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Lecture4 Electrokinectic Props of Colloids PDF
Lecture4 Electrokinectic Props of Colloids PDF
Table of Contents
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 is I 0 can be
determined as shown below. The Rayleigh scattering equation for a solution (at constant
temperature) is expressed by,
2
dn
2 2 nr r kTc
is
I0
dc
d
1 cos 2 (1.4.2)
r 2 4 o
dc
where is is the intensity of the light scattered per unit volume of solution. The gradient
of refractive index of the solution nr , is given by dnr dc . The osmotic pressure is given
by,
c B 2 c B
o RT c RT Bc 2 , B (1.4.3)
M RT M RT
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,
d o 1
RT 2 Bc (1.4.4)
dc M
From Eq. (1.4.2), we can write,
is
Kc 1 cos 2 (1.4.5)
I 0 r 2 1 M 2 Bc
dn
2
2 2 nr r
dc (1.4.6)
K
N A 4
From Eqs. (1.4.1) and (1.4.6) we obtain,
2
I s 2 Kc 1 cos sin d
(1.4.7)
I0 0 1 M 2 Bc
The value of the integral: sin 1 cos 2 d is 8 3 . Therefore, Eq. (1.4.7) becomes,
0
Is 16 Kc Hc
(1.4.8)
I 0 3 1 M 2 Bc 1 M 2 Bc
where H 16 K 3 is a constant. It is related to the refractive index, its gradient and
where is the wavelength of light in the solution and N A is Avogadro’s number. The
Hc 1
2 Bc (1.4.10)
M
Equation (1.4.10) is known as Debye equation. It predicts that the plot of Hc versus c
should be a straight line. From the intercept, the molecular weight M can be determined.
Solution: The plot of Hc vs. c is shown in the following figure. The data were fitted
by a straight line, as shown in Fig. 1.4.1.
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 jth fraction, we can write,
Hc j 1
(1.4.11)
j Mj
The experimentally measured concentration, turbidity and the average molecular weight
are correlated by Equation (1.4.11) as,
Hcexp 1
(1.4.12)
exp M
where,
cexp c j (1.4.13)
and
exp j (1.4.14)
From Eqs. (1.4.11)–(1.4.14), we obtain,
exp j H c jM j c jM j
M (1.4.15)
Hcexp Hcj Hcj cj
Since c j n j M j Vd , we have,
2
n jM j
M (1.4.16)
n jM j
important for studying the contours of solid surfaces, particle shape and
orientation.
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 1.3 1020 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 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.
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 ). 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. is known as
DebyeHückel 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
at the solidsolution interface. The ions of higher valence are more effective in
screening the charge.
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.
u 0
, Rs 100 (1.4.18)
E
Equation (1.4.18) is applicable for relatively high salt concentrations for which
is large.
Apart from these two limiting conditions, the zeta potantials for the other values
of Rs can be calculated by the following equation.
u 2 0
f Rs (1.4.19)
E 3
Therefore, by measuring the volumetric flow rate through the capillary, the -
potential can be determined.
For water, 78.5 , 1 103 Pa s , and the permittivity of free space is,
V 10 106 1103
0.1439 V = 143.9 mV
0 EA 78.5 8.854 1012 100
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 Es is the
k s Es
, Rc 1 (1.4.22)
0 p
where ks is the conductivity of the electrolyte solution. Equation (1.4.22) is valid
for the large values of Rc (where Rc 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 ).
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 vt when
the particle is uncharged, and vc is the velocity when the particle carries a surface
0
2
1
vc vt 1 , Rs 1 (1.4.24)
ks s
R
The experimental data agree with this equation within an order of magnitude. If
Rs 0.1 m, 25 mV and k s 1104 1 m1, 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.
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 = 1109 1 m1) if
the -potential is 0.025 V. The density of the oil is 700 kg/m3 and the volume fraction of
the dispersed aqueous phase is 0.05.
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:
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. Wennerström, 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).