Colloidal systems

FG

June 1, 2023 Phar 2091 1

 Disperse system
 a two-phase colloidal system consisting of the colloidal particles (disperse
phase) and the medium in which they are suspended (disperse medium)
 disperse systems are classified into:
1. Molecular dispersions (true solutions)
o Homogenous systems, e.g. salt, acid and base solutions
o Invisible in electron microscope
o Particles diffuse rapidly, and pass through ultra filter and semi
permeable membrane, e.g., glucose

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2. Colloidal dispersions
o particle size range: 1nm-1micrometer
o Particles are not visible in light microscope but electron
microscope
o do not pass semi permeable membrane or ultra filter
o diffuse very slowly
o pass through ordinary filter paper but retained by dialysis
or ultra filtration

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3. Coarse dispersions
o particle size greater than 1micron in
diameter
o visible under light microscope
o do not diffuse
o do not pass through semi permeable
membrane

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 Classification Based on Size

Class Size Examples

Molecular < 1.0 nm Oxygen gas, ordinary ions,

dispersion
glucose

Colloidal 1.0 nm to 0.5µm Silver sols, natural and

dispersion synthetic polymer latices

Sand, pharmaceutical
Coarse > 0.5 µm emulsions & dispersions,
dispersion red blood cells

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 Pharmaceutical applications of
Colloidal dispersions
 To enhance therapeutic activity.
-absorption is increased
 Used as pharmaceutical adjuvant.
eg, naturally occurring plant macromolecules
(colloids) such as starch, cellulose,
 As coatings to solid dosage forms to protect drugs from
atmospheric or gastric conditions,
-they have the ability to form monomolecule.
 Colloidal electrolytes are used to increase solubility and the
palatability of certain ingredients in aqueous and oily
pharmaceutical preparations.
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Sol:-general term used primarily for dispersions of solids in liquids,
but also for dispersions in solid or gaseous media

hydrosol - dispersion in water

alcosol - dispersion in alcohol

aerosol - dispersion in air
Colloidal systems are classified into three groups:

Lyophilic Colloids
– hydrophilic colloids

Lyophobic Colloid
– hydrophobic colloids

Association Colloids
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
Lyophilic Colloids
– thermodynamically stable systems

– strong and extensive interactions between dispersed phase

and dispersion medium (e.g. starch in water.

-form spontaneously, i.e., easily reconstituted even after the
dispersion system has been removed from the solid
particles.
-mostly are organic molecules such as gelatin, acacia, insulin,
albumin,…
-termed as hydrophilic & lipophilic or oleophilic based on the
dispersion medium

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Hydrophilic colloids can be sub classified into:
 True solutions
-formed by water soluble polymers. e.g., acacia, gelatin,
albumin,…
 Gelled solutions
e.g., high concentration of starch or gelatin
 Particulate dispersions
-formed where solids do not form solutions but
remain as discrete though minute particles.
- E.g., bentonite, microcrystalline cellulose

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
Lyophobic Colloids
– thermodynamically unstable systems
– little interaction e.g. silver in water

low adhesion forces

Generally composed of inorganic particles dispersed
in water, eg. sulfur, silver iodide

Need special method for preparation, because the
process doesn't take place spontaneously.

The dispersion is not easily reconstituted.

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 Methods to prepare lyophobic sol:
A. Dispersion
-breaking down of coarse materials to reduce
size into colloidal size range and dispersing.
B. Condensation
-materials of sub colloidal dimensions are caused to aggregate
into particles lying within the colloidal size range.
-achieved by either changing temperature or solvent.
Eg. Slowly pouring of solution of sulfur-acetone
into hot water,
C. Chemical reaction such as reduction, oxidation, hydrolysis . e.g.,
oxidation of H2S
2H2S + SO2 (aq. solution) 3s(colloid) + 2H2O
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
Association Colloids

– thermodynamically stable systems in which the dispersed

phase consists of aggregates of amphiphilic molecules or
ions (micelles)

at low concentration, these molecules exist in true
solution

at higher concentrations, they aggregate to form micelles

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 Amphiphilic Molecules

Polar region Nonpolar region

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 Micelle Formation


Micelles
 aggregates of amphiphilic molecules


Critical Micelle Concentration (cmc)
 concentration above which micelles begin to form

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 Solution of Amphiphiles

Concentration of surfactant
below the critical micelle
concentration.

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 Solution of Amphiphiles

Concentration of surfactant
below the critical micelle
concentration.

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 Solution of Amphiphiles

Concentration of surfactant
below the critical micelle
concentration.

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 Association Colloids

Concentration of surfactant above

the critical micelle concentration.

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 Solubility of non-polar solutes

Concentration of surfactant
below the critical micelle
concentration.

nonpolar solute
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 Micellar Solubilization

The interior of the micelle

represents a hydrocarbon (non-
polar) reservoir.

nonpolar solute
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 Properties of Association Colloids

Solubility of nonpolar solute

Magnitude of Surface
Property Tension
critical micelle
concentration

Concentration of Surfactant
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 Classification of Colloidal Systems
Classification Lyophilic Lyophobic Association
(Hydrophilic) (Hydrophobic
Dispersed Single Large collection Collection of
Phase Macro-molecule of ions surfactant
molecules
(micelle)
Interaction with Strong Weak Strong
Dispersion
Medium
Formation Spontaneous Special technique Spontaneous
above cmc.

Viscosity Dramatic No change Little change;

increase can increase at
high conc.
Examples Gelatin Silver Iodide Tween 80
Methyl-cellulose Gold Sols Bile Salts
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Properties of Colloids

I. Size and shape

II. Optical Properties

III. Kinetic Properties

IV. Electrical Properties

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a. Optical Properties
When light passes through a sol, its path becomes visible because
of scattering of light by particles.
It is called Tyndall effect.

This phenomenon was studied for the first time by Tyndall.

beam of light beam of light

solution
June 1, 2023 Phar 2091
colloid 26
• The intensity of the scattered light depends on the difference
between the refractive indices of the dispersed phase and the
dispersion medium.

• In lyophobic colloids, the difference is appreciable and,

therefore, the Tyndall effect is well - defined.
• But in lyophilic sols, the difference is very small and the Tyndall
effect is very weak.

• The Tyndall effect confirms the heterogeneous nature of the

colloidal solution.
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June 1, 2023 Phar 2091 26
Brownian Movement
– particles are generally small enough to be influenced by the
collision with molecules of the dispersion medium
– when particles are observed, they are seen to move in a
random, erratic manner,

Consequences of Brownian movement
– Stable colloids are systems in which the dispersed particles
do not settle, because the force of gravity is counteracted
by Brownian movement.
– Colloidal sols will diffuse from a region of high
concentration to a region
June 1, 2023 Pharof
2091low concentration. 27
 Questions


What is the effect of each of the following on the rate of
diffusion of a colloid?
– increasing particle size
– increasing temperature
– increasing viscosity of the dispersion medium

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 Questions

What is the effect of each of the following on the rate of
diffusion of a colloid?
– increasing particle size

decreases rate of diffusion
– increasing temperature

increases rate of diffusion
– increasing viscosity of the dispersion medium

decreases rate of diffusion
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 Sedimentation
-velocity of sedimentation of spherical particles having a

density of ρ s in a medium of density ρ o and a viscosity

 is given by stokes’ law,

V= 2r2 (ρ s- ρ o ) g or V= d2 (ρ s- ρ o ) g
9 18

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D. Electrical Properties

presence/absence and magnitude of charge is an important
factor in stability of colloidal particles,

most surfaces acquire surface electric charge in an aqueous
medium,

Charging mechanisms:

Ion dissolution

Ionization

Selective ion adsorption
Electrical double layer
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Ionization
- due to ionization of surface groups such as COOH on the particles
- charge formation is a function of PH and PK.
Eg, amino acids acquire their charge mainly through the ionization
of carboxyl and amino groups to give -COO- and NH+3

R-NH2-COO- alkaline solution

R-NH+3-COO- isoelectric point

R-NH+3-COOH acidic solution

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Ion dissolution
-ionic substances acquire a surface charge due to unequal
dissolution of oppositely charged ions present.

Selective ion adsorption

-charge is due to unequal adsorption of oppositely charged ions,
Eg, most particles in water acquire a –ve charge due to
preferential adsorption of OH ion, and thus cations are
more hydrated than anions so that the former have greater
tendency to reside in the bulk aqueous medium.

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 Electrical double layer
Particle Surface

-
I surface is negatively charged
-  cations in solution are called
I
- counterions
I
-  anions in solution are called
I
- similions (co-ions)
I
-
I
-
I

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Distance from particle surface
Particle Surface

- -
I Na
+
NO 3
- NO 3
- Na
+
I
Na
+
- Bulk Solution is
- Na
+
Na
+
I
I electrically neutral: equal
-
- - NO 3 +
I Na
+ I Na
concentration of similions &
- + +
counterions
I Na Na
-
NO 3
- -
I Na
+ NO 3
Na
+
+
- + Na
+
I Na Na

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Distance from particle surface
Particle Surface Diffuse region with excess
concentration of counterions

- -
I Na
+
NO 3
- NO 3
- Na
+
I +
- Na
+ + Na -
I
Na
I
- Bulk solution contains
- - NO 3 +
I Na
+ I Na
equal concentration
- + + of similions & counterions
I Na Na
-
NO 3
- -
I Na
+ NO 3
Na
+
+
Na
- Na
+
Na
+
I
Tightly bound layer
Double Layer
diffuse layer

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Distance from particle surface
 Double Layer


"Adsorbed" ions on the surface of the extended crystal.

Diffuse Layer with an excess of counterions to neutralize
surface charge.

Double Layer is electrically neutral.

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 Double Layer Theory

Colloidal Particle
- Surface Charge
-+ - + -
- - + + -
+ ++ + -
- + +
+- Diffuse Region with excess
- - ++ ++ + - "counterions"
-+ + -
- - -

Aqueous Dispersion Medium

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(Electrically Neutral)
Phar 2091 38
Stability of colloidal systems

1. Electrostatic repulsion
2. Steric hindrance

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Electrostatic repulsion

 Depends on:

-density of surface charge,

-thickness of double layer,

both of which govern the magnitude of zeta potential.

 Zeta potential is defined as the difference in potential
b/n the surface of the tightly bound layer and the electro
neutral region of the solution.
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 Lyophobic sol is thermodynamically unstable, thus can be
stabilized only by the presence of electrical charge on their
surfaces
-addition of electrolyte in small amount can stabilize
lyophobic sols.
-addition of electrolyte beyond that necessary for maximum
adsorption on the particles may result in coagulation due to
accumulation of opposite ions that reduces zeta potential
below its critical value.

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 Electrical Repulsion

- -
-+ - + - -+ - + -
- - + + - - - + + -
+ + + - + + + -
- + + - + +
+ +- + +-
- - ++ ++ + - - - ++ ++ + -
-+ + - -+ + -
- - - - - -

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Interpenetration of the Diffuse Double Layers

- -
-+ - + - -+ - + -
- - + + - - - -
+ + - + + ++ -
+ +
- + + - + +
+ +- + +-
- - + + + + + -- - + + + + + -
-+ + - -+ + -
- - - - - -

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 Coagulation

- -
-+ - + - - - -
- - - + -
- + + - + ++ -
+ + + -
+
- + + + +
+ + -+ +-
- - + + + + + +- + + + + -
-+ + - - + -
- - - - - -
Attractive forces overwhelm repulsive forces.
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 Colloidal Stability and the Diffuse Double Layer


Generally, the larger the diffuse double layer the greater the
repulsive force and the more stable the colloid.


What is the size of the diffuse double layer?

What factors influence the size of the diffuse double layer?

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 What is the effect of ...

increasing temperature
• higher kinetic energy may overwhelm repulsive forces
• increasing electrolyte concentration

increasing concentration and hydration ability of ions in the
dispersion medium correlates with increasing effectiveness
"salting out" hydrophilic colloids

increasing concentration and presence of extensively hydrated
ions makes it more difficult to hydrate added solid colloidal
material
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Hydrophilic colloids with opposite charges may separate from
dispersion medium and form a colloid rich layer called
coacervate.
e.g., at PH less than 4.7,
• gelatin is negatively charged
• acacia is positively charged
mixing such solutions may result in coacervation.

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Steric hindrance
 Surfactants and polymers when adsorbed at the particle
surface may stabilize lyophobic sol through sensitization
and protection steps.
 At low polymer concentration-bridging the gap b/n the
particles and thus pulling them together,
 low surface coverage
 At higher polymer concentration-bridging is unlikely and
thus the adsorbed polymer stabilizes the sol.
 In steric hindrance ,concentration of the polymer is the
rate limiting factor.
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•Addition of large amount of hydrophilic colloid (protective
colloid) stabilizes the system being adsorbed as a
monomolecular layer on the hydrophobic particles, such
phenomenon is known as protection
- no coagulation
Eg, gelatin, acacia …

The protective property is expressed in terms of gold number.

June 1, 2023 Phar 2091 49

•Gold number is defined as the minimum amount of lyophilic
colloid in milligrams which prevents the coagulation of 10 ml
gold sol against 1 ml of 10%NaCl solution.

•Coagulation of gold sol is indicated by color change from red to

blue when particle size just increases.

•More is the gold number less is the protective power of the

lyophilic colloid since it means that the amount required is more.

•The amount is taken in terms of weight in milligrams.

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The gold number of some colloids is given below.

Protective Colloids Gold Number

Gelatin 0.005-0.01
Hemoglobin 0.03
Potato Starch 25
Acacia 0.1-0.2
Sodium Oleate 0.4
Dextrin 6-20
Albumin 0.1
Tragacanth 2
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