Colloidal Dispersion (Unit I)
Colloidal Dispersion (Unit I)
BP403T
Dr. Asim Kumar Samanta
Assistant Professor
Dr. Vishwanath Karad MIT World Peace University,
School of Health Science and Technology,
Kothrud, Pune, Maharashtra 411038
Colloidal Dispersions
Unit I
2
Syllabus
• Colloidal dispersions:
• Classification of dispersed systems & their general characteristics
• Size & shapes of colloidal particles
• Classification of colloids & comparative account of their general properties.
• Optical, kinetic & electrical properties
• Effect of electrolytes, coacervation, peptization & protective action.
3
Introduction
• A disperse system is defined as a heterogeneous two-phase system in
which the disperse phase is distributed as particles or droplets throughout
another phase called as dispersion medium.
• Three Types of Dispersed Systems in Pharmaceuticals
• Molecular Dispersion: Homogeneous, forms true solutions
• Colloidal Dispersion: dispersed particles are intermediate in size between true
solutions and coarse dispersions
• Coarse Dispersion: droplet size exceeds 1 μm
• Example: Components of Blood as Dispersed Phases
• Nutrients (peptides, proteins, glucose) in plasma form a molecular dispersion.
• Red blood cells (~6 μm in diameter) carry oxygen - Coarse dispersion
• Serum albumin forms a colloidal dispersion in water (individual serum albumin
particles in solution is >1 nm)
4
Classification of Dispersed Systems Based on
Particle Size
Class Particle Size Characteristics of System Examples
Molecular Less Invisible in electron microscope. Pass through Oxygen molecules, ordinary
dispersion than 1 nm ultrafilter and semipermeable membrane. ions, Glucose
Undergo rapid diffusion
Colloidal From 1 nm to Not resolved by ordinary microscope (although may Colloidal silver sols, natural
dispersion 0.5 μm be detected under ultramicroscope) and synthetic polymers,
Visible in electron microscope Pass through filter cheese, butter, jelly, paint,
Paper. Do not pass semipermeable milk, shaving cream,
Membrane. Diffuse very slowly etc.
Coarse Greater than Visible under microscope. Do not pass through Grains of sand, most
dispersion 0.5 μm normal filter paper. Do not dialyze through pharmaceutical
Semipermeable membrane. Do not diffuse emulsions and
suspensions, red
blood cells
5
Colloidal systems
• Colloid is a heterogeneous dispersed system in which one substance is
divided into minute particles (colloid particles) dispersed throughout a
second substance (usually liquid).
• Possible types of colloidal dispersions
Dispersion Medium Dispersed Phase Colloid Type Examples
Solid Solid Solid sol Pearls, opals Gases are completely
miscible with each
Solid Liquid Solid emulsion Cheese, butter other (homogeneous
Solid Gas Solid foam Pumice, marshmallow system) & does not
Liquid Solid Sol, gel Jelly, paint form colloid system
8
Characteristic of dispersed phase
• Particle shape
• Particle shape depends upon
the chemical and physical
nature of the dispersed phase
and the method employed to
prepare the dispersion
• A colloidal particles in a
friendly environment, unrolls
and exposes maximum surface
area. Under adverse
conditions, it rolls up and
reduces its exposed area.
9
Characteristic of dispersed phase
• Surface area
• Particle size small- large surface area
• Effective catalyst, enhance solubility.
• For example, platinum is effective as a catalyst only when in
the colloidal form as platinum black.
10
Characteristic of dispersed phase
• Surface charge
• Positive (+)= gelatin, aluminum.
• Negative (-) = acacia, tragacanth.
• Particle interior neutral, surface charged.
• Surface charge leads to stability of colloids because of repulsions
11
Classification of colloids
1. Based of physical state of dispersed phase an dispersion medium.
2. Based of nature of interaction between dispersed phase and
dispersion medium.
3. Based on molecular size in the dispersed phase.
4. Based on appearance of colloids.
5. Based on electric charge on dispersion phase.
12
1. Based of physical state of dispersed phase
an dispersion medium
13
2. Based of nature of interaction between
dispersed phase and dispersion medium
• Lyophilic Colloids
• Lyophobic Colloids
• Association Colloids: Micelles and the Critical Micelle Concentration
14
Lyophilic Colloids
• Lyophilic colloids are systems containing colloidal particles that interact
significantly with the dispersion medium and leads to the spontaneous
formation of colloidal dispersions.
• They are often referred to as solvent-loving colloids due to their strong affinity
for the dispersion medium and are generally self- stabilized.
• These colloids are thermodynamically stable.
• Solvation: Attachment of solvent molecules to the molecules of the dispersed
phase.
• In hydrophilic colloids, where water is the dispersion medium, solvation is
termed hydration.
• Example: Gelatin, acacia, insulin, and albumin produce hydrophilic sols in aqueous dispersion
media.
• Rubber and polystyrene form lipophilic colloids in non-aqueous solvents.
15
Lyophobic Colloids
• Lyophobic colloids are characterized by materials that exhibit little to no
attraction for the dispersion medium.
• In contrast to lyophilic colloids, lyophobic colloids lack a solvent sheath around
the particles.
• These dispersions are thermodynamically unstable.
• Composition of Lyophobic Colloids:
• Lyophobic colloids typically consist of inorganic particles dispersed in water.
• Examples of materials forming lyophobic colloids include gold, silver, sulfur, arsenous sulfide,
and silver iodide.
• Stability Mechanism:
• Lyophobic colloids are stable due to the presence of a charge on particles.
• Like charges on particles create repulsion, preventing coalescence of particles.
• If the dispersion medium is water, the lyophobic colloids are called hydrophobic
colloid.
16
Association Colloids
• Association colloids, also known as amphiphilic colloids,
form the third group in colloid classification.
• Amphiphilic molecules or surface active agents
(surfactants) contain large hydrophobic moieties and
strong hydrophilic groups within the same molecule.
• Micelle Formation:
• At low concentrations in water, surface-active agents exist
individually as monomers with subcolloidal size.
• With increasing concentration, monomers aggregate to form
micelles.
• Each micelle may contain 50 or more monomers.
• Critical Micelle Concentration (CMC):
• The concentration of monomers at which micelles form is
termed the Critical Micelle Concentration (CMC).
• Below the CMC, surfactants are adsorbed at the air-water
interface.
17
Association Colloids
• The concentration of monomers at which
micelles form is known as the Critical Micelle
Concentration (CMC).
• Spontaneous Formation:
• Similar to lyophilic sols, the formation of association
colloids is spontaneous if the amphiphile
concentration exceeds the CMC.
• Micelle Shapes:
• (a) spherical micelle in aqueous-media
• (b) reversed micelles in non-aqueous media
• (c) Laminar micelle, formed at higher amphiphile
concentration, in aqueous media
18
Association Colloids
• Classification of association colloids:
• Amphiphiles may be anionic, cationic, nonionic, or ampholytic (zwitterionic),
19
3. Based on molecular size in the dispersed
phase
• Multi molecular colloids:
• Multimolecular colloids are particles formed by the aggregation of
smaller molecules (diameter less than 1 nm) when they are
dissolved in a solvent.
• Formed from particles having low molecular weights.
• Usually, these colloids have a lyophobic nature
• The particles are held by weak Vander Waal's forces.
• Example: gold sol, sulphur sol.
• GELS
• When a colloidal solution appear as solid.
• The rigidity of gel varies from substance to substance.
• Examples: jelly, butter, cheese, curd
21
5. Based on electric 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
• NEGATIVE COLLOIDS
• When dispersed phase in a colloidal
solution carries a negative charge.
• Examples: Ag sol, Cu sol
22
Properties of colloid
• Optical Properties
• Kinetic Properties
• Electrical Properties
23
Optical Properties of Colloids
• Faraday–Tyndall effect: When an intense beam of light is passed through a
colloidal sol kept in dark, the path of the beam gets illuminated due to the
scattering of light by colloidal particles.
• The illuminated path is called Tyndall beam
• Tyndall effect is not exhibited by true solutions. This is because the
particles present in a true solution are too small to scatter light.
24
Electron Microscope
• Visualizing size, shape, and structure of sol particles and particles approaching
molecular dimensions
• Principle: Focusing electron beam with electric and magnetic fields onto a
photographic plate
• Success of the electron microscope is due to its high resolving power.
• Resolving Power: Smallest distinguishable separation between two objects (d) →
The smaller the wavelength of the radiation used, the smaller is d and the greater
is the resolving power.
• Magnification: Achieving magnification up to 10,000 times
• Radiation Source: High-energy electrons with wavelengths around 0.1 Å → With
current instrumentation, this results in d being approximately 0.5 nm (5 Å)
• The optical microscope uses visible light as its radiation source and is able to
resolve only two particles separated by about 20 nm (200 Å). 25
Optical Properties of Colloids
• Light Scattering: This property depends on the Faraday–Tyndall effect.
• It can be used to obtain information on the shape and size of these colloid
particles and widely used for determining the molecular weight of colloids.
• Scattering may be described in terms of turbidity (τ) the fractional
decrease in intensity due to scattering as the incident light passes through
1 cm of solution.
26
Optical Properties of Colloids
• The turbidity can be calculated from the intensity of
light (scattered). → The molecular weight of
colloid can be calculated from the following
equation derived by Debye in 1947.
• Where τ is the turbidity in cm-1, c is the
concentration of solute in g/cm3 of solution, M is
the weight average molecular weight in g/mole,
and B is an interaction constant. H is an optical
constant for a particular system depending on the
value of refractive index that changes with
concentration and the wavelengths of light used.
• A plot of HC/τ against concentration results in Light scattering has been used to study
straight line with slope 2B. The intercept on HC/τ proteins, synthetic polymers,
axis is 1/M allowing the molecular weight to be association colloids, and lyophobic sols.
calculated.
27
Kinetic Properties of Colloid
• Kinetic properties of colloidal dispersions plays an important role in
study of -
• Stability of system
• Molecular weight of given sample
• Transport of kinetics of colloidal particles.
• Several properties that relates to the motion of the particles. It can
be-
• Thermally induced (Brownian movement, Diffusion, Osmosis)
• Gravitationally induced (Sedimentation)
• Applied externally (Viscosity)
• Electrically induced
28
Kinetic Properties of Colloid
• Brownian movement: The continuous zigzag movement of the
colloidal particles in the dispersion medium in a colloidal system
is called Brownian movement.
• According to kinetic theory, all matter is in motion; atoms and
molecules especially within liquids and gases are in constant
vibrating motion. These particles will travel in straight lines until
redirected by a collision.
• The Brownian movement decreases with an increase in the size of
colloidal particle →This is why suspensions do not exhibit this
type of movement.
• Increasing the viscosity of the medium, decreases and finally
stops the Brownian movement.
29
Kinetic Properties of Colloid
• Diffusion: Particles diffuse spontaneously from a region of higher
concentration to one of lower concentration until the concentration
of the system is uniform throughout.
• Diffusion is a direct result of Brownian movement.
30
Kinetic Properties of Colloid
• Diffusion can be expressed by Fick's first law.
36
Kinetic Properties of Colloid
• Viscosity: It is the resistance to flow of system under an applied
stress.
• The more viscous a liquid is, the greater is the applied force required
to make it flow at a particular rate.
• Einstein developed an equation of flow applicable to dilute colloidal
dispersions of spherical particles:
42
Electrophoresis
• 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.
• From knowledge of the direction and rate of
migration, the sign and magnitude of the zeta
potential in a colloidal system can be determined.
which yields the zeta potential, ζ, in volts, requires a knowledge of the velocity of migration, v, of the sol
in cm/sec in an electrophoresis tube of a definite length in cm, the viscosity of the medium, η, in poises
(dynes sec/cm2), the dielectric constant of the medium, ε, and the potential gradient, E, in volts/cm. The
term v/E is known as the mobility. 43
Electro-osmosis
• Electroosmosis is essentially opposite in principle to electrophoresis.
• In electroosmosis, if the solid is rendered immobile (e.g., by forming a capillary or
creating particles into a porous plug), the liquid moves relative to the charged
surface.
• Electroosmosis is named as such because it involves the movement of liquid
through a plug or a membrane across which a potential is applied.
44
Sedimentation potential
• The sedimentation potential also called the
(Donnan membrane effect).
• It is the potential induced by the fall of a charged
particle under an external force field.
• It is analogous to electrophoresis in the sense that
a local electric field is induced as a result of its
motion.
• If a colloidal suspension has a gradient of
concentration (such as is produced in
sedimentation or centrifugation), then a
macroscopic electric field is generated by the
charge imbalance appearing at the top and bottom
of the sample column.
45
Donnan Membrane Equilibrium
• NaCl is placed in solution on one side of a
semipermeable membrane → -ve charged colloid
together with its counterions R-Na+ is placed on the
other side
• Na+ and Cl- ions can pass freely across the barrier
but not the colloidal anionic (R-) particles.
• The volumes of solution on the two sides of the
membrane are considered to be equal.
• After equilibrium, the concentration (activity) of
sodium chloride same on both sides in dilute
solutions
• The condition of electroneutrality must also apply.
46
Donnan Membrane Equilibrium
• Donnan membrane equilibrium, gives the ratio of concentrations of the diffusible anion outside
and inside the membrane at equilibrium. The equation shows that a negatively charged
polyelectrolyte inside a semipermeable sac would influence the equilibrium concentration ratio
of a diffusible anion.
• When [R-]i is large compared with [Cl-]i, the ratio roughly equals square root of [R-]i
• On the other hand, [Cl-]i is quite large with respect to [R-]i, the ratio becomes equal to unity
• Higuchi modified the Donnan membrane equilibrium equation to demonstrate the use of the
polyelectrolyte NaCMC for enhancing the absorption of drugs such as sodium salicylate and
potassium benzylpenicillin.
• Concentration of the diffusible drug, anion [D-] at equilibrium, and [R-] is used to represent the
concentration of sodium carboxymethylcellulose at equilibrium, we have a modification of the
Donnan membrane equilibrium for a diffusible drug anion
• Therefore, the addition of an anionic polyelectrolyte to a diffusible drug anion should enhance
the diffusion of the drug out of the chamber.
47
Streaming potential
• Streaming potential is the process in which the application of a pressure gradient causes
a liquid to flow through a bed of particles or a capillary, generating an electric current
which leads to an electric field. Differs from electro-osmosis in that the potential is
created by forcing a liquid to flow through a bed or plug of particles.
48
Stability of Colloidal Systems
• Lyophilic colloid: stability is achieved by a protective solvent sheath
surrounding each particle.
• Lyophobic colloid: Stability is primarily influenced by the electric charge
present on the dispersed particles. Electric charge on dispersed particles
contributes to stability.
• Thermodynamically unstable; stabilized only by electric charges on particle surfaces.
• Like charges result in repulsion, preventing particle coagulation.
• Addition of electrolyte imparts charge, stabilizing the system.
• Zeta Potential and Critical Values
• Critical zeta potential indicates stability; oil hydrosol critical value is approximately 40
millivolts.
49
Stability of Colloidal Systems
• DLVO Theory: Derjaguin and Landau, Verwey and Overbeek produced a
quantitative approach to the stability of lyophobic colloid, what has come
to be known as the DLVO theory of colloid stability.
• This theory is useful to determine approximate amount of electrolyte
required to precipitate or stabilize a colloid.
• Stability of lyophobic colloids—DLVO theory: Theory is based on a
combination of attractive and repulsive forces and explains the aggregative
instability of two particles at any given separation distance. According to
the DLVO theory-
• Total potential energy of interaction (VT) = VA + VR
• Attractive forces (VA): London type-van der Waals attractive forces between colloidal
particles
• Repulsive forces (VR): Electrical repulsive forces between colloidal particles
50
Stability of Colloidal Systems
• Stability of lyophobic colloids—DLVO theory:
• At very small interparticle distance attractive forces
between particles predominate resulting in a deep
primary minimum.
• At intermediate interparticle distance double-layer
repulsion between particles dominates giving a primary
maximum in the curve.
• Secondary Minimum: Here particles form aggregates due
to attractive forces. This is significant in the controlled
flocculation of coarse dispersions.
• From this principle, one can determine
quantitatively the amount of electrolyte of a
particular valence type required to precipitate a
colloid.
• Schulze–Hardy rule arranges ions in the order of their
capacity to coagulate hydrophobic colloids. For example,
Al3+ is more effective than Mg2+ and Na+ 51
Stability of Colloidal Systems
• Stability of lyophilic colloids:
• The addition of moderate amounts of an electrolyte to a lyophilic colloid does
not result in coagulation. More salt is required to coagulate → Phenomenon,
referred to as “salting out”.
• The precipitation or coagulation power in lyophilic colloids is given by Hofmeister or
lyotropic series.
• According to this series the precipitation or coagulation power is based on ability of
electrolyte to dislodge solvent sheath from the colloidal particles.
• For anions in descending order of precipitation power are citrate > tartrate > sulphate >
acetate > chloride >bromide > iodide.
• For cation in descending order of precipitation are Lithium > Sodium > Potassium >
Ammonium > Magnesium
• Less polar solvent (eg. Alcohol and acetone) can also decrease the solubility
of hydrophilic colloids → the solvent mixture unfavorable for the colloid
52
Coacervation
• Mixing negatively and positively charged hydrophilic colloids can lead to
the separation of particles forming a colloid-rich layer.
• Colloid-rich layer is known as coacervate
• Phenomenon is referred as coacervation
• Example: Gelatin and Acacia
• Gelatin at pH below 4.7 (its isoelectric point) is positively charged.
• Acacia carries a negative charge relatively unaffected by pH in the acid range.
• Mixing solutions of these colloids in specific proportions results in coacervation.
• Coacervation may not necessarily involve the interaction of charged particles alone.
• Gelatin coacervation can be induced by the addition of alcohol, sodium sulfate, or
macromolecular substances like starch.
53
Peptization
• Peptization is the process opposite to coagulation, aiming to stabilize a colloidal
system.
• In freshly precipitated ionic solids, small quantities of electrolytes, especially
common ions, are incorporated → This stabilizing agent is known as a peptizing
agent.
• Example 1: Ferric Hydroxide (Fe(OH)3)
• A freshly prepared precipitate of ferric hydroxide is peptized by adding ferric chloride (FeCl3).
• The common ions in ferric chloride stabilize the system and prevent coagulation.
• Example 3: Peptization in Milk
• Milk is a colloidal dispersion of oil in water.
• Casein in milk acts as a peptizing agent for the hydrophobic oil in the colloidal system.
54
Protective Colloid
• When large quantity of hydrophilic colloid added to hydrophobic colloid
carrying opposite charge → hydrophilic colloid gets adsorbed on
hydrophobic particles forming a layer around it → The coagulation of
particles is prevented due to the layer → This phenomenon is known as
protection and the colloid that helps to stabilize the hydrophobic colloid is
called protective colloid.
• Examples: Gelatin, gum acacia, tragacanth, etc., are examples of protective
colloids commonly used for stabilization.
55
Protective Colloid
• Gold Number: The protective property of colloids is expressed in
terms of gold number → The higher the gold number, the lower the
protective power of the colloid
• The gold number is the minimum weight in milligrams of a hydrophilic
colloid (dry weight) required to prevent a colour change from red to
violet in 10 ml of gold sol on addition of 1 ml of 10% sodium chloride
sol.
• The gold sol is hydrophobic colloid (red colour) can be stabilized by
addition of protective colloid and prevent color change to violet.
56
End
57