Chemical Engineering

Univ. Sebelas Maret

2018
 COLLOIDS

 A colloid is a substance microscopically

dispersed throughout another substance
 The word colloid comes from a Greek
word 'kolla', which means glue thus
colloidal particles are glue like
substances.
 These particles pass through a filter paper
but not through a semipermeable
membrane.
 Colloids can be made settle by the process
of centrifugation.
The colloidal system consist of two
phases :
- A dispersed phase ( a discontinuous phase)
- A dispersion medium (a continuous phase)

 The dispersed-phase particles have a

diameter of between approximately 1nm –
100nm .
 Such particles are normally invisible in an
optical, though their presence can be
confirmed with the use of an ultramicroscope
or an electron microscope.
 SOLUTIONS
 Made up of particles or solutes and a solvent
 The solvent part of the solution is usually a
liquid, but can be a gas.
 The particles are atoms, ions, or molecules that are
very small in diameter.
COLLOIDAL SYSTEMS
 Has particles that are not as small as a solution and
not as large as a suspension.
 The particles are intermediate in size.
SUSPENSIONS
Made up of particles and a solvent its particles are
larger than those found in a solution.
The particles in a suspension can be distributed
throughout the suspension evenly by shaking the
mixture.
 Comparison of the Properties of
Solutions, Colloids, And Suspensions

Property True Solution Colloid Suspension

Particle Size Less than 1 nm 1 to 100 nm More than 100 nm

Appearance Clear Cloudy Cloudy

Homogeneity Homogeneous Homogeneous or Heterogeneous

Heterogeneous
Transparency Transparent but Often translucent Often opaque but
often coloured and opaque but can can be translucent
be transparent
Separation Does not separate Can be seperated Separates or settles

Filterability Passes through filter Passes through filter Particles do not

paper paper pass through filter
paper
Examples of colloids are milk, synthetic polymers, fog,
blood, jam, shoe polish, smoke, etc.
 The following forces play an important role in the interaction of
colloid particles:

EXCLUDED VOLUME REPULSION IN LIQUID THEORY :

In liquid state theory, the 'excluded volume' of a molecule is
the volume that is inaccessible to other molecules in the
system as a result of the presence of the first molecule.
 VAN DER WALLS FORCES
It is the sum of the attractive or repulsive
forces between molecules other than those
due to covalent bonds, the hydrogen bonds,
or the electrostatic interaction of ions with one
another or with neutral molecules or charged
molecules.

ELECTROSTATIC INTERACTION
Colloidal particles often carry an electrical
charge and therefore attract or repel each
other. The charges of both the continuous and
the dispersed phase, as well as the mobility of
the phases are factors affecting
STERIC FORCES
Steric effect arise from the fact that each atom within a
molecule occupies a certain amount of space.

If atoms are brought too close together, there is an

associated cost in energy due to overlapping electron
clouds (Pauli or Born repulsion), and this may affect the
molecule's preferred shape (conformation) and reactivity.
 CLASSIFICATION OF COLLOIDS
 Based of physical state of dispersed phase and dispersion
medium.
 Based of nature of interaction between dispersed phase and
dispersion medium.
 Based on molecular size in the dispersed phase.
 Based on appearance of colloids.
 Based on electric charge on dispersion phase.
BASED ON PHYSICAL STATE OF DISPERSED PHASE
AND DISPERSION MEDIUM
 BASED ON NATURE OF INTERACTION BETWEEN
DISPERSED PHASE AND DISPERSION MEDIUM

LYOPHILIC COLLOIDS
 Colloidal solution in which the dispersed phase has a
great affinity for the dispersion medium.
 They are also termed as intrinsic colloids.
 Such substances have tendency to pass into colloidal
solution when brought in contact with dispersion
medium.
 If the dispersion medium is water, they are called
hydrophilic or emulsoids.
 The lyophilic colloids are generally self- stabilized.
 Reversible in nature and are heavily hydrated.
 Example of lyophilic colloids are starch, gelatin,
rubber, protein etc.
 LYOPHOBIC COLLOIDS
 Colloidal solutions in which the dispersed phase has
no affinity to the dispersion medium.
 These are also referred as extrinsic colloids.
 Such substances have no tendency to pass into colloidal
solution when brought in contact with dispersion
medium.
 The lyophobic colloids are relatively unstable.
 They are irreversible by nature and are stabilized by
adding small amount of electrolyte.
 They are poorly hydrated.
 If the dispersion medium is water, the lyophobic
colloids are called hyrophobic or suspenoids.
 Examples: sols of metals like Au, Ag, sols of
metal hyroxides and sols of metal sulphides.
 Based on molecular size in the dispersed phase.

 MULTIMOLECULAR COLLOIDS
Individual particles of the dispersed phase
consists of aggregates of atoms or small
molecules having diameter less than 10-7cm .
The particles are held by weak vander waal’s
forces. Example; gold sol, sulphur sol

MACROMOLECULAR COLLOIDS

The particles of dispersed phase are sufficiently large in size

enough to be of colloidal solution. These are called Natural
Polymers.
 ASSOCIATED COLLOIDS
These colloids behave as normal electrolytes at
low concentrations but behave as colloids at
higher concentrations.
These associated colloids are also referred to as
micelles.
Sodium stearate (C18H35NaO2)behave as
electrolyte in dilute solution but colloid in
higher concentrations.
Examples: Soaps , higher alkyl sulphonates ,
polythene oxide.
 HOW DOES SOAP
• WORK?
When greasy dirt is mixed with soapy
water, the soap molecules arrange
themselves into tiny clusters called
micelles.

• The water-loving (hydrophilic) part of the

soap molecules sticks to the water and
points outwards, forming the outer
surface of the micelle.

• The oil-loving (hydrophobic) parts stick

to the oil and trap oil in the center where
it can't come into contact with the water.
With the oil tucked safely in the center,
the
 BASED ON APPEARANCE OF COLLOIDS
SOLS
When a colloidal solution appears as fluid.
The sols are generally named as dispersion
medium.
When the dispersion medium is water, the sol is
known as hydrosol or aquosol.
When the dispersion medium is alcohol or
benzene it is called alcosol and benzosol
respectively.
GELS
When a colloidal solution appear as solid. The rigidity
of gel varies from substance to substance. Examples :
jelly, butter, cheese, curd.
 BASED ON ELECTRICAL CHARGE ON
DISPERSION PHASE

 POSITIVE COLLOIDS
When dispersed phase in a colloidal solution
carries a positive charge.
Examples : Metal hyroxides like Fe(OH)3,
Al(OH)2, methylene blue sol etc.

 NEGATIVE COLLOIDS
When dispersed phase in a colloidal solution
carries a negative charge. Examples : Ag sol, Cu
sol
SEPERATION OF COLLOIDS
Mechanical Dispersion
Electrical dispersion or Bredig’s Arc Method
Peptization
Condensation Method
 Mechanical dispersion
In this method,
The substance is first ground to coarse
particles.
 It is then mixed with the dispersion
medium to get a suspension.
 The suspension is then grinded in
colloidal mill.
It consists of two metallic discs nearly
touching each other and rotating in
opposite directions at a very high speed
about 7000 revolution per minute.
The space between the discs of the
mill is so adjusted that coarse
suspension is subjected to great
shearing force giving rise to particles of
colloidal size.
 Colloidal solutions of black ink, paints,
varnishes, dyes etc. are obtained by this
method.
 By electrical dispersion or Bredig’s arc method

This method is used to prepare

sols of platinum, silver, copper or
gold.
 The metal whose sol is to be prepared is
made as two electrodes which immerge
in dispersion medium such as water etc.
The dispersion medium is kept cooled by
ice.
An electric arc is struck between
the electrodes.
The tremendous heat generated by this
method give colloidal solution.
The colloidal solution prepared is
stabilized by adding a small amount of
KOH to it.
 By peptisation
The process of converting a freshly prepared precipitate into
colloidal form by the addition of suitable electrolyte is called
peptisation.

Cause of peptisation is the adsorption of the ions of the electrolyte

by the particles of the precipitate.

The electrolyte used for this purpose is called peptizing agent or

stabilizing agent.

 Important peptizing agents are sugar, gum, gelatin and electrolytes.

 Condensation method

 In condensation method, the smaller particles of the

• 1)
dispersed
By change phase
of phare aggregated
al state: to form larger particles
of colloidal dimensions.
 Some important condensation methods are described
below:
a) Solutions of substances like
mercury and sulphur are prepared
by passing their vapours through
a cold water containing a suitable
stabilizer such as ammonium salt or
citrate.
 b)By excessive
cooling:solution of ice in an organic solvent like ether or
A colloidal
chloroform can be prepared by freezing a solution of water in
solvent. The molecules of water which can no longer be held in
solution, separately combine to form particles of colloidal size.

c) By exchange of solvent:
Colloidal solution of certain substances such as sulphur,
phosphorus which are soluble in alcohol but insoluble in water
can be prepared by pouring their alcoholic solution in excess of
water. For example alcoholic solution of sulphur on pouring into
water gives milky colloidal solution of sulphur.
d) Chemical methods:
Colloids can be prepared by following chemicals methods..
1) Oxidation:
Addition of oxygen and removal of hydrogen is called oxidation.
For example: Colloidal solution of sulphur can be prepared by oxidizing an
aqueous solution of H2S with a suitable oxidizing agent such as bromine
water.
H2S + Br2 → 2HBr + S
2H2S + SO2 → 2H2O + 3S
2)Reduction:

Addition of hydrogen and removal of oxygen is called reduction.

For example: Gold sol can be obtained by reducing a dilute aqueous
solution of gold with stannous chloride.
2AuCl3 + 3SnCl2 → 3SnCl4 + 2Au

3) Hydrolysis:
It is the break down of water. Sols of ferric hydroxide and aluminium
hydroxide can be prepared by boiling the aqueous solution of the
corresponding chlorides.
For example.
FeCl3 + 3H2S→ Fe(OH)3 + 3HCl
4) Double Decompostion
The sols of inorganic insoluble salts such as arsenous sulphide, silver
halide etc may be prepared by using double decomposition reaction.

For example: Arsenous sulphide sol can be prepared by passing H2S

gas through a dilute aqueous solution of arsenous oxide.

As2O3 + 3H2S → As2S3(OH)3 + 3H2O

 DONNAN MEMBRANE EQULIBRIUM
• When two solutions containing
electrolytes are seperated by membrane
which is impermeable to one of the ions of
the electrolytes.
• It was found that at equilibrium an
unequal distribution occurs for the
permeable ion on both sides of the
membrane.
• At equilibrium, the osmotic pressure of two
solutions will be different and if two
reference electrodes such as calomel
electrodes are put into the two solutions
then a difference of potential will be set up.
• This type of equilibrium is known as
DONNAN
 COMPONENTS OF A SOLUTION
 INTERNAL SOLUTION
It is a solution of an electrolyte containing non penetrating
ions of about colloidal dimension and ions small enough
to be penetrable.

 EXTERNAL SOLUTION
It is a solution of electrolyte containing both penetrable ions.

 SEMIPERMEABLE MEMBRANE
It separates the two solutions and is permeable to all
 Purification of colloids
There are three common methods used for purification of
colloids:
Dialysis
Electrodialysis
Ultra filteration
 Dialysis
The process of separating the particles of colloid from those
of crystalloid, by means of diffusion through a suitable
membrane.
 It’s principle is that colloidal particles can not pass through
a cellophane membrane while the ions of the electrolyte
can pass through it.
 The impurities slowly diffused out of the bag leaving behind
pure colloidal solution.
 The distilled water is changed frequently to avoid
accumulation of the crystalloids otherwise they may start
diffusing back into the bag.
 Dialysis can be used for removing HCl from the
ferric hydroxide sol.
 Electro dialysis
The process of dialysis is very slow.

The process is speeded up by application of electrical potential.

This is called electro dialysis.

Application of electro dialysis:
Artificial kidney machine make use of electro dialysis.
 Ultra filtration
Ultra filtration is a process of high pressure
filtration through a semi permeable membrane
in which colloidal particles are retained while
the small sized solutes and the solvent are
forced to move across the membrane by
hydrostatic pressure forces.
Application of ultra filtration:
Ultra filtration is a vital process that takes place in the kidneys.
PROPERTIES OF COLLOIDS
 PHYSICAL PROPERTIES OF COLLOIDS
• Heterogeneity: Colloidal solutions consist of two phases-dispersed
phase and dispersion medium.

• Visibility of dispersed particles: The dispersed particles present in

them are not visible to the naked eye and they appear homogenous.

• Filterability: 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.

• 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.
 OPTICAL PROPERTIES OF COLLOIDS
TYNDALL EFFECT
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 Tyndall effect is due to the scattering of light by colloidal particles.
Tyndall effect is not exhibited by true solutions. This is because the particles
present in a true solution are too small to scatter light.
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.
 MECHANICAL PROPERTIES OF COLLOIDS

BROWNIAN MOVEMENT
The continuous zigzag movement of the colloidal particles in the
dispersion medium in a colloidal solution is called Brownian
movement.
Brownian movement is due to the unequal bombardments of the
moving molecules of dispersion medium on colloidal particles.
The Brownian movement decreases with an increase in the size of
colloidal particle. This is why suspensions do not exhibit this type of
movement.
 ELECTRICAL PROPERTIES OF COLLOIDS

ELECTROPHORESIS
The movement of colloidal particles towards a particular electrode under
the influence of an electric field.

If the colloidal particles carry positive charge, they move towards cathode
when subjected to an electric field and vice versa.
 ELECTROSMOSIS
• 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.
• During electrosmosis, colloidal particles are checked
and it is the dispersion medium that moves towards the
oppositely charged electrode.
 • COAGULATION OR FLOCCULATION
• Coagulation may be defined as the phenomenon involving the
precipitation of a colloidal solution on addition of an electrolyte.

• Hardy-Schulze rule
The coagulation capacity of different electrolytes is different. It depends
upon the valency of the active ion are called flocculating ion, which is the
ion carrying charge opposite to the charge on the colloidal particles
• Flocculation value: The coagulating power of an electrolyte is usually
expressed in terms of its flocculation value which may be defined as
the minimum concentration (in millimoles per litre) of an electrolyte
required to cause the coagulation of a sol.
• A smaller flocculation value indicates the greater coagulating power
of the electrolyte. Thus,

Coagulating power α 1
Flocculation value

• The coagulation of colloidal solution can also be achieved by any

of the following methods.
By electrophoresis
By mixing two
oppositely sols By
persistent dialysis
 Biological significance of colloidal
systems
• Protoplasm is a Colloidal system:
Protoplasm is colloidal in nature.

• Amoeboid movements:
Amoeboid movements in amoeba occur
 Fruits:
Turns store a large amount of proteins and
starch. They also exhibit colloidal
properties.

Blood:
High plasma protein forms a colloidal system
in blood. This system maintains the pH and
osmotic concentration of blood.
 ADVANTAGES OF COLLOIDS
 Colloids allow the dispersion of normally insoluble
materials, such as metallic gold or fats. These can
then be used more easily, or absorbed more easily.
 Colloidal gold, for example, can be usedin medicine
to carry drugs and antibiotics, because it is highly non-
reactive and non-toxic.
 Pharmaceutical industry makes use of colloidal
solution preparation in many medicines. A wide
variety of medicines are emulsions. An example is Cod
Liver Oil.
 Paint industry also uses colloids in the preparation of
paints.
In milk, the colloidal suspension of the fats
prevents the milk from being thick, and allows
for easy absorption of the nutrients.

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 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).

Asphalt emulsified in water and is used for

building roads.
The sugar present in milk produces lactic acid
on fermentation. Ions produced by acid, destroy
the charge on the colloidal particles present in
milk, which then coagulate and separate as
curd.

Soap solution is colloidal in nature. It removes

the dirt particles either by adsorption or by
emulsifying the greasy matter sticking to the
Large numbers of food particles which we
cloth.
use in our daily life are colloidal in nature.
Example: Milk, butter, & ice cream etc
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