COLLOIDS

THE COLLOIDAL STATE:

While studying the diffusion of solutions through an animal membrane, Thomas Graham (1861)
observed that certain substances such as sugar, urea, sodium chloride etc. in the dissolved state
passed through the membrane, while the solutions of substances such as glue, gelatin, gum
Arabic etc. did not. This observation led him to classify the soluble substances into two
categories:
(i) Crystalloids
(ii) Colloids
According to Graham, crystalloids were those substances which could be obtained in crystalline
form and whose solutions were able to pass through an animal membrane. On the other hand,
colloids were those substances which were amorphous in nature and whose solutions were unable
to pass through the membrane. However, it was soon realized that the classification of dissolved
substances made by Graham was not tenable because certain substances could act both as
crystalloids and colloids.
Later on it was found that the diffusibility of crystalloids and non-diffusibility of colloids through
an animal membrane was due to the difference in the size of their particles. Crystalloids formed
smaller particles in solutions and therefore passed through the membrane. On the other hand,
colloids formed larger particles (larger than the dimensions of the pores of the membrane) in
solutions and were unable to pass through the membrane.
On the basis of the size of particles, the systems containing dispersed particles can be divided
into following three categories.
1. True solutions: True solutions are homogeneous system and have the size of dispersed
particles less than 1 nm, i.e. 10 -9 . The particles of solute present in a true solution are
either single molecules or irons and are homogeneously distributed throughout the
solutions. These particles are invisible and cannot be seen even with a microscope. Due to
very small size of dispersed particles, true solutions pass through ordinary filter paper as
well as through animal membranes. Sodium chloride, sugar, urea etc. form true solutions
in water.
2. Colloidal solutions: Colloidal solutions are heterogeneous systems and have the size of
dispersed particles lying between 1 nm-1000 nm (i.e. 10-9-10-6 m). The particles in a
colloidal solution are thus larger particles and are referred to as colloidal particles.
Although colloidal particles are larger in size, yet they are not large enough to be seen
with naked eye. However, they can be seen with the help of an ultra microscope.
Colloidal solutions can pass through ordinary filter paper but not through an animal
membrane, Gum Arabic, gelatin, glue etc. form colloidal solutions when dispersed in
water.
3. Suspensions: Suspensions are also heterogeneous system and have still larger particles.
The size of particles present in a suspension is more than 1000 nm (i.e., >10 -6m). These
particles are either visible to naked eye or can be seen under a microscope. The
suspensions neither pass through an animal membrane nor through an ordinary filter
paper. Stirred muddy water is an example of suspensions.

The three types of systems containing

dispersed particle of different size.
The three types of dispersed systems are diagrammatically shown in figure.
Table: Important Characteristics of True solutions,Colloidal solutions and Suspensions
S.No.
Property
True solution
Colloidal solution
Suspension
1.
Particle size
Less than 1 nm
Between 1 nm-1000nm Greater than 100nm
(i.e. 10-9m)
(i.e. 10-9m-10-6m)
(i.e. 10-6m)
2.
3.

Nature
Visibility of
particles

Homogeneous
Invisible

4.

Appearance

Transparent

5.

Filterability

6.

Setting of
particles under
gravity

7.

Diffusion of
particles
Scattering of
Does not scatter
light by particles light
(Tyndall effect)

8.

Heterogeneous
Visible under ultramicroscope

Generally transparent
but may show
translucence
Passes easily
Passes easily through
through ordinary ordinary filter paper but
filter paper as well not through animal
as animal
membranes
membranes
Particles do not
Colloidal particles do
settle
not settle under gravity.
However, they can be
made to settle under
high speed
centrifugation
Diffuses rapidly Diffuses slowly

Heterogeneous
Visible to naked eye
or under microscope
Opaque

Does not pass either

through ordinary
filter paper or
through animal
membranes.
Particles settle on
standing

Does not diffuse

Scatters light and

Tyndall effect may
exhibits Tyndall effect be exhibited

Classification of colloids based on Physical state

Colloidal systems (colloidal solutions) are heterogeneous in nature and consist of following two
phases:
(i) Dispersed phase: The substance present in the form of colloidal particles in a colloidal
system constitutes the dispersed phase. Thus, the dispersed phase may be defined as the phase
constituting the colloidal particles. For example, in a colloidal solution of ferric hydroxide in
water, the ferric hydroxide particles are of colloidal size and constitute the dispersed phase.
(ii) Dispersion medium: The medium in which the colloidal particles are dispersed is called
dispersion medium. For example, in the colloidal solution of ferric hydroxide in water, water is
the dispersion medium.
Classification Based on Physical State of Dispersed Phase and Dispersion Medium.
Depending upon the physical state of the dispersed phase and dispersion medium, eight types of
colloidal systems are possible. These are described in the table given below:
S.No.
Dispersed
Dispersion Common name
Examples
phase
medium
of the system
1.

Solid

Solid

Solid sol

Gems, ruby glass, coloured glasses,

pigmented plastics etc.
Gold sol, sulphur sol, ferric
hydroxide sol, As2 S3 sol, ink, most
of the paints, starch dispersed in
water, muddy water etc.

2.

Solid

Liquid

Sol

3.

Solid

Gas

Aerosol of solids

Smoke, dust etc.

4.

Liquid

Solid

Gel

5.

Liquid

Liquid

Emulsion

6.

Liquid

Gas

7.

Gas

Solid

Aerosol of
liquids
Solid foam

8.

Gas

Liquid

Foam or Froth

Cheese, butter, boot polish, jellies

etc.
Milk, emulsified oils, medicines
etc.
Fog, mist, clouds, Liquid sprays
etc.
Pumice stone, styrene foam, foam
rubber etc.
Lemonade froth, soap lather,
shaving cream foam etc.

Table: Types of Colloidal Systems

It is to be noted that the colloidal system of a gas into some other gas is not possible because a
gas mixed with some other gas always forms a homogeneous gaseous solution. Since colloidal
systems are heterogeneous, they cannot be obtained by dispersing a gas into some other gas.
Among the various types of colloidal systems listed above, the more common and more
important ones are sols (solids dispersed in liquid), gels (liquids dispersed in solids) and
emulsions (liquids dispersed in liquids).
Sol is a general term and refers to a colloidal system obtained by dispersing a solid into a liquid.
Depending upon the nature of dispersion media, sols are usually given different names. For
example, sols consisting of water as dispersion medium are usually called hydrosols. Those
consisting of alcohol as dispersion medium are termed as alcosols, while those having benzene as

the dispersion medium are referred to as benzosols. Similarly, aerosols are the colloidal system
having air as the dispersion medium.
Classification of Colloids Based on Nature of Interaction Between Dispersed Phase and
Dispersion Medium
Depending upon the affinity of the dispersed phase for the dispersion medium, colloidal systems
can be classified into following two categories.
(i) Lyophilic sols
(ii)Lyophobic sols
1. Lyophilic sols: These tem lyophilic means liquid-loving (i.e. solvent loving). Certain
substances have an affinity for certain liquids and readily form colloidal dispersions with them.
The substances which when mixed with a suitable liquid (dispersion medium) readily form
colloidal solutions are called lyophilic colloids or intrinsic colloids and the sols thus formed are
called lyophilic sols. When water is used as the dispersion medium, such colloids are termed as
hydrophilic colloids and their colloidal dispersion in water are known as hydrophilic sols.
Arabic gum, gelatin, albumin, starch etc. are some common examples of lyophilic colloids. Gum
sol, starch sol, sols of proteins in water, sols of polymers in organic solvents etc. is some
examples of lyophilic sols.
Lyophilic sols are stable and do not get precipitated easily. In fact, they are self stabilized, i.e.
they do not require any stabilizing agent to preserve them. An important characteristic of these
sols is that if dispersed phase is separated from dispersion medium (say by evaporation), the
dispersed phase can again be brought in the sol state simply by mixing it with the dispersion
medium. This is why hydrophilic sols are also known as reversible sols.
2. Lyophobic sols: The term lyophilic means liquid-hating (i.e. solvent-hating). The substances
which do not pass much affinity for the dispersion medium and do not readily pass into the sol
state when mixed with the medium are called hydrophobic colloids or extrinsic colloids. Their
sols are prepared by using special techniques and they are referred to as hydrophobic sols. Sols of
metals e.g. gold sol, platinum sol etc. and the sols of insoluble substances such as metal sulphides
and oxides are some examples of lyophilic sols.
Lyophilic sols are relatively less stable as compared to lyophilic sols. They are easily precipitated
(or coagulated) on addition of small amounts of electrolytes, by heating or agitation. Moreover,
the precipitated dispersed phase cannot be brought back into the sol state by simply mixing it
with the dispersion medium. This is why hydrophobic sols are also known as irreversible sols.
The lyophobic sols need stabilizing agents to keep them in the sol form for a longer time.
The important points of difference between the lyophilic sols and lyophobic sols are summarized
in the table given below:
S.No. Property

Lyophilic sols

Lyophobic sols

1.

Lyophilic sols can be prepared

easily by simply shaking the
lyophilic colloids with the
dispersion medium

Lyophobic sols cannot be

obtained simply by shaking the
lyophobic colloids with the
medium. They can be obtained
only
by
using
special
techniques.

Ease of preparation

2.

Hydration

They are heavily hydrated.

They are not much hydrated.

3.

Stability

Due to hydration, they are quite They are less stable and get
stable and are not easily coagulated by heating, by
coagulated.
agitating or on addition of small
amount of an electrolyte.

4.

Reversibility

Reversible

5.

Visibility

The dispersed particles are The dispersed particles, through

neither visible nor detected easily not visible can be detected
even under ultra-microscope.
easily under ultra microscope.

6.

Viscosity

The viscosity is much higher than The viscosity is almost the same
that of the dispersion medium.
as that of the dispersion
medium.

7.

Surface tension

The surface tension is usually The surface tension is nearly the

lower than that of the dispersion same as that of the dispersion
medium
medium.

8.

Charge on particles

The dispersed particles have little The dispersed particles carry a

or no charge on them.
definite charge which is either
positive or negative.

9.

Migration of particles in The dispersed particles may Depending upon the nature of
an electric field
migrate in either direction or may charge present, the dispersed
not migrate at all.
particles migrate in a particular
direction.

Irreversible

Classification of Colloids Based on Type of Particles of the Dispersed Phase :

Multimolecular, Macromolecular and Associated Colloids
We have already seen that the colloidal particles present in a colloidal system have size lying in
the range 1nm-100nm. Depending upon how different substances forming colloidal solution
acquire the size of particles in this range, colloidal solutions may be classified into the following
three categories.
(i) Multimolecular colloids
(ii)Macromolecular colloids
(iii)Associated colloids
1. Multimolecular Colloids: When a large number of atoms or small molecules (having
diameters of less than 1nm) of a substance combine together in a dispersion medium to form
aggregates having size in the colloidal range, the colloidal solutions thus formed are called
multimolecular colloids. The species (atoms or molecules) constituting the dispersed particles in
multimolecular colloids are held together by Vander Waals forces. The gold sol, sulphur sol etc.
are some examples of multimolecular colloids. A gold sol may contain particles of various size
composed of several atoms of gold. Similarly, sulphur sol consists of particles containing about a
thousand of S8 molecules.

2. Macromolecular Colloids: Certain substances form large molecules whose dimensions are
comparable to those of colloidal particles. Such molecules have very high molecular masses and
are termed as macromolecules. When such substances are dispersed in suitable dispersion
medium, the resulting colloidal solutions are known as macromolecular colloids. Thus, in
macromolecular colloids, the dispersed particles are themselves large molecules having very high
molecular masses.
Most of the lyophilic sols are macromolecular colloids. For example colloidal dispersion of
naturally occurring macromolecules such as starch, proteins, gelatin, cellulose, nucleic acids etc.
are macromolecular colloids. Synthetic polymers such as polyethylene, polypropylene, synthetic
rubber etc. also form macromolecular colloids when dispersed in suitable solvents.
3.Associated Colloids (Micelles): 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
micelles.
The associated colloids are usually formed by surfactants (surface active agents) like soaps and
synthetic detergents. These agents form micelles when present in solution at a concentration
greater than critical micellization concentration (CMC). The formation of a micelle can be
understood by taking the example of soap solution as described below.
Micelle formation in soap solution: The commonly used soaps are sodium or potassium salts of
higher fatty acids such as palmitic acid (C 15H 31COOH), stearic acid (C 17H35COOH) etc. The
most commonly used washing soap is sodium stearate, C 17H35COONa. In general, soap can be
represented as RCOONa, where R represents a long chain alky1 group. When dissolved in water,
soap ionizes to give RCOO and Na+ ions. The RCOO ion consists of two parts long
hydrocarbon chain R and the polar group -COO as shown diagrammatically. The hydrocarbon
residue R is hydrophobic, i.e. water repelling, whereas the -COO-group is hydrophilic, i.e. water
loving. Therefore, RCOO
end dips in water and the
group R stays away
groups of different RCOO-ions tend to stay away
from one another due to like charges,whereas the R-groups try to approach each other to form
other to form a bunch. This leads to the formation of a micelle as shown in the figure below.
Classification of colloids based Type of Particles of the Dispersed Phase: Multimolecular,
Macromolecular and Associated Colloids

(a)Diagrammatic representation of soap anion

(b) Aggregation of RCOOions to form a micelle
Thus a soap micelle is a negatively charged colloids particle in which the negatively charged COO groups are arranged in a spherical manner at the surface, while the hydrocarbon chains
point towards the centre. The -COO groups present at the surface of the micelle get surrounded

by Na+ ions which tend to drag the micelle in the bulk of the solution. A micelle may contain as
many as 100 molecules or more.
The cleansing action of soaps: Soaps are used for cleaning dirty clothes. Clothes become dirty
due to the deposition of dust and oily or greasy substances. Water is not capable of wetting oily
or greasy substances. However, the hydrocarbon residue R of the soap anion (RCOO ) can do so.
When a dirty cloth is dipped into a soap solution, the hydrocarbon residue R of RCOO ion
dissolves the oily or greasy dirt and encapsulates it to form a micelle. When the cloth is rinsed
with water, the micelles carrying the oily or greasy dirt get washed away.
The cleaning action of detergents such as sodium laury sulphate, CH 3 (CH2)11 SO4 Na+ or
sulphonates of long chain hydrocarbons is similar to that of soaps. In case of detergents, the polar
groups are sulphate (SO4) or sulphonate (-SO3) groups.
Preparation of Colloidal Solutions
As mentioned earlier, lyophilic colloids have a strong affinity for the dispersion medium and
readily form a sol by bringing them into contact or by warming them with the medium. For
example, sols of starch, gelatin, gum Arabic etc. can be prepared just by warming them with
water. Similarly, a colloidal solution of cellulose nitrate can be prepared by dissolving it in an
organic solvent such as ethyl alcohol. The product obtained is commercially called collodion.

The hydrocarbon residue R of RCOO ion dissolves in the greasy dirt on the cloth (b) Soap
micelle containing greasy dirt (Grease micelle)
Since lyophobic colloids practically have no affinity for the dispersion medium, they do not
readily pass into the medium to form a colloidal solution. Hence special methods are required for
the preparation of lyophobic sols. The methods used for the preparation of lyophobic sols can
broadly be divided into the following two categories.
(i) Dispersion methods
(ii)Condensation or aggregation methods
Dispersion Methods
In these methods, the bigger particles of a substances are broken down to form smaller particles
of colloidal dimensions thus obtained are stabilized by the addition of certain stabilizing agents.
Some important dispersion methods are as follows:

(i) Mechanical dispersion method: In this method, the dispersion of the coarse material (whose
colloidal solution is to be prepared) is carried out in a machine called colloid mill. It consists of
two heavy steel discs separated by a little gap. The gap may be adjusted according to the particle
size desired. The two discs rotate at high speed (about 8000 revolutions per minute) in the
opposite direction. A suspension of the substance in water is introduced into the mill. The coarse
particles present in the suspension are grinded to the particles of colloidal dimensions and get
dispersed in water to form a sol. Finer dispersion can be obtained by adding an inert diluents
which prevents the colloidal particles to grow in size. For example, glucose is used as diluents in
the preparation of sulphur sol.

Bredigs arc method

(ii) Electrical dispersion method (Bredigs are method): This method is used for the
preparation of sols metals such as gold, silver, platinum etc. In this method, an electric are is
struck between the two electrodes of the metal (whose colloidal solution is to be prepared)
immersed in the dispersion medium (say water). The dispersion medium is cooled by surrounding
it with a freezing mixture. High temperature of the arc vaporizes some of the metal. The vapour
condenses to the particles of colloidal size on cooling. The colloidal particles thus formed get
dispersed in the medium to form a sol. of the metal.

(iii)Peptization: In this method, a freshly prepared precipitate of the substance is made to pass
into the colloidal state by the addition of a suitable electrolyte. The process of dispersing a
freshly prepared precipitate into colloidal form by using a suitable electrolyte is called
peptization. The electrolyte added is called peptizing agent.
Some examples of peptization are given below:
(a) When a small amount of ferric chloride solution is added to the freshly precipitated ferric
hydroxide, a reddish brown coloured colloidal solution of ferric hydroxide is obtained. This
occurs due to the adsorption of Fe3+ ions over ferric hydroxide particles which causes them to
disperse into the solution due to the electrostatic repulsions between the similarly charged
particles.
(b) When a freshly prepared precipitate of silver iodide is shaken with a dilute solution of silver
nitrate, a colloidal solution of silver iodide is obtained.
Condensation Methods (Aggregation Method)
In condensation methods, the smaller particles of the dispersed phase are aggregated to form
larger particles of colloidal dimensions. Some important condensation methods are described
below.
1. Chemical Methods
Some chemical reactions may be used to aggregate smaller particles of atomic or ionic sizes to
form large particles of colloidal dimensions. These reactions actually involve the formation of the
dispersed phase as insoluble reaction products. Some important reactions leading to the formation
of hydrophobic sols are as follows.
(a)Oxidation: Colloidal solution of sulphur can be prepared by oxidizing an aqueous solution of
H2S with a suitable oxidizing agent such as bromine water, nitric acid or SO 2.

(b) Reduction: Sols of gold, silver, platinum etc. can be obtained by the reduction of dilute
solutions of their salts with a suitable reducing agent. For example, gold sol can be obtained by
reducing a dilute aqueous solution of gold with stannous chloride.

The gold sol thus obtained is called purple of Cassius.

(c) Hydrolysis: Sols of ferric hydroxide and aluminium hydroxide can be prepared boiling the
aqueous solution of the corresponding chlorides. For example,
FeCI3

+ 3H2 S

-->

Fe(OH)3

Colloidal ferric hydroxide

+ 3HCI

(d) Double decomposition: The sols of inorganic insoluble salts such as arsenous sulphide,
silver halides etc. may be prepared by using double decomposition reaction. For example,
arsenous sulphide sol can be prepared by passing H 2 S gas through a dilute aqueous solution of
arsenous oxide.
As2 O3
+
3H2S
-->
As2S3(OH)3 + 3H2O
Colloidal arsenous sulphide
2. Physical Methods
(i) Exchange of solvent: This method involves the pouring of the true solution to another solvent
in which the solute is insoluble but the solvent is completely miscible. An exchange of solvent
gives the colloidal solution of the solute. The method may be used for the preparation of the sols
of sulphur and phosphorus. For example, sulphur is soluble in alcohol but less soluble in water.
When an alcoholic solution of sulphur is poured into water, a colloidal solution of sulphur is
obtained.
Purification of Colloidal Solutions (Sols)
Colloidal solutions prepared by the above mentioned methods usually contain the impurities of
electrolytes. The presence of electrolytes in smaller concentrations stabilizes a sol but their
presence in large concentration tends to destabilize the colloidal solution. Therefore, it is
necessary to purify colloidal solutions by removing the impurities of electrolytes present in them.
Following methods are generally used for the purification of colloidal solutions (sols).
1. Dialysis: We have already seen that an animal membrane allows the passage of crystalloids
but retains the larger colloidal particles. This property of animal membranes is utilized for the
purification of sols. The process involved is called dialysis. It may be defined as follows.
The process of separating the impurity particles of true solution dimensions (crystalloids) from an
impure sol by means of diffusion through a suitable membrane such as parchment paper or
cellophane membrane is called dialysis.
The apparatus used in this method is called dialyser. It consists of a bag made of parchment or
cellophane. The bag is filled with the impure sol to be purified and is suspended in a tank through
which pure water is circulated. The impurities of electrolytes present in the sol diffuse out of the
bag leaving behind pure sol in the bag.
Electrodialysis: Dialysis is a slow process. However, it can be expedited by applying an electric
field. Under the influence of electric field, the impurity ions move faster to the oppositely
charged electrodes and the process gets quickened. This process is referred to as electrodialysis.

(a) Dialysis (b) Electrodialysis

2. Ultrafiltration: The pores of an ordinary filter paper are large enough to allow the passage of
both impurity particles as well as colloidal particles. Therefore an ordinary filter paper cannot be
used for removing the impurities of electrolytes from an impure sol. However, if the pore size of
ordinary filter paper is reduced, it can be used for separating the impurities from impure sols.
This is achieved by treating an ordinary filter paper with collodion or gelatin followed by its
hardening by dipping it in formaldehyde solution. This treatment reduces the pore size and
enables it to check the passage of colloidal particles through it. Filter papers thus obtained are
called ultrafilters. Filtration through ultrafilters is called ultrafiltration.

In ultrafiltration, the ultrafilter is supported over a wire mesh and the impure sol is poured over it.
The impurity particles (electrolytes) pass through the ultrafilter while the larger colloidal particles
are retained. The process is very slow. However, it can be expedited by applying pressure on sol
side or by using a suction pump on the filtrate side. By using a series of graded ultrafilters,
impurities of different size can easily be removed and it is even possible to separate colloidal
particles of different size from one another
3. Ultra-centrifugation: Ultracentrifugation involves the separation of colloidal particles from
the impurities by centrifugal force. The impure sol is taken in a tube and the tube is placed in an
ultra-centrifuge. The tube is rotated at high speeds. On account of this, the colloidal particles
settle down at the bottom of the tube and the impurities remain in the solution. This solution is
termed as centrifugate. The settled colloidal particles are removed from the tube and are mixed
with an appropriate dispersing medium. Thus, the pure sol is obtained.
General Physical Properties of Colloidal Solutions
The important properties of colloidal solutions are described below.
General Physical Properties
Heterogeneity: Colloidal solutions are heterogeneous in nature and consist of two phasesdispersed phase and dispersion medium.
Visibility of dispersed particles: Although colloidal solutions are heterogeneous in nature, yet
the dispersed particles present in them are not visible to the naked eye and they appear
homogenous. This is because colloidal particles are too small to be visible to the naked eye.
Filterability: Due to very small size, the colloidal particles pass through an ordinary filter paper.
However, they can be retained by animal membranes, cellophane membrane and ultrafilters.
Stability: Lyophilic sols in general and lyophobic sols in the absence of substantial
concentrations of electrolytes are quite stable and the dispersed particles present in them do not

settle down even on keeping. However, on standing for a long time, a few colloidal particles of
comparatively larger size may get sedimented slowly.
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 so having particles of size 150nm appears violet, whereas that
having particles of size 60nm appears orange yellow.
Colligative Properties of Colloidal Solutions
Colloidal solutions exhibit colligative properties, i.e., lowering of vapour pressure, elevation in
boiling point, depression in freezing point and osmotic pressure in the same way as the true
solutions of electrolytes and non-electrolytes do. However, the magnitudes of these properties for
colloidal solutions are much smaller than those obtained for true solutions. This is because
colloidal particles exist as aggregates. For a given mass of the substance, the number of colloidal
particles present in the colloidal solution of the substance will be much less than the number of
particles present in its true solutions. Since a colligative property depends upon the number of
particles, a colloidal solution will exhibit much lower value of a colligative property as compared
to that exhibited by a true solution having the same mass of the same substance.
As colloidal solutions have low values of colligative properties, it is quite difficult to measure
then accurately. However, they exhibit measurable osmotic pressures. The osmotic pressures of
colloidal solutions can be measured with a reasonable degree of accuracy. This property is used
for the determination of the average molecular masses of the colloids.
Mechanical Properties of Colloidal Solutions
Colloidal particles present in a colloidal solution exhibit a very important property called
Brownian movement. When a colloidal solution is viewed under an ultra microscope, the
colloidal particles are seen continuously moving in a zigzag path. The property was discovered
by a botanist Robert Brown in 1827, when he observed that pollen grains suspended in water
exhibit random zigzag motion. After the name of the discoverer, the property was named as
Brownian movement. It may be defined as follows.
The continuous zigzag movement of the colloidal particles in the dispersion medium in a
colloidal solution is called Brownian movement.

(a) Brownian movement (b) Unequal bombardments of the molecules of dispersion

medium on a colloidal particle.

Cause of Brownian movement: Brownian movement is due to the unequal bombardments of the
moving molecules of dispersion medium on colloidal particles. The moving molecules of the
dispersion medium continuously attack on colloidal particles from all sides and impart
momentum to them. Since the chances of their collisions are unequal, the net driving force on a
colloidal particle forces it to move a particular direction. As the particle moves in that direction,
other molecules of the medium again collide with it and the particle changes its direction. The
process continues. This results in a random zigzag movement of the colloidal particle.
The Brownian movement decreases with an increase in the size of colloidal particle. This is why
suspensions do not exhibit this type of movement. Brownian movement plays an important role
in imparting stability to a sol. This is because Brownian movement opposes the gravitational
forces acting on colloidal particles and prevents them from getting settled down.
Optical Properties of Colloidal Solutions
When an intense converging beam of light is passed through a colloidal solution kept in dark, the
path of the beam gets illuminated with a bluish light. This phenomenon is called Tyndall effect
and the illuminated path is known as Tyndall cone. The phenomenon was first observed by
Tyndall in 1869.

Tyndall effect
The Tyndall effect is due to the scattering of light by colloidal particles. Since the dimensions of
colloidal particles are comparable to the wavelength of ultraviolet and visible radiations, they
scatter these radiations and get illuminated. Tyndall observed that the zone of scattered light is
much larger than the particle itself. This is why colloidal particles look like bright spots when
viewed with a microscope at right angles to the beam of light as shown in figure. Thus, Tyndall
effect may be defined as the scattering of light by colloidal particles present in a colloidal
solution. Tyndall effect is not exhibited by true solutions. This is because the particles (ions or
molecules) present in a true solution are too small to scatter light. Thus, Tyndall effect can be
used to distinguish a colloidal solution from a true solution. The phenomenon has also been used
to devise an instrument known as ultra microscope. The instrument is used for the detection of
the particles of colloidal dimensions. Tyndall effect also establishes the fact that colloidal
systems are heterogeneous in nature.
Electrical Properties of Colloidal Solutions
Some important electrical properties of colloidal solutions are as follows:
(i) Presence of electrical charge on colloidal particles and stability of sols: One of the most
important properties of colloidal solutions is that colloidal particles posses a definite type of

electrical charge. In a particular colloidal solution, all the colloidal particles carry the same type
of charge, while the dispersion medium has an equal but opposite charge. Thus, the charge on
colloidal particles is balanced by that of the dispersion medium and the colloidal solution as a
whole is electrically neutral. For example, in a ferric hydroxide sol, the colloidal ferric hydroxide
particles are positively charged, while the dispersion medium carries an equal and opposite
negative charge.
The stability of a colloidal solution is mainly due to the presence a particular type of charge on all
the colloidal present in it. Due to the presence of similar and equal charges, the colloidal particles
repel one another and are thus unable to combine together to form larger particles. This keeps
them dispersed in the medium and the colloidal remains stable. This is why sol particles do not
settle down even on standing for a long time.
Based on the nature of charge, the colloidal sols may be classified as positively charged and
negatively charged sols. Some common examples of these sols are given below.
Positively charged sols:
Metallic hydroxide sols e.g., Fe(OH)3, Al(OH)3, Cr(OH)3 , etc., TiO2 sol, haemoglobin, sols of
basic dyes such as methylene blue etc.
Negatively charged sols:
Metal sols e.g., Au, Ag, Cu, Pt etc. sols, metal sulphide sols e.g., As2S3, CdS etc. sols; starch sol,
sols of acid dyes such as Congo red etc.
Origin of charge on colloidal particles:
There are several views regarding the origin of charge on colloidal particles. According to these
views, colloidal particles acquire charge due to the following reasons.
(a) Due to dissociation of the adsorbed molecular electrolytes: Colloidal particles have a
strong tendency to adsorb reactant or product molecules. The molecules thus adsorbed on the
surface of colloidal particles may undergo dissociation/ionization and may impart charge to them.
For example, during the preparation of sulphide sols (e.g., As2 S3 sol), H2S molecules get
adsorbed on colloidal particles. H2S molecules thus adsorbed undergo ionization and release H +
ions into the medium. Consequently, colloidal particles are left with negative charge.
(b) Due to the dissociation of molecules forming colloidal aggregates: The molecules
responsible for the formation of aggregates of colloidal dimensions may themselves undergo
dissociation/ionisation resulting in the development of charge on the colloidal particles formed by
their aggregation. For example, the soap molecules (RCOONa) dissociate to give RCOO - and
Na+ ions. RCOO- ions aggregate together to form micelles which carry negative charge as
explained earlier.
c) Due to preferential adsorption of ions from solutions: The colloidal particles have a
tendency to preferentially adsorb a particular type of ions from the solution. A colloidal particle
usually adsorbs those ions which are in excess and are common to its own lattice. This
preferential adsorption of a particular type of ions imparts a particular type of charge to colloidal
particles.For example, when a ferric hydroxide sol is prepared by the hydrolysis of ferric chloride
in warm water, the colloidal particles of Fe(OH) 3 formed have a tendency to adsorb preferentially
the Fe3+ ions present in the solution. This is because Fe3+ ions are common to the lattice of
Fe(OH)3 particle. The Fe3+ ions thus adsorbed impart positive charge to the colloidal particles
present in the sol.
Fe(OH)3

Fe3+

Fe(OH)3

Fe3+

Similarly, during the preparation of AgCl sol using excess of KCl solution, the Cl ions are
preferentially adsorbed and the colloidal particles acquire negative charge. However, if an excess

of AgNO3 is used, Ag+ ions get preferentially adsorbed and the colloidal particles acquire
positive charge.
AgCI
+
CI-->
AgCI : CI (colloidal)
(Chloride ions present
Preferential adsorption of CI- ions
particle)
in excess in the solution)
(Collodial particle acquires negative charge)
AgCI
(colloidal)
particle)

Ag+
-->
AgCI : Ag+
(Silver ions present in
Preferential adsorption of Ag +ions
excess in the solution) (Collodial particle acquires positive charge)

Electrophoresis: Due to the presence of a particular type of electrical charge, the colloidal
particles present in a colloidal dispersion move towards a particular electrode under the influence
of an electric field. The direction of movement of the colloidal particles is decided by the nature
of charge present on them. If the colloidal particles carry positive charge, they move towards
cathode when subjected to an electric field and vice versa. The phenomenon is called
electrophoresis and may be defined as follows.

(a) Before electrophoresis (b) After electrophoresis

The movement of colloidal particles towards a particular electrode under the influence of
an electric field is called electrophoresis.
The phenomenon of electrophoresis clearly indicates that the colloidal particles carry a particular
type of charge. The property can be used to find the nature of charge carried by colloidal particles
in a colloidal dispersion. Electrophoresis is an important phenomenon and finds several
applications in industry.
Electro-osmosis: When the movement of colloidal particles under the influence of the applied
electric field is checked with the help of a suitable membrane (semi permeable membrane), the
dispersion medium moves in a direction opposite to the direction in which the colloidal particles
would have otherwise moved. This phenomenon is called electro-osmosis and may be defined as
follows. The movement of dispersion medium under the influence of an electric field in the
situation when the movement of colloidal particles is prevented with the help of a suitable
membrane is called electro-osmosis. The electro-osmosis can be demonstrated with the help of
the apparatus shown in figure. The colloidal solution is placed between two partitions made by
semi permeable membranes. The outer compartments consisting of platinum electrodes and side
tubes are filled with water. On passing electric current, water level begins to rise in one of the

side tubs and falls in the other. The phenomenon can be explained as follows. We have already
seen that the colloidal particles and dispersion medium carry charges which are equal but
opposite in nature. Under the influence of an electric field, both have a tendency to move towards
the oppositely charged electrodes. Semi permeable membranes do not allow the passage of
colloidal particles. However, dispersion medium can pass through them. Therefore during
electro-osmosis, colloidal particles are checked and it is the dispersion medium that moves
towards the oppositely charged electrode.

Coagulation or flocculation: The stability of a sol is due to the charge present on the colloidal
particles. Due to similar charges, colloidal particles repel one another and are unable to combine
together to form larger particles. However, if the charge on colloidal particles is destroyed, they
are free to come nearer and grow in size. When the particles become sufficiently large, they get
precipitated. This phenomenon is termed as coagulation or flocculation. The coagulation of
colloidal solution can be achieved by the addition of an electrolyte. It is to be noted that a small
amount of electrolyte is necessary for the stability of a sol because the ions of the electrolyte get
adsorbed on colloidal particles and impart them some charge. However, when an electrolyte is
added in substantial amount the positively charged ions of the electrolyte neutralize the charge on
colloidal particles and compel the sol to get coagulated. Coagulation may be defined as follows.
The phenomenon involving the precipitation of a colloidal solution on addition of an
electrolyte is called coagulation or flocculation.

Hardy-Schulze rule: The coagulation capacity of an electrolyte depends upon the valence of ion
responsible for causing coagulation. As we have seen above, the ion responsible for causing
coagulation is the one which carries charge opposite to that present on colloidal particles. For
example, a positively charged sol gets coagulated by the negatively charged ions of the added
electrolyte. From a study of the coagulation behavior of various electrolytes towards a particular
sol, Hardy and Schulze suggested a general rule known as Hardy-Schulze rule. The rule can be
stated as follows.
The greater is the valence of the oppositely charged ion of the electrolyte added to a
colloidal solution, the faster is the coagulation of the colloidal solution.
Thus, higher the charge on oppositely charged ion greater is its coagulating power. For example,
the coagulation power of different cations for coagulating a negatively charged sol of As 2 S3
follows the order.
Al3+ > Ba2+ > Na+

Similarly, for the coagulation of a positively charged sol such as Fe(OH) 3, the coagulating power
of different anions follows the order.
[Fe(CN)6]4- > PO43- > SO42- > ClFlocculation value: The coagulating power of an electrolyte is usually expressed in terms of its
flocculation value which may be defined as follows. The minimum concentration (in millimoles
per litre) of an electrolyte required to cause the coagulation of a sol is called the flocculation
value of the electrolyte.
The flocculation values (in millimoles per litre) for the coagulation of negatively charged As2 S3
sol and positively charged Fe(OH)3 sol are given in the Table below.
Table: Flocculation Values of Some Common Electrolytes
For Negatively charged As2S3 Sol
For Positively charged Fe(OH)3 Sol
Electrolyte Flocculating Flocculation
Electrolyte Flocculating Flocculation
ion
value
ion
value
(millimoles/litre)
(millimoles/litre)
NaCl
Na+
52
KBr
Br138
+
KCl
K
50
HCl
Cl
132
+
HCl
H
30
KNO3
NO-3
132
2+
2MgCl2
Mg
0.72
K2CrO4
CrO4
0.315
2+
2BaCl2
Ba
0.69
K2 SO4
SO4
0.210
2+
2ZnCl2
Zn
0.68
K2C2O4
C2O4
0.238
AlCl3
Al3+
0.093
K3[Fe(CN)6] Fe(CN)6]30.096
It is to be noted that a smaller flocculation value indicates the greater coagulating power of the
electrolyte.Thus.
Coagulating power 1/(Flocculation value)
Some other methods for causing coagulation: The most commonly used method for causing
coagulation in a colloidal solution is the addition of an electrolyte as described above. However,
the coagulation of colloidal solution can also be achieved by any of the following methods.
(a) By electrophoresis: In electrophoresis, the charged colloidal particles migrate to the
oppositely charged electrode and get discharged. This results in the coagulation of the colloidal
solution.
(b) By mixing two oppositely sols: When two sols carrying opposite charges are mixed together
in suitable proportions, the colloidal particles of one sol neutralize the charge present on the
particles of the other sol and both get coagulated.
(c)By persistent dialysis: We have already seen that a small amount of electrolyte is essential to
make a sol stable. When a sol is subjected to persistent dialysis, the traces of electrolyte also pass
out through the membrane. In the absence of electrolyte, sol becomes unstable and gets
coagulated.
Protective Colloids and Gold Number
Lyophobic sols such as those of metals (e.g. Au, Ag, Pt etc.) are not very stable in the sense that
they get easily coagulated (precipitated) in the presence of an electrolyte. This poses a big

problem in their storage and usage. Contrary to this, lyophilic sols are much more stable and do
not get coagulated easily under similar conditions.
It has been observed that in the presence of certain lyophilic colloids such as gu m Arabic, gelatin,
starch etc. the hydrophobic sols acquire greater stability towards coagulation, i.e. they get
protected and do not get coagulated easily when an electrolyte is added.
The process of protecting a lyophobic sol from being coagulated (precipitated) on addition of an
electrolyte by the use of a lyophilic colloids is called protection and the lyophilic colloid used for
purpose is called a protective colloid.
For example, the addition of gelatin (a lyophilic colloid) to a gold sol (lyophobic sol) protects the
latter from being coagulated on addition of sodium chloride solution.
The exact mechanism of protection is not very clearly understood. However, it is believed that
the lyophilic colloid particles get adsorbed on the surface of the colloid particles present in the
lyophobic sol. The adsorbed lyophilic particles thus form an envelope around the lyophobic sol
particles and protect them from the action of electrolytes.

Protective action of lyophillic colloid particles

Gold Number: The protective power a lyophilic colloid is usually expressed in terms of a
number called gold number introduced by Zsigmondy (1901). It may be defined as follows.
The gold number of a protective colloid is its minimum amount in milligrams which is just
sufficient to prevent the coagulation of 10 ml of a gold sol on the addition of 1 mL of 10%
sodium chloride solution.
It is to be noted that the smaller the value of gold number, the greater is the protective power of
the protective colloid. The gold numbers of a few protective colloids are given in the Table
below.
Table: Gold Number of Some Protective Colloids
Protective (Lyophilic) Colloid

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

Applications of Colloids
Colloids play a very important role in nature, in our daily life and in industry. Some of the
important
applications
of
colloids
are
discussed
below.
1. Food stuffs and medicines: Many of our food stuffs are colloidal in nature. Milk, butter,
whipped cream, fruit jellies, ice cream, bread etc. are all colloidal in nature. For example, milk is
an emulsion of butter fat in water, stabilized by milk protein (casein). Ice cream is a dispersion of
colloidal ice particles in cream. Similarly, bread consists of air dispersed in baked dough.
Colloidal medicines are more effective and are easily absorbed by the body system. Therefore a
large number of pharmaceutical preparations are emulsions. Halibut-liver oil, cod-liver oil, skin
ointments etc. are emulsions. Antibiotics such as penicillin, streptomycin etc. are usually injected
in the body in colloidal form. Several metal sols are also used as medicines.
2. Purification of water: In water works, water is usually purified by the addition of certain
electrolytes such as potash alum, aluminium sulphate etc. This involves the phenomenon of
coagulation. The impure water usually contains dispersed colloidal particles which cannot be
removed by filtration. When potash alum is added to impure water, the negatively charged
colloidal particles of impurities get coagulated by the action of Al 3+ ions furnished by the alum
and can be removed by filtration or decantation.
3. Sewage disposal: Sewage water contains particles of dirt, mud etc. which are colloidal in
nature and carry some electrical charge. These particles may be removed by using the
phenomenon of electrophoresis. The sewage water is passed through a tunnel fitted with metallic
electrodes and maintained at a high potential difference. The colloidal particles present in the
sewage water migrate to the oppositely charged electrodes and get coagulated. This solves the
problem of sewage disposal. Moreover, the rubbish matter obtained on account of the coagulation
of colloidal dirt particles may be used as manure.

Cottrell smoke precipitator

4. Smoke precipitation: Smoke is colloidal system and consists of electrically charged colloidal
particles of carbon dispersed in air. As smoke is a big source of pollution. It is always desirable to
precipitate it, i.e., to remove colloidal carbon particles present in it. The removal of colloidal
carbon particles from smoke can be effected by using the phenomenon of electrophoresis. This is
achieved in an apparatus called Cottrell precipitator as shown in figure. Smoke is allowed to pass

through a chamber having a number of metal plates attached to a metal wire connected to a
source of high potential (20,000 to 70,000V). The electrically charged colloidal particles of
carbon and dust get discharged when come in contact with the oppositely charged plates and fall
down to the bottom. The clean hot air leaves the precipitator from an exit near the top.
5. Artificial rain: Clouds are colloidal systems and consist of water vapour mixed with dust
particles. The water molecules present in a cloud develop some electrical charge. Therefore,
clouds can be made to rain by neutralizing the charge present on colloidal particles (water
molecules). This type of rain is called artificial rain and may be carried out by spraying
oppositely charged colloidal dust or sand particles over a cloud. This neutralizes the charge on
water molecules and compels them to get coagulated, i.e. to rain.
6. Rubber industry: Latex obtained from rubber trees is an emulsion consisting of a dispersion
of negatively charged rubber particles in water. In order to obtain rubber from latex, the latter is
boiled when rubber particles get coagulated. The coagulated mass is vulcanized and sold as
natural rubber. Rubber-plated articles can be prepared directly from latex by electrically
depositing the negatively charged rubber particles over the article to be rubber-plated by making
the article an anode in the rubber-plating bath.
7. Leather tanning: During the tanning of leather, the positively charged colloidal particles of
raw skin and hides are coagulated by the negatively charged tanning materials which include
tannin and compounds of aluminium and chromium. On soaking hides in the solutions of tanning
materials, the coagulation of negatively charged tanning materials takes place in the pores of
hides and the latter get hardened.
8. Cleansing action of soaps: Soaps solution is colloidal in nature and removes dirt and oil from
clothes by forming water soluble emulsion as explained earlier.
9. Smoke screen: In chemical warfare, smoke screens are generally used to hide the movement
of troops. Smoke screens are the colloidal dispersions of very fine particles of titanium oxide in
air.
10. Formation of delta: When a river falls into the sea, extensive deposits of sand and clay are
formed at the mouth of the river in the sea. Such deposits are called delta. The river water
contains colloidal particles of sand and clay which carry negative charge. The sea water contains
a number of positive ions such as Na +, Mg2+, Ca2+ ion etc. When the river water comes in contact
with sea water, the negative charge present on colloidal sand and clay particles get neutralized by
the positively charged ions (present in sea water) and they get coagulated. The coagulated sand
and clay particles settle down and take the shape of delta in due course of time.

Formation of delta
11. Blue colour of the sky: The sky is the empty space around earth and as such has no colour. It
appears blue due to the scattering of light by the colloidal dust particles present in air (Tyndall
effect).

12. Preparation of Nano-materials: Nano-materials which are used as catalyst are prepared by
using reverse micelles.
13. Building roads: Now a day, roads are built asphalt emulsified in water. This technique does
not require the necessity of melting the asphalt.
14. Metallurgical operations: Several metal ores are concentrated by froth floatation process.
This process involves the treatment of the pulverized ore in emulsion of pine oil.

Emulsions
The liquid-liquid colloidal dispersions are called emulsions. An emulsion may be defined as
follows: The colloidal dispersion of two immiscible liquids in which one liquid acts as the
dispersion medium and the other as dispersed phase is called an emulsion.
Types of emulsion: Depending upon the nature of dispersed phase, emulsions can be classified
into following two types.
(i) Oil-in-water (O/W) type emulsions: In oil-in-water emulsions, an oil acts as the dispersed
phase while water acts as the dispersion medium. The most common example of oil in water type
emulsion is milk which consists of liquid fat globules dispersed in water.
(ii) Water-in-oil (W/O) type emulsions: In water-in-oil type emulsions, water acts as the
dispersed phase, whereas oil acts as the dispersion medium. This type of emulsions is also
referred to as oil emulsions. Cod liver oil emulsion is a typical example of this type of emulsions
in which water is dispersed in cod liver oil. The two types of emulsions are diagrammatically
shown in figure below.

(a) Oil-in-water type emulsion (b) Water-in-oil type emulsion

Preparation of emulsions: Emulsions are usually prepared by vigorously mixing the two liquids
by using either a high speed mixing machine or by using ultrasonic vibrators. The process is
known as emulsification. Since the two liquids used for the preparation of an emulsion are
completely immiscible, a stabilizing substance, known as emulsifying agent or emulsifier is
required to stabilize the resulting emulsion. The emulsifier is added along with the component
liquids. In the absence of emulsifying agent, the dispersed phase particles of colloidal size
combine together resulting in the breaking up of emulsion into two separate layers. Some of the
important emulsifying agents are soaps, detergents, proteins, gums and agar. Among these, soaps
and detergents are most commonly used emulsifiers.
Role of emulsifier: The emulsifiers for a protective film around the oil droplets dispersed in
water. This prevents them to come closer and to coalesce, i.e. to combine together. Thus, the
emulsion gets stabilized. For example, let us consider the role of soap which acts as an emulsifier

for an oil-in-water emulsion. When soap is added to an o/w emulsion, the soap molecule (RCOO Na+) arrange themselves in such a way that the polar end groups dip in water whereas the
hydrocarbon chains dip in oil droplet as shown in the figure below. Thus soap molecules get
concentrated over the surface of the oil droplet and form a protective film. This decreases the
interfacial
between
oil
and
water
and
the
emulsion
gets
stabilized.

Emulsification of an oil droplet by soap

Identification of emulsion type: The type to which an emulsion belongs can be known as any of
the following tests.
(i) Dilution test: This test is carried out by adding a few drops of water to the given emulsion. If
the added water mixes freely with the emulsion, the emulsion is of oil-in-water (o/w) type. In
case the added water does not mix up with the emulsion, the given emulsion is of water-in-oil
(w/o) type. The experiment can also be carried out by adding a few drops of oil instead of water.
If the added oil gets mixed up, the emulsion is of water-in-oil type.
(ii) Conductivity test: This test involves the addition of a small amount of electrolyte to the
emulsion under the examination followed by the measurement of its conductance. If the
conductance increases, the emulsion is of oil-in-water type. In case, there is no appreciable
change
in
the
conductance,
the
emulsion
is
of
water-in-oil
type.
(iii) Dye test: In this test, a small amount of an oil-soluble dye is added to the emulsion. If the
emulsion becomes coloured, it is of water-in-oil type. If no change in colour is observed, the
emulsion is of oil-in-water type.
Properties of emulsions: The size of the dispersed droplets in emulsions may be somewhat
larger as compared to the size of dispersed particles in sols. Still, emulsions are colloidal systems
and exhibit all the properties exhibited by colloidal solutions e.g. Brownian movement, Tyndall
effect, electrophoresis, coagulation etc.
Emulsions can be broken into their constituent liquids by physical methods such as heating,
freezing, centrifuging etc. or by destroying the emulsifying agent by a suitable chemical method.
The process of breaking an emulsion to yield the constituent liquids is called demulsification.
Applications of emulsions: Emulsions are very useful systems and find a number of
applications. Some important applications of emulsions are given below.
(i) A large number of pharmaceuticals are prepared in the form of lotions, creams and ointments
which are emulsions of oil-in-water or water-in-oil type and are easily absorbed by the body.
Similarly, many cosmetics are also sold as emulsions. Several oily drugs are also prepared as
emulsions to facilitate their absorption.

(ii) The concentration of sulphide one by froth floatation process involves the treatment of finely
pulverized one with an oil emulsion. When air is bubbled in the mixture, the ore particles present
in the emulsion are carried to the surface in the form of foam and may be collected.
(iii) Emulsifying properties of soaps and detergents are used in washing clothes, crockery etc.
Soaps and detergents emulsify the greasy dirt and carry it away in the water used for washing.
(iv) Digestion of fats in the intestine is facilitated by emulsification. A small amount of fat reacts
with the alkaline solution of the intestine to form sodium soap. The sodium soap thus formed
emulsifies the rest of the fat. This helps digestive enzymes to carry out their functions in a better
way and the fats get digested easily.
In spite of several applications useful in our daily life, formation of emulsions sometimes creates
difficulties also. For example, some all wells yield emulsified petroleum instead of petroleum
alone. However, such emulsions can be demulsified to yield the constituent liquids by physical
methods mentioned earlier.