7.

COLLOIDS (Dispersed Systems)

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 Contents

Colloidal systems
Preparation of colloids
Optical properties of colloids
Kinetic properties of colloids
Electrical properties of colloids
Applications of colloids
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 Dispersed system
• Dispersed systems are
systems which consist of:
1. Particulate matter (dispersed
phase)
– It is the component that is
present in small proportion
and is just like a solute in a
solution
2. Dispersion medium
(continuous phase)
• A component present in Dispersion
Dispersed
phase
excess and is just like a medium
solvent in a solution
3
 1. Dispersed system

Based on particle size:

 Molecular dispersion
 Colloidal dispersion
 Coarse dispersion

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 Property Molecular Colloidal Course
Particle < 1 nm 1 - 500 nm > 500 nm
size
Particles undergo Very slow Don’t diffuse
Diffusion rapid diffusion diffusion -e.g. -e.g.
-e.g. O2 & colloidal silver suspensions
glucose sol.
Particles invisible Particles resolved Particles are
Visibility in electron by electron visible under
microscope microscope ordinary
Pass through Pass through filter microscope
Do not pass
semipermeable paper but not pass through filter
Filtration membranes and through paper or
filter paper semipermeable semipermeable
membrane membrane 5
Dispersed system…
Introduction…..
Molecular dispersion
– Particles invisible in electron microscope,
– pass through ultrafilter & semipermeable membrane
– Less than 1.0 nm
• E.g: Oxygen molecules, ordinary ions, glucose
Colloidal dispersion
– Invisible by ordinary microscope
– visible in electron microscope,
– pass through filter paper but don’t pass semi-permeable
membrane
– 1nm to 0.5 µm in diameter
• E.g: Colloidal silver sols, natural and synthetic polymers
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Dispersed system…. Introduction…..

Coarse dispersion
– Greater than 0.5 µm

– Particles very visible under microscope,

– don’t pass through normal filter paper or dialyze

through semipermeable membrane, particles don’t
diffuse.

– Most pharmaceutical emulsions and suspensions

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 2. Types of Colloidal Systems

Based on the interaction of the dispersed particles with

the dispersion medium:
Lyophilic colloids : Hydrophilic
Lyophobic colloids : Hydrophobic
Association colloids : Amphiphilic

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 2. Types of Colloidal Systems…
2. Types of colloidal dispersions
1. Lyophilic colloids
– Also called as solvent loving colloids.
– The affinity of lyophilic colloids for the dispersion
medium leads to the spontaneous formation of
colloidal dispersions
– hydrophilic colloids: Water is the dispersion
medium
• acacia, tragacanth, albumin, cellulose
derivatives (MC)
– lipophylic colloids: when the medium is non-
aqueous, organic solvents such as benzene
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• Rubber and polystyrene form lyophilic colloids 9
 2. Types of Colloidal Systems…
Lyophilic…..
Lyophilic colloids….
• Stable
– Thermodynamically
– in presence of small conc. of electrolytes
• The dispersions forms spontaneously on adding
to the appropriate dispersions medium.
• The viscosity
– increase greatly on addition of the dispersed
phase.
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 2. Types of Colloidal Systems…

2. Lyophobic colloids
– May also be called as solvent hating colloids

– There is very little attraction b/n the dispersed

particles & the dispersion medium.

– Hydrophobic colloids: When the dispersion medium in

this type of colloid is water

– For example, colloidal dispersions of gold, silver and

sulphur in water.
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 2. Types of Colloidal Systems…

• Unstable
– Thermodynamically
– in presence of small conc. of electrolytes
• The dispersions forms with difficulty.
• The viscosity
– Does not change on addition of the
dispersed phase.

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 Association colloids
• These are also known as amphipilic colloids
• Amphiphiles (Small molecules or ions) exist separately
in dilute solutions
• But associate at the CMC to form micelle of colloidal
dimensions
• They are thermodynamically stable
• Salting out may occur at higher salt conc.
• The viscosity increases with increase in the conc. of
amphiphiles.

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 Types of Colloidal Systems
Lyophilic Lyophobic Association (amphophilic).
(solvent-loving) (solvent-hating).
Disperse Large organic molecules Inorganic Aggregates (micelles) of small
d phase lying within colloidal particles such as organic molecules or ions
size gold or silver whose size is below the
colloidal size
Solvatio Solvated little Hydrophilic or lipophilic
n portion of the molecules is
solvated depending on the
medium
Preparat Spontaneous by Needs special Spontaneous when conc. Of
ion dissolving in solvent procedure amphiphiles exceeds cmc
Viscosity Viscosity increased as Not greatly Increased as conc. Of
the conc. increase. At increased due to amphiphile increase as micelles
certain conc. sol gel unsolvation no. increase &
formation. become asymmetric
Effect of Stable in presence of Unstable due to CMC is reduced and salting out
electroly Electrolytes Desolvation neutralization of occur at high salt conc.
tes and salting out in high charges on
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conc. particles
 Properties of Colloids

Optical Properties of Colloids

kinetic Properties of Colloids
Electric Properties of Colloids

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 Optical Properties of Colloids

Faraday-Tyndall effect
 When a strong beam of light is passed through
colloidal sol; the light rays form a visible cone (Tyndall
cone) resulting from the scattering of light by the
colloidal particles.

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 Kinetic Properties of Colloids

Motion of particles with respect to the dispersion

medium may be:
Thermally induced: Brownian movement, diffusion
Gravitationally induced: sedimentation

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 Brownian Motion

Brownian motion results from asymmetry in the kinetic impact

due to the collisions of molecules of the dispersion medium on the
dispersed phase
Erratic motion resulting from the bombardment of the particles
by the molecules of the dispersion medium.

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 Brownian Motion
 Brownian movement is dependant on:
– Temperature
• Increase in temperature generally increases
Brownian motion of dispersed phase particles
– Particle size of dispersed phase
• The velocity of the particles also increases with
decreasing particle size
– Viscosity of the medium
• Increasing the viscosity of the medium
decreases Brownian movement

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 Consequences of Brownian Movement

Stable system:
The force of gravity is counteracted by Brownian
movement.
Diffusion:
 The colloidal sols will diffuse from a region of high
concentration to a region of low concentration

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 Diffusion
Direct result of Brownian movement.
Fick’s First Law:
The amount dm of substance diffusing in time dt across
a plane of area A is directly proportional to the change of
concentration dc with distance traveled dx

Negative sign because diffusion occurs in the direction

of decreasing concentration
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 Sedimentation

Stoke’s law: For spherical particles

V: rate of sedimentation
r: radius of the particle
d: particle diameter
ρ1: density of the particle
ρ2: density of the medium
η: viscosity of the medium
g: acceleration due to gravity
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 Limitation of stoke’s law

 Stoke’s law was derived for dilute dispersions and

does not take into consideration inter-particulate
interactions.

Thus, it may not be exactly applicable to the

concentrated dispersions.

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 Electric Properties of Colloids

The properties of colloids which depend on, or are

affected by, the presence of a charge on the surface of a
particle.
Physical stability of colloids
 Why particles in liquid are charged?
Ion dissolution.
Ionization.
Ion adsorption.

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 Electric Properties of Colloids
1. Ion dissolution
• Ionic substances can acquire a surface charge
by unequal dissolution of the oppositely
I-
charged ions. (AgI)m

I-
I-
• Examples;
– a) silver iodide in a solution with excess iodide 
Particles acquire – ve charge & vice versa, i.e., if excess
Ag the charge will be +ve
–since the conc. of Ag and I determine the electric
potential.
• b) Aluminum hydroxide in a solution with excess
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hydroxide particles acquire –ve charge & vice versa.
 Electric Properties of Colloids
2. Ionization
 Surface charge of colloidal particle is controlled by the ionization
of surface groupings
– Examples;
• Polystyrene latex has carboxylic acid group at the surface,
ionize to give negatively charged particles.
• Acidic drugs as ibuprofen & nalidixic acid acquire surface
negative charged.
• Amino acids & proteins have carboxyl & amino groups
whose ionization depend on the pH as follow;
NH2 -R- COOH
NH3+-R-COO- NH3+-R-COOH
NH2-R-COO- At low PH
At high PH Zwitter ion
Alkaline medium Acidic medium
Iso electric point
Negatively charged Positively charged
COOH  COO- Zero charge
NH2  NH3+
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 Electric Properties of Colloids
3. Ion adsorption:
• A net surface charge can be acquired by the unequal
adsorption of oppositely charged ions.
• Surfaces in water are more often negatively charged
than positively charged, because cations are generally
more hydrated than anions.
– Cations have the greater tendency to reside in the
bulk
– The anions have a greater tendency to reside at the
particle surface;
 Anions are the smaller, less hydrated.
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 Electric Double Layer

AgCI particle (AgNO3+NaCI) in an aqueous solution of

150 moles of NaCI:
 150 anions and 150 cations.
 100 anions are adsorbed on the colloidal particle.
 50 anions and 150 cations remain in the solution
Colloids

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 Electric Double Layer

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 Electric double layer
- Electroneutral solution
- +
` +

+ - - +

- -
-
-

•Nernst potential

Surface charge •Zeta potential

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 Nernst and Zeta potential

Electrothermodynamic, Nernst potential (E):

The potential at the solid surface aa’, due to the
potential determining ions.
 The difference in potential between the actual surface
and the electroneutral region of the solution
Electrokinetic, Zeta potential (ζ):
 The potential located at the shear plane bb’
The potential difference between the surface of tightly
bound layer (shear plane) and the electroneutral region
of the solution.

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 Physical stability of colloidal systems

 Physical stability of colloidal dispersions depends on

the balance of:

– Electrical forces of repulsion between dispersed

phase particles

– Forces of attraction between dispersed phase

particles

– Forces of attraction between the dispersed phase

and the dispersion medium
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 Physical stability of colloidal systems

• Important terms to be considered

in colloid science
• aggregation, coagulation
and flocculation
– Aggregation is a general term signifying
the collection of particles into groups.
– Flocculation
• the aggregates have an open structure
in which the particles remain a small
distance apart from one another.
– Coagulation
• The particles are closely aggregated and
difficult to redisperse.
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 Physical stability of colloidal systems
• Stabilization serves to prevent colloids from aggregation.
N.B:
 Hydrophilic and association colloids are thermodynamically
stable.
 Lyophobic or hydrophobic colloids are thermodynamically
unstable.
• Two main mechanisms for lyophobic colloid stabilization:
– 1-Steric stabilization
• surrounding each particle with a protective solvent
sheath which prevent adherence due to Brownian
movement.
– 2-Electrostatic stabilization
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• providing the particles with electric charge 36
 Applications
Application of
of colloids
colloids
Adsorption
e.g. Kaolin adsorbs toxins
– Colloidal Al(OH)3 neutralizes stomach acid

Therapeutic agent
– Dextran injection is a colloidal dispersion as
plasma substitute
– Silver colloid  germicidal
– Mercury colloid  Antisyphilis

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 Application of colloids
Pharmaceutical excipient
– E.g. suspending agents and protective agent
((stabilizing agents) like gelatin, albumin, acacia and
tragacanth)
Stability, solubility
– Colloidal coatings to solid dosage forms are used to
protect drugs that are susceptible to atmospheric
moisture or degradation under the acid condition of the
stomach.
– Association colloids are used to increase solubility &
stability of certain compounds in aqueous & oily
pharmaceutical preparations.

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 Drug delivery system
Hydrogels
• hydrophilic polymers within an appropriate
aqueous vehicle
• Hydrogels include ingredients that are
dispersible in water such as organic, natural
and synthetic gums and inorganic hydrogels
• Hydrophilic colloids- silica, bentonite,
tragacanth, pectin, sodium alginate, MC,
NaCMC,

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 Drug delivery system…
Microemulsions
• Liquid dispersions of water & oil that are made
homogeneous, transparent, and stable emulsion
• Their smaller droplet size- increases drug release,
superior physical stability.

• Nanoemulsions are emulsions with droplet size

below 1μ but usually between 20 and 200nm.

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 Drug delivery system…
Liposomes
– are of colloidal dimensions
• Liposomes are lipid vesicles (50-100nm) with
entrapped cpds in inner phase or bilayers
depending on physicochemical property.
– They are developed from phospholipids.
• applied as drug carriers due to their ability to
prevent degradation of drugs, reduce side
effects and target drugs to site of action.

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 Drug delivery system…

• .

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 Micelles
• Micelles are formed when amphiphilic surfactant or
polymeric molecules spontaneously associate in
aqueous medium to form core-shell structures or
vesicles.
• The inner core of a micelle is hydrophobic which is
surrounded by a shell of hydrophilic polymers e.g: PEG
– hydrophobic core enables incorporation of poorly
water soluble and amphiphilic drugs while
– hydrophilic shell and size (<100nm) prolong their
circulation time in the blood and increase
accumulation in tumoural tissues due to increased
vascular permeability
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 Micells…
.

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 (reading assignment)

Interaction of colloids

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