302 Colloids
302 Colloids
302 Colloids
colloids
By:
Dr. Hina Saleem
Assistant Professor
Department of Pharmaceutics,
Dow College Of Pharmacy,
D.U.H.S.
LEARNING OBJECTIVES
At the end of this topic, students will be able to;
• Describe disperse system and its types
• Describe different types of colloidal system
• Differentiate between different types of colloid system and their
main characteristics
• Describe different methods for the preparation of colloids
• Describe the methods for the purification of colloids
• Understand the main properties of the colloids and application of
these properties for the analysis of colloids
• Discuss the stability of colloids
Course Outline
• DISPERSED SYSTEM
– Colloids: Types, methods of preparation, properties (optical, kinetic,
electrical) Dialysis and artificial kidney, stability of colloids, protection
and sensitization phenomenon and applications of colloid in pharmacy.
• Lyophilic colloids;
– Relatively easy to prepare as they have great affinity towards the
dispersion medium.
– Disperse phase allowed to soak in an appropriate medium for some
time, and due to the affinity character it will interact considerably,
forming a colloidal dispersion
PREPARATION OF LYOPHOBIC COLLOIDS
• Lyophobic colloids;
– Difficult to produce a lyophobic colloid and generally two
methods are used;
• 1. Dispersion methods: By splitting coarse aggregates of a
substance into a colloidal size.
• 2. Condensation methods: By aggregating very small particles into
the colloidal particles.
1. DISPERSION METHOD
• Exchange of solvents
• There are a no. of substances whose colloidal solutions can be
prepared by taking the solution of the substance in one solvent
and pouring it into another solvent in which the substance is
relatively less soluble.
• CHEMICAL METHODS
– Oxidation method
– Reduction method
– Hydrolysis method
– Double decomposition method
PURIFICATION OF COLLOIDS
• Many methods of preparation of colloids may give product which is
a mixture of colloidally dispersed particles and particles in true
solution.
• Purification means removal of such materials from true solution
since coarse particles, if present can be easily removed by filtration.
• There are 3 common methods for purification of colloids
– Dialysis
– Electrodialysis
– Ultrafiltration
PURIFICATION OF COLLOIDS
I = IO exp- τl
Where
– I is intensity of incident beam
– IO is intensity of transmitted light
– τ is turbidity
– L is length of the sample
Light Scattering
• Where,
– τ= turbidity measured at 90o to the incident beam
– C= conc: of solute (g/L)
– M=mol:wt
– B=interaction constant (for any particular solvent/solute system and depends on degree of interaction
between the solvent and solute molecules)
– H=Optical constant
Kinetic Properties
BROWNIAN MOTION
• Colloidal particles in a sol are continuously bombarded by the molecules of the dispersion
medium on all sides.
• As a result, the sol particles show random or zig-zag movements. This random or zig-
zag motion of the colloidal particles in a sol is called Brownian motion or Brownian movement
• There is a continuous bombardment of the moving molecules of
the dispersion medium on the colloidal particles from all directions.
• This imparts a momentum to the particles to move in a forward
direction where again it collides with another particle. These
collisions result in the random zigzag movement of the colloidal
particle.
• The Brownian movement imparts stability to the sol. It opposes the
gravitational force acting on colloidal particles and prevents them
from settling down thus maintaining the stability of the sol.
• The Brownian motion:
– Increases with decrease in particle size
– Decreases with increase in viscosity of dispersion medium
Diffusion
P= C/M RT
Where;
– P is the osmotic pressure
– C is the conc. In grams of solute per litre of solvent
– M is the molecular weight
– R is the gas constant
– T is the temperature in Kelvin
Sedimentation
• The velocity of sedimentation is given by Stokes’s law;
V= d²(ρ-ρο)g /18ηo
Where;
V= velocity, of sedimentation
ρ= density of particles
ρ ο= density of medium
η o= viscosity
d= diameter of the particle
g is acceleration due to gravity
Viscosity
• It is the resistance to flow of system under an applied stress.
• The more viscous a liquid, the greater the applied force
required to make it flow at a particular rate
• The viscosity of a colloidal system is affected by:
– Shape of colloidal material
• Spherocolloids---- dispersion of low viscosity
• Linear particles--- more viscous dispersions
– Degree of solvation
Electrical Properties
• Electrical Double Layer
• The particles in a colloid are
almost
always electrically charged.
• This charge on the particle is
balanced by an opposite charge in
the surrounding fluid.
• There is a region around each
particle where the particle charge
attracts the free ions to form
an electrical cloud called
ELECTRICAL DOUBLE LAYER
• Electric Double Layer is the phenomenon playing a
fundamental role in the mechanism of the electrostatic
stabilization of colloids.
• Colloidal particles gain negative electric charge when
negatively charged ions of the dispersion medium are
adsorbed on the particles surface.
• A negatively charged particle attracts the positive
counterions surrounding the particle.
ELECTRICAL DOUBLE LAYER
• Electric Double Layer is the layer surrounding a particle
of the dispersed phase and including the ions adsorbed
on the particle surface and a film of the countercharged
dispersion medium.
• An electric double layer consists of three parts;
– Surface charge
– Stern layer
– Diffuse layer (Gouy- Chapman layer)
• The electrical potential within the Electric Double Layer has
the maximum value on the particle surface (Stern layer).
• The potential drops with the increase of distance from the
surface and decreases at the boundary of the Electric
Double Layer.
• When a colloidal particle moves in the dispersion medium, a
layer of the surrounding liquid remains attached to the
particle.
• The boundary of this layer is called slipping plane (shear
plane).
• The value of the electric potential at the slipping plane is
called Zeta potential, which is very important parameter in
the theory of interaction of colloidal particles.
ELECTROPHORESIS
• Colloidal particles of a sol either carry
positive or negative charge.
• The existence of charge on colloidal
particles can be demonstrated by a
phenomenon called electrophoresis
where the colloidal particles when
placed in an electric field, move towards
either cathode or anode depending upon
the charge on them.
Electrophoresis
• From the direction of movement of colloidal particles, it is possible to find out the
charge on colloidal particles.
• If the colloidal particles move towards the positive electrode, they carry negative
charge.
• On the other hand if the sol particles migrate towards negative electrode, they are
positively charged.
• The rate of the migration of the particles is observed by means of ultra microscope,
and is a function of charge on the particle.
• The rate-determining potential is the zeta potential.
Zeta potential is the potential difference between the dispersed medium
and the liquid adsorbed on the surface of the stationary or colloid
particles, denoted by symbol ζ.
• Where;
• ς = zeta potential in volts
• V = velocity of movement of colloidal particles in cm/sec
• η = viscosity of medium in poises
• Ɛ = dielectric constant of the medium
• E= externally applied electric potential in volts/cm
• The term v/E is termed as the mobility
• Electrophoresis permits the:
– identification of different colloidal components in a mixture
– to study the electrophoretic mobility of the components in a mixture
such as that of proteins
– to estimate the relative amounts present
ELECTRO-OSMOSIS
• When the movement of colloidal particles under the influence
of the applied electric field is checked with the help of a suitable
membrane (semi permeable membrane), the dispersion
medium moves in a direction opposite to the direction in which
the colloidal particles would have otherwise moved.
• This phenomenon is called electro-osmosis and may be defined
as the movement of dispersion medium under the influence of
an electric field in the situation when the movement of colloidal
particles is prevented with the help of a suitable membrane
ELECTRO-OSMOSIS
• A colloidal solution as a whole is electrically neutral in nature
i.e., dispersion medium carries an equal and opposite charge to
that of the particles of dispersed phase.
• When the movement of dispersed phase of colloidal solution is
prevented by suitable means, the dispersion medium can be
made to move under the influence of an applied electric field
or potential. This phenomenon is referred to as Electro-
Osmosis.
Demonstration of Electro-Osmosis
Sedimentation Potential
• The reverse of electrophoresis, is the creation of a potential when particle undergoes
sedimentation.
SEDIMENTATION POTENTIAL
Streaming Potential
• Streaming potential is opposite to electro-osmosis.
• If the electrodes in the electro-osmosis apparatus are replaced by a
galvanometer in the circuit, no current will be detected when the liquid is
stationary.
• However, if the liquid is forced through the tube, the galvanometer will indicate
a current.
• This streaming potential is due to the displacement of the charges equilibrated
in the double layer around the solid.
• which means the liquid carries away the ions with the charge opposite to the
surface, giving rise to a streaming current, consequently, leading to the
accumulations of charge at the ends and an electrical field
Donnan Membrane Equilibrium
• 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.
• It refers to the uneven distribution of charged particles on one
side of a semi-permeable membrane. These particles are not able
to evenly distribute themselves by diffusion across both sides of
the membrane.
Donnan Membrane Equilibrium
• When two solutions containing diffusible and non-diffusible ions
are separated by a semi-permeable membrane, the non-diffusible
ions enhance the diffusion of oppositely charged diffusible ions.
• The diffusion takes place towards non-diffusible ion containing side
• This also reduces the diffusion of liked charged ions to that side.
• As a result, on the side which contains non-diffusible ions,
diffusible counter-ions are more concentrated while the like
charged diffusible ions concentrate more on the opposite side.
• This is called Donnan effect.
INTERACTION OF COLLOIDS
• The following effects are observed on mixing different colloids:
1. MUTUAL PRECIPITATION
• When two oppositely charged hydrophobic colloids are
mixed, precipitation takes place.
• Charges necessary for stability get neutralized by each other
and attractive forces between particles dominate.
INTERACTION OF COLLOIDS
2. CO-ACERVATE FORMATION
• When oppositely charged hydrophilic colloids are mixed, the
particles may separated from the dispersion medium to produce
a layer rich in the colloidal aggregates.
• This colloidal rich layer is called as co-acervate and the
phenomenon is termed as co-acervation.
• Such a co-acervation is encountered when solution of gelatin
carrying positively charged gelatin particles are mixed with
negatively charged acacia particles
INTERACTION OF COLLOIDS
3. SENSITIZATION
– In the presence of very small amount of hydrophilic colloids, the
hydrophobic colloids may become even more susceptible to
precipitation from electrolytes.
– Sensitization is attributed to a reduction in zeta potential below the
critical value (the value at which coagulation occurs).
– It is also reasoned that it is due to the reduction in the thickness of the
ionic layer surrounding the colloidal particles.
INTERACTION OF COLLOIDS
4. PROTECTIVE COLLOID
– The addition of larger amounts of hydrophilic colloids increases
the stability of hydrophobic colloids towards precipitation by
electrolytes.
– The hydrophilic colloids adsorb on the surface of an
hydrophobic colloid particles and form a protective layer thus
preventing them from precipitation on addition of an electrolyte.
– This phenomenon is called protection and the added hydrophilic
sol is known as protective colloid.
– The common example of protective colloids are : gelatin,
casein, hemoglobin, egg albumin etc
STABILITY OF COLLOIDS
Stability depends upon two factors
1. Presence of charge on dispersed colloidal particles
2. Presence of a solvent sheath surrounding each dispersed particle
STABILITY OF COLLOIDS
• When the colloidal particles collide as a result of Brownian
movement, the above two factors will prevent mutual
adherence.
• It may be said that the stability of lyophobic colloid is largely
due to the electric charges on the surface of the dispersed
particles and
• For lyophilic sols, it is the solvent sheath that is significant in
stabilizing the system
STABILITY OF COLLOIDS
• In a lyophobic sol, the particles are stabilized by the presence
of electric charges on their surfaces.
• The like charges present on the surface prevent the
coagulation of the particles.
• Coagulation is the process where the colloidal particles
aggregate together resulting in the precipitation of the
dispersed particles and ultimately the colloid dispersion breaks
up.
STABILITY OF COLLOIDS
• SCHULZE-HARDY RULE
• Coagulation of colloidal dispersions can be brought about by the
addition of electrolytes which reduces the zeta potential.
• The effectiveness of an electrolyte to cause precipitation depends
not only on the concentration but also on the valence of the active
ion.
• “The higher the valency of ion, the greater is the precipitating
power”
• This is known as Schulze- Hardy Rule
“The higher the valency of ion, the greater is the precipitating power”