COLLOIDAL DISPERSION

By,
Dr. Vaibhav G. Bhamare
Ph. D, M. Pharm, MBA
 CONTENT
Classification of dispersed systems and their general
characteristics, size and shapes of colloidal particles,
classification of colloids and comparative account of
their general properties. Optical, kinetic and electrical
properties. Effect of electrolytes, coacervation,
peptization and protective action.
 INTRODUCTION
• Dispersed systems are defined as systems in which
particles are dispersed with the aid of an agent to lower
interfacial system.
• Dispersed phase (internal phase) dispersed in the
dispersion medium (continuous phase)
Dispersed Phase
Medium/Phases
Gas Liquid Solid
None
Liquid Aerosol
Gas (All gases are
Example: fog
mutually miscible)
Foam
Dispersion Emulsion Sol
Liquid Example: whipped
Medium Example : milk Example: blood
creams

Solid Foam Gel Solid Sol

Solid Example:
Example: styrofoam Example:gelatin cranbery glass
 Greater than 1
Size Less than 0.1nm 1.0 nm to 1.0 μm
μm
Dispersed Molecular Colloidal Coarse
System Dispersion Dispersion Dispersion
Calamine
Example Sucrose Solution Solution of acacia
suspension

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CLASSIFICATION OF DISPERSED SYSTEM
 ON THE BASIS OF DIFFUSION RATE
- Crystalloids: High diffusion rate
- Colloids: Slow diffusion rate
 ON THE BASIS OF MEAN PARTICLE DIAMETER
- Molecular
- Colloidal
- Coarse
 ON THE BASIS OF DISPERSION MEDIUM
- Hydrosol: water as a dispersion medium
- Alcosol: Alcohol as a dispersion medium
- Benzosol: Benzene as a dispersion medium
5 - Aerosol: Air or gas as a dispersion medium
CHARACTERSISTICS OF
DISPERSED SYSTEM
 Dispersed system
Characteristic Molecular Coarse
Colloidal dispersion
dispersion dispersion
Particle size Less than 0.1nm 1.0 nm to 1.0 μm Greater than 1 μm
Setting by
no settling Settles settles
ultracentrifuge
not visible with an visible by visible to naked
Visibility
electron microscope ultra microscope eye

Filtration Filtered Filtered cannot filter

Light scattering No Yes no

Diffusion Yes No no
Diffusion rate Rapid Slow do not diffuse

Example sugar solution polymeric solution Suspension

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 SIZE OF COLLOIDAL PARTICLES
• Colloidal systems are generally of a polydispersed nature

• dimension scale ranging from nanometers to micrometers (1nm-

1000nm )

• Colloidal solutions are not only formed by certain specific

substances as mentioned above but they can be obtained from any

substance by subdividing or aggregating its particles in the size
range.

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 SHAPE OF COLLOIDAL PARTICLES
 The exact shape of colloidal particle is may be complex.

 Colloidal particles can be classified according to shape as

corpuscular, laminar or linear.

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 SHAPE OF COLLOIDAL PARTICLES
 Many colloidal systems do contain spherical or nearly spherical

particles.

 Corpuscular particles which deviate from spherical shape can often

be treated theoretically as ellipsoids of revolution.

 High-polymeric material usually exists in the form of long

threadlike straight or branched-chain molecules.

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CLASSIFICATION OF
COLLOIDS

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 Classification based on interaction between dispersed phase
• Lyophilic colloids: The substances which when mixed with a suitable
dispersion medium readily form colloidal solutions are called lyophilic
colloids or intrinsic colloids.
• Lyophobic Colloids: 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
• Association Colloids: Association 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
12 aggregated particles.
 Classification based on charge present on surface of particles

 Positive solution: The colloids carrying positive charge are called as

positive sols.

 Negative solution: The colloids carrying negative charge are called as

negative sols.

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 Comparative account of their general property
Property Lyophilic Lyophobic Association
Solvent Loving Hating Amphiphilic
The considerable Less affinity Interaction of polar
attraction between between the or nonpolar part of a
Nature the dispersed phase dispersed phase particle depends on
and the aqueous and the aqueous types of dispersion
phase phase medium
Spontaneous special methods
Method of aggregation of
dissolution in a like dispersion or
preparation particle
solvent condensation
The high
depends on the
concentration of
Concentration --- concentration of
dispersed phase in
surface
medium
more stable due to
Less stable due to
formation of the
Stability charge on the Medium
sheath around the
14 surface.
colloidal particle
 Comparative account of their general property
Property Lyophilic Lyophobic Association
Particle size Small large Small
Less than Increases with the
Greater than
Viscosity dispersion concentration of
dispersion medium
medium micelle
Equal to the
Less than Less than dispersion
Surface tension dispersion
dispersion medium medium
medium
Reversible with Non-reversible Reversible with
Reversibility
temperature with temperature temperature
Does not depend
Depends on the Charged but solvated
Charge on the pH of the
pH of the medium micelle
medium

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OPTICAL PROPERTIES
OF COLLOIDS

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  The optical properties of a material define how it interacts with light.

 Light scattering: The resultant refraction or illumination of light upon

passing through colloidal solution underlines the light scattering

phenomenon. Refractive index effects on light scattering. In a crystal clear
medium, light passes without deflection and scatters if particles of
different refractive indices are present in a solution.

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  Tyndall effect: When a strong beam of light is passed through the

colloidal solution kept in dark and observes the path of the beam, its path
is visible due to scattering of light by the colloidal particles. The effect is
called as "Tyndall Effect" and the scattered beam is called "Tyndall beam".
This beam is most visible against a dark background.

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KINETIC PROPERTIES OF
COLLOIDS

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  Brownian motion: When a colloidal solution is viewed under an

ultramicroscope, the colloidal particles are seen continuously moving in a

zigzag path

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  Diffusion: Particles diffuse spontaneously from the region of higher

concentration to lower concentration until equilibrium reaches. Diffusion

is a direct result of the Brownian movement. According to Fick's First
Law, the amount of substance (dq) diffusing in time (dt) across a plane of
area (S) is directly proportional to the change of concentration (dc) with
distance travelled (dx).

dc
d q   DS dt
dx

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  Sedimentation: The velocity of sedimentation of the spherical particle

is given by Stoke’s Law. The lower size limit of particle obeying Stoke’s
equation is about 0.5 μ because Brownian movement becomes
significant and tends to offset sedimentation due to gravity and
promotes mixing. In order to bring sedimentation, stronger force must
be applied.

r 2 ( s   o ) g

18  o

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  Viscosity: Viscosity is an expression of resistance to the flow of a

system under applied stress. More the viscous liquid, greater the applied
force required to make inflow at a particular rate. Viscosity studies of
dilute colloidal system and how the viscosity data can be used to obtain
the molecular weight of material comprising the disperse phase.
Viscosity studies also provide information regarding the shape of
particles in solution.

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ELECTRIC PROPERTIES
OF COLLOIDS

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  The colloidal particles acquire charge due to dissociation of the adsorbed

molecular electrolytes, due to the dissociation of molecules forming

colloidal aggregates or due to preferential adsorption of ions from
solutions. The charge on colloidal particles is balanced by that of the
dispersion medium and the colloidal solution as a whole is
electrically neutral.

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  Electric double layer: Zeta potential & Nernst
Potential

4
  U  300  300 100


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  Electrophoresis

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  Electro-osmosis

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DONAN MEMBRANE
EQUILIBRIUM

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Cl 

 Frederic Donnan published on thermodynamic equilibrium involving ions

and polyelectrolytes.

 If NaCl is placed in solution on one side of a semi-permeable membrane

and negatively charged colloid together with its counter ion R-Na+ on the
other side, the Na+ and Cl- can pass freely across the Barrier except for
colloidal anionic particles

 After equilibrium has been established the concentration must be same on

both side of membrane.

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COACERVATION

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Cl 

 According to IUPAC, Coacervation is defined as the separation of colloidal

systems into two liquid phases.

 It was suggested by Oparin that Coacervates might have played a

significant role in the evolution of cells.

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Cl 

 Coacervation is a chemical method for producing polymer droplets in

dispersion based on the separation of two liquid phases into one
concentrated colloidal phase, being the coacervate, and another highly
dilute colloidal phase.
 Coacervates could be regarded as a liquid, which had lost its free mobility
to a certain degree and this explanation was mainly of the simple
coacervation phenomenon.
 Coacervation uses the principle of difference in ionic forces to cause the
polymer(s) to form droplets and drop out of solution. The role of
physiochemical parameters, such as ionic strength and pH, on the
coacervation formation, highlighted that the coacervation was a
33 consequence of electrostatic interactions.
Cl 

 Coacervation is an electrostatic interaction between two aqueous media in

which the liquid-to-gel transition occurs at normal conditions.

 Coacervation requires elimination of the stability factors, charge and

hydration.

 Phase separation in simple coacervation is brought about by addition of a

salt, pH or temperature change in the polymeric solution while in

complex coacervation is brought about by anion–cation interactions.
Complex coacervate gels can be formed by mixing of a polyanion with a
polycation.

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STABILITY OF COLLOIDS

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  Stabilization can be accomplished by:
- Providing charge to dispersed particle suitable for lyophobic
solution.
- Forming sheath surrounding dispersed particle suitable for
lyophilic solution.

 Electrostatic stabilization and steric stabilization are the two

main mechanisms for stabilization against aggregation.
- Electrostatic stabilization is based on the mutual repulsion of like
electrical charges.
- Steric stabilization consists of covering the particles in polymers
which prevents the particle to get close in the range of attractive
forces.
- A combination of the two mechanisms is also possible (electrosteric
stabilization).
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  The flocculation and settling of discharged particles (sedimentation) are

called as coagulation or precipitation of the sol.

 When a sol is colloidally unstable (i.e. the rate of aggregation is not

negligible) the formation of aggregates is called coagulation or

flocculation.

 The reversal of coagulation or flocculation, i.e. the dispersion of

aggregates to form a colloidally stable suspension is called deflocculation

(sometimes peptization).

 Sedimentation is the settling of suspended particles under the action of

gravity or a centrifugal field.

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  Particle sedimentation and also floating arises from a difference in the
density of the dispersed and the continuous phase.
 The higher the difference in densities, the faster the particle settling.
 A lyophobic solution is thermodynamically unstable and particles are made
stable by the presence of charges on their surface. Like charges produce
repulsion among them and result in Brownian motion and thus prevent
coagulation.
 Addition of small amount of electrolyte to lyophobic solution tends to
stabilize the system by imparting a charge to particles and to maintain zeta
potential above a critical value (zeta potential below critical value can
cause accumulation of ions).
 The minimum amount of an electrolyte (mmole) that must be added to
one liter of the colloidal solution to bring complete coagulation is
coagulation value of electrolyte.
39 Smaller the coagulation value, greater the precipitating power.
PROTECTIVE COLLOIDAL
ACTION

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  Protective colloid is a lyophilic colloid that when present in small quantities

keeps lyophobic colloids from precipitating under the coagulating action of

electrolytes.

 Higher concentrations of the same hydrophilic colloid usually protect the

hydrophobic sol from flocculation. This is considered to be due to reduction of

zeta potential below the critical value. This phenomenon is called protective
action.

 The particles of a protective colloid are believed to be adsorbed by lyophobic

colloidal particles and thus form a covering over the surface of lyophobic
colloidal particles. The lyophobic colloid thus behaves as lyophilic colloid and is
precipitated less easily by electrolytes. The adsorption so occurred prevents
precipitating ion to reach solution particle and thus coagulation prevented.
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  Now entire colloid can act as hydrophilic colloid which is
thermodynamically stable. The hydrophilic sol or lyophilic used to protect
a hydrophobic sol or lyophobic sol from precipitation is referred to as
protective colloids.

 It may be noted that protective colloid not only increases the stability of

lyophobic colloids but it also makes them reversible.

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  Protective property of colloid is expressed in a gold number.

 Gold number is defined as the minimum amount of protective colloid

required to prevent color change from red to violets in 10 ml of a gold

solution on addition of 1 ml of 10% NaCl solution.

 Gold solution is hydrophobic colloid red in color changes to violet on

addition of NaCl solution.

 Lower the gold number greater protective action.

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 Dr. VAIBHAV G. BHAMARE
(+91)7588176846
[email protected]

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