NPTEL Chemical Engineering Interfacial Engineering Module 1: Lecture 4

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Colloidal Materials: Part III








Dr. Pallab Ghosh
Associate Professor
Department of Chemical Engineering
IIT Guwahati, Guwahati781039
India


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Table of Contents


Section/Subsection Page No.
1.4.1 Determination of molecular weight by light scattering 3
1.4.2 Experimental characterization of colloids 69
1.4.2.1 Transmission electron microscopy 6
1.4.2.2 Scanning electron microscopy 7
1.4.2.3 Dynamic light scattering 8
1.4.2.4 Small-angle neutron scattering 8
1.4.3 Electrical properties of colloids 1019
1.4.3.1 Electrostatic double layer 10
1.4.3.2 Electrokinetic phenomena 12
1.4.3.2.1 Zeta potential 14
1.4.3.2.2 Reciprocal relationship 19
Exercise 20
Suggested reading 22
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1.4.1 Determination of molecular weight by light scattering
In liquid dispersions, the scattering of light is due to fluctuations in the solvent
density and fluctuations in the particle concentration. The total intensity of the scattered
light in all directions is given by,
( )
2
0
0 0
2 sin
s
s
i
I I r d
I
t
t | |
| |
=
} |
\ .

(1.4.1)
The second term inside the integral in Eq. (1.4.1) represents an area on the surface of a
sphere, where r is the radius of the sphere and | is the angle with the horizontal axis.
From the theory of Rayleigh scattering in a solution, the quantity
0 s
i I can be
determined as shown below. The Rayleigh scattering equation for a solution (at constant
temperature) is expressed by,
( )
2
2
2
2 4
0
2
1 cos
r
r
s
o
dn
n kTc
dc i
d I
r
dc
t
|
t

( | |
| (
\ .
= +
| |
|
\ .

(1.4.2)
where
s
i is the intensity of the light scattered per unit volume of solution. The gradient
of refractive index of the solution
r
n , is given by
r
dn dc . The osmotic pressure is given
by,
2 2
o
c B c
RT c RT Bc
M RT M
t
'
| | | |
= + = +
| |
\ . \ .
,
B
B
RT
'
=
(1.4.3)
Where M is the molecular weight of the solute, c is the concentration, and B is the
second virial coefficient. Therefore, the osmotic pressure gradient is given by,
1
2
o
d
RT Bc
dc M
t
| |
= +
|
\ .

(1.4.4)
From Eq. (1.4.2), we can write,
( )
( )
2
2
0
1 cos
1 2
s
Kc
i
I
r M Bc
| +
=
+

(1.4.5)
The quantity K is a constant, which is given by,
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2
2
4
2
r
r
A
dn
n
dc
K
N
t

(
| |
(
|
\ . (

=
(1.4.6)
From Eqs. (1.4.1) and (1.4.6) we obtain,
( )
2
0 0
2 1 cos sin
1 2
s
Kc d
I
I M Bc
t
t | | |
(
+
(
=
}
(
+
(


(1.4.7)
The value of the integral:
( )
2
0
sin 1 cos d
t
| | | +
}
is 8 3. Therefore, Eq. (1.4.7) becomes,
( )
0
16
3 1 2 1 2
s
I Kc Hc
I M Bc M Bc
t
= =
+ +

(1.4.8)
where ( ) 16 3 H K t is a constant. It is related to the refractive index, its gradient and
the wavelength of light in the medium by the following equation.
( )
2
3 2
4
32
3
r r
A
n dn dc
H
N
t

= (1.4.9)
where is the wavelength of light in the solution and
A
N is Avogadros number. The
quantity
0 s
I I is the turbidity, t . Therefore, from Eq. (1.4.8) we have,
1
2
Hc
Bc
M t
= + (1.4.10)
Equation (1.4.10) is known as Debye equation. It predicts that the plot of Hc t versus c
should be a straight line. From the intercept, the molecular weight M can be determined.

Example 1.4.1: The variation of Hc t with concentration for a polymeric colloid in
benzene is given below.
c (kg/m
3
) 2.5 4.0 6.5 8.0 10.0
( )
3
10 Hc t (mol/kg) 5.6 6.1 6.6 7.2 8.0

From these data, calculate the molecular weight of the polymer.

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Solution: The plot of Hc t vs. c is shown in the following figure. The data were fitted
by a straight line, as shown in Fig. 1.4.1.


Fig. 1.4.1 Variation of Hc t with concentration.
The intercept is,

1
0.0048
M
= mol/kg
208.333 M = kg/mol

If the system is polydispersed, Eq. (1.4.10) is applicable for each molecular weight
fraction. For dilute solutions, we can neglect the second term on the right side of Eq.
(1.4.10). For the j
th
fraction, we can write,
1 j
j j
Hc
M t
=
(1.4.11)
The experimentally measured concentration, turbidity and the average molecular weight
are correlated by Equation (1.4.11) as,
exp
exp
1
Hc
M t
=
(1.4.12)
where,
exp j
c c =
(1.4.13)
and
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exp j
t t =
(1.4.14)
From Eqs. (1.4.11)(1.4.14), we obtain,
exp
exp
j j j j j
j j j
H c M c M
M
Hc H c H c c
t t
= = = =


(1.4.15)
Since
j j j d
c n M V = , we have,
2
j j
j j
n M
M
n M

(1.4.16)
This average molecular weight (i.e., M ) is known as the weight-average molecular
weight.

1.4.2 Experimental characterization of colloids
+ Colloids are characterized by various methods. Some of these are, transmission
electron microscopy (TEM), scanning electron microscopy (SEM), dynamic light
scattering (DLS), and small-angle neutron scattering (SANS). Depending on the
properties of the colloidal matter, the appropriate characterization method is
selected.

1.4.2.1 Transmission electron microcopy
+ Many colloid particles are too small to be viewed in an optical microscope. The
numerical aperture of an optical microscope is generally less than unity, which
can be increased up to 1.5 with oil-immersion objectives. Therefore, for light of
wavelength 600 nm, the resolution limit is of the order of 200 nm.
+ To increase the resolving power of a microscope so that colloidal dimensions can
be directly observed, the wavelength of the radiation must be reduced
considerably below that of visible light. Electron beams can be produced which
have wavelengths of the order of 0.01 nm. These are focused by electric or
magnetic fields, which act as the equivalent of lenses. A resolution of the order of
0.2 nm can be attained after smoothing the noise. Single atoms appear to be
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blurred irrespective of the resolution, owing to the rapid fluctuation of their
location.
+ The TEM can be used for measuring particle size between 1 nm and 5 m. Due to
the complexity of calculating the degree of magnification directly, calibration is
done using pre-characterized polystyrene latex particles.
+ The use of electron microscopy for studying colloid systems is limited by the fact
that electrons can travel without any hindrance only in high vacuum. Therefore,
the samples need to be dried before observation.
+ A small amount of the sample is deposited on an electron-transparent plastic or
carbon film (1020 nm thick) supported on a fine copper mesh grid. The sample
scatters electrons out of the field of view, and the final image can be viewed on a
fluorescent screen. The amount of scattering depends on the thickness and the
atomic number of the atoms of the sample.
+ The organic materials are relatively transparent for electrons whereas, the heavy
metals make ideal samples. To enhance contrast and obtain three-dimensional
effect, various techniques (e.g., shadow-casting) are generally employed.

1.4.2.2 Scanning electron microcopy
+ In scanning electron microscopy, a fine beam of medium-energy electrons scans
across the sample in a series of parallel tracks. These electrons interact with the
sample to produce various types of signals such as secondary electron emission,
back-scattered-electrons, cathodoluminescence and X-rays. These are detected,
displayed on a fluorescence screen and photographed.
+ In the secondary-electron-emission mode, the particles appear to be diffusely
illuminated. Their size can be measured and the aggregation behavior can be
studied.
+ In the back-scattered-electron mode, the particles appear to be illuminated from a
point source, and the resulting shadows can provide good impressions of height.
+ The resolution limit in SEM is about 5 nm, and the magnification achieved is
generally less than that in a TEM. However, the depth of focus is large, which is
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important for studying the contours of solid surfaces, particle shape and
orientation.

1.4.2.3 Dynamic light scattering
+ If the light is coherent and monochromatic (e.g., a laser), it is possible to observe
time-dependent fluctuations in the scattered intensity using a suitable detector
such as a photomultiplier capable of operating in photon-counting mode.
+ These fluctuations arise because the particles are small, and they undergo
Brownian movement. The distance between them varies continuously.
Constructive and destructive interference of light scattered by the neighboring
particles within the illuminated zone gives rise to the intensity fluctuation at the
detector plane.
+ From the analysis of the time-dependence of the intensity fluctuation, it is
possible to determine the diffusion coefficient of the particles. Then, by using the
StokesEinstein equation (see Lecture 3, Module 1), the hydrodynamic radius of
the particles can be determined.
+ An accurately known temperature is necessary for DLS because knowledge of the
viscosity is required (because the viscosity of a liquid is related to its
temperature). The temperature also needs to be stable, otherwise convection
currents in the sample will cause non-random movements that will ruin the
correct interpretation of size.
+ Dynamic light scattering is also known as photon correlation spectroscopy (PCS)
or quasi-elastic light scattering (QELS). It is a well-established technique for the
measurement of the size distribution of proteins, polymers, micelles,
carbohydrates, nanoparticles, colloidal dispersions, emulsions and
microemulsions.

1.4.2.4 Small-angle neutron scattering
+ Neutrons from reactors or accelerators are slowed down in a moderator to kinetic
energies corresponding to room temperature or less. The wavelength probed by
SANS is quite different from the visible light. A typical range of wavelength is
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0.33 nm. This range is much smaller than that of visible light (i.e., 400700
nm).
+ The usefulness of SANS to colloid and polymer science becomes evident when
one considers the length scales and energy involved in neutron radiation. Light
scattering is indispensable for studying particles having size in the micrometer
range. For very small particles, neutrons are useful. The energy of a neutron with
0.1 nm wavelength is
20
1.3 10

J. Due to such low energy, neutron scattering is

useful for sensitive materials. For colloidal dispersions, where the distance
between the particles is large, the scattering angle is small (~ 20 t rad or less).
+ Light and X-rays are both scattered by the electrons surrounding atomic nuclei,
but neutrons are scattered by the nucleus itself. There is, however, no systematic
variation of the interaction with the atomic number. The isotopes of the same
element can show significant difference in scattering. For example, neutrons can
differentiate between hydrogen and deuterium. This has useful applications in
biological science in the technique known as contrast matching.
+ The interaction of neutrons with most substances is weak, and the absorption of
neutrons by most materials is very small. Neutron radiation, therefore, can be
very penetrating.
+ Neutrons can be used to study the bulk properties of samples with path-length of
several centimeters. They can also be used to study samples with somewhat
shorter path-lengths but contained inside an apparatus (e.g., cryostat, furnace,
pressure cell or shear apparatus).
+ The SANS technique provides valuable information over a wide variety of
scientific and technological applications such as chemical aggregation, defects in
materials, surfactant assemblies, polymers, proteins, biological membranes, and
viruses.

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1.4.3 Electrical properties of colloids
+ The electrical properties of colloidal materials lead to some of the most important
phenomena in interfacial engineering. The presence of electrostatic double layer
surrounding the particles results in their mutual repulsion so that they do not
approach each other closely enough to coagulate. An increase in the size of the
particles by coagulation would lead to a decrease of total area, and hence to a
decrease of free energy of the system. Therefore, union of colloid particles would
be expected to occur, were it not for the repulsion caused by the electrostatic
double layer. The stability of the charged colloid particles depends on the
presence of electrolytes in the dispersion.

1.4.3.1 Electrostatic double layer
+ Let us consider a solidliquid interface. Suppose that the interface is positively
charged and the atmosphere of the negatively charged counterions is around it.
This visualization of the ionic atmosphere near a charged interface originated the
term electrostatic double layer.
+ The Coulomb attraction by the charged surface groups pulls the counterions back
towards the surface, but the osmotic pressure forces the counterions away from
the interface. This results in a diffuse double layer.
+ The double layer very near to the interface is divided into two parts: the Stern
layer and the GouyChapman diffuse layer. The compact layer of adsorbed ions
is known as Stern layer. This layer has a very small thickness (say, 1 nm). The
counterions specifically adsorb on the interface in the inner part of the Stern
layer, which is known as inner Helmholtz plane (IHP) (see Fig. 1.4.2). The
potential drop in this layer is quite sharp, and it depends on the occupancy of the
ions.
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Fig. 1.4.2 Electrostatic double layer.

+ The outer Helmholtz plane (OHP) is located on the plane of the centers of the
next layer of non-specifically adsorbed ions. These two parts of the Stern layer
are named so because the Helmholtz condenser model was used as a first
approximation of the double layer very close to the interface.
+ The diffuse layer begins at the OHP. The potential drop in each of the two layers
is assumed to be linear. The dielectric constant of water inside the Stern layer is
believed to be much lower (e.g., one-tenth) than its value in the bulk. The value is
lowest near the IHP.
+ The diffuse part of the electrostatic double layer is known as GouyChapman
layer. The thickness of the diffuse layer is known as Debye length (represented by
1 k ). This length indicates the distance from the OHP into the solution up to the
point where the effect of the surface is felt by the ions. k is known as
DebyeHckel parameter. The Debye length is highly influenced by the
concentration of electrolyte in the solution. The extent of the double layer
decreases with increase in electrolyte concentration due to the shielding of charge
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at the solidsolution interface. The ions of higher valence are more effective in
screening the charge.

1.4.3.2 Electrokinetic phenomena
+ The phenomena associated with the movement of charged particles through a
continuous medium, or with the movement of a continuous medium over a
charged surface are known as electrokinetic phenomena. There are four major
types of electrokinetic phenomena, viz. electrophoresis, electroosmosis,
streaming potential and sedimentation potential. There is a common origin for all
the electrokinetic phenomena, i.e., the electrostatic double layer.
+ Electrophoresis refers to the movement of particles relative to a stationary liquid
under the influence of an applied electric field. If a dispersion of positively
charged particles is subjected to an electric field, the particles move towards the
cathode. Electrophoresis is perhaps the most important electrokinetic
phenomenon. Three types of electrophoresis are usually used, viz.
microelectrophoresis, moving-boundary electrophoresis and zone electrophoresis.
Electrophoresis is widely used in biochemical analysis for separation of proteins.
Another very important application of electrophoresis is electrodeposition. A
cylindrical microelectrophoresis cell for studying the movement of air bubbles
under electric field is shown in the Fig. 1.4.3.


Fig. 1.4.3 Setup for microelectrophoresis (source: A. Phianmongkhol and J.
Varley, J. Coll. Int. Sci., 260, 332, 2003; reproduced by permission from Elsevier
Ltd., 2003).

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+ Electroosmosis refers to the movement of the liquid of an electrolyte solution past
a charged surface (e.g., a capillary tube or a porous plug) under the influence of
an electric field. The pressure necessary to balance the electroosmotic flow is
known as electroosmotic pressure. To understand how electroosmosis occurs,
consider a glass capillary containing an aqueous electrolyte solution. The charge
on the wall of the tube can develop from either the dissociation of the surface
SiOH groups or adsorption of the OH

ions on the wall. This charge is balanced

by an equal and opposite charge in the solution, as shown in Fig. 1.4.4.


Fig. 1.4.4 Electroosmosis.

+ When the electric field is applied, the ions in the diffuse part of the double layer
move towards one of the electrodes depending on their charge. The motion of
these hydrated ions imparts a body-force on the liquid in the double layer. This
force sets the liquid in motion. Electroosmosis has been used in many
applications related to environmental pollution abatement.
+ Suppose that the electrolyte solution is forced to pass through a capillary under
pressure applied from outside. An electrical potential is generated between the
ends of the capillary. This is called streaming potential. The same phenomenon
can be observed when the solution is forced through a porous medium. If a
dispersion of charged particles is allowed to settle, the resulting motion of the
particles causes the development of a potential difference between the upper and
lower parts of the dispersion. It is known as Dorn effect and the potential is
known as sedimentation potential.
+ Therefore, the situations which give rise to streaming potential and sedimentation
potential are opposite to those of electroosmosis and electrophoresis, respectively.
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1.4.3.2.1 Zeta (,) potential
+ The surface charge of the colloid particles is expressed in terms of the zeta
potential ( ) , . It is the potential at the surface of shear.
+ When a particle moves in an electric field, the liquid layer immediately
adjacent to the particle moves with the same velocity as the surface, i.e.,
the relative velocity between the particle and the fluid is zero at the
surface. The boundary located at a very short distance from the surface at
which the relative motion sets in is known as the surface of shear.
+ The precise location of this surface cannot be determined exactly, but it is
presumed that it is located very close to the surface of the particle, may be
a few molecular-diameters apart.
+ The magnitude of , -potential provides an indication of the stability of
the colloid system. The pH of the medium strongly affects the , -
potential.

1.4.3.2.1.1 Determination of , -potential from electrophoresis
+ Let us consider the motion of a small spherical colloid particle moving with
velocity u in an electric field E . In a dilute dispersion, the mobility is given by
the Hckel equation,
0
2
3
u
E
cc ,

= , 0.1
s
R k <
(1.4.17)
where k is the DebyeHckel parameter, c is the dielectric constant of the
medium,
0
c is permittivity of the free space, is the viscosity of the liquid and
s
R is the radius of the sphere.
+ For large values of
s
R k , the relationship between the electrophoretic mobility
and ,-potential is given by Smoluchowski equation (also known as
HelmholtzSmoluchowski equation),
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0
u
E
cc ,

= , 100
s
R k >
(1.4.18)
Equation (1.4.18) is applicable for relatively high salt concentrations for which k
is large.
+ Apart from these two limiting conditions, the zeta potantials for the other values
of
s
R k can be calculated by the following equation.
( )
0
2
3
s
u
f R
E
cc ,
k

=
(1.4.19)
where ( )
s
f R k can be calculated from either Henrys or Ohshimas equation.
The latter equation is more convenient for computation.
( )
( ) { }
3
1
1
2.5
2 1
1 2exp
s
s s
f R
R R
k
k k
= +
(
+ (
+
(


(1.4.20)
This equation is valid for any value of
s
R k with maximum relative error less
than 1%.

1.4.3.2.1.2 Determination of , -potential from electroosmosis
+ When an electric field is applied across a capillary containing electrolyte solution,
the double layer ions begin to migrate. After some time, a steady state is reached
when the electrical and viscous forces balance each other, i.e., the force exerted
on the medium by the ions is balanced by the force exerted by the medium on the
ions.
+ If the steady state volumetric flow rate in a fine capillary due to electroosmosis is
V , then the , -potential is given by,
0
V
EA

,
cc
= , 1
c
R k >>
(1.4.21)
where
c
R is the radius and A is the cross-sectional area of the capillary.
Therefore, by measuring the volumetric flow rate through the capillary, the , -
potential can be determined.

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Example 1.4.2: An aqueous solution of sodium chloride is placed inside a capillary in an
electroosmosis apparatus and subjected to an electric field of 100 V/m. The
electroosmotic velocity in the capillary is observed to be 10 m/s. Calculate , -potential
from these data.

Solution: The electroosmotic velocity is given by,

6
10 10
V
A

= m/s
For water, 78.5 c = ,
3
1 10 Pa s

= , and the permittivity of free space is,
12
0
8.854 10 c

= C
2
J
1
m
1
. From Eq. (1.4.21) we obtain,

6 3
12
0
10 10 1 10
0.1439
78.5 8.854 10 100
V
EA

,
cc

= = =

V = 143.9 mV

1.4.3.2.1.3 Determination of , -potential from streaming potential
+ The , -potential can be correlated with streaming potential as follows. A pressure
difference ( ) p A across a capillary is applied which sets the liquid in motion
inside it. The charge of the double layer moves with the surrounding liquid
generating an electric current, which is known as the streaming current. On the
other hand, the charge transferred downstream generates an electric field in the
opposite direction. After a short time, the two currents due to pressure gradient
and reverse electric field balance each other. The streaming potential
( )
s
E is the
potential drop associated with this electric field.
+ The following equation gives the , -potential.
0
s s
k E
p

,
cc
| |
=
|
A
\ .
, 1
c
R k >>
(1.4.22)
where
s
k is the conductivity of the electrolyte solution. Equation (1.4.22) is valid
for the large values of
c
R k (where
c
R is the radius of the capillary). Therefore, it
is likely to give erroneous results when the concentration of salt is low (which
would result in a low value of k ).
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1.4.3.2.1.4 Determination of , -potential from sedimentation potential
+ An electric field is developed during the settling of charged particles. This is
known as sedimentation potential. Smoluchowski presented the first theoretical
estimate of the magnitude of the field. For a dispersion of solid non-conducting
spheres of radius
s
R , immersed in an electrolyte solution of conductivity
s
k ,
dielectric constant c , and viscosity , the sedimentation potential is predicted to
be,
3
0
sed
4
3
s
s d
gnR
E
k V
tcc ,

A
= (1.4.23)
where n is the number of particles and
d
V is the volume of dispersion. This
equation is valid in those situations where the thickness of electrostatic double
layer is small with respect to the radius of the particles ( ) 1
s
R k >> . It can be
observed from Eq. (1.4.23) that the sedimentation potential is proportional to the
amount of the dispersed phase.
+ The settling of fine droplets can generate high sedimentation potentials. For
example, the settling of water drops in the gasoline storage tanks can produce a
very high sedimentation potential owing to the low conductivity of the oil phase,
which can be dangerous. The value of sedimentation potential can be as high as
1000 V/m or above, even for a moderate value of the , -potential (e.g., 25 mV).
+ If the diameter of the droplets is larger than 100 m, they settle down completely
and the sedimentation potential becomes zero. If they are smaller than 1 m, the
sedimentation potential gradient reduces the rate of settling and a haze of water
drops floats in the electric field.
+ The sedimentation velocity is reduced by the sedimentation potential gradient. If
the steady state settling velocity (i.e., terminal velocity) of the particle is
t
v when
the particle is uncharged, and
c
v is the velocity when the particle carries a surface
charge, then for a single sedimenting particle,
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2
0
1
1
c t
s s
v v
k R
cc ,

(
| |
(
=
|
(
\ .

, 1
s
R k >>
(1.4.24)
+ The experimental data agree with this equation within an order of magnitude. If
0.1
s
R = m, 25 , = mV and
4
1 10
s
k

= O
1
m
1
, it can be shown that the
velocity of the particle in water will be reduced by 30%. This causes a haze of
fine water drops in oil.

1.4.3.2.1.5 A comment on the , -potential determined by various methods
+ The , -potential depends only on the properties of the phases in contact.
Therefore, its value must be independent of the experimental method employed
for its determination. Several scientists, using the Smoluchowski theory, have
found that , -potential obtained from streaming potential or electroosmotic
measurements is quite smaller than the value obtained from electrophoretic
mobility or sedimentation potential measurements.
+ These discrepancies can be due to the influence of surface conductivity on
streaming potential and electroosmotic flow.
+ If the condition 1 R k >>

(where R

is the radius of sphere, or the radius of

capillary) is not satisfied, then the Smoluchowski equation can yield inaccurate
values of the , -potential.
+ Two conditions must be satisfied to justify comparison between the values of , -
potential obtained by different electrokinetic experiments: the effect of surface
conductivity must be taken care of, unless it is negligible, and the surface of shear
must divide comparable double layers in all the cases. Fulfillment of the second
requirement depends upon the experimental procedure. For example, if the same
capillary is used for electroosmosis and streaming potential studies, the second
condition can be satisfied. On the other hand, the surfaces of a capillary and a
migrating particle can be quite different. Sometimes, the surfaces are coated with
a protein, and the characteristics of both surfaces are governed by the adsorbed
protein.
NPTEL Chemical Engineering Interfacial Engineering Module 1: Lecture 4

Joint Initiative of IITs and IISc Funded by MHRD 19/22


1.4.3.2.2 Reciprocal relationship
The cause and effect are interchanged in streaming potential and electroosmosis.
Similarly, the situation in sedimentation potential is the opposite of electrophoresis. From
Eq. (1.4.21), putting ( )
c s
E I Ak = , we can write,
0
c s
V
I k
cc ,

=
(1.4.25)
From Eqs. (1.4.22) and (1.4.25) we can write,
0 s
c s
E V
p I k
cc ,

= =
A

(1.4.26)
The coupling of two different electrokinetic ratios, i.e.,
s
E p A and
c
V I through Eq.
(1.4.26) is an example of the law of reciprocity of Lars Onsager.


NPTEL Chemical Engineering Interfacial Engineering Module 1: Lecture 4

Joint Initiative of IITs and IISc Funded by MHRD 20/22

Exercise

Exercise 1.4.1: Calculate the sedimentation potential for 50 m radius water drops in an
oil (dielectric constant = 2, viscosity = 0.5 mPa s, and conductivity = 110
9
O
1
m
1
) if
the , -potential is 0.025 V. The density of the oil is 700 kg/m
3
and the volume fraction of
the dispersed aqueous phase is 0.05.

Exercise 1.4.2: Calculate the electrophoretic mobility of a 50 nm diameter spherical
colloid particle in an aqueous solution of NaCl at 298 K. The ,-potential is 0.02 V. The
concentration of NaCl in the solution is 100 mol/m
3
. Given: The Debye length is ~1 nm at
this concentration of the salt.

Exercise 1.4.3: Application of 101.325 kPa pressure produces a streaming potential of 0.4
V in an experiment using aqueous NaCl solution. Calculate the ,-potential. Given:
1 1
0.01 m
s
k

= O and 1 = mPa s.

Exercise 1.4.4: Answer the following questions clearly.
a. What are the advantages and limitations of transmission electron microscopy in
the characterization of colloidal materials?
b. What are the different types of signals produced in a scanning electron
microscope?
c. Explain how dynamic light scattering can be used to measure the size of a colloid
particle.
d. For what types of colloids does the dynamic light scattering have advantage over
TEM or SEM?
e. What are the advantages of neutron scattering over visible light scattering? What
is small-angle neutron scattering? Where is it used?
f. Explain what you understand by electrokinetic phenomena.
g. What are the four major electrokinetic phenomena?
h. Explain electrophoresis. What are the major uses of electrophoresis?
NPTEL Chemical Engineering Interfacial Engineering Module 1: Lecture 4

Joint Initiative of IITs and IISc Funded by MHRD 21/22

i. What is zeta potential? Explain its significance.
j. Discuss the applicability criteria of Hckel and Smoluchowski equations.
k. What is electroosmosis? How does it differ from osmosis? What is electroosmotic
pressure?
l. Explain how you would calculate the zeta potential from electroosmosis.
m. What is streaming potential? How is it developed?
n. What is sedimentation potential?
o. Explain Onsagers reciprocal relationship.
NPTEL Chemical Engineering Interfacial Engineering Module 1: Lecture 4

Joint Initiative of IITs and IISc Funded by MHRD 22/22

Suggested reading

Textbooks
+ D. J. Shaw, Introduction to Colloid and Surface Chemistry, Butterworth-
Heinemann, Oxford, 1992, Chapters 3 & 7.
+ J. C. Berg, An Introduction to Interfaces and Colloids: The Bridge to
Nanoscience, World Scientific, Singapore, 2010, Chapters 5 & 6.
+ P. C. Hiemenz and R. Rajagopalan, Principles of Colloid and Surface Chemistry,
Marcel Dekker, New York, 1997, Chapters 5 & 12.
+ P. Ghosh, Colloid and Interface Science, PHI Learning, New Delhi, 2009,
Chapter 2.

Reference books
+ D. F. Evans and H. Wennerstrm, The Colloidal Domain: Where Physics,
Chemistry, Biology, and Technology Meet, Wiley-VCH, New York, 1994,
Chapters 4 & 8.
+ R. J. Hunter, Foundations of Colloid Science, Oxford University Press, New
York, 2005, Chapters 5 & 8.

Journal articles
+ A. Phianmongkhol and J. Varley, J. Colloid Interface Sci., 260, 332 (2003).
+ E. W. Anacker, J. Colloid Sci., 8, 402 (1953).
+ F. Booth, J. Chem. Phys., 22, 1956 (1954).
+ H. Ohshima, J. Colloid Interface Sci., 168, 269 (1994).
+ H. V. Tartar and A. L. M. Lelong, J. Phys. Chem., 59, 1185 (1955).
+ J. B. Peace and G. A. H. Elton, J. Chem. Soc., 2186 (1960).
+ L. Onsager, Phys. Rev., 37, 405 (1931).