COLLOIDS

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Introduction
 Dispersed system –A system in which one phase
(dispersed phase) is distributed uniformly as particles
throughout another phase (dispersion medium)

 Dispersed system can also be classified on basis of the

size of dispersed phase as
 Molecular dispersion
 Colloidal dispersion
 Coarse dispersion

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comparison of various types of dispersions

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Introduction
 The colloidal solutions or colloidal dispersions are intermediate
between
 true solutions size less than 10 Å or 1nm and suspensions size
more than 2000 Å or 0.5µm.

 In other words, the diameter of the dispersed particles in a

colloidal dispersion is more than that of the solute particles in a
true solution and smaller than that of a suspension.
 When the diameter of the particles of a substance dispersed in a
solvent ranges from about 10Å to 2,000Å, the system is termed a
colloidal solution, colloidal dispersion, or simply a colloid.

 The material with particle size in the colloidal range is said to be

in the colloidal state. 5
Particle size (indicated by diameter) range of true solution, colloidal
dispersion, and suspension.

True solution 1Ao Colloidal solution 10Ao Suspension 2000Ao

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 ColloidsAdvantages
1. Higher degree of catalytic activity: Due to increased surface area in
colloidal preparation, the activity of a catalyst is generally accelerated.
2. Color: Colloidal preparations generally possess attractive color.
3. Taste: Colloidal preparation may also be used to pronounce the taste of a
pharmaceutical preparation.

4. Better solubility, absorption and bioavailability

5. Compatibility with biological system: Ionic silver salt may itself produce
toxicity-argyria and less bioavailability due to the formation of silver
chloride which is insoluble and rapidly excreted from body. But it does not
occur when colloidal preparations are used.

6. Stability: Colloidal preparation are stable than suspension and emulsion.

 Colloids
Disadvantages
 As colloids are small in particle size so it is easily absorbed and gives extensive
bioavailability which may support toxicity.

 Preparation of lyophobic colloid is difficult

 Stabilization of colloids is often difficult as it may be destabilized by a lot of factors
(radiation, heat, drying etc.)

 There is a great restriction on the particle size of the particles.

Pharmaceutical application of colloids
 As a therapeutic agent-colloidal Cu in cancer
 Used as a diagnostic agent –colloidal gold for paresis
 As a additives- polymers used in P'ceutical preparation
 Bindings of drugs - protein
 As a plasma substitutes - dextran as plasma expander
 As a coating materials tablet & capsule coated with protect
drug
 Antibiotics –penicillin injection
 Foods
 Solubilization -surfactant
 Bioavailability –increase therapeutic activity
 Emulsion formation –emulgent colloidal in nature
 Gels 9
Types of colloidal systems
 As stated above, a colloidal system is made of a dispersed phase and the
dispersion medium.

 Because either the dispersed phase or the dispersion medium can be a gas,
liquid or solid, there are eight types of colloidal systems possible.

 A colloidal dispersion of one gas in another is not possible since the two gases
would give a homogeneous molecular mixture.

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Classification Based on the Nature of Interaction Between
Dispersed Phase and Dispersion Medium

colloids

Lyophilic colloids Lyophobic colloids Association colloids

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 Lyophilic colloids
 Lyophilic colloids, or "liquid-loving" colloids, are characterized by a
strong affinity between the dispersed phase and the dispersion medium.
 They are readily formed and tend to be stable, meaning they don't easily
coagulate or settle.
 Its also called as homogeneous colloids or reversible sols
 Hydrated colloids swell increasing viscosity of the system & Prepared by
simply dissolving the material in the solvent.
 Lyophilic (hydrophilic) colloids are very common in biological systems
and in foods. They can be classified in to two groups-
 Hydrophilic colloid:These are water-loving colloids. The particles are
attracted toward water. Example: acacia in water.
 Lipophilic colloid: These are non-aqoues loving colloids. The colloid
particles are attracted toward organic solvent. Example: rubber 13
Lyophobic colloids
 Lyophobic colloids, also known as liquid-hating colloids,
are colloidal systems where the dispersed phase (particles) has
little or no affinity for the dispersion medium (liquid).

 Lyophobic colloids are all inherently unstable; they will

eventually coagulate. However, "eventually" can be a very long
time (the settling time for some clay colloids in the ocean is
200-600 years!).

 Examples include certain metal sols (like gold and silver) and
some insoluble compounds.

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Methods of preparation of colloids
 Special method is required to prepare
colloids because of the weaker attraction between
particles & the medium.
1. Dispersion methods
 The general principle involves mechanical dispersion,
i.e., converting coarse particles are reduced in size
2. Condensation methods
 Materials of subcolloidal dimensions are caused to
aggregate into particles within the colloidal size range

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 Colloi
Differences ds
Association colloids

 Associated colloids, also known as micelles, are colloidal systems where

particles behave as separate molecules at low concentrations but aggregate
to form larger clusters (micelles) at higher concentrations.
 These aggregated particles, known as micelles, are formed by the joining
together of atoms or small fragments of the substance. Soaps and
detergents are common examples of associated colloids.
 Its also called as Amphiphilic colloids and micelles
 These possess polar & non-polar group (water loving & water hating
(mixture of both).
 Sodium stearate (C18H35NaO2)behave as electrolyte in dilute solution but
colloid in higher concentrations.
 Examples: Soaps , higher alkyl sulphonates, polythene oxide.

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Properties of different types of colloidal
dispersion systems
Property Lyophilic Colloids Lyophobic Colloids Association Colloids

Dispersed phase mostly organic molecules largely inorganic aggregation of surface

particles active agents
Nature of interaction stronger, solvent sheath little interaction aggregates are solvated
around particle
presence of charge less charged, but solvated highly charged charged micelles. but
solvated
Method of preparation readily form sol special methods are readily form when conc.
required ,is equal to CMC
Viscosity of the Higher than that of Nearly same as the Viscosity increases, but
dispersion medium alone dispersion medium not appreciably
Presence of electrolytes
low concentrations Stable Unstable Stable
high concentrations Coacervation ppt stable precipitates
Reversibility reversible irreversible reversible

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Preparation of
Colloids
Dispersion Method

Dispersion Method
In this method large particles of the substances are broken, into particles of colloidal dimensions in
presence of dispersion medium. Since the sols formed are highly unstable. They are stabilized by
adding some suitable stabilizer. Some of the methods employed for carrying out dispersion are as
follows:
1.Mechanical disintegration: this include three process-
⮚ Ball mill, Colloid mill, Mortar and pestle
2.By peptization
3.Bredig’s Arc Method
Dispersion Method
Dispersion Method
Dispersion Method
Aggregation
Method
Purification
 Purification

The process of removing ions (or molecules) from a sol by diffusion through a
permeable membrane is called Dialysis. The apparatus used for dialysis is called a
Dialyser.
Purification
Purification
Properties of colloids
3. Kinetic properties of colloids
 Brownian motion
1.Physical properties
 Diffusion
 Heterogeneous
 Osmotic pressure
 Stable
 Sedimentation
 Filterability
 Viscosity
 Particle size
4. Electrical properties of colloids
 Color
 The sol particles carry an
2. Optical properties of colloids electric charge
 The Faraday- Tyndall effect Electrophoresis
 Ultra microscope  Electro-osmosis
 Electron microscope  Streaming
 Donnan membrane effect
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 Properties of colloids
1. Physical properties
(i) Heterogeneous nature: Colloids are heterogeneous in nature. They consist
of two phases; the dispersed phase and the dispersion medium.
(ii) Stable nature: The colloidal solutions are quite stable. Their particles are
in a state of motion and do not settle down at the bottom of the container.
(iii) Filterability: Colloidal particles are readily passed through the ordinary
filter papers. However they can be retained by special filters known as
ultrafilters (parchment paper).
(iv) Particle size: The particle size of colloids generally varies from 1 nm to 1
um.
(v) Colour: The colour of a hydrophobic sol depends on the wavelength of
the light scattered by the dispersed particles. The wavelength of the
scattered light again depends on the size and the nature of the particles.
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 Optical properties: Light scattering (Tyndall
effect).
• When a strong beam of light is passed through a sol and viewed at right
angles, the path of light shows up as a hazy beam or cone. This is due to
the fact that sol particles absorb light energy and then emit it in all
directions in space. This ‘scattering of light’, as it is called, illuminates
the path of the beam in the colloidal dispersion.
• The phenomenon of the scattering of light by the sol particles is called
Tyndall effect.
• The illuminated beam or cone formed by the scattering of light by the sol
par ticles is often referred as Tyndall beam or Tyndall cone.
• True solutions do not show Tyndall effect. Since ions or solute molecules
are too small to scatter light, the beam of light passing through a true
solution is not visible when viewed from the side. Thus Tyndall effect can
be used to distinguish a colloidal solution from a true solution.
• Sol particles cannot be seen with a microscope. Zsigmondy
(1903) used the Tyndall phenomenon to set up an apparatus
named as the ultramicroscope. An intense beam of light is
focussed on a sol contained in a glass vessel.
• The focus of light is then observed with a microscope at right
angles to the beam. Individual sol particles appear as bright
specks of light against a dark background (dispersion
medium).
• An ultramicroscope does not give any information regarding
the shape and size of the sol particles.
• In an electron microscope, beam of electrons is focused by
electric and magnetic fields. This focused beam is allowed to
pass through a film of sol particles on to a photographic
plate. Thus it is possible to get a picture of the individual
particles showing a magnification of the order of 10,000.

• With the help of this instrument, we can have an idea of the

size and shape of several sol particles including paint
pigments, viruses, and bacteria. These particles have been
found to be spheriod, rod-like, disc-like, or long filaments.
Kinetic Properties of colloids
Viscosity
 The viscosity of a colloidal dispersion is affected by a variety of factors.
 Shape of the dispersed particles : Spherical particles impart relatively
low viscosity to dispersion, while particles of linear shape yield more
viscous systems.
 Affinity of particles to the medium : If linear particles are placed in a
medium having low affinity for particles, these tend to assume spherical
shape and the viscosity falls.
 Type of colloids : In general, lyophilic colloids have viscosities
manyfold greater than that of the dispersion medium. Lyophobic
colloids have viscosities almost equal to the dispersion medium.
 Molecular weight of the particles : Higher the molecular weight of the
material, greater will be the viscosity. Therefore, by measuring the
viscosity, molecular weight of the polymers can be determined,
examples: Dextran (plasma expanders), gelatin etc.
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Kinetic Properties of colloids
Viscosity
 Viscosity is an expression of the resistance to flow of a
system under an applied stress.

 The flow of a dilute colloidal system (having spherical

particles) is expressed by an equation developed by
Einstein.
η =η0(1+2.5Φ)

η0 = viscosity of dispersion medium

η = viscosity of dispersion
Φ = volume fraction of particle
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 Electrical Properties of colloids
The sol particles carry an electric charge
The most important property of colloidal dispersions is that all the
suspended particles posses either a positive or a negative charge.
The mutual forces of repulsion between similarly charged
particles prevent them from aggregating and settling under the
action of gravity. This gives stability to the sol.

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 Electrical Properties of colloids
Electrical Double layer
The surface of colloidal particle acquires a positive charge by selective adsorption of a
layer of positive ions around it.
This layer attracts counterions from the medium which form a second layer of negative
charges.
The combination of the two layer of +ve and –ve charges around the sol particle was
called Helmholtz Double layer.More recent considerations have shown that the
double layer is made of :
(a) a Compact layer of positive and negative charges which are fixed firmly on the
particle surface.
(b) (b) a Diffuse layer of counterions (negative ions) diffused into the medium
containing positive ions.
(c) The combination of the compact and diffuse layer is referred to as the Stern
Double layer.Because of the distribution of the charge around the particle, there is
a difference in potential between the compact layer and the bulk of solution across
the diffuse layer. This is called by Electrokinetic or Zeta potential 43
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 Electrical Properties of colloids
Electrophoresis: The movement of sol particles under an applied electric potential is called
electrophoresis or cataphoresis.
Thus by noting the direction of movement of the sol particles, we can determine whether they
carry a positive or negative charge.
Electro-osmosis: A sol is electrically neutral. Therefore, the dispersion medium carries an equal
but opposite charge to that of the dispersed particles, whether they carry a positive or
negative charge. The movement of the dispersion medium under the influence of applied
potential is known as electroosmosis.
Streaming Potential: Differs from electro-osmosis in that the potential is created by forcing a
liquid to flow through a bed or plug of particles.

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 Electrical Properties of colloids
Donnan membrane effect: The presence of charged macromolecules (colloid) on one side of a
semipermeable membrane affects the diffusion of small ions such as drug ions through the
semipermeable membrane. This effect is due to the electrical gradient across the membrane
and as a consequence, the charged drug ions of the same charge as the macromolecules are
driven to the opposite side of the membrane altering the concentration of the drug ions. This
is termed as Donnan membrane equilibium or simply Donnan effect.
The Gibbs–Donnan effect (also known as the Donnan's effect, Donnan law, Donnan equilibrium,
or Gibbs–Donnan equilibrium) is a name for the behavior of charged particles near a semi-
permeable membrane that sometimes fail to distribute evenly across the two sides of the
membrane.[1] The usual cause is the presence of a different charged substance that is unable
to pass through the membrane and thus creates an uneven electrical charge.[2] For example,
the large anionic proteins in blood plasma are not permeable to capillary walls. Because small
cations are attracted, but are not bound to the proteins, small anions will cross capillary walls
away from the anionic proteins more readily than small cations. 47
 Electrical Properties of colloids
Some ionic species can pass through the barrier while others cannot. The
solutions may be gels or colloids as well as solutions of electrolytes, and
as such the phase boundary between gels, or a gel and a liquid, can also
act as a selective barrier.
The electric potential arising between two such solutions is called the Donnan
potential.

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STABILITY OF COLLOIDS
 Stable colloidal system is one which the particles
resist flocculation or aggregation and exhibits a long
shelf life.

 This will depend on the balance of repulsive &

attractive forces that exist between particle as they
approach one another.

 If all particles have mutual repulsion then the

dispersion will remain stable.
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STABILITY OF COLLOIDS

Much denser form

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 STABILITY OF COLLOIDS
 In 1940's Derjaguin, Verway, Landau and Overbeek developed a
theory which dealt with colloidal stability (DLVO).

 To maintain colloidal stability, the repulsive forces between

particles must be dominant.

 Two fundamental mechanisms for repulsive forces are :

(1) STERIC REPULSION
(2) ELECTROSTATIC (CHARGE) REPULSION

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Stearic stabilization
 Its involves polymers added to the system adsorbing onto the
particles surface causing repulsion.
Electrostatic stabilization
 This is the effect on particle interaction due to the distribution
of charged species in the system.

 Stabilization or flocculation of a system may be modified

simply by altering the concentration of ions in a system. It is
reversible process and inexpensive.

 Zeta potential is a very good index of the magnitude of the

interaction between colloidal particles & measurements are
used to assess the stability of colloidal systems.
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SCHULZE-HARDY RULE (Hofmeister or lyotropic
series)
 Lyophilic & association colloids are thermodynamically stable
& exist in the true solution.

 They don’t coagulate on addition of moderate amounts of

electrolytes

 But they coagulate if sufficient amount of electrolyte is added as

was evident with Lyophobic colloids, called salting out

 Hardy – Schulze rule arranges ions in the order of their capacity

to coagulate hydrophobic colloids, the Hofmeister or Lyotropic
series ranks cations & anions in order of coagulation of
hydrophilic solution
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SCHULZE-HARDY RULE (Hofmeister or lyotropic
series)
 Anions of Hofmeister series in decreasing order of
precipitating power are
 Citrate > Tartrate > Sulphate > Acetate > Chloride

 It is depends upon the ability to dislodge solvent sheath from

the colloidal particles
 When negative & positively charged hydrophilic colloids are
mixed, the particles may separate from the dispersion to form a
layer rich in the colloidal aggregates
 The colloid rich layer is known as a coacervate & the process
is called as coacervation
 Eg gelatin & acacia

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Sensitization & protective colloidal action
 In the presence of very small amount of hydrophilic colloids or
hydrophobic colloids of opposite charge ,hydrophobic colloids
may become more susceptible to precipitation from electrolytes. It
is known as Sensitization

 When a large amount of hydrophilic colloid particles are added to

hydrophobic colloids, these get adsorbed on the hydrophobic
particles and form a protective layer around it. This adsorption
layer prevents the precipitating ions reaching the sol particle

 The colloid that helps to stabilize other colloids is called as a

protective colloid.
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