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 Unit 5 - Surface Chemistry
 Difference between adsorption and absorption:
Adsorption Absorption
 It is a surface phenomenon in which the  It is a bulk phenomenon in which the
concentration of adsorbate molecules is concentration of adsorbate molecules is
higher at the surface of the adsorbent higher in the bulk of the adsorbent than
than its bulk. The accumulated its surface. The adsorbate molecules
molecules of adsorbate remain at the distribute uniformly in the bulk of the
surface and do not go deeper in the bulk adsorbent.
of adsorbent. Examples-
Examples- (a) Water molecules are absorbed by
(a) Water molecules adsorb at the surface of calcium chloride (CaCl2)
silica gel (b) Absorption of water by tissue paper and
(b) Adsorption of gases like H2, O2, CO2, cotton
Cl2, NH3 etc. on the surface of activated
charcoal  Both adsorption and absorption can take
(c) Adsorption of dye molecules on place simultaneously also. This is
charcoal surface known as Sorption.
(d) Adsorption of ink on chalk surface
 The process of removal of an adsorbed
substance from a surface on which it is
adsorbed is called Desorption.
Note- Easily liquefiable gases (having strong intermolecular forces or high critical
temperature or high value van der Waals constant ‘a’) undergo adsorption rapidly.

 Mechanism of Adsorption
The bulk molecules of the adsorbent are surrounded from all sides by other molecules of
adsorbent and all forces acting between the molecules are mutually balanced. But the surface
particles of the adsorbent are not surrounded from all sides. Hence, surface particles have
 unbalanced or residual attractive forces. These forces are responsible for attracting the
adsorbate particles on its surface.
 Thermodynamics of Adsorption
When gases undergo adsorption then entropy i.e. degree of randomness (ΔS) decreases.
Therefore, ΔS becomes negative (ΔS = negative).

More ΔS
Less ΔS
Adsorption

Adsorbent Adsorbent

But for a process to be spontaneous, the ∆G (at constant temperature and pressure) must be
negative i.e. there must be a decrease in Gibbs free energy. According to the following
equation-
∆G = ∆H – T∆S
T∆S term becomes positive due to negative ∆S value. Therefore, to make ∆G negative, ∆H
must be negative and ǀ∆Hǀ > ǀT∆Sǀ. This implies that adsorption is essentially an exothermic
process. As the adsorption proceeds, ∆H becomes less and less negative ultimately ∆H
becomes equal to T∆S and ∆G becomes zero and equilibrium is attained.
 Types of adsorption phenomenon:
Physisorption Chemisorption
 It arises because of van der Waals’ forces  It is caused by chemical bond
between adsorbent and adsorbate formation
 It is non- specific in nature  It is highly specific in nature
 It is reversible in nature  It is irreversible

 It depends on the nature of gas. More  It also depends on the nature of gas.

easily liquefiable gases (having high Gases which can react with the adsorbent

critical temperature) are adsorbed readily show chemisorption

 Enthalpy of physical adsorption is very  Enthalpy of adsorption is very high about

low 20-40 kJ mol-1 80- 240 kJ mol–1

1  Chemical adsorption α Temperature
 Physical adsorption α
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
 With increase in temperature kinetic energy
With increase in temperature chemical
of adsorbate molecules increases and they
adsorption first increases due to activation of
start moving away from the adsorbent
adsorbate molecules. But at very high
surface. Therefore, physical adsorption
temperature bond between adsorbent and
decreases with increase in temperature.
adsorbate start breaking and chemical
adsorption decreases as adsorbate molecules
 No appreciable activation energy is
starting moving away from surface.
needed
 High activation energy is sometimes
 Physical adsorption α Surface area
needed.
(more number of adsorption sites)
 Chemical adsorption α Surface area
 Multilayer adsorption occurs on
(more number of adsorption sites)
adsorbent surface under high pressure
 Unimolecular or Monolayer layer
adsorption occurs here.

 Freundlich Adsorption Isotherm

 The variation in the amount of gas adsorbed by the adsorbent with pressure at constant
temperature can be expressed by means of a curve termed as adsorption isotherm.
 Freundlich gave an empirical relationship between the quantity of gas adsorbed by unit mass
of solid adsorbent and pressure at a particular temperature.
𝑥
= 𝐾 𝑝1/𝑛
𝑚
where x - mass of the gas adsorbed, m – mass of the adsorbent, p – pressure k and n are
Freundlich’s constants.
 K and n depend upon the nature of the adsorbent and the gas at a particular temperature

 These curves indicate that at a fixed pressure, there is a decrease in physical adsorption with
increase in temperature.
 After a particular pressure, the adsorption becomes constant due to occupation of all
adsorption sites. Thus this isotherm fails ate high pressure.
𝑥 1 𝑝
𝑙𝑜𝑔 = 𝑙𝑜𝑔𝐾 + 𝑙𝑜𝑔
𝑚 𝑛 𝑝0

 The value of n is always greater than 1 i.e. n >1 (generally between 0.1 and 0.5). Thus, this
isotherm holds good only in limited range.
1 𝑥
 If = 0, then = log K (constant), then adsorption is independent of pressure
𝑛 𝑚
1 𝑥
 If = 1, then α p, then adsorption varies directly with pressure
𝑛 𝑚
 Factors affecting adsorption process
(a) Nature of adsorbent- Surface of adsorbents must have residual forces so that they can
attract adsorbate molecules.
(b) Surface area- Powdered materials are highly effective in adsorption than crystalline
materials because they have large surface area and hence more number of adsorption sites
compare to crystalline materials.
(c) Pressure- Adsorption is directly proportional to applied pressure.
(d) Temperature- As we know adsorption is an exothermic process. Therefore, according to Le-
Chatlier’s principle, adsorption decreases with increase in temperature due to increase in
kinetic energy of adsorbate molecules and these molecules start moving away from the
adsorbent surface.
 Adsorption in solution phase
For gaseous adsorbates pressure is used in Freundlich’s isotherm but in solution phase
concentration is used in place of pressure and all other parameters remain the same. The
mechanism of adsorption is solution phase is not known completely.
 Applications of Adsorption
1. Production of high vacuum: The remaining traces of air can be adsorbed by charcoal from a
vessel evacuated by a vacuum pump to give a very high vacuum.
2. Gas masks: Gas mask (a device which consists of activated charcoal or mixture of
adsorbents) is usually used for breathing in coal mines to adsorb poisonous gases and viruses.
3. Control of humidity: Silica and aluminium gels are used as adsorbents for removing
moisture and controlling humidity.
4. Removal of colouring matter from solutions: Animal charcoal removes colours of
solutions by adsorbing coloured impurities.
5. Heterogeneous catalysis: The reactions in which reactants and catalysts have different state.
Reactants are generally gases or liquids and catalysts are solid in this case. Adsorption of
reactants on the solid surface of the catalysts increases the rate of reaction. There are many
gaseous reactions of industrial importance involving solid catalysts.
Example: Manufacture of ammonia – Haber process -Iron (Fe) catalyst
Manufacture of H2SO4 - Contact process- V2O5 catalyst
Hydrogenation of oils- Nickel powder catalyst
6. Separation of inert gases: Due to the difference in degree of adsorption of gases by
charcoal, a mixture of noble gases can be separated by adsorption on coconut charcoal at
different temperatures.
7. In curing diseases: A number of drugs are used to kill germs by getting adsorbed on them.
8. Froth floatation process: A low grade sulphide ore is concentrated by separating it from
silica and other earthy matter by this method using pine oil and frothing agent
9. Adsorption indicators: Surfaces of certain precipitates such as silver halides have the
property of adsorbing some dyes like eosin, fluorescein, etc. and thereby producing a
characteristic colour at the end point.
10. Chromatographic analysis: Chromatographic analysis is also based on the phenomenon of
adsorption. There are a large number of applications of these methods in analytical and
industrial fields.
Catalysis
 Catalysts are the substances which alters the rate of a reaction without consuming into the
reaction i.e. the chemical composition and quantity of catalyst remains the same after
occurrence of reaction. The catalysts which increase the rate of a reaction are known as
positive catalysts while those decrease the rate of reaction are known as negative catalysts.
(653- 873) K
(Without catalyst)
(473- 633) K
(Catalyst – MnO2)

 MnO2 catalyst makes reaction easy and same reaction can be carried out at low temperature
relative to un-catalyzed reaction. This phenomenon is known as catalysis.
 Promoters: These are the substances which enhance the activity of a catalyst in a reaction.
 Poison: These are the substances which decrease the activity of a catalyst in a reaction.
Example - In Haber’s process (synthesis of ammonia), Fe used is as catalyst while Mo is
used as promoter.
Fe - catalyst
Mo - promoter
 Types of catalysis
 Homogeneous catalysis
 When all the reactants, products and catalyst are in the same phase, then such catalysis is
known as homogeneous catalysis.
 Examples-
(a) Lead Chamber process-
NO (g)
(b) Acidic hydrolysis of Methyl ester (CH3COOCH3) -

HCl (l)
+

(c) Acidic hyderolysis of sugar –

Fructose
 Heterogeneous catalysis
 When the reactants, products and catalyst are present in the different phases, then such
catalysis is known as heterogeneous catalysis.
 Examples-
(a) Oxidation of Sulphur dioxide -

2S
(b) Haber’s Process: Synthesis ammonia in presence of finely divided iron (Fe) catalyst
Fe

(c) Oxidation of amonia to nitric acid –

Pt
4
(d) Hydrogenation of vegetable oils: Finely divided Ni catalyst
Ni

 Adsorption Theory of heterogeneous catalysis

This theory explains the mechanism of heterogeneous catalysis. This theory is a combination of
intermediate compound formation theory and the old adsorption theory.
Mechanism of heterogeneous catalysis
Step 1: Diffusion of reactants to the surface of the catalyst.
Step 2: Adsorption of reactant molecules on the surface of the catalyst.
Step 3: Occurrence of chemical reaction on the catalyst’s surface through collision of reactants
and formation of an intermediate
Step 4: Desorption of reaction products from the catalyst surface, and thereby, making the
surface available again for more reaction to occur
Step 5: Diffusion of reaction products away from the catalyst’s surface.

 The catalyst always has active sites (free valencies) on its surface. These active sites have
chemical forces of attraction. When a gas comes in contact with such a surface, then
molecules of the gases are held up by the active sites. After adsorption of gaseous molecules
side by side, they star reacting with each other and form new product molecules. These
product molecules evaporate from the surface and vacant the surface for the fresh reactant
molecules.
Note: This theory explains why the catalyst remains unchanged in mass and chemical
composition at the end of the reaction and is effective even in small quantities. But it does not
explain the action of promoters and poisons.
 Features of Solid catalysts
 Activity: The activity of a catalyst depends upon its ability to chemisorb reactants molecules
on its surface. The adsorption of reactants should be very strong to become active for product
formation. But the adsorption of reactants should not be so strong that they are immobilized
on catalyst surface and do not left space on catalyst for other reactants. It has been found that
for hydrogenation reaction, the catalytic activity increases from Group 5 to Group 11 metals
and group 7-9 elements show maximum activity.
Ni
 Selectivity: It is the ability of a catalyst to carry out a specific reaction, when under the same
reaction conditions many other reactions are possible. Selectivity of different catalysts for same
reactants is different.
Example -
Ni

Cu/ ZnO-Cr2O3

Cu

 Shape Selective Catalysis

The catalytic reaction that depends upon the pore structure of the catalyst and the size of the
reactant and product molecules is called shape-selective catalysis.
Examples-
 Zeolites are good shape-selective catalysts because of their honeycomb-like porous
structures. They are microporous aluminosilicates with 3D networks of silicates in which few
Si atoms are substituted by Al atoms giving Al–O–Si framework.
 Reaction taking place in zeolites depend upon the size and shape of reactant and product
molecules as well as upon the pores and cavities of the zeolites.
 Zeolites are used as catalysts in petrochemical industries for cracking of hydrocarbons and
isomerization.
 ZSM-5 is used to convert alcohols directly into gasoline (petrol) by dehydrating them to
give a mixture of hydrocarbons.
 Enzyme catalysis
 Enzymes are nitrogen based complexes organic compounds which are produced by living
plants and animals. They are actually protein molecules of high molecular mass and form
colloidal solutions in water.
 They are known as biochemical catalysts because they catalyze a number of reactions in
plants and animals to maintain life processes. This phenomenon is known as biochemical
catalysis.
Examples-
 (a) Inversion of cane sugar
Invertase

Cane sugar Glucose Fructose

(b) Conversion of glucose into ethyl alcohol

Zymase
Glucose Ethyl alcohol
(c) Conversion of maltose into glucose
Maltase
2
Maltose Glucose
(d) Conversion of maltose into glucose
Diastase
n
Starch Maltose
(e) Decomposition of urea into ammonia
Urease
+ C
(f) Conversion of milk into curd
(g) In stomach, the pepsin enzyme converts proteins into peptides while in intestine, the
pancreatic trypsin converts proteins into amino acids by hydrolysis.
 Characteristics of Enzyme Reactions
(a) High efficiency: One molecule of an enzyme may transform one million molecules of the
reactant into product per minute.
(b) Specific nature: Each enzyme is specific for a given reaction, i.e., one catalyst cannot
catalyze more than one reaction.
For example, the enzyme urease catalyzes the hydrolysis of urea only. It does not catalyze
hydrolysis of any other amide.
(c) High activity at optimum temperature: The rate of an enzyme reaction becomes maximum
at a specific temperature, which is called as optimum temperature. On either side of this
optimum temperature, the enzyme activity decreases.
The optimum temperature range for enzymatic activity is 298K -310K. Human body
temperature being 310 K is suited for enzyme-catalyzed reactions.
(d) High activity at optimum pH: The rate of an enzyme-catalyzed reaction is maximum at a
particular pH called optimum pH, which is between pH values 5-7.
(e) High activity in presence of activators and co-enzymes: The enzymatic activity is
increased in the presence of some substances, known as co-enzymes. Examples- Vitamins
Activators: They are generally metal ions such as Na+, Mn2+, Co2+, Cu2+ etc. These metal
ions, when weakly bonded to enzyme molecules, increase their catalytic activity.
Example - Amylase in presence of sodium chloride (Na+ ions) is catalytically very active.
(f) Influence of inhibitors and poisons: Like ordinary catalysts, enzymes are also inhibited or
poisoned by the presence of certain substances. The inhibitors or poisons interact with the
active functional groups on the enzyme surface and often reduce or completely destroy the
catalytic activity of the enzymes. The use of many drugs is related to their action as enzyme
inhibitors in the body.
 Mechanism of Enzyme catalysis
The surface of colloidal particles of enzymes has a large number of cavities. These cavities have
characteristic shape and active groups such as -NH2, -COOH, -SH, -OH, etc. These functional
groups act as active centres on the surface of enzyme particles. The molecules of the reactants
(substrate) which have complementary shape, fit into these cavities just like a key fits into a lock.
This leads to the formation an activated complex between enzyme and substrate. This complex
upon decomposition gives products.

Steps of mechanism -
Step 1: Binding of Enzyme to a substrate to form an activated complex
E + S ES’
Step 2: Decomposition of the activated complex to form product
ES’ E+P
 Examples of Industrial catalysts-
 Process Catalyst
Haber Process: Ammonia synthesis Finely divided iron, molybdenum as promoter
Fe Conditions: 200 bar and 723-773 K
Now-a-days, a mixture of iron oxide, potassium oxide
and alumina (Al2O3) is used
Ostwald Process: Nitric Acid Platinized asbestos
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g) Temperature -573K

2NO(g) + O2(g) → 2NO2(g)

4NO2(g) + 2H2O(l) + O2(g) → 4HNO3(aq)

Contact Process: Sulphuric Acid Platinized asbestos or vanadium pentoxide (V2O5)

2SO2(g) + O2(g) → 2SO3(g) Temperature 673-723K
SO3(g) + H2SO4(aq) → H2S2O7(l)
oleum
H2S2O7(l) + H2O(l) → 2H2SO4 (aq)

Colloidal Solutions
 Colloid: A colloid is a heterogeneous system in which one substance is dispersed (dispersed
phase) in form of fine particles in another substance called dispersion medium. The size of
dispersed phase particles lies in the range between 1 nm to 1000 nm.
 Crystalloid: A system in which size of solute particles is less than 1 nm. Same ssubstance
can acts as both colloid and crystalloid and it depends upon the particle size.
 Types: Depending upon the state of dispersed phase and dispersion medium-
 If the dispersion medium is water, the sol is called Aquasol or hydrosol and if the is
dispersion medium is alcohol, it is called Alcosol.
 Types: Depending upon the nature of interaction between the dispersed phase
and the dispersion medium-
Lyophilic or liquid loving (hydrophilic sols) Lyophobic or liquid hating (hydrophobic sols)
 There are favourable interactions between  There are non-favourable interactions
the DP and DM particles. between the DP and DM particles.
 They are very stable sols and do not  They are not very stable sols and can
undergo coagulation easily. undergo coagulation easily.
 They are Reversible in nature. If the  They are Irreversible in nature. Simple
dispersion medium is separated from the mixing of DP and DM do not give colloidal
dispersed phase (by evaporation), the sol solution. Special methods are used to prepare
can be re-prepared by simply remixing with them. They need protecting agent to prevent
the dispersion medium coagulation and for increasing their stability.
 These sols are thermodynamically stable.  These sols are Kinetically stable.
 They can be prepared by simple methods.  They are prepared by special methods.
Examples: Sols of gum, gelatin, starch, rubber Examples: Metal sols, sulphide etc.
etc.

 Types: Depending upon the type of the particles of the dispersed phase-
Multimoolecular Colloids Macromoolecular Colloids Associated Colloids (Micelles)
Some substances when Macromolecules or polymers Many electrolytes (ionic
dissolved in a solvent, a when dispersed in suitable substances) behave as normal
large number of atoms or solvents then they form strong electrolytes at low
smaller molecules of a solutions in which the size of concentrations.
substance aggregate their molecules may be in the But at higher concentrations
together to form species colloidal range. Such systems they undergo aggregation
having size in the colloidal are called macromolecular (association) and become
range (1 nm to 1000 nm). colloids. These colloids are colloidal in nature. These
The species thus formed quite stable and some of their aggregated particles are known
are called multimolecular properties match with the as micelles or associated
 colloids. properties of true solutions. colloids.
Examples- Gold sol and Examples- Sols of Starch,
Sulphur (S8) sol cellulose, proteins and
enzymes, and polythene,
nylon, polystyrene, synthetic
rubber, etc.
Kraft Temperature- The temperature above which micelle formation occurs.
CMC- The concentration above which micelle formation occurs is called critical micelle
concentration.
On dilution, these colloids revert back to individual ions.
Examples- Soaps and detergents
For soaps, CMC is 10–4 to 10–3 mol L–1. These colloids have both lyophobic and lyophilic parts.
Micelles may contain as many as 100 molecules or more.

 Micelle Formation
 Soap is sodium or potassium salt of a higher fatty acid and may be represented as RCOO–Na+
(e.g., sodium stearate CH3(CH2)16COO–Na+). When dissolved in water, it dissociates into
RCOO– and Na+ ions.
 The RCOO– ions consist of two parts- a long hydrocarbon chain R (also called non-polar
‘tail’) which is hydrophobic (water repelling) in nature and a polar group COO– (also called
polar-ionic ‘head’) which is hydrophilic (water loving).

The RCOO– ions are present on the surface with their COO– groups in water and the
hydrocarbon chains R staying away from it and remained at the surface. But at critical micelle
concentration, the anions are pulled into the bulk of the solution and aggregate to form a
 spherical shape with their hydrocarbon chains pointing towards the centre of the sphere with
COO– part remaining outward on the surface of the sphere. An aggregate thus formed is known
as ‘ionic micelle’. These micelles may contain as many as 100 such ions. Similar mechanism of
micelle formation also occurs in detergents like sodium laurylsulphate, CH3(CH2)11SO42– Na+.

 Cleansing action of soaps

The cleansing action of soap is due to the fact that soap molecules form micelle around the oil
droplet in such a way that hydrophobic part of the stearate ions is in the oil droplet and
hydrophilic part goes out of the grease droplet like the bristles.

Then polar groups can interact with water and the oil droplet surrounded by stearate ions is now
pulled in water and removed from the dirty surface. Thus soap helps in emulsification and
washing away of oils and fats. The negatively charged sheath around the globules repels each
other and prevents their aggregation.
 Preparation of Colloidal Solutions-
Chemical Methods Bredig’s arch method Peptization
Colloidal dispersions can be (Electrical disintegration method) It is defined as the process in
prepared by chemical reactions. This process involves dispersion as which a freshly prepared
First of all molecules are formed well as condensation. Colloidal sols precipitate is converted into
by reactions like oxidation, of metals such as Au, Ag, Pt etc. colloidal sol by shaking it with
reduction, hydrolysis and double can be prepared by this method. dispersion medium in the presence
decomposition. These molecules of a small amount of electrolyte.
then undergo aggregation to The electrolyte used for this
form sols. purpose is called peptizing agent.
Examples- In peptization, the precipitate
(a) As2O3 + 3H2S adsorbs either cation or anion of
Double decomposition the electrolyte on its surface and
As2S3 (sol) + 3H2O hence develops positive or
(b) SO2 + 2H2S negative charge on its surface. Due
Oxidation
to repulsive forces, this precipitates
3S(sol) + 2H2O In this method, electric arc is struck
break up into smaller particles of
(c) 2AuCl3 + 3HCHO + 3H2O between electrodes of the metal
colloidal size.
Reduction immersed in the dispersion medium.
2Au(sol) + 3HCOOH + 6HCl The intense heat produced
(d) FeCl3 + 3 H2O vapourises the metal, which then
Hydrolysis condenses to form particles of
Fe(OH)3 (sol) + 3HCl
colloidal size.

 Purification of Colloidal Solutions-

 Dialysis
It is a process of removal of dissolved substance from a colloidal solution by means of diffusion
through a suitable membrane. The smaller size particles of impurities (ions or molecules) can
pass through animal membrane (bladder) or parchment paper or cellophane sheet but not the
colloidal particles as they have larger size. The apparatus used for this purpose is called dialyser.

A bag of suitable membrane containing the colloidal solution is suspended in a vessel through
which fresh water is continuously flowing. The molecules and ions diffuse through membrane
into the outer water and pure colloidal solution is left behind.
 Electrodialysis
The process of normal dialysis is quite slow. Its speed can be increased by applying an electric
field if the dissolved substance in the impure colloidal solution is only an electrolyte. The
 process is then named electrodialysis.

The colloidal solution is placed in a bag of suitable membrane while pure water is taken outside.
The ions present in the colloidal solution migrate out to the oppositely charged electrodes.
 Ultrafiltration
In this process, colloidal particles are separated from the solvent and soluble solutes present in
the colloidal solution by using specially prepared filters. These filters are permeable to all
impurity substances except the colloidal particles.
Colloidal particles can pass through ordinary filter paper because the pores are too large in size.
But the pores of filter paper can be reduced in size by impregnating with collodion solution to
stop the flow of colloidal particles. The usual collodion is a 4% solution of nitro-cellulose in a
mixture of alcohol and ether. An ultra-filter paper may be prepared by soaking the filter paper in a
collodion solution. It is then hardened by formaldehyde and dried. Thus, by using ultra-filter paper, the
colloidal particles are separated from rest of the materials. Ultrafiltration is a slow process. To speed
up the process, pressure or suction is applied. The colloidal particles left on the ultra-filter paper
are then stirred with fresh dispersion medium (solvent) to get a pure colloidal solution

 Properties of Colloidal Solutions-

 Colligative Properties
Colloidal particles are bigger aggregates and the number of particles in a colloidal solution is relatively
small as compared to a true solution. Hence, the values of colligative properties (osmotic pressure,
lowering in vapour pressure, depression in freezing point and elevation in boiling point) are of small
order as compared to values shown by true solutions at same concentrations.
 Tyndall Effect
Colloidal solutions appear clear or translucent by the transmitted light. But they show a mild to strong
opalescence, when viewed at right angles to the passage of light. This is due to scattering of light by
colloidal particles in all directions in space and the path of the beam is illuminated by a bluish light.
 Tyndall effect was first observed by Faraday but deeply studied by Tyndall. Therefore, known as
Tyndall effect. The bright cone of the light is called Tyndall cone. Tyndall effect also observed during
the projection of picture in the cinema hall due to scattering of light by dust and smoke particles present
there. Tyndall effect is used to distinguish between a colloidal and true solution.

Conditions for Tyndall effect:

(i) The diameter (size) of the dispersed particles should be comparable to the wavelength of the
light used
(ii) There must be a large difference between refractive indices of the dispersed phase and the
dispersion medium
(iii) Zsigmondy (1903) used Tyndall effect to design an instrument known as ultramicroscope. An intense
beam of light is focused on the colloidal solution contained in a glass vessel. The focus of the light is
then observed with a microscope at right angles to the beam. Individual colloidal particles appear as
bright stars against a dark background.
(iv) Ultramicroscope does not render the actual colloidal particles visible but only observe the light scattered
by them. Therefore, ultramicroscope does not provide any information about the size and shape of
colloidal particles.
 Brownian Movement
It is defined as the continuous zig-zag motion of colloidal particles in dispersion medium. It can be seen
using a powerful ultramicroscope. It was first observed by the British botanist, Robert Brown. The
Brownian movement has a stirring effect which does not allow the particles to settle down. Therefore, it
is responsible for the stability of sols.

Brownian Movement α Independent of nature of colloidal particle

 1
α
𝑆𝑖𝑧𝑒 𝑜𝑓 𝑠𝑜𝑙 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒
1
α
𝑉𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡

The Brownian movement occurs due to the unbalanced bombardment of

the particles by the molecules of the dispersion medium.
Charge- Stability of colloidal solutions
Colloidal particles always have either positive or negative charge on their surface. Due to presence of
similar charge on colloidal particles, they repel each other in solution. This prevents their agglomeration
and dispersed phase particles undergo random motion in dispersion medium. This makes the colloidal
solution stable.
Positive Sols Negative Sols
These are the sols in which dispersed phase These are the sols in which dispersed phase
particles have positive charge on their surface. particles have positive charge on their surface.
Examples- (a) Hydrated metallic oxides Examples- (a) Metals like copper, silver, gold sols
Al2O3.xH2O, CrO3.xH2O and Fe2O3.xH2O (b) Metallic sulphides- As2S3, Sb2S3, CdS sols
(b) Basic dye stuffs- Methylene blue sols (c) Acid dye stuffs- Cosin, Congo red sols.
(c) Haemoglobin (blood) (d) Sols of starch, gum, gelatin, clay, charcoal
(d) Oxides like TiO2 sol
Reason of presence of surface charge
(i) due to electron capture by sol particles during electrodispersion of metals
(ii) due to preferential adsorption of ions from solution and/or due to formulation of electrical
double layer.
Examples-
The sol particles acquire positive or negative charge by preferential adsorption of either cations
(positive charge) or anions (negative charge). The adsorption of common ion from the dispersion
medium (DM) occurs on the surface of dispersed phase particle.
1. (a) When silver nitrate (AgNO3) is added to highly diluted potassium iodide
(KI) solution, the precipitated silver iodide (AgI) adsorbs iodide (𝐼 − ) ions AgI

from the dispersion medium (DM) and forms a negatively charged colloidal
sol.
AgNO3 + KI (excess)
(b) When KI solution is added to AgNO3 solution, then precipitated AgI adsorbs
(𝐴𝑔+ ) ions and forms positively charged sol. AgI

AgNO3 (excess) + KI
2. (a) When FeCl3 is added to the excess of hot water (H2O), then hydrated
Fe2O3
ferric oxide (Fe2O3) is formed and on its surface adsorption of Fe3+ ions
.xH2O
occurs. This leads to formation of positively charged sol.
FeCl3 + hot H2O Fe2O3. xH2O
(b) When ferric chloride (FeCl3) is added to NaOH solution a negatively charged Fe2O3
.xH2O
sol is obtained with adsorption of 𝑂𝐻 − ions.
FeCl3 + NaOH Fe2O3. xH2O
 Once the first layer of charge (either positive or negative) is formed on
colloidal particle then this layer r attracts counter ions from the dispersion
medium and forms second layer of charge on colloidal particle.
 The combination of the two layers of opposite charges around the
colloidal particle is called Helmholtz electrical double layer. The first
layer of ions is tightly bound and is termed as fixed layer. The second
layer is mobile which is termed diffused layer. The potential difference
between the fixed and diffused layer is known as the zeta potential or
electrokinetic potential.

 If two particles of a precipitate do not have double layers then they come closer to each other and
attractive van der Waals forces pull them together. This leads to their agglomeration. But particles
possess double layer the overall effect is that particles repel each other. And stay at large distances
of separation from each other. This repulsion prevents their agglomeration and particles. They
remain dispersed and colloid solution becomes stable.
 Coagulation or precipitation
It is defined as the settling or precipitation of colloidal particles due to removal of their surface charge.
Methods of coagulations: For Lyophobic Sols
(a) Electrophoresis: The colloidal particles move towards oppositely charged electrodes, get
discharged and precipitated.
(b) Mixing of two oppositely charged sols: Oppositely charged sols when
 mixed in almost equal proportions, then they neutralize their charges and get precipitated. Mixing of
hydrated ferric oxide (+ve sol) and arsenious sulphide (–ve sol) convert them into precipitated form.
This type of coagulation is called mutual coagulation.
(c) Boiling: When a sol is boiled, then collisions occur between DP and DM particles. This disturbs
double layer and reduces the charge on the particles. This leads to settling down of colloidal
particles in the form of a precipitate.
(d) Persistent dialysis: On prolonged dialysis, traces of the electrolyte present in the sol are removed
almost completely and the colloids become unstable and ultimately coagulate.
(e) Addition of electrolytes: When an electrolyte is added to a colloidal solution then sol particles start
interacting with oppositely charged ions of the added electrolyte. This causes neutralisation of their
charge and they undergo coagulation. The ion responsible for neutralisation of charge on the
particles is called the coagulating ion.
 Hardy-Schulze rule
Coagulating Power α charge number of the coagulating ion
Example- 𝐴𝑙 3+ > 𝐵𝑎2+ > 𝑁𝑎+ (in coagulation of a negative sol)
 Coagulating value: The minimum concentration of an electrolyte in millimoles per litre required to
cause precipitation of a sol in two hours is called coagulating value. The smaller the quantity
needed, the higher will be the coagulating power of an ion.
 Coagulation of lyophilic sols
Lyophilic sols are stable due to the presence of charge on their surface and their solvation in dispersion
medium. They can be coagulated by
(i) Addition of electrolyte
(ii) Addition of suitable solvent
When solvents such as alcohol and acetone are added to hydrophilic sols, they dehydrate dispersed
phase particles and break their solvation. Under such conditions, a small quantity of electrolyte can
easily coagulate the DP particles.
 Protection of colloids
Lyophilic sols are more stable than lyophobic sols due to higher solvation extent in lyophilic sols
compare to hydrophobic sols. Lyophilic colloids have a unique property of protecting lyophobic
colloids. When a lyophilic sol is added to the lyophobic sol, the lyophilic particles form a layer around
lyophobic particles and thus protect them from electrolytes. These types of lyophilic colloids are called
protective colloids.
 Gold Number: It is the minimum weight (in mg) of a protective colloid required to prevent the
coagulation of 10 mL of a standard hydro gold sol when 1 mL of a 10 % sodium chloride solution is
added to it.
𝟏
Gold Number α
𝑷𝒓𝒐𝒕𝒆𝒄𝒕𝒊𝒗𝒆 𝑷𝒐𝒘𝒆𝒓

 Colour: The colour of the colloidal solution depends upon following factors-
(a) wavelength of light scattered by the dispersed particles
(b) size and nature of particles
(c) method by which observer receives the light
Examples: A mixture of milk and water appears blue when viewed by the reflected light and red when
viewed by the transmitted light.
 Finest gold sol is red in colour. But as the size of particles increases, it appears purple, then blue and
finally golden.
 Electrophoresis
The presence of charge on colloidal particles is confirmed by electrophoresis experiment. When electric
potential is applied across two Pt electrodes dipping in a colloidal
solution, the colloidal particles move towards other electrodes. The movement of colloidal particles
under an applied electric potential is called electrophoresis. Positively charged particles move towards
the cathode while negatively charged particles move towards the anode.
When electrophoresis i.e. movement of DP particles is prevented by any method then dispersion
medium begins to move in an electric field. This phenomenon is termed electro osmosis.

 Emulsions: These are the colloidal solutions in which both dispersed phase and dispersion
medium are liquid in nature. The DP is present into finely divided droplets into DM.
 Oil dispersed in Water (O / W type) Water dispersed in Oil (W / O type)
DP – Oil and DM – Water DP – Water and DM – Oil
Examples - Milk, vanishing creams Examples – Butter, Cream
 Emulsifying agents - proteins, gums,  Emulsifying agents - heavy metal salts of fatty
natural and synthetic soaps etc. acids, long chain alcohols, lampblack etc.
 Emulsifying agents - Emulsions are generally unstable in nature and get separated into
two layers on standing. Therefore, to make them stable an extra component is added into
them. This component is called emulsifying agent. It forms an interfacial film between
suspended particles of DP and molecules of DM.
 Emulsions can be broken into constituent liquids by heating, freezing, centrifuging,
etc.
 Emulsions can be diluted with any amount of the DM. But when DP is added to them, it
forms a separate layer. The droplets in emulsions are often negatively charged and can
be precipitated by electrolytes. They also show Brownian movement and Tyndall effect.

 Applications of Colloidal Solutions-

(i) Blue colour of the sky: Dust particles along with water suspended in air scatter blue
light which reaches our eyes and the sky looks blue to us.
(ii) Fog, mist and rain: The moisture in air generally condenses on the surface of dust
particles present in air when air cools below its dew point. This lead to formation of very
fine droplets. These droplets being colloidal in nature continue to float in air in the form
of mist or fog. Clouds are aerosols having small droplets of water suspended in air. Due
to condensation in the upper atmosphere, the colloidal droplets of water grow bigger and
bigger in size and they come down in the form of rain.
Sometimes, the rainfall occurs when two oppositely charged clouds meet. It is possible
to cause artificial rain by throwing electrified sand or spraying a sol carrying
charge opposite to the one on clouds from an aeroplane.
(iii) Food articles: Milk, butter, halwa, ice creams, fruit juices, etc., are all colloids in one
form or the other.
(iv) Blood: It is a colloidal solution of an albuminoid substance. The styptic action of alum
and ferric chloride solution is due to coagulation of blood forming a clot which stops
further bleeding.
(v) Soils: Fertile soils are colloidal in nature in which humus acts as a protective colloid. On
account of colloidal nature, soils adsorb moisture and nourishing materials.
(vi) Formation of delta: 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.
(vii) Electrical precipitation of smoke: Smoke is a colloidal solution of solid particles such
as carbon, arsenic compounds, dust, etc., in air. The smoke is generally discharged
through a chamber in chimney containing plates having a charge opposite to that carried
by smoke particles. The particles on coming in contact with these plates lose their
charge and get precipitated. The particles thus settle down on the floor of the chamber.
The precipitator is called Cottrell precipitator.

(viii) Purification of drinking water: The water obtained from natural sources often contains
suspended impurities. Alum is added to such water to coagulate the suspended
impurities and make water fit for drinking purposes.
(ix) Medicines: Most of the medicines are colloidal in nature. Argyrol is a silver sol used as
an eye lotion. Colloidal antimony is used in curing kalaazar. Colloidal gold is used for
intramuscular injection. Milk of magnesia, an emulsion, is used for stomach disorders.
Colloidal medicines are more effective because they have large surface area and are
therefore easily assimilated
(x) Tanning: Animal hides are colloidal in nature. The positively charged hide is soaked in
tannin, which contains negatively charged colloidal particles. Due to this mutual
coagulation takes place. This results in the hardening of leather. This process is termed
as tanning. Chromium salts are also used in place of tannin.
(xi) Photographic plates and films: Photographic films are prepared by coating an emulsion
of the light sensitive silver bromide in gelatin over glass plates or celluloid films.
(xii) Rubber industry: Latex is a colloidal solution of rubber particles which
are negatively charged. Rubber is obtained by coagulation of latex.
(xiii) Industrial products: Paints, inks, synthetic plastics, rubber, graphite lubricants, cement,
etc., are all colloidal solutions.
 Previous Years’ Questions – CBSE/ state boards
1. Define adsorption, absorption, desorption and sorption by giving examples.
2. Why adsorption is always exothermic?
3. Write major differences between physisorption and chemisorption.
4. Out of NH3 and CO2 which gas will be adsorbed more readily on the surface of activated
charcoal and why?
5. Write few applications of adsorption.
6. Why is a finely divided substance more effective as an adsorbent?
7. Explain how the phenomenon of adsorption finds applications in the
(a) production of high vacuum
(b) Controlling humidity
(c) Heterogeneous catalysis
(d) Froth floatation process in metallurgy
8. What is an adsorption isotherm? Describe Freundlich’s adsorption isotherm.
9. Why are medicines more effective in colloidal state?
10. What type of colloid is formed when a liquid is dispersed in solid? Give an example.
11. What is the reason for stability of colloidal sols?
12. Out of BaCl2 and KCl which one is more effective in causing coagulation of a negatively
charged colloidal sol? Give reason.
13. In reference to surface chemistry, define dialysis.
14. A delta is formed at the meeting point of sea water and river. Why?
15. Write the dispersed phase and dispersed medium of smoke, butter and milk.
16. Give one example of sol and gel.
17. Differentiate between lyophilic and lyophobic sols by giving appropriate examples.
18. Which aerosol depletes ozone layer?
19. How can a colloidal solution and true solution of the same colour can be distinguished from
each other?
20. Define coagulation and peptization.
21. Define electrophoresis.
22. Explain the following-
(a) Same substance can acts both as colloids and crystalloids
 (b) Artificial rain caused by spraying salt over clouds
23. How are the following colloidal sols can be prepared-
(c) Sulphur in water
(d) Gold in water
24. What is difference between multimolecular, macromolecular and associated colloids? Give
one example of each.
25. Describe a conspicuous change observed when-
(a) A solution of NaCl is added to a sol of hydrated ferric oxide
(b) What will be the charge on AgI colloidal particles when it is prepared by adding small
amounts of AgNO3 solution to KI solution in water? What is development responsible for
the development of this charge?
26. Give the reasons for the followings-
(a) Leather gets hardened after tanning
(b) FeCl3 is preferred over KCl in case of cut leading to bleeding
27. What happens when-
(a) A freshly prepared precipitate of Fe(OH)3 is shaken with a small amount of FeCl3
(b) Persistent dialysis of a colloidal solution is carried out
28. Write short note on-
(a) Zeta potential
(b) Tyndall effect
(c) Brownian movement
 Competitive Examinations- JEE and NEET

1. Given
Gas H2 CH4 CO2 SO2
Critical Temperature (K) 33 190 304 630
On the basis of above data predict which of the gas shows least adsorption on the surface on
definite amount of charcoal- (JEE 2019)
(a) H2 (b) CH4 (c) SO2 (d) CO2
2. Which one of the following statement is not correct- (NEET 2017)
(a) Catalyst does not initiate any reaction
(b) The value of the equilibrium constant is changed in the presence of catalyst in the
reaction at equilibrium
(c) Enzymes catalyze many bio-chemical reactions
(d) Coenzymes increase the catalytic activity of enzymes
3. The mass of gas adsorbed (x) per unit mass of adsorbent (m) was measured at different
pressures p. A graph between log (x/m) and log p gives a straight line with slope equal to 2
and the intercept equal to 0.4771. The value of x/m at a pressure of 4 atm is (if log 3 =
0.4771) (JEE 2020)
(a) 48 (b) 58 (c) 42 (d) 54
4. Fog is a colloidal solution of- (NEET 2016)
(a) Solid in gas (b) liquid in gas (c) gas in gas (d) gas in liquid
5. 3g activated charcoal was added to 50 mL of acetic acid solution (0.06 N) in a flask. After an
hour it was filtered and the strength of the filtrate was found to be 0.042 N. The amount of
acetic acid absorbed (per gram of charcoal) is- (JEE 2019)
(a) 42 mg (b) 54 mg (c) 18 mg (d) 36 mg
6. For a linear plot of log(x/m) versus log p in a Freundlich adsorption isotherm, which of the
following statement is correct- (JEE 2016)
(a) Both k and 1/n appear in slope term
(b) 1/n appears as intercept
(c) Only 1/n appears as the slope
(d) log(1/n) appears as the intercept
7. Identify the correct molecular picture showing what happens at the critical micellar
concentration (CMC) of an aqueous solution of a surfactant (having polar head and non-polar
tail) (JEE 2020)

(a) C (b) A (c) D (d) B

8. A mixture of gases O2, H2 and CO are taken in a closed vessel containing charcoal. The
graph that represents the correct behavior of pressure with time is- (JEE 2020)

9. The Tyndall effect is observed only when the following conditions are satisfied- (JEE 2017)
(i) The diameter of the dispersed particles is much smaller than the wavelength of the light
used
(ii) The diameter of the dispersed particles is not much smaller than the wavelength of light
used
(iii) The refractive indices of the dispersed phase and dispersion medium are similar in
magnitude
(iv) The refractive indices of the dispersed phase and dispersion medium differ greatly in
magnitude
(a) (i) and (iii) (b) (ii) and (iii) (c) (i) and (iv) (d) (ii) and (iv)
10. In Freundlich adsorption isotherm of a gas shown in figure, x/m = pa. The value of a from
the figure will be- (JEE 2016)

(a) 2/3 (b) 1/3 (c) 3/2 (d) log(x/m)

11. On which of the following properties, coagulating power of an ion depend: (NEET 2018)
(a) The magnitude of the charge on the ion
(b) Size of the ion alone
(c) Both magnitude and sign of the charge on the ion
(d) The sign of charge on the ion
12. 0.27 g of a long chain fatty acid was dissolved in 100 mL of hexane as solvent. 10 mL of this
solution was added dropwise over a round plate. Now the solvent (hexane) is allowed to
evaporate off so that only fatty acid remains in the plate. The distance from the centre to the
edge of the plate is 10 com. Density of fatty acid is 0.9 gcm-3. Calculate the height of the
layer - (take π = 3) (JEE 2019)
(a) 10-4 m (b) 10-2 m (c) 10-8 m (d) 10-6 m
13. Which mixture of the solution will lead to the formation of negatively charged colloidal sol
of [𝐴𝑔𝐼]𝐼 − (NEET 2019)
(a) 50 mL of 0.1 M AgNO3 + 50 mL of 0.1 M KI
(b) 50 mL of 0.1 M AgNO3 + 50 mL of 1.5 M KI
(c) 50 mL of 1 M AgNO3 + 50 mL of 0.2 M KI
(d) 50 mL of 2 M AgNO3 + 50 mL of 1.5 M KI
14. The coagulation values in milimoles per litre of the electrolytes used for the coagulation of
As2O3 are given below
I (NaCl) = 52 II (BaCl2) = 0.69 III (MgSO4) = 0.22
The correct order of their coagulating power is- (NEET 2016)
(a) III>II>I (b) III>I>II (c) I>II>III (d) II>I>III
15. Among the following surfactants that will form micelles in aqueous solution of the lowest
molar concentration at ambient condition is – (JEE 2017)
 (a) 𝐶𝐻3 (𝐶𝐻3 )15 𝑁 + (𝐶𝐻3 )15 𝐵𝑟 −
(b) 𝐶𝐻3 (𝐶𝐻3 )11 𝑂𝑆𝑂3− 𝑁𝑎+
(c) 𝐶𝐻3 (𝐶𝐻3 )6𝐶𝑂𝑂− 𝑁𝑎+
(d) 𝐶𝐻3 (𝐶𝐻3 )11 𝑁 + (𝐶𝐻3 )3 𝐵𝑟 −
16. When O2 is absorbed on a metallic surface, electron transfer occurs from the metal to O2. The
true statement regarding this adsorption is (are)- (JEE Advanced 2017)
(a) O2 is physisorbed
(b) Heat is released
∗
(c) Occupancy of 𝜋2𝑝 of O2 is increased
(d) Bond length of O2 is increased
17. Molar conductivity of aqueous solution of sodium stearate, which behaves as a strong
electrolyte, is recorded at various concentrations. Which one of the following plots provides
the correct representation of micelle formation in the solution? (JEE
advanced 2010)

18. The correct statement of about the surface properties is (are)- (JEE Advanced 2017)
(a) The critical temperature of ethane and nitrogen are 563 K and 126 K respectively. The
adsorption of ethane will be more than that of nitrogen of same amount of activated
charcoal at a given temperature
(b) Cloud is an emulsion type of colloid in which liquid is dispersed phase and gas is
dispersion medium
(c) Adsorption is accompanied by decrease in enthalpy and decrease in entropy of the system
 (d) Brownian motion of colloidal particles does not depend upon the size of the particle but
depends on viscosity of the solution
19. Match the catalysts to the correct process- (JEE 2015)
Catalyst Process
A TiCl4 Wacker process
B PdCl2 Ziegler-Natta polymerization
C CuCl2 Contact process
D V2O5 Deacon’s process
(a) A - ii, B - iii, C - iv, D - i (b) A - ii, B - i, C - ii, D - iv

(c) A - iii, B - ii, C - iv, D – i (d) A - ii, B - i, C - iv, D - iii

17. Which of the following characteristics are associated with adsorption? (NEET 2016)
(a) ΔG and ΔH are negative but ΔS is positive
(b) ΔG and ΔS are negative but ΔH is positive
(c) ΔG is negative but ΔH and ΔS are positive
(d) ΔG, ΔS and ΔH are negative