COLLOID SOLUTION : Thomas Grahm from his investigation on the diffusion of various substance in a liquid medium

classified substance as :
1. Crystalloid : Substance whose solution can pass through filter paper and animal or vegetable membrane, having
higher rate of diffusion is called crystalloid. Ex. Urea, NaCl, Sucrose, Glucose etc.
2. Colloid : Substance whose solution can pass through filter paper and not animal or vegetable membrane, also having
slower rate of diffusion is called colloid. Ex. Starch, Protein, Gelatin, Silicic Acid etc.
Modern Concept : According to modern concept the term colloid does not apply to a particular class of substance but
it is a state of matter like solid, liquid, gas. Any substance can be brought into colloidal stage by suitable means eg.
NaCl, Behaves like a crystalloid in water while it behaves as a colloid in benzene.
Soap is a colloid in water while crystalloid in benzene.
From the above example it is clear that the concept of colloid and crystalloid do not hold good, thus we now talk a
colloid state instead of colloid.

Colloid State : A substance is said to be in colloidal state when the size of the particle of disperse phase is greater than
particle of true solution and less than that of suspension solution particle, their range of
diameters between 1 and 1000 nm (10–9 to 10–6 m).
Suspension solution Colloidal particle True solution
> 10-6 m 10–9 to 10–6 m < 10–9

Colloid solution : It is a heterogeneous system consisting of 2 phase :

(1) Disperse Phase (D.P ) : The phase which is dispersed through the medium is called dispersed phase or
discontinuous phase or internal phase.
(2) Dispersion Medium ( D.M ) : A medium in which colloidal particles are dispersed is called dispersion medium. It is
also known as continuous phase or outer phase or external phase.
Colloidal solution = dispersed phase ( D.P. ) + dispersion medium ( D.M.)
Ex. In Gold sol, Gold is D.P and water is D.M
Mono disperse Colloid & Poly disperse Colloid : If a colloid sol contain all colloidal particle of nearly the same size. It is
called Mono disperse colloids. However if it contains colloidal particles of different size, it called poly disperse colloid s.
Colloidal particles do not settle down under force of gravity even on keeping for long time, but may settle under
centrifuge.
Classification of colloids : Colloids can be classified as follows :on the basis of physical state of disperse phase and
dispersion medium
(1) On the bases of dispersion medium
(2) On the Basis of interaction of dispersed phase for dispersion medium
(3) On the basis of chemical composition
(4) On the basis of charge of on particles
(1)on the basis of physical state of disperse phase and dispersion medium :
SN D.P D.M Name Examples
1 S S Solid sol Some coloured glasses, ruby glass, precious stones, alloys, minerals,
pearls.
2 S L Sols Some paints, muddy water. Starch in water, cell fluids
3 S G Aerosols of solid Smoke, dust, dust storm, volcanic dust
4 L S Gels Cheese, butter, jellies, curd, boot-polish
5 L L Emulsion Milk, hair cream, emulsions
6 L G Aerosols of liquid Fog, mist, clouds, fine insecticide sprays
7 G S Solid foam Pumice stone, styrene , foam rubber, bread, .
8 G L Foam or froth Soap lather , Froth, whipped cream.

Solution of gas in gas is not a colloidal system because it form homogeneous mixture

2- On the bases of dispersion medium : Colloidal solution are classified as dispersion medium
S.N dispersion medium Name of colloidal system
1 Water Hydro sol or aquo sol
2 Alcohal Alco sols
3 Benzene Benzo sols
4 Air Aero sols
* Aqua dag & oil dag are the colloidal solution of graphite in water & oil respectively.
* Colloidal solution are often termed as sol.
3-On the Basis of interaction of dispersed phase for dispersion medium : There are two types-
(i) Lyophilic colloids / liquid loving sols / intrinsic colloid:The colloidal solution in which the particles of the dispersed
phase have a greater affinity (or love) for the dispersion medium, are called lyophilic colloids. These solutions are
easily formed and the lyophilic colloids are reversible in nature. In case water acts as the dispersion medium, the
lyophilic colloid is called hydrophilic colloid. The common examples of lyophilic colloids are glue, gelatin, starch,
proteins, egg albumin, rubber, etc.
(ii) Lyophobic colloids / solvent hating colloid / extrinsic colloid:The colloidal solutions in which there is no affinity
between particles of the dispersed phase and the dispersion medium are called lyophobic colloids. Such solutions are
formed with difficulty only by special methods. These sols are readily precipitated (or coagulated) on the addition of
small amounts of electrolytes, by heating or by shaking and hence are not stable. Further, once precipitated, they do not
give back the colloidal sol by simple addition of the dispersion medium. Hence these sols are also called irreversible
sols. They need stablising agents for their preservation. In case the dispersion medium is water, the lyophobic sol is
called hydrophobic colloid. For example, the solution of metals like Ag and Au, hydroxides like Al (OH) 3 , Fe(OH)3 ,
metal sulphides like As2S3 etc
* Lyophobic sols are also called suspensoids & hydrophilic are also called emulsoids .
* Lyophilic sols are more stable than lyophobic sols, the additional stability is due presence of an envelope of the
solvent layer (say water) around the colloidal particle, the process is known as hydration, To coagulate a hydrophilic
sols we have to add a dehydrating agent in addition to electrolyte.
3. On the basis of chemical composition :
Inorganic Colloids Organic Colloids
(i) Metal sols : Cu, Ag, Au, Pt, Sols. (i) Homopolar sol - In this type of colloid particles
(ii) Non Metal sols : S, I2 , Graphite carry similar type of charge. eg. Sol. of rubber in
benzene which contain - ve charge colloidal particle of
latex.
(iii) Sol. of oxide and hydroxide : (iv) Hydroxy Sol- Starch sol.
SnO2 , TiO2 , Fe2O3 , Fe(OH)3 , AI(OH)3 , Cr(OH)3
(iv) Salt Sol - AgBr, AgI, As2S3 , etc.
4. On the basis of charge of on particles -
(i) positive Sol. (ii) Negative Sol
(a) metal Oxide & Hydroxide - (a) Metal sol -
SnO2 , TiO2 , Fe2O3 , AI(OH)3, Fe(OH)3, Cr(OH)3 Ag, Au, Pt, Cu
(b) Basic Dyes- Methylene blue vismark brown (b) Acetic dye - congo red, eosin
(c) Sulphide Sol- CdS, HgS, As2S3 , Sb2S3.
(d) natural sol - Blood, clay charcoal, latex rubber, dust
particle in water, starch carbon particle in smoke,
Multi molecular, macro molecular and associated colloids :
Multi molecular colloids : In this type, the particles consist of an aggregate of atoms of small molecules size less than
1 nm.
For example, sols of gold atoms and sulphur (S8) molecules. In these colloids, the particles are held together by
VanderWaal’s forces.
Macro molecular colloids : In this types, the particles of the dispersed phase are sufficiently big in size (macro) to be of
colloidal dimensions. These macro molecules forming the dispersed phase are generally polymers having very high
molecular masses. These colloids are quite stable and resemble true solutions in many respects. Naturally occurring
macro molecules are starch, cellulose, proteins, enzymes, gelatin, etc.
Associated colloids (Micelles): These are the substances which behave as normal strong electrolytes at low
concentration but behave as colloidal particles at higher concentration. These associated particles are also called
micelles.

SN Property Lyophilic sols Lyophobic sols

1 Ease of Prepared easily by directly mixing with Cannot be prepared directly. Prepared by special
preparation the liquid dispersion medium. methods only.

2 Stability They are quite stable and are not easily They are unstable and easily precipitated by
precipitated or coagulated by addition of a small amount of a suitable
electrolytes electrolyte.

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3 Hydration They are highly hydrated. They are not much hydrated.

4 Reversible & They are reversible in nature i.e. once They are irreversible in nature i.e. once
irreversible precipitated can reform the colloidal precipitated cannot form the colloidal sol by
sol by simply remixing with the simple addition of the dispersion medium.
dispersion medium.

5 Nature of These sols are usually formed by the These sols are usually formed by the inorganic
substances organic substances like starch, gum, materials like metals, their sulphides etc.
proteins etc.

6 Viscosity Their viscosity is much higher than that Their viscosity is almost the same as that of the
of the medium. medium.

7 Surface tension Their surface tension is usually lower Their surface tension is nearly same as that of the
than that of the dispersion medium. dispersion medium.

8 Visibility Their particles are neither visible nor Their particles, though not visible, can be easily
detected easily by the ultra-microscope detected by an ultra-microscope.
(by the scattering of light).

9 Migration in an Their particles may migrate in either Their particles migrate in only one particular
electric field direction or may not migrate at all. direction(towords anode or cathode ) in the
electric field.

10 Tyndall effect Less distinct More distinct

11 charge Carry no or very little charge depending They have characteristic charge ( positive or
upon pH of medium negative)

12 Example Starch , protein gelatin etc Metal sol, and oxide and sulphide sol

Preparation of Colloidal Sols :

[A] Condensation methods : In these methods particles of atomic or molecular size are induced to combine to form
aggregates having colloidal dimensions. For this purpose chemical as well as physical methods can be applied.
(a) Chemical methods. Colloidal solutions can be prepared by chemical reactions leading to formation of molecules by
double decomposition, oxidation, reduction or hydrolysis. These molecules then aggregate leading to formation of sols.
(i) Double decomposition : When a hot aqueous dilute solution of arsenic oxide (As2O3) is mixed with a saturated
solution of H2S in water, a colloidal sol of arsenous sulphide (As2S3) is obtained.
As2O3 +3H2S  As2S3(sol) + 3H2O

.
Colloidal sol of prussian blue may be prepared by mixing very dilute solutions of FeCl3 and K4Fe(CN)6
3K4[Fe(CN)6] + 4 FeCl3  Fe4[Fe(CN)6]3(sol ) +12 KCl
Sols of arsenic sulphide and mercuric sulphide are obtained by passing H2S into the saturated solutions of
corresponding soluble
salts of their oxides,
As2O3 + 3 H2S  As2S3(sol )+ 3 H2O ,
Hg(CN)2 + H2S  HgS (sol )+ 2HCN
(ii) Oxidation : A colloidal sol of sulphur is obtained by passing H2S into a solution of sulphur dioxide.
SO2 + 2 H2S (saturated solution in H2O)  3S (sol) + 2H2O
Sulphur sol can also be obtained when H2S is bubbled through Br2 water or nitric acid (oxidizing agent).
2H2S (aq.) + Br2 (aq.)  2HBr (aq.) + S (sol).
or by bubbling O2 (g) through a solution of H2S :
2H2S (aq.) + O2 (g)  2H2O (l) + 2S (sol).
(iii) Reduction : Colloidal sol of metals like gold, silver solution are obtained by following method.
2 AuCl3 + 3 HCHO + 3H2O  2Au(sol) + 3HCOOH + 6HCl.
(purple of cassius)
* Sol. of gold is also known as purple of cassius.

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 3 SnCl2 + 2 AuCl  Au(sol) + 3 SnCl4
AgNO3 + tannic acid  silver sol.
NH2NH2 can also be used as reducing agent.
(iv) Hydrolysis : A colloidal sol of metal hydroxides like Al(OH)3 , Fe(OH)3 or Cr(OH)3 is obtained by boiling a dilute
solution of FeCl3 , AlCl3 or CrCl3 .
FeCl3 + 3H2O  Fe(OH)3 (sol) + 3HCl. ,
AlCl3 + 3H2O  Al(OH)3 (sol) + 3HCl
The colloidal sol of silicic acid is also obtained by hydrolysis of dilute solution of sodium silicate with Hydro chloric acid.
Na4SiO4 + 4HCl  Si(OH)4 (sol) + 4NaCl.
A beautiful red sol of ferric hydroxide is prepared by boiling ferric acetate in a beaker having distilled water (500 ml).
(CH3COO)3Fe +3H2O  Fe(OH)3 (sol) + 3 CH3COOH
(b) Physical methods : The following physical methods are used to prepare the colloidal solutions.
(i) By Exchange of solvent : When a true solution is mixed with an excess of the other solvent in which the solute is
insoluble but solvent is miscible, a colloidal sol is obtained. For example, when a solution of sulphur in alcohol is
poured in excess of water, a colloidal sol of sulphur is obtained. when a solution of phenolphthalein in alcohol is poured
in excess of water a white sol of phenolphthalein is found. Phenolphthalein, I2 , sulphur sol can be prepared by this
methods.

(ii) Excessive cooling : on excess cooling molecules of certain substance condense together to from colloidal size
particle. The colloidal sol of ice in an organic solvent such as CHCl3 or ether can be obtained by freezing a solution of
water in the solvent. The molecules of water which can no longer be held in solution Separately combine to form
particles of colloidal size.

(iii) By condensing vapours of a substance into solvent : A colloid solution of certain elements like sulphur and Hg is
obtained by passing their vapours through cold water containing small amount of stabilizing agent like ammonium
salt or citrate ).

[B] Dispersion Methods : In these methods large particles of the substance are broken into particles of colloidal
dimensions in the presence of dispersion medium. These are stabilized by adding some suitable stabilizer. Some of
the methods employed are given below :
(a) Mechanical dispersion (By colloidal mill) : Here the substance is first finery
powdered. it is shaken with the D.M. to form a suspension. This suspension is
passed through a colloidal mill. The simplest type of colloidal mill is disc mill
which consists of to metal discs nearly touching each other & rotating in opp.
direction at a high speed (7000 revolutions per minute). The suspended
particles are broken to produce colloidal size particle.
* This method is used to prepare printing ink.

(b) Electrical disintegration or Bredig's Arc method: This process involves

dispersion as well as condensation. Colloidal sols of less reactive metals such as
gold, silver, platinum, copper, lead etc., can be prepared by this method. In this
method, electric arc is struck between electrodes of the metal immersed in the
dispersion medium as shown in fig. The intense heat produced vaporises the
metal, which then condenses to form particles of colloidal size by surrounding
cooling mixture (ice).
*A slight trace of KOH is added in water to stabilized colloidal solutions.

Ultrasonic dispersion : Ultrasonic vibration (having frequency larger than audible range) can bring about the
transformation of coarse suspension or liquids like oil, mercury etc. colloidal range.
*This is the latest method for preparation of metal oxides and metal sulphide sols from their coarse suspension.
*It is a suitable technique for oils also. This method also comprises both dispersion and condensation.
(c) Peptization: The term has originated from the digestion of proteins by the enzyme pepsin. Peptization may be
defined as the process of converting a precipitate into colloidal sol by shaking it with dispersion medium in the
presence of a small amount of electrolyte. The electrolyte used for this purpose is called peptizing agent. This
method is applied, generally, to convert a freshly prepared precipitate into a colloidal sol. During peptization, the
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precipitate adsorbs one of the ions of the electrolyte on its surface. The ion adsorbed on the surface is common either
with the anion or cation of the electrolyte. This causes the development of positive or negative charge on precipitates
which ultimately break up into smaller particles having the dimensions of colloids.

For example :
(i) When freshly precipitated Fe(OH)3 is shaken with aqueous solution of FeCl3 (peptizing
agent) it adsorbs Fe3+ ions and thereby breaks up into small-sized particles.
3+ 3+ 3+
FeCl3  Fe + 3Cl– , Fe(OH)3 + Fe  Fe(OH)3 | Fe
(ii) Freshly prepared stannic oxide on treatment with a small amount of dilute hydrochloric acid forms a stable colloidal
sol of stannic oxide, SnO2 ; Sn4+ .
SnO2 + 4HCl  Sn4+ + 2H2O + 4Cl– .
(iii) Freshly precipitated silver chloride can be converted into a colloidal sol by adding a small amount of hydrochloric
acid, AgCl : Cl– .
(iv) Cadmium sulphide can be peptised with the help of hydrogen sulphide, CdS : S2– .

Purification of Colloidal Sols -The colloidal sols obtained by various methods are impure and contain impurities of
electrolytes and other soluble substances. These impurities may destabilise the sol. Hence, they have to be removed. A
very important method of removal of soluble impurities from sols by a semipermeable membrane is known as dialysis.
A. Dialysis : It is a process of removing a dissolved substance from a colloidal solution by means diffusion through
suitable membrane. Since particles in true solution (ions or smaller molecules) can pass through animal membrane
or parchment paper or cellophane sheet but colloidal particle do not, the apparatus used for this purpose is called
Dialyser.
A bag of suitable membrane. containing the colloidal solutions is suspended in a vessel through which fresh water
continuous flow. The molecules and ions (crystalloids) diffuse through membrane into the outer water & pure colloidal
solution is left behind. Movement of ions across the membrane can be expedited by applying electric potential through
two electrodes as shown in fig. This method is faster than simple dialysis and is known as Electro dialysis.
*The most applications of dialysis is in the purification of blood in the artificial kidney machine. In case of kidney
failure, blood cannot be purified. under such condition, the blood is separated from dissolved toxic impurities by
dialysis and re-introduced in the bloods stream.
*Dialysis is not applicable for non-electrolytes like glucose, sugar, etc.

Fig -

B. Ultra Filtration : In this method, colloidal sols are purified by carrying out filtration through special type of graded
filters called ultra-filters. These filter papers allow only the electrolytes to pass through. These filter papers are made of
particular pore size by impregnating with colloidal solution and subsequently hardened by soaking in formaldehyde
collodion . In order to accelerate the filtration through such filter papers, increased pressure or section is employed.
*Collodion-4% solution of nitro Cellulose is peptized by organic solvent such as ethyl alcohol, ether. The product
obtained is commonly collodion.

C. Ultra- centrifugation : In this method, the colloidal sol is taken in a tube which is placed in an ultra-centrifuge. On

5
rotation of the tube at high speeds, the colloidal particles settle down at the bottom of the tube and the impurities
remain in the solution called the centrifugate. The settled colloidal particles are mixed with an appropriate dispersing
medium to regenerate the sol.

Important properties of colloidal sols :

Heterogeneous character : Colloidal sols are heterogeneous in character as they consist of two phases.
(a) dispersed phase and (b) dispersion medium.
Visibility : Due to scattering caused by the colloidal particles, it will appear as a bright spot moving randomly.
Filterability : Colloidal particles pass through an ordinary filter paper. However, the particle do not pass through and
other fine membranes.
Colligative Properties : Colloidal sols show the colligative properties viz. relative lowering of vapour pressure, elevation
in boiling point, depression in freezing point and osmotic pressure. However, due to high average molecular masses of
colloidal particles, mole fraction of the dispersed phase is very low. Hence, the values of the colligative properties
observed experimentally are very small. Only osmotic pressure measurements are used in determining the molecular
mass of polymers.
Optical Properties-Tyndall effect : Tyndall, in 1869, observed that if a strong beam of light is passed through a
colloidal sol placed in a dark place, the path of the beam gets illuminated. This phenomenon is called Tyndall effect,
which is due to the scattering of light by the colloidal particles. The illuminated path of beam is called Tyndall cone.
This phenomenon is due to scattering of light from the source of colloidal particles. In a true solution there are no
particles of sufficiently large diameter to scatter light & hence the beam is invisible.
*The intensity of scattered light depends on the difference between the refractive indice of the D.P and D.M.
In lyophobic colloids this difference is appreciable and therefore the Tyndall effect is quite well defined but in lyophilic
sols the difference is very small and the Tyndall effect is very weak. Thus in sols of silicic acid, blood serum, albumin,
etc. there is little or no Tyndall effect.

Example of Tyndall Effect

(1) Blue colour of sky and sea water (2)Visibility of tail of comets (3) Light thrown from a projector in cinema hall.
(4)Appearance of dust particle in a semi darkened room.
Application Of Tyndall Effect :
(i) In making ultra microscopes. (ii) In finding heterogeneity of solution.
Example - Under what conditions is Tyndall effect observed ?
Solution. Tyndall effect is applicable when :
(a) The diameter of the dispersed particles is not much smaller than the wavelength of the light used.
(b) The refractive indices of the dispersed phase and the dispersion medium must differ greatly in magnitude.
Example -In the lower layer of the atmosphere, there is a great deal of dust. When the weather is fine, it is possible to
see the magnificent rd colour of the setting sun. What have these observation to do with colloids ?
Solution. -Dust in the atmosphere is often colloidal. When the sun is low down on the horizon, light from it has to pass
through a great deal of dust to reach your eyes. The blue part of the light is scattered away from your eyes. You see the
red part of the spectrum, which remains. Red sunsets are the Tyndall effect on a large scale.

Mechanical Properties : Brownian movement:Robert Brown, a botanist, discovered in 1827 that pollen grains placed in
water do not remain at rest but move about continuously and randomly. Later on, this phenomenon was observed in
case of colloidal particles when they were seen under an ultra microscope. The particles were seen to be in constant
zig-zag motion as shown in fig. This zig-zag motion is called Brownian movement.
Brownian movement arises because of the impact of the molecules of the dispersion medium with the
colloidal particles. It has been postulated that the impact of the molecules of the dispersion medium on the colloidal
particle are unequal leading to zig-zag motion. However, as the size of the particle increases, the effect of the impacts
average out and the Brownian movement becomes slow. Ultimately, when the dispersed particle becomes big enough
to acquire the dimensions of suspension, no Brownian movement is observed.

6
 Factors Affecting Brownian Movement :
(i) If particles is large then Brownian movement becomes less. (ii) Brownian movement increases with increasing
temperature.
(iii) The Brownian movement does not change with time & remains same for months or even for a year.
Important :
(i) In confirmation of kinetic energy. (ii) Determination of Avogadro numbers.
(iii) Stability of colloidal solution : Brownian movement does not allow the colloidal particles to settle down to gravity &
thus is responsible for their stability.
Electrophoresis ( cataphoresis) : The particles of the colloids are electrically charged and carry positive or negative
charge. The dispersion medium has an equal and opposite charge making the system neutral as a whole. Due to
similar nature of the charge carried by the particles, they repel each other and do not combine to form bigger particles.
That is why, a sol is stable and particles do not settle down. Arsenic sulphide, gold, silver and platinum particles in their
respective colloidal sols are negatively charged while particles of ferric hydroxide, aluminium hydroxide are positively
charged. The existence of the electric charge is shown by the phenomenon of electrophoresis. The phenomenon of
the 'movement of colloidal particles either towards the cathode or anode, under the influence of the electric field' is
called electrophoresis . The apparatus used for electrophoresis as shown in fig.

The colloidal solution is placed in a U-tube fitted with platinum electrodes. On passing an electric current, the charged
colloidal particles move towards the oppositely charged electrode. Thus, if arsenic sulphide sol is taken in the U-tube, in
which negatively charge particle of arsenic sulphide move towards the anode. *Earlier this process was called
cataphoresis because most of the colloidal sols studied at that time were positively charged and moved towards
cathode.
Electro -osmosis : The movement dispersion medium (D.M) from a colloidal solution in electric field by prevented the
movement of colloidal particle (D.P) with some suitable means ( porous diaphragm or semi permeable members) is
called as electro- osmosis.
Take the pure solvent (dispersion medium) in two limbs of U-tube. In the lower middle portion of U-tube, a porous
diaphragm containing the colloidal system is present which divides the U-tube in two sections. In each section of U-
tube,an electrode is present,as shown in figure.When the electrode potential is applied to the electrodes, the solid
phase of sol .(colloidal system) can not move but the solvent(dispersion medium) moves through the porous
diaphragm towards one of the electrodes.The direction of migration of dispersion medium due to electro-osmosis
determines the charge on sol. particles e.g., if the dispersion medium moves towards the cathode (negative electrode),
the sol. particles are also negatively charged because the dispersion medium is positively charged as on the whole
colloidal solution is neutral.

Sedimentation potential or Dorn potential : When the charged colloidal particles are made to settle down under
centrifugal field, the colloidal particle get distributed under the gravity , heavy particles at the bottom and light particles
at the top , such a movement and distribution of colloidal particle under the influence of gravity is called sedimentation ,
a potential is developed between the top and the bottom layers , such a potential is called sedimentation potential ,
since this effect was first observed by Dorn , so it is also known as called Dorn effect and the potential difference

7
thus developed is also called Dorn potential
This process is reverse of electrophoresis.
Iso-electric point : The H+ concentration at which the colloidal particles have no charge & do not move under influence
of electric field is known as the iso-electric point. At this point stability of colloidal particles becomes very less .
Streaming potential : A potential difference is developed across a porous partition or capillary when the dispersion
medium of a
charged colloid is forced through it. This is called Streaming potential. This process is reverse of electro-osmosis.
Charge on colloidal particles : Colloidal particles are either positively charged or negatively charged. This cahrge is due
to preferential adsorption of either positive or negative ions on their surface. There is adsorption of common ion
present in excess.
Fe(OH)3 sol prepared by the hydrolysis of FeCl3 solution adsorbs Fe3+ and this is positively charged.
FeCl3 + 3H2O Fe(OH)3 + 3HCl
3+
Fe(OH)3 + FeCl3 [Fe(OH)3 ]Fe : 3Cl
Fixed part Diffused part.
Positive charge on colloidal sol is due to adsorption of Fe3+ ion (common between Fe(OH)3 and FeCl3 .
As2S3 colloidal sol is obtained when As2O3 is saturated with H2S :
As2O3 + 3H2S  As2S3 + 3H2O.
As2S3 adsorbs S2– ions (common between H2S and As2S3 and thus is negatively charged).
2– +
As2S3 + H2S |As2S3 |S : 2H .
Fixed part Diffused part.
AgI in contact with AgNO3 forms positively charged colloidal sol due to adsorption of Ag+ ion.
AgI + AgNO3  [AgI]Ag+ : NO3– ,
Fixed part Diffused part.
AgI in contact with KI forms negatively charged colloidal sol due to adsorption of I– ion
AgI + KI  [AgI]I– : K+.
Fixed part Diffused part.
SnO2 in acidic medium forms positively charged colloidal sol due to adsorption of Sn4+ formed.
SnO2 + 4H+  Sn4+ + 2H2O ,
SnO2 + Sn4+  [SnO2 ] : Sn4+
Fixed part Diffused part.
SnO2 in alkaline medium forms negatively charged colloidal sol due to adsorption of SnO3 2– formed.
SnO2 + 2OH–  SnO3 2– + H2O ,
SnO2 + SnO3 2–  [SnO2 ] : SnO3 2–
Fixed part Diffused part.
Electric Double Layer Theory or HELM-HOLTZ Electric double layer : The surface of colloid particles acquire a positive
or negative charge by the selective (preferential) adsorptions of common ions carrying positive or negative charge
respectively to form first layer. This layer attract counter ions from D.M with from a second layer. The combination of
two layers of opposite charge around the colloidal particle is called Helm Holt Electric Double Layer. The first layer of
ions is firmly held and is termed fixed layer while the second layer is mobile which is turned as diffused layer. The
charge of opposite ions of fixed and diffused layer double layer results in a difference in potential between these
layer , this potential difference between two opposite charge layer is called. The electro kinetic potential or zeta
potential which can be given by

Example : When silver nitrate solution is added to KI solution, the precipitation of AgI adsorb iodide ions from
the D.M with the formation of fixed layer and negatively charged colloidal solution form, however when KI solution is
added to AgNO3 solution positive charge sole result due to the adsorbs of Ag+ ions from D.M.
–
AgI/I AgI/Ag+
Negative charged Positively charged.
This fixed layer attracts counter ions from the medium forming a second layer.
Example Classify the following sols according to theirs charges :
(a) gold sol (b) ferric hydroxide sol (c) gelating (d) blood (e) sulphur (f) arsenious sulphide (g) titanium
oxide.
Solution. -Negatively charged colloidal sol : (a), (c), (e), (f). positively charged colloidal sol : (b), (d), (g).

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Example -SnO2 forms positively charged colloidal sol in acidic medium and negatively charged colloidal soln in basic
medium. Explain ?
Solution. - SnO2 is amphoteric reacting with acid and base both. In acidic medium (say HCl) Sn4+ ion is formed which
is preferentially adsorbed on SnO2 giving positively charged colloidal sol :
SnO2 + 4HCl  SnCl4 + 2H2O
SnO2 + SnCl4  [SnO2 ]Sn4+(positively charged) + 4Cl–.
Example -The particles of a particular colloidal solution of arsenic trisulphide (As2S3) are negatively charged. Which
0.0005 M solution would be most effective in coagulating this colloidal solution. KCl, MgCl2, AlCl3 or Na3PO4 ? Explain.
Solution. Since As2S3 is a negatively charged colloidal sol hence positively charged ion will cause its coagulation. By
Hardy-Schulze rule “greater the charge on ion, greater the coagulating power to coagulate oppositely charged colloidal
sol”, hence out of K+ , Mg2+, Al3+ and Na+ , Al3+ would be most effective.
Coagulation/Flocculation : The presence of small amounts of appropriate electrolytes is necessary for the stability of
the colloids.
However, when an electrolyte is added in larger concentration; the particles of the sol take up the ions which are
oppositely charged and thus get neutralized. The neutral particles then start aggregating giving particles of larger size
which are then precipitated. This process of aggregation of colloidal particles into an insoluble precipitate by the
addition of some suitable electrolyte is known as coagulation. At lower concentration of electrolytes, the aggregation
of particles is called flocculation that can be reversed on shaking while at higher concentration of electrolyte,
coagulation takes place and the same cannot be reversed simply by shaking.The stability of the lyophobic colloids is
due to presence of charge on colloidal particles.If, somehow, the charge is removed, the particles will come nears to
each other to form aggregates and settled down under the force of gravity
Coagulation of lyophobic sols can be carried out by the following methods.

(i) By electrophoresis
(ii) By mutual precipitation : It is a process in which oppositely charged sol. are mixed in proper proportion to neutralize
the charge of each other causing coagulation of both the sol.
Example : Positively charged Fe(OH)3 and negatively charged As2S3 colloidal particle containing sol. on mixing get
coagulated.
(iii) By Prolonged Dialysis : On prolonged dialysis, traces of the electrolyte present in the sol are removed almost
completely and the colloidal unstable and ultimately coagulate.
(iv) By Boiling : Sols such as sulphur and silver halides dispersed in water may be coagulated by boiling because
increased collisions between sol particle and the water molecule removed the adsorbed electrolytes. This takes away
the charge from the particles and helps them to coagulate.
(v) By cooling : Certain sol can also be coagulated by lowering temperature. For example, acculation of cream on the
surface of milk on cooling. This is because at lower temperature the dispersion medium
molecules do not exert sufficient force on to the dispersed particles and hence the Brownian motion becomes less
effective.
(vi) By the addition of electrolyte : When excess of an electrolyte is added, the colloidal particles are precipitated.
Coagulation value or Flocculation value : It needs to be noted that 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 concentration of electrolyte in millimoles required to cause coagulation of a one litre of colloidal solution in
two hours is called coagulation value. It is express in terms of millioles/litre.
Coagulation value = milli moles of electrolyte / volume of sol in litre
1
Flocculation value 
Coagulatin g power
Comparison of relative coagulating power of two electrolyte for the same colloidal solution : The coagulation value
decrease with increase in charge of the coagulating ion.

Factor-Affecting Coagulation :
(i) Nature of sols : The lyophobic colloid can easily coagulate because it is a less stable colloid, but lyophilic colloids
can not coagulate easily due to protective layer of D.M. surrounding the colloidal particle. It can easily coagulated by
the addition of electrolyte
(ii) Nature of electrolyte : In equimolar electrolyte strong electrolyte have greater coagulating power than weak

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electrolyte. Example :
0.1 M NaCl > 0.1 M CH3COOH.
Hardy-Schulze Rule : According to this rule , greater is the valency of coagulating ion , greater will be its coagulation
power to precipitation. This is known as Hardy-Schulze. In case of positive charged particle sol,
the coagulating power of anion is in the order of –
[Fe(CN)6]4– > PO4 3– > SO4 2– > Cl–.
In case of negative charged particle sol, the coagulating power is in the order of.-
Si +4 > Al3+ > Ba2+ > Na+.
The coagulating power of bivalent ion is 20.80 times higher than monovalent ion and coagulating power of trivalent is
many times more than bivalent.
Protection of colloid : Lyophilic colloidal sols are much more stable than lyophobic colloidal sols. This is due to the
extensive
solvation of lyophilic colloidal sols, which forms a protective layer outside it and thus prevents it from forming
associated colloids. Lyophobic sols can easily precipitate by addition of small amount of an electrolyte. They can be
prevented from coagulation by previous addition of some lyophillic colloid. This is due to formation of a protective
layer by lyophilic sols outside lyophobic sols. This is process is protecting the lyophobic colloid solution from
precipitation by an electrolyte due to previous addition of some lyophilic colloid is called protection of colloid and
lyophilic colloidal sols are called protective sols.
Eg : Gelatin, Sodium caseinate, Egg albumin, Gum arabic, Potato starch etc.,
Gelatin (lyophilic) protects gold sol (lyophobic) colloids is expressed in terms of gold number.
Some examples of protective colloids are :
(i) Soluble substance like Ca3(PO4)2 are held as colloids in blood due to protective action of protein in blood.
(ii) To prevent clogging in pens ; superior pen inks contain some protective colloids.
(iii) Casein in human milk is better protected than in the cow's milk. It is because of this that cow's milk is more
easily coagulated.
(iv) Protargol and Argyrol podwers are the protected forms of colloidal silver.
Gold Number : Protective power of colloid can be express in terms of a Gold no. This is defined as ‘’the minimum
amount of the protective colloid in milligrams required to just prevent the coagulation of a 10 ml of a gold colloidal
solution by addition of 1 ml of 10% solution of sodium chloride is added to it’’. It may be noted that smaller of the gold
number, greater will be protecting power of the protective colloid.
Protecting power  gold number
Gold Number = weight of lyophilic sol in mg x 10 / volume of gold sol in mL
The gold numbers of a few protective colloids are as follows :
S.N protective colloids Gold number
1 Gelatin 0.005 - 0.01
2 Haemoglobin 0.03 - 0.07
3 Egg albumin 0.1 - 0.2
4 Gum arabic 0.15 - 0.25
5 Dextrin 6 – 6.2
6 Starch 20 - 25
Congo Rubin number : Ostwald introduced Congo Rubin number to account for protective nature of colloids. It is
defined as the amount of protective colloid in milligrams which prevents colour change in 100 ml of 0.01% Congo
Rubin dye to which 0.16 g equivalent of KCl is added.
Uses of protective action :
(i) Gelatin is added in the preparation of ice cream to protect the particle of ice.
(ii) Protargol ( nose and ear) and Argyrol (used as eye drop) is a silver sol protected by organic material.
Applications of Colloids : Colloids including emulsions find a number of uses in our daily life and industry. Some of the
uses are given below.
1- In medicines : A wide variety of medicinal and pharmaceutical preparations are emulsions. Colloidal medicines are
easily adsorbed by the body tissue because of large surface area.
* Colloidal antimony is used in curing kala-azar (black fever ).
* Milk of magnesia, an emulsion, is used for stomach disorder.
* Colloidal gold is used for intramuscular injection.
* Colloidal sulphur are used as germicides.
* Argyrol is a silver sol used as an eye lotion.
* Colloidal Fe(OH)3 is given to arsenic poisoning patients as it adsorbs arsenic and then gets vomited out.
2-Tanning : Animal hides are colloidal in nature. Which contain positive charge colloidal particles of protein. This hide is
kept in a tank containing tanning acid, which contains negatively charge colloidal particle. Therefore, mutual
coagulation takes place this results in hardening of leather this process is termed as tanning of leather. Chromium
salts are also used in place of tannin.
3- Rubber Industry : Latex is a colloidal solution of rubber particle which are negatively charge. Rubber is obtained by
coagulation of latex.

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 4-Photographic plate & Film : Photographic plate or films are prepared by coating an emulsion of the light sensitive
silver bromide in gelatin over glass plates or celluloid films. Gelatin prevent the coagulation of colloidal particle of AgBr.
5- Rubber plating : The negatively charged rubber particles from rubber sol are deposited on wares and handles of
different tools. Rubber gloves are formed by rubber plating on suitable templates.
6-Sewage disposal : Sewage water contains charged colloidal particles of dirt, rubbish, etc., and these do not settle
down easily. The particles can be removed by discharging them at electrodes. Dirty water is passed through a tunnel
fitted with metallic electrodes which are maintained at high potential difference. The particles migrate to the oppositely
charged electrode, lose their charge and get coagulated. The deposited matter is used as a manure and the water left
behind is used for irrigation.
7-Cottrell smoke precipitator : Smoke is a dispersion of negatively charged
colloidal particles of carbon in air and can be made free of these colloidal
particles by passing it through cottrell precipitator as shown in fig. installed
in the chimney of an industrial plant. It consists of two metal discs charged
to a high potential. The carbon particles get discharged and precipitate,
while gases come out from the chimney.

8-Formation of deltas : The river water contains colloidal particles of sand and clay which carry negative charge. The
sea water contains +ve ions such as Na+ , Mg2+, Ca2+, etc. As the river water meets sea water, these ions discharge the
sand or clay particle which are precipitated in the form of delta.
9-Artificial rain : Cloud consists of charge particle of water disperse in air. Rain is caused by aggregation of these
minute particles, artificial rain can be done by throwing electrified sand or Agl from aeroplane, colloidal H2O particle
present in cloud will get coagulated by these sand or Agl particles to form bigger water drops causing rain.
10-Stop bleeding from a cut : Blood is a colloidal solution containing a –ve charge colloidal particle (Albuminoid),
bleeding can be stopped by use of alum or FeCl3 solution. The addition of Al3+ or Fe3+ causes coagulation of blood, so
bleeding stops.
11-Stop Screen : It is used warfare for concealment and camouflage by spraying very fine particles of titanium oxide
from aeroplane. As titanium oxide is very heavy, the smoke screen drops down rapidly as a curtain of dazzling
whiteness. This is due to scattering of light by colloidal particles.
14-Preparation of nano-materials : These materials are prepared for use as catalyst by using reverse micelle.
15-In disinfectants : The disinfectants such as dettol and lysol give emulsions of the oil-in-water type when mixed with
water.
16-In metallurgical operations : Emulsions play an important role in industry. The metal ores are concentrated by froth-
flotation process which involves the treatment of the pulverized ore in emulsion of pine oil.
17- Building roads : Asphalt emulsified in water is used for building roads without the necessity of melting the asphalt.
STEM TECHNOLOGY : The size and shape of the colloidal particles is determined with the help of an electron
microscope which has much more resolving power (of the order of 10–12m.) The different techniques used to study
the colloidal particles are :
(i) Scanning electron microscope (SEM)
(ii) Transmission electron microscope (TEM) and
(iii) Scanning transmission electron microscope (STEM).
Emulsions : Pair of immiscible liquid is called emulsion. Emulsion are unstable and some time they are separated into
two layers on keeping still, for the stabilizing of an emulsion, a 3rd component is added called emulsifying Agent from
an inter facial film between D.P. and D.L. Emulsion droplets are bigger than sol particles and can be seen under an
ordinary microscope and sometimes even with a magnifying glass.
Example : Milk is an emulsion in which liquid fat is D.P. and liquid water is D.M. and casein is emulsifying agent.
Demulsification : The separation of an emulsion into its constituent liquids is called demulsification.
Various techniques employed for this are freezing, boiling, centrifugation, electrostatic precipitation or chemical
methods which destroys the emulsifying agents.
Demulsification can be brought about by :
(i) Freezing (ii) Heating (iii) Centrifugal action (Separation of cream of milk done by centrifugation).
(iv) Removable of emulsifiers by adding a better solvent for them like alcohol, phenol etc, called demulsifiers
Types of emulsions : Depending on the nature of the dispersed phase, the emulsions are classified as :
(a) Oil in water emulsions (b) Water in oil emulsions
(a) Oil in water emulsions (o/w) : This type of emulsions is formed when oil is D.P. and water is D.M.
Ex. :- Milk and vanishing cream are oil - in - water type emulsions. These are also called aqueous emulsions
(b) Water in oil emulsions (w/o) :
This type of emulsions is formed when water is D.P. and oil is D.M.
Ex. : - Cold cream and cod liver oil. These are also called oil emulsion

11
Inversion of phase : The conservation of emulsion of oil in water (o/w) into water in oil (w/o) or vice versa is called the
inversion of phase.
[A] Identification of the type of emulsion : These two types may be identified by :
Dilution test : An emulsion can be diluted with any amount of the dispersion medium, while the dispersed liquid, if
added, forms a separate layer. Thus if a few drops of water added to the emulsion are soluble in it, it is oil in water type
and if immiscible, it is water in oil type.
Dye test : If a small amount of oil soluble dye gives a uniform colour to the emulsion, it is water in oil type otherwise it
is oil in water type.
Electrical conductivity test : If conductivity of emulsions increases significantly by adding a very small amount of
electrolyte, it is oil in water type and if there is no significant increase in conductivity, it is water in oil type.
Applications of emulsions : Disinfectant like phenyl, dettol when mixed with water form emulsion. Digestion of fat in
small intestine occurs easily due to emulsion. In metallurgical process the concentration of ore by froth flotation
method is based upon emulsion. Milk is an emulsion of liquid fat in water in which casein emulsifying agent.
Cleansing action of soap is due to formation of emulsions. Soaps and detergents emulsify the grease along with the
adhering dirt and carry them away in the wash water. For concentrating ores, the finely powdered ore is treated with an
oil. Oil forms emulsion with the ore
particles. When air is bubbled into the mixture, emulsion containing the particles of the mineral are carried to the
surface.
Several oily drugs are prepared in the form of emulsions to facilitate their absorption in the body. Many of the lotions,
creams and ointments are emulsions of oil - in - water or water - in oil type.
Petroleum products get emulsified in the oil - well, causing problems. However, they can be demulsified into
constituent liquids by physical methods such as centrifugation, freezing, filtration, electrostatic precipitation etc.
Asphalt emulsified in water can be used for building roads without the necessity of melting the asphalt.
Properties of emulsion : Emulsion exhibit properties like Tyndall effect, Brownian movement, electrophoresis
coagulation as shown by colloidal sols. Emulsions can be broken to yield the constituent liquids.
Harmful effects of emulsion :
(i) Emulsion of water in petroleum found in oil wells creates problems during the distillation.
(ii) Petroleum in water emulsion in ground water is found in the areas where a small amount of petroleum is present.
This makes the ground water unfit for human consumption.
(iii) Emulsion of petrol in water in sea during oil seepage from oil tankers causes a great damage to aquatic life.
Gel : There are some sols that have high concentration of dispersed solid and change spontaneously into semi solid
form (gelly-like) on cooling, these are known as gel and the process in known as gelation.
Ex : Gelain dissolved in water forming a colloidal. Sol Which when cooled sets into a gelly.
*Gel have honey-comb structure :
Ex : Sillicic acid, Gum arabic, Sodium oleate, Gelatin, Solid alcohol, etc.
Types of Gel :
(i) Elastic gel : Those gel which have elastic properties. Ex. Gelatin, Starch, Agar-Agar etc.
(ii) Non- elastic gel : Those gel which are rigid. Eg : Silica gel.
Properties of Gel :
1. Syneresis/weeping of gel : The spontaneous liberation of liquid from a gel is called syneresis or weeping of gels. It
is reverse of swelling. Eg : Gelatin, Agar-Agar show syneresis at low concentration while silicic acid shows it at high
concentration.
2. Imbibition or swelling of gel : When gel is kept in a suitable liquid (water) it absorb large volume of liquid. The
phenomenon is called.
3. Thixotropic : Some gels when shaken to form a sol, on keeping changes into gel are termed as thixotropic gel and
phenomenon is called thixotropy .
Eg : Gelatin and silica liquefy on shaking changing into corresponding sol and the sol on keeping changes back into gel.
[C] Associated colloids (Micelles) : There are some substances which at low concentrations behave as normal, strong
electrolytes but at higher concentrations exhibit colloidal behaviour due to the formation of aggregated particles. The
aggregated particles thus formed are called micelles. These are also known as associated colloids. The formation of
micelles takes place only above a particular temperature called Kraft Temperature (Tk) and above a particular
concentration called Critical Micelle Concentration (CMC). On dilution, these colloids revert back to individual ions.
–4
Surface active agents such as soaps and synthetic detergents belong to this class. For soaps, the CMC is ~ 10 to
–3 –1
10 mol L . These colloids have both lyophobic and lyophilic parts. Micelles may contain as many as 100 molecules
or more. Mechanism of micelle formation: Let us take the example of soap solutions. Soap is sodium salt of a higher
– + – +
fatty acid and may be represented as RCOO Na e.g., sodium stearate viz.CH3(CH2) 16COO Na which is a major

12
component of many bar soaps. When dissolved in water, it dissociates into RCOO- and Na+ ions. The RCOO– ions,
however, consist of two parts i.e., long hydrocarbon chain R (also called non-polar 'tail') which is hydrophobic (water
repelling) and the polar group COO– (also called polar-ionic 'head') which is hydrophilic (water loving). The RCOO– ions
are, therefore, present on the surface with their COO– groups in water and the hydrocarbon chains R staying away from
it, and remain at the surface, but at higher concentration these are pulled into the bulk of the solution and aggregate in
a spherical form with their hydrocarbon chains pointing towards the centre with COO– part remaining outward on the
surface. An aggregate thus formed is known as ‘Ionic micelle'. These micelles may contain as many as up to 100 such
ions.

Aggregation of RCOO– ions to form an ionic micelle.

Similarly, in case of detergents, e.g., sodium lauryl sulphate viz. CH3(CH2) 11SO4– Na+ , the polar group is SO4- along with
the long hydrocarbon chain. Hence, the mechanism of micelle formation is same as that of soaps.
Critical micell concentration [CMC] : The minimum concentration required for micell formation is called critical micell
concentration. Its value depends upon the nature of D.P. and D.M. For eg. Surface active agent (surfactants, which
decrease the surface tension) like soaps and detergents form micellies beyond CMC
(~10–3 mol/litre for soaps).
* Usually longer the hydrophobic chain, smaller is its CMC.
* Also CMC increase with decreasing polarity of the D.M.
* The micelles ‘formation takes place only above a particular temperature called as Kraft Temperature (Tk ).
*At CMC, the micelles are spherical in shape, but that startflattening with increase in concentration and ultimately
form sheet or film like structures which have a thickness of two molecules. These are called lamelar micelles or
McBain Micelles.
Example of micell :
(i) Sodium stearate C17H35COO–Na+ (Soap).
(ii) Sodium lauryl sulphate CH3 [CH2]11 SO4– Na+ (Detergent).
(iii) Cetyl trimethyl ammonium bromide (Detergent). CH3(CH2)15N+ (CH3)3Br–.
(iv) Sodium p-dodecylbenzenesulphonate (Detergent).
(v) Acidic (negative colloids) and basic (positive colloids) dyes.
[D] The Cleansing Action of Soaps : It has been mentioned earlier that a miscelle consists of a hydrophobic
hydrocarbon like central core. The cleansing action of soap is due to these micelles, because oil and grease can be
soluble in their hydrocarbon, like centre which are not otherwise soluble in water. This is shown diagrammatically in
Fig. The dirt goes out along with the soap miscelles.

Fig. : The cleansing action of soap. (a) A sodium stearate molecule (b) The simplified representation of the molecule
that shows a hydrophilic head and a hydrophobic tail (c) Grease (oily substance) is not soluble in water (d) When soap
is added to water, the non-polar tails of soap molecules dissolve in grease (e) Finally, the grease is removed in the form
of micelles containing grease.
Surfactants :
They can be ionic as well as non-ionic. The ionic are soaps and detergent. The surfactant gets adsorbed at the
interface between the dispersed droplets and dispersion medium in a form of mono molecular layer and lowers the
inter facial tension between oil and water so as to facilitate the mixing of two liquids.

13