NPTEL Chemical Engineering Interfacial Engineering Module 1: Lecture 5

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Colloidal Materials: Part IV








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


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Table of Contents


Section/Subsection Page No.
1.5.1 Hofmeister series 3
1.5.2 Electroviscous effect 3
1.5.3 Gelation 4
1.5.4 Imbibition 5
1.5.5 Syneresis 5
1.5.6 Gold number 6
1.5.7 Rheological properties of colloidal dispersions 816
1.5.7.1 Einsteins equation of viscosity 11
1.5.7.2 MarkHouwink equation for colloidal polymers 13
1.5.7.3 Deborah number 14
1.5.7.4 Peclet number 15
1.5.8 Surfactants 1618
1.5.8.1 Properties of surfactants 17
1.5.8.2 Adsorption and micellization 18
Exercise 19
Suggested reading 21
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1.5.1 Hofmeister series
+ Small amounts of electrolytes diminish the , -potentials of lyophilic sols, but
coagulation does not take place. If a large amount of electrolyte is added to a
lyophilic system, the dispersed substance precipitates. This is known as salt-out,
which is different from the coagulation observed with the lyophobic colloids.
+ It is believed that the stability of the lyophilic systems depends upon their charge
and hydration. Large amounts of electrolytes dehydrate the particles in addition to
reducing their , -potentials. It is generally accepted that salting-out depends on
the nature of the ions. Based on experimental observations, a series has been
created for anions and cations reflecting their ability to salt out. This series is
known as Hofmeister series.
Cations: Mg
++
> Ca
++
> Sr
++
> Ba
++
> Li
+
> Na
+
> K
+
> Rb
+
> Cs
+

Anions: Citrate
=
> Tartrate
=
> SO
4
=
> Acetate

> Cl

> NO
3

> ClO
3

> I

> CNS

+ Salt-out of a hydrophilic sol frequently produces a liquid aggregate in place of a
solid. This sometimes appears in the form of viscous drops. This phenomenon is
known as coacervation and the droplets are known as coacervates.
+ The coacervates are formed most readily when two hydrophilic sols carrying
opposite charges (e.g., gelatin at pH < 4.7 and gum acacia sol) are mixed in
suitable proportions. It is believed that the shells of tightly-bound water
molecules surrounding the particles prevent them from coagulation. On the other
hand, the electrostatic attraction holds a number of particles together.
Redispersion of coacervates can be achieved by the addition of iodide or
thiocyanate ions which favor hydration of the particles. Otherwise, ions of high
valence can be added, which would diminish the , -potential of either sol.

1.5.2 Electroviscous effect
+ The lyophilic sols have significantly higher viscosity than the lyophobic sols.
This is due to the extensive solvation of the dispersed-phase particles, which
increases the resistance to flow. The viscosity of very dilute lyophilic sols (e.g.,
gamboge, mastic and protein) obeys the Einsteins equation.
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+ The addition of a small amount of an electrolyte to a lyophilic sol produces a
marked decrease in viscosity. For example, KCl at 2 mol/m
3
concentration can
decrease the viscosity of an agar-agar sol by 20%. Experiments with salts
containing ions of different valence have shown that the influence increases with
the increasing valence of the counterion.
+ Therefore, it can be surmised that the decrease in viscosity is associated with the
electrostatic double layer surrounding the colloid particles. A small amount of
electrolyte cannot appreciably affect the solvation of the particles. Therefore, it is
evident that the ,-potential is an important factor in determining the viscosity of
the dispersion. The role of electrical charge of the particles on the viscosity of the
sol is known as electroviscous effect.

1.5.3 Gelation
+ The cooling of a not-too-dilute lyophilic sol (e.g., gelatin or agar-agar) results in
the formation of a gel. A gel can also be obtained by the addition of electrolytes
under suitable conditions to lyophobic sols which exhibit some lyophilic
character (e.g., silicic acid and ferric oxide). The gels do not differ fundamentally
in their structure and properties from gelatinous precipitates. The gelation process
is accompanied by a large increase in viscosity.
+ Two types of gels can be distinguished: elastic and rigid gels. Partial dehydration
of an elastic gel (e.g., gelatin) leads to the formation of an elastic solid. The
original sol can be generated readily by the addition of water (and subsequent
warming, if necessary). Rigid gels (e.g., silica gel) become glossy or powdery,
and lose their elasticity on drying. Furthermore, mere addition of water may not
regenerate the sol. The walls of the capillaries formed upon the dehydration of
elastic gels are supple, but they are stiff for the rigid gels. Dehydrated silica gel
has a honeycomb structure with fine capillaries, which renders it a valuable
adsorbing agent. The dehydration and rehydration of the partially dried gels is the
most important distinction between the elastic and nonelastic gels.

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1.5.4 Imbibition
+ A gel imbibes a considerable amount of liquid when placed in a suitable liquid.
The volume of the liquid imbibed can be several times the volume of the original
gel. Imbibition is thus accompanied by a large increase of volume. For this
reason, this phenomenon is often called swelling. This can produce a large
amount of pressure. For example, if dry gelatin is placed in a tight porous vessel
and kept in water, swelling can break the vessel! However, the net volume
decreases in the imbibition process.
+ Sulfate, tartrate, citrate and acetate inhibit the swelling of gelatin and similar gels,
and their inhibiting effect decreases in the sequence mentioned. On the other
hand, chloride, chlorate, nitrate, bromide, iodide and thiocyanate favor the
imbibition of water, and the effect of chloride is the least. For iodide solutions,
the gel often disperses at the room temperature and forms the sol spontaneously.
Otherwise, the swollen gel is warmed to form the sol.
+ The Hofmeister series gives the order of temperature to which the gel must be
heated in presence of the anions to convert it to sol.
+ Imbibition of liquid by porous media has important applications in the cleaning
and deposition. Fig. 1.5.1 illustrates the imbibition of different liquids on a
porous micropatterened surface.


Fig. 1.5.1 Imbibition of liquids by polygonal spreading on surfaces (source: L.
Courbin, E. Denieul, E. Dressaire, M. Roper, and A. Ajdari, Nature, 6, 661, 2007;
reproduced by permission of Macmillan Publishers, 2007).

1.5.5 Syneresis
+ Many gels exude small amounts of liquid on standing (e.g., concentrated silicic
acid gels and dilute gels of gelatin and agar-agar). This phenomenon was first
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observed by Thomas Graham, and he called it syneresis. Examples of syneresis
are drainage of lymph from a contracting clot of blood, and collection of whey on
the surface of yoghurt. Syneresis in jam is shown in Fig. 1.5.2.
+ Syneresis is believed to be due to the exudation of water held by the capillary
forces between the heavily-hydrated particles constituting the framework of the
gel.

Fig. 1.5.2 Measurement of syneresis in jam.

1.5.6 Gold number
+ When a lyophilic sol is added to a lyophobic sol, the sensitivity of the latter
towards electrolytes is altered. Some lyophilic sols enhance the stability of the
lyophobic sols and render them less sensitive towards electrolytes.
+ The protective effect of a lyophilic sol is different for different lyophobic sols.
Zsigmondy set up a standard by which the protective capacity can be expressed. It
is known as gold number. The gold number of a lyophilic sol is the amount (in
mg) of the dispersed phase of the lyophilic sol (in dry condition) which ought to
be added to a 10 cm
3
standard gold sol (0.0053% 0.0058%) to prevent it from
turning to blue (from red) upon the addition of 1 cm
3
of a 10% solution of sodium
chloride.
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+ The change in color reflects the onset of coagulation. Therefore, a low value of
the gold number indicates good protective ability of the lyophilic colloid. Gold
numbers of some lyophilic sols are presented in the Table 1.5.1.

Table 1.5.1 Gold numbers of some lyophilic sols

Sol Gold number
Gelatin 0.0050.01
Hemoglobin 0.030.07
Albumin 0.10.2
Gum arabic 0.150.25
Dextrin 620
Potato starch > 25

+ Historically, gold number has some very important applications, although many
of them have been replaced by more accurate modern analytical techniques. For
example, albumins have higher gold numbers than globulins. Consequently, the
changes occurring in blood plasma in tetanus, where the albumins are converted
into globulins, can easily be detected by determining the gold number.
+ The protective effect of lyophilic colloids has been attributed to a homogeneous
encircling of the suspended particle by the particles of the protective colloid,
forming a protective sheath. According to Zsigmondy, this theory is applicable to
coarse particles only, not to the fine colloids such as the red gold sols. Zsigmondy
observed that particles of gelatin did not form a sheath around the gold particles.
However, one particle of gelatin adsorbed several gold particles. He, therefore,
suggested that the stability was due to the mutual adsorption of the particles of
hydrophobic and hydrophilic colloids. The union of the particles of the two
colloids formed a complex which imparted the stability.

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1.5.7 Rheological properties of colloidal dispersions
+ The flow behavior of the colloid dispersions is important in numerous
applications in our daily life and in chemical industries. The particles present in
the dispersion exert a significant influence on its flow properties. Therefore, the
colloid dispersions can display a wide range of rheological behavior.
+ Charged dispersions and sterically-stabilized colloids show elastic behavior. If the
interparticle interaction is not important, the behavior of the dispersion resembles
ordinary viscous liquids. Most of the colloid dispersions can be classified as
Newtonian and non-Newtonian fluids.
+ The rheological behavior of fluids can be expressed by their profiles of shear
stress ( )
s
t versus shear rate ( ) at a constant temperature and pressure as
illustrated in Fig. 1.5.3.


Fig. 1.5.3 Shear stress versus shear rate behavior.

+ The simplest relation between shear stress and shear rate is,
s
t =
(1.5.1)
+ This is known as Newtons law of viscosity. The proportionality constant, , is
known as viscosity. Gases and many liquids (e.g., water) obey Newtons law of
viscosity, and these fluids are known as Newtonian fluids.
+ The flow behavior of most colloidal dispersions, however, does not follow this
simple behavior. The deviations occur mainly due to two factors: (i) interparticle
hydrodynamic interactions, and (ii) colloidal forces (electrostatic or steric)
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between the particles. The hydrodynamic effects exist even for neutral particles
when the concentration is large. The electrical and steric interactions can be
important in dilute dispersions if the range of the forces is large enough.
+ For a Newtonian fluid, the slope of the
s
t versus curve is constant. Therefore,
the viscosity does not vary with shear rate. However, for non-Newtonian fluids
such a plot can be non-linear, and the slope varies from point to point. Therefore,
the viscosity of such fluids depends upon the shear rate even at constant
temperature and pressure.
+ The non-Newtonian fluids can be divided into two categories: (i) fluids whose
s
t behavior is independent of time, (ii) fluids whose
s
t behavior depends
upon time, and (iii) viscoeleastic fluids. The non-Newtonian fluids such as
Bingham plastic, pseudoplastic and dilatant belong to the first category. Their
s
t behavior does not depend on the history of the fluid, and a given sample
of the material shows the same behavior no matter how long the shear stress has
been applied. Polymer solutions and paper pulp in water are examples of
pseudoplastic fluid. Dispersions of starch and sand are examples of dilatant fluid.
Examples of Bingham plastic fluid are clay dispersions, drilling mud and
toothpaste.
+ On the other hand, the
s
t curves for the non-Newtonian fluids belonging to
the second category depend upon how long the shear has been applied. These
fluids can be divided into two categories, viz. thixotropic and rheopectic. The
thixotropic fluids show a decrease in viscosity with time under a constant applied
shear stress. The classic example of thixotropic behavior is displayed by the
flocculated sols of iron (III) oxide, alumina and bentonite clay gels, which can be
liquefied on shaking and solidified on standing. Many paints show thixotropic
behavior. In these colloid systems, there is a time-dependent aligning to match
the induced flow. The behavior of rheopectic fluids is opposite: the apparent
viscosity increases with time by the application of shear. Certain clay suspensions
and gypsum pastes, which thicken or solidify while shaken but sets slowly on
standing, are examples of rheopectic fluid.
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+ The relation between shear stress and shear rate for many non-Newtonian liquids
can be expressed by the power-law model.
( )
s p
k
o
t = (1.5.2)
where o is called flow-behavior index and
p
k is called consistency index. This
model is also known as Ostwaldde Waele model. For 1 o = and
p
k = , this
model predicts Newtonian flow behavior.
+ The Ostwaldde Waele equation can be written as,
s
t q = , ( )
1
p
k
o
q

= (1.5.3)
where q is known as apparent viscosity. For pseudoplastic fluids, 1 o < , and the
apparent viscosity decreases with increasing rate of shear. For dilatant fluids
( ) 1 o > , the apparent viscosity increases with increasing shear rate.
+ The Bingham plastic fluid behaves like a solid until a minimum yield stress ( )
0 s
t
is applied, and subsequently the shear stress varies linearly with shear rate.
0 s s B
t t = +
(1.5.4)
If the dispersion is such that the t behavior is non-linear once the flow starts,
the HershelBulkley model can be used.
0 s s H
|
t t = + (1.5.5)

Example 1.5.1: The data on the variation of viscosity with shear rate for a mixture of an
anionic surfactant and a nonionic surfactant are given in the following table.
( )
1
s

( ) Pa s q
( )
1
s

( ) Pa s q
0.11 680.2 6.62 13.6
0.18 482.8 10.80 9.1
0.41 184.7 16.80 6.0
0.67 114.8 27.30 3.7
1.04 76.3 42.40 2.0
1.61 46.8 65.75 1.2
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2.49 31.1 102.10 0.8
4.06 20.5

Determine the parameters of the Ostwaldde Waele model from these data.

Solution: From Eq. (1.5.3) we have,
( )
1
p
k
o
q

=

( )
( )
( ) ( ) ln ln 1 ln
p
k q o = +

The plot of ( ) ln q versus ( ) ln is shown in Fig. 1.5.4.

Fig. 1.5.4 Variation of ( ) ln q with ( ) ln .

From this plot, the slope and the intercept are 0.98 and 4.4, respectively. Therefore, the
parameters of the Ostwaldde Waele model are, 0.02 o = and 81.45
p
k = Pa s
o
.

1.5.7.1 Einsteins equation of viscosity
+ Albert Einstein derived an equation for the viscosity of an infinitely-dilute
dispersion of very small rigid spheres. His theory is based upon the following
assumptions: (i) density and viscosity of the fluid are constant, (ii) the flow
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velocity is low, (iii) no slippage of the liquid at the surface of the spheres, and (iii)
the spheres are large enough compared to the liquid molecules so that the liquid
can be regarded as continuum.
+ The Einsteins equation of viscosity is,
1 2.5
d

= +
(1.5.6)
where is the viscosity of the pure liquid,
d
is the viscosity of the dispersion
and _ is the volume fraction of the spheres. Equation (1.5.6) has been found to
agree well with many experimental results reported in the literature.
+ Deviation from Einsteins equation can result from factors such as electroviscous
effect, swelling, flocculation, and adsorption of water on the surface of the
particles.
+ For dispersions with higher volume fractions of the particles, Einsteins equation
can be extended as,
2 3
1 2
1 2.5
d
k k

_ _ _

= + + + +
(1.5.7)
Equation (1.5.7) gives a better fit to the data for dispersions which are not very
dilute. Several attempts have been made to extend Einsteins equation for
concentrated dispersions.
+ Equation (1.5.6) can be written in terms of the molar volume of the colloid as,
1 2.5
d
sp m
v c

= =
(1.5.8)
where
sp
is the specific viscosity,
m
v is the molar volume and c is the
concentration.

Example 1.5.2: The specific viscosity of a dispersion of glass spheres having 160 m
diameter in water varies with the volume fraction of the spheres as given below.
_
0.01 0.02 0.03 0.04 0.06 0.08 0.10
sp

0.02 0.04 0.07 0.08 0.14 0.19 0.24

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Verify whether these data obey the Einsteins equation of viscosity, or not.

Solution: The given data are plotted as shown in Fig. 1.5.5.


Fig. 1.5.5 Variation of specific viscosity with volume fraction.

The best-fit least squares straight line through the data (shown by the pink line) has slope
= 2.34, which very close to 2.5, as predicted by Einsteins equation (shown by the green
line). Therefore, it can be concluded that the given data obey Einsteins equation of
viscosity.

1.5.7.2 MarkHouwink equation for colloidal polymers
+ The polymer solutions have particle-size in the colloidal dimensions. Often there
is a considerable interaction between the solute (i.e., the macromolecule) and the
solvent. The viscosity of polymer solutions is distinct because such solutions,
even at a dilute concentration, can display high viscosity.
+ This may be caused by the very extensive solvation of the solute molecules,
which immobilizes the bound liquid, or the long polymer molecules may be
intertangling with each other as they move. Many polymers show a strong
propensity to imbibe the solvent.
+ The average molecular weight of polymer can be determined by dilute solution
viscometery. The MarkHouwink equation correlates the viscosity-average
molecular weight
( )
v
M with the intrinsic viscosity of the solution
| |
as,
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| | ( )
a
m v
K M = (1.5.9)
+ The intrinsic viscosity
| |
is defined as,
| |
0
1
Lim
d
c c

( | |
=
( |
\ .

(1.5.10)
+ The viscosity average molecular weight
v
M is defined as,
1
1
a
a
i i
v
i i
n M
M
n M
+
| |

= |
|

\ .
(1.5.11)
+ The parameters
m
K and a are the characteristics of a particular polymersolvent
combination. In ordinary good solvents, the constants
m
K and a are valid only
within a rather limited range of molecular weight. The values of
m
K and a for
many polymer systems are tabulated in the literature.
+ To determine these two parameters,
| |
is experimentally determined for several
known molecular weight fractions of the polymer by dilute solution viscometry.

1.5.7.3 Deborah number
+ The Deborah number is a dimensionless number used to describe the influence of
time on the observed flow properties.
+ Whether a material deforms under applied stress or not, depends on the
magnitude of the stress and the time of observation. Even some apparently-solid
materials flow if they are observed long enough (e.g., silicone putty).
+ In interacting dispersions, it is important to consider the time over which the flow
behavior is observed relative to the time scales over which the shear force alters
the local structure of the dispersion. Deborah number is the ratio of the relaxation
time of the material ( )
r
t and the observation time ( )
o
t .
De
r
o
t
t
=
(1.5.12)
+ The difference between solids and liquids is defined by the magnitude of De. If
the time of observation is very large, or, conversely, if the time of relaxation is
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very small, the material is seen to be flowing. On the other hand, if the time of
relaxation of the material is larger than the time of observation, the material, for
all practical purposes, can be considered a solid.
+ The name of this number was coined by Markus Reiner in 1964 from a biblical
quote. Prophetess Deborah sang after the victory over the Philistines, The
mountains flowed before the Lord. It symbolizes the fact that the mountains
flow, as everything flows, and they flowed before the Lord (not before man) for
the simple reason that man in his short lifetime cannot see them flowing, but the
time of observation of the Lord is infinite.

1.5.7.4 Peclet number
+ The Peclet number is a very important dimensionless number for the colloid
dispersions. It compares the effect of shear with the effect of diffusion of the
particles.
+ In a quiescent colloidal dispersion, the particles move randomly due to Brownian
motion. An equilibrium statistical distribution of the particles is established,
which depends on the factors such as the volume fraction occupied by the
particles and the force of interaction between the particles. Now, if a shear is
imposed on the dispersion, the distribution of the particles is altered. The
Brownian motion of the particles tries to restore the equilibrium structure.
+ The time taken by a particle to diffuse a distance equal to its radius,
s
R , is of the
order of
2
s
R D, where D is the diffusion coefficient. This is the time-scale for
diffusion ( )
d
t . The time-scale for shear flow ( )
s
t is
1

, where is the shear
rate.
+ The Peclet number is defined as,
2 2
Pe
1
d s s
s
t R D R
t D

= = =

(1.5.13)
+ This ratio signifies the relative importance of shear and diffusion. If the Peclet
number is small, the Brownian motion dominates and the behavior of the particles
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is dominated by the diffusional relaxation of the particles. On the other hand, if
the Peclet number is large, the shear-effect dominates the distribution.

1.5.8 Surfactants
+ A large number of phenomena at gasliquid, liquidliquid and liquidsolid
interfaces is controlled by a special class of organic compounds known as
surfactants or surface-active agents. These compounds have the unique property
that they tend to adsorb at the interface.
+ A surfactant is added in rather small quantities to the system. Nonetheless, it
alters the interfacial free energy significantly.
+ When the surfactant molecules adsorb at the interface, a significant reduction in
the tension results in most cases. Inorganic electrolytes can strongly influence the
adsorption of certain surfactants. Various intermolecular and surface forces are
responsible for these effects.
+ The traditional use of surfactants has been in household products, foods, coating
processes, petroleum industries, synthesis of microporous materials, and in
chemical reactions such as emulsion polymerization. At present, novel techniques
are being used to design new surfactants with specific chemical, biological,
electrochemical and photochemical properties.
+ Theoretical understanding of the surface activity has also progressed significantly
in the past decade, with high-speed computer simulations. The focus is on the
properties of multi-surfactant systems, behavior is electrolyte solutions, and in
concentrated surfactant solutions.

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1.5.8.1 Properties of surfactants

+ A surfactant molecule has two parts: one part is soluble in the solvent, and the
other part is insoluble. The part of the urfactant molecule that has unfavorable
interaction with the solvent is known as the lyophobic part. On the other hand, the
part which has favorable interaction with the solvent is called the lyophilic part.
+ For example, consider a sodium stearate molecule [molecular formula:
CH
3
(CH
2
)
16
COO

Na
+
]. In water, the lyophobic part is the hydrocarbon chain,
C
17
H
35
whereas the lyophilic part is, COO

. This type of structure is known as

amphipathic structure, as shown in Fig. 1.5.6. The part of a surfactant molecule
that is lyophilic in a polar solvent such as water, may be lyophobic in a
hydrocarbon solvent such as cyclohexane. Therefore, a surfactant that is useful in
water may not be effective in another solvent. In fact, it may not dissolve in
another solvent.

Fig. 1.5.6 Amphipathic structure of surfactant.

+ When the solvent is water, the lyophobic and lyophilic parts are called
hydrophobic and hydrophilic parts, respectively. Examples of hydrophilic head-
groups are COO

and N(CH
3
)
3
+
.
+ The hydrocarbon tail can be made of straight-chain alkyl groups, branched-chain
alkyl groups, long alkyl benzene chain, rosin derivative, alkene-oxide polymer,
polysiloxane group or lignin derivative.
+ If the hydrophobic group is very long, its solubility in water can be small. For
example, let us consider the sodium salts of fatty acids, which are the main
ingredients of soap. When the number of carbon atoms is less than 10, the soap is
readily soluble in water (however, its surface activity would be low). As the
number of carbon atoms increases (i.e., the hydrophobic tail becomes longer) the
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solubility decreases. When the number of carbon atoms reaches 20, the soap is
almost insoluble in water.

1.5.8.2 Adsorption and micellization
+ When the surfactant molecules come in contact with water, they disrupt the
hydrogen bonds between the water molecules. This increases the free energy of
the system. Since this is thermodynamically unfavorable, the surfactant molecules
are sent away toward the airwater (or waterhydrocarbon) interface.
+ The air molecules are similar to the hydrophobic groups of the surfactant because
they are essentially nonpolar. This encourages the surfactant molecules to adsorb
at the airwater interface putting their hydrophobic tails in air, and hydrophilic
head-groups in water.
+ If a sufficient number of surfactant molecules is present in the medium, the
interface becomes covered with a closely-packed monolayer.
+ The long hydrophobic groups favor formation of assemblies known as micelles
and liquid crystalline phases. These are discussed in detail in Lecture 6, Module
1.


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Exercise

Exercise 1.5.1: The shear stress versus shear rate data for a dispersion of colloidal silica
Aerosil R805 (mean diameter = 32 nm) in polypropylene triol are given below at 298 K.
( )
1
s

( ) Pa
s
t
( )
1
s

( ) Pa
s
t
( )
1
s

( ) Pa
s
t
4
1 10

9.4
2
3 10

16.8 10 65.5
4
3 10

10.6
1
1 10

19.8 30 107.5
3
1 10

11.6
1
3 10

24.3 100 216.9
3
3 10

12.6 1 31.1
2
1 10

14.8 3 41.6


Fit an appropriate rheological model to these data.

Exercise 1.5.2: The intrinsic viscosities (at 298 K) of eleven molecular weight fractions
of cellulose nitrate dissolved in acetone are given below.
Mol. wt. 10
3

(kg/kmol)
| |
(dm
3
/kg)
Mol. wt. 10
3

(kg/kmol)
| |
(dm
3
/kg)
77 123 846 1490
89 145 1270 2450
273 354 1550 3030
360 550 2510 3100
400 650 2640 3630
640 1060

Determine the MarkHouwink parameters from these data.

Exercise 1.5.3: The data on the relative viscosity with the volume fraction of a
dispersion of spheres of poly(methyl methacrylate) cross-linked with divinylbenzene in
benzene are tabulated below.
NPTEL Chemical Engineering Interfacial Engineering Module 1: Lecture 5

Joint Initiative of IITs and IISc Funded by MHRD 20/21

_
0.042 0.053 0.070 0.084 0.105 0.137 0.168
d

1.11 1.14 1.22 1.28 1.36 1.59 1.77

If
d
can be correlated with _ by equation (1.5.7), use the polynomial up to the term
containing
3
_ , and determine the parameters
1
k and
2
k . Discuss the importance of
swelling of the particles.

Exercise 1.5.3: Answer the following questions clearly.
(a) What is salt-out? How does it differ from coagulation?
(b) Explain the significance of Hofmeister series.
(c) What is coacervation?
(d) What is electroviscous effect?
(e) Explain gelation and imbibition.
(f) Explain the significance of gold number.
(g) Explain the difference between a Newtonian fluid and a non-Newtonian fluid.
What is the difference between pseudoplastic and dilatant fluids?
(h) What is the difference between a thixotropic fluid and a rheopectic fluid?
(i) Give one example each of (i) pseudoplastic (ii) Bingham plastic, and (iii) dilatant
fluids.
(j) Explain the power-law model.
(k) Explain Einsteins equation of viscosity and its limitations.
(l) Explain MarkHouwink equation.
(m) Explain the significance of Deborah number.
(n) What is the significance of Peclet number?
NPTEL Chemical Engineering Interfacial Engineering Module 1: Lecture 5

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

Suggested reading

Textbooks
+ D. J. Shaw, Introduction to Colloid and Surface Chemistry, Butterworth-
Heinemann, Oxford, 1992, Chapter 4.
+ P. C. Hiemenz and R. Rajagopalan, Principles of Colloid and Surface Chemistry,
Marcel Dekker, New York, 1997, Chapter 4.
+ P. Ghosh, Colloid and Interface Science, PHI Learning, New Delhi, 2009,
Chapters 2 & 3.
+ S. Glasstone, Textbook of Physical Chemistry, Macmillan Publishers, Delhi,
1986, Chapter 14.

Reference books
+ D. F. Evans and H. Wennerstrm, The Colloidal Domain: Where Physics,
Chemistry, Biology, and Technology Meet, Wiley-VCH, New York, 1994,
Chapter 1.
+ G. J. M. Koper, An Introduction to Interfacial Engineering, VSSD, Delft, 2009,
Chapter 5.
+ J. C. Berg, An Introduction to Interfaces and Colloids: The Bridge to
Nanoscience, World Scientific, Singapore, 2010, Chapter 3.
+ M. J. Rosen, Surfactants and Interfacial Phenomena, John Wiley, New Jersey,
2004, Chapter 1.
+ M. R. Porter, Handbook of Surfactants, Chapman and Hall, London, 1994,
Chapter 4.

Journal articles
+ L. Courbin, E. Denieul, E. Dressaire, M. Roper, A. Ajdari, and H. A. Stone,
Nature, 6, 661 (2007).
+ M. Reiner, Phys. Today, 17, 62 (1964).
+ N. L. Abbott, AIChE J., 47, 2634 (2001).