CH5014- INTERFACIAL SCIENCE ENGINEERING

TITLE: ELECTROKINETIC PHENOMENON

NAME ROLL NUMBER

KUSUMITHA KAMPARA CH17B054

PRAGNA DAYALWAR CH17B042

DATE OF SUBMISSION: 22/11/2019

TABLE OF CONTENTS
➢ INTRODUCTION
➢ CHARACTERISTICS OF ELECTROKINETIC SYSTEMS
➢ MATHEMATICAL TREATMENT OF ELECTROKINETIC PHENOMENA
▪ Electroosmosis
▪ Electrophoresis
▪ Streaming Potential
▪ Sedimentation Potential
➢ THE STRUCTURE OF THE DOUBLE LAYER
➢ CONCLUSION
➢ REFERENCES

INTRODUCTION
Electrokinetics is the subject dealing with the relationships of the electromotive force
and the mechanical motion at an interface of a solid and a liquid. The electrokinetic potential
at an interface is due to the formation of an electric double layer which arises from the
unequal distribution of the potential determining ions which in turn is based upon lattice
forces. The condenser-like theory of the structure of the double layer of Helmholtz has been
abandoned in favour of the diffuse double layer of Gouy or the combination of the latter two
as presented by Stern. The theory of Debye and Huckel is as important in the study of the
structure of the double layer as in the theory of electrolytes. Newer developments that are
likely to influence this field are the application of statistical mechanics to the double layer
and studies on the hydration of ions.
Electroosmosis and Electrophoresis are the electrokinetic phenomena of the first
type. The production of the Sedimentation potential or the Dorn effect and Streaming
potential are the electrokinetic phenomena of the second type.
Electrokinetic phenomena result from the existence at a phase boundary of excess
charges that are grouped as two oppositely charged layers called an Electrical double layer.
An electric field applied in the direction parallel to a phase boundary causes the
displacement of an ionic layer relative to another resulting in the relative displacement of
the phases i.e, in electroosmosis or electrophoresis. Effects that are the converse of
electroosmosis or electrophoresis are similarly observed in the flow of a liquid or in the
sedimentation of particles from a dispersed phase.
Any electrokinetic phenomenon may be used to determine the zeta potential or
electrokinetic potential which is denoted by ᶎ.
 FIGURE-1. ELECTROKINETIC PHENOMENON IN CLAY

CHARACTERISTICS OF ELECTROKINETIC SYSTEMS

A potential difference exists at the boundary of two phases. At a solid-liquid
interface this potential difference was originally assumed to lie in a rigid electric double
layer much like that assigned to a flat plate condenser. The potential across the double layer
was called the Electrokinetic potential or the Zeta potential (ᶎ).

FIGURE-2. GOLD NANOPARTICLE ZETA POTENTIAL

The phenomena electroosmosis, electrophoresis, streaming potential, and
sedimentation potential which can be explained by means of the double layer and which
measure the potential across it by means of formulas that will be subsequently developed
are called electrokinetic phenomena.
 The characteristic feature of electrokinetic phenomena is that one phase is displaced
mechanically along the boundary of another phase accompanied by a coexisting
electromotive force. One of the phases must be a liquid while the other is generally a solid.
Four cases can arise:
(A) An external electromotive force produces motion:
1. Of a liquid against a solid—electroosmosis.
2. Of solid particles against a liquid—electrophoresis.
(B) An external motion produces an electromotive force:
1. The liquid is moved relative to the solid surface —streaming potential.
2. The solid body is moved relative to the liquid— sedimentation potential.
The classification can also be made on the basis of the moving phase. The liquid moves in
electroosmosis and streaming potential while the solid moves in electrophoresis and
sedimentation potential.

MATHEMATICAL TREATMENT OF ELECTROKINETIC PHENOMENA

Electroosmosis
Every interface is the seat of an electric field which may arise from the difference in
“solubilities” of the electrons in the two phases or from adsorption phenomena. In the case
of metal interfaces, the potential developed is used to measure temperature differences in
the ordinary thermocouple. At solid-liquid interfaces, this field is easily demonstrated by the
application of a potential parallel to the interface. There occurs a sizable displacement of
the liquid relative to the solid wall, providing that the surface of the solid is sufficiently large
in relation to the volume of the liquid.

FIGURE-3. ELECTROOSMOSIS

It has been mentioned that Quincke suggested the electric double layer as a means
of explaining electrokinetic phenomena and in particular electroosmosis. If the positive layer
is in the liquid and the negative layer is firmly attached to the wall of the capillary, a
potential gradient parallel to the wall will displace the positively charged layer along the
rigid negative layer dragging the rest of the liquid along with it by the force of friction.
 it was Helmholtz who originally treated the properties of the double layer of two-
phase boundaries in tangential motion to one another from a mathematical point of view by
combining the laws of electrostatics with the laws of hydrodynamics. The general form of
the equations he developed are still in use although modified in several minor respects.
In his treatment, Helmholtz made the following assumptions.
1. The liquid is oppositely charged to the rigid wall forming along the wall, an
electric double layer.
2. The thickness of the double layer is extremely small, but not vanishingly so—
about molecular dimensions.
3. The layer of water molecules in contact with the wall is not movable (called
the rigid layer). It is fixed to the wall regardless of the mechanical force
impressed—there is no slip. The rest of the molecules in the liquid, near the
wall and in the double layer (the strongly adsorbed layer), are movable and
are subject to the ordinary laws of friction for normal liquids.
4. Only laminar flow of liquid can occur.
5. The external difference of potential is simply superimposed upon the
difference of potential in the double layer itself.
6. The wall is an insulator and the contained liquid is an electrolytic conductor.
If σ is the charge density on the wall, δ the mean electrical thickness of the double layer,
and D the dielectric constant of the media between the two layers then the potential across
the layers ᶎ on the basis of the Helmholtz theory
𝟒𝜫𝝈𝜹
ᶎ=
𝑫
Consider the stream line flow of liquid through a narrow capillary aa, of cross-sectional area
A as in Figure to which a longitudinal voltage, V1 — V2, is applied so as to be uniform across
the cross-section.

If there is a charge q, anywhere in the liquid, the electrical force dFe, acting on that charge
is:
𝑑𝑉
𝑑𝐹 = −𝑞
𝑑𝑥

Select a cylinder of unit length and of radius r enclosing the charge, the total normal
induction over the cylinder by Gauss’s law, is (4Πq)/D where D is the dielectric constant of
the media in which this charge is immersed. The curved area of this cylinder is 2Πr, and the
electric force outward from the curved surface is — (d V/dr). Hence
4𝛱𝑞 𝑑𝑉
= 2𝛱𝑟(− 𝑑𝑟 ) (2)
𝐷

If u is the velocity of flow after a steady state has been reached, the electrical force moving
the water is just slightly greater than the frictional force Ff, opposing that motion.
Fe = Ff — dFf
and
dFe= dFf — d2Ff (3)

The differential of the second order can be neglected. The force of friction against the area,
from the definition of viscosity is where η is the coefficient of viscosity:
𝑑𝑢
dFf = -η𝑑𝑟 .2Πr
Substituting in (3):
𝑑𝑉 𝑑𝑢
−𝑞 𝑑𝑥 = −2𝛱𝑟𝜂 𝑑𝑟 (4)
Eliminating q from equations (2) and (4):
𝑑𝑢
𝑑𝑉 4𝛱𝜂
𝐷 = 𝑑𝑟
𝑑𝑟 𝑑𝑉
−
𝑑𝑥
From Ohm’s law, the electric current across the section A with a specific resistance R, is
given by:
I = -(A/R).(dV/dx)
Therefore:
𝑑𝑉 4𝛱𝜂𝐴 𝑑𝑢
= .
𝑑𝑥 𝐷𝑅𝐼 𝑑𝑟
It is to be noted that this equation is independent of the particular distribution of the
electric charges.
If Vm and um are the potential and velocity of a point on the tube axis and vw and 0
the corresponding values for the tube wall:
ᶎ = Vm - Vw = (4ΠηAum) / (DRI) (5)
If the charges in the liquid that form a part of the double layer are in close proximity to the
tube wall, there will be no charge in the bulk of the liquid that is for q = 0, du/dr = 0 (from
equation (4)). In other words, the bulk of the liquid has the same velocity. The total liquid
flow U, will consequently be um A. Therefore:
U = DRI.( Vm - Vw)/4Πη (6)
or
ᶎ = 4ηΠU/DRI (7)
The electrokinetic potential ᶎ, is the drop of potential across the double layer and is
of the order of magnitude of ten to one hundred millivolts. The amount of liquid
transported depends upon the nature of the liquid (D, R, and η) and the current I, but is
independent of the dimensions of the tube or diaphragm.
If the experiment is conducted in a U-tube, rather than in a horizontal one, a hydrostatic
head is built up that gives rise to a flow of liquid in the opposite direction to that caused by
the electroosmotic flow. For the simple case of the ordinary capillary, Poiseuille’s law for the
flow of liquids in tubes can be combined with equation (6) to give:
ᶎ= PΠ2r4 /2(DRI)l (8)
where P is the pressure gradient, r the radius of the capillary, and l the length of the
capillary.

Electrophoresis
The phenomena of electrophoresis can be discussed from two points of view—from
the theory of ionic migration or from a standpoint similar to that used for electroosmosis.
From the first point of view, colloidal particles behave as individual ions of high
molecular weight and charge (called “Gegenionen”) and show a migration rate in an electric
field that approximates that of the common ions, except hydrogen and hydroxyl. Size has
little effect upon the rate since a large radius corresponds to a large surface with a larger
charge which counteracts the effect of the increased viscosity. Colloids with a positive
charge migrate to the cathode while those with a negative charge go to the anode. This
migration occurs in pure water or in solutions of electrolytes. There are some colloids that
do not move in an electric field when suspended in pure water, but a great many of these
are positive in acid solution and negative in basic ones.
From the second point of view, a double layer arises on the surface of the particles.
An electric field will tend to displace the negatively charged particle with respect to the
positively charged liquid. The particle is more free to move than the liquid, which is retarded
by its own viscosity, and consequently exhibits a migration.

FIGURE-5. ELECTROPHORESIS

Considering the particles as “Gegenionen,” an electric field acts upon them with a
force, Fe, which is equal to the product of the field strength E, and the charge z e, where z is
the number of elementary charges e.
Fe = zeE
The frictional force acting upon a spherical particle Ff, is, from Stokes’s law,
Ff = —6Πηrc
where r is the radius of the particle and c its velocity. At the steady state the two forces
balance, so:
 zeE = —6Πηrc
c = —zeE/6Πηr (9)
But ze is the charge q, and the potential of a sphere in a medium with a dielectric constant
D, is:
ᶎ = q/Dr
Therefore equation (9) becomes:
−𝐸 𝑞 −EζD
c=6πη . 𝑟 = 6𝜋𝜂 (10)

The electrophoretic velocity is proportional to q/r. If q is directly proportional to r, c will be

independent of the size of the particle.
The assumptions in this proof are: spherical form, a rigidly attached layer of water
that produces friction with the main body of the liquid, no orientation of the water by the
electric field of the "Gegenionen,” and no disturbing fields as would arise from the presence
of other ions.
It is readily seen, however, that an independent derivation of the electrophoretic
equation is unnecessary since electrophoresis is the negative of electroosmosis— in the first
case the solid moves, while in the second the liquid moves. Many independent derivations
are to be found in the literature. Porter finally arrives at the equation:
ζ=-4πηv/DRj (11)
where v is the electrophoretic velocity and j the current density. In this case the area enters
into the current term instead of the flow term as in electroosmosis.
Equation (11) solved for v and equation (10) are equivalent, having the same
dimensions, but differ in that equation (10) has the numerical factor 1/6 while equation (11)
has the factor 1/4. Debye and Hiickel in their derivation of the formula describing
electrophoresis arrive at an expression for the total force of the system:
k= -A1vη+A2DEζ

where A1 and A2 have the dimensions of length and in general, are not known. At
equilibrium, k = 0, so:
𝐷𝐸𝜁
v= (A2/A1).. 𝜂 (12)

At/A1 is a dimensionless quantity which depends upon the shape of the particle under
consideration. For a sphere it is 1/6Π and for a cylinder it is 1/4Π.
Experimentally it has been found that the migration velocity does not vary with the
shape of the particle . An examination of the assumptions used explains the difficulty. Those
made by Smoluchowski were :
(1) The presence of the particle produces a distortion of the electric field in such
a way that the electric current passes tangentially along the surface of the
sphere.
(2) The double layer is so thin that the electric field can be considered to be
parallel to the double layer in the entire range of the latter.
(3) The electric field does not deform the double layer.
Streaming Potential
If instead of applying a potential to the electrodes of the electroosmotic apparatus
and allowing the liquid to stream through spontaneously, the liquid is forced through the
diaphragm, it is found that there exists a potential difference across the electrodes. The
movable part of the double layer is being forced to travel between the two electrodes, thus
setting up the potential difference. This streaming potential is most easily calculated by the
method presented by MacDougall.

FIGURE-6. STREAMING POTENTIAL

The streaming potential set up is sufficient to send an equal current in the opposite
direction. The velocity, c, of the liquid in the capillary of radius r varies with the distance, x,
from the axis. This variation is given by the expression :
c = P(r2-x2)/4ηl (13)
where P is the pressure difference and l the length of the capillary. Poiseuille’s equation
states that the total flow of liquid U, is:
U = πr2.r2P/8ηl

The average value of c is:

u = U/πr2 = Pr2/8ηl

The velocity of the movable part of the double layer Cd, can be found if (r — δ) is set equal
to x in equation (13) where δ is the thickness of the double layer. Since δ is small in
comparison to r, δ2- can be neglected and the following is obtained:
Cd = Pδr/2ηl = 4uδ/r

The current I from the motion of that charged layer is:

I = 2Cdπr𝜎= πr2𝜎δP/ηl

σ being the charge density. The equal current in the opposite direction set up by the
streaming potential is given by the equation:
I=πr2kS/l

where k is the specific conductance of the liquid in the capillary. Equating the two currents
and solving for S, the streaming potential:
S=P𝜎δ/ηk
Substituting into the fundamental equation (1):
S = PᶎD/4Πηk (14)
And
ζ = 4πηkS/PD (15)
The streaming potential is independent of the dimensions of the capillary.
Ettisch and Zwanzig found that the above equation did not hold exactly at higher
pressures but that the curve approached a limiting value. This indicates that the double
layer is broken closer to the solid surface the greater the mechanical force applied.
The above equation can also be derived from the electroosmotic equation in one of
the early stages of development analogous to equation (5) by combining it with Poiseuille’s
equation and then equating the mechanical and electrical work . Thus all the equations
developed for the electrokinetic phenomena can be obtained from a common source.

Sedimentation Potential
In this effect the solid moves relative to the liquid and produces an electromotive
force by dragging part of the double layer along with it. Just as the electrophoretic equation
was found to be the same as the electroosmotic equation, the general equation for the
streaming potential also should be valid for the sedimentation potential (S) where P would
be the pressure difference produced by the falling particles. For small spheres, P will be the
apparent weight of the particles in the liquid.

FIGURE-7. SEDIMENTATION POTENTIAL

This method has not been capable of yielding quantitative results and attempts to
devise an empirical formula by Gortner and his colleagues have failed. This is due, no doubt,
to the fact that large particles have complicated formulas of motion and small particles do
not fall in a straight line, being subjected to Brownian movement.
This method is convenient, however, for measuring the sign of the charge on the
particles.
THE STRUCTURE OF THE DOUBLE LAYER
The non-identity of the electrokinetic and the thermodynamic potentials led to the
development of the theory of the diffuse double layer. Helmholtz's concept of the double
layer assumes that the opposite but equally charged layers are at molecular distances from
each other. In electrokinetic displacements, the shear occurs between the layer of positive
and negative charges. All the potential drop occurs exclusively in the rigidly adsorbed layer
close to the. wall. In this case the thermodynamic and the electrokinetic potentials must be
identical. Therefore, this conception of the double layer must be modified. Gouy supplied
this modification by considering that the ions of the double layer are subjected to two sets
of forces: those electrical that tend to make them accumulate at an interface, and those of
diffusion (heat motion) that tend to re-establish the original condition of uniform
distribution of the positive and negative ions.

FIGURE-8. ELECTRIC DOUBLE LAYER

CONCLUSION
The field of electrokinetic phenomena is still in a highly undeveloped state. The
physical meaning of the electrokinetic potential as expressed by the various equations that
have been derived is very much in doubt. McBain states, “It is evidently not realized how
large an element of speculation and personal opinion is introduced by expressing data in
terms of the contact potential instead of experimentally observed quantities.” The
discussion with regard to the terms entering into the equations brings out this point most
emphatically. It should be noted that the zeta potential has never been measured as such.
To most workers, however, this method of expressing data is most convenient for the
purpose of comparison.
Most investigators in this field today are not so much interested in the physics or
chemistry of the subject as in its biological applications. This is pardonable, since
electrokinetics is very important in the field of cell physiology because many of the life
functions of the cell can be explained in terms of the contact potential that exists at the cell
walls. The entire subject of colloid chemistry is significant here since protoplasm itself is a
colloid.
Theoretical developments that will have an important place in the further evolution
of the theories concerning the structure of the double layer are the application of statistical
mechanics to the double layer and a study of the hydration of ions.

REFERENCES
• Abramson, H. A,, ‘'Electrokinetic phenomena,” Chemical Catalog Co., New York City,
1934, Chapter I.
• Freundlich, H., "Colloid and capillary chemistry,” translated by H. S. Hatfield, E. P.
Dutton and Co., New York City, 1926, p. 240.
• Electrokinetic Phenomena: Principles and Applications in Analytical Chemistry and
Microchip Technology, 1st Edition., Anurag Rathore, Andras Guttman
• Figure-1: https://www.researchgate.net/figure/Electrokinetic-phenomena-in-
clay_fig1_264003836
• Figure-2: https://commons.wikimedia.org/wiki/File:Gold_nanoparticle_Zeta-
potential.png
• Figure-3: http://www.kirbyresearch.com/images/etc/textbook/mae28.jpg
• Figure-5: https://en.wikipedia.org/wiki/Electrophoresis
• Figure-6: http://www.kirbyresearch.com/images/etc/textbook/mae74.jpg
• Figure-7: http://soft-
matter.seas.harvard.edu/images/thumb/8/81/SedimentationPotential.png/400px-
SedimentationPotential.png
• Figure-8: https://web.nmsu.edu/~snsm/classes/chem435/Lab14/double_layer.gif