Surface Chemistry

Absorption:
When the molecules of a substance are uniformly distributed throughout the body
of a solid or liquid, this phenomenon is called absorption.
Adsorption:
It is the phenomenon of attracting and retaining the molecules of a substance on
the surface of a liquid or solid resulting in a higher concentration of molecules on
the surface is called adsorption.
Adsorbate:
The substance which gets adsorbed on any surface is called adsorbate.
Adsorbent:
The substance on the surface of which adsorption takes place is called adsorbent.
Adsorbents may be solids or liquids.
There are two types of adsorption:
1. Physisorption (Physical Adsorption):
It arises when the adsorbate molecules accumulate on the surface of the adsorbent
on account of the weak van der Waals’ forces.
2. Chemisorption (Chemical Adsorption):
It arises when the adsorbate molecules accumulate on the surface of the adsorbent
on account of the chemical bonds.
Differences between Adsorption and Absorption:
ADSORPTION ABSORPTION
It is a surface phenomenon. It is a bulk phenomenon.
The substance is only retained on the
The substance is uniformly distributed,
surface and does not go into the
through the body of the solid or liquid.
interior of the solid or liquid.
The concentration of the adsorbed The concentration of the adsorbed
molecules is greater at the free phase. molecules is low at the free phase.
It is fast at the beginning. It occurs at the uniform rate.
Differences between Physisorption and Chemisorption:
PHYSISORPTION CHEMISORPTION
Low heat of adsorption usually ranges High heat of adsorption usually ranges
between 20-40 kJ/mol. between 50-400 kJ/mol.
It is reversible. It is irreversible.
It forms multimolecular layers. It forms monomolecular layers.
It does not require activation energy. It requires high activation energy.

Factors affecting adsorption of gases on solids:

1. Nature of adsorbent, surface area and state of subdivision: The solid adsorbent
must possess a residual force field on its surface. Higher the magnitude of this
residual force field, greater is its tendency to undergo adsorption. Since adsorption
is a surface phenomenon, its extent also depends upon the surface area of the
adsorbent. The surface area of an adsorbent increases with an increase in the state
of subdivision. Coarse particles possess much less surface area as compared to the
finely divided particles of the same mass. Finely divided metals are good
adsorbents and are used as catalysts in several reactions.
2. Nature of adsorbate: The gases having high critical temperatures are adsorbed
more readily as compared to the gases having low temperatures. This is because
liquefiable gases (gases having high temperatures) are able to develop van der
Waals’ forces efficiently and attach to the surface of the adsorbent through these
forces.
3. Temperature: Adsorption decreases with an increase in temperature, only if gas
molecules are attached to the surface of the solid through van der Waals’ forces. If
the molecules form chemical bonds with the adsorbent, adsorption increases and
then decreases with a rise in temperature.
4. Pressure: Adsorption of a gas on a solid
increases with pressure. At low temperatures,
adsorption increases quickly with pressure in
the beginning. On the other hand, at higher
temperatures, the adsorption tends to
decrease. The effect of pressure on
adsorption is best described in terms of an
adsorption isotherm shown below.
Freundlich Adsorption Isotherms
The relation between the amount of substance adsorbed at constant temperature by
a fixed amount of an adsorbent and the equilibrium pressure or concentration is
usually expressed in terms of a mathematical relation known as adsorption
isotherm.
In order to describe the relationship between the amount of a gas adsorbed per unit
mass of the adsorbent at constant temperature and the equilibrium pressure,
Freundlich suggested the following empirical equation/expression known as
Freundlich adsorption isotherm.

x/m = k.P1/n (n > 1)

where x  mass of the gas adsorbed
m  mass of the adsorbent at equilibrium pressure
P  equilibrium pressure
k, n  constants whose values depend upon the nature of the adsorbate,
nature of the adsorbent and temperature.
This can be shown using a graph:

Not only limited to isotherms, adsorption can be applied in other fields too.
Applications of Adsorption
Adsorption is used in many fields such as:
1. In the removal of colouring matter: Adsorption is used for the removal of
undesirable colouring matter from juices, raw sugar solutions, vegetable oils
etcetera. Activated charcoal and animal charcoal are adsorbents that are used for
this purpose.
2. In dyeing: The dyeing of the vegetable or animal fibres occurs through the
adsorption of the dye on the fibre.
3. In softening of hard water: The use of ion exchange resins in the softening of
hard water is based on selective adsorption from solutions.
4. In chromatography: The chromatographic technique used for the separation of
the components of a mixture makes use of the phenomenon of selective adsorption
of certain substances from a solution by a particular adsorbent.
5. In separation of noble gases: A mixture of noble gases is usually separated by
adsorbing them on activated charcoal. The separation is based on the difference in
degree of adsorption of these gases by charcoal.
Catalysis:
The substance which alters the rate of a chemical reaction without being used up in
the reaction is called a catalyst and the phenomenon is called catalysis.
Types of Catalysis:
1. Positive catalysis: When a catalyst increases the rate of a reaction, it is termed
as a positive catalyst. Some examples are as follows:
(i) Oxidation of sulphur dioxide into sulphur trioxide is enhanced in the presence
of vanadium pentoxide:

(ii) Decomposition of KClO3 is facilitated in the presence of MnO2:

2. Negative catalysis: When a catalyst decreases the rate of a reaction, it is termed
as a negative catalyst. Some examples are as follows:
(i) The oxidation of chloroform by air is retarded in the presence of ethyl alcohol.
Here, ethyl alcohol acts as a negative catalyst:
1
CHCl3 + 2 O2  COCl2 + HCl
(ii) Decomposition of hydrogen peroxide gets retarded when some glycerine is
added to it:

2H2O2  2H2O + O2
3. Homogeneous catalysis: When a catalyst mixes homogeneously with the
reactant to form a single phase, it is said to be a homogeneous catalyst. In
homogeneous catalysis, the catalyst is present in the same phase as are the
reactants. Therefore, they mix thoroughly and form a single phase. Some examples
are as follows:
(i) Oxidation of sulphur dioxide to sulphur trioxide with nitric oxide as the catalyst:

(ii) Hydrolysis of an aqueous solution of sucrose in the presence of dilute sulphuric

acid as the catalyst:

4. Heterogeneous catalysis: In heterogeneous catalysis, the catalyst is usually

present in the solid phase and the reactants usually in the gas phase. The catalyst is
unable to mix homogeneously with them and forms a separate phase. Some
examples are as follows:
(i) Manufacture of ammonia from N2 and H2 by Haber’s process using iron as the
catalyst:
(ii) Oxidation of ammonia to nitric oxide in the presence of a platinum catalyst:

Intermediate compound theory

According to intermediate compound theory, the homogeneous catalyst combines
with the reactant to form an unstable intermediate compound, the formation of
which occurs at a lower activation energy. The intermediate compound thus formed
either reacts with other reactants or decomposes to give the desired end-products
and the catalyst is finally regenerated. Thus, the catalyst enhances the rate of
reaction by providing an alternate path of lower activation energy.
Examples:
 In the lead chamber process used for manufacture of sulphuric acid, sulphur
dioxide is oxidized to sulphur trioxide in the presence of nitric oxide as the
catalyst:
2NO +O2 → 2MO2
NO2+SO2 → SO3+NO
 Conversion of potassium chlorate to potassium chloride:

Adsorption Theory
According to this theory (also known as the theory of heterogeneous catalysis),
heterogeneous catalysis is a surface phenomenon and involves the chemisorption
of reacting gases on the surface of the solid catalyst. The solid catalyst provides a
number of free valencies at its surface through which chemisorption of gases on
the surface takes place.
Characteristics of a catalyst
1. Activity: The ability of a catalyst to accelerate chemical reactions is called
activity. In some cases, the degree of acceleration can be as high as 1010 times.
2. Selectivity: The ability of a catalyst to direct a chemical reaction to yield
particular product(s) is called selectivity. For example, H 2 and CO reacting to form
different products:

Enzyme Catalysis
Mechanism: According to the Lock and Key mechanism, an enzyme catalyzed
reaction involves the following steps:
STEP 1 – Binding of enzyme to the substrate to form an enzyme-substrate
complex:

STEP 2 – Product is formed in the complex and is released from the enzyme:
Colloidal State:
Scientist Thomas Graham, in 1861, classified soluble substances into two
categories: crystalloids and colloids. It was later found that this classification was
based on particle size. Crystalloids formed smaller particles
in solutions and colloids formed larger particles in solutions
and were unable to pass through the membrane.
A system containing substances distributed as very small
particles of a solid, droplets of a liquid or tiny bubbles of a
gas in a suitable medium is termed as a dispersion system.
The distributed substance is called the dispersed phase,
while the medium in which the dispersion takes place is known as the dispersion
medium.
Colloidal systems (heterogeneous) can be classified into two categories:
1. LYOPHILIC COLLOIDS: The substances which when mixed with a suitable
liquid readily form colloidal solutions are called lyophilic colloids.
2. LYOPHOBIC COLLOIDS: The substances which do not possess much affinity
for the dispersion medium and do not readily pass into the solution state when
mixed with the medium are called lyophobic colloids.
Classification of Colloidal Solutions
Colloidal solutions are classified into three categories:
 Micromolecular colloids: When a large number of atoms or small molecules
of a substance combine together in a dispersion medium to form aggregates
having a size in the colloidal range, the colloidal solutions thus formed are
called multimolecular or micromolecular colloids.
 Macromolecular solutions: When some substances form large molecules
whose dimensions are comparable to those of colloidal particles which have
 very high molecular masses, the colloidal solutions thus formed are called
macromolecular colloids.
 Associated colloids: Associated colloids are those colloids which behave as
normal strong electrolytes at low concentrations but exhibit colloidal
properties at higher concentrations due to the formation of aggregated
particles. The aggregated particles thus formed are called associated colloids
or micelles.

Preparation of Colloid Solutions

Preparation of Lyophilic Colloids
 Lyophilic colloids have a strong affinity for the dispersion medium and
readily form a solution by bringing them into contact or by warming them
with the medium.
 For example, starch or gelatin solutions can be prepared by dissolving them
in a finely divided state in a suitable solvent (water) in heat, followed by
cooling at room temperature. The dispersed phase can be recovered by
evaporating the dispersion medium (water).
 Similarly, a colloidal solution of cellulose nitrate can be prepared by
dissolving it in an organic solvent such as ethanol.
 The product formed is called collodion.

Preparation of Lyophobic Colloids

 Lyophobic colloids do not possess any affinity for the dispersion medium so
they do not readily pass into the medium to form a colloidal solution.
 Special methods are required for the preparation of lyophobic solutions.
 These methods are classified into two categories:
 Dispersion Methods
 Condensation Methods
Dispersion Methods –
1. Mechanical Dispersion (colloid mill): The dispersion of the substance or
the coarse material, whose colloidal solution needs to be prepared, is carried
out in a machine called the colloid mill.
First, the material is finely ground. It is then
mixed with the dispersion medium, protective
materials are also added when a coarse
suspension is obtained.
This suspension is passed through a colloid
mill which consists of two heavy metal discs
placed one on top of the other separated by a
small gap between each other. They rotate at a high speed in the opposite
direction at about 7000 revolutions per minute.
Using this method, solutions of indigo, sulphur, toothpaste, printer ink,
paints, ointments etc.. can be prepared.
2. Electrical Dispersion (Bredig’s arc method): This method is used to
prepare metal solutions like platinum, silver, gold, copper etc..
A dispersion medium (conductivity water) and a trace of sodium hydroxide
(the stabilizing agent) is taken in porcelain
or glass (non-conducting) vessel. The
vessel containing the dispersion medium is
surrounded by a freezing mixture.
The metal to be dispersed is dipped in the
vessel in the form of the electrodes, which
are connected to the high voltage source.
The ends of the electrodes in the dispersion
medium are very close to each other.
A very high voltage is applied and then an
electrical arc is struck between the tips of
electrodes. This creates a large amount of heat due to which metal rods melt,
evaporate and are suddenly cooled due to freezing mixtures gives rise to the
colloidal solution of the metal.

3. Peptization: The process of converting a freshly prepared precipitate into

colloidal form by the addition of suitable electrolyte is called peptization.
The electrolyte is used for this purpose is called peptizing agent or
stabilizing agent.
The cause of peptization is the adsorption of the ions of the electrolyte by the
particles of the precipitate.
Example:
Freshly prepared ferric hydroxide can be converted into a colloidal state by
shaking it with water containing Fe 3+ or OH- ions, namely FeCl3 and NH4OH
respectively.
Fe(OH)3 + FeCl → [Fe(OH)3Fe]3+ + 3Cl–
Condensation Methods -
1. Oxidation: The colloidal solution of sulphur can be prepared by oxidizing
an aqueous solution of H2S with bromine water, nitric acid, SO2 or any other
suitable oxidizing agent.

2. Reduction: Solutions of gold, silver, platinum etc. can be obtained by the

reduction of dilute solutions of their salts with a suitable reducing agent.
Example: Gold solutions can be obtained by reducing a dilute aqueous
solution of gold with stannous chloride. The solution is known as purple of
Cassius.

3. Double Decomposition: A solution of arsenic sulphide is obtained by

passing hydrogen sulphide through a cold solution of arsenious oxide in
water.

As2O3 + 3H2S  As2S3 + 3H2O

4. Exchange of solvent: This is a process for recovering an organic acid or a
metal salt. Colloidal solutions of certain substances like sulphur and
phosphorus which are soluble in alcohol but insoluble in water can be
obtained by preparing their alcoholic solution in excess of water.
For example, the alcoholic solution of sulphur (sulphur-ethanol solution) on
pouring into water gives a milky colloidal solution of sulphur because
sulphur is less soluble in water than in ethanol.
5. Hydrolysis: It involves the use of boiling water to obtain a reduced
solution of ferric chloride.

FeCl3 + 3H2O → Fe(OH)3 + 3 HCl

Purification of Colloids
The following methods are generally used for the purification of colloids:
1. Dialysis: The process of separating the particles of colloids from those of
crystalloids, by means of diffusion through a suitable membrane is called dialysis.
Its principle is based on the fact that
colloidal particles cannot pass through a
parchment or cellophane membrane/bag
while the ions of the electrolyte can pass
through it.
The impurities slowly diffuse out of the
bag leaving behind a pure colloidal
solution. The distilled water is changed frequently to ensure that the crystalloids do
not diffuse back into the bag.
2. Ultrafiltration: In this method, special
filters are used, which are permeable to
all substances except the colloidal
particles. An ultra filter paper may be
prepared by soaking the filter paper in a
colloidal solution, hardening by
formaldehyde and then finally drying it.
Thus, by using ultra filter paper the
colloidal particles are separated from rest
of the materials. The colloidal particles
left on the ultra filter paper are then
stirred with the fresh dispersion medium
(solvent) to get a pure colloidal solution.
3. Ultracentrifugation: Ultracentrifugation involves the separation of colloidal
particles from the impurities by centrifugal force. The impure solution is taken in a
tube and the tube is placed in an ultracentrifuge. The tube is rotated at high speeds.
The colloidal particles then settle at the bottom of the tube and the impurities
remain in the solution, called the centrifugate.
The settled colloidal particles are removed from the tube and then mixed with an
appropriate dispersion medium. The pure solution is obtained.
Properties of Colloidal Solutions
General Properties
1) Homogenous appearance: Even though colloids have suspended particles and
are heterogeneous in nature, they appear as if a homogenous solution. This is
because the suspended particles are so tiny that they are not conceivable by the
naked eye.
2) Stability: Colloids are relatively stable in nature. The particles of the dispersed
phase are in a state of continuous motion and remain suspended in the solution.
3) Colour: The colour of a colloidal solution depends upon the size of colloidal
particles present in it. Larger particles absorb the light of longer wavelength and
therefore transmit light of shorter wavelength. For example, a silver solution
having particles of size 150 nm appears violet, whereas that having particles of size
60 nm appears orange yellow.
Kinetic Properties
Brownian Movement:
The continuous and rapid zig-zag motion of the colloidal
particles is called Brownian movement. It is more rapid when
the size of the particles is small and the solution is less viscous.
It is caused due to the bombardment of colloidal particles by the
molecules of the dispersion medium. The intensity of the motion
depends on the particles size and the viscosity of the dispersion
medium.
Tyndall Effect:
John Tyndall observed that when a strong beam of light is focused on a colloidal
solution the path of the beam becomes visible and when viewed through a
microscope placed at a right angle to the path of light, the colloidal particles appear
as pin points of light moving against a dark background in a colloidal solution.
This phenomenon is known as Tyndall effect. This is due to scattering of light by
colloidal particles.
 Electrical Properties
Coagulation:
The stability of the colloidal solution is due
to mutual repulsion between similarly
charged colloidal particles. When the charge
on the colloidal particles is neutralized by the
addition of an electrolyte or oppositely
charged solution, the precipitation takes
place. Thus the process of precipitating a
colloidal solution is known as coagulation.
For example, the negatively charged As2S3 solution is readily coagulated on
addition of a solution of BaCl2. The positively charged Fe(OH)3 solution is readily
coagulated on addition of a solution of NaOH.
Electrophoresis:
The phenomenon of movement of colloidal particles under an applied electric field
is called electrophoresis. If the particles
accumulate near the negative electrode, the charge
on the particles is positive. On the other hand, if
the solution particles accumulate near the positive
electrode, the charge on the particles is negative.
The apparatus consists of a U-tube with two
platinum electrodes in each limb.
When electrophoresis of a solution is carried out
without stirring, the bottom layer gradually
becomes more concentrated while the top layer
which contains pure and concentrated colloidal
solution may be decanted.
Electro-osmosis:
The migration of the dispersion medium of a
colloidal solution under the influence of the
electric field when the movements of colloidal
particles are prevented is called electro-osmosis.
The colloidal solution and pure dispersion
medium in a glass tube are separated by a
semipermeable membrane. The dispersion medium has an opposite electrical
charge as compared to that of the particles of the solution.
Protection of Colloids
The phenomenon of preventing the coagulation of a lyophobic solution due to the
addition of some lyophilic colloid is called solution protection or protection of
colloids.
In the presence of certain lyophilic colloids such as gum arabic, gelatin, starch,
etc., the hydrophobic solutions acquire greater stability towards coagulation.
For example, the addition of gelatin (lyophilic colloid) to a gold solution
(lyophobic solution) protects the latter from being coagulated on addition of
sodium chloride solution.

Gold Number:
The protective power of a lyophilic colloid is usually expressed in terms of a
number called gold number introduced by Zsigmondy in 1901.
The number of milligrams of a lyophilic colloid that will just prevent the
precipitation of 10ml of standard gold solution (containing 0.5 to 0.6gm of gold per
litre) when 1 ml of 10% sodium chloride solution is added is called the gold
number.
The smaller the value of the gold number, the greater the protective power of the
protective colloid.
Protective Colloids Gold Number
Gelatin 0.005-0.01
Casein 0.01-0.02
Haemoglobin 0.03-0.07
Egg albumin 0.08-0.10
 Gum arabic 0.10-0.15
Dextrin 6-20
Starch 20-25
Hardy-Schulze Rule:
The Hardy-Schulze Rule states that the effective ions of the electrolyte in bringing
about coagulation are those which carry charge opposite to that of the colloidal
particles. These ions are called coagulating ions.
Greater is the valency of the coagulating ion, greater is its power to bring about the
coagulation.
For example, the coagulation power of different cations for coagulating a
negatively charged solution of As2S3 follows the order
Al3+ > Ba2+ > Na+
Similarly, for the coagulation of a positively charged solution such as Fe(OH) 3, the
coagulating power of different anions follows the order
[Fe(CN)6]4- > PO43- > SO42- > Cl-
Emulsions
An emulsion is a colloidal dispersion in which both the dispersed phase and the
dispersion medium are liquids.
The emulsion is generally prepared by shaking the mixture of two colloids
strongly. These emulsions are generally unstable. The substance added to the
mixtures to stabilize them is called an emulsifier or an emulsifying agent.
The process of mixing liquids to form an emulsion is called emulsification.
Examples:
Egg yolk is an emulsion containing the emulsifying agent lecithin.
Butter is an emulsion of water in fat.
Mayonnaise is an oil in water emulsion that is stabilized by the lecithin in egg
yolk.
The photosensitive side of photographic film is coated with an emulsion of silver
halide in gelatin.
Crema on espresso is an emulsion consisting of water and coffee oil.
Surfactants
A surfactant is a widely used contraction for surface active agent. The surfactant
may be viewed as a molecule consisting of a
lyophilic and a lyophobic part. The term interface
denotes a boundary between any two immiscible
phases. The five different interfaces are solid–vapor
surface, solid–liquid, solid–solid, liquid–vapor
surface and liquid–liquid. One characteristic feature
of surfactants is their tendency to adsorb at
interfaces. Another fundamental property of surface
active agents is that unimers in solution tend to
form micelles.
Examples:
Soaps
Fatty acid sulfonates
Ethoxylated compounds
Micelles
The aggregated particles in a colloidal solution are called micelles. The surfactants
form micelles at a concentration greater than critical micellization concentration
(CMC).
In water, the soap molecule is uniquely oriented which helps to keep the
hydrocarbon part outside the water. When the clusters of molecules are formed
then hydrophobic tail comes at the interior of the cluster and the ionic end comes at
the surface of the cluster and this formation is called micelle. When the soap is in
the form of micelles then it has the ability to clean the oily dirt which gets
accumulated at the center. These micelles remain as a colloidal solutions. Therefore
the dirt from the cloth is easily washed away.
The soap solution appears cloudy as it forms a
colloidal solution which scatters light.
Examples:
Polystyrene
Soap bubbles
Detergents

Applications of Colloids and Emulsions in daily life

Applications of Colloids:
i. Food stuffs and medicines: Colloids have great application in food industries
and food stuffs. Many of the food materials which we
eat are of colloidal nature. Bread is a colloidal system
in which air is dispersed in baked dough.
Colloidal medicines are competitively more effective
as they get easily absorbed in the body. Penicillin is
injected in the body in the form of a colloidal solution
so that they get absorbed easily.
ii. Smoke screen: It is generally used to hide the movement of smoke troops. The
smoke screens are also colloidal systems in which the particles of titanium oxide
are dispersed in air.
iii. Formation of delta: Negatively charged
colloidal particles of the river are
neutralized. As it is very expected, the
river water contains colloidal particles of
sand and clay which are negatively
charged. On the other hand the salty sea
water contains a number of positive ions.
When the river water comes in contact
with water of sea, the negative charge
present on colloidal clay particles
present in river water get neutralized by the positively charged ions present in
sea.

Applications of Emulsions:

i. Healthcare: Many cosmetic and pharmaceutical

dosage forms are in the form of emulsions.
Cosmetics such as lotions, creams, biphasic
makeup removers are in fact emulsions. Many
oral, as well as topical dosage forms, are
emulsions. Microemulsions are used to deliver
vaccines and kill microbes. Cod liver oil, cortisol, polysporin are some examples
of emulsion formulations.
ii. Chemical Synthesis: Emulsions are used in the manufacturing of polymer
dispersions. These include primary components of glues and paints.
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