Electrical Properties

of Dispersed
Systems

PhD Halina Falfushynska

 Electrical Properties of Colloidal
Solutions
• (i) Presence of electrical charge on
colloidal particles and stability of sols
• (ii) Electrophoresis
• (iii) Electro-osmosis
• (iv) Coagulation or flocculation
 Electrical double layer theory
• A double layer of ions appear at the surface of solid.
• The ion preferentially adsorbed is held in fixed part and
imparts charge to colloidal particles.
• The second part consists of a diffuse mobile layer of ions.
This second layer consists of both the type of charges. The
net charge on the second layer is exactly equal to that on
the fixed part.
• The existence of opposite sign on fixed and diffuse parts of
double layer leads to appearance of a difference of
potential, known as zeta potential
 Gouy-Chapman Double Layer
• Gouy suggested that • The kinetic energy of
interfacial potential at the counter ions will, in
the charged surface part, affect the
could be attributed to thickness of the
the presence of a resulting diffuse double
number of ions of given layer.
sign attached to its
• n = noexp(-zeY/kT)
surface, and to an equal
number of ions of • where no = bulk concentration
z = charge on the ion
opposite charge in the e = charge on a proton
solution. k = boltzman constant
 Electrical double layer
• appears on the surface (solid
particle, a gas bubble, a liquid droplet, or a
porous body)
• I - surface charge, comprises
ions adsorbed directly onto
the object due to a host of
chemical interactions.
• II -is composed of ions
attracted to the surface charge
via the coulomb force,
electrically screening the first
Schematic of double layer in a liquid at
contact with a negatively-charged solid. layer.
 The fundamental role of DL
• The stability of a colloidal
solution is mainly due to the
presence a particular type of
charge
• Milk exists only because fat
droplets are covered with a DL
that prevent their coagulation into
butter.
• DLs exist in practically all
heterogeneous fluid-based
systems, such as blood, paints,
inks, ceramic slurries and cement
slurries.
Helmholtz Double Layer
• This theory is a simplest
approximation that the
surface charge is neutralized
by opposite sign counterions
placed at an increment of d
away from the surface.
• The surface charge potential
is linearly dissipated from
the surface to the
contertions satisfying the
charge.
 Stern Modification of the Diffuse
double Layer
• The double layer is formed in order
to neutralize the charged surface
and, in turn, causes an
electrokinetic potential between
the surface and any point in the
mass of the suspending liquid.
• This diagram serves as a visual
comparison of the amount of
counterions in each the Stearn
Layer and the Diffuse Layer of
smectite when saturated with the
three alkali earth ions, as in the
above table.
 Zeta potential (ζ-potential)

Zeta potential is the

electrokinetic potential
difference between
the dispersion medium and
the stationary layer of fluid
attached to the dispersed
particle.
Diagram showing the ionic concentration and
potential difference as a function of distance
from the charged surface of a particle
suspended in a dispersion medium.
• The significance of zeta potential is that its value can be
related to the stability of colloidal dispersions (e.g., a
multivitamin syrup).
• The zeta potential indicates the degree of repulsion
between adjacent, similarly charged particles (the vitamins)
in a dispersion.
• For molecules and particles that are small enough, a high
zeta potential will confer stability, i.e., the solution or
dispersion will resist aggregation. When the potential is low,
attraction exceeds repulsion and the dispersion will break
and flocculate.
 Stability behavior of the
Zeta potential [mV]
colloid
Rapid coagulation or
from 0 to ±5,
flocculation
from ±10 to ±30 Incipient instability

from ±30 to ±40 Moderate stability

from ±40 to ±60 Good stability

more than ±61 Excellent stability

 Presence of electrical charge on
colloidal particles and stability of sols
• In a particular colloidal solution, all the colloidal
particles carry the same type of charge, while
the dispersion medium has an equal but
opposite charge. Thus, the charge on colloidal
particles is balanced by that of the dispersion
medium and the colloidal solution as a whole
is electrically
neutral.
 Colloidal sols may be classified
• Positively charged sols:
Metallic hydroxide sols e.g., Fe(OH)3,
Al(OH)3, Cr(OH)3, etc., TiO2 sol,
haemoglobin, sols of basic dyes such
as methylene blue

Negatively charged sols:

Metal sols e.g., Au, Ag, Cu, Pt etc.
sols, metal sulphide sols e.g., As2S3,
CdS etc. sols; starch sol, sols of acid
dyes such as Congo red etc.
{n(AgCl), mAg+, (m – x)NO3–}x+xNO3–

.
 Origin of charge on colloidal particles
• Due to dissociation of the adsorbed molecular
electrolytes. Colloidal particles have a strong tendency to
adsorb reactant or product molecules. During the preparation of
sulphide sols (e.g., As2S3 sol), H2S molecules get adsorbed on colloidal
particles. Consequently, colloidal particles are left with negative charge.
• Due to the dissociation of
molecules forming colloidal
aggregates. The soap molecules
(RCOONa) dissociate to give RCOO- and Na+ ions.
RCOO- ions aggregate together to form micelles which
carry negative charge as explained earlier.
• Due to preferential adsorption of ions from
solutions. The colloidal particles have a tendency
to preferentially adsorb a particular type of ions
from the solution. This preferential adsorption of
a particular type of ions imparts a particular type
of charge to colloidal particles.
• FeCl3 + H2O (warm)

Fe(OH)3 + Fe3+ --> Fe(OH)3 : Fe3+

(colloidal (ions common preferential adsorption of Fe3+ ions
particle) to the lattice of (colloidal particle acquires
colloidal particle) positive charge)
 AgCI + CI- --> AgCI : CI-
(colloidal) (Chloride ions present Preferential adsorption of CI - ions
particle) in excess in the solution) (Collodial particle acquires negative
charge)

AgCI + Ag+ --> AgCI : Ag+

(colloidal) (Silver ions present in Preferential adsorption of Ag +ions
particle) excess in the solution) (Collodial particle acquires positive
charge)
 Electrophoresis
• Due to the presence of a
particular type of electrical
charge, the colloidal particles
present in a colloidal
dispersion move 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.
 Electrophoresis

• Electrophoresis is the motion of dispersed

particles relative to a fluid under the
influence of a spatially uniform electric
field
 Electrophoresis
• If the particles accumulate near the negative electrode, the
charge on the particles is positive.
• When electrophoresis of a sol is carried out with out stirring, the
bottom layer gradually becomes more concentrated while the
top layer which contain pure and concentrated colloidal solution
may be decanted. This is called electro decanation and is used
for the purification as well as for concentrating the sol.
• The reverse of electrophoresis is called Sedimentation
potential or Dorn effect. The sedimentation potential is setup
when a particle is forced to move in a resting liquid. This
phenomenon was discovered by Dorn and is also called Dorn
effect.
•  is the electrophoretic mobility,
• epsilon is the electric permittivity of the
liquid
• ξ the zeta potential,
• eta is the viscosity
Electrophoresis
Practical implementation of
Electrophoresis in medicine
 Electro-osmosis
•

When the movement of colloidal particles under

the influence of the applied electric field is checked
with the help of 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.
• The reverse of electro-osmosis is called streaming
potential.
Electro-osmosis
Electro-osmosis
 Coagulation or flocculation
• The stability of a sol is due to the charge present on
the colloidal particles. However, if the charge on
colloidal particles is destroyed, they are free to come
nearer and grow in size and get precipitated. This
phenomenon is termed as coagulation or flocculation.
• The coagulation of colloidal solution can be achieved
by the addition of an electrolyte. It is to be noted that
a small amount of electrolyte is necessary for the
stability of a sol because the ions of the electrolyte get
adsorbed on colloidal particles and impart them some
charge.
 Hardy-Schulze rule
• The coagulation capacity of an electrolyte depends
upon the valence of ion responsible for causing
coagulation. The ion responsible for causing
coagulation is the one which carries charge opposite
to that present on colloidal particles.
• The greater is the valence of the oppositely charged
ion of the electrolyte added to a colloidal solution,
the faster is the coagulation of the colloidal solution.
Coagulation power of different cations

• Negatively charged sol of As2S3

Al3+ > Ba2+ > Na+
Positively charged sol Fe(OH)3
[Fe(CN)6]4- > PO43- > SO42- > Cl-
 Flocculation value
The coagulating power of an electrolyte is
usually expressed in terms of its flocculation
value.
The minimum concentration (in millimoles
per litre) of an electrolyte required to cause
the coagulation of a sol is called the
flocculation value of the electrolyte.
 Additional methods for causing
coagulation
(a) By electrophoresis: In electrophoresis, the charged colloidal particles
migrate to the oppositely charged electrode and get discharged. This results in
the coagulation of the colloidal solution.

(b) By mixing two oppositely sols: When two sols carrying opposite
charges are mixed together in suitable proportions, the colloidal particles of one
sol neutralize the charge present on the particles of the other sol and both get
coagulated.

(c) By persistent dialysis: We have already seen that a small amount of

electrolyte is essential to make a sol stable. When a sol is subjected to persistent
dialysis, the traces of electrolyte also pass out through the membrane. In the
absence of electrolyte, sol becomes unstable and gets coagulated.