the
reactant and product molecules
Zeolites are good shape-selective catalysts
because of their honeycomb-like structures
. An important zeolite catalyst used in the
petroleum industry is ZSM-5. It converts alcohols
directly into gasoline (petrol) by dehydrating
them to give a mixture of hydrocarbons.
MECXHANISM OF CATALYSIS

of charge
ANS (I) AgI/I- , because KI is in excess (B) AgI/Ag+
3 Arrange the following electrolytes will have
maximum coagulating value for AgI/Ag+sol?
(i)Na2S(ii) Na3PO4(iii) Na2SO4 (iv) NaCl
4. Match the items given in Column I and
Column II
1. Adsorption and activation of the reactants

2. Migration of the adsorbed reactants on the

surface
3. Reaction of the adsorbed substances
4. Escape, or desorption, of the products
Enzymes Enzymes are catalysts in biological
systems.
Mechanism of enzymes
Step 1: Binding of enzyme to substrate to form
an activated complex.
E + S ES
Step 2: Decomposition of the activated
complex to form product
ESE + S
The substrate fits into the active site of the
enzyme much like a key fits into a lock.
Enzyme catalysis is unique in its efficiency
and high degree of specificity.
characteristics are :
(i) Most highly efficient: (ii) Highly specific
nature:
(iii) Highly active under optimum
temperature:. The optimum temperature
range for enzymatic activity is 298-310K. . (iv)
Highly active under optimum pH: which is
between pH values 5-7. (v) Increasing activity
in presence of activators and co-enzymes:

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1 What role does adsorption play in

heterogeneous catalysis?
Heterogeneous catalysis:A catalytic process in
which the catalyst and the reactants are present in
different phases is known as a heterogeneous
catalysis. This heterogeneous catalytic action can be
explained in terms of the adsorption theory. The
mechanism of catalysis involves the following steps:
(i) Adsorption of reactant molecules on the catalyst
surface.
(ii) Occurrence of a chemical reaction through the
formation of an intermediate.
(iii) De-sorption of products from the catalyst
surface
(iv) Diffusion of products away from the catalyst
surface.
What is the difference between multimolecular and
macromolecular colloids? Give one example of each.
How are associated colloids different from these two
types of colloids

2 Explain what is observed

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(i) When a beam of light is passed through a colloidal

sol.
(ii) An electrolyte, NaCl is added to hydrated ferric
oxide sol.
(iii) Electric current is passed through a colloidal
sol?

3 Explain the following terms:

(i) Electrophoresis (ii) Coagulation

(iii) Dialysis (iv) Tyndall effect.
4 Out of PO43,, SO42,, Cl,, which wil act as the
best coagulating agent for for Fe (OH)3
5 Out of NaCl, MgSO4, Al2 (SO4)3, K4[Fe(CN)6],
which one will bring about the coagulation of
a gold sol quickest and in the least of
concentration ?
6
(i)Why the sun looks red at the time of setting ?
Explain on the basis of colloidal properties.
(ii)What is the purpose of adding gelatin to ice
cream ?
(iii)Bleeding is stopped by the application of alum to
a wound. Why
3. 7 What happens when freshly precipitated Fe (OH)3
is shaken with a little amount of dilute solution of
FeCl3 ?
8 If we add equimolar amounts of ferric hydroxide
sol and arsenic sulphide sol, what will happen ?
9 On passing H2S through dilute HNO3 the colourless
solution becomes turbid. Why
10 Out of CO and NH3 which is adsorbed on
activated charcoal to a large extent and why
11 Why CO is removed from habers process of
ammonia