INDEX

[Link] TOPICS [Link]

Week 1
1 Introduction and motivation 4

2 Colloidal dispersions, terminology and classification 27

3 Stability in colloids 39

4 Source, synthesis and characterisation of colloids 48

5 Characterisation of colloidal particles - I 73

Week 2
6 Characterisation of colloidal particles - II 88

7 Introduction to forces acting on an individual colloidal particle 99

8 Introduction to interaction between colloidal particles 115

9 Application of Brownian force: Measument of diffusivity and size 124

10 Radiation used to study colloidal systems 139

11 Radiation used to study colloidal systems 149

Week 3
12 Molecular origin of Van der waals forces 174

13 Vanderwaal interactions between particles 194

14 Problem on scaling of Vanderwaal interactions 207

Calculation of Vanderwaal's forces between semi-infinite blocks and

15 Hamaker constant - I 213

Calculation of Vanderwaal's forces between semi-infinite blocks and

16 Hamaker constant - II 225

Theories of Vanderwaal forces based on bulk properties and

17 calculation of Hamaker constant using bulk properties 234

Week 4
18 Effect of medium on Vanderwaal's interactions - I 264

19 Effect of medium on Vanderwaal's interactions - II 275

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20 Colloid Polymer mixtures 287

Colloid polymer mixtures: colloid-solvent interactions &

21 colloid-polymer interactions 300

22 Colloid polymer mixtures: Depletion flocculation 308

23 Colloid polymer mixtures: Depletion stabilisation 318

Week 5
24 Depletion interactions 326

25 Steric interactions/osmotic repulsion 335

26 Tutorial problem on depletion interactions 346

Colloidal Interactions: Introduction to electrostatic

27 interactions/electrical double layer interactions 353

Introduction to models of electrical double layer: Helmholtz

28 model/capacitor model 364

Review and summary of Helmholtz model (or capacitor model) of

29 electrical double layer 371

Week 6
Models of electrical double layer: Diffuse double layer
30 model/Gouy-Chapman model 381

Potential distribution near planar surfaces: Derivation of the

31 Poisson-Boltzmann equation 392

Potential distribution near planar surfaces: Solution to the linearised

32 Poisson-Boltzmann equation 403

Potential distribution near spherical surfaces: Solution to linearised

33 Poisson-Boltzmann equation 412

34 Comparison of Capacitor model and Diffuse double layer model 426

Week 7
35 Models of electrical double layer: Gouy Chapman Theory - I 433

36 Models of electrical double layer: Gouy Chapman Theory - II 448

37 Structure of Electrical double layer 456

38 Force of Repulsion between interacting surfaces 466

39 Potential Energy of repulsion between Planar double layers and 474

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 DLVO Theory
Week 8
40 Zeta Potential and Electrophoretic mobility of an ion 488

41 Electrokinetic Phenomena 503

42 Relation between Electrophoretic mobility and Zeta potential - I 515

43 Relation between Electrophoretic mobility and Zeta potential - II 533

44 Colloidal particles at interfaces:Introduction 547

45 Characterization of Particles at interface 560

Experimental Observations -Concept of Electrostatic interactions and

46 Stability at interfaces 569

Implications from Surface energy balances & Estimation of energy

47 required for detachment 586

48 Colloidal interactions at interface 601

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-01
Colloidal Dispersions, Terminology and Classification

Okay yeah, so this course is called colloids and surfaces. So, you will see that there are okay and
so before I begin, why this course is kind of called colloids and surfaces. So, what I will do is I
will first give you a okay.
(Refer Slide Time: 00:40)

So, this is the course sub, you know, book that I am going to follow okay, so that is a picture of
you know the front cover. And this textbook is titled colloids and surface chemistry, which is
you know written by Hiemenz and Rajagopalan okay, it is a good book very basic okay. I have
learned a lot of things by you know reading this book, that is going to be the course textbook, I
have a copy of it in case if you want to take a look.

Of course library will also have a copy in case if you would like to go and refer. Apart from the
course book I have a lot of reference books listed here about four of them. Some of them are
advanced, some of them are very basic okay, you can take a look at them you know in case if
you would like to refer to some specific topic okay. So, what I will do is I will begin with talking
to you about introduction to the course okay.

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The aim of today's class is to essentially define what is colloids. I will just do that, followed by I
am going to give you several examples, you know where you know we have we used colloids
and, you know, different, different fields okay. So, you know that is to motivate you from
learning colloids okay. So, I am going to take some examples from different, different fields.
And then tell you, you know how the colloids principles are exploited to learn some make some
new materials and things like that okay that is okay.
(Refer Slide Time: 02:21)

So, that is a long list of what I am going to cover in the maybe next few lectures. But for today
most likely, I will just define what is colloids and then I will follow it up with talking to you a
little bit about motivation to study colloids okay, why are we trying to look at this colloids. And
if there is some time I may look at you know something on classification of colloids okay that is
for today.
(Refer Slide Time: 02:47)

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Now, definition is a textbook definition, you will see in a lot of forums as well. A colloid okay is
any particle okay, which has at least one dimension, at least one dimension in the size range
between 10 power - 9 meter and 10 power - 6 meter that corresponds to one nanometer to about a
micro meter particle okay. So, the moment you have any particle in this size range. That is what
is called as a colloid.

The reason why you have at least one linear dimension is because often you may be working
with particles that are spherical okay. In such a case, you know, you need only one dimension to
characterize such particles. The moment you think about other shaped particles, it could be, you
know, ellipsoids, it could be cylinder like or rod like okay, then you have more than one
dimension okay.

So, if I take a two dimensional ellipsoid you need, you know the length of the major axis and
length of the minor axis okay, to define the size of the, you know particles. So, therefore, in such
a case, if one of them, you know in this case b is smaller as long as b is, you know, in the size
range from 1 nanometer to 1 micrometer, that is still called colloidal dispersion. So, as long as
one of the dimension, one of the linear dimension of the particle that we are dealing with is in
this size range. That is what is called as a colloidal dispersion okay.
(Refer Slide Time: 04:33)

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Now, it turns out that a lot of materials that people work with okay and a lot of materials that are
biologically important, for example, DNA, virus, proteins okay and a lot of, you know, consumer
products which have, for example, detergents and shampoos which have surfactants right. So, all
these molecules okay. When you put them in solution, when you put them in water, they form
aggregates okay, whose size again, comes in the size range between 1 nanometer to 1
micrometer okay.

Or you could have a particles present in some fluids, for example milk, okay milk contain some
particulate matter. Again, the size of these particular matter, you know is in this in a 1 nanometer
to 1 micrometer, size range. Therefore, there is a lot of relevance, looking at colloids in many
different fields. So, this is a triangular diagram on one apex you have polymers, the other apex
you have particles, solid particles.

And other apex you have, you know, surfactant molecules which are also called as amphiphiles
okay and several different things that will unite this DNA, polymers block of polymers, proteins
right. So, all these materials, okay when people are working with them in solution, they
invariably form okay, aggregates of 1 nanometer to 1 micrometer dimension, therefore there is a
lot of interest in looking at such systems okay.
(Refer Slide Time: 06:14)

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So, just to give you some examples. Again, I have taken a few examples from again biology. So,
what you are looking at is this is an image of a virus is what is called as a fd-virus okay. And so
this fd-virus has a length of about 800 nanometers and the diameter this dimension right, it is
about 6.8 nanometer okay that is an, you can think about this an example of a rod like, you
know, a particle right. So, people are working with you know such virus particles.

If you put them in fluid in water for example, they form a nice model system to look at a rod like
particles in water okay, or dispersion of rod like particles, right and another example again from
biology is this E-Coli which, you know, is looks elliptical in shape right and that is a scale bar
that you have you and that is scale bar is about 5 micrometer okay. Therefore, if I look at the
dimensions of these things again, they are you know in that 1 nanometer 1 micrometer size range
okay.

So, that is so therefore, these are again classic example of colloids, but in the field of biology
okay. Now I have another example here, so what you are looking at here is a polymer. It is an
example of what is called a block of polymer okay, so go back here. So, this is a schematic that
you see this is a polymer. So, typically people show polymer as you know some kind of a chain
right, which basically has several repeating units which are connected by some covalent bond.

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But you could have a system where I can have 2 polymers, which are connected by a covalent
bond is an example that is given here. So, that is orangish color is one type of polymer and the
blue is another type of polymer, again they are connected by a covalent bond okay, that is an
example of a block of polymer. You have 2 different, you know, polymer molecules which are
joined together right. That is why it is called as a di-block polymer.

You can have 3 different chains, some of those are tri-block polymer and so on and so forth
okay. So, when such polymers which are again represented by, you know the pink and the blue
color here. So, when you take such things and put them in water they can form different
structures, they could again I am going to introduce these terms a little later something called as
vesicles, some kind of spherical aggregates.

If you again look at these, you know, images here. If you look at the scale bar here again 200
nanometer here and 50 micrometer. So, the moment you put these things in water, they
automatically assemble okay, what is called as a self assembly, they self assemble to form these
aggregates and these aggregates have a dimension 1 nanometer to 1 micrometer, there is a lot of
interest in looking at such systems as well okay.
(Refer Slide Time: 09:10)

Now, to, again further motivated you, why people are looking at colloids, you will see several
examples where people talk about drug delivery people are using, you know, some kind of

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containers for drug delivery, one common object or one common kind of a container which is
used a lot in such application is something called a liposome. I do not know how many of you
have heard this term.

A lipo means lipid okay, so this is a spherical structure. It looks like a sphere okay, again,
example was shown here, right this is an example of a structure, very similar to liposome, but it
is made by polymer. Therefore it is called as a polymerizome okay. Similarly, if you make such
structures which lipids, is what is called as a liposome. So, the way these structures are made is
you take a lipid molecule.

So, lipid molecules are represented by something like this, they have a chemical group, which is
hydrophilic okay. And it has some group, which is hydrophobic okay, typically lipids have one
head group, which is hydrophilic okay and 2 tail groups which are hydrophobic. So, when you
take several such molecules okay, in water what I do is I simply mix it up okay, I just put in a
sonicator or you know or a high energy mixer.

I just mix it up. In the end, what you do is you basically get structures which look like spheres
okay and the inside this, you can think about this as a core shell kind of a structure where the
core has water because the surfactant molecules or these lipid molecules are put in water okay.
And inside has water, this region here okay, the shaded region is actually this layer okay, and
that layer is made up of what is called as a lipid bilayer okay.

What lipids do is, they kind of arrange, you know, kind of arrangement like this. There is one
layer of lipid, this is a second layer. That is what is called as a lipid bilayer okay. And these lipid
bilayers fold to make these spherical structures okay, So, what you are looking at here is a cross
section of one such liposome. If you cut it up okay, what do you see is, these lipid molecules are
nicely arranged in a bilayer fashion okay.

Now, because these, the tails, okay because these are hydrophobic right these lines that you see
here, they are hydrophobic. I can use this region for incorporating a hydrophobic molecules, for
example, what is put here is a what you are looking at this elliptical looking like thing is a

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hydrophobic thing that can happily sit in the bilayer region okay and I can have this hydrophobic
part, which could be happily being in water.

Therefore, I can use such containers to either carry hydrophilic material or a hydrophobic
material or any complex structures which can be there, both in the hydrophilic part and the
hydrophobic part. So, you can actually use them as cargo carriers. That means, if I take such
things and if I, you know make such formulations and you know, give it as a medicine for
example, okay, I can put both a hydrophilic drug and a hydrophobic drug in such things.

And I can easily transport them into the body okay. So, therefore, people are looking at such
colloidal structures for as cargo carriers for applications and cosmetics, medicine, genetics and
things like that okay. So, this is, you know, one of the motivations why one would be interested
in looking at you know colloids. This is an example where people have taken surfactant
molecules or lipid molecules and make structures which are colloidal in lengthscale and then
looking at some of these interesting aspects okay.
(Refer Slide Time: 13:44)

Now, we come to a second example of why should one look at and I have taken some examples
from materials, where there is a specific key field called colloidal processing of ceramic
materials okay. So, ceramic material is one could be interested in looking at SiO2 or aluminum
oxide, you know, or any such system. And one of the ways of making such materials is by using

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what is called as a you know colloidal processing group in which what you do is you start with a
uniform.

You start with the particles okay I have particles I could buy them as like a powder form okay,
and it has uniform particles of exactly same size okay. Now what I do is I take such particles, I
put them in a fluid okay. To make what is called a sol okay, which essentially is a dispersion of
particles in a fluid okay, that is about it okay. Now, what do I do, from the sol. Now what I do is
I have a sol.

And from this sol if I know everything about the particles that are present in the sol I am going to
talk a little bit about, you know, a few things later on in the course. If I know what is called as
how the particles are interacting in the fluid. Again, as I said, I am going to talk about these
things a little later in the course okay, but at this point what you should remember is that I have
something like this which can easily flow okay, it has fluid plus particles, I have this.

That is my sol and I think exactly the same thing. I do some simple manipulation to go from such
a state to something where things don’t flow okay, this is an example where I have gone from a
sol, where I have a nice dispersion of particles into a kind of a solid like thing, which does not
flow anymore right. And I will tell you how we do that, in the meantime. Now, that is an
example of what is called a wet gel.

Because it still has a fluid okay and the particles that I have in the sol are kind of they form a
nice network okay. And this network spans the entire volume okay, I can go from one end of the
sample into the other end, just along the particle network okay that’s what is called as wet gel is.
Now what I do with this. I take this and then I evaporate the fluid to get what is called as a dry
gel okay. And you can do other processing I can actually do what it was a compaction.

If I want a porous material I can process this. If I want a more denser material I can go to this
route okay. In the end, what you do is I take this and I do what is called a sintering okay,
sintering is a process where I take some sample like this, which has particles. And then I heat
that to a very high temperature, close to the melting point of the particles. And what this does is

12
it facilitates what is called as a solid state diffusion, because of which the particles can form a
nice bond okay.

And once that bond is formed I finally have a hard ceramic material. okay, so that’s the final
specimen that people have made either I can get a final hard specimen like this or I can also get a
porous material like this, which will essentially have all the void that you had in the sample I can
do that just by sintering process okay, I can either do this, or the other way of doing this would
be, I take the sol and I deposited a small layer of fluid on a substrate okay.

And I let the particles deposited on the substrate and I can still sinter it and I can also get a thin
film okay. So, there is a lot of interest in looking at such studies where in order to do colloidal
processing, where you start with a powder, make sol, gel and ultimately ceramic material. So, all
of this can be done if you have a really good understanding of colloid’s principles okay. So, what
are colloids, you know, how do I go from a solid state to gel state okay, how to handle these
matters right, things like that.
(Refer Slide Time: 18:15)

So, another example again, I am going to talk about some new material development. So, what
you are looking at is, they look like spherical objects right. They look like spherical objects to
you. And that’s your that’s 250 micrometer right, really large right. So, therefore, these are

13
actually droplets okay, these are drops, how these are made by a simple experiment. What you
do is I take water okay. And I have an oil. I put in particles.

So, in this case, this contains about 2.2 micrometer positively charged particles and a little larger
this is 9 micrometre negatively charged particles. You take that we have oil, and you just simply
mix it. That’s it okay. That’s it right. Now what you do is you create what are called as
emulsions okay, when you do that, you make emulsions. In this case, the emulsions that form
their water droplets in oil.

Now whatever particles that you had in the fluid, they go and sit at the interface okay. So, what
you are, this is a droplet like this. And if I, because these particles are big enough right 2
micrometer 9 micrometer they are big enough, I can do microscopy, if I look on the droplet
surface, what you have is this nice arrangement of 9 micrometer particles and 2.2 micrometer
particles okay.

You are able to emulsify 2 fluids, which otherwise don’t mix. I am able to make an emulsion by
using particles okay. So, this is an example of what are called as particle stabilized emulsions,
also called as Pickering emulsion okay. Pickering because, Pickering was a scientist who found
this for the first time in the 1900s okay. Now, you can ask me what is the use of such things.
(Refer Slide Time: 20:47)

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So, I am going to show some examples. So this is a, I talked about liposome right. I talked about
polymerizome, similarly, these structures that you see, they what are called us colloidosomes.
Because, these again a shell, which is made up of particles. What you are looking at is a hollow
shell. Inside is hollow okay and outside as a layer of single layer particles, can you see that those
particles here, right, you can see these nice spherical particles are very nicely arranged right.

These are actually made, starting with particle stabilized emulsions okay, in which the emulsions
are stabilized by single type of particles. I take these structures. And then I evaporate the fluid. I
can make a hollow structure and I can this empty space that is within these containers right, I can
again use them for again some drug delivery applications right or I can have several such things.

I can compact them and I can do the sintering I was talking about right, I can take particle size
stabilized emulsions and I can do sintering and I can actually get porous materials okay. So,
these are examples of porous materials in which people have taken these Pickering emulsions or
the particle stabilized emulsions and you compact them. And you remove the fluid and then you
sinter them, people have done metallic materials in a porous metallic materials porus ceramic
materials and stuff like that okay.

And we have another example here, which is kind of made by a similar technique okay, this is
the work of one of the PhD student. So, what you are looking at is a, you can imagine a some
container like this okay, which has a, you know, Pickering emulsion or particle stabilized
emulsions. And what was done is now what I can do is, now I have these droplets. When the
droplets are touching what I can do is I can do a cross link right.

I can actually connect the droplets by doing some simple reactions okay, now what will happen
is, in such a case, I can actually get a it looks like a you know the chalk piece right, piece of
chalk but it is not okay, it is a material which is made from some particles, some polymer is very
soft I can squish it. Whoops, it broke, not strong enough okay, it’s brittle, but I can make
materials like this right, again done everything from starting with colloids understanding them
and things like that okay.

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So, therefore people can make either oil in water emulsions or water in oil emulsions stabilized
particles and they can use them for making either hollow capsules for again applications in
medicine or you can make porous materials okay.
(Refer Slide Time: 23:37)

Okay, I am going to talk about some inspiration from nature okay. So, what we are going to do is
I am going to take some examples from nature and then tell you that look the colloidal scale
structures do exist in nature and there is an interest in looking at such things from you know that
point as well okay. Any examples that you may have you have anything that you think is in
nature and that is colloidal in length scale.

So, milk was one example of course Yeah, so anything else. How about this, within this some
connection between this and colloids. Yes. No. okay, so there is a whole lot of people looking at
what is called structural colours okay, so, you know in chemical engineering right when people
look at things like paints right, paints of different colors. One of the understanding is that there
are a lot of pigments that have a specific color. And you can make paint of a specific color by
right that is one thing, but there are a lot of things in nature, where the fascinating colors that you
see that comes about.

Because these things have some structures, whose length scale is such that, so when the, the light
falls on them right, like the light that is reflected okay, because of the nature of the colloidal

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scale structure, that are there on these species okay, those colors okay come about because of the
interaction of light, with the way the colloidal scale materials are arranged on such fascinating
creatures okay.

Now, so if you look at a peacock, right. So, these are some, you know, the micro structures that
are from peacock feathers okay, again I would like you guys looks at the land scale okay 5
nanometers 2 micrometer and look at these rod like things right. These are about 1 micrometer,
you know, so this is 1 micrometre, therefore the length is about the order of 1 micrometer or the
diameter would be may be about, you know, less than 100 nanometers, right. So, therefore, so
this is not the only example.
(Refer Slide Time: 26:08)

So these are again some pictures of a student of mine who took some years ago again, butterfly
wings okay, this is a about 20 micrometer, but if you look at these structures here that again very
much colloidal in land scale, 1 nanometer to 1 micrometer.
(Refer Slide Time: 26:28)

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Plus, you have, again some examples from literature. So, these are 2 birds. okay, which have,
you know, both of them are bluish in color right one is, you know, the light blue and other one is
slightly different, right. Now, if you look at the feathers of these creatures right these birds. They
have different structures okay. So, this is again the length scale is about 500 nanometers.
Therefore, you look at this small dots okay.

That is definitely sub 100 nanometers in length scale, right. So, therefore, so the interaction of,
you know the light with such structures, whose you know size is smaller than the wavelength of
visible light right. So, that those interactions is what leads to such colors, which is an example of
what is called as structural color which are not created by pigments, but the way these
nanostructures interact with light okay.

Now, so what people do is they kind of use these as inspiration and you can make such colors in
the lab okay, there are some examples.
(Refer Slide Time: 27:38)

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So, this is an example where what you are looking at is 5 different samples okay. What they have
done is what is was a drop casting okay. Drop casting is a simple technique where you basically
have a substrate and I just put a liquid drop okay, that is called drop casting. And this has some
particles in there okay. And once the liquid is gone, what you have is a deposition of particles on
the substrate right.

The liquid is gone and the particles are deposited on the substrate. So, you have 5 different
samples okay. And in all these samples they contain particles which are 226 and 265 nanometer
in size is a polystyrene particles. And what is being changed in the sample from 1 to 5 is the
fraction of some carbon black okay. That is added to the sample okay, the concentration is given
in weight percentage.

That goes from 1 weight percentage to 5 weight percentage and you can clearly see that the
colors are very different right. And, if you can do microscopy.
(Refer Slide Time: 28:47)

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You know the microscopy of the sample 3 will look something like this okay. Therefore, so
when you have such drop casting and the particles are finally deposited okay, so they kind of,
you can clearly see from this, you know it is not a regular arrangement right is more like a
amorphous you know irregular kind of arrangement okay. So, therefore, so that you are trying to
kind of mimic. Know, the kind of structures that you kind of obtain when you know there is a
amorphous.

You know, or not so regular arrangement of colloidal scale structure that represent in such things
okay, you can think about designing such things in the lab where I take particles of different
sizes, slightly different sizes and you know I add an additive. And then I make a kind of a
deposit of particles that kind of exhibits different colors depending upon the concentration or
some of the additives okay.

So, therefore, there is a lot of interest in kind of looking at nature and mimicking that you know
by looking at colloid science as a field. And then, you know, so one of the motivation could be
along these lines.
(Refer Slide Time: 29:53)

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Now so, this is another example of again a common example that everybody gives right.
Something called is a lotus leaf effect okay, that means it is a lotus leaf is an example of a self
cleaning surface right the moment if you have a lotus leaf, the moment water drops fall on it,
they just roll down right. And in that process they take whatever dirt that is there on the lotus leaf
they just carried okay.

And it turns out that this lotus leaf effect okay is comes because of what is called a hydrophobic.
Not only hydrophobic what is called as a super hydrophobic nature of the material that means if I
have a lotus leaf okay. And if I put a water drop it will. So, there are, if I put a water drop any
surface it can take a shape like that okay or it can completely spread like a thin film or I can have
a case where the droplet may form something like this right okay.

Everything depends on the nature of the substrate that you are dealing with okay, so if it makes a
perfect sphere there is an example of a super hydrophobic surface or completely hydrophobic
surface okay, where the. So, if form something like this is an example of a hydrophilic surface
right. Now, so it turns out that the, this the self cleaning nature arises because if you look at these
lotus leaf under a microscope.

So, there are large structures okay, there are hills okay. The size of this could be as much as
about 10 micrometer. Plus you also have this small nanoscale roughness right a combination of

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this nanoscale and microscale roughness is what leads to such. So, you know, self cleaning or
superhydrophobic, you know nature of lotus leafs okay. So, therefore, there is a lot of interest in
looking at these things understanding again nature. And then try and come up with a way of
creating such structures in the lab.
(Refer Slide Time: 32:13)

And one of the way of doing that by is again by a simple technique okay, which is the this is
what is done in this particular example if you are interested, you can go and read up a little bit
more about this, very simple example anybody could have done it right. So, what you have is a, a
glass substrate. Take a candle right and you burn it. And when you burn a candle you get a soot
right. And you just deposit that soot on the glass substrate okay.

And the soot essentially consists of some carbon particles right. So, the soot it looks flaky, right,
the flakiness of the soot actually comes because it has very, you know, open network of particles
like this okay it is not individual particles. The way it comes out it is, they are kind of connected,
they form some kind of loose kind of aggregates. And so, these loose kind of aggregates or kind
of deposited on the glass substrate.

And I can take that I can do some simple treatment in the lab okay, I can expose that to different
molecules and stuff like that. So the bottom line is, there is a suit that deposited on the particle on
the substrate. And if you look at again the land scale is about 100 nanometers and the size of

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individual particles would be again much, much smaller than that okay. So, you have colloidal
scale particles. They are deposited on a substrate.

And that gives you a contact angle of 165 which is an example of a superhydrophobic surface
right, very close to 180 okay. Non only water I can create surface which have a contact angle of
165 not only for water also for hexadecane, it is an oil right. Therefore I can create both water
liking substrates or water hating substrate or a oil hating substrates right. Therefore I can create
what are called as omniphobic okay. These are materials which even like water nor like oil okay,
so you can make things like that .
(Refer Slide Time: 34:26)

Final motivation hopefully okay is there is a lot of interests looking at colloids also what are
called as model atoms okay. If you look at atoms or molecules right they are sub nanometer in
size, right, they are very small. You cannot see them okay. And we know that anything that is
made up of atoms or molecules does exist in, you know, 3 forms right solid, liquid and gases
right.

Now, of course, there have been large developments and people know what these materials are.
But one of the ways of achieving all these states, the gas like state and liquid like state and solid
like state and visualize them live okay, is I can use colloidal particles okay. And I can actually

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create all these structures, okay all these materials. So, therefore, so there is, lot of interest in
using colloidal particles okay, as it is possible to directly observe okay.

I can make a material. I can take something which can go from a liquid like to a solid like state. I
can in-situ observe how does that happened. How does something go from a liquid state to a
solid state, I can observe it, you know, in-situ okay, with doing microscopy and things like that
okay. And how is it done, as we learn in the course. It is done by tuning interaction forces okay,
the way the particles interact with each other.

And it can also be done by playing particle concentration, again, I will give you some examples.
So, this is a something called as a phase diagram okay, that people first found from simulations.
So, the number that you are seeing here it is these numbers. These are what are called as volume
fractions okay, which is defined as the volume of solids or the particles that you have in the fluid,
divided by the total volume okay.

So, all this is telling you is depending upon the, volume fraction of the particles in the fluid. It
either exists as a fluid state okay, or there is a coexistence of fluid crystal, fluid you know where
there is a disorder arrangement of particles and a crystal like arrangement okay, or ultimately a
glass like arrangement okay. So, this is a phase diagram that was a kind of depict, that is kind of
found from several simulations you know several decades ago okay.
(Refer Slide Time: 37:21)

24
Now so, this is an example where what has been done is experimental visualization of what was
predicted by simulation is done through experiments. If you want you can just look at more
details at this page. Now what can you say about things here right, this is so the dark thing that
you see the spherical looking things. These are particles okay, about 1 micrometer in size. And
what can you say about the arrangement here right, it is very irregular right.

They are kind of, you know, distributed in space. There is no specific arrangement. The
arrangement is very much like what will happen if you take a liquid right. Now, you increase the
concentration of the particles, this is about, you know, if you go beyond 0.494 volume fraction,
there is more than 50% a little bit about 50% more. You clearly see that there are regions where
the crystalline arrangement.

Can you see that, what is marked that every particle has 6 neighbors. Very nice arrangement, but
of course there are you know regions, you know, like here, where it is still a fluid like right. So,
that is a fluid crystal coexistence. You go up in concentration, very periodic arrangement, every
particle has 6 neighbors. Example of a crystal right. And if you go further up in concentration
okay, you are at some concentration rates you essentially get again a disordered arrangement.

What is called as a glass okay, the microstructure is very much similar to, you know, I can
roughly say like glass, like fluid. But only thing the particle concentration is larger that is all

25
okay, the arrangement here and here, arrangement, here, and here, very much similar. The only
thing that is different is a concentration of the particle that glasses, glasses, a little larger than
what you see right.

So, therefore, all that has been done in this example is that they have taken the fluid and you go
on adding particles okay, If I systematically increase the concentration of particles, you see a
transition from a fluid state to a fluid crystal state to a crystalline state to a glass like state okay.
And because these objects are micrometer in size I can do this experiment under a microscope,
and I can observe these transitions live okay in-situ I can do it okay.

So, therefore, these are a few different examples from different sources to tell you that look,
there is an interest in studying colloids from lot of different backgrounds okay. And, and I do not
know what is motivating you guys from learning collides. But that you would have to, you know,
think a little bit and then you know take this course. So, you know, you kind of adopt some of
the principles that you are going to learn in this course in your, you know work.

26
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-02
Colloidal Dispersions, Terminology and Classification

(Refer Slide Time: 00:13)

Okay, so we will do a quick recap of what we have done in the yesterday’s class. So, we defined
what is a colloid, we just mentioned that it is any particle which has at least one linear dimension
in the size range between 1 nanometer to 1 micrometer. Then we went through several examples
in which I illustrated the motivation to study colloids, namely we looked at liposomes, which are
used as carriers, you know for transporting things in medicine and cosmetic industry.

We looked at ceramic processing, inspiration from nature way we looked at structural colors, and
super hydrophobic surfaces plus, I ended up talking about colloids as model atom to understand
the phase behavior in materials and how do we use colloids as a model system to look at such
things okay, that is what we have done so far.
(Refer Slide Time: 01:12)

27
So, what I will do today is hopefully these 3 topics okay. I have defined what is a colloid okay,
we are going to look at what is a colloidal dispersion to begin with, then we will briefly talk
about classification of colloids. And also we look at what is called as a stability of colloids or
stability of colloidal dispersions okay, that is the plan for this lecture.
(Refer Slide Time: 01:43)

So, colloidal dispersion is essentially defined as if you have colloids in a suspending medium
right. Therefore, now you have 2 components, you have colloid and you have suspending
medium. So, in the picture here. So, you have these red things. These are the colloidal particles
okay. And the blue thing is the suspending medium. Now we have, as I said more than 1 phase
now okay.

28
And these dispersions essentially consists of at least 2 phases, there could be more, I will be
looking at particles plus some other thing plus a fluid okay, there could be more than 2 as well
okay. And typically, these particles, you know, which are present in such medium they are what
are called as a dispersed phase okay, that is these red particles here, they are the dispersed phase
and the liquid medium or a fluid medium in which the particles exist.

It is what is called as a continuous medium okay. And of course, whenever you say a colloidal
dispersion, a dispersion is a homogeneous mixture. What I mean by homogeneous mixture is
that, imagine that I have this container. I take out a small sample volume, okay I take I go here
and I take up a small sample volume and find out what is like say the number of particles present
in that volume okay.

Now I go to another region, I take out the same volume of fluid okay, if the number of you
know, particles that you have in these 2 regions are essentially similar okay. You cannot say
exactly same, but if they are similar in number, then I can say, it is a homogeneous mixture,
right, that means there are no continuous medium rich, you know, regions and a dispersed phase
rich medium okay.

So, therefore, the particles are homogeneously dispersed throughout the medium okay. So,
therefore, you can say that colloids are actually homogeneous. If you look at them on a what is
called a macroscopic scale, okay when I say macroscopic scale. I could think about, like say
some small volume of, you know, the of course the dispersion as a whole, that is macroscopic.
And of course, if I take a few ml of fluids or a few microliters of fluids, it is hope, you know,
homogeneous macroscopically.

However, if I go to the microscopic scale or if I go to the length scale which is of the order of
particles are smaller than that, there is not actually homogeneous right because you have a solid
and the liquid, you know, are 2 different phases that exist right. Therefore, a colloidal dispersion
it is a homogeneous mixture of at least 2 phases, dispersed phase and a continuous phase. And of

29
course you can have cases where I may have more than 2 phases as well okay, so that is what is
called as a colloidal dispersion.
(Refer Slide Time: 04:57)

So in the previous example, okay I said that the dispersed phases a particle right. But the
dispersed phase can be of any different type okay. So, therefore, you can have different types of
dispersed phases. And, of course, different phases, different types of continuous phases well
right. So, if I have a continuous phase of gas okay and you may have liquid as dispersed phase
okay.

If you have a system like that okay then, you would have heard of a term called aerosol, do you
heard of this term right. So, aerosols essentially what will happen is, like, say, if you let say for
example fog, right, fog is you have water droplets which are condensed right, these are water
droplets condense which exist in ambient air okay, there is actually a dispersion of a liquid in
gas, right. So, similarly, I could have a solid in gas okay.

This could be you know the vehicular emissions you know the particulate matter that are emitted
by vehicles. So, if you have solid particles in these emissions okay, that dispersion ambient air
again is an example where the dispersed phase is solid and the continuous phase is a gas right.
So, for example smoke, dust, even pollen rain right, the particles that are you know of plant
origin, when they are in air.

30
That is an example of aerosol. Of course you could have continuous phases, as a liquid and the
dispersed phase could be either gas liquid or a solid okay, now in colloid course, mostly you are
going to look at this system right. In most of the course that I am going to teach okay, you want
to have a solid particles dispersed in a liquid. They are what are called as sol okay example of sol
are ink. If you take muddy water which is actually example of clay particles in water okay, or if
you look at paint.

For example right, so all these are examples of sols, in which the dispersed phase is a solid and
the continuous phase is a liquid, of course, there is a lot of interest in looking at emulsions and
foams right. So, emulsions are liquid in liquid dispersions and foams are gas in solid dispersions,
again you know there are several examples that are listed here. We will mostly not look at cases
where, you know, your continuous phases is solid okay.

There are other people who look at such systems, you know, for example, an example of a solid
emulsion okay, could be liquid and solid okay. For example, butter is an example of that okay, a
concrete, which is solid and in solid dispersion, right. So, but of course these things people in
other fields worry about for in classic colloids course, we will mostly look, at systems, where
your dispersed phase is either gas or liquid or solid okay. And the continuous phases is liquid
okay, that is what we are going to look at mostly.
(Refer Slide Time: 08:24)

31
Now, so you will, when you when you read up literature on colloids you will see that there are
several people who use a the term colloidal dispersions or you know, colloidal suspension. So, I
just want to make you know terminology clear. So, whenever people mentioned the term
dispersion. Typically, the term dispersion is used when the size of the dispersed phase is in the
colloidal size range.

That is 1 nanometer to 1 micrometer, so whenever somebody says a colloidal dispersion okay,

then that size range has to be in the colloidal size limit okay. And whenever somebody mentions
a suspension typically the size of the particles are larger than a micrometer okay. So, if I want to
compare dispersions and suspensions, I can say that because of the fact that the particles in the
dispersion are smaller in size.

They exhibit a better stability for sedimentation, that means the things in a dispersion are more
likely not to settle. Whereas, the suspension because the particles are larger than a micron, the
gravity may come into picture. If you have a container which is filled with particles as a function
of time in a suspension, you may see things settling at the bottom. However, dispersions may
exhibit you know better stability, against sedimentation okay.

And you should also know a little bit about true solutions or solutions which it actually refers to
a molecular mixture okay. So, you can think about you take water and put in the salt right, or you

32
take water and add a little bit of sugar right. So, in which case you what you get is a molecular
solution. In this solution so typically the size of the dissolved species okay, it is comparable to
the size of the dispersed phase itself or continuous phase itself, right.

That means, if I take salt, put it in water, if I look at you know the salt molecules right or Na +
and Cl - the size of that is very much comparable to the size of water molecules that you have in
the system right. So, whenever the size of the dispersed phase of the continuous phase is
comparable. That is when you refer to as what is called as a true solution okay. So, is the
distinction clear yeah, hmm, yeah. No, no.

So, see lets go back here, so the question is something like this, so he is asking a question. Look,
we mentioned that the dispersed phase has to be in the colloidal size range right, he is asking a
question is to what about the continuous phase, does it also have to be in the colloidal size range,
right. See, when you say the continuous phase, right. So, when you talk about, like say this case,
where we had let me just do something okay, okay.

Let’s look at this example, right, I am going to look at this example okay, where you have a
dispersion of a solid, gas liquid or solid in a liquid right. Now these are the dispersed species
right. This is a continuous phase okay, now the fact that the continuous phase is liquid. If you
take liquid, you know, which will have some molecules right if I take water or any organic
solvent or you know any fluid right, it will have some molecules, obviously the size of those
molecules would be less than a nanometer right.

So, whenever we talk about colloids right. So, what we are talking about is the size of the
dispersed phase okay. So, in this case continuous phase is liquid automatically the length scale or
size of the molecules are definitely even less smaller than a colloidal length scale okay. Is that
answer your question. Yeah, yeah, yeah, we will talk a little bit about that. Yeah, so his question
is, do they exhibit Brownian motion, so we will talk a little bit about that in the few lectures to
come.
(Refer Slide Time: 13:12)

33
Now we will move on to something called as classification of colloids. There are different ways
of classification. In fact, you can even think about this particular table also as a classification,
right, this is a classification based on the type of the dispersed phase and the continuous phase
right, you can also think about, you know in along those lines okay. Therefore, if you want to
classify colloids based on the type of the dispersed phase and the continuous phase.

I can, you know, classify them into several different classes like emulsions foams, sols, aerosols,
you know, things like that right. So, the other ways of looking at classification is based on the
nature of interaction between dispersed phase and the continuous phase okay. Again, we will talk
a little bit more about interactions in the coming lectures. For today, what we will do is when I
say interaction the only thing that I mean, is whether the dispersed phase.

And the continuous phase, like each other, or they do not like each other okay, so very loose
term okay. So, therefore, in colloids, what are called as lyophilic colloids okay. Lyophilic
colloids, lyo means liquid, philic means you know something that likes a liquid okay. So,
therefore, in such colloids the dispersed phase likes the dispersion medium okay. The dispersed
phase likes the dispersion medium.

So, in such colloids the dispersed phase does not precipitate out easily okay, if you put such
particles in water, it does not precipitate out or it does not settle down, or it does not aggregate

34
and form large clumps okay. And the sols are quite stable okay. An example is given something
here. I will tell you what exactly this vial is in a while. And what is called lyophobic colloids, the
dispersed phase has little affinity okay.

There may be some affinity towards the dispersion medium or it may not like it okay. And these
colloids they easily precipitate out of the solution. And therefore, such dispersions are typically
not stable okay. So, what you are looking at the vial 1, what we had done is we went to one of
our colleague’s lab we got CNT right, carbon nanotubes, which are commercially available.

We took, these particles, we put them in water okay, we try to mix them okay. As I said,
typically for mixing people use either sonication or high energy mixing or manual shaking okay
depending upon the kind of system that you are working with okay. So, therefore, these are pure
CNT okay, or CNT as received right in water okay, no matter what you do, you mix them and
leave it for a while, you can clearly see.

There is a phase separation right that there is a liquid here. That is water and then all the particles
are at the bottom okay. So, this is an example of what is called lyophobic colloids. I can also call
them as hydrophobic because in this case, the dispersion medium is water okay, they are
example of hydrophobic colloids which do not disperse in water and they would like to phase
separate okay.

Now, in this vial what was done is, we took exactly same particles, as received. And then we did
what is called as a surface functionalization okay. Again, the details are not important. The
surface functionalization is done as simple as taking these CNT particles put them in an acid
solution okay and then sonicated for some time. So, the idea is you have the CNT molecules and
on these molecules, you can form some acid groups okay, maybe COO - or something like that
okay.

Now we take such particles, put them in water and then they happily disperse okay. So,
therefore, whether a particle is a hydrophilic colloid or a hydrophobic colloid, or lyophilic
colloid or lyophobic colloid. It really does not depend on the type of the colloid that you are

35
working with okay, what it really matters what is the, the surface functionalization right that is
important.

And we will talk a little bit about that in the coming classes as well okay. So, therefore, in this
kind of classification based on the nature of interaction medium between the dispersed phase,
and the continuous phase. When I say the nature what I mean is, whether the particles likes the
dispersion medium or does not like, depending upon that in classify them as lyophilic colloid and
lyophobic collides okay, that is one.
(Refer Slide Time: 18:36)

So, we can also ahh classify colloids based on the types of particles, you know that are dispersed
okay, I shown this triangular diagram, you know, in the last class, so you have polymers here.
What is shown here is a colloid okay. Now, what can you say about this particular picture. What
can you say about this particular picture okay. So, while you guys think okay the third apex is
amphiphiles right.

What it actually tells you is that if you take any colloidal particle okay. This colloidal particle is
essentially made up of a lot of atoms right or the molecules. Whenever I say I have a gold
particle okay. Of course it is made up of several gold atoms okay right. Therefore, so if you have
such solid particles okay, which are dispersed in a fluid. It is what is called as a multimolecular

36
colloids, because each particle is made up of a large number of atoms or the molecules okay,
which are essentially dispersions of solid particles in a liquid okay.

Examples could be as I said right. If I have water with, say, gold particles or you know, the CNT,
you know that I talked about or any kind of solid particles in a fluid. That is an example of what
is called as a multimolecular colloids, second type of, you know, dispersed species the people
work with. It is what is called a macromolecular colloidal, which essentially are dispersions of
polymer in a solvent okay.

So, the polymer another name for polymer is macromolecule right, a large molecule, which is
essentially made up of a large number of repeating units right, that is what we talked about in
yesterday's class. And the third type of colloids what are called as association colloids. Any
thoughts. What, association colloids could be okay. The name already tells you something right
okay, they are formed, because of association okay.

So, these are dispersions of what are called as aggregates, which are formed, because of
association of molecules okay, any examples what is that surfactant molecules right. So, what
you do is if you have water right all of you know about what is called as a micellization. Where
you have heard of term right micellization. So, if you take water and I add surfactant molecules.

Surfactant molecules as I said are typically you know represented like a head and a tail okay, this
head is typically hydrophilic, tail is hydrophobic. Now, when you put such molecules in water,
what will happen is initially, you will have some free molecules okay. And because of the fact
that they are amphiphilic. Some of them may go to the interface. I go on adding more and more
surfactant right. More and more free molecules may form here.

And of course and more and more occupied the interface. When you add enough that the entire
interfaces completely occupied the surfactant molecules. Anything more that you add okay, it
will go and form, what are called as molecular aggregates, what are called as micelles right.
Typically, you know they represent micelles like this right okay, all the tail groups are held
together at some common location.

37
And you have head groups that face water, okay because you have water right. This is a
hydrophilic group and hydrophilic group, you know, is happy being in water right. So, therefore,
so these aggregates are formed, because of association of several number of molecules that come
together okay. So, that could happen if you are working with surfactants it could happen if you
are working with, you know, as I said, these block copolymers and things like that okay.

So, a lot of amphiphilic molecules, when you put it in either water or any other fluid they form
molecular aggregates, which are examples of what are called as association colloids okay. So,
therefore, depending upon the types of the particles of the dispersed phase, you can classify
colloids into multimolecular colloids, macromolecular colloids and association colloids okay. So,
that is, you can think about this as another way of classifying collides into different types.

38
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-03
Stability in Colloids

(Refer Slide Time: 00:14)

So, we will talk a little bit about stability of colloidal dispersions okay. So, what do you
understand if I say that the colloidal dispersions are stable, any thoughts, some thoughts. So, we
can think about a table stability has in 2 different ways right. As I mentioned already, I can think
about something called as stability against sedimentation right.

It means I have the same dispersion if I leave it for a while everything goes here right, they all
settle down. But typically, I said that such a thing will only happen if you are working with what
are called as colloidal or suspensions right okay. Typically, this will happen when you are
working with suspensions, where the particles are larger in size. And because you work with
very small particles, it is assumed that the gravity does not play a role okay.
(Refer Slide Time: 01:38)

39
However, what could happen is this right. What you are looking at is 2 pictures. Picture A, where
you have a stable colloidal dispersion really not defined what is stability. But I am saying that it
is stable because all the particles are in their individual state, okay they are having being in the
fluid okay. However, we know that because the particles are very, very small in size, they have a
high surface area right, which makes them prone to what is called as aggregation okay.

Again people used term called aggregation, coagulation okay and things like that okay. So, what
do you have here is an example where you have form, what is called as an aggregate, which
contains multiple particles okay. So, why do you think things will go from this state to this state,
or can you think about ways by which things can go from this to this state okay. So, the answer
that I get is that if the interaction between the 2 particles okay is more favorable than the
interaction between the particle and the fluid okay.

Yeah so you can think about along those lines. Now, okay we can again spend a little bit of time
talking about interactions in the next few lectures. So, what will happen is this right. So, if you
have particles in a fluid, you know that these particles are not stationary right. They are being
continuously hit by the solvent molecules in which the particles are dispersed. That means for
every particle there are a lot of solvent molecules which are hitting okay.

40
They are hitting everywhere okay, because of which the particles can move around okay. So,
whenever you take a dispersion okay and if you say that I have this dispersion at a temperature T
okay, so the energy that the particles have okay. It is given by what is called as kBT or the
thermal energy okay. This kB is what is called a Boltzmann constant okay, which has a value of
1.38 × 10 - 23 joules / Kelvin okay.

That multiplied by the temperature will give you a unit joule which is a unit of energy right.
Therefore, the moment you have any fluid or a colloidal dispersion at some temperature T
invariably all the molecules, as well as the particles in the fluid have this terminology kBT okay.
Now, you can ask a question as to what now I am drawing these particles very far apart right.
The sufficiently far apart what can bring the particles close to each other with this thermal energy
right.

The thermal fluctuation they are moving around okay when they are moving around they could
approach another particle okay, when they approach another particles the particles may either
attract or repel okay that depends on the type of the particle that you are trying to deal with okay.
(Refer Slide Time: 05:54)

Now here is an example okay where. So, what do you have is some energy. In this case it is
called as its interaction energy okay or also called as a free energy okay, that is this and you will
see in colloids literature that whenever people talk about interaction energy, you always scale

41
with kBT okay. The reason is this right, when you do interaction energy calculations I said that
the Boltzmann constant is 10 power - 23 right.

Now, if I multiply that by, you know like, say if the temperature is 300 right. This energy will be
of the order of 10 - 21 right. So, when you do calculations, when you get numbers which are 10 - 21
joules. So, you may say that look you know is too low, you know, reading is not important okay.
So, just to get a feel for the numbers that you get out of such calculations, you typically always
scale the interaction energy with thermal energy.

So, that I can compare and say, hey, the interaction energy that we are obtaining, it is one times
kBT, 2 times kBT, 10 times kBT something like that okay. Therefore, you will always see that
people who do interaction energy calculation they always scale the interaction energy with the
thermal energy. So, what is plotted here is this interaction energy okay, as a function of
separation distance.

That is plotted on the x axis okay. So, the way to think about is interaction energy is it is the
energy with which the particles attract or repel given whatever distance they are at okay. So, if
you look at this, lets trace this plot okay, that is your x axis okay. So, the interaction energy goes
something like that, you know, right. So, people typically talk about this minima that you have is
what is called as a primary minima okay or also called as a global minima okay.

This is what is called as a secondary minima okay. Now, what you have here is a, a barrier okay.
So, in order for the particles to approach and reach this primary minima the global minima, they
have to cross this energy barrier okay. Now, if the energy barrier that you have okay, if it is of
the order of kBT okay because the particles, already have a thermal energy and that thermal
energy in fact is kBT.

If the energy barrier is also of the order of kBT, what can happen is, these particles can easily
cross the energy barrier. And then they can come and reach this global minima state where the
particles can form aggregates like this okay. Now, once the particles form such aggregates,

42
which are essentially at a very small separation distance right, this is delta, this is a separation
distance okay, that corresponds to, you know, this global minima okay.

So, once they reach that place they are aggregated, it is very difficult to separate them out okay,
you can do sonication. Of course this again depends on how, what is this you know the minima is
right, what is the location of the minima, the location of the minima is really, really large. That
means, it is practically impossible to separate these particles once they aggregate.

However, if you know this minima is of the order of maybe few times kBT, then sonication or
anything you know may be able to rip them apart okay. So, therefore, so if you have cases where
the energy scale associated with this barrier is of the order of thermal energy. Such dispersions
are said to be what is called as kinetically unstable, because the kinetic energy that the particle
posses, because of the thermal energy.

It is good enough to overcome the barrier and then make it go from this state to this state, okay
such, you know, a process or such a you know case is referred to as a case where you have
dispersions, which are kinetically unstable okay. On the other hand, you could have a case where
the energy okay, which corresponds to this barrier, it could be much, much larger than kBT okay,
when I say much, much larger than kBT, it could be, you know, 100 times kBT or you know,
several orders of magnitude larger than kBT okay.

Such dispersions are set to be kinetically stable okay, that means there is an energy barrier
associated with the particles being in a dispersed state and a destabilized state okay, if the height
of this energy barrier is of the order of kBT, then the dispersions are kinetically unstable. If the
height of this energy barrier is much, much larger than kBT then such dispersions are kinetically
stable okay.

Yeah so any questions with this okay. Now, one can ask it yeah, yeah. Yes. Yeah, so first stable
collides also everything depends on this energy, right. So, if I have a stable dispersion okay, I
could have. So, again stability is a very relative term right. When I say stable you know I could
have a dispersion of particles okay, homogeneous dispersion.

43
You know it may be stable for a day. You know, but if you wait for a few days you know, things
may, you know coagulate okay, so everything depends on so what will happen is this right. So,
the particles are moving around because of Brownian motion, they approach each other. Now, if
okay let me put it this way. So, what you can do is I can play with this energy barrier right, I can
play with this energy barrier.

Now say that I have dispersion where this energy barrier is like say 1.5 kBT okay. Now, you
could ask a question as to look something where the energy barrier is 1.5 kBT, is it highly stable.
No right because you know, so, of course, if you look at one times kBT and 1.5 times they are
comparable okay. Of course, if I talk about 1 kBT and 100 kBT. There are 2 orders of magnitude
larger therefore definitely such colloids will exhibit a better stability okay. So, I will come back
and answer you a question.
(Refer Slide Time: 13:55)

Before that I want to talk a little bit about something called as a thermodynamic stability okay.
So, these are dispersions, which exhibit, what is called as ultra long stability. Because such a
colloidal dispersions are formed, because of what is called as a thermodynamically favored
reduction in the free energy of their formation okay. I talked about the formation of micelles
right. So when you start with, you know fluid and start adding surfactants.

44
I said that they form micelles right, the formation of micelles is a process where there is a overall
reduction in the free energy of the entire system. Therefore, okay such association colloids in
water. They do exhibit ultra-long stability that means I take a dispersion of micelles, keep it for
years and years. You know if you, if things do not change if the temperature does not change. If
the solution conditions do not change, they continue to exist as micelles okay.

Another example is what is called as a micro emulsions okay, which are typically formed when
you have oil, water and surfactant. What you are looking at is some example from our lab. This
is a pure diesel, you know, a fuel that people use right. And then, this is diesel micro emulsion.
This has diesel plus water plus a surfactant called AOT okay. If you look, macroscopically you
do not see anything right.

You know it is very difficult to say that look I have water in there okay, it has some amount of
water and some surfactant but it looks very transparent okay. That is because it contains very
tiny reverse micelles okay. So, the micelles are you know something that I said, right, reverse
micelles will have water inside, add an oil outside and the surfactant molecules are arranged
something like this.

Now, if we look at the size of the dispersed phase okay, that is these micelles reverse micelles in
water in oil, you look at the size right, this is measured as a function of time 180 days that is 6
months okay, tactically there is almost no change okay. However, if you take a dispersion of
kinetically stable colloids okay. You could also have a case where there are kinetically stable
colloids, which are available in the market, which do exhibit a shelf life of years if you want
okay.

But however, I cannot say that such colloids are infinitely stable or they are stable forever okay,
because, you know, at some point, you know the thermal energy is going to overtake and they
are going to aggregate.
(Refer Slide Time: 17:05)

45
So, these are 2 examples of what are called as thermodynamically stable colloids, the other
examples of thermodynamically stable colloids are solutions of polymers okay. I can take water,
put a polymer like PVA or polyvinyl alcohol, you know make a solution you know keep it for
you know we do not see any changes to that size or no aggregates, no aggregation, right. So,
final example of thermodynamic stable state one to achieve is cases where you work with charge
stabilized colloids.

Now I said that when I say charge stabilized colloids you should imagine that I have a
dispersion, say the continuous phase is water and a dispersed phase is particles and the particles
have some charge okay. That is a charge stabilize dispersion okay. In such a case, what you will
have is, there is a high energy barrier for them to aggregate and they are actually an example of
kinetically stable colloids.

Because they have an energy barrier much larger than kBT for their aggregation okay, however
when you have a large collection of such particles in the fluid, what will happen is they exhibit a
crystal state okay. I was showing you some images, the other day right. So, these particles they
formed what is called a crystalline state where, you know, they are closely packed periodic
arrangement okay.

46
And such crystals again are an example of thermodynamically stable states, because again, their
formation leads to reduction in their free energy okay. So, that is something about the stability,
maybe I will stop here. And then we will look a little bit about some properties of colloidal
dispersion in the next class okay. Yeah, Thanks.

47
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-04
Source, Synthesis and Characterisation of Colloids

(Refer Slide Time: 00:14)

Ok, so this is a class 3, so this is what we have done so far ok. We looked at the definition of
colloids, motivations to study them, definition of colloid dispersions, classification and the
stability ok.
(Refer Slide Time: 00:33)

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So, what we will do in today's lecture is hopefully 2 things one is to look at source of colloidal
particles. That is to tell you a little bit about where do they come from you know and then
followed by that we will talk a little bit about a characterization of colloidal dispersions, I have a
long list of things. So, I will try to introduce each of these terms to begin with and then I will tell
you a little bit about you know the definition.

And what are the typical methods that people use for finding these you know physical and
chemical properties of colloids ok. And most of the content that I am going to do is taken from
Coulson and Richardson's chemical engineering series, ok. That is the particulate systems and
particle technology chapter 13, ok.
(Refer Slide Time: 01:23)

49
So, any thoughts about the source of, so where do the colloidal particles come from ok. The first
topic, ok.
(Refer Slide Time: 01:45)

So, the answer for that would be I mean it could come from any process right there could be an
industrial process, you know you could have may be things like say size reduction for example,
you have larger particles and you are trying to break them into smaller sizes. In that process you
know you could get particles which are again in this you know colloidal length scale right, you
could you know.

50
That could happen through industrial processes which could also come from vehicle emissions
you know the lot of stuff that comes out you know from the vehicles. I give an example of
burning of candles right the other lecture ok. So, it could come from burning of things like that I
can add one more to the list d you could have from natural resources right, ok. Like I was talking
about this bacteria, virus, ok or you know the latex, rubber latex and things like that right. So,
you could also have you know particles from any source ok.
(Refer Slide Time: 02:55)

But however as I showed right the particles that come when you burn candle, I had shown a
picture in which I said that you know they are of course each particle is colloidal length scale.
But then you know there were very complex right ok, the particles that are produced in any of
these processes are they are they have a very complex shape and structure ok right.
(Refer Slide Time: 03:27)

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So, that is because their formation occurs in not so well controlled environment ok. Because
when you burn you know candle right, so you have oxygen you have you know. So, essentially
the environment around the candle burning process is not very well controlled, ok there could be
fluctuations in temperature and stuff like that, right. That is what leads to the formation of such
complex particles of different you know structure, sizes and shapes and things like that ok.
(Refer Slide Time: 04:09)

So, of course you know there is a lot of interest in studying such particles right because one
could be interested in looking if you look at industrial processes right. So, one could be
interested look at to assess the health hazard right. So, that you know one could be interested to

52
ask a question as to what will happen if there are fine particles that are producing an industrial
process and then if we inhale them and things like that, right.

So, the particles that are produced by each of these processes are important, ok. There are people
who were trying to look at health hazards of such things, people who are trying to look at fate
and transport of aerosols. For example you know how do these particulate matter that are emitted
because of you know vehicular emission you know how do they, how are they carried around
you know how are they you know present in the environment stuff like that.

And of course people have also used particles that come from the sources as I was telling to
design what are called super hydrophobic surfaces and so on and so forth, right. So, of course
particles from such origin are important, there is a interest to look at these systems. But in colloid
science what people are looking at are what are called as model particles, ok, what are mean by
model particles, is that these are particles of well defined size, shape and surface properties, ok.

So, if you really want to investigate fundamentally a particular phenomena in colloidal science,
what you do is, you go to these model particles which essentially are particles of well defined
size, shape and surface properties, ok, so that is the need ok.
(Refer Slide Time: 06:08)

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And again how do you get these particles, actually a lot of particles are commercially available
you know you do not have to worry about synthesizing them. They are commercially available
what you are given is an example of 4 different types of particles A and B, these are actually
silica particles ok. And if you look at the again the length scale, they are you know, some 100
nanometer, so this is about 100 nanometer right, it is 100 nanometer.

So, if you look at these particles there may be about 30 nanometer in dimension and these are
about 50 nanometer in dimension ok. They are kind of sold and by a commercial name called
Ludox particles, you can buy them, they come in liters and liters not very expensive. And these
two are examples of silica particles SiO2 and this is a polystyrene ok and as you can see they are
very homogeneous, uniform you know exactly similar size ok.

So, you can buy them and then design experiments to study whatever colloidal phenomena that
you would like to ok. So, that is one source of you know a model particles which people have
been using for several years to study in a lot of interesting phenomena and colloids.
(Refer Slide Time: 07:34)

Of course, you can synthesize them in the lab, ok, so these are some examples of synthesis from
our lab. So, these are all you know synthesized by different people in the lab by well defined
procedures are available in the literature, ok, this is not invented by us, so things are already

54
existing. So, all that you have to do is follow these procedures and then know systematically and
then you know control condition.

And you will be able to produce you know the particles of the spherical in shape or elliptical in
shape these 2 right. So, the first set of particles, these are example of again silica particles which
are produced by a technique called Stober synthesis, ok. Again, this is the name of the scientist
who found this technique for making these particles.
(Refer Slide Time: 08:37)

Now, so this particular Stober synthesis it is a very simple reaction, it will involve water, some
ammonia, ethyl alcohol and a reagent called TEOS, that is tetraethyl orthosilicate, ok that is a
source of your Si in the particles ok. Ultimately I am going to get SiO2 particles ok. And just by
playing with the concentration of you know these reagents I can actually produce particles of
very different sizes, ok.

And there is a lot of work that has gone in you know in the development of this synthesis
procedure. It actually involves 2 reactions, a hydrolysis reaction and a condensation reactions, if
you want to more details you can refer to the literature. But what people have done is they have
come up with the correlations that I can use for designing particles of a particular size.

55
So, this Dp is a size of the particle that I am generating by this Stober synthesis. And you know I
can control that by so it depends on the concentration of the water that I am using ok, that is
these 2 right. And of course the parameters A and B which in turn depend on the concentration
of the TEOS ammonia, you know and a few other things right. So, therefore if you want a
particle of a particular size, what I can do is I can choose my reagents in appropriate proportions.

And then actually designed particles of different sizes ok, so that is about Stober synthesis. These
elliptical particles that I was talking they are obtained by a again a very simple technique called
force hydrolysis ok. Again it is a very simple chemical reaction which involves again iron salt
you know water you know and a few other reagents, ok. And if you are interested again more
you can read up literature.

So, I do not want you guys to know the procedure for synthesis but I just want to tell you that
look there are things available in the literature which you can read up and then follow up. And
then essentially make model colloids of your choice in the laboratory ok. And the last one is by a
simple technique which anybody could do in the lab is called is nano precipitation ok.
(Refer Slide Time: 11:26)

56
It is a very simple process ok.
(Refer Slide Time: 11:29)

All that involves is that I take a solution ok and this solution contains it is the solution of a
polymer, it could be polystyrene, it could be you know PMMA or you know PVA any polymer,
ok it does not matter ok. And that is dissolved in a solvent, so that I get a homogeneous solution
of this polymer in the solvent. Now what I do is I take this and I add a drop of that into another
container which has another solvent, another fluid which is a non solvent for the polymer ok.

So, initially the polymer is dissolved in a what is called as a good solvent that means, this is all
one in which the polymer dissolves completely, I am able to get a homogeneous solution. And I
take that solution and added to into a fluid ok and the fluid is a non solvent for polystyrene, that
means this polymer does not like to be in that solvent ok.
(Refer Slide Time: 12:41)

57
So, as soon as you do that and then if you stir it, you essentially have generation of spherical
particles ok. That is because the polymer does not want to be in water and it precipitates out and
it precipitates out as spherical particles ok. Again there is lot of literature can read up a little bit
about it ok.
(Refer Slide Time: 13:02)

So, what we are done in our lab is to use this polystyrene waste ok, this is what is called as EPS
expanded polystyrene that comes as a packing material, right. For a lot of electronics that you
buy, ok you can take that and you can dissolve that into solvent such as THF tetrahydrofuran.
Acetone, Lutidine does not matter any solvent in which the polymer dissolves, you do that, ok
you get a homogeneous solution and simply add that to water.

58
And you can actually precipitate these particles, ok and I can control the of course I cannot make
particles of single size. As you can see, there are different sizes ok there are ways by which I can
control that as well. But I can play with the polymer concentration ok, I can play with the amount
of water that I am using for precipitation and I can play with the mixing speed right. So, what has
done here is when I added I am mixing it rigorously right I can you know, play with the mixing
speed. And thereby I can actually control you know the size of the part that I am able to generate
ok.
(Refer Slide Time: 14:21)

So, this is again some you know information about you know the source of particles where do we
get them from you know and how to synthesize in the lab right. Following that, we will move
onto defining or characterizing colloidal dispersion ok. So, now the moment I have a colloidal
dispersion ok, that is dispersion of these particles in a fluid right. Now I may have to worry about
several different physical, chemical or physicochemical properties of both the particles as well as
the dispersion right.

So, if you talk about the particles themselves ok one may be interested to know what is the size
of the particle, ok, what is it is, shape, right And of course the density of the particle is important
you know it is a useful quantity that you should know for several different things as we will see
little later ok.

59
(Refer Slide Time: 15:36)

Specific surface area, ok which is essentially defined as the surface area of the particle divided
by mass of the particle, right. That is your ok specific surface area ok or if you want to call it as
surface area you know specific or something like that ok. So, that is the surface area of the
particle divided by the mass of the particle and it typically will have units of meter square per kg
or you know meter square per gram right ok.

And this quantity is actually useful if people are trying to use colloidal particles for adsorption
studies and things like that right where the surface area becomes important ok. So, one may also
be interested to look at the properties of the dispersion itself ok. So, for example one maybe
interested in look at the density of the dispersion ok. One could also be interested look at what is
called as a volume fraction of particles in the dispersion right, ok which is defined as phi.

Typically people refer to it as phi ok is volume of particles in the dispersion divided by the total
volume of the dispersion right ok, that is how it is defined, ok. The lower this number is that
means the concentration of particles in your dispersion is smaller ok and higher this number is
the concentration of the particles in your dispersion is higher, right.
(Refer Slide Time: 17:30)

60
Now have you heard of this term grafting density, somebody heard of this term no, ok. If you
look at the images that I showed of these particles, right, ok. These are all solid particles right. In
some cases, people work with particles which looks something like this ok. This is your solid
particle ok and on the surface they can put some long chain molecules ok. These long chain
molecules are can be put by 2 different ways one is by doing a chemical reaction.

If I know what is the surface chemistry of the particle, if I know what is the surface of the
particle is made up of, I can take a long chain molecule, I can design a reaction. So that these
chains kind of get attached onto the surface ok there are you know ways of doing that, ok. Or
what I can do is I can have a particle a solid particle and I can add in some long chain molecules
which can physically adsorb you know it is not a chemical reaction, ok.

However there is a physical interaction maybe you could think about maybe an attraction or you
know something like that. Because of which you will invariably have particles which have some
molecules on the surface, ok. When you have cases like that, that means when you have a
chemical modification to the surface to give no chemical grafting, ok or a physical grafting
which is more because of the adsorption of you know some molecules on the surface.

You can actually define what is called as a grafting density which essentially is defined as the
number of molecules of these number of molecules that you have put on the surface divided by

61
the surface area ok. This is number of molecules ok maybe per particle, that means if I have a
particle ok and if I say that look you know I have put in I do not know some 10 chains ok. And if
I say that you know the particle surface area is like say for example say 100 micro meter square
ok this is example.

Then you grafting density is going to be 10 divided by 100 micro meter square right. So,
typically this will have units of you know some per you know micro meter square or meter
square or something like that, right. So, that is your grafting density, we will tell you a little bit
about why this you know chemical grafting or physical adsorption is important as we go along.

But at this point what is important is that there are particles which may have some long chain
molecules on the surface and one would be interested to know what is the number of molecules
on the surface of these particles. And that is characterized by a quantity which is what is called
as a grafting density ok.
(Refer Slide Time: 21:22)

Now that I have mentioned what is grafting density, you should be able to guess what is surface
charge density right, what do you mean by any thoughts, surface charge density. So, the surface
charge density as the name itself says become important if you have particles which have
charges right, I could have a negatively charged particle you know or I could have a positively
charged particle ok.

62
If I know the number of charges on the particle surface ok, typically surface charge density is
will have units of Coulumb per meter square right. And that you know the so this essentially
comes from the total charge on the particle surface, ok. If I have like say 100 like say charges for
example say that you know I have a particle surface where my surface group COO - ok.

If you have 100 such groups, ok, then the charge that is going to be on the particle surface is
going to be 100 times the charge of the electron, right. That is your total charge on the particle
surface divided by again the surface area of the particle will tell you what is the surface charge
density, ok.
(Refer Slide Time: 23:12)

So, before we talk a little bit about you know what is surface charge density, what I will do is I
will tell you a little bit about the origin of surface charge. So, where do this charge on the particle
surface come from ok. There are different mechanisms that by which the particles can get as
charged. One is by what is called as dissociation of charged or they say dissociation of surface
groups.

So, what I mean by this is that see the synthesis chemistry right you know the people who do
colloidal particle synthesis. The chemistry is so advanced that you know you can make particles
with well defined charged groups on the surface you know what I can do is. If I may ask

63
somebody they will be able to give me a polystyrene particle which has COOH groups on the
surface.

They will be able to give me polystyrene particles with maybe SO3H group on the surface ok.
Now, what happens when you have such particles in water, the moment I put such particles in
water, what will happen is. These, the groups that you have it dissociate and it will leave out H+
ions in solution ok. So, therefore that happens for all the groups that are there on the surface
ultimately you will end up with a particle that has a charge.

Therefore the dissociation of surface groups is one of the mechanisms by which the particles can
acquire charge, ok that is one mechanism.
(Refer Slide Time: 25:13)

Now, the second mechanism that you can think of one of the simplest ways is dissociation of
surface group right. Any other examples that you can think of or any other means by which the
particles can get charged. Polarization then you are bringing what is it, it is a polar molecule you
are saying that the particles themselves are made up of something that is polar in nature. See,
when we talk about charge right, you are talking about the charge on the surface, right.

So, I mean polarization of course will lead to you know the regions where there is more charge,
regions where they are less charged ok. Typically we talk about something like that when it

64
comes to molecules right. When it comes to particles you know itself you know, I do not think
people think about this polarization as a. So, what people can do is there are cases by which, so
this is you know shifting of electron crowd’s right.

But there are cases where I can of course polarize the particle but if I put them in electric field
and things like that, you can do that, ok. But you know in pure solutions, there are other
mechanisms by which the particles can acquire charge, ok. So, the second example I am going to
give you is by if I have say particles right. Now say these are not functionalized particles, they
are homogeneously smooth right.

Then what you do is I can add different things to this fluid right, I have a colloidal dispersion ok.
I can add a charged polymer ok or I can add a charged surfactant or I could add in some reagents
which have some positive or negative ions, ok. So, what happens is in such a case all these things
that I have added, ok they can go and adsorb onto the particle surface. And if I have you know
charged polymer, so charged polymer I am going to represent it something like this, it is a long
chain molecule.

But it may have some surface groups, right because it is a charged things, it has charges.
Therefore I can invariably end up with a particle that has adsorbed macromolecules, adsorbed
poly electrolytes which can give rise to charge on the particle. Similarly I could have a case
where I have a particle and a surfactant that I add you know it can have a charge groups you
know either positive or negative ok.

Thereby the particles can acquire charge because of either the adsorption of polymers charged
polymers or adsorption of surfactant or adsorption of charged ions itself ok. There could be a
physisorption or chemisorption adsorption of charges onto the particle surface ok. And ions onto
the particle surface and that could lead to the charges on the particle surface, ok. So, therefore
people think about these 4 different mechanisms by which the particles can acquire charge. And
once you are dealing with charged particles in a fluid, therefore it makes sense to characterize
them for surface charge density ok.
(Refer Slide Time: 29:12)

65
So, I have some examples listed here again whatever I wrote up in a schematic form, this is
example where you know you have a group which is SO3 OSO3 - ok, that gives negative charge.
And you have a NH2 NH + group here right that gives a positive charge on the particle surface.
This is a case where there is adsorption of you know H + or OH - ions which can make the
particle positive or negatively charged ok.

Or the surfactant molecules or adsorb or the charge polymers that adsorb ok. So, you can you
know think about these different ways by which the particles can acquire a charge ok.
(Refer Slide Time: 30:04)

66
What can you say about this quantity, surface heterogeneity, have you thought of this, surface
heterogeneity, some other. So, she says there is some of the surface or the particles, some other
ok, so she is saying that look I have a particle ok. And she says that some of the surface you
know may have positive charges ok, some of the surface may have negative charges ok, yeah.
So, this is an example of a surface heterogeneity but in this case this is an example of what is
called as a surface charge heterogeneity right.

So, therefore surface heterogeneity can be of 2 types, one is physical surface heterogeneity or it
could be chemical surface heterogeneity, ok. The physical surface heterogeneity refers to cases
where I may not have a perfectly smooth surface, I could have a particle where the things are
rough ok, the surface is not atomically smooth ok. It has some undulations in the surface, there
could be hills and valleys, right.

And there is an example where you have a physical heterogeneity or you could have a case like
this where I have patches on the particle surface where things are positively charged. And
patches were negatively charged or you could also have a case where I can have a patch which is
hydrophilic, I could have a patch which is hydrophobic right, these are examples of cases where
you can think about a chemical heterogeneity and one also needs to characterize them for this ok.

So, this is you know the last point is a bit more complex to characterize such things. Of course
there are indications in the literature as to how do we characterize such things especially the
chemical heterogeneity. The physical heterogeneity, the surface roughness you know how to do
it, ok but however the chemical heterogeneity is still you know something that people are still
trying to study, ok, yeah right yeah, yeah maybe I will talk a little bit about that maybe in the
next class ok.

Yeah you can think about them as so what he is trying to talk about is that look I can have a
particle ok where some part of the surface has some chemistry ok and other part has some other
chemistry ok. Of course that will come into case where you have a broadly right it can say that
you know this is a particle which has a surface heterogeneity, in this case it is a chemical
heterogeneity, right.

67
So, yeah, you can think about particles like that as well. So, any questions so far all these terms
are they clear. The particle size, shape, density, specific surface area, grafting density, charge
density and heterogeneity.
(Refer Slide Time: 33:59)

Now let us so I would not spend a lot of time on this but maybe one class or maybe one and a
half class ok. So, first characterizing particles for size and shape ok, so how do we do that. So, I
somebody has given me a colloidal dispersion ok and then they will ask you to find out what is
the size of the particle or shape of the particle that you have in the dispersion ok, what do we do,
what is that.

She says dynamic light scattering ok, microscopy techniques anything else microscopy
technique, dynamic light scattering technique, anything else ok. There are also techniques called
static light scattering right ok. Again in microscopy you have optical microscopy also electron
microscopy, right. Again electron microscopy you have scanning electron microscopy and
transmission electron microscopy right.

But what technique that you use for measuring the particle size ok, depends and if you have any
a priori knowledge about a typical sizing that you may have in the dispersion if you know that.
Then you can choose one of the techniques appropriately ok, that means you know if the

68
particles are a few microns in size then I would go for optical microscopy ok. If typically
dynamic light scattering technique you know of course if you look at the manufacturer's
specification they say you can measure sizes from 1 nanometer to you know close to about ok 8
to 10 micrometers, ok.

And if you look at static light scattering technique, you can measure sizes all the way from 10
nanometer to you know a few millimeters itself ok, very large size range. Of course electron
microscopy is you know suited especially transmission electron microscopy suited when you are
looking at particles which are nanometer length scale, right. So, we would not go into the details
of all these techniques, I just want to mention that there are techniques available in the literature.
And you should be able to characterize particles for size as well as shape, ok.
(Refer Slide Time: 37:23)

Now, so what you are looking at is a schematic where what can you say about this schematic.
These are particles of they look very same size right, they look like the diameter of each of the
particles that you have looks exactly the same, right.
(Refer Slide Time: 37:50)

69
And of course you can make such particles in the lab, ok. And so such particles where the
particles are of identical size, they are refer to what is called as mono-disperse particles ok. That
means, so all these particles are of exactly same size ok. But however I showed you this example
of a nano precipitation right. If you looked at the microscopy image carefully these particles
were of different sizes, right.
(Refer Slide Time: 38:34)

Of course, there are other you know examples, so this is done by a again a Stober synthesis
which can give very uniform particles like this. However if your reactions are not controlled, if
you are not careful in doing your synthesis you know what will happen is you will end up with
the particles like this ok, where you have particles of very different sizes ok. When you have

70
particles of this kind ok such a dispersions we can say that they are what are called as
polydisperse.

That means you have particles of different sizes that exist in your dispersion ok. Now, if you
look at the first case right mono-disperse, if I want to completely characterize you know the
particles for shape, I can just say that look you know there are spherical particles and then there
are of same size and that is my size ok, I can characterize them like that, ok. However when you
have you know polydisperse samples you talk about what is called as a mean size ok.

And of course you also talk about what is called as a standard deviation right, how much does
this mean size ok deviate, right.
(Refer Slide Time: 40:09)

So, again what people do is, you can get microscopy images like this ok, I have there are
methods by which I can find out the size of each particles that I have in the sample ok. And
typically you do that for a large population of particles 50 not enough, 100 not enough, 1000 not
enough ok. So, when I say that I just want to go back to these techniques right, I said that people
do dynamic light scattering and static light scattering and these microscopy techniques, right.

One of the a very important difference between the light scattering techniques and microscopy
techniques is that when you do your size analysis you are focusing on a very small region of your

71
sample in microscopy ok. That means you look at this right this is an image from microscopy,
right all you have is you know maybe 20, 30 particles, right. Of course I can play with a
magnification I can get large number of particles in this window.

However when you do analysis people typically limit the number of particle that they analyze to
maybe 50, 100, 200 something like that ok. However when you look at light scattering
techniques, what happens is that you have a sample ok in which there are particles ok. And you
have a beam of light ok that falls onto the sample ok. And then what you do is, it basically is
when you say a beam of light has some dimension, right.

People talk about you know 0.1 millimeter beam and things like that ok. Now people talk about
what is called as a scattering volume ok. So, in that volume even if I take a very dilute dispersion
like say 0.001% particles. The number of particle that you are going to have is if you say like say
silica particles of 50 nanometer diameters ok. You can roughly calculate and show that the
number of particles could be of the order of 10 power 15 or 10 power 13 some numbers like that.

That means, so the number of the size that you obtain by light scattering it is an average of a
large of size that you know the scattering that occurs because of a large number of particle that
are in that volume ok. Therefore the sizes that one report from light scattering technique would
are more representative of the sample that you dealing with than the techniques in which you use
microscopy, ok.

So, that is ok, so we will come back to that, now if you have a way of you know finding out the
size of the particles, then maybe I will stop here, ok. So, I think this is about time, so I just stop
here, so what we will do is we will continue with the characterization in the next class, hopefully
I will try and finish up the characterization by the next lecture itself, yeah, good, thanks.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-05
Characterisation of Colloidal Particles-I

(Refer Slide Time: 00:14)

Ok, so, this is a class 4. So, we will continue with the characterization of colloidal dispersions.
We briefly started looking at how to characterize particle size and shape.
(Refer Slide Time: 00:28)

73
I had mentioned that you know there are several techniques available for characterizing particles,
light scattering based and microscopy based in which we briefly discussed about, you know
dynamic light scattering, static light scattering. And in terms of microscopy, there is optical
microscopy, electron microscopy. So, all these techniques can be used. And what you are
looking at the pictures here are cases where you have something called as a monodisperse
particles.

That means particles are all of identical size, right. But that need not be the case always because
whenever you do synthesis you will always end up with something like this.
(Refer Slide Time: 01:09)

You may have a distribution of sizes, this is what is called us polydisperse, right ok. So, when
you have monodisperse particles, the only parameter that you have to characterize the particles
for is in terms of the physical dimension just the size, right. If it is a spherical particles, you just
say diameter of the particle or the radius of the particle that is good enough ok.
(Refer Slide Time: 01:41)

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However, when you have a polydisperse particle, so what you typically do is you kind of do
something like this, ok. So, what you are seeing is an example where what is been done and so,
they have considered 400 spherical particles. And then size has been measured by could be
microscopy, right. So, you have pictures of particles in the picture which has particles of
different sizes.

And then what you do is you categorize these particles into classes, ok, this class essentially
means this is a, what is called the class boundary out of all the particle that I have. So, I am going
to put them into classes of you know size ranging from in this case 0 to 0.1 micrometer ok and
the second class is 0.1 to 0.2 like that, right. So, therefore, you out of all the sizes that you have
measured, you classify them into different bins.

If you want to call them as all different classes of some size range, right. And corresponding to
that class, or a bin you are going to have average size, right. So, therefore, if 0 and 0.1 is your
bin, ok then your average size is going to be 0.05 micrometer right, so you do that and then of
course you tabulate what is the number of particles that you have in each of these classes, ok.
And I can actually get what is the fraction of total number of particles in each of these things,
right.

75
If my total number is say 400, so 3 by 400 will give you this number, ok and of course, you can
look at cumulative numbers and things like that, ok, So, now you will always have a question as
to how many classes that I should divide the entire particle size distribution into, I think what
you should do is, you should not go for 2 fewer classes you know. For example, I cannot have 2
classes.

I cannot say that, hey, look, I want to go from 0 to 0.6 micrometer is one class and then 0.6 to 1.2
micrometer you know what you have is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 classes. But you know,
I cannot say I will only take 2 classes, right. Because if you do that, then you know, you are
going to end up with not a good representation of the size distribution that you have, ok. On the
other hand, you should also not have too many classes because you know what it will do is it will
increase the calculation that you are going to do, right.

You know is it really worth dividing them into 10 classes or maybe 20 classes, 30 classes, ok.
Then we would end up spending a lot of time for not so much improvement in the accuracy with
which you can get the size data, ok. So, therefore there is an optimum number that one has to
worry about, ok, that you should think a little bit you know when you are going to do these
things, ok.
(Refer Slide Time: 04:26)

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And typically when you get data like this, you represent the size distribution in a what is called is
a histogram, ok or a bar chart, right. And that is your first class, second class, ok all these vertical
lines that you see these are the average size that corresponds to each of these classes therefore
you get a distribution like this ok. And once you have a distribution like this, so from this what
you can do is I can get what is the average size.

And I can also get what is the standard deviation ok, that is the best way to represent your data
when you have polydisperse sample. And once you have this is what is called as a discrete
distribution, right. Because you are depending upon the number of class I am going to have, ok, I
can have a few of these bars or a large number of them, ok, that still is a discrete representation
of the data that you have obtained from your image analysis for example.
(Refer Slide Time: 05:25)

So, what people do is, you can actually use some continuous distribution function something
called as a normal distribution function, it is also called as a Gaussian distribution function or
what is called as a log normal distribution function which are actually represented respectively
by these 3 expressions. And then I can fit these known distribution function to the discrete data
that you have obtained.

And the more class that you are going to have, the more closer would be your discrete
representation to the continuous you know representation that is represented by these lines, ok.

77
And if you have a log you know a normal distribution, so this f of x into dx will tell you
something about what is the fraction of the particles that you have in the size range from x to x +
dx you know in a particular the fraction of particles in that size range, ok.

And of course you are going to have a maxima right and that base response to x bar, which is the
average size of your distribution. And if it looks like a bell shaped curve, that means around the
mean is very symmetric, then you typically use this normal distribution a Gaussian distribution.
And if you have cases like this ok where your size data is skewed, either towards the smaller size
or a larger size then you go for what is called as a log normal distribution function, ok.

And the objective of fitting these functions to the size distribution data as I said is to get the
average size x bar and your standard deviation, ok. So, once you have done that you have been
able to characterize your particles for the average size and the standard deviation. And there are
ways by which I can calculate what is called as a polydispersity index from such you know x bar
and sigma.

And this polydispersity index typically varies from 0 to 1 more closest to 0 it is, that means it is
mono disperse a sample are, and if the values are larger, then it is poly dispersed. Typically for
all practical purposes if your polydispersity index is less than about 0.1 you can practically
consider them to be monodisperse you know samples, ok. That is about the characterization the
particle size.
(Refer Slide Time: 07:46))

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Of course, you can have particles of different shapes, right. So, what you are looking at is a cases
where I have some particles which looks like a peanut right like a dumbbell kind of a shape or
you could have something called as a spherocylinder which is basically a cylinder with 2 caps,
right, something called as a spherocylinder. You could have cube like particles right perfect
cubes ok or you can have rod like particles which are in this case this rod with a small kind of it
is like a bullet shaped particle ok.

So, of course you can have particles of different shapes you know and we kind of make them in
our lab. But there are definitely procedures available for you to make it what you can do in such
cases is you know.
(Refer Slide Time: 08:30)

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I can of course get what is the length distribution, what is a distribution in the, the length of the
particles or I can get the distribution in the diameter of the particle or you can define what is
called as a aspect ratio AR which is defined as the length of the particle divided by the diameter
ok. So, therefore, I can either characterize the particles for the length and the diameter or for a
complete characterization, I would have to look at length, diameter as well as your aspect ratio,
ok.

So, therefore I can use a similar principle that I used for analyzing spherical particles like you
know getting the size distribution and fitting the distribution to a known function like Gaussian
distribution or log normal distribution and an extract the average size and the sigma ok. I can do
a similar thing also for each of the physical dimensions for non spherical particles ok, that is
what you typically do.
(Refer Slide Time: 09:30)

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So, now that we have characterized the particles for you know the size and the shape. Let us look
at some other parameters that you can use for characterizing the particle. So, I am going to start
with particle density.
(Refer Slide Time: 09:41)

So, question again, so how do you characterize particles for the density, can you think of any
method. So, I will give you a sample of colloidal dispersion and I will tell you go and tell me
what is the density of the particle, how do you do it. Let us say that I have a container and it has
particles, ok and I have characterize these particles for size and shape is done. Now let us look at
how do we get the density ok.

81
Of course there are different methods available in the literature, I am going to tell you a method
which is based on what is called as a solution densitometry, ok. In which what you do is I take
my dispersion, ok of particles, ok, I prepare a series of solutions where I have particles of
different concentrations, maybe a little bit low and maybe without particles ok.

I basically have a series of solutions, ok or series of dispersions if you want to call them of
dispersion of particles of different concentration, ok. This let us think a little bit how do we from
that how do we get the particle density data. So, what we will do is, I am just goanna rub this off
quickly ok. Let us think about.
(Refer Slide Time: 11:49)

So, if I have a dispersion, ok, if M d is the mass of the dispersion that I have ok, I can write that
as mass of the particles are have in the dispersion plus mass of the solvent is that ok right. And
this is only true if I am considered what is called as a ideal mixing. Because you could have
cases you know where I can mix 2 dispersions or you know 2 fluids and I could have you know
change the volume as well, right ok or there could have change in the mass as well, right.

So, therefore you know what I will do is, I am going to say that volume of the dispersion is equal
to volume of the particle that I have in the dispersion plus volume of the solvent, right, ideal
mixing assumption, no change in the volume. So, what I will do is I will divide everything by

82
mass of the dispersion, ok, I am dividing the entire equation by mass of the dispersion of on both
the left hand side and the right hand side.

And Vd by MD is equal to Vp I am going to divide this by mass of the particle in the dispersion
multiply that by the mass of the particle divided by ok. I have MD here plus volume of the
solvent divided by again mass of the solvent multiplied by mass of the solvent again MD, is that
ok yeah a simple manipulation. So, this parameter, right, volume of the dispersion divided by
mass of the dispersion that is same as 1 over rho of dispersion ok, that is the density of the
dispersion right.

I have a solution ok, I have a dispersion of particles and I have you know if I have a way of
measuring the density of the dispersion that is what is your 1 over rho D is equal to this is 1 over
rho of particles, right multiplied by MP by MD I am just going to keep it the way it is plus this
quantity is 1 over rho of solvent multiplied by again I am going to keep the MS by MD. This MP
by MD, that is a mass of the particles in the dispersion divided by MD mass of the dispersion.

I can write it as 1 over rho p into multiplied by capital X, where X is the mass fraction of
particles you have the dispersion ok. Mass fraction of particles that is mass of particles divided
by mass of the dispersion ok plus 1 over rho s into MS by MD. It is going to be 1 minus capital X

83
right, which is the mass of the solvent that you have in the dispersion. Because you know the
total mass fraction is 1 therefore the mass of the solvent is going to be 1 over 1 - X.

Therefore I can simplify this as 1 divided by rho p into I have rho p here and rho s here - 1 over
rho of solvent into X + 1 over rho s, is that ok what is that, now right it is fine, right. So,
therefore what I have ended up is a equation which says 1 over rho of d is equal to 1 over rho of
particle - 1 over rho of solvent multiplied by X + 1 over rho of solvent, ok. Now what you do is,
we will go back to the you know the experiment that we are saying right

I am going to have a dispersion. I am going to prepare a series of dispersions in which I know

what is the mass fraction of particles ok. And it is easy to find a mass fraction, right I take a
dispersion and I evaporate all the fluid and I made I get the mass of the particles or dispersion
right just by evaporating all the fluid and measuring the mass. Therefore the difference in the
weights is going to give me what is the X, ok, therefore if I have a series of solutions, if I were to
plot.

And if I have a way of measuring density of the dispersion that is 1 over rho d, I am able to
measure that by using a densitometer. And then if I plot there is a function of X which is the
mass fraction of particles in the dispersion, I would get a straight line where the intercept is
going to be 1 over rho of s. And the slope is going to be 1 over rho P - 1 over rho s, ok, from the
intercept I know what is 1 over rho s.

I can actually get 1 over rho p from that I can actually extract what is rho p which is the density
of the particle, ok. This is a very simple way of preparing solutions of different concentrations
and then measuring the density of the dispersion. And from that, I can extract out the density of
the particle. Typically, the guideline is that if you are working with dispersions, you should
consider dispersions of concentration X ok should be less than you know about 0.1 ok.

Anything more than 10% do not use it, therefore when you do densitometry measurements if you
consider mass fraction of the particles should be less than about 10%. So, you prepare a series of
variations within that range and then measure densitometry and get your particle density ok.

84
Now it is a simple parameter, right density of the particle is one of the most basic parameter it
turns out there is a very useful quantity.
(Refer Slide Time: 17:54)

Because I can use that data also to get what is called as a specific surface area right, we define
the specific surface area as the surface area of the particle divided by the mass of the particle,
right. That is how we are defined and I said this has units of meter square per gram, right. So,
therefore, if I have a spherical particle, ok, say that this spherical particle as a density sorry it has
a size of Dp here that is your diameter of the particle that you have.

Therefore your surface area is going to be 4 pi R p square that is your radius or pi D p square,
right that is your surface area ok divided by your mass of the particle. Mass of the particle is
going to be density of the particle times volume of the particle, right. So, this is pi D p square,
divided by rho p into volume of the particle is pi by 6 D p q right ok. So, that gets cancelled, I
have that also gets cancelled therefore this is going to be 6 by rho p into D p.

So, for a spherical particle your specific surface area is 6 divided by rho p into D p. If I have a
way of measuring the size of the particle, if I have a way of measuring the density of particle I

85
can actually directly get what is the specific surface area, ok. Of course there are other methods
for measuring surface area you would have heard of a technique called Blain's apparatus, have
you heard of this. In which what is typically done is you basically make a bed of particle.

So, if you have these particles you make them into a powder, you make a bed of particles and
then you basically use the flow through pack bed, concept ok to measure the particle surface area
So, we are not going to do that but I think this is one of the simplest way of measuring you know
the specific surface area, you measure the size of the particle and your density and then size of
particle then you get ok.
(Refer Slide Time: 20:20)

Now, the next parameter phi, ok we have defined this already, so phi is defined as the volume of
particles divided by volume of the dispersion right ok. So, the volume of particle is going to be V
p divided by the volume of the dispersion, right. And I can convert, so volume of the particle is
going to be ok. So, therefore, your V p is going to be mass of the particle divided by density of
the particle right.

So, Vp is going to be mass of the particle divided by density of the particle multiplied by VD ok.
Therefore if you have a dispersion of some concentration, you dry out all the fluid, I can
measure, what is the mass of the particle in the dispersion. And I have measured what is the

86
density of the particle again by solution densitometry. And if you know the volume is a
dispersion that you are using for your experiment, I can actually plug in all these numbers, I can
get the mass fraction, ok.

Again, there are other ways of measuring particle volume fraction you could think about you
know if you have. Like for example, you say that you know I have a dispersion that contains
particles right ok. So, if this is in a 3-dimensional volume what you can do is I can actually get
the images of this container which has these particles and I can get immediate every location.

That means I take a slice I can get what is the basically for every slice I can actually get what is
the area of fraction that the particle occupies ok. And I can basically put them together and I can
construct a 3-D volume ok you can also do there are techniques like that where you know you
can do a 3-D imaging of the entire dispersion. And from that you can calculate you know the
volume fraction.

But this is one of the simplest ways of doing it, all that it requires is measurement of the mass of
the particle and the density of the particle. And if you know the volume of dispersion that you
are dealing with, I can get phi directly from these data, ok.

87
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-06
Characterisation of Colloidal Particles-II

(Refer Slide Time: 00:14)

We will move on to the grafting density okay. So, we have kind of defined this parameter in
the last class. So, this becomes important if you are going to have particles okay which have
some long chain molecules that you have on the surface right and the grafting density okay
you can call it a sigma g if you want to you know okay is defined as what did we say number
of grafted molecule per particle divided by surface area right you know.

In this case if it is a spherical particle is pi D p square ok, how do we get that some random
thoughts as to how do we get this thing, see one of the technique that people use in the
literature is something like this okay.
(Refer Slide Time: 01:12)

88
So, typically when you take these particles that have these molecules right okay, say that I
have a silica particle Si O 2 or you know I could have a maybe a gold nano rod okay which
again may have these things in the surface right, what I can do is I can take a known quantity
of the sample ok, and then I can subject it to a heating process okay. Now when you have
silica particles or gold nano rods we know that you can heat them to a fairly high
temperature.

They would not decompose, however these long chain molecules that you have you know it
could be C 18 chains you know or it could be C 12 chains or something like that okay, what
will happen is, if you are heating a sample to a you know what you do is you take a sample
which has a known amount of particles. And you start heating it okay. Now when you start
heating it at some you know characteristic temperature all these grafted molecules can
thermally decompose okay.

What you do is because you have particles of known mass right and then you know this is
typically there is a technical TGA right thermo gravimetric analysis in which what you can
do is you can take a sample I can you know heat it at a controlled rate you know control
temperature okay. As you do that what you do is you look for the change in the mass okay.
So, these molecules start decomposing at a particular temperature and the decomposition
ends at a particular temperature okay.

Therefore if you know the temperature range where they decompose and you basically
estimate what is the change in the mass okay that occurs in that temperature window, I can

89
actually get what is the total mass of all the grafted molecules that I have in the sample okay.
If that is the total mass of the grafted you know chemical species that you have in the sample
if that is your mp okay or mg okay that divided by the molecular weight of the grafted species
what will it give macro environment, it will give me the number.

No, no it will give me the moles right, it will give me the, the moles of the grafted molecules
that I have in the sample that multiplied by Avogadro number will give you what is the
number of molecules okay. Number of molecules of the grafted molecules on all the particle
that I have in the sample right, I divide this by the number of particles that you have in the
sample okay.

That will give me what is the number of grafted molecule per particle right and that divided
by your surface area, if it is a spherical particle it is pi D p square that is what will give me
sigma g that is the grafting density okay. That is how it is typically done there are other ways
of doing it okay in this simple TGA base analysis what you do is you calculate what is the
characteristic in a mass change that is associated with a particular chemical species.

That is either grafted onto the particle by a covalent bond or physically adsorbed and you
measure what is the mass corresponds to those species that divided by the molecular weight
right. Multiplied by Avogadro number will give me the total number of molecules that I have
in the entire sample divided by the number of particles okay divided by your surface area will
give you what is the grafting density okay. So, the next one that is specific that is surface
charge density okay.
(Refer Slide Time: 06:07)

90
So, before we do that I have taken an MSDS right, people who work with any chemicals you
would have heard this right MSDS material safety data sheet right. So, like for any chemical
there is also MSDS you know or a data sheet for particles okay and this is a typical data sheet
I have taken it for from a website okay. So, if you look at this is actually for a PS okay
polystyrene particles.

Let us look at what all do they give, they give you the density of the particle okay 1055 kg
per meter cube, refractive index they give you a lot number okay, all the particles that you
buy are kind of identified by this number that means people can get this lot number and then
you know whether it is supplied here or elsewhere in the world you will get particles of
exactly identical you know nature right.

The mean diameter that is measured by TEM okay that is the standard deviation right
something like this which is obtained by I said right you get this histogram you know I can fit
a distribution function I can get the, the mean size and the standard deviation hmm, there are
other few parameters you can think a little bit about it. I would like to highlight this quantity
of course they also show what is the specific surface area right.

I said you know for spherical particles it is 6 divided by rho p into D p right you can get that
and this is the surface charge density okay 7.3 micro coulombs per centimeter square right. I
said that the surface charge density is defined as the total charge q okay on the particle
surface divided by again the surface area which for a spherical particle is pi D p square okay,
that is how it is obtained okay.

91
And there are other 2 nice parameters you can think about packing area per carboxyl group
okay. So, if you look at the surface area is pi D p square right, that will give you the total
surface area okay. Now if I divide that by the number of the charge group that I have in the
surface okay. This is an example of what is called a carboxyl latex, that means it has carboxyl
groups on the surface okay.

And if I know so they also give you this quantity right carboxyl groups per particle, that
means on the carboxyl you know on the particle surface there are 2.3 into 10 power 5 number
of molecules right, number of charge groups okay. Therefore this pi D p square divided by N
p okay number of you know this number of charge groups okay number of charge groups will
give you this quantity right that is area per carboxyl group okay.

So, all these parameters are important you know if you really trying to do good set of
experiments with your colloidal particles you should worry about every physical and
chemical properties of your particles okay only when you do that okay only when you have a
complete characterization of your particles that is when you know your experiments in terms
of designing.

And you know in terms of interpreting the data that you get out of the experiments is
becomes more meaningful okay when you have such a characterization like that okay.
(Refer Slide Time: 10:00)

92
So, with that again we have already defined the surface charge density okay. So C for charge
sigma for density, so which is defined as the q, the total charge that the on the particle surface
divided by a pi D p square right. Now there are different ways by which you can get q we
will talk a little bit about that this in detail a little bit later.
(Refer Slide Time: 10:28)

At this point I know how many of you heard of a parameter called zeta potential, have you
heard this parameter zeta potential okay. So, just to tell you in a simplistic term if I make. So,
this zeta potential kind of tells you something about the charge of the particle okay. If the zeta
potential is positive okay that means the particles are positively charged okay. The zeta
potential is negative you know like here right, they are negatively charged okay.

And this is a unit of milli holes okay, we will learn that whenever you are working with
charged particles in a fluid it turns out that the mathematical treatment okay becomes much
simpler if you not work with charge but a quantity called surface potential okay and again we
will define what is surface potential in a while okay. So, this zeta potential for all practical
purposes can be taken as a surface potential and okay that is somehow related to q okay.

Let us put it that you know this way at this point okay. Now there are methods by which I can
measure surface potential okay or the zeta potential and from that there are ways by which I
can get q and once I have q I can get you know the charge density okay. So, typically this
zeta potential is actually measured by a technique called electrokinetics okay in which what
you do is I have a dispersion of particles either positively charged or negatively charged
okay.

93
And you apply a voltage okay and you make them move okay whenever you have a charge
species it does respond to the electric field that you apply okay and depending upon the
velocity with which they move okay. There are you know I can measure what is called the
velocity which is the particles move okay and from that I can back calculate what is the
charge in the particle okay let us put that there you know that way at this point okay.

There are other methods of measuring it not only electro kinetics there are ways by which
people do what is called a conductometric titration okay or potentiometric titrations okay in
which what you do is you take a dispersion of particles. And then you add a salt okay or an
acid or a base and then you measure the change in the conductivity or pH okay and the way
this conductivity and pH changes okay as a concentration of the this you know the electrolyte
or the acid or base changes from that you can actually calculate you know.

The charge on the particle okay and once you have that I can actually calculate what is the
surface charge density. The last parameter surface heterogeneity I have mentioned that there
are 2 types of heterogeneity right a physical and a chemical heterogeneity.
(Refer Slide Time: 14:08)

An example of a physical heterogeneity is particles that are rough okay, what you are looking
at is a nice example where what has been done is they have taken 960 plus or minus 36
nanometer size particles or large particles, they are put into a solution which has 12 okay 39
okay or a mixture of you know 39 and 12 okay and 72 + 12 okay. So, these are examples
where I have a positively charged particles.

94
I have a large personally charged particle, they are put into a solution which have negatively
charged particles okay or different sizes okay, in one case only 12, second case a mixture of
39 and 12, a third case a mixture of 72 and 12 and because they are oppositely charged, these
smaller particles are going to get deposited on the surface of larger particles right, just
because of the electrostatic interactions.

And thereby they are able to get particles which have different roughness right, in this case
very small scale of roughness, in this case you have roughness of different of different degree
if you want to call it okay. Now once you have particles like this I would have to characterize
such particles also for roughness okay.
(Refer Slide Time: 15:51)

So, what people do is people typically use techniques such as surface profilometry which is
an interference based technique for measuring the heterogeneity of the surface okay or people
can use AFM atomic force microscopy or any other technique okay and then what you get is
what is called a roughness profile okay. This is as simple as if I have a surface like this.

And if I draw a line what I am going to have is I am going to have hills and valleys right.
They are going to be hills and valleys okay and you get what is called a line profile okay and
then you kind of discretize it and then you look at your discretize into n equally spaced
intervals and then look at what is the height of the hills and the valleys okay. So, therefore if
you do that and from this the height of the peak or the valley I can get what is called a
arithmetic mean roughness okay.

95
Arithmetic mean roughness which is simply 1 over n sigma of 1 to n okay the average you
know the size of this height or the valley right or you can get what is called as a root mean
square roughness ok by this simple formula right. So, therefore if you have particles that have
physical roughness okay or you know a physical heterogeneity one of the ways of quantifying
such a thing would be measuring what is called the arithmetic roughness or a root mean
square roughness okay.
(Refer Slide Time: 17:32)

Similarly we kind of roughly touched upon this point that this could also be what is called as
a surface heterogeneity, what you are looking at is an example in this case where you have a
particle which is homogeneously charged okay what I mean by homogeneously charged is
that we looked at it quantity right carboxyl groups per particle okay. Now what I can do is I
can do a similar exercise.

And I can go back and ask you a question as to I have a particle whose surface area is pi D p
square right, I can take different regions you know I am going to take a small section on the
particle surface, I can ask a question as to what is the total number of carboxyl groups in that
area I go to a different location I consider the same area again and I can ask a question as to
what is the number of carboxyl groups okay.

If that number here and here or anywhere across the sample is exactly same that will give you
a surface which is chemically homogeneous okay. Of course you could have cases where I
could have a particle which is similarly charged but I could have you know if this is my

96
average data potential I could have - 50 here or it could be - 55 in some region or - 40 in
some region okay.

That will still is an example of a case where I have a surface heterogeneity, that means there
are pockets on the particle surface where the zeta potential is not same okay or you could
have designed experiments where I could have a particle where some case you know some
regions the particles are possibly charged that may have positive zeta potential and some
region may have negative okay.

That is again an example where this is an example of a particle what is called bipolar
particles, that means these are particles which have both positive charges and negative
charges on the particle surface okay or you could have cases where I have some region which
is hydrophilic or hydrophobic right. This is an example of a surface heterogeneity but
chemical heterogeneity.

And such things are more difficult to characterize okay, it involves more advanced techniques
you know for example you know I was talking about this electrophoresis right you could
have a case where I have a charged particle which may move in a particular direction when
you apply a electric field. However, if you have particles which have you know heterogeneity
like this whereas the patches where these things are positively charged negatively charged
such particles could rotate in the electric field okay.

You could use exploit properties like that and you can actually characterize the particles for
chemical heterogeneity okay, but that is you know it involves more advanced techniques
more involved kind of work. So, if you are interested to know a little bit more about this you
can read up some references that is here okay.
(Refer Slide Time: 20:43)

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Okay with that I think we will end with the characterizing the particles we will try and talk
about a few of the other things in the next lecture okay.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-07
Introduction to Forces Acting on an Individual Colloidal Particle

(Refer Slide Time: 00:14)

Yeah, so today what we will do is I would like to introduce you to forces and interactions in
colloidal systems ok, that is goanna be you know the objective of today’s class . So, I am going
to do that through a little bit of history ok.
(Refer Slide Time: 00:33)

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So, this is some really good books if you are interested you should read first one is of course
something on microscopical observations, this is actually written by Robert brown ok. And the
second one is actually a titled atoms which is actually written by John Perrin ok who was you
know I am going to tell you little bit about him and you know what he has done. So, I mean the
original book is in French, it is translated to English ok.

And this is a recent book it is written by a physicist called Mark Haw ok. And that is titled
middle world and if you look at the alright it says the restless heart of matter and life ok, so that
is the these are all very good books, I think you should deed up because you know you will get a
account of some other developments in colloidal science ok. I have taken a lot of contents from
you know this book and this book ok, so for today's lecture, ok.
(Refer Slide Time: 01:50)

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So, I am going to show you a movie to begin with. So, if you look up because I copied just the
file ok. Anyway, so this there is a movie that is in the youtube ok what you do is you should go
back and just type you know Brownian motion, you will have several movies that may come up.
So, what I wanted to show you was that you know these you have this image ok and these dark
regions in the bright regions and the bright regions are the particles ok, they are very tiny, there
is no scale bar here.

But the size of these particles I guess is about less than a half of micron ok. And then if you see
this movie, you will see you know they are moving around ok, they are jiggling around not in
any particular direction is a chaotic motion, ok. And that motion comes about because you have
these particles embedded in a fluid and these fluid molecules are constantly hitting you know or
bombarding the particles ok, that is what ok, , so that is what is called a Brownian motion ok.

Brownian motion is the random movement of particles ok in a fluid ok, it could be liquid or a gas
ok and that results from a bombardment or you know in a constant you know hitting ok of a atom
or a molecule that is in the continuous medium, ok.
(Refer Slide Time: 03:26)

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So, these are some typical trajectories of the particles that were recorded we back in the 1920s
ok. And this is from the work of Perrin ok and what he did is, he used colloidal particles of 0.53
micrometer you know in radius. And he prepared a sample, he observed them under microscope
and he was able to. So, every point that you see, that is every dot or the every point that you see
that is the position of a particle at some time instant, ok.

And later time instant where it has moved, so he was able to track these particles and then he has
trajectories of 1, 2, 3 particles, ok, that is what you see here.
(Refer Slide Time: 04:27)

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Now, of course this is a 1920s I said right, now way back in 1827 ok. So, Robert Brown what he
was trying to do was, he took a droplet of water ok. And this droplet contained pollen particles
ok pollen and he observed them under microscope. So, his intention was to answer questions like
this ok. How does pollination occur ok or how do these tiny pollen particles they spread the
message of life from plant to plant ok, that was a kind of question that he was trying to ask.

And he did a lot of experiments and you know ultimately he could not you know make a
conclusion of you know what he was trying to do, ok.
(Refer Slide Time: 05:23)

And these are actually the particle that we are used in you know Brown’s experiment, this is a
more recent you know stuff from 2010 ok. So, these are actually pollen grains from a flower
called Clarika Pulchella ok. So, and you look at this scale bar you know 50 micron large enough
. But they still he was seeing that you know they were constantly moving around ok.

And later on, it turns out that you know there is experiments of Robert Brown were essential to
kind of answer this question what the matter is made of ok. That means, ok, we know that you
know atoms are the building blocks of everything right. So, his experiments were instrumental in
you know telling you that look atoms at the basic building blocks of everything that is around us
right ok.
(Refer Slide Time: 06:18)

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So, what Perrin did was, he did very controlled experiments ok, so unlike you know Pollen’s ok,
which as you saw, right. They were you know they come in different sizes, different shapes ok,
so what Perrin was able to do is, he did very careful experiments and he was able to prove the
very existence of atoms, I will tell you a little bit about how he did that. And this he achieved by
a careful choice of particles ok, I think that is very important whenever you are trying to do any
experiments.
(Refer Slide Time: 06:55)

I have some again some pictures from his book, ok, these are the particle that he used ok. They
look you know spherical, they look more or less of same size, ok and this is an experimental
setup that he used, ok, that is a microscopy objective, ok. Typically whenever people want to do

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these Brownian motion experiments, what they do is they take 2 glass slides, ok and your
dispersion of particles is embedded between these 2 slides ok and then you basically seal the
entire container.

Because you know you do not want any influence of external conditions there could be some air
all the types, you want to minimize all the disturbances as much as possible. And you put this
onto a microscopy stage and then you look around, right. And then you basically record either
the frames, images or the videos, right, that is how you typically do it.
(Refer Slide Time: 07:46)

So, now so he did those experiments and because he knew the position of the particles you know
at any given instant in time, he was able to calculate a quantity called mean square displacement
ok. That is, what is the distance that the particles you know travel ok you know in a given time
alright. And he knew this observation time ok he had done experiments over a time window, he
knew that ok.

And he was actually able to calculate this D that is the diffusivity of the particles, this small d
here corresponds to the dimension. So, D is going to be 1, if you are looking at 1 dimensional
Brownian motion d is equal to 2. If you are looking at 2 dimensional system or D is equal to 3
ok. So, from his experiments he was able to calculate the mean square displacement ok and from
that he could back calculate what is the diffusivity of the particles ok.

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(Refer Slide Time: 08:53)

Now once you do that, so he used something called as Stokes Einstein equation ok which relates
the diffusivity of the particles to this thermal energy ok, the radius of the particle and mu which
is the viscosity of the fluid in which the particles are embedded. Because he knew what is R right
I said that you know he had done he had microscopy observations of his particles themselves ok.
Therefore, ok the value of R is known, and from these Brownian motion experiments he was able
to calculate D ok.

And viscosity of the fluid he knew, ok, and the temperature at which the experiments were done,
also he knew. From that what he did is, he calculate k B that is a Boltzmann constant, ok. And
that is equal to R which is the, the universal gas constant divided by Avogadro number ok.
Because he calculated from his experiments, this is known, he was able to calculate what is NAV
ok, that is what he did.
(Refer Slide Time: 10:11)

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This is some data from his this is a tabulation of you know this N the Avogadro number that is
obtained from such experiments ok, not bad, right. This is 80 in to 10 power 22 right with you
know 8 into 10 power 23, ok fairly close to you know the Avogadro number ok, right, there are a
series of numbers ok.
(Refer Slide Time: 10:39)

From this, I have taken this again from his book, so he made this statement, ok from these
experiments. I shall therefore, get this Avogadro number to be 68 or 6.85 into 10 power 23, ok
that is the value he assigns. And then he is also able to calculate what is a charge of the electron
you know and the mass of the hydrogen atoms stuff like that, ok.

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So, therefore Perrin’s experiments were very much instrumental, ok in you know kind of coming
up in the alternative way of measuring you know the Avogadro number, ok, which in turn he was
able to kind of conclude that you know atoms do exist and the fact that you know this particles
are undergoing Brownian motion is indeed because of the atoms of them or the molecules of the
fluid in which the particles are dispersed, ok, that is ok. So, we will do you know exercise where
will be able to calculate some numbers like this ok, in the next lecture or so, ok.
(Refer Slide Time: 11:41)

Now Brown’s experiments 1827, right and then it took a very long time you know for perin to do
these nice experiments you know and you know prove the existence of atoms, right. And the
reason why he was able to do it and then the other people could not is because he was able to
choose perfect particle for his experiments ok. Anytime you design an experiment what is really
important is, you should ask a question as to what is the aim of my experiment ok.

And what is my objective ok and then depending upon what you want to study you should be
able to choose a colloidal system of interest. So, there you know to for example, if I was
interested to look at sedimentation for example, ok. Then if you do experiments with you know
like say 10 nanometer particles, they would never settle, right or it will take a really long time to
settle, right.

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So, therefore, so it is good to ask a question is to look this is my object of my experiments ok.
And then based on that you have to really designer a nice model colloidal system, ok to achieve
that objective right. So, now, so how to choose perfect particles first, I mean this is a ok, the
particles must have to behave themselves. That means they should neither attract nor repel with
other particles in the system right.

Because say because you are trying to measure Brownian motion of particles, right, this is
typically done with a very dilute fluid. That means, the concentration of your particles in the
fluid is very, very low. Typically you know your phi could be as low as you know 0.0001 or
something like that, ok. The reason for that is the particles have to be sufficiently far, that means
there is no interaction between the particles ok.

That means the motion of the particle is not influenced by the other particle that you have in the
system, right. So, therefore, so the particles in the system should neither attract nor repel with
other particles, ok, nor stick to the walls of the microscope slides. Because you know you are
doing these experiments under confined you know walls ok. And if the particles get stuck to the
walls then in what will happen is again it is going to hinder the motion of the particles, right ok.

So, he basically says because the particles are immersed in water ok which may contain some
charges right you know you could have some dissolved ions in the fluid ok. So, all that could
influence the way the particles you know feel each other. So, therefore it is necessary to avoid
what is called is a long distance forces, ok such as electrostatic repulsion. So, if you have charges
in the system you know electrostatics could kick in.

So, therefore it is good to avoid all of that when you are trying to do an experiment of this short
ok. This is very specific to the experiment that he had done, ok. Now the next thing is that the
particles ok would have to be as spherical as possible ok, what it means is that. If you have a
particle like this ok which is like say a rod like particle. Then people talk about you know what is
called is a orientation dependent diffusion, ok, you could have translation, ok you could also
have rotation, ok.

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Therefore you know but that is because the Einstein theory right that was actually developed for
perfect spherical particles, ok. But as you saw from the microscope image on the pollen grains
that were used by Brown, they were aspherical right ok. Therefore the next requirement for his
experiments was that the particles will have to be as spherical as possible. But the pollen
particles are more often they are either tiny tubes or cylinders ok.

Therefore the calculation of diffusion coefficient for such things you know would not be
straightforward, ok, this is a second you know kind of requirement you can say.
(Refer Slide Time: 16:10)

Now, thirdly there is a density problem, what I mean by that you know you have these particles
in a you know to geometry like this right. Now the particles that you are going to use for such
experiments should be such that the density should be close enough to that of water ok. That
means they should neither sink to the bottom ok or they should not float to the surface, right.

Because you know you do experiments for a particular time window, at least in that time
window, you should never have any influence of density of the particle or the gravitational forces
on the particle. Therefore the particle that you have should always be suspended in the fluid, they
should neither sink nor float. And the next requirement is that the particles have to be of
appropriate size, ok, what I mean by that is.

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That the bigger the particles the more it resisted being pushed by the surrounding fluid ok, the
slower it moved, right. That means if I am doing experiments with the larger and larger particle
as the particles becomes larger and larger, the inertia becomes important, ok. If it is too heavy or
too big then the solvent molecules only have this thermal energy kBT ok, they cannot move a
larger stuff around, ok.

Therefore so the particles would have to be small enough that means if the if the particles are
bigger, they resist the motion ok they do not move. Because the energy that the molecules have
is not big enough to move the particles around ok. So, therefore the particle is too big would
have very slow Brownian motion or they may not even exhibit Brownian motion, right.

So, if it is very slow, then you know you may have to do experiments for a very long time or if
they do not move, you do not even have a chance of measuring Brownian motion, right. So,
therefore the particles have to be of right size, ok. Now, if the particles were too small, ok, on the
other hand if the particles are too small, they would move very fast ok. And if it moves too fast,
ok, if you have a really good camera right you know in a which you can actually capture fast
moving things you can still do experiments.

However maybe at that point in time, ok, so he could not do you know you could not get away
by using to smaller size because they were moving too fast and you know and he really could not
reliably track the particles ok. So, therefore if he was going to succeed in his experiments Perrin
needed particles that had a precise size and of course they also have to be in the narrow size
window, ok.

This again comes back something that we have discussed mono dispersity right, ok. That means,
if imagine that you know I have track these particles, ok. And I have measured diffusion
coefficient, ok, now if thereof different sizes, ok then I am going to get different values right. So,
therefore you know or if the size distribution is too big depending upon it whether a small you
know or the average or right.

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So, therefore he really needed to choose particles which are of a particular size and they also
have to be as you know a narrowly dispersed as possible, ok. Now, like whatever the
requirements that I have said right, this is for choosing appropriate size of particles for Brownian
motion experiments for example, ok. Now, if I were to generalize this for any experiment, right,
can I classify whatever few point that I have mentioned into different classes.

So, what I mean by that is that, so if you look at the first part right, so there is you know it says
that the particles should neither attract nor repel, ok. And they should neither stick to the walls of
the container right ok, that is one requirement. The second one is you know there should be you
know there should be as spherical as possible that is a requirement for this particular experiment.

And if you look at you know the density problem, ok, that mean they have to be not too big, not
too small, ok and they have to be of precise size and monodispersity, ok. So, therefore I can
classify these requirements into some categories ok.
(Refer Slide Time: 21:51)

I am going to add another one here, you have to work with model colloids right, the particles of
you know maybe monodisperse, known size ok known you know surface properties all of that
ok. And then let us say model colloids it need not be monodisperse always ok, there are a lot of
people who are trying to look at what is called is the effect of polydispersity on some colloidal
phenomena ok.

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Or one maybe interest to look at I want to measure what is the viscosity as a function of volume
fraction, ok and I want to compare what if it is monodisperse versus polydisperse, right. In such
cases you may be interested in look at you know maybe your model colloids would be both
monodisperse as well as polydisperse of controlled polydispersity ok. So, therefore you know, so
this model colloid requirement need not be always monodisperse ok, it depends on again what
problem you are trying to look at.

So, the other point that we have discussed so far can be kind of clubbed into two main categories,
you should have a knowledge of the forces acting on the particles in the dispersion ok. That was
you know this gravitational settling right, so, that you know I can get an idea about whether the
particles will sink or float. If I know about what is the gravitational force acting on the particle,
right.

The gravitation force may not be the only force that is you know relevant in this scheme, look at
a few different forces that are important. And the second thing is we should have an idea about
the interaction forces between the particles in the suspending medium ok, plus of course the
interaction also between maybe the particles and the container itself, right you know. For
example, it could be wall or it could be if you are storing these particles in a you know in the
case of you know Brownian motion experiments is the interaction between the particle and the
wall.

If you have particles like say a beaker is a interaction between the particles and the walls of the
beaker itself, right, these are also important, yeah. Any questions so far yeah ok, we will move
on, ok. Now ok let’s talk about the forces acting on the particles, ok, what do you think are the
forces that are acting on the system. So, we are talking about, so let us think about like this right.
I have a container, ok, I have particles in the container and there is a continuous medium ok,
what are the forces acting on the particle.

Of course one we already said right gravitation force, van der Waal forces yeah see I just want to
make a distinction. So, there is now so let me put it this way let us talk about the forces on the
individual particles, ok, let us put that way ok right. That is what I have written here, this is force

113
on the individual particles in the dispersion ok. Definitely gravitation is 1, right everybody
agrees, right, anything else.

Buoyancy I mean if you say a net gravitational force that takes care of buoyancy as well, right ok
anything else. Viscous force ok, electrostatic charges I mean see when you talk about ok let’s say
like this right. I have a particle ok, I have this is you know there is charged ok. Now the
electrostatic you know interactions become important, if I have a very dilute fluid, right, you
know there is absolutely nothing nearby ok.

Then electrostatic interaction you know electrostatic forces you know see you talk about
electrostatic forces between 2 things right. I mean if you look at coulomb's law you have you
know charge 1, charge 2, right you know this is a force of repulsion or attraction depending upon
nature right. How about hydrodynamic force, you heard of this term hydrodynamic force, these
forces come into picture whenever there is a flow right.

Now, if you look at particulate systems right, which if they are tiny enough, the particles are
moving. Now, whenever you have a particle moving in a fluid you have what is called as a drag
force ok which acts in the direction opposite to the movement of the particle right. So, the second
force is a hydrodynamic force, we can also call it as hydrodynamic drag force. Third force, there
was a Brownian force ok and lastly something called as a osmotic pressure force, osmotic
pressure force.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-08
Application of Brownian Force: Introduction to Interaction Between Colloidal Particles

(Refer Slide Time: 00:14)

Okay, so you know hydrodynamic all of you know this expression already. So, this is the
famous Stokes law right okay, the hydrodynamic force acting on a you know a particle it is 6
pi eta m is the viscosity of the medium in which the particle is dispersed a is the okay it is the
size of the particle okay and V is the velocity which is the particles are moving okay. People
also call it as a friction force right and a is the radius of the particle okay.

And typical numbers if you do experiments it turns out that you know the if you measure the
velocity which is the particle moving if you have a 1 micrometer radius particle okay and
typically you know the velocity of the particle would be of the order of again 1 micrometer
per second. And if they are in water okay it turns out that this Fh the hydrodynamic force is of
the order of 2 into ten power - 15 newtons okay which is 2 femto newtons right that is a
number okay.
(Refer Slide Time: 01:52)

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The second force is the Brownian force, it is so basically this kBT right that is the thermal
energy I mentioned right, thermal energy as units of joules right okay joules that is newton
meter if I want to convert that to force I should have some length scale I am going to use the
size of the particle itself is a length scale. Therefore the Brownian force is given by kBT
divided by a okay.

And again if you take 1 micrometer particle it turns out that this Brownian force is of the
order of 4 femto newton okay here. So, for that all you have to do is kB a is you know 1.3 into
ten power - 23 joules per Kelvin right and then multiply that with the temperature and then
you can get these numbers okay and as we already said this Brownian force arises because of
the random you know collisions of the molecules with these particles right.
(Refer Slide Time: 03:01)

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The force of gravity that is the density difference multiplied by the volume of the particle
multiplied by g right and again if you put in typical numbers like you know the density is
1100 for the particles density of you know the fluid is about 1000 if you take 1 micrometer
particles it turns out that your Fg is of the order of again 4 femto newton. What is interesting
to note is that you know if you look at this 4 femto newton that is what you got for
gravitational force is very much comparable to the 4 femto newton that you got for the
Brownian forces okay.

Therefore if you take particles of colloidal length scale okay of 1 micrometer size you know
the gravity and Brownian force are very much comparable okay. Therefore now if you make
the particle bigger okay then your gravity will dominate okay. Therefore you will see that
your F gravity start becoming greater than F Brownian, if it is too large it is much, much
larger.

Therefore gravity is going to overweigh okay. So, the Brownian force would like to keep the
particle suspended in the fluid but the gravity would like to make it sink right. So, that is so
you have to think a little bit about these numbers.
(Refer Slide Time: 04:30)

The last force I am going to talk about is something called as the osmotic pressure force
which is defined as pi which is equal to n times kBT where n is the number density of atoms
okay . So, basically this comes from what is called as a ideal gas law kind of a concept where
the pressure okay, that is exerted. So, what you do is you take a container okay. And say that
I have I put a some kind of you know plate for example okay.

117
Now you can ask a question as to what is the pressure that is generated because of an ideal
gas law okay and say that the number density of atoms in the container is n okay. So, the
pressure that this plate would feel okay, it will go as n times kBT okay. Now people have
translated the same thing to particulate systems okay. So, there again the reason why this
ideal gas law and this particular system kind of analogy is because again you are working
with a very dilute dispersion okay, very few particles in the fluid okay.

You can bring in analogy from the ideal gas or gas like state to colloidal dispersions okay and
in such a case you know your pi the osmotic pressure force okay goes as again n, where n in
this case is the number density of the particles in the system okay which is number of
particles divided by the volume of the dispersion okay right. So, again the units match right
because n is number density which is number per volume number per meter cube and your
kBT has units of joules.

That is newton meter okay 1 meter, 1 meter you can cancel that becomes n newton per meter
square which is pressure right okay. So, therefore it is a good idea to know a little bit about
the magnitude of all these individual forces that are acting on the system.
(Refer Slide Time: 06:59)

When you look at term you know dilute dispersions or you know when you are looking at
particulate systems. The second point brings down to what is called as the colloidal
interactions okay. So, again this becomes important when you are working with colloids or a
dispersion where the particles are sufficiently close, that means if I take you know the

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dispersion with like say phi is equal to 0.0001 okay or something of that order right or even
0.01 for example okay.

The distance with the particle is so large that there is I can practically say that there is no
interaction between the particles okay. Therefore whenever you are using like say dynamic
light scattering setup for measuring particle sizes okay. One other thing that one people
ensure is that you are working with a very dilute dispersion okay. So, if you get a size by
using a dilute dispersion.

And if you get size by a concentrated dispersion okay or at least a reasonably concentrated
system you will see that the size that you get okay R1 and R2, they are very different because
in the second case the size that you get is also could also be because there is a interaction
between the colloids as well okay. Therefore these the interactions become important when
you are working with the sufficient dispersion of sufficient concentration.
(Refer Slide Time: 08:56)

And before I tell you a little bit about the colloidal interactions I just want to introduce you to
the concept of interaction itself okay. How many of you have heard of Lennard-Jones
potential okay 1 no 2 okay. So, 2 people have heard okay this is I mean Lennard-Jones
potential is people use it for mimicking what is called a molecular interactions okay. If you
look it up that is a total potential okay.

And there are 2 terms here right Xi x power - 12 - beta x power - 6, typically whenever you
talk about interactions in any system in general phi total that is a total interaction will

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typically be a summation of phi attractive plus phi repulsive, as in general of course you
should have cases where there could be only attraction, only repulsion okay, but typically it
could be a combination of the 2 okay.

Now so what you are seeing here is a plot of phi, that is the total interaction as a function of
separation distance okay. So, all these interaction potentials that people talk about they tell
you that if you have an idea about the interaction potential you can say something about
whether at any given distance the particles are attracting each other, repelling each other or is
the combination of both are important okay. That is what it will tell you okay.

Now if you look at this plot, if you look at this region right, your both the repulsive term goes
to 0, attractive term goes to 0, the total also goes to 0 right. Therefore if these molecules in
this case any molecule that obeys Lennard-Jones potential, what is plotted here is a case of 2
methane molecules okay, what I can for sure say is that if the distance between the 2 methane
molecules is more than 0.8 nanometers.

There is no interaction between them right, I can say that for sure right. Now if I bring them
closer right at some point you know they are going to start repelling that is given by this
curve and of course they are going to start attracting as well as given by these and because
you have repulsion and attraction which have opposing tendencies when you are going to add
them up you are going to have a minima right.

This minima tells you something about okay what is the stable okay at equilibrium if I were
to have you know a container which is filled with methane molecules okay. So, they are
going to have a separation distance typically of the order of you know maybe 0.4 to 5
nanometer and the energy corresponding to that equilibrium configuration is something like
about - 2 into 10 power 21 okay, - 21 because you know you have 10 power 21 here.

So, therefore this value is going to be - 2 to 10 power - 21, if I divide that by kBT okay, that is
like say 300 times 1.38 into 10 power - 23 right. If you do that you know you can kind of get
an idea as to you know what is the total interaction energy in terms of kBT okay. Now this is
for a molecular system right. Now you can kind of use a similar concept to look at interaction
between colloidal particles as well okay.

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The only difference is that again we will talk a little bit about this later, if I have colloidal
particles, this is the particle 1 and particle 2 okay. Now we know that these particles are also
made up of atoms and molecules right. If these are the atoms that constitute the particles
right, maybe something like this. So, what do I mean by interaction between the colloidal
particles is that if I look at this attractive term okay.

This comes from what is called the van der Waals interactions okay, this is in the case of
methane molecules, if I want to kind of adapt this concept to van der Waals interaction
between 2 particles what I have to do is I should take one atom find out the van der Waals
interaction of that with another atom present with other particle, again the same atom go to
the next one, I do what is called as a pairwise addition okay.

I find out what is the total number of molecules or atoms in one particle, I find out what are
the total number of atoms of you know molecules in the other particle and then I start doing
pairwise addition of the interaction between the individual molecules okay and total pairwise
interaction is what will be the total van der Waals interaction between the colloidal particles
okay.
(Refer Slide Time: 14:46)

Now so in colloidal system 2 are more particles in the dispersion can interact via several
forces okay, one is the van der Waals interactions, there are also what are called as surface
forces, depletion forces and hydrodynamic interactions okay. Now we will have a whole
chapter dedicated to van der Waals forces in maybe starting next week. So, the van der Waals
forces they arise because of what is called the quantum mechanical effects okay.

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Because we know that you know atoms and molecules have electron cloud around them right,
a fluctuation of atoms you know electrons in these clouds gives rise to some you know
attractive interactions okay. That is what is you know the van der Waals forces.
(Refer Slide Time: 15:48)

Now the surface forces I mean as the name itself says right, these interactions become
important if you have particles you know and surfaces are ubiquitous of the particle right.
The moment I have a particle I have a surface of the particle right. Now whenever you have 2
particles whose surface come into close proximity okay, when I say close proximity I will
again go back to this diagram okay.

Close proximity is again relative okay, it depends on what you are trying to deal with for the
case of you know the methane molecules here, close proximity is any distance that is less
than 0.8 nanometer okay, anything beyond that it is not close proximity right okay. So,
typically what will happen is whenever you have a colloidal particle you may have the
surface of the particle that is charged okay.

You could have adsorbed ions okay, the particles can even have nanoparticles on the surface
okay, the particles could have surfactant molecules on the surface or polymers you know the
grafted polymers you know are absorbed polymers right and now whenever you have such
things on the surface and if the particles come to close proximity that is when you are going
to have the surface forces or surface interactions okay.

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Depletion forces are typically come into picture whenever you have a system which has
colloidal particles and you add polymer molecules to them okay. So, that is they arise from
soluble polymers or nanoparticles and typically when you had such things there are some
attractive interactions that come about okay. Again we will have a chapter dedicated to you
know depletion forces in you know in a few weeks.

And the last kind of interaction what is called a hydrodynamic interaction that come
whenever you have a dispersion and they are kind of disturbed by some kind of flow field
okay, that means I could have 2 particles in a fluid you know and if I apply some kind of a
shear they could come together, they could be a attractive interaction that is purely because of
the flow that you have induced okay.

And such kind of you know interactions are what are called as hydrodynamic interactions
okay. These kinds of interactions only are important whenever you have such dispersions
under flow okay, under stagnant conditions they are not important okay, under stagnant
conditions what are important are the van der Waals forces, the surface forces and the
depletion forces okay.

Maybe we will stop here think through a little bit of these things and so, I think with this we
kind of finished the intro part of the colloidal course okay, we will try and look at some you
know advanced topics from next week onwards.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-09
Application of Brownian Force: Measurement of Diffusivity and Size

(Refer Slide Time: 00:14)

Okay, so we will begin right. So, in the last class we introduced forces and interactions in
colloidal system.
(Refer Slide Time: 00:33)

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And the way we did that was by looking at Brownian motion, right. This video did not play the
other day. So, I just want to play this. So, that is these are fluorescently labeled particles, which
appear bright, you know, they more like look spherical, right. They are spherical particles, which
are being continuously bombarded by the solid molecules and if you look carefully they are not
really moving in any particular direction, right.

They are just about there in some location and they are jiggling around, right. And that is what is
called as a Brownian motion. And what we did was we use this as an example. And then I told a
little bit about how carefully these experiments were designed right to estimate, you know, the
Avogadro's number right. And then, in doing so, we just said that, you know, there should be
absence of certain forces on the system.

And there should be some absence of interaction between the particles and the particles on the
wall right in which the experiments are done. So, therefore, that is how we kind of, you know,
introduce you to the concept of interaction of force on the particles and then interaction between
the colloidal systems in terms of force, we talked about the force of gravity right Brownian force
okay, we talked about hydrodynamic force okay.

It is also called as you know drag force as well in this case, plus we also mentioned something
about osmotic pressure force okay. Okay and having an idea about what is the typical you know
magnitude of each of these forces on the particles or the magnetic forces in a colloidal system
would help you to design in a good experiment okay. And similarly we said that you know
whenever you have many more particles, okay.

If the particles are very, very far apart, then you do not have to worry about interactions, but you
know typically when you work with you know a dispersion which contains large number of
particles, when the particles are sufficiently close, then we should talk about what are called as a
inter particle interactions okay, that is not on the individual particles, but if you have particles in
the immediate vicinity okay then you talk about the interaction between the colloidal particles.

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When I say vicinity, again it is relative right depending upon the kind of forces that you are
dealing with okay. For example, if you talk about van der Waals forces, which will you know,
expand further typically, you know, this van der Waals force of interactions is operative and the
distance between the particles is about you know 10 nanometer or less okay. That means, if you
have any distance which is larger than this, you do not have to worry about van der Waals force
of interaction, okay.

So, we talked about van der Waals force of interaction, we talked about surface forces right and
surface forces we said that the surface forces can come about if you have particles that could
have charge and the particle you know, which could have some adsorbed ions, absorbed
polyelectrolytes, surfactants, nanoparticles right. So, it could be anything on the surface of the
particle and that could lead to some interactive forces.

Then we also mentioned about something called as a depletion interactions, okay. And we
mentioned that such interactions would only come into picture whenever you have a colloidal
particles you know in a fluid and to that, you add a polymer or any particles such that the size of
the polymer or the particle that you added is much, much smaller than the particles, you know,
which make up the dispersion okay.

So, again we will discuss this at length plus we also mentioned the final type of interaction what
are called as hydrodynamic interactions okay and we said that such interactions would only come
into picture whenever there is flow, right, that is where we had stopped okay.
(Refer Slide Time: 05:06)

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So what we are going to do today is to look at, you know, the analysis of, you know, the
Brownian motion a little bit more than what you have done so far okay. And then we look at its
application okay. That is what we are going to do today okay, more specifically, I am going to
look at these 3 things. Use of Brownian motion for measurement of what is called as a particle
diffusivity okay and extend that to measuring the size of the particle.

And then I will also hopefully give you some, you know, hint as to how can one use this
Brownian motion for looking at what is called as a Sol gel transition, okay, that is what we will
try and do in this lecture okay.
(Refer Slide Time: 05:50)

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So, this is again, I have already showed this right, 3 tracks of this is track 1 you know track 2,
track 3 of 3 particles that are exhibiting Brownian motion. And so you have these dots right.
These dots correspond to particle position, okay at some time okay. So, in this case, I could say
that this could be particle position at time T is equal to 0, okay. Next whatever dot that you see
here it is at time T is equal 30 seconds okay.

And the next one again, you know from here it has come somewhere here, right. That is your,
you know, so basically the way it is done is you take a video of a particle exhibiting Brownian
motion, okay and I locate the particle position, right. This is a 2D space, right x and y okay, I can
find the coordinates of the particle. I get that and that is what I plotted here okay, and I take
another frame 30 seconds apart.

I look at what is a particular position in that image and I put that here okay, I go on doing that,
you know, until I have done sufficient averaging. In this case, what do you see is you know is for
example, if you look at this, I think there are about 30 segments, what do you mean by segment
is the distance between, you know, particles in 2 consecutive frames, that is a segment okay. So,
there are 30 segments and each segment is 30 seconds apart, okay.

I mean, if you look at right if I look at the distance between the 2 particles, it has traveled so
much distance in 30 seconds, okay. Now, so if I have a figure like this, okay, from this, let us say
that I want to calculate what is called as a mean square displacement okay. I can do that by an
image like this okay. So, what information that I know is I should know that what is the scale of
one division right.

Because this is a graph okay and this one division that is the distance going from maybe like say
this to this right that distance okay that is 0.0003125 centimeter I know that distance okay, if you
want to do it manually what I can do is I can print it on a you know sheet of paper and I can take
a scale okay and I can find out what is the distance between this and this right in you know if you
are going to use a scale which are centimeters.

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I am going to say it has some say x centimeter okay. And I can I can similarly I can get what is
the, this distance in terms of centimeter that is a y centimeter okay, if we know the scale and
what are the actual distance I can actually get what is the actual distance that the particle you
know as moved for every 30 seconds, right I can do that, right.
(Refer Slide Time: 09:09)

So, that data is basically plotted here okay. So, this is a segment number, okay, starting from 1
all the way up to 30 here, okay and in the first segment the distance that is measured, okay, in
millimeter is about 38 okay and the last one is 32 okay, let us go back and look at these right The
first one was here, right. That is your first and the last one is your right okay, that the distance
look comparable, right.

You know one is 32 38, other one is 32. Looks like that they start from here. That is your first
segment okay, and then go on tracing it and come all the way there right. So, that is the distance
that you know the particle has moved okay in every 30 second time interval okay. Now of course
you know you can use a scale and all of that you know your scaling factor all that and you can
get what is the actual distance that the particle travels in a given 30 second interval.

Now, I have the actual length the particle has traveled, I can take the square of that okay, the
square of the distance the particle has moved, okay, okay in the first segment, second segment I
can do all of that for all the segments, okay. And then so this is basically your now if I add them

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up all and if I divide the number that you get by 30 that is what will give you what is the mean
square displacement okay.

Typically it is given by you x bar square okay, that is your mean square displacement, okay. So,
it turns out that if I add all these numbers up, okay. Now here, what you get is something like
this it is 6634.8 into 10 power - 8 centimeter square, okay. And if I want to convert that into
meter square, so that is going to be 10 power - 4, right meter square right. And that divided by 30
okay, we will give you a number which is something like 2.2116 into 10 power - 10 okay.

Because you have 8 here that becomes 12 right and you have a you know, this is 1000 right. So,
it becomes something like -10 meter square okay, that is the x bar square, right, that now you
have, so I said that every segment is you know it is at a 30 second time interval right. And
therefore, I can actually calculate what is the total time right, the total time is going to be, I have
30 segments, okay right multiplied by 30, right, that is going to be your okay 900 okay.
Therefore, divided by 900 second okay, that is going to be my x bar square divided by t okay.
(Refer Slide Time: 13:04)

Now we kind of introduced this equation that was derived by Einstein, right. So, where the mean
square displacement, okay is equal to 2 times d times capital D times t, where d corresponds to
the dimension, right. So, if you are doing experiments in 1 dimension d is going to be 1. If you
are doing experiments in 2 dimension, d is going to be 2, right. Therefore, if I put all these

130
numbers, okay, turns out so that because this is a trajectory in 2 dimensions, okay. Therefore,
whatever x bar that I have calculated, right.
(Refer Slide Time: 13:43)

This is for 2 dimension, okay. If I want to get what is diffusivity, what I need is delta x square of
t, that is average divided by 4 times t right, because I am doing experiments in 2 dimensions,

Therefore, your D is going to be whatever the number that you got here, that is 2.2116 into 10
power - 8 divided by 4 into 900 right, can you get this number for me if you have a calculator.
Let’s do that. It is 2.2116 divided by 4.

And then divided by 900 okay, that comes out to be something like 6.1 into 10 power - 12. Yeah,
that is going to be in meter square per second. So, from these experiments, what you can do is
you can actually get what is the diffusivity of the particles right. So, you can ask a question as to
what is the why do we need diffusivity right, it turns out that I can use these diffusivity
measurements for calculating what is that.
(Refer Slide Time: 15:22)

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So, in these experiments, so, wherein did experiments with particles whose size was known
okay, 0.52 micrometre was the size of the particle right. Now, if you do not know the size, I can
actually use these mean square displacement calculations okay, from which I can get diffusivity
to estimate what is the size of the particle okay. The way it is done is by using what is called as
Stokes-Einstein relation okay.

So, again you know what we are trying to do is we want to relate the Brownian motion that the
particles exhibit to the diffusivity of the particles okay. Now, whenever you have a particle
moving in a fluid we say that you know there is going to be a drag force right, that is the force
that is exerted in the direction of flow right. So, the drag force is exerted in the direction opposite
to the flow of fluid right okay.

So, if the particle is moving like this, okay and this movement is going to be hindered by the, the
fluid, right and it is going to experience a force in the direction opposite to its movement, right.
So, again you would have learned this concept of drag coefficient in fluid particle mechanics or
in your mechanical operation course, where this the drag coefficient goes as what is called FD by
Ap. This Ap is what is called a projected area that the fluid of the particle right.

132
If I have ahh like say if you have a stationary column of liquid and you know if the particle is
falling like this, if I see from the top, what I see is this circle, right, that is your projected area,
right. And of course, if it was to fall like this, okay, then I am going to see you if it is going to be
cylinder, I am going to see a rectangle, right. So, that is your projected area. So, that is Ap is the
projected area and FD is the drag force and u0 is the velocity with which the particles moving
okay. And rho is a density of the fluid okay. Now okay.
(Refer Slide Time: 18:04)

So, because we are working with colloidal particles, okay it turns out that because of the fact of
the particles that we dealing with are very, very small right of the order of 10 power - 9 meter to
10 per - 6 meter, it turns out that the Reynolds number that you calculate for any problem that
involves colloidal particles is going to be very, very small okay. That means, you know Reynolds
number which is the ratio of inertial forces to viscous forces is going to be always small okay. In
such cases, your CD go says 24 divided by Reynolds number okay.

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(Refer Slide Time: 18:47)

Now, I can substitute for Reynolds number that is going to be mu divided by Dp, u0 into rho
okay. And if I do some simplification, because I know that you know, if CD is 24 divided by
Reynolds number I know that now, because your CD is again FD divided by Ap divided by rho u
square by 2, right and Ap the projection area is going to be the area of the circle right okay, that
is going to be pi Dp squared.

If a substitute for all of that you get FD as 3 times pi mu u into Dp, this is again the well known
Stoke's drag right okay essentially, you end up with the expression for drag for a spherical
particle moving in a fluid right. Again you can do this you know by again starting with this
stokes equation, you know, start with the general equation I can do appropriate modifications and
I can also obtain a similar expression.

But it is one of the simpler ways of doing it. So, all that we have done is we got an expression for
the drag for that is experienced by the particle right.
(Refer Slide Time: 20:13)

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Now because the particles are constantly moving in the fluid the net velocity u0 okay with which
the particles are moving is the average distance the particle moves, okay, in a given time interval,
right, that u0 is x bar divided by t, but now whenever a particle is moving, okay it has to get some
energy right okay or okay, so the work that is done okay by the moving particle is FD multiplied
by x bar.

That is force times the distance okay, the average distance that it travels okay that is your the
work that has to be done you know in moving the particle right. Now that energy where does it
come, it comes from the, the thermal energy right therefore, the equating the thermal energy to
the work that is required you know for moving the particle okay what I can do is I can equate
them okay and because I know what is FD.

I can substitute for FD from the Stokes drag right. And this I mentioned that your you have u here
right u0 okay is x bar divided by 2 okay and you have an x bar here. Therefore, it becomes x bar
square divided by t okay. And because you have Dp here, okay and Dp is 2 times R right.

135
Therefore, this becomes 6 here therefore, KBT is equal to 6 pi mu R x bar square divided by t
okay.

(Refer Slide Time: 22:14)

The cause for Brownian motion is the constant bombardment of the fluid molecules with the
particle. Yeah, that is because see, if you take any container right say that you know I have water
right and say that this water is maintained at a temperature T, okay. Now, so, the energy that
every molecule of water in this container will have is KBT yeah, every molecule will have this
energy correct.

Now, that is what is being used for the mobility of the particle. No, we are saying that the
molecules of water will have this energy and this energy is being used for moving the particle
which will have constant velocity yeah the particular will have a u know some average velocity.

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See, if you go back here, right okay, let me put it this way. I mean, if you look at the length that
we have got, right.

Let’s look at these numbers, right. The length of the every segment is what is calculated right,
look at the length here, so you have 152.1 10 power - 8 centimeter squared, but you have
numbers which are as low as 2.6 10 power - 18 okay, I mean if you want to calculate okay
velocity for every segment it will vary in a certain range right. But if you know, watch them for
sufficiently long time if you calculate the velocity it will have I mean you know, if you go back
when we did this force calculation right on different okay.

We said that you know, micrometre particle will typically you know move with 1 micrometre per
second velocity okay, numbers like that are kind of obtained from experiments like this, okay.
Yeah so on an average particles in a fluid, which is maintained at a particular temperature will
move with the velocity which is typically again depends on the size of the party right if you have
10 power - 9 meter size particle, nanometer size particle.

Of course, it is going to move with a much larger velocity in a compared to 10 power some
particle which is a 10 power - 6 meter size right. Yeah. Now this x bar square by t that is what is
the diffusivity you know of the particle okay. Therefore, even you have an expression which
relates the diffusivity of the particle to the thermal energy and the viscosity of the fluid in which
the particles are dispersed or the particles are moving right.

R is a size of a particle therefore, if I have done an experiment where I have studied the
Brownian motion, if I am able to calculate, what is the diffusivity, if I know what is the viscosity
of the fluid u know a particle dispersed, I can actually use this expression measured what is the
size of the particle okay. Therefore, in essence, I could use some technique like microscopy,
wherein I have measured Brownian motion.

And I can back calculate what is the size of the particle if you do not know what is the size okay.
So, you can think about this as a one nice application of Brownian motion where people exploit

137
you know, this particular phenomena and then estimate the size of the particle right. Any
questions. No okay.
(Refer Slide Time: 26:37)

So, we will okay, now you can go back and you know, take a look at so because we are
measured diffusivity, right from, you know, the earlier track that we looked up, right. And if you
take the water, say 0.001, you know, Pascal second, right, that is your that is viscosity and you
know, putting appropriate values for kBT 1.38 into 10 power - 23 and temperature I think what is
taken in this reference is 290 Kelvin.

If you put in all of that you can back calculate R and the value that you should get should be very
close to 0.52 10 power of - 6 meter okay. You can try and do that and see know how it works out
okay.

138
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-10
Origin of Scattering

(Refer Slide Time: 00:14)

Okay, so I just want to spend a little bit of time talking about something called as a dynamic
light scattering technique, again in this you have a way of extracting the particle diffusivity
okay and from that you can get the size of the particle okay, yeah any thoughts what do you
know anything about Brownian motion, sorry anything about dynamic light scattering, what
is it. Any basics of scattering, no okay let us okay.
(Refer Slide Time: 01:00)

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All of you may know this right what is this, yeah this is a laser show right, I mean you know
very popular right and why do you get this fascinating beam of light, why do you think you
get these things, this is not nothing to do with the color of light I do not know if you have
gone to any laser show you will see that they make something right I mean you know if you
have clean air you would not get this yeah right.

They create some synthetic particles right, some fog or smoke like thing or something like
that right, only then you see this right, yes right. So, in that case you can think about you
know this liquid in air dispersions okay or particle in air dispersions right we talked about this
right there are different classification of dispersions and one of the dispersions are you know
if you have a dispersed species could be liquid or a solid particle.

And that is in air right. So, in something like a laser show your continuous medium is the
ambient air and they have created some particles okay which essentially scatter light okay.
(Refer Slide Time: 02:38)

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Now okay so the origin of scattering right. So, any kind of scattering okay is due to what is
called a localized non uniformities in the sample okay, it becomes clear from the previous
example right, if I had only air clean air, then you would not see these colors right. So, you
need to have a localized non uniformities okay. In this case what do I mean by that is you
should have may be air with some particles okay or liquid some particles right.

That is okay the particles in that case constitute non uniformities in the sample okay. Now
people use different light sources in experiments okay, you can use a visible light okay or
white light right or you can use x-rays okay, you can use lasers, you can use neutrons okay
and depending upon the light source that you use okay, the scattering is kind of attributed to
different reasons okay.

If you use visible light okay then the scattering originates from the refractive index variations
okay I have a particle that has some refractive index n1 a fluid medium that has some
refractive index n2 okay, only when you have the refractive index difference is when you will
have scattering okay So, now what I mean by that is if I want to do a dynamic light scattering
measurements okay.

If you have a fluid which has a refractive is n1, if I have dispersed species whose refractive
index is very close to that of the medium itself then you cannot do scatting experiments okay,
the same thing is true for microscopy as well, when you are doing microscopy experiments if
I have a solution okay and you can do these experiments okay, people do what is called as
refractive index matching right.

141
That means there are some classic videos in youtube you can look it up okay I have a
container, I have glass you know this say a beaker right and there is a glass light okay. Now
when there is nothing in the container because there is enough refractive index difference
between the glass and the ambient air which is right you can see the glass rod right.

Now what you do is you put water you can still see the glass you know rod because there is
again a refractive is difference between your water and the rod right. Now if I replace this
with you know fluid you know maybe up to this level and you know and if that fluid has
same refracted index the only thing that you will see is what is above okay that immersed
portion you would not be able to see okay.

So, therefore depending upon okay in scattering okay the scattering originates from either the
refractive index difference or if you use x-rays uh what is important is the spatial fluctuations
in the electron density within the material okay, that is what gives rise to scattering when you
do when you use x-rays okay. Similarly when you use neutrons people talk about what is
called a scattering length density difference okay.

So, you can read up a little bit about this you know when you go back the idea is there has to
be some heterogeneities or non uniformities some difference in particular properties and that
is when you can carry out scattering experiments.
(Refer Slide Time: 07:24)

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So, these are typical wavelengths right, if you use laser light typical wavelength of the laser
light is about you know it will be in depending upon whether you use blue laser, red laser
okay, your wavelength would vary but typically you can say is about 500 nanometer, if you
use x-ray scattering okay, this wavelength is smaller okay. If you use again neutron scattering
again the wavelengths are much smaller.

So, depending upon the wavelength that of the light that people use that will give you the
length scale, that you can obtain from scattering measurements okay and that length scale is
kind of expressed as some parameter again not important at this point which is expressed as
nanometer inverse and 2 pi by this parameter okay S will give you the length scale that you
can obtain from the scattering experiments okay.

Let us think about it okay. So, 2 pi divided by is 10 power - 3 to 4 into 10 power - 2 right.
Therefore the length scale that I can get from scattering experiment when I use a laser light it
is 2 pi into 10 power 3 to 2 pi into 0.5 pi into 10 power 2 right okay that is in nanometer
okay. Now let’s do the same thing for this one okay. So, these numbers are smaller right, if I
look at 2 pi divided by these numbers these numbers are smaller right compared to these
numbers okay.

That means if I want to measure size of smaller things okay if I want to measure the size of
smaller things okay I should use the light source whose wavelength is smaller okay, that is
what I wanted to say okay.
(Refer Slide Time: 09:45)

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Now okay this is a there are different types of scattering experiment that people do we want
to introduce these terms but maybe what I will do is I will come back here okay.
(Refer Slide Time: 09:57)

People do different kind of scattering experiments, one is what is called a static light
scattering experiment, other one is what is called a dynamic light scattering okay. In static
light scattering what is measured is the time average okay, time average intensity of the
scattered light okay is what is measured okay.
(Refer Slide Time: 10:24)

A typical experiment looks something like this you know I have a light source okay and I
have a sample and this light beam is incident on the sample okay and the local heterogeneities
or the non uniformities in the sample will make the light deviate or scatter light and that is
actually collected on a screen okay and this screen is typically a camera okay.

144
(Refer Slide Time: 11:08)

What you record is something called as a pattern like this okay, this is what is called a
scattering pattern okay and what you see here is related to what is the microstructure of the
sample or in other words what is the spatial arrangement of particles in the fluid okay, what
you are seeing here is a case where particles have form chain right. Now if you have a case
where the particles have formed chains you will get a scattering pattern which is kind of
elongated in a particular direction.
(Refer Slide Time: 12:04)

Or this is an optical microscopy image okay where the particles are nicely arranged right
everything is a hexagonal pattern right it is a hexagonal pattern. Now this is a microscopy
image okay by an optical microscope we have taken that converted that into a FFT pattern
and what you again see is a hexagonal pattern right, can you see here okay in a way one way

145
to think about this static light scattering experiment would be I am imaging microstructure
but not in the real space in what is called as a Fourier space okay that is all that is there okay.

So, therefore in a typical static light scattering experiment what you do is you measure time
average intensity of the scattered light okay and it is measured by fixing you know your
screen or a camera at a particular location okay and depending upon the location of that okay
whether it is very close to the beam, very closer sample or very far away from the sample
okay. This theta will vary right.

Depending upon the theta you know the variation of the theta you can essentially obtain
information about different length scale okay present in your system ok. Let me put it at that
you know in that way at this point okay.
(Refer Slide Time: 13:52)

Now yeah so that is something about static light scattering okay in the dynamic light
scattering what you do is what you measure is a fluctuations in the light intensity as a
function of time is measured. In one case you measure the a time average intensity that is in
static light scattering, in the dynamic light scattering what you measure is a fluctuation in the
light intensity itself as a function of time okay.

That is the difference between the static light scattering and the dynamic light scatting okay.
The instrument for dynamic light scattering it looks something like this is a one of the table
top devices that is available and you can actually use this for a measurement of size of the
particle okay or polymers or some surfactant structures I talked about this liposomes right or

146
vesicles you can measure size of that. You can also use such an instrument for measuring
charge in the particle, molecular weight of polymers there is a lot of okay.
(Refer Slide Time: 15:13)

Within the instrument you know what essentially there is a laser source, there are set of
lenses and these lenses as I said are useful in you know sending a collimated light right okay
and it falls onto the sample okay and there is a detector okay, typically these detectors what
they do is they are what are called as they are called as photon detectors okay, they
essentially measure the number of photons okay scattered okay.

And that is your sample that has some particles okay, again I had mentioned about the
scattering volume at some point the intersection between the incident beam this is your
incident beam right and the scattered beam okay, that gives you some finite volume right and
that contains the particle that you have in the fluid. Therefore the scattering volume contains
okay a much larger I mentioned this point right.

If you look at the scattering volume so if even if it is like say you know of the order of say
millimeter cube volume okay that millimeter cube volume will have really large number of
particles okay, even if you take 0.001 weight percentage sample it turns out that number of
particles in 1 ml would be as high as 10 power 12 to 10 power 14 particles okay. Therefore
the scattering volume really contains a large number of particles than what can be analyzed
by something like microscopy you know where you look at only a small section of your
sample okay.

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For example something like this right if I am going to analyze particle size from this okay of
course they look monodispersed but then you know I will be limited to maybe few 100s of
particles right. However, if you do scattering experiments the scattering volume will contain
essentially large number of particles okay. Therefore you get a better average you know for
the particle size when you do DLS experiments. (Video Starts: 17:50)

Maybe I will stop here, we will continue with you know talking about how does one use DLS
for measuring particle size. (Video Ends: 17:56)
(Refer Slide Time: 17:57)

Plus we will also talk a little bit about using Brownian motion for looking at what is called as
a sol gel transition okay, that is what we will try and do in the next class thanks.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-11
Relation Used to Study Colloidal Systems

(Refer Slide Time: 00:14)

Okay, so we will continue with analysis of Brownian motion, yesterday we looked at

measurement of particle diffusivity and then we also derived an expression or an equation
which is what is called as a Stokes Einstein relation, that will help you to calculate what is the
dimension of the particle if you know the diffusivity right, that is what we had done.
(Refer Slide Time: 00:46)

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And in that connection we had just started with what is called as a dynamic light scattering.
So, I just want to clarify a few things.
(Refer Slide Time: 00:56)

(Refer Slide Time: 01:03)

So, I had mentioned that you know the scattering of light typically comes about if you have
any localized non uniformities or heterogeneities in the sample okay and light scattering is a
consequence okay of interaction of photons right, because you know whenever you take any
light source you know it is made up of photons right and interaction of the photons that make
up the light with the electronic structure of the atoms or the molecules that make up the
particle okay or the dispersed phase is what gives rise to what is called as light scattering
okay.

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And whenever people do light scattering measurements what they do is they measure what is
called as scattered light intensity okay and the way it is measured is they will have a
instrument which can measure radiation right and typically photons okay and this photons
again it depends on the kind of radiation measurement device that you are using , typically
people use a PMT you know what is called a photo multiplier tube okay in which what is
done is you basically collect the number of photons that fall onto the device that you are
using.

And typically the measurement of photon or the intensity is expressed in something called the
KCPS kilo cycles per second okay and depending upon the kind of a scattering unit that you
have okay this the photon count that you measure it varies okay, in general one thing that you
should know is that any scattered intensity okay I that is detected by any device that one is
using, it is actually proportional to volume of the particle that you have in the dispersion to
the power 2.

If Vp is the volume of the particle that you have in the dispersion, the scattered intensity goes
as volume of the particle to the power 2 that means larger particles will have will scatter more
light okay or the intensity of the light that is scattered by a larger particle is higher compared
to the intensity of the light that is scattered by a smaller particle okay, then as I mentioned
people can use a white light , laser light, laser source or x-rays or neutrons for scattering right
as a light source.

And as I mentioned when one uses white light okay what is exploited is the difference in the
refractive index between the particle and the medium is what is exploited, if x-rays are used
okay the scattering actually comes because of the interaction of x-rays with the electron
clouds you know that the atoms and the molecules will have and if you have neutrons as a
source of the radiation.

Then the scattering occurs because of the interaction of the neutrons with the nucleus of the
atoms or the magnetic moments of the atoms of the molecules that constitute the particles
right. So, that is a difference, but except for the origin of scattering the way the data is
analyzed okay, the way the scattered intensity is analyzed from any of these experiments
where you use light x-ray or neutron the analysis is very similar okay. But only thing is the
scattering originates from different, different reasons okay.

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(Refer Slide Time: 05:07)

I mentioned this so we typically people do 2 kinds of scattering experiments what is called as

a static light scattering okay in which what is basically measured is you have a sample, you
have a detector and then you go on accumulating intensity as a function of time and then
what you know what you get out of the measurement is a time average intensity okay, time
average scattered intensity okay. There is a term here is called a scattering vector okay.

So, that scattering vector actually is defined something like this is typically people use either
q or s it goes as 4 pi okay divided by lambda, where lambda is the wavelength of the radiation
source that you are using multiplied by sin theta by 2, where theta is the angle at which you
are collecting the radiation you know the scattered intensity okay. So, in static light scattering
what is measure the time average intensity is what is measured.

In dynamic light scattering what are measured are the fluctuations okay in the light intensity
as a function of time okay that is what is measured and typically whenever people do static
light scattering there is a radiation source, there is a sample okay and you collect scattered
intensity across many detectors okay, that means I am basically collecting scattering intensity
at different theta right okay.

That is what is typically so what you get from the static is it is I of q okay, that is q here okay
as a function of q is what you get from static light scattering experiments, you are measuring
the scatter intensity as a function of you know this scattering vector okay, that is a data that

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you get and you analyze that data to get any meaningful quantity that you want to get out of
your experiment okay.

And in the dynamic like scattering measurements what is measured is a fluctuations in the
light intensity, what you are measuring is your I of t okay, that is your measuring scattering
intensity as a function of time okay, that is the difference between the static light scattering
and the dynamic light scattering okay.
(Refer Slide Time: 07:59)

So, this s I have already defined that right it goes as 4 pi by lambda into sin theta by 2 okay.
So, now depending upon the wavelength of the light source okay, depending upon the
wavelength of the light source you know the range of s that I have access to will vary okay, if
lambda is more okay your q right or s is going to be smaller right, if the lambda is small your
q is going to be larger okay.

You should think about q okay, so inverse of q okay you see the q will have a unit of
nanometer inverse, therefore inverse of q will have units of some length scale. So, therefore
what you are changing okay what you are doing by changing the wavelength is that I am
basically able to access different length scale by using different radiation length source and
that length scale that you have access to okay if you call it as you know some length scale L
is proportional to 1 over q inverse okay or 1 over s right.

Now therefore if you use x-rays and neutrons okay which have a lower wavelength then they
can help us probe structures at much shorter length scale okay, I am able to go to much

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smaller and smaller length scale and I am able to access micro structural information at a very
small length scale compared to what you would do if you use laser or visible light okay.
(Refer Slide Time: 09:49)

Yeah so typical light scattering experiments, so this is for the case of static light scattering as
I mentioned earlier. So, there is a beam of light in this case x-ray wavelength lambda okay
and there is a sample and I had mentioned that typically you know these the sample and the
detector are actually kept in a vacuum environment you do not want you know light to scatter
off from you know whatever medium in which it is typically as I said you can get okay.

So, in this case the detector is what is called a 2 dimensional detector okay because it is a
basically a screen okay, you should think about there is a sample, there is a x-ray beam and
something is scattered and it falls onto a beam okay and then this q is again 4 pi by lambda
into sin theta by 2 okay, that is au know scattering vector.

And typically what is done is there is actually something with a beam stop the role of the
beam stop is the intensity that is in the center will be very, very high okay, if you do not have
beam stop it could damage your screen itself, therefore typically you put some you know
carbon source or some stuff which really absorbs you know it does not cause some kind of
damage to the and it also acts as a reference right.

Because when you are changing theta okay, theta in the center is going to be 0 right okay,
you are because you know your incident beam and the scattered beam the angle between

154
them at that particular location would be 0, you can you know and therefore if you go
outward okay what is changing is theta and in turn what is changing is your q okay.
(Refer Slide Time: 11:45)

So, typically you know one gets patterns like this and these patterns will have information
about you know the structure okay that is you know inherent to the sample that you are
working with okay. In this case there is a chain of particles and if you have a chain okay you
will typically get a pattern which looks something like this okay and what people do is you
can go back and read up a little bit about it.

So, what people do is they do what is called a radial averaging okay, what I can do is I can of
course this pattern is not very symmetric right, but if you have a pattern which is very
symmetric what I can do is I can do what is called a radial averaging. So, if I do, if I go from
here to this direction and what I do is I rotate that basically I am taking a particular line where
I am basically changing the radius right okay from the center which in turn I am basically
changing q right.

And if I average it across many lines like that like you know the many, many lines okay or all
the lines that I could draw then I get a average intensity as a function of q okay. This is so
basically from the 2D patterns you do radial averaging to get 1 dimensional you know
scattering intensity patterns. So, therefore your data would look something okay, I have q
may as a function of q you know may look something like that it depends on your sample
again okay maybe at some point I will show you some data you know from a particular
sample which has some well-defined particles of some sizes.

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(Refer Slide Time: 13:22)

And I had mentioned that you know what you are doing you can think about scattering as
imaging in a Fourier space okay or what is called as a reciprocal space okay, this is an
example so that is a microscope image, if I to do Fourier transform your patterns would look
like this, that means if I have any sample which has you know arrangement like this like what
is shown here. Then if you do experiment your scatting pattern would look something like
this okay.
(Refer Slide Time: 14:00)

So, before we move on further , so this is again will tell you something about the typical sizes
that one can measure by using scattering experiments. So, if you look at SLS the static light
scattering what is measured is the angle dependence of the scattered light okay and typically

156
you can measure anything of size larger than about 50 angstrom that means about 5
nanometer and above okay is what you can measure with SLS okay.

And there are instruments where I can measure you know by using SLS principles you can
measure things up to a few millimeters as well okay, it really gives you a very large you
know size window that you can measure with this technique. DLS what is measured is time
or frequency dependence of the scattered light and typical size range one could measure uh
there are instruments where you can go to you know as low as you know a nanometer okay.

And typically yeah, so I will come back when I talk about DLS I will mention this point. So,
his question is in DLS is the wave vector constant okay. So, we will come back to that okay
and of course there is something called as s stands for small a small angle x-ray scattering
okay and small angle neutron scattering okay, these experiments are similar to SLS but you
are using you know x-ray and neutron as a source.

And typical length scale that I can have access to is you know about 0.5 nanometers or
depends on the wavelength of the x-ray one could generate but you can you know look at
sizes of this order okay.
(Refer Slide Time: 16:00)

So, now you know we will move on to DLS okay. I said this is a commercially available you
know example of a commercially available instrument I would mentioned you know you can
use it for measuring size of the particles polymer surfactant structures people also use you

157
know this for measuring charge in the particle also it gives you a way of measuring molecular
weight as well.
(Refer Slide Time: 16:28)

Typical if you open the instrument right so typically this is what it will have essential
components would be laser okay which basically will give you, you know radiation of a
particular monochromatic light of a particular wavelength and there is set of lenses basically
to get a collimated beam and there is a sample okay. So, this what is shown here are 2
beakers right.

There is 1 beaker here and there is a small beaker there okay and the reason why not every
instrument will have this kind of a setup, the reason why it is done is that when you have a
beam coming in it is coming typically in air right and then it is going to go into your sample
okay. Now when that happens there is going to be a change in the refractive index right, you
do not want any of that happening.

So, what is done is you let you take your sample and you put this sample say that this sample
is in a glass cuvette okay and you immerse that sample in a container which has a fluid whose
refractive index is same as that of the glass okay. Therefore it will essentially you know avoid
you know some scattering effects that may come from the cuvette itself okay change the
refractive index.

So, but you know but if you do not use glass cuvette these days you know you have you
know a plastic cuvette which you know can be used without this path of fluid okay and

158
typically you will have a PMT or some kind of a device where you can measure the photons
that are that are scattered from the sample.

And this theta right and as you can see here right, so these photons are corrected at a fixed
location okay, typically if you go back and look up instruments there are instruments where
this theta you know you can collect it at 90 degree okay, you can collect at something like
135 degree somewhere here or you can also collect at some 15 degrees. So, it depends on the
instrument specifications of course there are instruments where I have access to changing the
length as well okay.

In such a case I can vary it across a large range of theta and I can do both DLS and SLS with
the same instrument, because you know basically if I can do DLS measurements at every
theta that is as good as doing a SLS measurements right, they are instrument like that but a lot
of table top instruments typically work at fixed theta, that means your q is fixed ok.

Therefore your scattered intensity that you are collecting is always done at a fixed q yeah and
I mentioned something with scattering volume the interaction of the light beam and the
incident beam and the scattered beam will give you what is called as a scattering volume and
unlike microscopy based technique this scattering volume will have a large number of
samples.
(Refer Slide Time: 20:03)

Therefore you get a better average okay of the size of the particle that you have. I have
mentioned this already, it can be measured you can measure the size of the particles micelles,

159
vesicles, polymers you name it okay. The only thing is there should be a enough refractive
index difference okay between the dispersed phase and the continuous phase right. Again size
range I had mentioned that you can measure sizes as long as particles exhibit Brownian
motion okay.

And what is measured is a fluctuations in the scattering as a function of time, it looks

something like this okay, here this is your intensity okay, s is same as q okay, but of course q
is fixed here. So, either I can call it as IFT itself because you know your q is fixed for in the
case of DLS measurements and that is measured as a function of time okay. These are the
fluctuations that you have okay. That is how it varies, it varies around a mean value okay.
(Refer Slide Time: 21:13)

Now okay why are we interested in the scattered intensity as a function of time because the
variation of scattered intensity with time contains information on the random motion of the
particles okay. Let us get the intensity fluctuation that you saw here that arises because the
particles are not fixed in space if you somehow fix them in space okay. Then what will
happen is your intensity is going to be a constant.

But the fact that the particles are continuously moving around is what gives rise to this
fluctuation the intensity okay and this can be used for measuring the diffusion coefficient and
once the diffusion coefficient is known I can actually get what is the size of the particle right.
(Refer Slide Time: 22:10)

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And typically size of the particles are measured by something called as Stokes Einstein
relation, this is applicable if you have monodisperse particles, this particular expression right
because the particles are of same size okay and of course it is the particles are spherical and
one has to ensure that you work with dilute solutions okay. This is one of the important
requirements whenever you do DLS measurements okay.

So, what do I mean by dilute solutions is where the inter particles spacing okay inter particle
spacing is very large that means there are no particle, particle interactions okay. That is one
reason why you should be working with dilute dispersion, the second reason why you should
be working with dilute dispersions is also because if you have too many particles okay. If you
have too many particles what will happen is your incident beam it is diffracted or it is
deviated when it hits a particular particle.

And before it comes to the detector it may hit many other and come out okay, there could be
what is called as multiple scattering events okay, when you have multiple scattering events
okay you cannot apply the analysis that we are going to do you know for such you know the
typical analysis that is applicable for monodisperse you know dilute dispersions okay. That is
because as I said the scattered intensity we are assuming that whatever is scattered is because
of the a single particle motion alone okay.

And if you have too many particles close by you know the other particles could also influence
this fluctuation okay and what is typically measured in DLS is what is called a hydrodynamic
radius okay which is the size of the particle in the solution okay, what I mean by that is that

161
so if I were to take some particle dispersed in a fluid okay and say that I have taken a same
particles okay a small drop of it and I have dried these particles.

Now the particles are on a substrate okay, now I do some microscopy okay. So, in this case I
get the size of the particles you know in the dry form and in the second case if I do DLS
measurements I get the size of the particles in solution, it turns out that typically the size that
you measure with the DLS measurements is always slightly larger than the size of the particle
that you measure in the dry form okay.

And the reason is because you know you could have a particle that could have some charges
on the surface, the effective size of the particle may be slightly larger because you know you
have charges okay you know depending upon you know like say the surface charge density
depending upon the arrangement of water molecules around the particle surface typically you
may measure sizes that is slightly larger than what you would measure with a dry technique
okay. So, the sizes that you measure with DLS is what is called as a you know hydrodynamic
size.
(Refer Slide Time: 26:10)

Again I have taken this example from you know the source what you are looking at is a
schematic of cases where you have you know these are all water molecules right, these are all
water molecules okay and they are essentially bombarding the particle right, this is a large
particle, this is a small particle what can you say about these two small particle has more
Brownian motion okay which is reflected by the fluctuations are too many right okay.

162
And that is a little here of course what is not apparent in this is that I said that your scatter
intensity goes as volume of the particle square right. Therefore if I were to look at you know
the average value of the intensity this will be much larger for this compared to what you
would see for this right. So, these are some, so when you do your experiments you can you
know you can look for all these things. So, then you will get an idea as to whether you know
what I am measuring is something reasonable or not yeah okay.
(Refer Slide Time: 27:37)

So, now okay that is what you measure.

(Refer Slide Time: 27:45)

So, there are instruments where you can actually access this information okay, if you take a
commercially available instrument a DLS instrument there are instruments where they
display this scattered intensity as a function of time, but many instruments do not okay, but

163
what they show when you use any particular instrument is looks something like this okay.
This is actually obtained from you know that scattered intensity measures a function of time
okay.

That is g1 of tau ok because I know how I of t varies as a function of time I can guess this
quantity right, this is intensity at a particular time, intensity at a particular time plus some
delay okay and intensity at a particular time right. I have access to all these information, I can
calculate g2 of tau and this is what is called the instrument constant. So, what I am trying to
say is that the scattered intensity as a function of time is reported as what is called as a
electric field auto correlation function okay which is derived from the fluctuation in the
intensity that you measure okay.

Now this function okay you can fit that to a exponential function okay and from that
exponential function I can get - D times q square right you have g1 of tau as a function of tau
is what you measure and you should look for this number okay, this is tau is in microsecond
depending upon the length scale of the particles that you have as a dispersed phase you know
your this unit would vary okay.

If you have very large particles you know then you will see that you know this decay right it
happens somewhere you know towards a larger tau, if you have very small particles you
know it will have it will happen to a u know in the decay right, it will decay at a lower tau
okay, therefore one could actually look at you know where does it decay to 0 and then
already kind of infer about what is the size of the particle that you have in the dispersed phase
okay.

So, now from the exponential fit I can actually get what is - D times q square I know q square
because I am doing experiments at a fixed q and I get this and from that I can actually get
what is the size of the particle okay, that is what you know is typically done.
(Refer Slide Time: 31:10)

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So, this is some data where you know we were trying to look at these are example of what is
called the emulsion fuels ok, these have very tiny water droplets in diesel okay, the work
done in our lab with Preetika and Niket okay and what is being measured is whenever you
have an emulsion fuel right, you would want the fuels to be stable right for a long period of
time. So, we were trying to look at what happens to the fuel if you store them for a long
period 6 months right.

And this is the autocorrelation function measured as a function of decay time and one thing to
notice is I know all of them you know overlap right almost lie on top of each other that means
if I were to extract size of the particles from this experiment I would expect the size to remain
the same right. And that is what you actually see okay which is done by a simple exponential
fit okay I get D times q square okay I know what is q and from that I get D okay and then use
Stokes Einstein and get the size okay. So, you can do analysis like this okay.
(Refer Slide Time: 32:44)

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But it is not necessary then you should always have you will have monodispersed particles
right. So, if you do not have monodisperse particles what you do is instead of expressing g1
of tau as a single exponent you basically express that as a sum of exponents okay. So, you
can express them as depending upon if you have bi-dispersed particles then I can say that you
know it will be sum of 2 exponential functions.

If you have tri-disperse you know I could use you know 3 exponential functions therefore in
general if you have a size distribution then I can express g1 of tau as summation of many,
many exponential functions.
(Refer Slide Time: 33:32)

And if you have something like that then what you do is you can expand exponential function
around some average tau bar okay, this tau bar is what is called as a decay constant okay, it is

166
what is called as a is s the decay constant and then if you know kind of leave out all the
higher order terms okay so you what you do is if you plot ln of g1 of tau versus tau is what
you have access to right.

Then I can fit a function and I can get what is tau bar and what is mu by 2 okay and from tau
bar you know if it is tau bar I can get the effective, that is the effective diffusion coefficient
not D anymore because you have particles of many different sizes and because I am
interested to get what is the average size I will get what is D effective okay and this mu will
have information about the polydispersity of the sample okay.
(Refer Slide Time: 34:45)

These are again some experiments where we were trying to measure again some size as a
function of time for a different kind of emulsions where as a function of time you see that you
know this is as a function of time okay, this variation already tells you that there is something
changing right, there is a change in the size as you wait for many, many days okay and that is
the data that you obtain okay.

For the first sample that is the size okay, second sample that is the size right and for the last
sample that is the size and I can extract what is called a polydispersity index okay. So,
therefore you can you know work with either monodisperse samples or polydisperse sample
you can extract you know the size or the polydispersity index from such measurements.
(Refer Slide Time: 35:39)

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I have couple of more example this is a using a light scattering to measure what is called a
CMC right, critical micellar concentration right. So, typically what happens is if I have say
for example water and I add surfactant molecules right which are represented something like
this, that is the head group or the hydrophilic part and that is a tail group or the hydrophobic
part, the moment I put them in water initially at low concentration you will have individual
surfactant molecules.

And then some of them may go to the interface because of the surface active nature and then
with increase in the concentration you will reach a case condition where the interface is
completely populated with surfactant and when you add more surfactant that is when you get
these micelles right and that concentration is what is called as a critical micellar concentration
right, what you are measuring here is the intensity I mentioned right.

It is intensity is in KCPS and on the right side you have hydrodynamic size okay, I mentioned
that if you look at because intensity I said intensity is proportional to volume square right
initially you have only monomers right or small aggregates you know you do not have any
scattering or very little scattering but at a particular location you see that the scattering
basically increases right.

That you can think about this could be because of the change in the size from maybe a small
aggregate to a micelle right. So, therefore that point you could think about as a CMC okay,
the other way of looking at this would be that of course when you do use DLS measurements

168
below a particular concentration again you have small species your sizes are going to be very
small okay, maybe below the detection limit of the instrument itself.

But at a particular concentration you see that you know you get a size a significant size which
can be measured with you know with reasonable accuracy with these instruments okay and
that is where essentially, so you can see that you know the whatever I whether I look at the
intensity at a particular concentration or the size both of them coincide right okay, that you
can think about as a CMC.
(Refer Slide Time: 38:30)

This is another experiment where they were looking at a dispersion which have what is called
a VPT volume phase transition and that volume phase transition happens what do I mean by
volume phase transition, you have a particle, it is an example what is called a micro gel
particles okay and these micro gel particles you should think about them as there is a center
where there is a high cross linking density.

These are polymeric particles, however with the center where the polymers are highly cross
linked and a outer region where there is a the crossing density is less okay, such particles a
particular class of such particles called pNIPAM polynipam okay which stands for something
like this okay. These particles if you put them in water and if you heat them up okay if you
subject them to temperature change they have a transition going from a expanded state to
more like a collapsed state okay.

169
So, what is done here is measurement of size as a function of temperature okay and at some
so this is you know as you decrease the size, so as you increase the temperature there is a
decrease in the size right, you can do measurements like that to infer about volume phase
transitions and in dispersions like this okay.
(Refer Slide Time: 40:11)

So, now the last part that I wanted to look at is analysis of sol gel transition in materials by
probing motion of colloidal particles okay. I have taken an example here just to give you
what is sol gel transition, this is an example where you have oppositely charged particle
mixtures you could think of this as positive recharge negatively charged particles you mix
them okay.

And this number that you see here it tells you the mixing fraction okay. So, 0 means is
completely one type of particle, 1 means is completely other type of particle 50 .5 means both
of them are in equal proportion okay. Now I want to ask you a question as to of course they
look very different right to visually they look very different, if I want to ask you is there a sol
gel transition okay in these samples.

If I want to do that what will you do. So, we understand what is sol gel right, in sol you have
particles in the gel the particles form a network right I had mentioned that you know is a solid
like right, there is a space panning network of the particle right.
(Refer Slide Time: 41:45)

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One of the simplest way of doing this would be just invert the wires right, very simple you
just invert the wires okay you see that liquid here it just flows there is in this case there is
some you know a solid and some is fluid, but however at some concentration everything you
know remains right, so right. Now if you want to infer sol gel transition in materials.
(Refer Slide Time: 42:10)

What people do is they use a technique called microrheology okay in which what you do is in
the system that is undergoing gelation, you put in some probe particles okay. These probe
particles if you are using microscopy typically you take particles which are you know micron
size length scale. So, in this case they have taken polystyrene microspheres of you know 1.05
plus or minus 0.01 micrometer dimension.

171
You put these probe particles in a solution which is undergoing gelation okay and then the
only thing that you should ensure is that the concentration of these particles is is very low and
these particles in no way should influence the gelation process right and what you do is you
look at these probe particles and you measure their Brownian motion I can get mean square
displacement okay as a function of time okay.

We have discussed you know how to do that right and what you are looking at is 2 separate
systems okay in one case it is a peptide in other cases it is a polymer okay and what is being
measured is means displacement as a function of time and we learned that your mean square
displacement okay will actually go as t that means your pre factor okay will have a slope of 1.
If the particles are in a viscous fluid they are purely diffusive right they are in a viscous fluid.

However when the gelation happens your del square of r of tau should almost become 0
because the particles are stuck in a network okay and they do not exhibit any Brownian
motion anymore okay. That is what you see here right, if you look at this case what they have
done is that they have added a reagent which will induce gelation okay. When there is
nothing here the slope of this you know mean square displacement as a function of time is 1.

But with increase in the concentration your it is almost flat okay. Therefore just by measuring
mean square displacement as a function of time I can infer something about a sol gel
transition okay, people also use these ah kind of probes to look at what is called as a
structural heterogeneity okay. Again I am going to take this example of gels right. So, if I
have a colloidal gel, now when I say colloidal gel.

So, this is say that you know this is a particle network okay. So, now if you look at a colloidal
gel so it will have say that I have taken a dispersion which has say 50% particles by volume
and I have made that to gel okay I have induced gelation. So, you will have 50% still water
right or the fluid. The continuous phase okay whatever that you had it is still 50%. Now if I
have a probe particle then depending upon the whether a probe particle is in that free space
okay or whether it is embedded in the network okay.

It will either exhibit you know this random motion or it does not right depending upon okay
whether it is in the part of the network or whether it is in the you know pores okay or the
fluid between in the network okay. Therefore by doing some experiment like that I can

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actually look at what is a structural heterogeneity okay. So, therefore measurement of
Brownian motion is a very powerful tool you could use it for you know studying particle size.

You can you know do experiment like this you know where I can infer something about
gelation time or the dynamics leading to gelation and things like that okay. So, maybe with
that I will stop here.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-12
Molecular Origin of Van Der Waals Forces

Okay.
(Refer Slide Time: 00:14)

So, we will start with the module 2 which is going to be on what are called as van der Waals
interactions.
(Refer Slide Time: 00:29)

So, this is going to be the content that I would most likely you know follow throughout you
know this module. We will start with talking about molecular origin of van der Waals

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interactions. So, that would need you know you know little bit of intro to dipoles, induced
dipoles , then we will talk a little bit about you know molecular interaction between ions and
molecules.

That is important for us to have a background because we are going to extend that concept to
van der Waals interaction between particles later okay. So, therefore we will start with talking
about van der Waal forces in molecules and atoms and then we will try and see how can we
extend those concepts to talk about van der Waals interaction between particles. Then we
have bunch of things which concern van der Waal's interaction between particles we will you
know discuss a little bit about scaling of van der Waals interactions.

And derive an expression for van der Waals interaction between you know different objects.
We will introduce a concept of Hamaker constant because when we talk about van der Waals
interaction between atoms and molecules we need information about you know dipole
moment we need information about something called as a polarizability, we need to know
something about you know the frequency of vibration of atoms and molecules okay

All of that are required for you to estimate what is the van der Waals interaction between
atoms and molecules. Now in order to calculate van der Waals interaction between molecules
all the physical parameters okay are kind of clubbed together into a constant what is called as
a Hamaker constant, we will try to tell you a little bit about how does this come about . Then
so, followed by.

So, there are some theories that people have developed okay which are useful in obtaining the
van der Waals forces. For example we are going to touch upon a theory where we are going
to show that this Hamaker constant on which the van der Waals you know forces depend on
you know you can obtain that from bulk properties of the materials like by measuring surface
tensions or by measuring you know the dielectric constants you know.

So, we will try and relate the Hamaker constant to some measurable you know properties of
the materials and then we will see how you know that can be used for obtaining van der
Waals interactions. Finally we will talk about it turns out that the you know when we say that
the van der Waals interaction between 2 particles , it is also important in which medium you

175
are putting the particles, is the medium in which the particles are present is it water, is it air,
you know or is it vacuum right.

So, the medium in which the particle dispersed is also important. So, in that context we will
talk a little bit about what is the effective medium on van der Waals interactions, how is the
presence of a medium affect the van der Waals interactions and then finally we will end with
talking something about combining relations. These combining relations are useful when you
have information about the van der Waals interaction between 2 atoms or molecules or
particles in vacuum I can use that information to obtain van der Waals interaction between
the particles in any medium okay.

So, therefore these combining relations become important. So, this is what is going to be the
flow of you know this particular module.
(Refer Slide Time: 04:19)

Just a bit of introduction one thing that you should be aware is that the van der Waals
interactions are always present okay, you take any colloidal system be it particles in a fluid
you know association colloids in a fluid or any colloidal dispersions you talk about the van
der Waals interactions are always going to be there. Okay that is okay they are the most
important forces in colloids and surface chemistry or physical chemistry or colloids and
interfacial science.

So, these van der Waals forces have their origin, they originate because every atom or a
molecule will have some dipoles and induced dipoles which are inherent to you know these

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molecules or atoms , we will again discuss some of these you know terms as we go along and
therefore such interactions they are really important when you want to really look at any
aspects of material study okay.

Whether you are trying to look at formulating new materials, whether you are trying to tailor
some properties of you know material. So, these become very, very important.
(Refer Slide Time: 05:36)

In a nutshell there are actually 3 sub class of interactions which contribute to van der Waals
okay. That means if you have a total van der Waals interaction, it has contributions from
something called as a Debye interactions. This Debye interactions are interactions between 2
permanent dipole and a induced dipole okay. That is the Debye interactions. And something
called a Keesom instructions which is interaction between 2 permanent dipoles okay.

If you have 2 permanent dipoles and the interaction between them would be phi Keesom and
what is called the London dispersion forces or London interactions which is interaction
between induced dipole and induced dipole okay. You take any material you know it could be
like say you know if you have a container with water okay or any you know liquid or any you
know condensed phases okay.

You will see that there will always be van der Waals interaction and this interaction would be
combination of the interactions that come because of what are called as Debye interactions,
Keesom interactions and London dispersion forces or London interactions okay. So, before

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we talk a little bit about each of these things we will try and do a very quick intro to dipoles
and induced dipoles okay.
(Refer Slide Time: 07:08)

So, all of you already know a dipole, it is essentially a pair of electric charges okay which are
of equal magnitude okay, but they have opposite sign and they are separated by some
distance d and for that you define something called as a dipole moment which essentially is
the product of the magnitude of the charge multiplied by the distance right. That is what is a
dipole.

And typically whenever you represent dipole you start with you know a line starting from the
negative charge and you kind of draw an arrow and the arrow typically points from the
negative to positive okay. That is a typical convention that people use, that is what is called
as a dipole okay.
(Refer Slide Time: 08:04)

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Let us talk a little bit about what is called as a permanent dipole okay, any thoughts what is a
permanent dipole some thoughts, water molecules yeah. So, water molecule has a permanent
dipole right, whenever you are seen you know water molecules people represent something
like this okay. That is your oxygen and that is your hydrogen okay, people typically say you
know oxygen end will have some negative charge.

And okay the hydrogen end will have some positive charge right okay, that is an example of a
molecule which has a permanent dipole okay. So, the of course you can think about other
examples right HCl is another example hydrochloric acid okay. So, typically permanent
dipoles are found in molecules in which one of the atom is strongly electronegative okay,
when one of the atom is strongly electronegative okay.

If you take the case of HCl it turns out that its chlorine has 7 electrons in the outermost shell,
chlorine has 7 electrons in the outermost shell and it wants to share an electron with hydrogen
okay. So, that you know it can complete its outer layer more shell right. So, therefore
typically what will happen is when you talk about sharing of electrons we talk about a
covalent bonds right.

In covalent bonds it is you know and the electron that are shared they kind of belong to both
the atoms right and because you know chlorine is a strongly electronegative you know atom
what it does is, it will pull the electrons a little bit towards itself okay. So, because of which
you know the end of the molecule which has a stronger electronegative atom you know
acquires a partial negative charge.

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And the end which has a less electronegative atom will basically you know achieve a you
know it will have a slight positive charge okay. So, therefore whenever you have many such
molecules you know what will happen is there is going to be. So, if I take for example
another you know HCl molecule, again I can write a similar configuration this end is going to
be slightly positively charged.

This is going to be slightly negative charge and there is going to be a attraction between the 2
molecules which have permanent dipole okay. So, therefore and so typically molecules which
have similar symmetry. For example in oxygen, methane, CO2, all these molecules do not
have permanent dipoles okay, one of the requirement for a molecule to have a permanent
dipole is one of the atom or molecule has to be more electronegative than the other molecule
okay. That is what is called as a permanent dipole okay.
(Refer Slide Time: 11:42)

So, then what is called as induced dipole. So, induced dipoles what I can do is there could be
an atom or a molecules which is a neutral atom or a molecule now. So, if an ion approaches
you know such a neutral atom or a molecule or if I have a molecule which has a dipole if that
approaches a neutral atom what will happen is. So, it will disturb the electron cloud around
the neutral atom.

So, because of which you know the neutral atom can also be polarized it can also acquire
either positive or negative charge depending upon whether it is approached by a cation or an
anion or which end of the permanent dipole is near to the neutral atom okay. That is what you

180
know then what I would say that you know this there is a dipole that is induced in the neutral
atom okay.

The other ways by which you know you can have an induced dipole is that even if you take a
neutral atom okay we know that you know if you look at electronic structure you have in a
nucleus okay then you have different orbitals right and you know the electrons are kind of
revolving around these you know orbitals right. Now what will happen is but of course
because they are continuously they are not fixed in space right.

They are changing their position what will happen is momentary there could be a case there
could be some imbalance in the distribution of electrons you know in these you know orbitals
because of which one end of the atom can have a more number of you know electrons on one
side compared to the other side okay and that depends on you know it is probabilistic process
right.

So, therefore what could happen is even in a neutral atom at momentarily there could be a
case where one region of the atom is slightly negatively charged and correspondingly the
other end will have a positive charge okay. So, therefore induced dipole can be either can
occur if you have a neutral atom and if an ion or a permanent dipole approaches a neutral
atom or the fluctuations in the electron position you know can also lead to induced dipole ok.

So, therefore we go back to again now these interactions, now we know each of these terms.
So, therefore this Debye interactions are the interaction between a permanent dipole and a
induced dipole okay, you could think about a case like this right. There was a permanent
dipole okay and then in the case of a neutral atom okay you could have. So, one way to think
about this would be that let us think about a case.

See water has a permanent dipole right. Now if you look at some organic species okay which
is say sparingly soluble in water okay. So, we know that you know typically organic
molecules will not have a permanent dipole right. There what are called as non polar right
and water is an example of a polar molecule. If you have cases like that then you have some
molecules which have a you know a permanent dipole right okay.

181
And some non polar species which does not have any charge okay. Therefore you can think
about an interaction between a permanent dipole and an induced dipole right or if I take an
example where I have only non polar molecules okay, then what will happen is they will have
what are called as induced dipole, induced dipole interactions okay. That will be the more
dominant interactions.

Correspondingly if you take something like water molecule which has known to have a
permanent dipole, then the permanent dipole, permanent dipole interactions are going to be
more common okay.
(Refer Slide Time: 16:32)

So, this is a table uh which lists all the molecular interactions okay between atoms you know
or ions okay or the molecules that constitute matter right. So, I will just quickly go through
this table that is a description it will tell you what is the interaction between in this case this is
a interaction between ion 1 and ion 2 and that is an expression for the interaction potential
okay.

So, ion 1 has charge ze okay, the valency multiplied by the charge in the electron of 1 you
know ion similarly ze2 that is a valency again multiplied by e for the second one and 4 pi
epsilon 0 x okay. That is the interaction potential for 2 ions right and. So, therefore this goes
as 1 over x okay you know. So, the general form is phi going as x power – n, n for this case is
1 because you have 1 over x here right.

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Similarly you can think about interaction between an ion and a dipole okay. In this case the
ion will have a charge ze1 again, a mu 2 is it permanent dipole, it is a dipole moment of the
dipole 2 okay. Therefore this mu 2 here and cos theta is the angle right. For example I could
have a you know dipole here okay and my ion could be here right, you know that the theta
refers to the angle right and.

So, it has a 4 pi epsilon 0 x square dependence, therefore your exponent is going to be 2 okay.
So, I can go on so on and so forth okay. I can derive an expression again for the interaction
between 2 permanent dipoles in that case it will go as mu 1 mu 2 divided by x cube where
exponent is 3 right.
(Refer Slide Time: 18:47)

So, we have done these exercise already right, one exercise we have done in the class right.
So, if you look at the potential energy of interaction between 2 ions okay. So, I said that the
interaction potential if you want to calculate is the negative integral of the force times the
distance right. The force you know if you take 2 ions it goes as q 1 q 2 divided by 4 pi epsilon
0 into 1 over x square.

So, if I you know integrate that out right you get U to be q 1 q 2 divided by 4 pi 1 over x
right. This is exactly the first entry okay. So, if I rub this up right, that is actually your first
entry, only thing is q 1 you know q 1 is ze 1 and q 2 is ze 2 and you have 4 pi epsilon 0 that
this one and you know 1 over x right.
(Refer Slide Time: 19:47)

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I can do the similar thing for potential energy of interaction between an ion and a dipole right.
So, I have a ion whose charge is ze okay and there is a dipole okay, you know something
which you know in which you have 2 charges of equal magnitude opposite sign separated by
some distance in this case l okay and the this distance is okay R 12 right. So, I can write a
similarly I mean this first term you know.

So, this is ze times q okay, ze times q divided by 4 pi epsilon 0 into 1 over distance between
the 2 right, this is R 12 ok plus l by 2 because if you say that l is a you know the distance
between. So, this distance is going to be l by 2 l by 2 right okay. So, therefore this is going to
be l right. This is small mistake right this is going to be right, because if you look at what is it
R 12 would be yeah.

So, yeah, yeah that is true, let us do like that okay. So, now if I look at this okay. Let us do
that right yeah. So, if I say that R 12 is the distance of the center of the dipole okay from
okay, this is the distance from the center of the dipole to the ion. Therefore your the distance
that the q + q is from the ion is R 12 + l by 2 right. Similarly this is going to be at a distance
R 12 - l by 2 right.

And I can simplify this a little bit. So, I can just do the right. So, therefore your denominator
becomes R 12 square - l square by 4 okay and this, this gets cancelled okay. So, - l by 2 - l by
2 that is l okay and there is ze times q q times l is club because that is a dipole moment okay
cos theta . Now in this case what will happen is because you have okay. This is for a case
where I have a okay let us not for a moment consider this is not there okay.

184
So, your I have ze here right, that is this term q times l and negative sign that comes because
of the you know there was a - l here right and 4 pi epsilon 0, now if you consider a case
where you know this R 12 is much, much larger than l I can kick this out therefore it becomes
1 over distance square okay.
(Refer Slide Time: 22:56)

Now I can do a similar exercise, but for a case where it is an oriented dipole right, you know
this dipole is oriented at a particular angle to the ion that I have okay, then this theta becomes
important you know I could similarly if R - and R + are the distance of these 2 you know
charges which make up the dipole I can actually write the total interaction energy is zeq
divided by 4 pi epsilon 0 into 1 over R + - 1 over R -.

These are just these 2 separation distances right okay and of course I can you know derive an
expression that connects these distances to R 12 right. I can do that, again if you use the
approximation if you do some simplification it turns out that you know the interaction
between the ion and the dipole for any arbitrary orientation okay goes as zeq l cos theta
divided by 4 by epsilon 0 into 1 over distance square okay.

So, that is the this term right. So, similarly I could do a construction and I can actually also
get what is the interaction between the 2 right, if you want to think about you know I could
take 2 dipoles + q - q okay, again other you know + q - q right and I can get the separation
distance to be x okay. If this is the l and l are you know distance between the ions that form
the dipole.

185
I can either take a fixed dipole, that dipoles are fixed in space I can calculate what is the total
energy of interaction exactly the similarly right. So, you can do that right, you know how to
do that right. So, if you go back here. So, when we did the 2 dipoles is the interaction
between this plus the interaction between this right. Similarly if you have a dipole, dipole
interaction is the interaction of these 2 plus these 2 okay.

These two plus these two, there will be 4 terms right, you can simplify that if you do that then
you will end up with a expression wherein you will have 1 over x power 3 dependence okay.
(Refer Slide Time: 25:34)

Now okay. So, this is again the same table right. So, if you look at you know the expressions
for phi right. This phi can be either positive or negative. That means the interaction can be
either repulsive or attractive depending upon whether you know you are dealing with ions of
same charge or you know. So, therefore in the table that I showed there are some entries
which sign may be positive or negative.

It depends on the kind of ionic species that you are dealing with okay. However, there are a
few entries okay which are marked here okay, that is a permanent dipole, induced dipole
interaction and a permanent dipole, permanent dipole interactions and induced dipole induced
dipole interactions you know they are always attractive okay and all of them have 1 over x
power 6 dependence okay.
(Refer Slide Time: 26:47)

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So, these 3 entries which are always attractive and which have 1 over 6 dependents are what
are called as van der Waals forces okay. So, that is your phi Debye okay phi Keesom and phi
London okay. So, because let us look at this right, this is a interaction between 2 permanent
dipoles of course you know it should depend on the magnitude of the dipole moments okay.

And this is you know 1 over 4 pi epsilon 0 that comes from the electrostatics right and you
have kB T, the thermal energy and 1 over x power dependence. So, therefore the terms which
have only dipole moments they are the Keesom interactions because they are the interaction
between the permanent dipoles okay and if you look at the Debye interactions which are
interaction between the permanent dipole and the induced dipole.

So, you have these are the dipole moments okay, then this alpha 0 1 and alpha 0 2, these are
what are called as polarizability okay which tells you something about I talked about you
know this induced dipole right.
(Refer Slide Time: 28:31)

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So, I said that okay I say that no I have a neutral atom okay and I said that if I have you know
if a charged species approaches a neutral atom or if a permanent dipole approaches you know
this neutral atom you know I say this can acquire okay, this can be polarized right okay. The
extent to which the approaching atom you know or a molecule or a charge species can
influence the electron distribution okay or distribution of electrons in the cloud okay is
basically measured by alpha okay.

So, higher you know. So, for some molecules it may be easier to influence the distribution
okay. So, we say that they are highly polarisable, but for some it may be very difficult to you
know influence the electron distribution okay. They are less polarizable okay. So, alpha tells
you something about the polarizability okay. So, therefore the term that have you know the
polarizability and the dipole moments would be the Debye by interactions.

Because that is the interaction between a permanent dipole and a induced dipole okay and the
third contribution London dispersion forces . So, we know what is alpha now okay, again 1
hour x power 6 dependence h is, what is h Planck’s constant right. yeah Planck’s constant and
this nu 1 and nu 2 okay, that what are called as the frequency of vibration okay of the atoms
and the molecules okay.

Now for a given atom or a molecule if you know all these you know parameters I can plug in
all of them and I can actually estimate what is the van der Waals force of interaction okay.
(Refer Slide Time: 30:53)

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So, we have done that. So, there is phi attractive or phi van der Waals is essentially the
summation of the 3 okay, because everything has 1 over x power you know - 6 dependence I
have taken x power - 6 out here okay and this 1 and 2 right 1 and 2 correspond to you know 2
atoms or 2 molecules right. Now if I have identical atoms, if I talk about just water molecule
for example.

Then you know your 1 is equal will be 2 right because you know we are talking about
interaction between same atoms or same molecules okay, you know this expression is for 2
atoms and molecules which are not identical, but if I have identical atoms and molecule for
example if I am worried about the van der Waals interaction between water molecules okay
in a container which has only water.

Then you know your 1 is equal to 2 right because you are talking about interaction between
like atoms or like molecules. Therefore your alpha 0 1 will be equal to alpha 0 2 right.
Therefore I have written this as 2 times alpha 0 1, again mu 1 is equal to mu 2 because the
dipole moment of water will be the same right. Therefore this becomes 2 times alpha 0 1 mu
1 square.

Similarly this term will you know simplify to 2 by 3 mu 1 power 4 right divided by k B T + 3
h by 2, this becomes 2 nu and 2, 2 gets cancelled right and then I have nu square here again 1
nu 1 nu gets cancelled. Therefore you have 1 over nu and you have alpha 01 alpha 02 which
will be alpha 0 1 square right okay. Now this pre factor is actually you know called is given
like beta 11 right.

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1 1 because again it is a interaction between same identical molecules and that has x power -
6. Now you should think about in a similarity of this attractive part to phi Lenard Jones,
remember we wrote this as x bar - 12 - beta x power - 6 right. This part essentially is the van
der Waals interactions right okay. So, now we know where does this come from right. This
essentially comes from the van der Waals attractions okay which has 3 parts okay London
dispersion forces, Keesom interactions and Debye interactions.

We kind of we did not derive expression for this, we kind of know how they come about and
you should be able to identify each of these terms to have an idea as to which one is you
know phi l which one is phi D and which one is phi K.
(Refer Slide Time: 34:18)

So, I just want to . So, this is a table, this is a really good table I think you can learn a lot
about van der Waals forces from this particular table. So, this is a compound okay the
molecules of interest to you and that is mu dipole moment you know its units is Debye right
and if you look at like say. So, if you look at this term right, if you look at this expression you
have 1 over 4 pi epsilon 0 whole square.

And there is alpha 0 1 right alpha 0 1. So, it is actually this term okay. So, right. So, alpha.
So, basically this will give you what is alpha okay, the polarizability right and that is beta
okay, that is this term right beta 11 and this tells you about the percentage contribution okay
and we said that there are 3 contributions okay, what is the individual contributions to the
total van der Waals force of interaction okay.

190
That is the Keesom interaction, that is between permanent dipoles okay, that is London
induced dipoles and Debye between the permanent and induced okay, what can you say about
this table, look at these numbers, I want you to make a comment about what can you say
about this table, this is a unique feature over the number that you have you okay, that feature
is that look at this entry, it is always non-zero okay.

That means you take any atom or any molecule London dispersion forces are always present
okay right, that is one thing and if you look at the other 2 terms right, there are cases where
this 0 here 0 here 0 here right. So, therefore depending upon the molecules that you work
with okay, this Keesom and Debye interactions may be there, may not be there but the
London dispersion forces are always present okay.

And let us look at cases where if you look at London dispersion forces here right, here for
these 2 molecules which are benzene and CCl 4, again CCl 4 is again another example of a
symmetric molecule right, symmetric molecule where only induced dipoles would be present
okay. So, the cases where for the non polar molecules okay, for non-polar molecules you will
see that the contribution of London dispersion forces would be highest.

Examples are benzene and CCl 4 okay. However, on the other hand if you take molecules
which have permanent dipoles, for example water right or if you take even ethanol right
okay, they are example of polar molecules right and if you look again the numbers it turns out
that the contribution of the permanent dipole permanent dipole interactions is highest for such
molecules right.

So, if I look at water. So, 84.8% is the phi K okay and if you take ethanol you will see that
again of course London dispersion was also important but there are significant contributions
from the phi K itself right. So, therefore so I can say that you know this phi K + phi L + phi D
divided by the total phi right, phi total or phi van der Waals. Phi van der Waals should be
equal to 1 right.

That is what it will turn out right. So, if you look at this number, this 5.5 + 6 right that is
going to be 11.5 + 88.5, that is going to be 100% right okay. So, that is yeah. So, this induced
dipole I talked about 2 ways in which you know this induction can occur right, one is if I

191
have a container you know which has a mixture of both you know neutral molecules and
charge molecules okay right.

That is one example, but even in cases where I have only neutral molecules okay the
disturbance you know to the distribution of ions you know the electrons in the cells that can
also lead to induced dipoles. For example if you look at like say benzene right benzene. So,
you see I mean everything comes from the induced dipole interactions ok. That means if I
have like say a container which has benzene right.

Now we will have only you know every benzene molecule will only see other benzene
molecules right. But the fact that they are also neutral okay you know yeah, it is not because
it is not that you know one benzene molecule will come near another benzene molecules and
it will induce a dipole you know it will induce the formation of the dipole okay.

Yeah yes, yeah right, that is what if I have a neutral atom if a charged species comes near it
of course it can disturb the distribution of ions in around the yeah, it does not have a a
permanent dipole yeah okay. I am thinking if 2 benzene molecules come together yeah, then
both are getting induced, that is why it is called induced, induced intervals. No what will
happen is this right okay. Let me just make that point that is clear. So, that is a good point.
So, what he is trying to say is this.
(Refer Slide Time: 41:45)

See one thing that is important is that you know see for the induced dipole interactions you
know to occur the orientation of the molecule is also important right, ok the orientation of the

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you know for example if I have like say HCl molecule ok which is say this is slightly
negative, this is slightly positive right. Now you know if only if Cl - end comes near H +,
there is going to be attraction right okay.

So, anyway. So, in the case of induced dipole what will happen is this right. Now I said that
because of the fact that the electrons are not mobile they are moving around, there is going to
be a fluctuation in the electron density right, that means if I take you know even a neutral
atom or a molecule ok. If you look at some regions of the atom at some particular instant in
time they may have a higher density of electrons compared to other regions okay.

So, therefore so the region where there are more electrons will acquire a negative charge and
the region where you know there is less electrons will acquire a positive charge. Now this
will happen for as I said right this only occurs momentarily and this can happen for may
happen may not happen is a statistical process right, it can happen for a large number of
molecules which may be in a container.

Now if the orientation of the molecules are such that ok, if there is another you know again a
neutral atom which has been polarized because of the change in the fluctuation right.
Therefore so if there is a negative end and there is going to be. So, if you sum up all the
interactions such interactions it will turn out that okay, the overall interaction is going to be
attractive okay.

It will go as 1 over x power 6 dependence okay yeah, if you can read up a little bit about it
okay. So, what I will do is I mean so yeah so maybe I will just stop here okay. So, we have
kind of talked about the van der Waals interaction between you know atoms and molecules. I
have introduced you different terms, we know where the van der Waals interactions come
about now okay.

So, we will try and extend these concepts to van der Waals interaction between colloidal
particles okay. If I have colloidal particle 1, colloidal particle 2 okay. So, we will see how do
we think about van der Waals interaction between particles in the next class okay.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-13
Vanderwaal Interactions Between Particles

(Refer Slide Time: 00:14)

So, far what you have done is we have looked at molecular origin of van der Waals
interaction , we did a little bit of basics looking at dipole, induced dipole and then we talked
about following that I showed you a table where you know we had listed several molecules or
atoms and we were looking at molecular interactions and what is the contribution of the
Debye interaction, the Keesom interaction and London dispersion forces to the overall van
der waals interaction okay that is what we are done.

So, what we will try and do today is these 2 topics, one is looking at van der Waal interaction
between particles now and we will look at a very simple and nice concept called scaling of
van der Waals interaction for macroscopic objects, what I mean by that is, if you so
macroscopic objects corresponds to particles right, you know or any you know colloidal
length scale species right okay.
(Refer Slide Time: 01:28)

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So, just to do a quick recap. So, this is what we had done in the last lecture. So, if I have 2
atoms or molecules which are separated by a distance x we said that the total contribution to
the van der Waals forces or van der Waals interaction comes by the Debye interaction,
Keesom interaction and London dispersion forces and this is what we wrote if we have 2
dissimilar you know atoms or molecules 1 and 2.

And that kind of simplifies to this equation if you have interaction between 2 similar atoms
and we said that this all this constant here that is your beta, right that is what we had done and
I also mentioned that this is analogous to you know the attractive term in the Leonard Jones
potential right. That is what we are done okay.
(Refer Slide Time: 02:23)

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Now so, if you want to calculate the van der Waals interaction between colloidal particles
you know we can actually extend. So, here we are assuming that you know there are 2 atoms
or 2 molecules which are interacting. Now you can consider a colloidal particle 1 and a
colloidal particle 2 as consisting of collection of large number of atoms and molecules right.
In fact we can calculate that right, if I know what is the size of the particle that I am dealing
with.

And if I know you know the chemistry of the particle, if it is in a gold, silica or anything right
I mean I should be able to calculate the number of atoms and molecules that constitute the
colloidal particle that we are considering right. Now the interaction between colloidal
particles are essentially summation of the pairwise interaction of the constituent atoms or
molecules that make up the particle okay.

That means okay in this case I am considering a case where I have 4 ok 16 you know a
particle which is made up of 16 atoms okay, similarly there is another particle which is again
made up of similar number of atoms right. I take one particle and I look at you know its
interaction with all of them okay, all the 16 right, then I go to the next one okay and again I
look at the interaction with all the other 16 atoms of molecules.

And I sum them up okay. So, this pairwise addition of the interaction of every atom or the
molecule that constitute a particle with the atoms and the molecules in the other particle is
what gives rise to the total van der Waals force of interaction between colloidal particles
okay.
(Refer Slide Time: 04:15)

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So, that is again just like you know atoms and molecules the van der Waals force of
interaction or van der Waals interaction between colloidal particles are again they have their
origin in the dipole and the induced dipole interaction just like the atoms in the molecules,
but one thing to keep in mind when you compare the interaction between molecules and
particles is that the strength of van der Waals attraction okay.

In the case of macroscopic objects that is colloidal particles okay are much larger because
each particle has a large number of atoms and molecules, that means if I were to calculate the
strength of van der Waals interaction between atoms and molecules and compare that to the
strength of van der Waals interaction between 2 macroscopic particles okay at a particular
separation distance you will see that the strength of van der Waals interaction for the
macroscopic particles is larger compared to that for the molecules and the atoms at the same
separation distance okay.
(Refer Slide Time: 05:29)

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So, the other thing to notice is that they are relatively long ranged compared to the atomic or
molecular forces okay and they can have interval of influence ranging from about 0.2
nanometer to 10 nanometer okay, everybody understand the statement okay. Let us go back
okay, I just want to make a point that they are long-ranged compared to the atomic or
molecular forces okay.

For that I will again go back to this picture okay Leonard Jones potential okay, you look at
both the repulsive part and the attractive part okay and if I were to write what is the range of
interaction I can say it is up to about 0.8 nanometer right, beyond that distance you know you
do not have to worry about the you know both the terms are essentially 0 that means you do
not have to worry about these interactions beyond the distance okay.

But however if you take you know van der Waals forces between colloidal particles they
have a range going from about 0.2 nanometer to 10 nanometer compared to 0.8 nanometer
they are more long ranged right, that is the point that I want to make.
(Refer Slide Time: 07:10)

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Now we will do a very simple exercise which is what is called as scaling of van der Waals
interaction between large bodies or large particles okay. Good thing about this exercise is that
it will also help you to think about how do people calculate van der Waals force of interaction
between the particles okay or the macroscopic particles. So, what you have is a case a and
case b okay.

That is you know there is a subscript a that corresponds to case a and there is a subscript b
that corresponds to case b. So R is a radius of the particle and they are separated by distance r
a in the first case and r b in the second case okay and both for case 1 or and case 2 or case a
and case b the particles are of equal size okay and we are saying that they are spheres of
equal size.

And they are separated by some distance okay, we will assume that the spherical particles are
of same composition okay, that means if I were to think about a case a if I have taken say
silica particles okay, the other particle will also be silica particle and then similarly all the
particles will have the same composition okay. That is done just to keep things simple okay.
You can do a similar kind of exercise also for you know the cases where the composition
need not be same.

But you know for simplicity we have done that okay. So, these 2 individual cases case a and
case b are in a way related because the radius of spheres in a and b are related by this R b is
equal to f times R a okay, that means if you know because if f is greater than 1 the size of R b

199
is greater than the size of the particles you know that you see in you know this R a by a factor
f okay.

Similarly the distance of separation between the spheres in a and b are again related by a
similar kind of way where r b is again f times r a okay. So, we will ask a question as to what
can we say about the van der Waals force of interaction in the case a and what is the van der
Waals you know force of interaction in the case b okay. That is a exercise that we will try and
do okay.
(Refer Slide Time: 10:15)

So we will take configuration a that is given here okay. Now if I consider one atom in a and
one atom in particle 1 and one atom in the particle 2 okay we know that there is a attractive
van der Waals force of interaction okay, that means every atom in sphere 1 attracts every
atom in sphere 2 with an attractive potential or energy which is given by phi a is equal to
okay - beta 11 x power - 6 okay.

So, we know where that comes from okay. Now because we want to calculate the total
interaction okay, before that what we have to do is we should calculate the number of atoms
in particle 1 or sphere 1 and the number of you know atoms in particle 2 or sphere 2 right. If
you define NA as the total number of atoms okay, if you define NA is the total number of
atoms in the particle the number of atoms per unit volume is NA divided by volume.

I can you know relate volume to the density and the mass, therefore the number of atoms per
unit volume okay is given by rho N A divided by M, is it ok right. N A is the total number of

200
atoms divided by the volume of the particle will give you the number per unit volume right,
number of atoms per unit volume right and that number is going to be same for both the
particles right.

In fact whether I take because these are made up of same composition their same composition
whether I take N A into rho divided by M, that is the number of atoms per unit volume
whether I take particle 1 here, particle 2 here, or particle 1 here, particle 2 here, that number
is going to be exactly same right, because their composition is same okay. Now if you take
some differential volume element okay dV is a differential volume element in sphere 1 in
configuration a okay.

This dV 1 a corresponds to a differential volume dV in sphere 1 in case a right, that is here,

that is your case a. Similarly if dV 2 a is the differential volume that you consider in sphere 2
okay and again corresponding to case a, then this term and this term will give you the total
number of atoms right, it will give you the total number of atoms that you have in the
differential volumes d V 1 a and d V 2 a is it okay.

Yeah N is the total number of atoms you know yeah, in fact but the cases are different. Now
so you are considering both have the same number of atoms in both the cases is the same, you
see if I take a colloidal particle right I am saying that I have a colloidal particle okay. If it is a
chemically homogeneous okay, if it is say gold nanoparticle for example, whether I take a
very small fraction of the particle.

And I calculate what is the number per unit volume by considering this or I take another
small volume and I calculate or I calculate for the entire particle itself it will be the same
number right. So, therefore this rho N A by M, that is what I was trying to say right, whether
I take case a or case b okay or any particle this number is going to be same because they are
of same composition okay.

The total number of pairwise interactions are essentially the product of the total number of
you know atoms that we have in the differential volume d V1 a and in the differential volume
d V 2 a okay, that is the total number of pairwise interactions okay one of the way to think
about this would be that imagine that I have 2 particles okay. There is a colloidal particle, just
for the sake of simplicity.

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There is a colloidal particle which has only 2 atoms okay. So, the number of pairwise
interactions are interaction of this with this and this with this that makes it 2 okay and the
interaction of this with this and this with this that makes it another 2 okay, therefore the total
number of pairs interactions are 4, therefore the number of atoms in this multiplied by the
number of atoms in this will give you the total number of pairwise interaction that you should
consider right. That is this.

So, yeah I mean okay so N A is defined as the total number of atoms okay. Now okay, so do
you guys have a confusion that why is this rho N A by M same for both the cases, is that your
confusion, I mean okay let me put this way okay. So, say that I have gold nanoparticles okay
and say that they are prepared say that you know I have made particles of different
dimensions okay by a same technique for example.

I have used identical you know reaction to make these particles but I have a way of tuning the
size okay, maybe you know we define this aspect ratio right, this is l divided by d is aspect
ratio and aspect ratio is different in the 3 cases. Now if the reaction chemistry that is involved
in the preparation of all of these are the same, then I would expect particles of same
chemistry right, same composition right.

Now if the particles are of same composition whether I take this particle or this particle
calculate the number of atoms per unit volume okay will be same for all of them right. So, all
I am trying to do is define a quantity called number of atoms per unit volume okay, let us not
say that you can say that N A is the number of atoms right okay in a given volume right.
Therefore you can define number of atoms per unit volume that will be this quantity.

And because the compositions are the same this is going to be same for all the particles if you
considered, is that okay. Therefore the total number of pairwise interactions okay between the
volume elements that we have considered okay is this.
(Refer Slide Time: 18:41)

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So, now instead of considering individual atoms or molecules, if I taken a differential volume
now okay dV 1 a and dV 2 a right, then I can think about what is called as a the increment in
the so they were interacting by some energy earlier, now because I am considering a large
number of atoms right in each of these differential volumes. Then the increment in the
interaction is given by, this is the this term that we had for interaction per pair right.

So, let us go back right this okay is a interaction per pair right multiplied by the number of
pairs okay, the number of pairs multiplied by the interaction per pair okay will give you the
increment in the interaction potential, if I want I can integrate that okay over the entire
volume of the spheres, then I would get the total van der Waals you know force of attraction
between every atom you know between the 2 particles now right.

Because I have considered all the atoms now, that is going to be a double integral right is
going to be a volume integral right okay. So, I just have to integrate this okay because this is
constant I have taken it out, beta is also constant because once the material that you are
considering is fixed, beta is fixed therefore double integral of r a power - 6 because r a is the
separation distance here right.

That is a separation distance now multiplied by the 2 differential volumes right. So, that is the
total interaction potential between all the atoms in particle 1 which has a radius R a and the
particle 2 which also has you know radius R and they are separated by a distance r a right.
(Refer Slide Time: 21:32)

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I can do a similar exercise okay, what do you mean which are not related yeah I mean I could
have in fact you know you know you do not have to go through this concept of differential
volumes okay, you can also take the entire sphere and I can do it okay. Then it will be a much
simpler you know exercise as well okay you can do that as well yeah. Now I can do a similar
exercise okay and I can calculate the van der Waals force of interaction for the case 2 right.

For the case 2 we had again sphere 1 and sphere 2, they are separated by a distance R b right
and of course there radius were also R b right and if I do that I will get a similar expression
okay only thing is instead of r a I would have r b to the power of - 6 and you will have
differential volume 1 in the case b, this is case b right. And the differential volume 2 in the
case b.

Now we know that R a and R b are related right. R b is larger than R a by a factor f okay and
because the volume goes as R to the power of 3 okay I can relate differential volume in the
case of b to the differential volume in the case of a okay as dV 1 b is f cube times dV 1 a
right. Similarly I can say dV 2 b that is the volume of the differential volume v 2 that I have
considered in the case b is a factor f cube times differential volume in a right.

If I put them back into this expression. So, I have f R a power – 6, there is f 3, f 3 okay, this
essentially gets cancelled what you end up with is whatever that you had for phi a, therefore
this tells you that the van der Waals force of interaction in the case b is same as the van der
Waals force of attraction in the case a okay. So, the implications of this is that if I take like
say 100 nanometer particles okay.

204
And if I am talking about the van der Waals force of interaction between them like say at 10
nanometer okay or I take 10 nanometer particle and I am asking a question as to what is the
van der Waals force of interaction at a separation distance 1 nanometer right. So, 100 divided
by 10 is the scaling of the size okay, that is by a factor of 10. Let us look at scaling the
distance 10 divided by 1 again there is a factor of 10.

In cases like this 100 nanometer particles at a separation distance of 10 nanometer will
experience the same van der Waals force of attraction as the case where you have 10
nanometer particles separated by a distance of 1 nanometer okay. So, that is the implication
of this result okay yeah. So, that is all I wanted to say today.
(Refer Slide Time: 25:53)

And then what we will do is so yeah, so this is again I have kind of a similar thing that I
mentioned right, if you take 0.3 yeah basically the same concept that I mentioned right, yeah.
(Refer Slide Time: 26:11)

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Yeah, yeah that is why right I mean we were saying the scaling of van der Waals interaction
right, that is what you know so that means if I take 2 cases where both the dimensions of the
particles and the separation distance scale in the same way okay in 2 cases, in such cases the
van der Waals force of attraction in the 2 cases will be identical okay, that is the you know
crux of the result.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-14
Problem On Scaling of Vanderwaal Interactions

(Refer Slide Time: 00:14)

So, there is a table that is given to you okay, you are supposed to calculate the fractional or
percentage contribution of Debye, Keesom and London dispersion forces to the van der
Waals attraction for each pair of molecules at 298 Kelvin okay. So, what you have been given
different compounds ethanol, water, Toluene 3 cases okay.

And you have been given what is the dipole moment right and the term that involves
polarizability is given and beta is also given okay. So, that means if I take a container which
has ethanol okay, the large number of atoms and molecules of ethanol right okay. So, if I take
a case like that okay what is the contribution of these 3 interactions to the total van der Waals
interaction right that is the question.

So, how do we go about doing that?. So, with whatever we have discussed so far do you think
we can attempt this problem yes, no, yes right okay.
(Refer Slide Time: 01:52)

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Let us look at this. So, this is if you have 2 identical molecules right 1 and 1 that will be the
total van der Waals force of interaction right. So, each of the terms okay as well as the overall
interactions have the same x power - 6 dependence right. If that is the case what I can do is I
can take each pre-factor right divided by this term beta that will give you the fractional
contribution of okay Debye, Keesom and London dispersion forces right. So, if you go back
and look at okay then you can calculate each of them right.

So, that is a same term right. So, every pre-factor that you have here 1, 2 and 3 that divided
by beta will give you the fractional contribution okay. Let us try and calculate one by one.
(Refer Slide Time: 03:26)

So, if you go back to the problem so I have been given mu right, the dipole moment okay,
that is given to me okay, temperature is given, beta is given okay. I can calculate this right 1

208
divided by 4 pi epsilon 0 is 8.82 into 10 power - 12 right - 12, it is a coulomb square per
newton meter square okay.

That is the unit SI units okay, that is whole square okay multiplied by 2 by 3 into yeah 1 by 4
pi epsilon 0 is directly 9 into 10 power - 12, you can also use that yeah, you can do that as
well yeah, yeah 2 by 3 times mu 1 okay mu 1 is given to 1.73 right is 1.73 Debye, okay I
need to convert Debye into Si units for that you are going to use a conversion factor which is
3.33 into 10 power - 30 okay.

That the unit will be coulomb meter right it is a dipole moment, charge times the distance
right. So, that is coulomb meter okay, that is to the power 4 right, because you know you
have mu 1 to the power of 4 there okay divided by kB is 1.38 into 10 power - 23 times 298,
that is the temperature that is given whole divided by beta 11, that has also been given to you
it is 3.4 into 10 power - 77 okay. You just work it out quickly and then let me know what the
number that you get.
(Refer Slide Time: 06:38)

Okay, so is the number that you get, the number that I have is 0.427 what I have okay. There
is a lot of exponents with very large numbers right. So, - 77 you have 10 power - 30 times 4
will be - 120 right yeah, yeah 0.41, that is fine yeah 0.41 is okay I mean you know 0.41 yeah
okay anyway. So, that is the order that you should get okay. So, similarly I can go back and
look at f D.

209
That is the Debye interaction which is the interaction between a permanent dipole and a
induced dipole right. Therefore you have a term that corresponds to the permanent dipole
right. That is the dipole moment and the induced dipole then there is a term that with alpha
which is polarizability okay. Therefore so this is the fractional contribution to the Debye
interaction.

So, this quantity has been given to you alpha 0 divided by 4 pi epsilon is given in the table
multiplied by 1 over 4 pi epsilon 0 okay mu 1 square divided by beta 1 1 right. So, 2 is here 1
over 4 pi epsilon 0 is this, alpha 0 divided by 4 pi epsilon 0 is given 5.49 into 10 power - 30,
that is been given to you and there is again mu 1 square 1.73 3.35 10 power - sorry this is
3.33 10 power - 30 whole square now okay divided by beta which is 3.4 10 power - 77 okay.

If you work this out the number that you should get is 0.097 okay. So, let us go back 0.097
that is 0.0 not that okay, this is 0.097 right and this came out to be 0.427 right. Now we want
to calculate f L right, we have done that, we have done this we want to calculate what is the
contribution of the London dispersion forces?. So, how do we do that?. So, you know this
value okay, what is that yeah right you can do that right f L + f D + f K should be equal to 1
right.

The fractional contribution has to be 1, therefore 1 - of 0.097 right 0.427 should give you
what is f L right, you could have calculated but of course you can get planks constant but you
do not know what is nu right, but other parameters are given okay. But if you knew nu I
could have calculated but we do not know that. So, therefore f L what is the f L that you get?
Right 0.476. Let us look at if our calculations are right.
(Refer Slide Time: 11:53)

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Okay that was ethanol right. So, we just calculate this to be 0.476, that is a percentage
contribution multiplied by 100 should give you 47.6 exactly the same number right, you are
again 9.7 and 42.6 right. So, similarly you can do a repeat the same calculation for the other
molecules that have been asked. So, one is water, other one is toluene right okay. So, you can
try and do a similar exercise.

So, this basically gives you a feel for calculating numbers and you know and then you know
see if you have done the right thing right. So, because we are talking about fractions, so you
know everything has to be less than 1 right and all of them should sum up to 1, the total
fraction contribution should show you know sum up to 1 okay. So, if you know that you
should be able to get this out okay. Yeah. So, maybe we will stop here.
(Refer Slide Time: 13:01)

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So, what we are going to do in the next class is to look at if you have 2 blocks okay, we will
do a simple exercise where I have 2 semi infinite blocks, we will try and calculate the van der
Waals force of interaction between them. Exactly similar way that we did for you know when
we did the scaling arguments okay. We will try and work out an expression you know that we
could use for calculating van der Waals force of interaction between 2 blocks. So, that is what
we will try and do in the next class.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-15
Calculation of Vanderwaal’s Forces Between Semi-Infinite Blocks and Hamaker
Constant-I

(Refer Slide Time: 00:14)

So, we are at module 2, we are looking at van der Waals interactions and what we have done
so far is these 4 you know pieces we have introduced van der Waals interactions you talked
about the molecular origin of van der Waals interactions. Then we briefly discussed about
van der Waals interaction between ions and molecules. Then how does one think about van
der Waals forces between the particles.

And then we discussed what is called as a scaling of van der Waals interaction for
macroscopic objects in which we found that you know if you have 2 particles separated by a
particular distance d 1 and other set of particles separate by distance d 2, if the radius of these
particles is R 1 identical particles and in this case if is R 2 okay, as long as the sizes and the
distances scale in a similar fashion.

We said that the van der Waals force of interaction in the case 1 will be exactly same as van
der Waals interaction in the case 2 okay. That is what we are done and today what we will do
is we will try and talk about these 2 aspects, one is will try and derive an expression for van
der Waals interaction between semi infinite blocks and then will introduce a constant which

213
is what is called as Hamaker constant which is useful if you really want to quantitatively
calculate the van der Waals force of interaction.
(Refer Slide Time: 01:59)

So, what we are going to do is a simple you know derivation in which you have block 1 okay
and block 2, they are separated by distance d, in this case d is the surface to surface
separation distance, we would like to calculate what is the van der Waals force of interaction
between the 2 blocks okay and the reason why they are called semi-infinite is because. So, if
you look at you know if I just write a coordinate system okay.

So, the length in this direction is finite okay and the length in this 2 directions are infinite
okay, what I mean by this length is the only thing that you have to worry about is these
dimensions are much, much larger compared to the separation distance okay, that is all it
actually means okay. So, how do we go about doing this okay and the procedure followed is
very simple.

So, first what you do is all of us know that you know if I take like say a molecule present in
block 2 and a molecule present in block 1 and if they are separated by a distance d or you
know or x whatever right, the separation distance I know how to write an expression for the
van der Waals force of attraction between the 2 atoms okay one present in each of the blocks
right. Then what we will do is we will consider a disk like element.

Disk like element could be something like this okay. So, this is a thin disk okay of some
dimension okay and then we will calculate what is the interaction between an atom and a disk

214
like element that we have considered in block 2 okay. Then that is a step 2 okay, step 3 would
be what I will do is I will integrate the van der Waals interaction between this and you know
the disk like element that we have considered over the entire volume to get an expression for
the van der Waals force of interaction between an atom and the entire block okay.

That is your step 3 okay, then fourth step what we are going to do is we are going to assume
that I am going to consider a thin section and then have this molecule embedded in that thin
section and then again do another integration essentially to get the van der Waals force of
interaction between this block and this block okay, that is the procedure okay, start with
interaction between 2 atoms present in each block.

Then interaction between the atom in one block or a molecule in one block and a disk like
element, third step is to get an interaction between you know this molecule and the entire
block then the block, block interaction okay, that is the typical procedure right.
(Refer Slide Time: 05:02)

So, for that what we will do is we will do some simple. So, the interaction between the atoms
we already know right. So, we know that phi a or phi van der Waals interaction would be
something like some - beta times x bar - 6 right. We already know what is the van der Waals
if I were to take one molecule here and maybe another molecule there okay, the van der
Waals interaction between the 2 is given by this right.

That is going to be minus because of the attraction right. Now what we do is we have a
molecule here and I have a disk like element okay and that disk like element is so the this

215
distance y okay is the from the center okay what is the this distance okay, that is your y okay
and the thickness of I know the disk is dy okay, this the distance between the surface of the
block and the molecule is z.

And I am assuming that this particular element is at a distance zeta from the surface okay. So,
this particular disk like element is located somewhere inside the block right. That is what we
have written right. So, consider a molecule located at O okay at a distance z from the surface
that is this distance okay and of course the assumption here is that block 1 and block 2 are
made up of the same material right.

That goes without saying that when we talk about when we are trying to derive an expression
for the van der Waals force of attraction between the 2 blocks we are assuming that the block
1 and block 2 are made up of the same material okay. Of course you can you know work out
and you can think about derive an expression for 2 blocks if the materials they are made up of
dissimilar material.

But for this particular class we will assume that they are made up of the same material okay,
then we are going to take a ring shaped volume element okay as I said it is at a distance zeta
from the surface. Now and of course there are 2 thickness right okay, one is the thickness you
know along this zeta other one is a thickness along this y direction right. And the 2
thicknesses are d zeta and dy okay.

So, therefore we know that the volume of this you know ring shaped element that we have
considered is dV is equal to 2 pi y dy into dz right, that is the volume of the ring shaped
element that has been considered is that okay right. Now if you look at any molecule okay, if
you look at any molecule that is on this disk I can say that every molecule on this disk okay.
Because we are we are taking a disk which is of very small dz and dy I can assume that every
molecule is at a separation distance x right.

So, I can say that, so therefore the this particular molecule is located at a distance x okay
from all the molecules in the ring shaped element right, I can make the statement right, then
what you can do is I can actually write up an expression. So, instead of considering 2 single
molecule the fact that I have considered a molecule you know in one block. And a ring
shaped element I can write an expression for what is the increment in the van der Waals force

216
of attraction between this molecule and all the molecules that you have in the ring shaped
element right.
(Refer Slide Time: 09:07)

We can do that. So, that I can write it as d phi is equal to what do we write the increment in
the van der Waals force of attraction okay, when I have considered a molecule in one block
under ring shaped element in the other block instead of 2 molecules present in each of the
blocks that for d phi is going to be number of pairs of interaction multiplied by interaction per
molecule right okay.

That is what we are done right, that is number of pairs multiplied by the interaction per pair is
what is going to give you what is the increment in the van der Waals force of attraction right.
So, then how do we calculate the number of pairs. So, we had defined rho NA by M right,
what does that give you, that is the number of atoms or number of molecules per unit volume
right, that is what it will give you.

Okay multiply it by the volume okay, that is 2 pi y dy into d zeta okay, that is the volume of
the ring shaped element that we have considered multiplied by the interaction per pair is
going to be - beta times x power - 6 right, that is the increment in the interaction between the
molecule and the block okay and in this case molecule and the ring shaped element that we
have considered right okay.
(Refer Slide Time: 11:19)

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That is what this is right, yeah, yeah, this is attraction towards the block, what is that yeah I
mean depending upon so, the question is there is the attraction towards each other, yeah both
the block too I mean. So, one okay so what you can also imagine. So, this is the attraction
between the blocks right. I mean are you saying that you know if I have block 1 is it that the
block 1 drags the particles towards block 2 is that what you are trying to ask or which angle
no, no see.

The simple concept that we are trying to do is I mean I think there is a reason why people
considered this ring-shaped element because you know your x is going to be identical right,
that is the reason why they have considered okay. So, now so when you say so what you are
trying to say is that you know is it that, so your question is it that this block is going to be
moved in some other direction is that what you are trying to ask, no correct. Why 2 forces,
suppose there is a ring then equal in opposite direction there will be 2 particles right okay,
correct.
(Refer Slide Time: 13:05)

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Now in this case what we are trying to do is I i have a molecule one here and there is another
molecule one there, what is the force of attraction between the 2 okay. Next there is one here
and another molecule of course there right because there are several molecules in the ring
okay. So, we are talking about the force of attraction between the molecule one present here
and a molecule there, that is about it okay.

And then we just adding it right, that is what we discussed you know when we talked about
the van der Waals you know interaction between macroscopic particles, all that we are trying
to say is that look it is the interaction between every atom or a molecule present in one with
the every molecule or an atom present in the other one okay. So it is the mutual interaction
between you know the molecules in each of the particles.

And then the pairwise addition okay, in that connection it is an attraction towards each other
okay, that is what I would say at this point yeah right. So, we know how we wrote this up
right. Now what I want to do is I want to calculate the van der Waals force of interaction
between this molecule and all the molecules in this block okay. So, what do we do for that.
(Refer Slide Time: 14:39)

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Okay so, we know that so this x right, this x is the separation distance okay and we know that
and x as I said for every atom or a molecule present on the disk because we are considering a
very small disk, this x is going to be same and I can relate x to the other distance that we have
right, you have z here, zeta and y. Therefore your x square is going to be z + zeta whole
square + y square okay.

Therefore combining these 2 what I can do is I can write d phi is equal to - rho N A divided
by M okay and I am going to take this constant beta and you have 2 pi okay, you have y dy d
zeta divided by instead of x power 6 I am going to write as z + zeta whole square + y square
to the power of 3 right. We have done that, now I have to integrate this expression to get what
is the total van der Waals force of attraction between this molecule and all the molecules in
block 1, okay.

So, that is going to be a double integral right, because you know you have dy and d zeta here.
So, I would have to do a double integral and because the variation in the y and zeta are not
dependent what I can do is I can do integration one by one.
(Refer Slide Time: 16:28)

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So, what I can do is I can consider the first term that is y dy okay divided by z + zeta whole
square + y squared to the power of 3 okay, I can do the integral okay from you know the
distance I mean y can go from 0 to infinity right. So, if I do that I can substitute for if you say
y square is equal to u 2 y dy is going to be du. Therefore this becomes 1 over 2 du divided by
z + zeta whole square + u to the power of 3 right okay.

And that is between 0 to infinity, therefore this becomes 1 over 2 if I integrate this, this is
going to be z + zeta whole square + u into - 3 + 1 divided by - 3 + 1 okay 0 to infinity that is
equal to 1 over 2 there is a - 2 here that I will become - 4 1 over 4 and at infinity you know
you have 1 over z + zeta whole square + u square right and 0 to infinity. Therefore this
becomes 1 over 4 into 1 over z + zeta.

At infinity this becomes 0 right okay 0 - 1 divided by z + zeta to the power of 4, therefore
you know if I do the first integral what I get is 1 over 4 1 divided by z + zeta to the power of
4 is what I get that okay yeah. So, you have yeah first is 0, first term is going to be 0, that is
what is sorry okay first term is going to be 0. So, one more thing why are you integrating
from 0.

Because I mean I have considered a ring shaped element okay and if I say that you know the
coordinate system I am going to start with the center of the disk you know the coordinates are
0 0 okay it can be infinite in the other direction, we are trying to calculate for the whole block
yeah, yeah. So, y is the see if you go back here right, see that is your y right. So, I can have a
very small disk okay.

221
So, essentially you can your y could vary from 0 when you are at the center and you it can go
all the way up to infinity yeah, should be the yeah I mean so all that we are trying to say that
these distances we are thinking about is of course if you see we are talking about when you
say semi-infinite blocks okay. So, all that we are trying to say is that look I see we have been
saying that van der Waals force of interactions typically.

If you work with any case where the van der Waals force of interaction we said that you
know + or - 10 nanometer you know up to over 10 nanometer is when you should bother
about the van der Waals force of interaction right. That means any distance more than that it
does not matter okay. But for the sake ease of derivation what you are doing is you are
assuming that okay it is a semi-infinite block.

That means the dimension that your of the block that you are considering are much, much
larger than the separation distance that you are trying to deal with okay. That is the only
significance here okay. So, similarly I can do the yeah, you have a question, we can go back,
yeah, yeah, yeah, one more slide, okay yeah. So, is this okay everybody gets this point right,
that essentially is the number of pairs multiplied by you know the interaction per pair, that is
okay right.

And then all that we are doing here is your separation distance is related to your you know z
zeta and y through this relationship okay. And then therefore and I said if you want to the
interaction between this molecule and the entire block okay I would have to do a double
integral right and because the variation in y and zeta are independent I can do integration one
by one okay. So, we considered one of the you know the y dy divided by z + zeta whole
square + y square to the power of 3 right and you can substitute for you know y square is
equal to u 2 y dy is equal to du right.

And therefore I can instead of y dy I can substitute dy divided by 2 should be done here okay,
divided by z + zeta whole square + instead of y square I am substituting u okay and if I
integrate this I get z + zeta whole square + u to the power of - 3 + 1 divided by - 3 + 1 okay.
Therefore I have a 1 over 2 and 2 - 1 over 4 factor here okay and therefore I have 1 divided
by z + zeta whole square + u whole square.

222
And when you have y is infinite this becomes 0 - 1 divided by. So, in this case you know
when you say y goes from you know 0 to infinity u also goes from 0 to infinity right okay,
therefore when u is infinity this becomes 0 - 1 over z + zeta to the power of 4 okay. So, that is
we essentially end up with this okay.
(Refer Slide Time: 23:25)

Similarly I can do the next one now. So, therefore now I have done this. So, therefore your
phi is going to be okay I will just write those things back rho N A by M into beta 2 pi okay.
Now integral from 0 to infinity d zeta divided by z + zeta whole to power 4 right okay,
because see we had we were doing a double integral okay. So, this I am retaining this okay
and the result of you know integrating this okay would be right.

And of course I have 1 over 4 right, yeah, yeah, yeah. This is also negative here sorry, yeah
okay let us do this derivation. So, 1 over if you do in a similar way so integral of d divided by
z + to the power of 4 okay 0 to infinity if you do that so therefore this becomes again z + zeta
- 4 + 1 divided by - 4 + 1 going from 0 to infinity, is it okay yeah.

Therefore this becomes 1 over z + zeta whole cube 0 to infinity and I have - 1 over 3 here
okay. Therefore your phi is going to be again. So, this - 1 over 3 into, this becomes 0 - 1
divided by z cube, is it okay. So, therefore your phi becomes there is 1 over 4 minus, minus
will become plus right, this is going to be 1 over 3 into z cube. Therefore if I substitute this
back here. So, I have 1 over 12. 4 3 is a 12 okay rho N A divided by M into beta 2 pi into 1
over z cube with a minus yes, because the minus sign is carries okay.

223
So, that is the, so this is now what we have done is this is the interaction between the
molecule one that was here and all the molecules of block 1 okay.
(Refer Slide Time: 26:27)

Okay that is what is actually done here okay. So, we had this as an incremental in the
interaction so we wrote x square in terms of you know the other distances okay, the
combining the 2 expressions we wrote this and then in doing a double integral okay for
varying y from 0 to infinity and zeta from 0 to infinity we essentially end up with you know
an expression like this right.
(Refer Slide Time: 26:55)

That is in the end that is what we have okay, that is again attractive there is a negative sign
here okay and that is the number per unit volume okay and beta is the coefficient and we have
2 pi and 1 over z cube.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-16
Calculation of Vanderwaal’s Forces Between Semi-Infinite Blocks and Hamaker
Constant-II

(Refer Slide Time: 00:14)

Now what we do is, we say that, I am going to say that this molecule O, it is now embedded
in block 2 okay. And again, it is made up with the same material right. And we say if this is
your molecule O and we are going to embed that in a small block of thickness dz okay. And
that is located at a distance z from the surface of another block right. Now, again I can write
up an expression for the increment in interaction okay. Exactly the way we wrote up okay.
(Refer Slide Time: 01:09)

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Let us go back and look at the expression right okay, it is I know that this is the interaction
between every molecule that is in this small element and the entire block right. Now my
interaction per. So, I will again, the same concept right. The number of pairs multiplied by
interaction per pair. Now, the interaction per pair now is actually it is - rho NA by M into
beta into 2 pi, right into 1 over 12 z cube, you guys agree, right.

There is the interaction per pair, now multiply by the number of, you know, pairs. So, I am
going to multiply this only by dz okay. And I am going to say that the interaction that I am
going to calculate is interaction per unit area okay, ideally, I should multiply this by the
number of molecules in this small strip, dz, okay, which is dz times rho NA by M, into some
area, right.

Because that is the volume. So, this will give me the number of atoms or molecules in their
small thin section, dz right. That is area times dz will be the volume that multiplied by
number per unit volume. But I am going to say that the d phi, or the phi that I am going to
calculate, it is actually energy per unit area. And then I am going to multiply this interaction
pair only by rho NA by M multiplied by the dz okay.
(Refer Slide Time: 03:28)

226
Therefore, I have rho NA by M whole square, I had 2 beta and there was 12 there. So, there is
a you know factor of 2 I have removed. So, beta pi into dz divided by 6 z cube is what you
get. Yeah, so this is yeah, yeah. I mean, this is the area of the surface area of the block if you
want to consider yeah okay. So, now, what I can I want to do is if I want to now get the
overall interaction between block 2 and block 1.

What do I do, I again have to do an integration and this integration is going to be from d
which is the distance of closest separation to again, infinity right, I could have them really far
apart, the separation distance is going to be infinite. And then I can bring them to any
distance d, okay. So, if you do that, your phi is going to be rho NA divided by M whole
square beta pi divided by 6 okay, again, z power - 3 + 1 divide by - 3 + 1 okay, 0 d 2 infinite
okay.

I have a negative sign here, right okay. So, therefore, this becomes - rho NA by M whole
square into beta pi by 6 into 1 over d square okay and there was 2 there right, there was a 2
here this becomes well right, because the - 2 right - 3 + 1 is 2. Therefore, 6 2 is 12 okay.
(Refer Slide Time: 05:31)

227
So, therefore, what you actually end up is the overall interaction phi A okay is going to be
row NA by M whole square beta times pi divided by 12 into 1 over d square, there are a
cluster of constants, this rho NA by M is a constant for a given material that you consider and
you have B okay, that is again beta, again constant for a given material okay, you can
multiply this by pi and divide by pi you know to get a particular form okay.

And then you know your phi A essentially goes as - A divided by 12 pi into 1 over d square
and this A actually is a cluster of constants which is what is called Hamaker constant okay,
which has all the material properties, right. It has what is beta, the density of the material that
you are considering Avogadro number and this is the molar mass right.
(Refer Slide Time: 06:46)

228
So, now, that is the interaction between 2 you know blocks right. Now, in fact, that is what
we derived here, okay, - A divided by 12 pi into 1 over distance square okay, that is for 2 flat
surfaces. And that is what I mentioned right, this interaction if you calculate I will come back
to this point little later, okay. Now, if you had 2 atoms or small molecules, you know your
energy of interaction goes as 1 over distance power 6.

Now, if you have 2 flat plates, the energy of interaction goes is 1 over distance square okay.
Similarly, you have expression for different you know, types of particles that you are going to
deal with okay, if you have 2 spherical particles of you know different radii R 1 and R 2 and
if they are again this you know separated by a distance d, then the energy of interaction goes
as - A divided by 60 times R 1 R 2 divided by R 1 + R 2.

If the particles are of same size this becomes R square divided by 2 times R right, if you have
particles of same size, then this gets cancelled. Therefore, regimentation will be - A divided
by 12 times my AR divided by 12 times d right, that is if you are working with 2 spherical
particles and if you would like to calculate what is the van der Waals force of interaction
between 2 identical spheres of same radius.

Then the energy of interaction is going to be - AR divided by 12 d okay. So, therefore and
this is the interaction between 12 a spherical particle under a flat surface the energy of
interaction goes as - AR divided by 6 times d.
(Refer Slide Time: 08:40)

229
So, there are expressions like this which are available in the literature, which you could use,
okay. So, this is, so this column is for the energy of interaction. And of course, as I said, if
you know the energy of interaction, I can also calculate what is the force of interaction just by
- dW by you know if you differentiate this with respect to distance, okay, that is when you get
the force of interaction right.
(Refer Slide Time: 09:11)

Now, before I would like to make a point, but before that, I would think about what is the
units of Hamaker constant, right. Let us, so this is the expression for Hamaker constant, right,
that is what we derived. So, rho has units of kg per metre cube, right. That is your density. NA
is number per mole right divided by and you have M is a molecular weight that is, you know
grams per mole right or kg per mole or grams per mole, right.

What is that, Yeah, yeah so that is finite. So, right, everything is cancel. So a beta was in your
beta.
(Refer Slide Time: 10:02)

230
I do not know if you pay attention beta actually has units of joules metre per 6 okay, it has
units of okay joules, okay metre per 6 right, this unit is joules metre per 6 and you have 1
over metre cube okay again whole square. So, therefore this metre power 6 metre power 6
gets canceled. Therefore, Hamaker constant will have a unit of joules right. Then let us think
about typical values for Hamaker constant okay.

I know the magnitude of beta for several materials, let us take a simple case of water, beta is
okay 2.10 into 10 power - 77 joules metre per 6 right this beta okay multiply that by density
of water is 1000 okay let us say some number typical number kg per metre cube Avogadro
number is 6.023 10 power 23, you have pi divided by molecular weight of water it is 18
grams per mole okay.

That is 18 divided by 1000 okay, that is kg per metre cube whole square right, if you put in
all the number that I get is about 2.32 okay that is A is going to be 2.32 into 10 power - 19
joules is what you get okay. If you put in the typical values you know for the constants right.
So, this for water or typical number that you get is 2.3 to 10 power - 19. So, typical range of
Hamaker constant for any material is in the range from 10 power - 20 to 10 power - 19 joules
okay.
(Refer Slide Time: 12:12)

231
Now, this is a list of Hamaker constant for different materials taken from different sources ,
what is interesting to note would be that this is water if you look at this number right 4.35 is
very close to what we calculated right of course, this is an approximation right, it is very
close to what we calculated. Now, if you look at metals okay, the numbers are I know about
16 to 45 you know 10 per - 20 okay.

This is 10 power - 20. This is when you say is 10 power 20 there is going to be - 20 right.
Now, and if you look at gold. So, what it means is that if I have a polystyrene particles okay
of some size say 10 nanometer for example, okay whose Hamaker constant is about say 10
okay 10 power - 20 joules or if I take gold particles of again exactly the same size whose
Hamaker constant is about 45 okay into 10 power - 20 okay.

The gold particles would experience a greater van der Waals force of attraction compared to
the polystyrene particles because the Hamaker constant for gold particles are much larger
than the Hamaker constant for polystyrene, okay, that is the implications. Therefore, you go
back and look at literature, whenever you people talk about gold nanoparticles, you will
always see that the moment you may gold particles they cluster together.

And they form large aggregates because of the large magnitude of van der Waals force of
attraction, if you want to keep particles of metals, okay in a dispersed state, what people
typically do is they make particles and then they typically put a stabilizing layer. It could be
grafting, okay, it could be putting a surfactant layer on the top okay, something like that there
is always done.

232
If you do not do that, the van der Waals interactions are going to dominate and they will lead
the particles could aggregate a cluster because of van der Waals forces, okay. So, before we
finished just one point one thing that you should watch out is whenever you have an
expression for energy, in some cases, the energy is expressed as energy per unit length. If you
look at this, right, A has units of joules.

This is metre per half right, there is R right and you have metre power 3 by 2, okay, this gets
cancelled therefore, energy is going to be in okay, joules per unit length. And of course, you
had a case where you know the energy was expressed in terms of energy per unit area, okay
or if you can take cases like this energy is expressed just in terms of joules itself, okay, one
thing that you should worry about whenever you get an expression, you can have an
expression in which you calculate the interaction energy.

Or interaction energy per unit area, or interaction energy per unit length, you have to be
careful, that is all okay, so with that we will stop. So, what we will do tomorrow is we will
talk a little bit about the limitation of the approach that we followed, okay. And then we are
going to come up with some simple methods by which I can relate a Hamaker constant to
some measurable properties of the materials, okay, it is what we are going to look at in the
next class. Thanks.

233
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-17
Theories of Vanderwaal Forces Based on Bulk Properties and Calculation of Hamaker
Constant Using Bulk Properties

(Refer Slide Time: 00:14)

Ok, so in the last class we were talking about deriving an expression for van der Waals force of
attraction between macroscopic bodies.
(Refer Slide Time: 00:23)

234
I just want to make a few points clear, one is that when you say between macroscopic bodies
what it actually means is that these are not atoms or molecules, these are things that are much
larger than that ok. And that means in this particular course this corresponds to the interaction
between particles which are colloidal in size range ok.

You should not think macroscopic as really large bodies ok, this is what we are looking at is van
der Waals interaction between semi infinite blocks where see the reason why you consider a
semi infinite block is because when you do this integration, right. I do not have to you know I do
not have to of course if I assume that there are finite blocks when I do this integration here right.
(Refer Slide Time: 01:25)

235
I would have another term which will come because of the finite size effects ok. So, to avoid you
know these complications, so you have assume them to be semi infinite.
(Refer Slide Time: 01:38)

And the other question that was concerning you know some other discussion that we had is that.
(Refer Slide Time: 01:43)

See what we are doing here is the pair wise addition of interaction, ok. If I was doing the pair
wise addition of you know the interaction forces, ok which will have you know in units of
Newton. Then I would have to worry about resolving, ok because if we assume that the
interactions act along the line that connects these 2 molecules, ok instead of interactions if I

236
assume forces, then I would have to resolve that into 2 components one vertical and one
horizontal.

And I would have to and I think because of the symmetry the vertical component would cancel
each other. And the only you are goanna add only the horizontal component, right. You would
have to do that if you are working with if you are derive an expression for the interaction force.
But because we are doing you know we are working out the expression where the interaction
energy, I do not have to worry about this, I just do the pair wise addition, ok.
(Refer Slide Time: 02:40)

Now, that is where we actually stopped right. So, we had listed down Hamaker constant for
different materials. We mentioned that if you take a close look at you know these entries metals
typically have a very high Hamaker constant, what essentially means is that if I have a dispersion
of metallic particles, they are more prone to aggregation because of van der Waals forces
compared to other materials that are listed here, ok, that is the ok.
(Refer Slide Time: 03:15)

237
So, today what we will do is, we will try and look at what is called as theories for van der Waals
forces based on bulk properties ok. And the reason why we want to do that is because the
approach that we have followed so far there are some limitations ok. So, essentially the adding
together of these molecular interaction that we have done so far it is an oversimplification, ok.

In this approach there are several things that are overlooked ok because of which this approach
may not be applicable for all cases. That means you know there could be cases where we may
have some limitation in terms of applying these theories, ok.
(Refer Slide Time: 04:02)

238
And again to give you a few indicators as to you know what we have kind of missed, ok. So, if
you look at you know macroscopic bodies like this, right. And if it is semi infinite blocks, we
said that you know this Vander Waals force of attraction goes as - 1 over 12 pi A into 1 over d
square, right, that is what we derived, ok. Now, this d is the separation distance, right, that is the
surface to surface separation distance ok.

However if you look at you know these blocks itself there are molecules that are close to the
surface, ok. And there are molecules which are buried underneath ok, that is buried below the
surface, ok. And we know that in this case of course you know the interaction goes is 1 over d
square, right. That means the molecules that are closer to the surface ok. If I look at the
interaction with the molecules on the surface of the 2 you know they will be more stronger.

However if I look at you know the molecular you know buried underneath ok they will have a
weaker dependence ok what I mean by that is that if you have any 2 bodies interacting through
vacuum ok. There is nothing in between these objects ok, the molecules near the surface ok will
screen the interaction ok of the molecules that are you know buried underneath the material.

And because you have this inverse polar dependence ok, the molecules that are closer to the
surface will contribute much more to the interaction than the molecule that are you know buried
underneath ok. So, these kind of aspects were not considered in the derivation that we did ok.
(Refer Slide Time: 06:02)

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The other effect that one may have to worry about is that you could have cases where you have
particles and on the surface there could be molecules which have permanent dipole ok. Now if
your particles like that when such particles are sufficiently close, there could be some orientation
effect that may come into picture because of the presence of dipoles on the surface itself ok.

And if you look at you know Debye interactions and Keesom interactions which essentially deal
with interaction between permanent dipole and permanent dipole and induced dipole ok. So, we
kind of neglected such you know effects when we derived you know expression for when we
talked about van der Waals force of interaction.
(Refer Slide Time: 06:52)

240
The other issue could be that I mentioned that this is a expression that you can use for calculating
Hamaker constant, right. And if I know Hamaker constant I can actually calculate what is the van
der Waals force of attraction, if I know the geometry of the 2 objects that are interacting right.
And if I want to calculate Hamaker constant then I should know beta, ok and beta may or may
not be available for all the materials, ok.

And we know that this beta again in turn will depend on the dipole moments and the
polarizabilities right. If I do not have access to those values, I cannot calculate beta then further I
cannot calculate A and then further I cannot calculate interaction potential, ok. So, therefore
there is a need to look at theories in which I can kind of relate the van der Waals force of
interaction to the bulk properties of the material itself ok.

If I have a material and if I am able to get hold of some physical property or some property that
is specific to the material. And if I have a way of measuring it and if I am able to relate Vander
Waals forces to those properties then you know I can have a way of assessing what is the Van
der Waals force of interaction between the colloidal particles, right.
(Refer Slide Time: 08:07)

So, therefore there is enormous interest in theories based on measurable bulk properties, ok,
when I say measurable properties I mean we are talking about properties like you know surface
tension ok. There are properties like say dielectric constants and things like that, ok. If I can

241
measure the certain bulk properties and if I have a way of relating these bulk properties to the
Hamaker constant or the Vander Waals force of interaction rather than the molecular properties.

Then there is an interest in doing that because of the limitation that I have discussed so far, ok.
So, we are going to look at some of these theories one by one.
(Refer Slide Time: 08:54)

Before I do that I would like to introduce a concept that certain properties of a material they are
frequency dependent, ok. So, for that I have taken an example where see in materials right. You
can classify materials into 3 classes in terms of their what is called the flow behavior ok, viscous
materials ok and elastic materials, ok. These are more liquid like you know simple fluids that you
can think of elastic materials are solids.

But there are materials which are in between they what are called as viscoelastic ok. And one of
the common example of such material could be something like let us say paste for example or
toothpaste that people use, ok, or ointment and things like that, ok. Now so while you can use for
viscous materials you can use a property called viscosity right, to characterize it is flow behavior.
If you have if one works with you know solids then you can talk about something like called
elastic modulus ok.

242
But for materials which are viscoelastic people talk about something called as a complex
viscosity ok or something called as a complex modulus, ok. And the way these measurements are
done is ok, you take a we know that whenever you want to obtain any mechanical response of
materials, you apply stress and measure the strain, right, that is what you do, right. Now if you
take like say solids ok and if you apply some stress ok and look at what is the response that is
strain in the material.

Then you will see that there is a phase shift between the stress and the strain. And then that phase
shift is typically 0 this delta right I mean you know. That means if I have a stress it will you
know essentially strain will also be something like that ok. However if you do a similar
measurements when you apply a stress and then monitor what is the strain for a viscous material,
you will see that you know the stress and the strain are completely out of phase, that means your
delta is going to be 90, ok.

However for these viscoelastic materials you know your phase shift is going to be between 0 and
90. And depending upon the extent of phase shift you can say something about whether the
material is closer to viscous behavior or the material is very close to the elastic kind of a material
ok. And so therefore what people do is and you know I can apply this stress and strain in a
sinusoidal way.

Then measure what is called as a frequency dependent you know material response ok. And that
frequency dependent response it will have 2 terms one is what is called G prime or the elastic
modulus also called as storage modulus ok, which represents something about the energy stored
in a material. Because we know that you know when you take a solid ok if you are below the
yield limit right, you can if I apply any stress to the material and if you release it right.

I mean you know say essentially it stores the energy that you know you apply right. And
similarly you have G double prime which is what is called as a loss modulus or viscous modulus
which represents the viscous component. Or it will tell you something about you know how
much the energy is dissipated ok into the material, ok. And again there are ways of measuring it

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ok depending upon whether G prime is greater than G double prime or G double prime is greater
than G prime you know one kind of tells you something about you know.

If G prime is greater than G double prime, then typically these materials are mostly like paste
like for example, ok. Or if G double prime the viscous component is more than G double prime
is going to be more liquid like and things like that, ok. So, therefore there are cases where people
are interested to measure frequency dependent properties. I have given an example of a case
where the frequency dependent properties are measured for particular material in which you
wanted to assess their flow behavior, ok.

Now if yeah. So, typically the way these experiments are done is something like that ok. I have a
like say there is a shaft ok. And then I have at the end there is a it could have a it is like say disk
for example, ok. And then there is a bottom plate ok, you put your material here, ok, this is a
classic example of what is called as a plate-plate geometry ok. And then what you do is I have a
way of controlling the osil I mean what I can do is I can take the top plate and I can move it back
and forth ok.

And I can do the back and forth movement either slowly or very fast ok, thereby I can actually
change the frequency right, ok. So, then you look at you know if you are doing that in a stress
control Rheometer what you do is you know what stress you applied, ok. And there are ways by
which I can measure the strain, ok. And if I know the stress strain behavior, I can actually back
calculate what is you know G, G prime, G double prime G star, there are ways to do that, ok.
(Refer Slide Time: 15:02)

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Now another property which would be of interest for this particular you know lecture is a
something called a complex dielectric constant ok. In which again what you do is you take a
material of interest ok and then you measure the dielectric response ok to a periodic variation of
the applied electric field ok. And I can of course change the frequency of the applied dielectric
field ok.

And I can measure what it is called as a E star which is the complex dielectric constant which
will again have 2 components you know epsilon prime and epsilon double prime are analogous
to what I mentioned earlier. So, there is a storage component ok that is the permittivity
component that is related to the energy storage ok. And there is a permittivity component, that is
related to the energy loss ok.

And if you have a material where E prime dominates people typically call it as what is called as a
capacitive response. Because we know that the capacitors are known to storage electric energy
right, there are devices where you can store electric energy. And if E double prime is prominent
people call it as what is called as a resistive response ok which is the dissipative component ok.
(Refer Slide Time: 16:43)

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So, with this background there is one particular theory which is ok. Before I do that I just want to
mention one more you know important point. So, whenever you have table like this ok, when
you say A is given you know there is list of tables, what this A essentially what it means is that
this is the Hamaker constant for interaction between similar blocks ok or similar materials. This
should actually be A11 ok, that means it is the energy of interaction between like say in this case
acetone and acetone molecule ok or a block of acetone and a block of acetone ok, right.

But for more general convention is to write A11 with another number in between ok, this number
tells you something about the medium in which these materials are placed ok, 0 if it is in vacuum
ok. Therefore your A should actually be A11 or A101 ok, these are Hamaker constant for you
know interaction of the same material interacting you know through vacuum ok.
(Refer Slide Time: 18:09)

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So, there is the first theory is something called as a DLP theory ok. Again derivation is beyond
the scope, but I would like to point to this particular expression because it tells us some nice
things, ok. So, when you say A213 that is interact in a Hamaker constant for interaction of 2 with
3 and 1 is the medium in between them ok which goes as 3 divided by 8 pi square, h is a Planck's
constant, ok, 0 infinity.

And so we have written, so this is the frequency right. So, we said that you know if you look at
epsilon star ok is epsilon 1 in this case plus for some reason here this i is taken inside the. But
anyway so there is a storage component and there is a loss component, ok. And, what you do is,
so basically what is important in this case is that look, I should have measured the frequency
dependent epsilon for all the 3 materials of interest, ok.

So, once I have access to that, I can substitute that in this expression and I can actually evaluate
A212 that is all that is required at this point, ok.
(Refer Slide Time: 19:57)

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Now the other nice things this tells you is that look at these numbers ok what you have is the you
have the difference in the dissipative component of so they whatever is with i is the dissipative
component of the dielectric constant. And what you have is a difference right, there is a
difference in the dissipative component of the dielectric response between the particle 2 you
know epsilon for the particle 2 and that for 1 and similarly that for 3 and that for 1 ok.

Now because you have the difference ok, if you have cases where if the dissipative component
for a dielectric constants match for all the frequencies for 1, 2 and 3. Then this quantity can be 0,
this quantity can be 0, therefore your A213 can indeed be 0 ok. If whenever you have A212 is 0
you know your Hamaker constant is 0. That means your van der Waals force of attraction would
also be 0. So, therefore the knowledge that ok that van der Waals forces are always present ok,
you can defy that ok.

If you are working in a with materials where for example, there are people who would be
interested in look at experiments where the van der Waals forces can be switched off and then
look at other kinds of interactions ok. So, in such cases you know something like this will help
you know I can design an experiment where I choose a material 2, 1 and 3. Such that the
frequency response you know are the same ok, the frequency response of the dissipative
component are the same, therefore your A212 is going to be 0.

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Therefore I can completely get rid of van der Waals force of in attraction, I can look at other
effects that you may be interested to study, ok. So, that is about this DLP theory ok.
(Refer Slide Time: 22:31)

So, the other approach you know is to kind of relate you know this Hamaker constant or the van
der Waals force of attraction. In turn that van der Waals force of attraction to surface tension, ok.
So, we know we can talk about all of us know about work of cohesion, right. That means if I
have 2 blocks, ok and if I just bring them together, ok. Then because you are people typical talk
about the work of addition or cohesion as 2 times gamma, right, where.

Because you have 2 surfaces, you are joining them, ok, right, and this gamma is the surface
tension, right. But other way of looking at cohesion process, ok, what do you mean by other way
of looking at cohesion you know is that I have 2 blocks that are infinitely far apart. I bring them
close and I join them, ok, when I joined them I can think about the distance between the
molecules could be some value say let us say d0, right.

So, we know that if you look at any material there is some equilibrium separation distance
between the particles, right, ok. Let us think about an experiment, right, so I have you know this
imaginary experiment. So, I have a let us say a block of water, ok, I have 2 blocks of water,
initially they are far apart, I just bring them together and I make a single block ok. Now if I
calculate what is the energy ok.

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So, in this concept what is thought about is that I can think about the work of adhesion ok, as the
van der Waals force of attraction between the 2 blocks, ok. In which what you do is, so you
initially your materials are separated you know by like say very large distance what you do is,
you kind of bring them close. And then join them such that the this is a separation between the
molecules is now d0 ok.

In this d0 is the equilibrium spacing between the molecules of a bulk sample ok. So, if I do that
you can actually calculate what is the change in the interaction energy to bring a block from
infinity to d0 ok. That essentially is - A divided by 2 pi 1 over d square because I am considering
a case of 2 semi infinite blocks ok infinity - A by 2 pi 1 over d square d0. Yeah, what do you
mean by equilibrium spacing.

See in this case, if I am talking about block of water, ok. So, we know that because you have
various interactions between water molecules the fact that they are still you know in the liquid
state is because there is some overall interaction energy, ok. The balance of the attraction and
repulsion all this will give you. So, if you look at like say Lenard-Jones potential, right, if you
look at, ok, we talked about if you add the 2 components, so, you had something like this, right.

So, I am talking about that separation distance, that is a equilibrium separation distance between
you know the atoms that constitute the bulk material. Yes, this is going to be in sub you know
nanometer kind of ok, so, I mean maybe let us put it this way, right. When this cohesion
happens, right ok, it is a process of bringing 2 blocks together and then joining them, ok. Now, if
I were to think about what happens between the surface of the molecules that are on you know
one block and the surface of the material on the other block.

When you are joining them you know in essence what it actually means is that they were very far
apart initially. I am putting them together, so that the separation distant become d0 ok and that
separation distance is same as the separation distance that there and the separation distance there,
ok that is the concept, right, yeah, ok. Therefore your the change in the interaction energy is A

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divided by 12 pi into 1 over d0 square, where d0 squared is the inter particle inter you know
molecular spacing.
(Refer Slide Time: 27:40)

And, the same as I said the work of cohesion is actually 2 times gamma, ok. Therefore I can
equate the two and thereby I can get an expression which is a you know Hamaker constant A
goes as 24 pi gamma into d0 square, ok. And you can actually work a few things out, right. So, if
you take, for example there is an example that is given here, if you take something like decane
for example, ok, C10H12, right that is decane.

So, typical values of surface tension are about 25 you know milli joules per meter square or 25
milli newton per meter, ok, that is the surface tension, so I have that value. And d0 is the spacing
between the molecules, ok, typically you know 0.2 nanometer. If I put in these numbers, it turns
out that you know the value that of A that I get is actually A is 7.5 into 10 power - 20 joules, ok,
which is actually very close to what is been predicted.

So, at least for simple fluids, if you are working with dispersions which have like say emulsions
for example, ok. If I have an emulsion of like say decane droplets in water, ok, if I want to
calculate what is the interaction between the two. If you do not have access to the Hamaker
constant, ok, then actually I can approach you know I can go with this approach wherein I know
what will be the surface tension, ok.

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And I know what is the equilibrium separation distance between the molecules that constitute
you know the droplets. And I can actually get A from which in turn and if I assume that they are
a spherical you know droplets, then I can actually go by and say that phi A goes something like -
A times R divided by 12 D, right, that was a formula that we looked up, ok, I can actually
calculate van der Waals interactions in this way, ok.
(Refer Slide Time: 29:57)

So, there are I mean this is what we have just done right. So, you know 24 pi gamma d0 square.
There are also approaches where you relate A instead of to gamma you relate that to what is
called as a gamma d ok. Where gamma d is what is called as it is the dispersion component of
the surface tension ok, what it actually means is that.
(Refer Slide Time: 30:34)

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If you look at surface tension in general ok there seems to be some that should be gamma there
ok, this is U divided by 2a square ok. So, whenever you talk about surface tension right, I mean
the classic picture that you will see in the textbooks is that you know I have a container. If I look
at a molecule in the bulk ok, it is being pulled in all direction you know by an equal you know
force, right.

That means you know that the interactions are kind of isotropic right. However if you look at a
molecular on the surface you know there is only interactions you know the you can think about
the interaction being absent in the outer fluid, right. So, therefore you know I can define
something like you know if the energy interaction between the molecules in the bulk is U, ok.

Now because of the fact that you know there if you look at a molecule at the surface, you can say
that the on average the energy of interaction is going to be U by 2 because you know it is only
interacting with maybe half the neighbors right. So, now if you know what is the area that the
molecule occupies at the surface, I can actually calculate U divided by 2 times a square, where a
square is the area that the molecules occupies to the surface, right ok.

So, you can kind of relate you know interfacial tension to the energy of interaction ok, where U
is the energy of interaction between the molecules in the bulk ok. If I know that I can relate
surface tension to the energy of interaction the bulk and the area that the molecules occupy, right.

253
Now by that concept what I can do is I can say that the overall contribution for the surface
tension comes from the various intermolecular forces you know there is a dispersion component
ok.

There could be some kind of a dipolar interaction, there could be hydrogen bonding interaction
or metallic interaction, so on and so forth, ok. Therefore when we talk about the surface tension,
ok one should understand that the surface tension the contribution to the surface tension comes
from various types of interactions that are present for a between the molecules of a given
substance.

And there could be various contribution and depending upon the nature of the material that we
are trying to deal with you know gamma d could be dominant. If we look at as we said like for
non polar species like decane and you know other material ok. Then gamma d would be the more
dominant species of course if I goanna work with water then you know one has to worry about
you know dipole interactions being important.

And you know, so people have kind of this is the you know this is for water, right, the overall
surface tension and these are the different contributions that come from the different forces, ok.
So, therefore, so you could actually relate A which is Hamaker constant you know if you are
working with either a cases where several different forces contribute to you know surface
tension.

Then you know you would have to consider the dispersion component of the contribution and
then you can calculate what is the Hamaker constant.
(Refer Slide Time: 34:22)

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I just want to briefly now these are some tables in which so we have done this right. We know
how to we got that, that is by equating the you know cohesion energy and the van der Waals
interaction between the blocks, this were we considered you know instead of gamma, gamma d.
This is one of the expressions that we would have looked up earlier, this is an expression for the
London dispersion forces, ok.

And this we looked up earlier in which we relate Hamaker constant to beta and the other material
properties ok. And there are also expressions where I can relate you know the polarizability you
know and the permittivity to refractive index and you know the molar mass and you know stuffs
like that, ok. So, what is been done here is they have calculated, so this is let me put it this way.

This is d0, so calculations, so this is 67 and 68 that is these 2 ok. So, if you know the dispersion
component, right gamma d. And if I know d0, I can get A by this expression, right, because I
know gamma d and d0 square right. And of course if I, so the point that I want to make is that if
the value is calculated from this, this you know or this they give comparable you know numbers
ok.

And again you know for several materials is what is you know I wanted to mention, ok. So, you
can the approach that I have mentioned you can use as approaches and wherever you do not have

255
access to Hamaker constant you should be able to use one of these expressions and then calculate
Hamaker constant for the material of interest ok, that is the point ok.
(Refer Slide Time: 36:39)

So, there are so again people have proposed, so we had expression which is 24 pi d0 square
gamma, right, ok. There I mean if you look at this approach I mean one wanted to bring in what
is called as a molecular anisotropy ok. If you have I said you know the U by 2 by a square ok is
what gives you know in a way gamma, right. Now you know the a square is the area that the
molecule occupies the interface.

Now you could have cases where you may be working with asymmetric shape molecules ok. If
you look at molecular shapes, I mean there are objects which can be you know thought of very
close to spherical shape and there are also cases where you know you have some non spherical or
asymmetric shape molecules. Then you know what d do you consider? ok, what is the separation
distance ok, is it the I mean if you have you know molecules like this you know whether the
separation distance between this and this, center to center or this you know.

So, you will have issues you know finding out what is the actual d that you have to consider.
Therefore there are approaches where I can relate A to the surface tension and a m, where a m is
the surface area of the molecule itself. Then I know I do not have to worry about the separation
distance, I can relate A to the surface area of the molecule directly ok.

256
So, this is one approach where A is kind of related to the surface area of the molecule and the
surface tension of the material.
(Refer Slide Time: 38:25)

Yeah, yeah that small a is the not that , a is the surface area of the molecule correct, correct. This
A yeah oh then I have not made my point clear ok, this A that we are talking about what is this A
will come back, will comeback, what is this a.
(Refer Slide Time: 38:47)

Oh small a m, this one here, no here A Oh, this is ok let us say ok, here right, yeah. So, this a
gamma is 2 a2 divided by sorry it is ok, U divided by 2 a square, ok. This is actually the area that

257
the molecules occupy at the surface or at the interface one molecule, yeah. See, we are trying to
think about like say we are trying to relate gamma which is the interfacial tension to the
interaction energy ok.

Now if U is the interaction energy between the molecules in the bulk ok, U by 2, if you assume
that you know there are only half neighbors, then you know U by 2 is what would the interaction
energy for the molecules at the surface divided by a because you know surface tension is
defined. You can think about this as energy per unit area right, this U will have units of energy
and the area that it occupies a meter square right.

So, this essentially you know energy per unit area, right there are also approaches where you
relate you know. Now this A goes as 6 am multiplied by gamma where a m is the surface area of
the molecule and gamma I can relate it to again some thermodynamic properties, ok. If I know
how the internal energy varies with in the volume of the material at a constant temperature.

And if rho is the then number density on the material, I can actually estimate gamma and I can
plug that value of gamma into this expression. And in turn I can calculate a itself, ok, yeah,
molecule yes. So, see this gamma was a surface tension, yeah right, gamma was the surface
tension that we agree, right. So, if you have a cohesion process 2 times gamma will be the work
of cohesion, ok.

So, this is the work of cohesion and you can think about this as a again work of cohesion will
again have a units of energy, right. In this case again will be energy per unit area, right and you
know we looked at right this again is a interaction energy between 2 blocks again this will also
have units of again joules per meter square, right, ok. Now I am trying to relate gamma is the
interfacial tension and I can relate interfacial tension to molecular properties, right.
(Refer Slide Time: 41:56)

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And that is how this was brought in, right, if you look at right, let’s, ok, so to have here is gamma
is U divided by 2 a square. So, all I am trying to say here is the gamma in a way is related to the
area that the molecules occupy the surface, ok. So, let me put this way, right, now say that I have
a container say that there are 2 molecules in the bulk and the interaction energy between them is
U, right, ok.

Now I say that now these molecules are now at the surface, ok you know I can think about that
now the energy of interaction would be not be the same, ok. I say it is going to be half, ok, that is
U by 2, ok. Now surface tension you can it will have units of milli newtons per meter or joules
per meter square either force per unit length or energy per unit area, ok. Now I know the
interaction energy between the molecules at the surface at U by 2, ok, I want to get in the area
you know into the picture.

And I say that this area that the molecules occupy the surface no, no I am yeah it will be
proportional to some length square, ok. So, that it can be some time the a I mean the am is the
yeah so it is some length square, ok. This some area right, ok and I am saying that this area is the
area that the molecule occupies at the surface, is that ok. So, see no see the surface area so say
that I have a spherical particle, say that the molecule that I am considering is spherical.

259
Now if these spherical molecule in the bulk then the surface area is going to be 4 pi R square,
right. But what we are interested is the surface area that it occupies at the surface, the area that
the molecule occupies at the surface, that is not pi R square, ok. It depends on the orientation of
the, it depends on the shape of the you know molecule it depends on the orientation all of this,
right. So, therefore, ok that is, ok, so in this case your A is related to gamma, ok times.

So, this in a way this am right, so I essentially have this pi d square, ok. That is an area term, right
and all that is been done here is that look if you have cases w here you have you know some
complex shape molecule. Instead of worrying about the distance of you know equilibrium
separation distance you think about the surface area of the molecule, ok, that is what is done.

And now one of the way of getting gamma is to relate that to you know again some
thermodynamic properties in this case how the internal energy of the material changes with
volume at the constant temperatures. So, if you have this data, if I know what is rho I can plug
this in this expression and I can get A, ok.
(Refer Slide Time: 45:44)

So, the other approaches there are cases where I can relate A which is the Hamaker constant to
the thermal energy and Vr which is the reduce volume. And again there are expressions where I
can relate if I know ok this essentially comes from the if you look at Lennard-Jones potential,
right. So, typically Lenard Jones potential is an example of a 6, 12 potential, right.

260
So, where m equal to 6 and n is equal to 12 I can get you know from that I can get this parameter
and there were also expressions where I can relate Vr which is the reduce volume to the you
know the coefficient of thermal expansion you know. And other measurable properties, so
therefore there are various theories available where I can relate Hamaker constant to measurable
properties.

And depending upon the materials that I am working with I should be able to go back and of
course some approaches are more suited for liquids, some are you know are more suited for polar
liquids, some are more suited for other kind of materials. So, we have to think a little bit about
which is the best theory that I should go to when applying them. However there are guidelines in
the literature to look at appropriate you know theories to relate A to measurable quantities.

And you should be able to pick that up and then use them in your calculations to obtain what is
the Hamaker constant, ok.
(Refer Slide Time: 47:17)

And just to end people have been able to measure van der Waals forces I would like you guys go
back and read up some papers in the literature. That is something called as surface force
apparatus, ok. And what is being measured here is force divided by radius as a function of

261
distance, ok, force divided by radius. I will just go back to that expression, so we had that in one
of the classes, right.
(Refer Slide Time: 48:01)

So, if you look at this interaction force, ok between where is that, so that was here, ok. If you
have 2 flat planes the interaction energy was A divided by 6 pi D cube, right. Now ok so that is
your force, right, now I can so therefore , so if you look at this is the measurement, so the data
point that you see that is the filled circles open circles and other experimental data that have been
measured you have been able to measure force is a function of distance.

And that line is the fit, ok, so which, so there are direct measurements of van der Waals forces
which people have been able to measure. And it kind of complies with you know this is actually
done between 2 flat mica sheets, ok. And they are separate by a distance D for several distances
you this will get these you know force divided by radius. And then plot that and it looks like it
actually follows you know what is been predicted by theory, ok.
(Refer Slide Time: 49:22)

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So, I am stop here , so the next topic that I am going to do is to look at effect of medium on the
van der Waals attraction, ok. So, instead of vacuum you know if you have air between the
particles or if you have some other fluid between the particles how would van der Waals force of
attraction be you know altered is what we goanna look at, so thanks.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-18
Effect of Medium on Vanderwaal’s Interactions-I

(Refer Slide Time: 00:14)

Okay, so we come to the last 2 topics in this module, one is looking at effect of medium on
Vander Waals forces. And then the second one is to look at what are called as combining
relations for Hamaker constant.
(Refer Slide Time: 00:32)

So, this particular picture highlights the role of medium on the van der Waals force of
attraction, what you are looking at is a case where you have silica particles, ok, in embeded in

264
air, these are the 2 silica particles that and this one, and they are embedded in air and then
they are interacting via you know the interactive medium in this case is through air. And the
effective Hamaker constant that people have reported for this case is A is 6.5 10 power - 20
joules, okay.

Now, the same particles when they are put in a different medium, in this case, water, again
the same particles interacting via water, it turns out that the Hamaker constant is 0.8 into 10
power - 20, ok. So, though the you know this is the same, but there is a significant reduction,
right. Though the order is the same, ok, there is still a decrease in the value of Hamaker
constant.

That means that if I were to think about calculating the van der Waals force of attraction
between silica particles and air and compare it to silica particles in water, when the medium
is changed from air to water, the effective Hamaker constant is lower that means the effective
van der Waals interaction is going to be okay lower right, that is the gist okay. So, therefore,
in general, what is understood is the presence of any medium other than vacuum, ok is always
going to reduce the magnitude of Hamaker constant. That in turn would reduce the magnitude
of van der Waals forces ok, that is the gist ok.
(Refer Slide Time: 02:30)

So, in order to consider the effect of medium on van der Waals forces, one of the approach
that is followed is by using what is called as combining relations okay for obtaining a general
you know, this is a general method that is available to obtain Hamaker constant between

265
maybe similar or dissimilar particles embedded in the medium. So, in this case you have
medium as j and there are 2 dissimilar particles you know i and k.

And the Hamaker constant for this particular case is designated as aijk, the first you know,
subscript corresponds to you know the one index for that one particle second substrate
corresponds to the next particle and what is in between is the as the medium, right, that is a
general convention. So, in essence, what we are going to do is to these are the important
details that we are going to discuss okay.

So, what you have is a case where you have 2 similar particles particle 1 and again particle 1
interacting via medium 2 okay and it turns out that you know for such a case Hamaker
constant that is a sorry this is 2 ok sorry that ok, the particle is described as 2 and 1 is a
medium in such a case I can write A212 as the Hamaker constant between the species
involved, that is A22, that is a particle A11 does for the particle.

And these are Hamaker constants when the medium is vacuum okay. So, therefore, A212 goes
as A11 power half - A22 power half okay to the power of 2, okay. And you could have a case
where I have 2 distinct particles that is particle 3 and particle 2, which are interacting via
medium 1, okay, for such a case, A312 goes as A33 power half - A11 power half, multiplied by
A22 power half - A11 power half, okay.

So, we are going to look at you know how do we get such relations okay. And then we will
try to talk a little bit about what are the implications of these results, ok, that is what we are
going to do.
(Refer Slide Time: 04:52)

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So, one of the approach that has been available in the literature is to use what is call as a
reaction engineering approach. What you have is a schematic, okay that is particle 2, okay
and so you should think about this case, okay. There is a particle 2 interacting via a medium
1, okay. Now, if you have a case like this and if you say that look you know I can imagine
that for every dispersed particle there is going to be some solvent molecules surrounding it
right.

There is going to be for every particle that you have the dispersion there is going to be some
solid molecule surrounding it okay. That means you know you have a dispersed phase and the
solvent phase, I am thinking about a reaction okay, where I have dispersed phase and solvent
phase which coexist together okay, that kind of you know combines okay with a another
particle and dispersed phase giving rise to an aggregate right.

So, you can think about this is a doublet okay, which is formed because of van der Waals
forces okay. And similarly you know this solvent molecules again they combined to give a
again a doublet of solvent molecules, okay. And so, you can also think about you know in the
before this aggregation happens, because of van der Waal forces, both the disperse phase and
the solvent phase, they are free to move wherever they want.

They are kinetically independent. However, when this aggregation occurs, when it forms a
doublet they become kinetically dependent on each other okay, wherever this would go the
other one would also follow right. In that sense, there is the kinetic dependence you know
independent is lost okay, they become kinetically independent okay. So, what is being shown

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here is a pseudo chemical reaction okay initially you have a dispersed phase and a satellite
solvent particle okay.

Because as I said that you know in solution you will always have particles coexisting with
solvent okay. And they are kinetically independent to begin with okay. However, because of
the action of van der Waals forces, okay. So, what you do is in this particular process, you get
a doublet of 2 dispersed particles come together to form a doublet and the solvent molecules
again come together to form a doublet. And they become kinetically independent right
critically sorry with that kinetically dependent right, okay.
(Refer Slide Time: 07:49)

So, now, if you want to think about you know you can think about writing an expression for
what is the change in the potential energy okay or change in the interaction energy okay, that
accompanies such a process okay. If delta phi is the change in the interaction energy I could
write going to the reaction engineering concept okay. That is the energy associated with the
formation of a doublet of solid molecules.

And the energy associated with the formation of a doublet of the dispersed particles 0k -
energy associated with the phi 1 2, right you know and then another - phi 1 2, right.
Therefore, delta phi becomes phi 11 + phi 22 - 2 times phi 12 okay. So, this is a general
picture, I could have imagined that you know I could have you know what is shown here is a
looks like a spherical particle right.

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But you know I could write a similar thing for a cube like particle or any geometry right. But
what would be interesting to note is that, if you look at each of the terms, ok, the moment I
fixed the geometry of the dispersed particles and the solid molecules, phi dependence, okay,
the each term on the right hand side, the phi depends in the same way on the size and the
distance parameters.

What I mean by that is if I were to imagine these to be spherical particles, we know that phi
van der Waals okay phi van der Waals is going to be - A times R divided by 6 D, right, where
D is the separation distance, A is the Hamaker constant, R is a radius of particle right or if I
were to think about block you know semi-infinite blocks van der Waal force of attraction
goes as - A divided by 12 pi 1 over d square right.

So, that means all these phi 11 phi 22 and phi you know 12, they depend in a similar way on
the distance of separation as well as the size of the particles okay. Now, if that is the case
then what we can do is I can actually cancel out the distance dependence okay. And in
essence I can you know reduce this particular expression to A212 is equal to A11 + A22 - 2 A12
okay.

I can do that, because I am assuming that or because it comes from the fact that each term
here the phi depends the same way on the size and the distance parameters okay. And it
differs only in the molecular parameters and because it differs only in the molecular
parameters, the only parameter that will be different for each of these terms is the Hamaker
constant right, that is the concept okay.
(Refer Slide Time: 11:18)

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So, now I am able to write A212 as A11 + A22 - 2 times A12 okay. So, I know from the tables
that are available, I know what is A11 and A22. And of course, I can use the some of the
theories that we discussed in the last lecture, I know I can relate A11 to you know the
dielectric constants, right, we talked about it, I can relate A11 to like say the surface tensions,
right.

If I know how the interior energy changes with volume you know at a constant temperature,
okay. So, I can you know there are theories available where I am either like, they are already
tabulated, or I have a way of calculating this Hamaker constants for when the species interact
in vacuum, okay. But however, I do know A12, okay. So, A12 is the Hamaker constant for
interaction between 1 and 2, okay interacting via vacuum, okay.

I do not have that information, okay. So, what people do is again, they make some
approximation. So, one of the approximation that is typically done is to use what is called as
a geometric mixing rule, okay. So, in which, what is stated is that the interaction between 2
dissimilar bodies, okay, is given by the geometric mean of the homogeneous interactions
were the 2 species considered separately, okay.

That means you are A12, you can actually write it as A11, A22 power half, okay. That is a
geometric mean, okay, that is via geometric mixing rule, okay. So, if I use our approximation,
okay for 2 A121 I can substitute it as - 2 A11 A22 power half okay. And which I can further
reduce it to A11 power half - A22 power half to the power 2 right. So, that means, so, this is a

270
effective value of the Hamaker constant to be used in evaluating the attraction between like
particles okay.

That is similar particles that are embedded in a medium, okay. So, therefore, by this
approach, if I know, what is the Hamaker constant of interaction for the solvent molecules
and the particles when they are interacting via vacuum I can use that information to assess
what is the interaction between them when they are embedded in a fluid okay, that is 1 okay.
So, that is what you know one of the combining relation is all about.
(Refer Slide Time: 14:06)

Now, okay. So, there are some really nice consequence of this particular result okay, that is
when you have 2 particles that is 2 okay, interacting while fluid 1, okay, your A212 is A11
power half - A22 power half right. So, what you can learn from this particular expression is
that the effective Hamaker constant there is A212 is always positive, okay, because it is A11
power half - A22 you know whole square, therefore, okay,

This is always going to be positive regardless of the magnitude of A11 and A22, okay. That
means if you take identical particles, okay, which was the case right. We took 2 identical
particles. They are identical in terms of surface chemistry okay. If you take such a case then
they exert a net attractive force on each other due to van der Waal forces in a medium okay
and that is also true for also in vacuum as well okay.

The other important you know result that comes out of this particular formula, we already
discussed it. So, embedding a particle you know a medium generally diminishes the van der

271
Waals force of attraction right. Because you have a difference term here right, if you know
A11 was some x and if A22 was some y okay because you have a difference term okay, your
A212 is going to be smaller right.

Therefore, A212 is going to be smaller if you compare the particles being in vacuum okay
right. So, if this is A101 if you want to call it you know make it more clear, 0 for vacuum –
A202 okay. Again okay for vacuum right okay, this is van der Waals. This is interaction
between the same particles in vacuum okay that is the interaction of the solid molecules
therefore, okay.

So, the magnitude of A212 is always going to be smaller than A202, there is A22 yeah, ok or A22
okay. Therefore, embedding particles in a medium generally diminishes the van der Waals
force of attraction between them. Again you can take some examples if you take A11 is equal
to so much and A22 is equal to so much, then you know A22 you know turns out to be A bar
10 power - 21 joules almost 2 orders of magnitude less than the individual particle.

So, okay. See, these relations that we are trying to write up right okay or let me go back to the
table that we had put up okay.
(Refer Slide Time: 17:12)

So, we have this table right, what you have is a list of different materials and different
Hamaker constant right. Whenever you see a value like this okay, A 10 power whatever, you
know this number right. If nothing is given, you should assume that these are Hamaker

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constant of interaction between a acetone molecule and another acetone molecule which are
interacting via vacuum, okay, that is what is okay. That is your basis okay.

And the theories that we talked about right, you know like for example yeah. So, yeah. So,
now, but however, you could or for example, this one right a gold particle that is A gold, gold
is what you have okay 45.3 into 10 power - 20 joules okay. Now, if you want to work with
like say gold particles, you know Ag, Ag and if you want you know if the medium now is not
vacuum, okay, this is the value you know when the medium is vacuum.

And if they are in water now, how would you calculate what is the effect to Hamaker
constant right, that is what we are after okay. It turns out that for this particular example
okay, this particular example okay, your A gold, gold interacting via water okay is going to
be equal to A water, water half - A gold, gold half whole square okay. So, A gold, gold you
can get from the table that is there.

A water, water also you can get the from the table that was there okay, I can actually
essentially get what is the Hamaker constant for interaction of gold particles you know via
water medium okay. So, the first implication is that you know the effect Hamaker constant
especially when you are dealing with identical particles, okay is always positive, okay. And
embedding the particles in a medium generally diminishes the van der Waals force of
attraction between them.

The next one is you could of course, have a case where A112 is equal to A22, you know I could
design an experiment you know where I could choose a solvent such that A11 is equal to A22
okay. Therefore, you could have a case where the van der Waals force of attraction indeed
could be 0. That means this condition essentially corresponds to no net interaction between
the particles okay.

Therefore, it is possible to tune the solvent or the medium okay and I can essentially get rid
of van der Waals force of attraction okay. And one of the important consequences of that
could be now that I choose a solvent such that you know the van der Waals force of attraction
is not there. Now, if I choose such a solvent that is if A11 is a Hamaker constant for that
particular solvent.

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Now, I know that I can relate A11 to 24 pi d0 square gamma right. If I choose a solvent I can
actually add that because I know the surface if I know the surface tension of those fluids, I
can easily calculate A11 okay in turn I can get A22 okay, you could actually use this approach
for. So, what I do is I take a particle put them in different fluids and identify a fluid where A11
is equal to A22.

If I achieve that condition and because for the solvent molecules, there are easier ways of
getting the surface tension which in turn will let me calculate A11. If I know A11 the fact that
A11 is equal to A22, I can exploit that to actually calculate you know the Hamaker constant
itself for the particles of interest yeah. So, what do you do I mean, yeah, so, yeah, you should
know that condition. For example, yeah, this is a kind of what is it, we can make it that way.

I mean, this is an approach that one could use, that is what I am trying to say okay, this is an
approach that one could essentially use to calculate. For example, if you have a particle fluid
combination, and if you know that look, there is no other type of interactions. For example,
like say you know electrical double layer interactions and steric interactions or other kinds of
interactions if you know that the only interaction that are you know present are van der
Waals, okay.

Now, if you have such a dispersion and if you see that they are very highly stable, okay, then
that could be a case where you know your phi van der Waals you know be 0, right. Now if
you have conditioned like that. So, it could you know give you a way of actually calculating
what is A22 okay by that approach is what I was trying to mention. Yeah.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-19
Effect of Medium on Vanderwaal’s Interactions-II

(Refer Slide Time: 00:14)

Now let us look at a case where I have 2 dissimilar particles exactly similar approach ok, instead
of similar particle that you had you have 2 dissimilar particles. That means I have a container
where you have a particle 2 and particle 3 which are interacting via a medium 1. Then exactly
similar fashion I can write what is the change in the potential energy or the change in the
interaction energy, ok.

But again if I assume that you know each term depends in a exactly similar way on the distance
of separation and the dimension of the particles. Then I could write A312 as A11 + A23 - A12 - A13,
right. And this A11 ok, I can write it as A11 power half multiplied by A11 power half, right it is
just a right. Now A23, I can write it as A22 power half you know A33 power half this is actually
from again the geometric mixing rule ok.

Similarly I can write A12 as A11 power half multiplied by A22 power half and this is A11 power
half multiplied by A33 power half ok, I can rearrange a few things. So, if I look this up, right, so,

275
what is common here I can take this term ok and this term. So, therefore I can write it as A11
power half to the power A11 half – A33 half right, that is if I take these 2 terms, right, A11 power
half is common, right, I have taken that.

So, what is left here is A11 power half - A33 power half, now here what I can do is plus I can do A
I can take minus, I can take let us do this way, what is common here is A22 I take + A22 power
half right this plus here right. So, A33 power half - A22 power half right, is it ok, with these 2
terms ok. Now, what I can do is what is that, no this is A11 sorry, this is A33, this is A11 right ok.

And you know I can rearrange this, so if I were taken minus here, ok, then what I would have
had is + A11 power half - A33 power half right. So, therefore A11 power half - A33 power half
multiplied by A11 power half - A this is you know this no ok, let me do it again, let us do it again,
ok.
(Refer Slide Time: 03:55)

So, if you look at these 2 terms A11 power half, right that is common. So, what I can do is I can
write A11 half I can take it out, right. And I have A11 half - A22 half is that ok, that is with these 2
terms, yes, ok, plus I have A33 half I have taken this is common. Now I have A22 half - A11 half
that is ok. Now what I do is because you know, I have one is positive other one is negative here,
right.

276
So, what I can do is I can take like say A22 half - A11 half common, ok, I am going to take this as
common, therefore this becomes minus I have - A33 half, sorry that becomes plus right, that is
correct, that becomes plus, ok. And I have minus, so - A11, then it is correct, it is - A11 half, right,
see, it does not match with no it matches. So, it matches, I will tell you it matches, right.
(Refer Slide Time: 05:08)

So, what I do, so, I take A22 half - A11 half as common right, multiplied by because I have taken
this is ok, therefore this becomes negative right, - A11 half ok, negative. And I have + A33 half
right, that is A33 half - A11 half that is this term, right this term ok and this is this term, is that ok.
(Refer Slide Time: 05:43)

Now.

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(Refer Slide Time: 05:48)

So, there are again very nice implications of this expression ok. So, therefore Hamaker constant
in the case where you have 2 dissimilar particles that is 3 and 2 interacting via you know 1 ok.
So, you can write them you know in terms of the Hamaker constant for individual species when
they are you know interacting in vacuum, ok. So, one of the see if you look at this expression,
you could have a case where either the first term could be negative and the second term is
positive.

Or you could have a case, so I could have a case where the first term is negative and the second
term is positive. And the first term is positive second term is negative right and both could be
positive, both could be negative, the first and second term ok. Now if you have this and this case
overall Hamaker constant is going to be positive ok, in which case you can have a attractive
interaction between the 2 particles 3 and 2 interacting via medium 1.

But however if you have case 1 and 2, you have A312 will become negative. That means instead
of Van der Waals attraction, you have what is called as a repulsive interaction that kick in
because of Vanderwaal’s forces, ok. So, one other factor in the above equation can be positive
and one can be negative right, in which case the effect Hamaker constant itself becomes
negative, ok. That is the pair wise attraction between the bodies it actually results in a net
repulsive forces if you have dissimilar particles ok.

278
We mentioned that if we have same particles that is you know 2 and 2 interacting via 1 or 3 and
3 interacting via 1, we said that the net Vanderwaal’s forces are always attractive is what we
mentioned. But however, if you have a case where I have 2 dissimilar particles interacting via
medium 1, ok, turns out that you can have a net repulsive force between the particles ok. And
this will happen when each term in this particular expression ok would be of different sign right.

As I said one could be positive other one could be negative ok or the vice versa ok and that
would actually happen when this particular condition is met. A22 must be greater than A11 greater
than A33 or A33 should be greater than A11 should be greater than A22. That means if the value of
A for the continuous phase ok is intermediate to the Hamaker constant for the 2 particles that you
are considered.

If that is the case, that is when this particular condition is met ok. So, if the Hamaker constant for
the solvent molecules or the continuous phase or the liquid in which the particles are dispersed.
If that is in between the Hamaker constant for the 2 particles are dispersed. In such a case you
could have A312 will be negative, that means you will have a net repulsion between the particles
ok.
(Refer Slide Time: 09:43)

279
So, you can also think about you know extending this particular concept, further in which
because we have kind of developed we have discussed macroscopic theories that people have
developed in which you can relate you know Hamaker constant to you know the equilibrium
separation distance between the molecules and gamma ok. So, you could actually I can substitute
for A ok A for each of these Hamaker constants.

And of course if you assume that on an average if d0, that is the equilibrium separation distance
between the molecules is very similar ok. For both the particles and the dispersed phase and the
continuous phase, if I take this d0 out, I can actually express A312 as 24 pi d0 square multiplied by
gamma 3 half - gamma 1 half multiplied by gamma 2 half - gamma 1 half ok.

So, you can also you know work out like this, I mean this I think would be a nice approach if you
are looking at something like say emulsion for example. See if you look at like say water
droplets in you know Deccan for example ok. An oil or if you are looking at you know droplets
in water ok you know. In such a case when you are working with liquid in liquid dispersion ok.
You can assume that you know your d0 ok it is very similar in magnitude, if that is a case you
know I can actually take d0 out.

And then I can express gamma 312 in terms of the surface tension values itself ok. That again is
of course an approximation ok, we are assuming that you know d0 values you know they are
typically in an narrow range, if you look at d0 values for different liquids.
(Refer Slide Time: 11:47)

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You will see that I can there was a table here, so let me just go back to the table. Let us look at
this table, right, this is d0 ok these are compounds, ok. There is heptane, dodecane, Eicosane,
SIO2, polystyrene, water, ok. You look at in the numbers there you know except for water, right
0.22, 0.18, 0.26, 0.22, ok all nanometers say it is a fairly narrow range, right.
(Refer Slide Time: 12:23)

So if you have cases like that, you know I could indeed you know go and look at approaches like
this, you know where you know I can express Hamaker constant in terms of the surface tension
itself. Because you know value of d itself would be in a fairly narrow range, ok. I just want to
end with talking a little bit about Van der Walls attraction in nature, ok. Any examples that you

281
have come across where you think that you know there exist cases where you can you know
think about Van der Waals forces or Van der Waals attraction in nature.

Very famous example that everybody gives, its geckos right ok. So, there is a lot of you know
there have been a lot of recent experiments you know where people talk about how do these
geckos stick to the walls, ok. And it turns out that it is because of Van der Waals forces, ok, there
are some really nice experiments that people have done, ok.
(Refer Slide Time: 13:28)

This is some this is a result from a paper that appeared in NATURE 2000. So, what they do is,
they say that you know this is the magnitude of adhesive force that they can produce, 10
Newton’s that is really large, ok. And everything is kind of what they do is, this is a macroscopic
you know picture of a gecko, right. And then you can look at the mesoscopic structure you know
when you look at you know it is palm for example.

Then if you zoom in, and if you look at it you know with a microscope, right, it turns out that
they have what is called as setae, ok. And each of this actually has a large number of tiny you
know tiny flat structures, ok. And that is the length scale here, that is 1 micron ok. And you can
look right there are so many number that if you calculate the Vander Waals force of adhesion
between each of these you know fibre like things.

282
And the wall and if you add them up you know because there are so many number, ok, so the
number is something like that, ok. There are about 5000 per nanometer square sorry per
millimeter square, right 5000 per millimeter square, ok. And if assume that you know typical if
you look at a big gecko you know you could have you know hundreds of millimeters square you
know area, ok.

And if you sum up the van der Waals interaction because of each of them, ok with the wall, it
turns out that you know you really get a very huge number, ok. So, this is one example where
you can think about of course there are other examples as well. So, I would like you guys to go
back and read up a little bit about you know these aspects looking at van der Waals you know
attraction in things that you see in nature, ok. So, that would be the end of module 2.
(Refer Slide Time: 15:48)

So, we have kind of looked at various aspects, so what I will do is we will try and think about
some tutorial you know in the next class.
(Refer Slide Time: 16:05)

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So I have one problem, we can just quickly run through it. African green monkey kidney cells,
ok, you can think about that as component 2 ok were cultured ok, on a suspension of collagen
coated dextran particles. So, what you should think is you have a dextran particle ok and that is
coated collagen ok. And because you know collagen is biocompatible because collagen is
biocompatible you know you can kind of you know you can grow cells on it, right.

You can think about something like, ok, this could be I will say kidney cells, ok. So, harvesting
such cells is traditionally accomplished by scraping or ultra sonication or the use of chelating
agents to disrupt cation bonding between surfaces 2 and 3, ok. So, that means if you have a
dextran particle which is coated with collagen and if you know culture such cells on the surface.
It turns out that you know if you want to take the cells off now, after you are cultured them, ok, I
should somehow get them off from the surface, right.

And people have practiced different kinds of things scraping that is a using physical force or
using sonication or you could add some agents, ok, which essentially some kind of chelating
agents which so if there is a kind of bonding between the cells and the dextran, ok. I add in the
reagent and it helps you in you know disrupting that bond and you know you can actually take
kidney cells off from the surface ok.

284
Now, there is a study ok, in which the reason that cells might be eluted, that means cells can be
taken off from the surface by lowering the surface tension of the suspending medium 1 ok.
Whenever you do these things, you do it in a medium right. That means I should imagine that I
have a container with medium 1, ok, and I have dextran which is coated with collagen that is
your component 3 ok.

And on that you have kidney cells, which is competent 2 ok. Now, ok because people have
reasoned out that cells might be eluted or easily removed from the surface of you know these
particles of type 3 or the component you know 3 particles by lowering the surface tension of the
suspending medium that is of component 1, ok. So, the question is, what is the basis for this
explanation, why do you think that they are saying that I can reduce the surface tension of the
medium and then elude the cells.

So, DMSO was incrementally added to cell carrier particle suspension ok. I have a fluid in which
I have you know the components 2 which is attached onto particle 3 they are in a fluid medium
1, ok, the fluid medium 1 is water. And to that they systematically add DMSO ok, so this is an
aqueous buffer solution is what they have, that is 1 is a aqueous buffer solution and to that they
are adding DMSO ok. And the surface tension of the eluting liquid ok, the surface tension of the
fluid that elutes the particle ok and the percentage yield of the harvested cells is given here.

So, this is the volume percentage of DMSO that is added. So, which is of course, increasing 0
corresponds to case when you have only the buffer solution in water and that is the surface
tension. And this is the percentage yield, that means the amount of cells that have been you know
extracted or eluted, ok. And it turns out that you know if you add about 19% you know by
volume of DMSO, your yield goes up to 80.1 % ok.

So for the solid because you know 2 and 3 are solids, right. Your 2 is a dextran coated with
collagen, that is a solid particle, ok, that is number 3, right, the solid particle. And 2 is the kidney
cells, ok, so they have estimated the surface tension values are just given, ok. Now the fact that
with increasing the DMSO concentration, the yield goes up is this observation, ok, is observation
qualitatively consistent with the expectation, is that what he expect ok.

285
Suggest some factors that might be reasonable for any quantitative discrepancy, ok, that is a
problem, ok. Take a look at this problem, think about you know what could be happening so
maybe we will try and discuss that in the next class, yeah.

286
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology-Madras

Lecture-20
Colloids Polymer Mixtures

(Refer Slide Time: 00:14)

Ok, so this is module 3 we are going to look at what are called as colloid polymer mixtures. We
are goanna talk a lot about in effect called depletion effects or depletion interactions and then I
will briefly touch upon steric effects you know towards the end, ok. So, before we go into colloid
polymer mixtures you know we could.
(Refer Slide Time: 00:46)

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So, you will see that the lot of contents from in this particular module or taken from lecture notes
in physics. There is a book or notes dedicated to you know depletion interactions if you are
interested in know more you should read of this book.
(Refer Slide Time: 01:06)

So, the again motivation ok, why are polymers added a colloidal dispersions. So, there are you
know you can think about as many motivations as possible, some of the common ones are to
achieve required flow characteristics ok. In that sense they are used as what are called as
viscosity modifiers, if you look at lot of products like paints for example you know or a shampoo
you know or any you know material like that.

288
Or even you know the oral suspension that you know syrups and all that right. So, the way they
flow of the bottle ok becomes important, ok, so to achieve the right you know flow properties
people do add certain amount of polymer. In a sense then it will affect it is viscosity and it will
affect the way it comes out of you know the containers and things like that. We have talked
about ceramic processing when you start with a nice dispersion of particles ok.

And then I just mentioned that you know from that you can actually go to interconnected
network called as a gel I said there is a sol gel transition. And from the gel you can make ceramic
materials, ok, after you take this gel dry it up and then you do what is called sintering right. Now
during drying or during sintering it so you know often what happens is that you know because of
the drying induce stresses these material there would not hold together they may lead to this
could be some crack you know there could be you know there maybe defects in the material that
you develop.

So, what binders do is they kind of provide you know the right amount of adhesive forces
between the particles. So, you will see lot of applications where polymers are added as binders in
ceramic processing you know which could be which is a method for obtaining porous materials
or dense you know porous material so. Other motivation to look at polymer addition is you can
use polymers for tuning particle-particle interactions, ok.

Again if you look at lot of products you know like you know in food, cosmetic or paint industries
you would like to have a product which has a very high shelf life you know you want to keep it
in the shelf for a year or 2 year you know you do not wanted to go bad . So, one of the ways of
doing that would be to add polymers when you do that what you are actually doing is of course
you are increasing viscosity which will kind of you know help you in you know dealing
sedimentation effects, right.

Because if the things become more viscous, they will take a little longer to settle, right. And on
the other hand you can also tune what is called as particle-particle interactions you know I can
make the particle-particle interaction either repulsive or attractive depending upon you know

289
what product that I am trying to look at, ok. So, these are some you know different fields where
you know you will come across polymer colloid mixtures.

And it is also known that if you take like say a polymer film, right and if peoples are trying to
look at you know it is Tg that is a glass transition temperature the polymer it is know that the
addition of particles to such a films will also alter the Tg of the film, ok. So, therefore there are
several you know cases where you will see that the polymer and the particles they coexist, ok.
And therefore it will be interesting to look at what happens to the interactions between particles
when the polymers are present, ok.
(Refer Slide Time: 05:27)

These are some examples from literature again I have taken from the book that I will just
mentioned. This is a photograph of polystyrene dispersions you know this is polystyrene
particles they are spherical particles, ok. And they have 16% particles in volume ok, I talked
about this phi right, phi is the volume fraction, the volume fraction is going to be 0.16 in this
case, right.

They are in 10 millimolar NaCl, ok there is a you know some salt in the system. And everything
is at pH 7, ok. To this what is been done is they were added a polymer which is called
hydroxyethyl cellulose HEC, ok. And they are add in different weight percentage ok which is

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indicate here, that is 0.15, 0.3, 0.67, ok. And what they done is that you know picture ok of the
vials which contain these dispersions, ok.

So, the concentration the particles are same pH conditions are same you know salt is a same. The
only thing that is different in these 4 vials is a presence of polymer, that is right. Now so this is a
the what you see below is the same picture, ok, in which what is being done is all these vials
have been slightly tilted, ok. So, I was mentioning that you know this is one of the nice way of
seeing whether something else become you know gel like or you know solid like right, ok.

So, now what they do is they have tilted the vials and what it does is it demonstrates the
difference between rigid colloidal solid liquid and colloidal fluid, gas liquid ok maybe let me
explain a little bit. So, let us look at this particular vial ok, so what can you say about the bottom
phase. So, there are 3 phases right, ok, this one phase here, one phase here and other phase here,
ok.

The bottom phase is this is straight right, that means it is become gel like ok I can say it is a
solid, ok, what about the next one, it is liquid like right. So, right, it is liquid like, ok, the upper
one is also liquid like, right. But however if you look at the liquid that is this liquid there is a the
concentration of the particles there is higher, right. Because that is evident from the turbidity
right, typically I mean turbidity can mean different things.

But if you look at this vial, right, this contains only particles and the salt and you know and the
pH is 7, ok. So, because this is turbid, so I can say that this is a dispersion of if you take any latex
dispersion, dispersion of polystyrene particle it will appear you know white ok. So, this looks
very similar to I will come back to your question, this looks very similar to this, right. But the
only thing the only difference between this liquid and this liquid these two is that the
concentration of the particle is higher here, higher phi I will say and it is low phi.

So, whenever you see a liquid ok with a low concentration of particles you refer to that as a
colloidal gas, ok. The analogy is you know if you look at gas like state right I mean you know
typically if you look at number of molecules per volume, ok. In a gas like it is goanna be lower

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compare to what you are see for the liquid and you know and lower much lower than what you
see would for the solids right. So, in that context whenever you have fluid which lower
concentration of particles it is called a colloidal gas, ok. Therefore if you ok, so if you look at
this second vial here, so you have a fluid that is actually a colloidal fluid, ok.

That is colloidal fluid and you have a colloidal so let us look at the first one, right. So, the
difference between the rigid colloidal solid right, that is a rigid colloidal solid was this, right.
And liquid, ok, colloidal fluid or colloidal liquid, right, and of course there is also a transition
between the gas like region and the liquid like region, ok. So, this is one way of you know
visually telling something about the phase transitions, right.

Visually telling something about what is happen to your colloid you know colloidal solutions
after you added polymer. And if you look at the again the third vial right, so here they talk about
the coexistence of 3 phases, right, ok, this phase 1, phase 2 and phase 3, right. So, there is a ok
for 0.3 concentration 3 phase coexistence occur, ok any question you had a question. It is just
like a lamella classifier, what is it, what do you mean lamella classifier, sir it is a instrument sir,
when we tilt the bottle the normal in color solution what happens the rate of settling is faster in
that sir.

So, amount of the when it straight when it tilted when the amount of liquid is still same as in the
top sir. I have a doubt because these things we have done at our lab scale. Also here the amount
of liquid on the top is still same, because you have a same. See if you look at these vial, right on
the average I was say that the volume of the fluid in all of them are the same. Now if I tilt it also
why would the volume be different, right.

So, I mean you right, I mean you know volume of the fluid whether you take volume of the fluid
you know in this particular vial in this state or the volume of the fluid in this container I mean it
is tilted, the volume has to be same you know. Why would there will be a difference in the
volume. I yeah I mean do not know in what context you are asking yeah, see you said I mean
yeah the sedimentation, right, yeah.

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There is work which shows you know if you have sedimentation you know carried out in the vial
like this was a sedimentation in a vial which is carried like that. There are differences, ok, that is
a different aspect, so you know here what you doing is you are really not looking at
sedimentation problem the whole idea is look I prepared a solution with whatever composition.
And I would like to have a rough idea has to what is happen to you know the contents of the vial,
ok or if something is solidified if something is remaining as liquid.

So, when you want to get a quick you know kind of a inference you can just tilt it and then look
up you know what happen that is all, ok, yeah. HEC yeah, so this is a the hydroxyethyl cellulose
a polymer, ok. So, this experiment essentially shows that depending upon the concentration of
the polymer that you added, ok, your solutions can behave very differently, ok. And phase
separation is occurring you know things are becoming gel like here, right.

So, this looks like a more or less a solid right you know it is not perfectly flat but you know there
is a, ok, right. So, yeah so this is to illustrate that the addition of polymers can significantly
change the appearance of the fluid itself you know to begin with, ok.
(Refer Slide Time: 14:24)

These are some experiments where what is done is, so it is a mixture of polystyrene particles, ok
and a polymer. In this case it is sodium polyacrylate, ok and so that is and a different
concentrations. And this is ok same concentration 185 milligrams ok per liter, the same

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concentration the polymers added. However one is taken at 25 minute then second one is taken at
55 minute, ok. And if you take a sample like this and if you observe them under microscope, ok
you know you will see images like this.

And you know these white dots are mostly the particles, ok. And you know there is you can think
that you know there is some kind of a particle clustering or you know or there some you know
phase that occurs right. So, this is to show that there is a macroscopic change in the you know
the appearance itself. But that is because microscopically also things are changing, ok, so that is
a the scale bar is about 10 micrometer, if you want to know more you can just read this up, ok .
(Refer Slide Time: 15:58)

And again another example this is at a higher concentrations, so if you look at these 2, right this
was it a low concentration 185 milligrams per liter and this is at you know 370 milligrams per
liter which is 25 minutes after the addition, ok. If you compare this with this, right, this is exactly
at the same time this is at 25 minute but 185 milligrams per liter concentration, this is at 25
minute but however at a higher concentration.

You can clearly see that means quite different, ok. That means you are able influence that you
know this domain formation and that seems to you know the kinetics of domain formations
seems to have increased if you have higher concentration of you know the polymer, ok.
(Refer Slide Time: 16:51)

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So, ok, so this is ok these are few examples to show that both macroscopically and
microscopically the colloid polymer mixtures behave differently from a pure colloidal
dispersions, ok. Now in general the addition of polymer can lead to some of these things, ok.
There is fluid-fluid de-mixing, ok, what I mean by that is you could have you know dispersion of
particles, ok.

And I could add a little bit polymers ok, then this could essentially phase separate, ok in which
there could be you know maybe a particles in one region and maybe polymer in one region. And
both of them you know could be liquid like ok, both the regions could be liquid-liquid ok and the
polymers could go to one region polymer could be you know something like could happen, right.

So, you know the addition of polymer can lead to fluid-fluid de-mixing , it can lead to
flocculation. That means if you have particles like this, ok, it can form you know aggregates
right. And if the concentration of the particles is high enough you know these aggregates could
form a space spanning network. That means it could gel, ok, it could lead to crystallization, ok.
So, say that you know the particles are kind of randomly arranged in a dispersion I add polymer
it could bring in these particles together.

And it could form you know maybe nice hexagonal lattice some things like that, right. And
further lead also lead to what is called as glass transition, ok, so it can you know make, so

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typically when people talk about the behavior of colloids in general you have sol then there is
gel, ok. At some concentration it becomes a glass, ok typically at very high concentration maybe
of the order of you know 55% by volume and more something like that, ok. They can mix what
is it, they can mix like in a stable form yeah, yeah, yeah it can yeah, yeah, ok.
(Refer Slide Time: 19:24)

So, now what are the parameters that control or that are important to understand the phase
behavior of colloid-polymer mixtures, ok. So, we looked at you know the polymer concentration,
right. As we said that the first example that I gave you this was you know HEC right, a polymer
it was at a different concentrations. We saw that the polymer concentration does influence the
phase behavior.

The second parameter that would become important is the size ratio of polymer to the particle,
ok. So, when I what I mean by that is I could have a particle, right in a dispersion, particles in a
dispersion. When they add polymer to it typically people characterize you know these polymer
the size of the polymer by a quantity called Rg ok the radius of which gyration of the polymer. If
R is the size of the particle, your Rg by R becomes an important factor, ok.

So, whether Rg by R is very, very small or Rg by R is very, very large, so depending upon the
size ratio of the polymer to the particles become important, ok. And of course the interactions are
important and when we talk about colloid polymer mixture we have a solvent-polymer

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interaction, particle-particle interaction and particle-polymer interactions, right. So, this would
again be you know depending upon the type of the solvent that you are working with depending
upon the type of the polymer and the type of particle each of them could be very different, ok.

And of course temperature because temperature can both affect you know the polymer-polymer
you know interaction as well as the polymer-solvent interactions, right. You could have a
condition or you could have particular temperature where the polymer would in a crude sense be
happy in a solvent. That means you know it want to stretch out more or you know and there
could be cases where the polymer does not like to be in you know a particular fluid at a
particular temperature you know it would like to coil up, ok.

So, therefore the temperature becomes important of course the particle concentration, right you
know. So, we saw an example where you know the particle concentration was fix at 0.16 but
however if I were to have a different concentration of particles. So, these whatever these changes
that we see there could either be shifted to lower concentration or higher concentration, ok or at
lower polymer concentration you know or higher polymer concentration depending upon the
concentration of particle that you have, ok.

And of course time, right, that was listed in this particular example where we saw that the same
mixture. But if you look at different time you know it would microscopically it will be very
different. And at the same would also be true in terms of the macroscopic behavior as well, ok.
(Refer Slide Time: 22:50)

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So, we will again this is a cartoon which tells you something about the size ratio of the polymer
to particle. Typically this people refer to a quantity called q, ok which is as I said is a ratio of the
size of the polymer divided by the size of the particle itself, ok, you could have a case where you
know q could be you know very small, ok, you could have a case where the q could be of the
order of 1, ok and q could be much larger than 1, right.

So, when people talk about typically q less than 1, ok people use a term called colloid limit, ok.
That means I have added a polymer whose size is much smaller than the size of the particle that I
have in the dispersion, ok, that is what is called as a colloid limit. And when you have the q is
larger than 1, ok, people use a term called protein limit in which case the size of the polymer that
you have added is much larger than the size of the particle itself, ok.

The reason why a thing is called protein limit is because I think when you add people have used
polymer for crystallization of proteins, ok. That means I have a solution of protein, ok I add a
polymer and I would like to crystallize protein out of the solution, ok when that happens the
protein molecule size of the protein molecules are much smaller compare to the size of the
polymer that I had, ok.

Therefore it will invariably fit into q much, much larger than you know 1 or 2 you know larger
than one case, ok. So, therefore if you have cases where the size of the polymer is much larger

298
than the size of the particle which is what is depicted in this cartoon, ok, what is called as a
protein limit, ok. If you have a case where the size of the particles are much larger than this is a
polymer, ok, it is called a colloid limit, ok.

So, whenever you know you are trying to look at colloid polymer mixture, ok, it is good to
identify whether you are working in this regime, this regime or this regime, ok depending upon
you know any of these regimes you are colloidal interactions going to be different, the phase
behavior is going to be different, ok.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 21
Colloid Polymer Mixtures: Colloid-Solvent Interactions & Colloid - Polymer Interactions

(Refer Slide Time: 00:14)

So, the polymer solvent interactions so it is what is known is that the conformation the polymer
takes what you are looking at is 2 confirmations one case is what is calls expanded you know
configuration is more like a collapse configuration. So, whether the polymer is in this state or in
this state in a solution depends on the, polymer solvent interaction in a crude sense you can say
that if the interaction the intermolecular interaction between the polymer chain and the solvent
depending upon if the energy associated with this interaction is.

You know either positive or negative depending upon that it like this take this configuration or it
will take this configuration people typically something called as a good solvent and a poor
solvent or a bad solvent. So, in the case of good solvent the interaction between the polymer
segments and the solvent molecules are energetically favorable. And therefore, it will cause the
polymer coil to expand.

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On the other hand, when some polymers are put in a solvent what are called as poor solvents, the
polymer-polymer self interactions of preferred the polymer would like to be in contact with its
own molecule rather than being in contact with the fluid. Therefore, the polymer coils and it will
contract or it will you know, it will collapse. And of course the quality of the solvent that means
you know whether the solvent is good solvent or bad solvent depends on the chemical
composition of the polymer and the solvent and also the solution temperature as well.

If you look at when people study polystyrene polymer the good solvent for polystyrene is THF
you know, and then if you look at like say PVA polyvinyl alcohol a good solvent for PVA is
water. And the same time if I take this you know, polystyrene if you put in water will collapse,
we know the water is a poor solvent for polystyrene.

So, depending upon the composition of the polymer and the solvent and the solution temperature,
the polymers can either take this configuration and this configuration. Now, if it takes this
configuration if I am working with like say the particles of certain size if the particle size is same
in both the cases. Now, you can as you can imagine, your q is going to be different, because q is
a the size of the polymer divided by the size of the particle.

Now, if the polymers in expanded state it will be more likely that you know, if the particles are
very small it could be a protein limit. However, in this case, you know, if of course, I have drawn
very small particle if I take a particle like that. So, you know, if I have a case where you know,
the your Rg / R could be less than 1. So, therefore, the polymer solvent interactions become
important both in terms of deciding on. You know, maybe which regime you are in in terms of
the size, particle size to polymer ratio.
(Refer Slide Time: 04:06)

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And of course, it will also influence you know, the, other kind of interaction in the system.
(Refer Slide Time: 04:20)

Now, so, these are 2 phase diagrams. This is for the cases where q is large, so, this is a state
diagram for a colloid polymer mixture, for large q when I say large q, this is going to be the
protein limit q large q is for the protein limit that means q is you know Rg / R This is you know
it is much you know larger than 1 or larger than 1 And what is drawn here is you know phi p that
is the volume fraction of the polymer in the solution and phi which is the volume fraction of
particles in the solution.

And again we mentioned this. So, you could typically when the concentration of the polymer is
very low state like this if I take a point like this the concentration of the particle is low and the

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concentration particle both the polymer the particles are low, you know, you will expect you
know the state of the you know mixture can be fluid like however, if I am at an appreciable
concentration of polymer and particles, you could have a gas liquid kind of coexistence and if I
again go to higher concentration of particle in the polymer I could have a gel like system.

So, therefore, this kind of gives you know, depending upon it is not a I mean, you know, what
you can do what has been done here is people have done experiments with a variety of polymer
colloid mixtures. And you know, you can think about the different phases that come about when
you work with colloid polymer mixture can be broadly classified into these, you know, states and
it will tell you what is the typical concentrations that which, you know, each of these phases may
come about. So, that is for the large q case.
(Refer Slide Time: 06:25)

And this is for a small q case, where, you know, this q that is Rg / R. Yes, is smaller than 1, in
the same similar plot phi P versus phi and so, again, there is a range of at particular you know,
the polymer particle concentration you have a gel like behavior. And then you could have a case
where I know it could be a dense gel, it is a space spanning network, but with more concentration
of particles, maybe it will have a higher modulus compared to these gels.

And of course, at sufficiently high concentration of particles, you can have a glasses crystals or
repulsive glasses and things like that. So, this is basically gives you a broad picture of you know,
what is the different states that people observe in colloid polymer mixtures. Any questions so

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far? Before we go further? So, phase separation, any experimental technique that you can use it
for?
(Refer Slide Time: 07: 52)

One simple would be just, I mean, first, of course, it is a visual observation method? That is a
simplest one that you can think of. What people see, there are lot of I mean, of course, one could
be that you know, you can microscopy could be good technique. You can take you can start with
you know, one fluid system and you basically take a small sample sandwich them between 2
plates for a microscope and then keep observing, you record you know, that is one way to look
at.

I mean, people have kind of looked at onset of phase separation by light scattering as well you
know, you can you know, depending upon whether the if I take 2 fluid mixtures say that these
fluids are miscible at a particular temperature and then if you just heat it up they become you
know, they de-mix, they become 2 individual phases as you do a temperature you know, either
heating or cooling cycle.

I can put a small sample and I can shine a beam of light I can look at you know, what will
happen to the scattered intensity, there are other there ways by which you can you know extract
out phase separation by experiment like that, I will say these are the 2 techniques you know, that
comes to my mind at this point.
(Refer Slide Time: 09:23)

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So, this is a kind of picture which tells you what will happen, what are the different mechanisms
that people have proposed, in order to understand what happens to a dispersion of colloids, when
you add polymers to them. So, the addition of polymer to dispersion can promote stability or it
can also destabilizes dispersion both is possible. That means I have dispersion which is
inherently not stable at polymer it can become stable or I could have a dispersion is already
stable then add polymer it becomes no unstable.

It can be destabilized and that depends on the nature of interaction between the polymer and the
solvent and between the polymer and the dispersed particles it depends on lot of factors that I
mentioned can be listed several parameters it depends on all of that. So, other way to think about
this problem would be you know what is also important is the polymer solution thermodynamics
that is when you know the conformation of the polymer you know, whether it is in a coil state
expanded state or that becomes picture very important.

Also, you should also worry about you know, the typical interactions that exists between you
know, the different components that you have in the solution.
(Refer Slide Time: 11:12)

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So, typically when the concentrate of the polymer is low people have observed what is called is a
bridging flocculation this will happen in cases where the polymer could adsorb on the surface of
the particle I have 2 particles in the solution I add a polymer one end of the polymer gets
attached to the you know on the surface the other end kind of attaches to the other you know the
polymer. So, therefore there is a bridging.

And when you when many such particles and polymers come together, you could have this you
could have bridging flocculation. And this typically happens in cases where the polymers are
adsorbing, that is one of the requirements for the bridging to occur. If the adsorption does not
occur, then the polymer continues to be the solution. And continues to be in the solution as
maybe individual molecules therefore, the bridging will not be a possibility.

So, at certain concentration people have seen what is called a steric stabilization. In which case
what will happen is the polymer that are added it adsorbs onto the polymer. And it forms brush
like layers, which is depicted here it forms brush like layers and these brushes can extend over
sufficiently long distance, when I mean, but what I mean by that sufficiently long distance. So,
we said that the van der Waal force of attractions I know can be operative almost up to about 10
nanometer.

Now, if you somehow make sure that the particles never approach a distance which is less than
10 nanometer then you can actually get rid of the influence of van der Waals forces what these

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brush likes layer do. They extend you know they basically mask the influence of van der Waals
force of attraction and therefore, they can impart stability to the dispersion and this mechanism is
what is called a steric stabilization people also call it what is called a steric hindrance.

So, for steric stabilization what are the 2 things should happen? Either the polymer molecules
must adsorb on the particle surface or they can be anchored on the particle surface that means
what you have seeing is an example where the polymer is adsorbed onto the particle surface, I
could have a case where I could have a particle and these polymer molecules are coherently
bonded onto the surface both in this case and this case you will have steric stabilization.

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 Colloids and Surfaces
Prof. Basavaraj Madival Gurappa
Department of Chemical Engineering
Indian Institute of Technology Madras

Lecture - 22
Colloid Polymer Mixture: Depletion Flocculation

(Refer Slide Time: 00:14)

So, this is a module 3. What you looked at so far is if you have colloidal particles in a fluid if you
add polymers to it we will looked at you know what are the consequences that means some
applications where you know such a thing would happen plus we have discussed about different
states or the state diagram of the different diagram of the different states that you know form
when you mix colloidal dispersions and polymers and we have briefly talked about different
parameters that would affect the behavior of colloidal polymer mixtures.

And then we went on to talk about some specific aspects such as bridging flocculation and what
are called as steric effects. And we just said that in general addition of polymer can both stabilize
as well as de-stabilize colloidal dispersion that is what we have done so far.
(Refer Slide Time: 01:45)

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We will continue further with an important concept called depletion flocculation. Depletion
flocculation can occur at moderate to high polymer concentration that means, I have a dispersion
of particles and I have added polymers and if the concentration of the polymers is moderate to
high again moderate and higher, very general terms, it depends on the type of particle polymer
system that you are dealing with.

And I want to read what is written here and then explain later. The free polymer chains in the
solution begin to so if you look at this particular cartoon, what is shown here is particle 1 and
particle 2, and these dark region at you see this is the polymer that is adsorbed, that is the
adsorbed polymer. When the particles are very close to each other, that is at surface to surface
distance less than or equal to approximately the radius of gyration or the size of the particles size
of the polymers. Then what happens is the polymer chains, are excluded from the region between
the 2 particles, that results in something called as a depletion flocculation.
(Refer Slide Time: 03:31)

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This is basically a cartoon, so, what is shown here is particle 1, and particle 2. And there is a
dashed line. The dashed line, the size of that dashed line is, it is what is called the depletion
layer. I will talk a little bit about it later. And the size of the dashed line is actually half the size
of the polymer. Now, if you look at the picture of 1, that is this one. You see that on an average
there is same number of polymer neighbors that particle 2 has and the similar number of
neighbors will be there for particle 1 as well.

Now, the other images that are shown are what happens if the particles approach each other.
Now, this is a case where you know, these dashed lines exactly touch. And I said that, you know,
the typical size of this dashed line, which is also has a depletion layer is half the size of the
polymer. So, in this configuration, the polymer molecules still have access to the, gap between
the particles. Now, the next picture that is number 3 here, it shows a case where the distance
between the 2 particles is smaller than the size of the polymer molecules.

What will happen then these polymers can no longer be in the gap between the particles they
move out of the gap. And so, if you look at this region, this is what is called a depletion volume.
And if you compare this and this the depletion volume in figure 4 is larger than the depletion
volume in figure 3.
(Refer Slide Time: 05:51)

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Now, what happens when the polymers move out of the gap is basically explained in this
particular picture. So, you get what is called a depletion zone and this depletion zone is a zone
between the 2 particles which is depleted of polymer molecules. Now, we defined something
called as a osmotic pressure force and if you remember osmotic pressure force F osmotic we
define it as number density of the particles multiply by kBT.

This number density is number per unit volume. This was defined for particles, but I can define
the same thing also for the polymer molecules as well. Now, if I look at the osmotic pressure in
the region between the 2 particles because there are no polymer molecules there, the osmotic
pressure there is going to be 0. However, on the region outside the you know particles you have
enough number of polymer molecules there is going to be therefore, there your osmotic pressure
force is going to be finite.

But however, now, you have the imbalance in the osmotic pressure. The osmotic pressure here is
lower the osmotic pressure is higher there. Because of this imbalance in the osmotic pressure, the
particles are essentially pushed together. That leads to what is called as depletion flocculation.
So, the origin of depletion flocculation is related to the formation of depletion zone and the
creation of depletion zone leads to the osmotic pressure imbalance.

311
And this excess pressure, what are the arrows that you see here, these arrows essentially show
you the, the way these excess pressure is going to act, that is what will bring the, particles
together. Now, the schematic that you have shown, this is actually a schematic picture for
colloidal spheres, these are the particles. And they are in a solution with non adsorbing polymer,
in this case, the particles the polymer continues to remain in the solution, they are non adsorbing.

So, therefore, a mixture of particles plus non adsorbing polymer will exhibit depletion effects.
That is number 1. Number 2, you could also have a case when you know what that is what is it
depicted here, you could also have a case where initially the polymer continues to adsorb out of
the particle surface and then when the polymer when the particle surface is saturated with the
polymer, then the depletion can kick in.

Depletion can also be seen in cases where I have particle plus adsorbing polymers as well. Only
difference between the 2 would be the in the case of particle plus absorbing polymer, you know,
combination, the depletion effects will obviously occur at a much higher polymer concentration
than what would happen for the particle plus non adsorbing polymer case. That is number 2 so, I
just want to write down again.

So, the depletion effects can be absorbed in particles plus non adsorbing polymer case. Number 2
particle plus adsorbing polymer case. Can you think of other cases where the depletion can
occur? So, if you go back and look at the way we talked about again one of the criteria for
depletion to occur is that q which is defined as the size of the polymer divided by size of the
particle should be less than 1.

That is the condition under which the depletion interactions would become important. Can you
think of other systems where I can have a similar analog? So, you could have a case the third
case is where I have a solution which contains large particles, say that they are negatively
charged. Now, another combination of very small particles or a colloidal particle plus
nanoparticle mixture, where the particles both the particles are similarly charged can also exhibit
depletion interactions.

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That is a third system. A particle, particle combination can also you know a similar phenomena
about you know, the particles not having access to the region between the particles can also
occur in the case where you have a combination of large sized particles and a small sized
particle. And the fourth combination where this could happen is a system where I have particle
plus micelles.

We know that typically micelles are the structures which are formed because of self assembly of
surfactant molecules and typical size of micelles will be very, very small of course, it depends on
the kind of suffering that you are dealing with. Imagine that you know, I have let say SDS,
sodium dodecyl sulfate. Now, sodium dodecyl sulfate, the surfactant molecule is negatively
charged.

Now, if I have a micelles that is form because of SDS, it looks something like this, the micelles
would be negatively charged because the head group is negatively charged. And I have this in
combination with large particles, which are also negative charged. When you have a combination
like this, you can also people have done experiments and shown that the depletion effects can
also occur in the case of particle surfactant combination in which both the particle and the
surfactant structures or the micelles will be of similar charged. So, these are the 4 instances
where you can think about depletion interactions.
(Refer Slide Time: 13:06)

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Again, this is just a schematic which tells you about the depletion volume. If you have a case
where the particles are really far apart your depletion volume is 0 as soon as the overlap of
course, you are going to have this lens like region in the case of spherical particles and if as long
as if you so this the volume of this lens, is what is called as a depletion volume and of course,
that will depend on the the separation distance.
(Refer Slide Time: 13:40)

Now, so, this is a just like we wrote Lennard Jones potential I mean, we know how to write if
your phi is a function of separation distance. So, we said you know, Lennard Jones is going to
have one you know contribution because repulsion other contribution because of attraction, we
wrote this overall potential and stuff like that. Similarly, people have kind of developed in the
you know, if you have colloidal particles immersed in a pool of polymers, people talk about
depletion interactions and the depletion interaction expression is given by this.

So, we will try and derive it a little later. So, what does this tell you. So, in this case 2 delta is the
delta is the half so, let us go back. This case now, for any distance that is larger than 2 times Rg
of the polymers, that means the gap between the 2 particles is in a big enough for the polymers to
be there for any distance greater than 2 times Rg, the polymers will have access to the region
between the particles that means the osmotic pressure imbalance is not set in. The osmotic
pressure in both regions are the same.

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For such a case, your interaction the W depletion, where h is a separation distance now is going
to be 0, for any distance that is greater than 2 times the Rg of the polymer, or 2 times delta in this
case the depletion forces are going to be not there that is 0. Now, for any distance of separation
that is less than 0, your W depletion is going to be infinite. That is very similar to the repulsion
between the electron clouds, of the particles.

I mean, there is so this is not a practical situation, I mean, you really will not have any situation
where you know, you are, you know, is gonna be less than 0. How about this, this is the,
separation distance going from 0 to 2 times delta 2 times delta essentially corresponds to when
these 2 overlap that is 0. When, the particles are getting sufficiently close, right now I have
something like this. I am going to draw another one is actually touching. That is the closest that
they can go as h = 0.

That is h = 0 all the way going to 2 times delta, the depletion interaction is given by P times V
overlap. V overlap is the overlap volume and P is the osmotic pressure. P is the the osmotic
pressure which is determined by the, concentration of polymer that you have in the solution. And
you know, people have worked out what this overlap volume would look like. Of course, it is a
function of h. Overlap volume in the case this is a lens. If you look at this, it looks like a lens.
There are ways by which I can calculate what is the volume of the lens.

As h changes that is the distance of separation changes, it turns out it is given by pi / 6 2 times
delta - h whole square multiply by 3 times R + 2 delta + h / 2. R is the size of the particle ,2 delta
is the size of the polymer that you have at initial separation distance.

(Refer Slide Time: 18:17)

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So if you plot this expression, it would look something like this. It will, it looks something like
this. W of h, where h is the separation distance, it is scaled with kBT, thermal energy. This is the
point where h = 2 times delta any distance beyond that the interaction potential is 0. And it is
attractive in the range from h = 0 to h = 2 delta and h = 0,we have a spike that corresponds to W
of h, divided by kBT being equal to infinity. That is your case here. And this is W of h divided by
kBT going to 0 and this region here is where W of h divided by kBT causes minus P times V
overlap. So that is I mean this is actually for depletion interaction between 2 hard spheres.
(Refer Slide Time: 19:30)

So, this particular concept of the depletion interaction, was actually the expression that we see
here. This was actually first proposed by 2 scientists Asakura and Oosawa. That is also called as
AO potential the depletion potential. It is also called as AO potential that is because of the people

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who you know gave this concept of depletion interactions and things like that. That is about
depletion you know, attraction or depletion interaction.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 23
Colloid Polymer Mixtures: Depletion Stabilizations

(Refer Slide Time: 00:14)

Other concept which is what is called the depletion stabilization. Now, when I say that so, we
mentioned that for the depletion attraction to occur the polymers have to more of the gap. Now
the polymer depleted regions they are generally created by de-mixing of the polymer chains and
the solvent could you understand this statement so, when I said that the polymer will go to the
gap i can think about that as a de-mixing initially the solvent and the polymer everything was in
a mixed state there was a homogeneous solution.

Now, the fact that in the previous case you know the particle so, the polymer left the gap you
have a region of pure fluid and a region of polymer plus fluid you can think about this as a de-
mixing process. So, therefore, the polymer depleted regions are generally created by de-mixing
of polymer chains and the solvent. However, if the solvent medium is such that it is a good
solvent for the polymer that means, if there is a favorable interaction between the solvent and the
polymer.

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This de-mixing process becomes unfavorable that means, it is be very hard or it will be very
difficult to or it will be practically impossible to move this particle out of the gap. That means,
so, the region between the particles will continue to have polymer so, because the de-mixing is
what should happen only then the particles can come sufficiently close. But however, if
somehow this de-mixing is prevented then what will happen is you will always have the region
between the 2 particles will always be having particles polymer plus the fluid.

And such a case is referred to as what is called depletion stabilization. So, depletion stabilization
is a case where the formation of depletion zone is not favored so, that is, you have some
question? No, so, I think a look as it is mentioned, you are, it really depends on the polymer
solvent combination that you are using, whether depletion stabilization will occur or not, it will
depend on the polymer solvent combination. Because, I said that you know, if you have a case
where the polymer molecules are happy to be in a solvent that is a good solvent case. Now, if
you have a good solvent too.
(Refer Slide Time: 04:09)

So, one way of thinking about you know, this, like, let us go back to this carton. So, if you look
at this depletion zone formation.
(Refer Slide Time: 04:27)

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So you can other way of saying which it look, I have I am able to create regions of no polymer
and regions with polymer. So now, there are cases where such you know, things are not favored.
So, one of the case in which this does not happen is a polymer good solvent combination so that
is. What is the reason for this depletion stabilization? I think this does not depend on the particle
concentration it depends solely on the particle solvent, polymer know solvent combination that
you use. So, let me put another thing. I want to make this clear.
(Refer Slide Time: 05:20)

When I say that, when you? Let this carton? So I am, when I was explaining I said that. You
know, there is a depletion volume, you know and it you know it kind of the depletions volume
increases is what I mentioned? So, what brings the particle together? Or what you know, so of
course, these depletion interactions will kick in only when the particles sufficiently close. Now,

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what brings them together to such distances? Again, Brownian motion, you are not, externally
doing anything

You have particles in a fluid, they are jiggling around. And they because they are free to move,
because they have thermal energy, they are free to move. And if it so happens, that because of
this no chaotic motion that they are exhibiting, if the distance between the particles, you know,
could reduce depends, it depends on the particle concentration, it depends on the diffusivity of
the particles, all of that.

Now, if you if there is a case where the separation distance becomes smaller than this, you know,
2 times Rg or 2 times delta, is when all these depletion effects will kick in. Any question with so,
we looked at? Depletion flocculation. And we also looked at depletion stabilization so far. Any
questions with these 2 concepts? So in one case, so again, this is another case you know, again,
to read, you know, this read what I have said.

So, this is a case where the addition of polymer leads to destabilization is again a case where the
additional polymer does lead to stabilization. Again, it depends on the polymer plus particle plus
solvent combination that we are trying to use.
(Refer Slide Time: 07:40)

We can think about get back to the simple way of deriving an expression for depletion potential
we will take a very simple case. And this particular geometry is chosen because again, it is very

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easy to do calculation. So, the objective is to calculate the depletion potential between 2 plates,
which was separated by distance h. And that is plate 1 that is plate 2. And you have, so, these
dotted lines that you see you can imagine them to be you know, polymer molecules.

So, they you know, it says, penetrable hard spheres, but you can think of them to be you know,
polymer molecules, the size of these molecules is sigma. And h is the separation distance and so,
this K is the force between the 2 particles.
(Refer Slide Time: 08:53)

And K is actually the force per unit area between the 2 parallel plates which are separated by
distance h. That is the difference between the osmotic pressure inside and the osmotic pressure
outside, this is when the, plates is sufficiently far apart when the plates are sufficiently far apart,
this Pi would be equal to Po, and essentially your K of h is going to be 0 that means there is no
force that is either pushing the, you know them towards each other.

So, if the so, let us look at 3 cases, case 1, where P0 = Pi in this case, you know, there is
essentially no force between the 2 because, you know, on an average the number of molecules
polymer on either side is the same therefore, you are in the osmotic pressure outside and osmotic
pressure are the same and the case 2 could be where Po is greater than Pi that means osmotic
pressure outside is larger than Pi in such a case the plates are going to be you know pulled they
could be pushed towards each other.

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And the third case could be where you know your Po is less than Pi in such a case the polymer
concentration higher is in the center is going to be higher than the exterior region that is when the
particle pushed apart these are the only 3 situations that can happen. Now, if you have case like
this, if you go back to what we wrote up earlier, the depletion potential as a function of h is going
to be is 0 if h is greater than or equal to sigma?

That is what we wrote up earlier when this distance of separation between the plates is greater
than sigma could be reduced 2 times delta there? So just a change of symbols 2 times in this case
2 times delta is same as sigma. So any distance greater than the diameter of the particles or
diameter of the polymers or diameter of these dotted objects? Is distance greater than that your K
of h going to be 0 And for any, distance less than sigma is going to be minus n b into kBT That is
what we would like to prove?

Now, that is the expression for the force. So, essentially, the force and the potential are related in
this particular way. And so, if you look up this so, what is written here essentially comes from
this expression right.
(Refer Slide Time: 12:08)

You guys do not if you guys let me just do it again. What is written here actually comes from
this expression. Because for any distance h greater than or equal to sigma, for any distance
greater than or equal to sigma, your Pi is = Po Therefore, your h is going to be 0 For any
distance, which is between h and sigma. Essentially, Pi is going to be 0. Therefore, K of h is

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going to be minus Po. And minus Po, Po is the osmotic pressure, which essentially is nb times
kBT, that is how the osmotic pressure was defined, because it is force per unit area.

Therefore, it is I have only written up n b into kBT this is this will also have units of force per
unit area. So, this will have n b will have number per volume, meter cube kBT will have units of
energy that is newton meter is cancelled, so, it is so therefore, it is consistent. So we know how
to write this up. Now and when you want to look at h, when you want to get W all had to do is I
know what is you know the dependence of k with h you know, I will just integrate that I would
get an expression for interaction potential.

That, so therefore, I need to take this minus n b kT. And that is going to be K of h. So therefore,
if you want it is integral from 0 to infinity times dh, if you want W, W is going to be integral of n
b times kBT into dh going from in this case your you should go from 0 infinity. I can split this
integral from 0 to sigma. Or any distance of separation h to sigma h could be 0 as well plus going
from sigma to infinity the contribution sigma to 0 infinity is going to be 0 because we know that
any distance greater than sigma you know the interaction is not there.

So, therefore, this going to be 0. So, when you know work this out minus n b kBT dh you will get
essentially this. So, you had n b kT minus is going to be sigma - h that is what you simple
integral. Now, if you look at this term, I have W of h, I said this is the energy per unit area
interaction energy per unit area. If I take h to the other side, I can write this as minus n b kT into
sigma - h multiplied by A this area multiplied by the separation distance is essentially the
depletion volume.

Therefore, the W of h becomes this is P, there is an osmotic pressure force multiplied by overlap
volume sigma - h multiplied by A is the overlap volume that will that essentially is the area of
the plate multiplied by the distance between the plates that essentially is the volume and
depending upon h by overlap volume is going to be change. So, essentially we recover an
expression like this.
(Refer Slide Time: 17:09)

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For any distance greater than, you know, 2 delta or sigma you have W depletion is 0. And for
any distance between 0 and you know 2 times delta, you have depletion interaction going yes.
The osmotic pressure force multiplied by osmotic pressure multiplied by the overlap volume,
that is. So this is a simple derivation to think about how you know, the expression for depletion
interaction is calculated, so maybe we will stop here.
(Refer Slide Time: 17:45)

We will talk a little bit about how do people do when you have 2 spherical particles and in a
medium, how do people think about obtaining an expression for depletion forces is what we will
do in the next class.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 24
Depletion Interactions

(Refer Slide Time: 00:22)

We will continue with deriving an expression for depletion interaction. So, what we had done in
the last class was this we took a very simple case of 2 plates which are embedded in a polymer
solution and we found out what is the depletion interaction between the 2 plates. This is one of
the simplest geometry and it will you know help you to calculate this calculation is fairly simple.
So, what we said is that, if you have 2 plates which are separated by distance h then the force that
acts between the 2 plates P’s.

We wrote it up as Pi - Po where Pi is the osmotic pressure force in the region between the plates
and Po is the osmotic pressure force in the region outside the plate. And I mentioned that
depending upon you know whether P i = Po or P i is greater than Po or you know Pi is less than
Po the plates will be pulled towards each other in this case in this case the plates will be in that
not in this case. If this is a case then the plates would be pulled towards each other because
osmotic pressure in the interior is less than the osmotic pressure outside.

326
The you know the plates would attract and if you have a case where Pi is greater than Po then the
plates to be pushed apart and Pi = Po is the plates will continue to exist in whatever configuration
they are in. And now, because we have you know, when we are talking about depletion
interaction, we have been saying that, when the distance of separation is larger than you know
the size of the you know the particles in this case or the polymers in this case.

The depletion you know force are 0 that means, in this case, Pi = Po when the distance between
the plates is much much larger than you know sigma, this Pi = 0 Pi = Po therefore, the depletion
interaction becomes 0. But for any distance which is h less than sigma your Pi becomes 0,
therefore, Pi - Po = - Po itself. And where P o is the osmotic pressure force which is governed by
the constant which is determined by the concentration of the polymer that you added to the
sample.

And that becomes n b times kBT. That is what we have. That is by the definition of osmotic
pressure force. So, we know how we got this, starting from this, then, to obtain the interaction
potential W of h, that is what is interested, that is what we are interested in and W of h is the
interaction force per unit area in this case. And you can just simply integrate, you know, W of h
is going to be integral of K of h into dh. And that is how you obtain this expression. So, it was a
fairly straightforward derivation.
(Refer Slide Time: 03:44)

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However, if you go to you know, other geometries like you know, if you want to calculate what
is the depletion interaction between spherical particles, then the derivation becomes a little bit
more involved. And in this case, so, now, if you look at this spherical configuration, so, you
have, this is the, the, overlap volume, or the, it is the this is the the lens that is formed, this is the
lens that is formed when there is a overlap of the depletion layers.

Now, in the previous case, we talked about whether the pressure is 0 here and you know, what is
the pressure there? But in this case, it turns out that, you know, the osmotic pressure force does
not act all across the surface. That means, if I take one surface here, and one point here and one
point here the concentration of the polymers in this region is going to be same? That means there
is not going to be any osmotic pressure either attraction or repulsion because of the imbalance of
the osmotic pressure, it would not act so it only acts in certain cone.

And so, typically, it acts in a cone, which is, you know, theta = 0 to theta = 2 times theta 0,
where the magnitude of this theta 0 depends on the overlap itself. Is there a higher overlap or
lower overlap. That means, it will essentially depend on this lens volume. Whether the volume of
the lens is something like this, or something like that? Depending upon the extent of overlap,
your theta is going to change. Now, to calculate depletion force, what you should do is, I am
going to take a point there, I am going to take so I am going to take multiple points.

In that in the cone region and I would like to calculate I am going to join them then go to
calculate what is the pairwise interaction. It turns out that if I do like that, and if I you know, it
turns out there are no I will have 2 components one is the horizontal component and the vertical
component I would have to add them up. Now, it turns out that the vertical component will
cancel each other, what I mean by that is, if this is the, line of force that connects the 2, you
know, points.

So, therefore, I am going to have a horizontal component which is going to be the cos theta
component and vertical component that going to be sin theta component, because of the
symmetry of the problem, the sin theta component is going to cancel each other. The only

328
contribution that will is going to come is going to be because of the cos theta component, if P is
the osmotic pressure, then P cos theta will give you the component of the force.

That is acting you know, across you know the 2 point that we are considered and the summation
of that is what is going to give you the total osmotic pressure force. So, it is a little bit involved
you know, like the previous case, it is not as simple you know method to do it people have
worked it out if you want to read a little bit more than you can go back and look it up it turns out
that you know, the surface or which you know, this the surface that is you know, this particular
surface or which the depletion forces are acting.

You know is given by something like 2 times Rd square sin theta into d theta and with this Rd is
given by Rd is = R + sigma / 2 there is a effective volume of the particle where R is the radius of
the particle that we consider sigma / 2 is the half the size of the polymer molecules. That will be
the effective size and it goes as to Rd square sin theta into theta if you want to get the overall
force I would have to I can integrate this over all angle going from 0 to theta, theta 0. So, from
that you can actually get what is the expression for the force that is acting between the 2
spherical particles.
(Refer Slide Time: 08:28)

And then once you know the force, you can actually get the depletion potential again if again you
know in this case, it is represented K of r if you know this, that is going to be again minus d of W
or you know, W of t is going to be minus or d of W of d or in this case r divided by dr. So, I can

329
integrate that and then so, essentially you will have a expression similar to what we have seen.
So, for any you know distance less than 0 you know you go to have the repulsion that is come
because of the overlap of the electron cloud that is this.

And you are going to have an osmotic pressure times the overlap volume, when the distance is in
this particular range, and this overlap volume we can actually get it as you know, if you do the
derivation all that. So, you will get the overlap volume, which is something like the grade
depends on the extent of overlap, it depends on this is the separation distance. So, h is essentially
the separation distance, but it is the surface to surface separation distance.

And R is the size of the particle 2 times delta is the size of the polymer molecule that has been
considered. So, you will see that in a lot of cases, people kind of they use sigma or Rg you know
R you know, so, in sigma / 2 times sigma is the size in some cases you will take the size to be 2
times Rg and stuff like that, but you just have to look it up you know what exactly each of these
terms mean in this case 2 times delta is same as sigma that is the if you look at this
nomenclature, sigma is same time the same as 2 times delta again this is going to be sigma itself,
that is the expression.
(Refer Slide Time: 10:33)

Now, again, so, the other way to think about this calculate the overlap volume is going to be you
know, there are expressions available for what is the so, if I have a spherical cap, if I have a
sphere, if I cut this up I am going to be get what is called as a spherical cap. Now, there are

330
expressions that are available for calculating what is the volume of the spherical cap it depends
on you know, this height h that is this height h, it depends on what is the you know the when you
cut the sphere you get a circle, you know.

So, you have part of the so, you will have again a circular surface that is the area of that circle
and h is the separation distance. Now, if you look up the depletion volume, what you actually
have is 2 spherical caps that are put together. So, there are expression that are available for
calculating how does this you know the volume of the spherical cap change you know with the
height or the radius of the particle.

And it turns out that of course, in this case this h you know is going to be the height of the lens
that you get is typically is going to be sigma - h that is the height of the lens that is this
particular. So, this the half of this distance is going to be sigma - h. And similarly, there are
expressions you can actually calculate what is going to be the so, essentially, if I know the extent
of overlap, I can actually use an approach like this.

Where there are expressions available for what is the volume of the lens that is formed between
the 2 spherical particles as the particles overlap. And you can also use an approach like this also
to calculate what is the depletion volume? So, the important point is in any calculation that
involves you know depletion interactions, only thing that you have to worry about is how do we
get the overlap volume. So, as long as you have a method of obtaining that and as I said it is
much simpler to get an expression for overlap if you look at simple geometries.

However for sphere-sphere case and for other cases, it becomes a little bit more complicated.
And as long as you have a approach of getting it that is what will help you to calculate what is
the depletion volume.
(Refer Slide Time: 13:23)

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These are there are some again literature reports where you depletion interaction does depend on
the particle geometry. So, there are 3 expressions that are given 2 spherical particles spherical
particle and a plate and 2 plates. So, in this case, h is the, separation distance h is the separation
distance on a surface or surface separation distance and Vd is the depletion volume, Vd is the
depletion volume Rg is the radius of gyration of the part the you know the polymer that is added.

And there is a term called phi p l p l stands for polymer phi is the volume fraction of the particle
of polymer that is poured. So, we used to have a n times kBT where n is the number of number
per unit volume? So, you know, of course, I can also express n also in terms of the volume
fraction of the polymer, so, that is phi p. And, of course, a is the, characteristic dimension of the
particle that we are considering. So, this is an expression for a sphere-sphere, the sphere plate
and this is for 2 plates.
(Refer Slide Time: 14:59)

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So, an interesting observation if you plot these 3 quantities, it turns out that you know the in this
case V d is the depletion potential. So, the depletion potential that is scaled with the volume of
the polymer multiplied by kBT it shows a trend which is like this. Now we are mentioned that for
any distance greater than 2 times Rg your depletion interactions are not present that means is
essentially 0, but if you look at the distance between 0 to 2 times Rg the trend looks something
like this this is for sphere-sphere case sphere-plate and plate- plate.

So, any thoughts as to why this why the variation is in this way. So, simple explanation is more
overlap volume that means, if I look at a 2 plates like this if remember the entire area between
the 2 plates was contributing to the overlap volume. However, if I look at 2 sphere case there is
only a small area that is between the 2 particles was contributing to the overlap volume and of
course, if I take the 2 case of sphere and a plate, again the overlap polymer is going to be
something in between.

So, in this case everything else has been kept constant the concentration of the polymer is kept
constant the particle you know and the temperature is the same. So, if you just plot the scaled
depletion potential as a function of separation distance, it turns out that the strongest attraction
would be felt for the plate, plate combination and the least you know for a given separation
distance the least you know attraction would be felt for the sphere-sphere.

333
You know plate this is solely because of the effect that comes from the fact that the depletion
volumes for the 3 cases are different and it increases in this order least for the spheres. The next
highest is going to be sphere-plate and the highest you know the overlap volume is going to be
further the plate-plate combination. So that is about depletion interaction.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 25
Steric Interactions / Osmotic Repulsion

(Refer Slide Time: 00:14)

So, when we talked about steric interactions that is if you have cases where you have you have
particles and on the surface of the particle you have you know some long chain molecules that
are either covalently bonded to the surface or they could be adsorbed onto the surface. So, if you
have cases like that, then I had mentioned that there will exist what is called a steric repulsion,
you can think about steric repulsion also as something as an osmotic repulsion.

So, we will see we know what it actually means. So, when the polymer chains are in good
solvent. That means the polymer molecules are happy being in a solvent, then you can say that,
when you say that the chains are swollen, that means they are in a, you know, expanded
configuration. And in a sense, that the reason that they know they are in an extended
configuration that means they do not like to be in contact with you know, the polymer chains,
they are happy being in contact with the solvent molecule.

That means you know, this, the chains essentially repel each other. So, now, so, if you have a
case where so, this is a case, where the particles are sufficiently far apart, now, this is a case

335
where the particles have come sufficiently close to each other, then what will happen is that, as
the 2 particles which are with these polymer chains, which are attached covalently are adsorbed,
when they approach each other, you can think about it as a there is a local increase in the osmotic
pressure force, what you can think about is if I look at the region here.

Now, there are many more polymer molecules you know, in the volume in the region between
the 2 particles, than you have the polymer molecules elsewhere, it is exactly the reverse of
depletion interaction. In depletion, we said that, when they overlap, when you have polymers that
are not adsorbed.
(Refer Slide Time: 02:50)

When they when you have a non adsorbing polymer, I said that, when the particles come to
sufficient the particles come sufficiently close, you get a region where the polymers are depleted
that means, there are no polymers there. However, in the case of steric repulsion, what happens is
something that is contrary, on an average, there is an increase in the concentration of polymers in
the gap between the particles.

Therefore, I can say that effective osmotic pressure force in the region between the particles,
there is inner is going to be larger than the osmotic pressure force that is outside in the region
that is outside. So because of which, now there is going to be a force it is going to be the
opposite direction. To what we saw for the depletion attraction case that means the particles are
going to be pushed away.

336
So, therefore, when they approaches to the local osmotic pressure increases dramatically, due to
you know, the fact that you know, there is a competition you know, between the polymer chains
to occupy that volume and this competition, what leads to repulsive interaction.
(Refer Slide Time: 04:14)

And this is essentially a plot of interaction energy as a function of separation distance. So now,
there is a dotted line, that dotted line corresponds to the interaction where correspond to the case
when you have absence of steric repulsion, there could be van der Waals or other kind of
attractive forces in the system, that is this particular curve, there is a dotted dashed line. And
however, this continuous line that you see is, you know, where you have steric interaction,
present the system.

And it essentially is going to again, depending upon the separation distance and depending upon
the concentration of polymer molecules, you know, in the gap between the particles is going to
increase. So that is a typical thought that you will see. When I say polymer repel each other, you
should think about it more like they are more happy being in contact with solvent molecules than
with the polymer molecule, maybe you can think about along these lines. So, that means I have a
particle, which is in a pool of solvent.

It would rather prefer because, you know, we are talking about a good solvent, the polymer
would prefer to be in contact with solvent given a chance. If you talk about bad solvent, the

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polymer does not want to be in contact to the solvent, therefore, the polymer you know
interactions are preferred. So that is the analogy. So, the steric interaction the only thing it does is
see there are some you know, like say if you look at say that I have a system of particles.

And you know, we know that we are always going to have this van der Waals attraction between
the particles. Now, how do I get rid of such interactions? One of the ways we thought about is if
I take these particles, if I put them in a medium where the Hamaker constant of the medium and
the particles of the same then you know I can get rid of van der Waals interactions. Now, the
other way of you know, somehow negating the effect of van der Waals interaction.

Is to look at a case where I somehow ensure that the particles would never approach the
separation distance know where the van der Waal forces become important. So, one of the ways
of doing that would be by introducing some change on the particle surface. So, that know that
now, the separation distance between the 2 particles is never going to be less than 10 nanometer
something like that. So, that you know, you do not have van der Waals attraction dominating in
the system.

One of the ways of thinking about you know, the steric interactions could be in terms of osmotic
repulsion. So, that the fact that you know, locally you know, so, for example, so, this phi star that
is seen here is the you can think about this as a grafting density . In a phi star you know, it refers
to the concentration of polymer molecules that is attached onto the surface, we think we are
grafting density.

Now, what will happen is when they are sufficiently close, you know, the in the region between
the polymers a particles your know your the overall concentration is definitely going to be
greater than phi star. So, when that happens, there is a the osmotic pressure imbalance again in
this case only thing is it is opposite to the direction that we saw for the depletion attraction case,
that is the crux.
(Refer Slide Time: 08:39)

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Now, it turns out that the steric repulsion depends again on the polymer configuration you know,
whether you know the polymer that is adsorbed or grafted onto the surface is it you know, does it
take a shape like this or does it shape it you know, take a shape like this, this one because a brush
like configuration, this something becomes a mushroom like configuration, these configurations
are seen.

When the polymer chains or polymer molecules are covalently bound to the surface such
configuration is when you have polymer molecules that are adsorbed onto the particle surface.
So, depending upon it will depend on the configuration of the polymer it will depend on the
grafting density itself, what is the number of chains per unit area that is, attached to the surface.
So it depends on a lot of factors. Calculating, you know, steric interactions is a little bit more
complicated than the depletion because of all these effects?

Because, you know, you would have to have an idea about the configuration of polymer chains,
you should have a definite understanding of, or measurement of the grafting density, all of that.
So I do not have any more stuff on steric repulsion, again, the book that I mentioned does have
sufficient bit of you know chapters on steric interactions if you want to read more, you can go
back and read up a little bit.
(Refer Slide Time: 10:06)

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So, this is again general it like in any colloidal system, the total interaction potential will always
be a summation of van der Waals + W brush in this case w brush essentially corresponds to W
steric if you want to call it as. And the steric repulsion or W brush is going to be repulsive, that is
this and the van der Waals is going to be attractive. So, the whole idea of putting W brush is that
you know or the steric repulsion is the overall interaction would still be repulsive.

That is your W total depending upon you know the contributions of polymer molecules
depending upon the grafting density everything. So, this curve could be shifted up or down
depending upon what problem you are trying to look at. So, this is essentially to tell you that the
total interaction in a case where you have steric repulsion is a summation of van der Waals
interaction plus the interaction that comes because of the adsorbed polymers.

This is actually this is so, this W total is the particle, particle interaction. See, when we plotted
this, let me do it this way, this plot, let us see that you know, so, we are worried about just 2
particles. And say that I want to calculate what is the van der Waals force of interaction between
the 2. So, we know that you know, it goes something like this. And if given that the particle sizes
R, and the separation distance is d, we know that you know, this basically goes as something like
a times R divided by 6d, something like that. So we know how to do that.

Now, what you have is, I have 2 particles, on which I have these grafted chains. Now we are
again, I am still talking about the particle, particle interaction. Now, in this case, in the case of

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particle, particle interaction with these grafted chains, so it turns out that depends. So if they are
in a configuration like this, of course, the interaction is going to be 0? I do not have any steric
effects at all? Now, of course, that will happen for large separation distance? Now, when there is
not overlapping.

So there is going to be again the lens that is formed. And the moment that lens you know, or the
overlap occurs, then phi star is going to be larger, so that is typically is happening here. That is
where you know, you are see start seeing some repulsion that happens here. And then of course,
depending upon the overlap, now you are going to have an increase in this case again, it is the
interaction between the particles, with the grafted molecules on the surface. So, if we go back
here I mean. Similarly, if you look at expressions like this.
(Refer Slide Time: 13:45)

This again is the particle, particle interaction is nothing to do with you know, the polymers on
the you know, in this case of course, you have polymer molecules in the solution. But these
expressions are again the, particle-particle interactions is what we are talking about.
(Refer Slide Time: 14:15)

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I have a this is a recent people some nice work, so, you can what they have is a, this is a movie it
shows the formation of cubic crystals. And the way this is done is they have a dispersion of cubic
particles. And to that, they add 0.8 grams per liter of PEO polyethylene oxide is a polymer of so
much molecular weight. That is the movie (15:09) definitely there were few individual particles
to begin with you know, as time goes, you see that you know more and more you know the
particles come.

And this is a you know, video microscopy image which tells you that there is a, they talk about
formation of a simple cubic crystal or if you look at, you know, like it is a cubic crystal. So, that
is movie 1 in which case a polymer has been added. Everything is exactly the same, all that is
being done is I have a container with particles. And then to that you add a polymer particles, this
is cubic particles. So, again an example where the depletion forces come into picture to form
large crystals.
(Refer Slide Time: 16:01)

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This is another experiment, where instead of I mentioned about I can induce depletion effects, by
adding up a polymer by adding a small particle or by adding a Micelle solution. So, this is an
example where to a dispersion of cubes, they have added a particle which is called a poly
NIPAM micro gel I had introduced this at some point, when I talked about DLS measurements,
dynamic light scattering measurements, had mentioned that there are particles which are which
can shrink, or which can expand, depending upon temperature.

So, that is a microgel particles, and these particles at 40 degrees centigrade, pNIPAM particles
shrink, causing a reduction in their depletion interaction. So in this case, we know that the
strength of depletion interaction depends on the, size of the polymer molecules you know, Rg,
we will be talking about. So if I am using pNIPAM as a depleted, or pNIPAM is something that
is causing depletion interaction, depending upon the size of the pNIPAM particle, pNIPAM
particle, I can tune the effective attraction between the particles.

So and then what they do is they do an experiment where they heat the sample to from they start
with 20 degrees centigrade. So they start with 40, they cooled it to 20. And again, they heated
back to 45, this is a state to where, this is the crystals are already formed. I guess the temperature
scale is not given, but you can imagine that they are heating up. So let us see what happens. So,
you should imagine that you know, the crystals were already there.

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Now, you know, you can see that now the crystals melt away, they all become, you know,
individual particles. Then you can recreate them let us come back here. So, this is basically what
is being done is I can work with a system of cube like particles, and this pNIPAM this pNIPAM.
So, I can just subject that to heating and cooling cycles, I can tune the depletion interaction
depending upon their size.

I am keeping the, number of pNIPAM particles same, because you know, I am not playing with
that I kept this concentration of pNIPAM particles, but just by making it either larger or smaller,
I am able to control the strength of depletion attraction that leads to either the formation of a
large aggregate or a crystal or I can melt the crystal away, just by tuning the dimension.
(Refer Slide Time: 19:23)

So I have just found a problem based on this it is a tutorial problem to an aqueous suspension
consisting of these are actually core-shell cubic particles, what they do is they form a particle
which is made of hematite, and then they coat it with a layer of silica and then, if you put these
particles in HCL solution, what happened is you can remove the inner core. You get a core-shell
particle, this is hollow that silica, so it is a core-shell cubic particle the length of the cube is given
the shell thickness is also given.

And pNIPAM micro gel particles of 65 nanometer are added to induce depletion attraction given
a schematic diagram. So that is you know the cubic particle you can think about a depletion
layer, the size of this depletion layer is going to be Rg / 2. And this is when you know then when

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they are sufficiently close there is going to be a depletion volume. Now, so that is a schematic
the depletion volume is delta V.
(Refer Slide Time: 21:04)

Now, the geometrical arguments can be used to show that the depletion volume delta V for the, 2
cubes in contact can be given by this make some approximations and calculate the strength of
depletion attraction as a function of separation distance in units of kBT. So, the following data
has been given the typical depleted number density is this that is 6.9 10 power 20 particles per
meter cube that’s the.

And temperature of the suspension is also given to you on that is so you are supposed to
calculate what is the strength of depletion attraction given these 2 conditions? The other question
that has been that you can ask is on increase of the water temperature to 40 degrees centigrade,
the pNIPAM micro gel particles shrink. So then what will happen is your Rg is going to change.
Then you are supposed to think about what would happen to the strength of depletion attraction,
so that is what will be asked to you.

So think of, I will just post this problem. Take a look at it. Read up a little bit. We can discuss the
solution in the next class. Which is essentially based on the work that is there in this paper so,
thanks.

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 Colloids and Surfaces
Prof. Basavaraj Madival Gurappa
Department of Chemical Engineering
Indian Institute of Technology Madras

Lecture - 26
Tutorial Problem on Depletion Interactions

(Refer Slide Time: 00:14)

So, we were looking at this tutorial problem in the last you know lecture. So, this basically
concerns a system where you have particles which are cuboids and the dimensions of the
particles are given and it is mentioned that these are core-shell particles the core is made up of
you know core is hollow and the shell is a silica cell. And what has been done is they have added
pNIPAM particles of 65 nanometer radius. And you have been there added to induce depletion
attraction.
(Refer Slide Time: 01:10)

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And you have been asked to calculate a few things. That is a make a approximation, you know,
some approximations and calculate the strength of depletion attraction as a function of separation
distance in units of kBT and what has been given to you is also that the concentration of the
depletants or the pNIPAM particles are 6.9 10 power 20 and the temperature is given to be 298
Kelvin. The second bit of question is on increase of the temperature of the dispersion from 298
Kelvin to 40 degree centigrade.

The pNIPAM micro-gel particles are known to shrink that means, if they are bigger in size, they
will become smaller, and what would happen to the standard depletion interaction that is what is
being given to you.
(Refer Slide Time: 02:01)

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And what was also mentioned was the, the depletion volume was given something like this. So
what we looked at is a case where if you look at what we are derived in the class, we had, you
know, 2 plates. We had 2 plates. And, and we talked about what is the depletion volume, that is
the region between the place the depletion volume. Now, if you look at this case, because of this
roundedness, because these are cuboids.

You have a roundedness at these ends, edges, and because of which, in the depletion volume is
going to be different. In this case, the depletion volume was something like the area of the plates
multiplied by the separation distance. If sigma, is the, the size of the polymer that you are putting
- h, which was the depression volume. Where h is the center of, which where h is the separation
distance.

So now what we are going to do in this particular problem is we are going to assume that these
are perfect cubes. Because we do not have we do not know what is delta. That delta is the
roundedness we do not have a way of calculating this. So we do not know this. Therefore, what
we will do is we will assume that the face of the cubes are flat, in which case I can actually go
ahead and use the expression that we developed for the depletion interaction between 2 flat
surfaces.

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So, we had mentioned that in W of h, it depends on this is the osmotic pressure and that is a so,
this is per unit area. If you remember, the way we did the calculation, this W of h is the
interaction energy as a function of separation distance per unit area. So, therefore, I have the
osmotic pressure I can calculate that because nb is given to me the number concentration of
depleted in the system is given and that is a thermal energy. Sigma - h which is going to be the
separation distance. And of course, that is when h is less than sigma and for h greater than or
equal to sigma your, the depletion interaction is going to be 0.
(Refer Slide Time: 04:38)

So there is a simple questions what I have done is I have taken of course, I should go on and then
do it for 65 nanometers, that is the 2 times 69 nanometers, that is a distance or separation can be
anywhere from 0 to 2 times the size of pNIPAM. When we say 2 times size 2 times the radius of
pNIPAM particle. That is the range over which the interactions should be operated. So, therefore,
I know what is h and I can calculate sigma - h that simply is 2 times the radius of the pNIPAM
particles minus h that is a separation distance.

And that multiplied by A is going to give me what is the depletion volume. And the osmotic
pressure force is given by P = nKT, n has been given. n is given as 6.9. 6.9 into 10 Power 20
number per meter cube has been given and kBT is a thermal energy that is 298 times Kt which is
1.38 into 10 power - 23. So, I can calculate this of course, it has to be minus P V overlap because
it is a attractive interaction. Now that I know W of h, I can scale everything with kBT and you
know, you get numbers which, which are like this.

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So, this calculation actually what I have done is I have taken sigma to be 2.5 6.5 itself, that is the
calculation I have done are taken sigma itself to be 6.5. So, I have taken some values of h going
from 0.65 all the way up to 6.5 and this is the value of sigma - h you get that is overlap volume.
So, therefore, you can see that the depletion interaction you know varies from about 0 kBT or 0 kt
when the separation distance is 6.5 that is sigma = 6.5 and when the separation distance becomes
h is 6.5 when the separation distance becomes 0.65.

The thermal energy when you this becomes 7.22. So, this interaction energy is several times kBT.
Therefore, if they were to reach such a separation distance in order the particles will be attracted
to each other and the energy corresponding to that attraction is given by 7.2 kBT and this is much
larger than the thermal energy therefore, we can say that, you know once they stuck, the
Brownian motion would be the energy due to Brownian motion would be not sufficient to pull
them apart.
(Refer Slide Time: 08:10)

Now, I have done a similar calculation. So, I am going to assume that so, again the size
information is not given 40 degrees centigrade, we know that they shrink. They become 298
Kelvin, or 25 degrees centigrade. So, the size is, you know, say 65 nanometer. So we know that
it is going to shrink, I do not know what is the data for the size at 40 degree centigrade. So, I am
going to assume that it is in a 40 nanometer.

350
If I assume that, I can do again a similar calculation. Again, what I have done is I have taken
sigma to be 4 and I am showing the calculation here. So, therefore, a similarly what you can you
know, what you can see is that the interaction energy. It varies from at least or the distance that I
have taken, it varies from 0.98 to about 4.4 kBT.
(Refer Slide Time: 09:06)

If I plot both the data, one for the 40 degrees centigrade and other one for 298 Kelvin, this is
what is expected. So, I would expect that the, because of the fact that the size of the pNIPAM
particles are larger or 298 Kelvin, you would expect that you know the range over which you
know that these interactions are going to be effective is much larger. So, both the range plus the
magnitude of the depletion interaction at 25 degrees centigrade are higher compared to both the,
the range and the magnitude at 40 degrees centigrade.

Where the particle essentially shrink that is what these calculation would show you. So that is a
simple problem in which you can think about. One good thing to note is that, you know the
number that you are getting. So they seem reasonable. You know, typically when people talk
about attractive strength, they talk about, you know, some numbers which are, you know, 10s of
kBT or, you know, several 10s of kBT. If you get some values, which are like, you know,
thousand kBT or something, you know, they are not, they are unreasonable.

So, typically, when you do this calculation, you should look at, you know, what is the, the
attractive strength as a function of you know you should always kill it with kBT or kt, and you

351
just look at the numbers that will give you an idea as to whether these interactions are kind of
more dominant over by the walls and are they compatible. So, you know, an idea like that would
help you guys to understand, you know, the, the system that you are dealing with better. That is
about the depletion interactions. And that brings to the end of colloidal polymer mixtures.

352
 Colloids and Surfaces
Prof. Basavaraj Madival Gurappa
Department of Chemical Engineering
Indian Institute of Technology Madras

Lecture - 27
Colloidal Interactions: Introduction to Electrostatic Interactions/Electrical Double Layer
Interactions

(Refer Slide Time: 00:14)

So the next module is module 4, in which we are going to look at, again, colloidal interactions.
But looking at what is called as, electrostatic interactions, they are also called as electrical double
layer interactions that is what we are going to do it for the next few lectures.
(Refer Slide Time: 00:44)

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That is going to be the contents? We will start with one by one. Today we will most likely look
at the importance of electrostatic effects and origin of charges at the surface of particles. And if
you have some time we will also try and look at models for electrical double layer. So, coming to
the importance of electrostatic effects. Any thoughts? Why is there a need to look at electrical
double layer interactions or electrostatic effects in dispersions some thoughts? So, due to some
surface charges there can be attraction or repulsion.
(Refer Slide Time: 01:38)

So, it turns out that these interactions are very important. Because one of the example could be
the stability of a variety of colloids. Be it food colloids you look at you know, colloids which are
found in know pharmaceutical dispersion paint as well as waste water may have a lot of
contaminants which will have the colloidal dimension length scale and the stability of all such
things are affected by the surface charge on the particles.

So, this is an example of a stable system, unstable system. So, if you want to think about you
know, having a stable colloidal system, one of the ways of achieving that would be by
incorporating charge on the particle surface. So, that is 1 example.
(Refer Slide Time: 02:38)

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So, the electrostatic forces also plays an important role in the conformation and structure of
macromolecules. So, if you look at several charge systems, that is polyelectrolytes, which are
charged polymers or you could have polymers with you know, ions adsorbed onto the surface, or
you could have proteins, which are charged and the kind of confirmation that they take in
solution that means whether they would be in a extended configuration or they would coil up.

So that is determined by the surface charge that the these molecules may have, so there is
therefore there is a lot of interest to look at you know, electrostatic effects in charge polymers
and uncharged proteins with an intention of understanding what is the structure of these you
know, macromolecules or structure of these entities when you put them in solution, that is one
another reason to look at charge effects in the systems.
(Refer Slide Time: 03:54)

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Third is if you look at people use a lot of virus particles as molecules systems. In the initial class,
we talked about ft virus you know TMV particles like this. Now, so these in these virus
essentially is made up of made by the self assembly of a large number of molecules. And so,
basically the neighboring molecules, from which the virus are, you know, made off, they are
actually held together by electrostatic interactions.

So, that means the electrostatic interaction between the, molecules of adjacent layers, you know,
in a virus are held together, because of the electrostatic interactions between, you know, the
between the molecules that make up these virus particles.
(Refer Slide Time: 04:53)

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The other examples could be that if you look at measuring rheology are the flow behavior of you
know solutions or flow behavior of multicomponent mixtures if it has like say polymers or
charged colloids it has been found that in the transport properties such as viscosity is indeed
affected by whether you have a dispersion with charged particles or uncharged particles people
talk about what is called as a electro viscous effect.

In which we can know one studies what is the contribution of the charges or the particles to the
viscosity of the dispersions and finally, people also use particles dispersed the charged particles
dispersed in a medium and you can actually manipulate the spatial organization of particles. So,
if I have next a container and say that they have charged particles. Now, when you are trying to
use such a system for display applications.

What you should be able to do or you should have a control about the way the particles
organized in the solution that will lead to a definite display that one wants. And one of the way to
do that would be that I take this dispersion and apply an electric field, thereby I can modulate the
spatial organization of particles in the solution. So, therefore, in electrophoretic display panels,
one uses charged particles and I can control their organization by applying in the field.

Therefore, there is also a lot of interest to understand such phenomena how do charge particles
behave in electric field, what leads to you know, the changes in the display behavior. So,
problems like that. So, that is to tell you that you know, there are various fields. Or there are
various reasons why one could be looking at charge effects. If you come to the origin of charges,
we have discussed this in the initial stages.
(Refer Slide Time: 07:21)

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People typically talk about 4 different mechanisms by which the particles can acquire charge,
preferential adsorption of ions, adsorption of ionic surfactants, both you look cationic anionic
and adsorption of charged polymers, the 4th mechanism is dissociation of surface charges we
have talked about these things, you know, so, if I say that I have a particle which has know
COOH group, if I put them in water what will happen is you have COO - CO - + 2 H plus.

So, that is a dissociation of the surface charges leading to the charges in the particle surface
similarly, we looked at you know adsorption of you know maybe H plus ions or adoption of H
minus ions, you know can make either a particle positively charged or negatively charged.
Similarly, I could have a case where I have a particle and then if I add a charged surfactant, it
could go on sit onto the particle surface.

And I could either acquire a positive or negative charge depending upon whether you are
working with the cationic surfactant or in anionic surfactant. Similarly, the charged polymer can
also go on sit on the particle surface and then make the surface either positively or negatively
charged. We have discussed this already earlier. So I just I am just trying to quickly.
(Refer Slide Time: 08:57)

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Now, when you have charged particles in the medium, so what is depicted here is particle which
is negatively charged and particle that is positively charged. And you can think about this could
be a dispersion medium. Or a solvent or a continuous medium, so do you think this is a correct
picture? So if one asked you to imagine charged particles in a fluid. Do you think this is the
correct picture? Maybe somebody says maybe yes, somebody says yes, I would say no.
(Refer Slide Time: 09:46)

The correct picture is this, it should imagine that you have charges in the particle surface, plus,
you also have so this the system as a whole has to be electrically neutral. So, if you take solution
the total number of positive ions or positive charges should be equal to the total number of
negative ions in the solution. So, if you take a charge stabilize dispersion, if I count the total
number of positive charges should be equal to the total number of negative charges.

359
(Refer Slide Time: 10:30)

So, people talk about 2 terms, which you should remember something was a co -ions and a
counter-ions. So, co-ions are the ions, which have the same polarity as the charges on the particle
surface. So, if I have in this case, I have a particle which is negatively charged? If I put in like
say NaCl into the system, I am going to have Na plus and Cl minus, there is the Cl minus has a
same polarity as the charges on the particle surface.

Therefore, in this example, co-ions is going to be Cl minus in this case, the co-ions is going to be
Cl minus and counter ions are the charges which have which are opposite to the polarity on the
part of the surface in this case, Na plus which comes from the NaCl that I have added plus also
the other ions that come because of the dissociation both of them are counter ions in this case.
So, therefore, whenever you talk about charged particles in a medium, you should know there
will be co-ions and the counter-ions.

Which respectively are the charges which have the same polarity as the particles as a charge of
the particle surface and the opposite polarity as what is there on the particle surface.
(Refer Slide Time: 12:17)

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If you look at that ratio, it turns out that as I said, this is a charged table display charge dispersion
and some medium. If you look at all the body of work that has gone in colloid literature on
charged particles in a fluid, it turns out that in most cases electrostatic interactions have been
studied in aqueous system or aqueous medium and you will see very little work on of course,
there is a body of work but you will not see much literature all studying electrostatics in organic
medium.

Although it is possible to design particles that have charges when you put them in organic
solvents, if you look at the bulk of the work has been done using aqueous medium as a
continuous phase you know as compared to organic medium. That is the point that I wanted to
make.
(Refer Slide Time: 13:27)

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Briefly, I want to mention electrical double layer, what is electrical double layer? This is going to
be important because we are going to talk about this enough for several lectures you know, in the
next few weeks or so. So, whenever you have charges on a particle surface, that is what is
depicted here this is charges on the particle surface. The surface charge on the particle surface
causes an electric field.

So, whenever you have a point charge, we know that you know, if I look at you know, think
about at any particular location E or any particular location, I can calculate what is the electric
field. So, it is given by a simple. So, if F is q 1 q 2 divided by 4 pi epsilon 0 epsilon r, if that is
the coulomb’s law r square. So F = q 1 q 2 divided by 4 pi epsilon 0 epsilon r square. If that is
the force between the 2 charges, now if I ask a question is to at a distance R from q 1, what is the
electric field is actually given by F / q.

If it is, let us say that I take a simple case when I have 2 equal charges. And if I want to ask a
question as to at any location the distance R from this charge the electric field is given by E is F /
q and this electric field that is generated because of the charges on the particle surface, what it
will do is it will attract the counter-ions. Therefore, if you look at this picture, so, there is a layer
of charges on the particle surface in the immediate vicinity there is a layer of counter-ions.

And these counter-ions are attracted to the charges on the particle surface, because of the electric
field that is created because of the charges on the particle surface. So, therefore, there is a layer

362
of ions on the particle surface and there is a layer of ions in the immediate vicinity of the charge
surface. So, these 2 layers of charges put together, they what are called as, electrical double
layer, the layer of surface charge and the counter-ions in the solution. That is what is called as a
electrical double layer.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology – Madras

Lecture – 28
Introduction to Models of Electrical Double Layer: Helmholtz Model / Capacitor Model

(Refer Slide Time: 00:14)

So we are going to look at models of electrical double layer. So I am going to start with a
simplest model, it is what is called as Helmholtz model. This is one of the first models that
was put forward and so, in this case what is you know thought of is the counter ions, they are
directly bound to the surface of the so, if what you are looking at is a picture where you have
a solid surface.

It could be you can think about it as a part of a spherical particle. So I could, you know, look
at a spherical particle, I am only looking at a small portion that is a solid surface that is a
particle of interest it could be. And these are the charges on the particle surface, but these are
the counter ions. So, in this Helmholtz model, what is assumed is that the counter ions are
directly bound.

They are directly bound or attached, you know, to the particles surface and they neutralize the
charges on the surface, they neutralize the charges on the surface giving an arrangement
which looks more like a capacitor. So capacitor we know you have you can think about 2
plates which are you know oppositely charged. So that is a capacitor like arrangement so, in
this particular double layer model.

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It is assumed that the counter ions directly bound to the surface, and then they neutralize the
surface charge and give you some kind of arrangement which look like a capacitor, this point,
we will come back to it later. So, what is mentioned here is the electric field generated by the
surface charges in such a system is limited to the thickness of a molecular layer that I will
come to this particular point a little later.
(Refer Slide Time: 02:38)

So, what is shown here is a 2 arrangement like a capacitor like arrangement so have a charged
plate. So, this could be the charge you know the plate that is because of the counter ions in
the solution and that is the charges you can think about this as the charges that arise because
of the particle surface. And in case a, you have vacuum between the 2 particles, in case b you
have some medium, which will be the case if you look at, you know, colloidal particles in
solution, you will always have some medium between the 2 layers.

And in so, what we are going to do is we are going to use a concept called line of forces,
which you will you would have seen in electrostatics. So you say that, you know, if I have a
charge plate, say that, you know, some, you know, there is a positive or negative charge on
the surface. You talk about you know, the lines of force that start from a negative charge and
they go to the positive charge and you know, they can continue so, we are going to use a
concept like that.

So, the lines of force that start from one charge surface, they start from one charge surface
and they terminate at the other charge surface. And if you assume that the particles I mean the

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surfaces have a area A suppose that the plates are of area A and the total charges that each of
these plates carry is q, then we can define a quantity called the surface charge density which
essentially is the charge per unit area I can define that, this is the, surface charge density
sigma star, which is the total charge divided by the area of the plates.
(Refer Slide Time: 04:43)

Now, what you can do is that, so, since a line of force, is associated with each unit charge, for
every charge that you have there is going to be a line of force. So, because you have a charge
density q / A I can say that there are q / A lines of forces that cross from one you know the
charge plate to the other charge plate. And therefore, you can say that this E0 that is the
electric field that is arising because of you know q / A lines of forces is (q /A) / 1 over
epsilon.

So, that is in a way this tells you what is the force see, this is q /A is the number of lines of
forces and the electric field generated is proportional to the number of lines of forces and of
course, you know you have you know to take care of the effect of the medium between the 2
plates in one case the medium between the 2 plates is a vacuum therefore, you have 1 over
epsilon 0 in the second case, when you have a medium dielectric medium present, you know
this factor you want to replace that with 1 over epsilon 0 into epsilon r.

So, in essence this epsilon r and epsilon 0 tell you something about what is the electric field
that is generated because of the 2 arrangements which are shown here. So, if you look at this
expression this very similar to what we what I was mentioning about so, we had mentioned
that so, in a way, we will come back to that point.

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(Refer Slide Time: 06:58)

Now, so, now I would have to relate this is the electric field. You will see that in Colloids
literature when people work with charged particles. You will always see that say turns out
that you know for getting working equations for like say the interaction potential for example
phi you know electrical double layer interaction you will see that you know the such the
expressions that deal you know that concern electrical double layer interactions.

They are always represented you know in terms of the surface potential you know, you do not
see the charges directly in the expression, but you will see that you know, all the equations
have the psi which is what is called as electric potential. And that electric potential is related
to the electric field that is that is generated because of the charges and which in turn is related
to the charges that are associated with the particles.

And this electric field E is given as negative gradient of the electric potential. Therefore, what
I can do is if I assume that the drop in the potential is very, very small I can replace d psi /
delta psi and this dx is the distance over which the potential is you know the distance over
which the potential is changing and this delta there is a distance between the capacitor plates.
And that will be equal to sigma star / epsilon 0 into epsilon r.

That is for the case where you have a medium of you know epsilon is a dielectric constant of
the medium between the 2 plates. Now, to show that so now I will come back to this point we
had mentioned that the electric field generated by the surface charges is accordingly limited
to the thickness of a molecular layer.

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(Refer Slide Time: 09:35)

I just to make the point, what I am going to do is to calculate few, so this is in essence, what
is the capacitor model? So, if you have, you know, you could have a positively charged plate
for example, and negatively this is the charges on the particle surface and this could be the
charges in the counter ions, that is that these are the ions which are tightly bound to the
charges surface and that is the distance delta and this psi B - psi alpha is the potential drop
and you can do some simple calculation.
(Refer Slide Time: 10:17)

I have taken a case where you have a so let us think about a simple case where I have a
charge surface and imagine that you know this is a charge surface which is because of a
surfactant molecules which are attached to the particle surface. Now, if the charged
monolayer so I am talking about monolayer because I have a single layer of surfactant

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attached to the particle surface if the charge monolayer has an area which is 10 nanometers
square, a charged monolayer of area 10 nanometers square is what I am considering.

Now, if you for a monovalent ion, this corresponds to charge density. So, what you can do is
say that you know, I have a 10 nanometer square area and I have 1 ion per 10 nanometer
square if I have 1 ion, the charges on the ion is going to be 1.6 into 10 power - 19 coulombs
per ion therefore, I can get a charge density. So, you should imagine that you know I have a
monolayer surfactant.

And if I say that there is 1 ion for every 10 nanometer square area, for every 10 nanometer
square, there is 1 ion present then the charge density is going to be 1 ion per 10 nanometer
square therefore, this number becomes 1.6 into 10 power - 19 coulomb divided by you know
per ion that is a charge per ion therefore, you get a sigma star which is 1.6 into 10 power - 2
coulomb meter square coulomb per meter square.

And you calculate epsilon electric field that is sigma star we go back here sigma star I
plugged in sigma star here 1.6 into 10 power - 2 coulomb meter square and epsilon 0 that is
epsilon 0 and that is epsilon r therefore your epsilon you know E epsilon becomes 2.26 into
10 power 7 volts per meter and typically when people talk about you know, charged surfaces,
typical potential drop you know are of the order of 0.1 volts or 100 millivolts, that is a typical
potential drop people talk about.

If I substitute for a delta del epsilon or the change in the drop in the potential I can get delta
and the delta comes out to be 4.4 nanometer. So, therefore, you can say that you know,
because we are assuming that the counter ions are directly bound to the particle surface and
typical the thickness of the double layer one can think about is of the order of 4.4 nanometers
in this particular example.

Therefore, in the capacitor model we should assume that the electrostatic interactions. So, in
a way this tells you something about the range of distance over which the electrostatic
interactions are operative. Can I make the statement this is what we are saying is that if you
look at this particular picture, that’s a charged that is the charge surface. And we are saying
that you know the surface charges are bound to the counter ions are bound to the particles
surface they are strongly bound in essentially neutralizing the entire surface.

369
And because of the fact that they are strongly bound, you know, we can imagine that the, the
electric field that is generated by the surface charges, is would be of the order of molecular
layer thick. That is what we kind of proved by looking at some typical numbers of the delta
that we get for a particular case. So maybe just go back and take a look at this again, maybe
we will discuss this example again in the next class.
(Refer Slide Time: 15:24)

So, the first simple picture that we looked at is Helmholtz model but the more realistic picture
is that the such a strong binding that is, you know, kind of assumed in the electrical in the
Helmholtz model is actually not completely true. That is because the counter ions there that
are there in solution, they are also free to move around. They know they also have you know,
thermal energy KT and because of the thermal energy they can also, you know, go away from
the surface.

And then, you know, you get a kind of a distribution, which is not exactly, you know, like a
capacitor arrangement. Of course, there is going to be a larger concentration of counter ions
close to the surface, but the arrangement is not exactly like a capacitor kind of a concept. We
will try and talk about it in the next class.

370
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 29
Review and Summary of Helmholtz Model (or capacitor model) of Electrical Double Layer

(Refer Slide Time: 00:14)

So, in the last class we started off with module 4, which is colloidal interactions, in terms of
looking at what are called as electrostatic interactions or also called as electrical double layer
interactions. So, we had briefly talked about what is the importance? Why are we trying to look at
this particular module? And also about what are the different ways by which the particle surface
gets charges? I had also mentioned what is an electrical double layer concept as well I just want to
quickly recap that.
(Refer Slide Time: 00:53)

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So, what you are looking at is a colloidal particle which has negative charges, which is
represented by minus here. And the moment you have and of course, you are going to have these
are the counter ions in solution. And whenever you have a charged species is going to generate
this charged species is going to generate electric field and because of the electric field that is
generated.

Because of the charges on the particle surface is going to attract oppositely charged ions or the
counter ions are going to be attracted to the surface because of the electric field. Therefore, you
are going to have a layer of charges on the particle surface and of course, you are also going to
have the charges in solution which are kind of attracted to the surface because of the electric field
generated.

Because of the charge on the surface and this particular arrangement where you have 2 layers of
ions, which are opposite in polarity that is what is called as a electrical double layer what is really
important when we are trying to look at electrical double layer interactions is that we are
interested to ask a question such as what is the spatial distribution of co-ions and counter-ions in
solution?

This is the question that we were trying to ask, and it turns out that answering this question is
really important, if you want to understand the electrostatic interactions or the electrical double
layer interactions. So, therefore, we are going to look at some models in which people have
proposed different models, which kind of depict what is the distribution of counter ions and co
ions in solution?

So, in that context there are, you know, some old models which are not valid anymore, I mean,
but, you know, this kind of this capacitor model which I am going to discuss, they started off you
know, the field of in a electrical double layer models. And then the more recent ones talk about
what are called as a Debye-Huckel, you know model for electrical double layers or Gouy-
Chapman model for electrical double layer. So, these are more of recent developments. So, we
will try and look up each of them and then discuss a little bit about what these models say.
(Refer Slide Time: 03:51)

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In that context the first model that we looked at was, so, there was a Helmholtz model for
electrical double layer, in which it is assumed that the counter ions, these are the ions which have
the charges that are opposite in polarity to the charges on the particle surface, in this case, the
particle surface is negatively charged and these are the counter ions which are positively charged,
the counter ions directly bind to the surface, they are kind of attached, you know, to the charge
surface, and they kind of try and neutralize the surface charges.

We know very much like a capacitor. When I say neutralize, you can see the, for every, you
know, there is an ion pair. For every charge on the solid surface, there is a charge in the solution
which is kind of attracted to the surface and they are tightly bound and the charges in the solution,
they essentially neutralize the charges on the particle surface that is one of the simplest model of
electrical double layer.

And so to understand so, what we are trying to do is we are trying to develop an expression for a
kind of a quantity which is if I have to so, this basically arrangement tells you something like
capacitor. So, I have a, some charged some plate which is negatively charged, I have another plate
which is positively charged. So, we would like to relate, what is the potential drop?

If I say that the potential drop is delta psi, del psi, and if the distance between the 2 plates if they
are at a distance x 1 and x 2, your delta is going to be x 1 - x 2 or x 2 - x 1, that is the separation
of these plates, we want to relate delta psi / delta 2 parameters such as the surface charge density
and the dielectric constant of the medium between the 2 plates, that is what we would like to go
about.

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(Refer Slide Time: 06:17)

So in doing that, we would like to exploit a concept called a concept of line of force. You would
have seen in electrostatics pictures like this, if I have a plus q charge or a minus q charge, we
would have seen some lines like this. And if you remember, what are they? They are the electric
field lines by convention, if it is a negative charge, then you know the field lines are going to be
inward.

And if it is a positive charge, the field lines are going to be outward. So, this electric field it is
actually you can calculate it as this electric field that is generated because of a point charge it
essentially is given by force divided by the charge and the force is 1 / 4 pi epsilon 0 into epsilon r
into r square into q that is F / q. Now, what I can do is, I can express this as q / epsilon 0 epsilon r
and I have 1 / 4 pi r square.

Now, instead of assuming a point charge, if I assume that the charges are located on the surface of
a sphere, this 1 / 4 pi r squared gives me the area therefore, I can write this as q / A into 1 / epsilon
0 epsilon r. Therefore, this q / A is essentially the surface charge density that is a number of
charges divided by area that is going to be sigma star / epsilon 0 epsilon r. And we know that.

So, whenever we talk about this, so the understanding is if I have a test negative charge, and if I
bring in a, you know, test positive charge and if I bring in a test negative or a positive charge near
it, near to it, it is going to each of the charges are going to experience some force and you can
imagine that this force acts along some line. And this is an imaginary line and that is what is
called as a line of force.

374
Depending upon you know; the number of charges that you have, you know; there going to be so
many number of lines of charges, in a way. So, you can think about line of force as a imaginary
line, over which, you know, the a test charge, which is going to be brought into the vicinity of
either positive or negative charge, the force that the test charge is going to experience. So and
depending upon the polarity of the charge, this force can be either attractive or repulsive. So we
are going to use concept like this.
(Refer Slide Time: 09:14)

“Professor - student conversation starts”

So now, sir, yeah, is the same as field lines? Same as field line is this see, I mean, so see when I
wrote this field line. So I mentioned that, so I can also imagine, instead of calling this as a lines
that come up because of the field, I can also say that, you know, you can imagine that there is a
there if I have 2 charges; there is going to be some force of attraction or repulsion now, and the
force of attraction or repulsion is going to act along some line.

If I take a point charge is going to be acting along some line and this line is what are we are
talking about. The lines of forces for some charge; and midline is for the unit charge, I mean. So
if you see, when you talk about expressing the only difference would be that if you talk about
forces, I would have to worry about, you know, resolving them if they are not acting in a
particular line and stuff like that so you can.
“Professor - student conversation ends”
So now what you are looking at is 2 arrangements. One is, so you can imagine the minus to be the
charges on the solid surface that is the charges on the solid surface. And these are the counter

375
ions; that is a capacitor like arrangement. And in this case, they are in vacuum in this case there is
a medium of some dielectric constant epsilon between the 2 plates. So we are going to we all
these lines that you are seeing these are the lines of forces.

And depending upon the charge on the each plate then lines of forces are going to be different that
means the spacing between these lines depends on the charge total charge. If I have very high q,
you are going to have many more lines closely spaced and however if you know the, if the q is not
very high, you are going to have sparsely populated lines. Now, so, what is so and by convention
as we said that the lines of force they start from positive and they go towards negative that is the
convention that is followed.

Now, if the plate carries a charge q. And if the area of the plate is A then I can define the surface
charge density which is q / A. Now, the lines of forces that you see there, they start from one
charge surface and they terminate at the opposite in the place which has the opposite charge.
(Refer Slide Time: 12:11)

Now, we kind of derived this you know a while ago, so this electric field that is generated in the
case where you have vacuum, I can write that as the surface charge density multiplied by 1 /
epsilon and because q / A is defined as sigma star, therefore, E0 essentially becomes sigma star /
epsilon and similarly, if I replace the vacuum with a medium with a permittivity epsilon and I am
going to write E epsilon as sigma star / epsilon 0 epsilon r.

And the understanding is that the number of lines of forces is a measure of the field strength. So,
the more the number of lines of forces more is a field and of course, it is dictated by the whether

376
the region between the 2 plates has vacuum or some medium with the dielectric constant epsilon
r.
(Refer Slide Time: 13:18)

So, now, this electric field and the potential they are related this way electric field is a negative
gradient of the potential we are going to use potential in the calculation that involves electrical
double layer because of the fact that you know we know that the force depends on the charge if I
know the force I can get electric field if I know electric field I can get psi therefore, if I have a
way of finding out what is the surface potential?

Then I will have a way of telling something about what is this charge q on the particle surface so,
there but the reason why everything that we are going to do will have psi because doing math is
much, much easier if you work with science. So, now, so, this del psi / del x if I assume a small
drop in the potential I can replace this d psi / delta psi and dx / delta and that is equal to sigma star
/ epsilon 0 epsilon r where delta psi is the potential drop between the 2 plates which are separated
by a distance delta and this particular expression.

It actually relates the charge density which is sigma star and the potential difference that is delta
psi, and the distance of separation between the 2 places which is delta.
(Refer Slide Time: 15:02)

377
Now so, in the electrical double this essentially is the electric you know Helmholtz model for
electrical double layer what you are seeing is a depiction where this alpha and beta they
essentially refers to 2 phases in this case. So, we have we had a charged surface and they are
going to be counter ions now, when I say 2 phases in this case one is a solid phase other one is a
liquid phase.

Now, and this kind of arrangement that we are seeing it is actually seen at the interface at the
interface of the as I go from one phase to another phase at the interface is what you are going to
have arrangement like this. So, this is alpha psi beta and psi alpha refer to the potential at the 2
phases alpha and beta and they are separated by distance x1 and x2 and what this particular model
predicts is that the variation of potential in the gap between the 2 plates the variation is linear.

So, the variation of the electric potential across the double layer according to the capacitor model
is a linear variation of the charge. So, if I know what is the potential here? If I know what is the
potential drop? That is delta psi is equal to say if I say point 1 you know millivolt or something
like that, I should be able to calculate what is the how the potential varies across the entire gap.
So, that is the, what is called as an electrical double layer model.
(Refer Slide Time: 17:08)

378
The capacitor model for electrical double layer so, we had again done this. So, if I take a case
where I have a charged monolayer, charged monolayers are found in the several you can imagine
that I have a spherical particle and say that I have charges on the surface. So, and if I look locally,
I really have a flat region because you know, if I compare the size of the ions corresponding to the
size of the particle, you know, you can imagine it is a flat line.

So, therefore, I am really going to have a charged monolayer in this case, other way to imagine
charge monolayer could be I have a container I have water in it I add charged surfactant. And
charged surfactant, are represented by something like that it could be positively charged or
negatively charged, because the surfactants have a tendency of going to the interface.

If I look at interface, the arrangement looks something like this interface will have and because
each of them will be charged under this dissociation, and we will have a monolayer of surfactant
that is charge. So, if you take a case of a charge monolayer, where the monolayer has 1 charge it
has 1 charge per 10 nanometer square area. So, I am basically looking at an arrangement either
like this or arrangement like this.

I take an area, which correspond to 10 nanometer square if there is only 1 charge on the surface,
then I can calculate sigma star the surface charge density that is 1 ion per 10 nanometers square it
becomes 1.68 power - 9 coulombs per ion that is the charge on the 1 ion divided by 10 nanometer
square. If I do that, I get sigma star to be 1.6 into 10 power - 2 coulomb per meter square. So, now
to calculate now, if I assume that this is immersed this is in water, I have a charged monolayer
and if that is in water, then I can calculate what is epsilon s?

379
We can go back to this expression. So, epsilon s is essentially sigma star / epsilon 0 epsilon r I
know what a sigma star divided by this is epsilon r this is epsilon 0. So, I get epsilon you know E
epsilon as 2.6 into 10 power 7 volt per meter inverse and typically you know if you know when
we talk about the potential drop across such charged monolayers.
(Refer Slide Time: 20:24)

So, if I look at the potential drop in case like this. So, it typical value that people talk about is
about point 1 volts if I substitute for point 1 volt I can actually get delta. So, this delta it is in a
way it tells you something about the thickness of the electrical double layer the double layer in
this case corresponds to this and this the thickness of the double layer is given by delta in a turn
so, that I can calculate that and it turns out to be something like 4.4 nanometer.

So, therefore, you can say that the electric field that is generated by the surface charges it is in
molecular dimension it because of the fact that the numbers are 4.4 nanometer, you know it is
very close to the molecular dimensions. So, that is the kind of conclusion that you can draw if you
work with what is called as a capacitor model or the Helmholtz model for electrical double layer
and if you look at several different problems and if you calculate the double layer thickness, it
will be few nanometers in dimensions.

380
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 30
Models of Electrical Double Layer: Diffuse Double Layer Model / Gouy-Chapman Model

(Refer Slide Time: 00:14)

So, what you are looking at is a Helmholtz model and the second one is a model which is
proposed by Gouy and Chapman, it is what is called as a diffuse double layer model can you
look at and tell me what is the difference between the picture on the left and the right the name
says it all diffuse. So, if you look at here the counter ions there if I look at a similar distance
here I look at similar distance.

The number of counter ions that you have, for a particular distance say in this case x and a
similar distance x, definitely the number of counter ions here are more compared to their right
that you can get and the fact that there are also counter ions here you can say that the thickness
of the double layer now it is kind of a little bit expanded. It is a little bit more. So, it turns out
that this picture is more true than what was you know what comes out of Helmholtz model.

The reason for that is that the Gouy-Chapman model what is also taken into account is the
thermal motion of the ions. So, we are saying that of course, you know, they could be bound to
the charge surface. However, these ions can still exhibit thermal motion, you know, they can be
disturbed because of the thermal motion these thermal fluctuations tend to drive the counter ions

381
away from the charge surface, this leads to the formation of what is called as a diffuse double
layer, which is extended more than a monolayer thickness.

So, that is a prime difference between Helmholtz model and the Gouy-Chapman model in
which it is assumed that because of the fact that these ions exhibit thermal motion, these thermal
fluctuations can drive the counter ions away from the particles surface away from the charge
surface and the layer of counter ions is more diffused compared to what was the case for
Helmholtz double layer model.
(Refer Slide Time: 03:08)

Now, again, similar to what we did for Helmholtz model, we are kind of interested to look at the
distribution of counter ions in solution. So, we are interested in understanding distribution of
counter ions as well as co ions in solution number 1, number 2, we also want to understand what
is the thickness of double layer? If you would like to, you know, kind of get quantitative
information of these quantities. So, for the diffuse double layer model, the starting point in
obtaining the diffuse double layer model description is the, what is called the Poisson equation.
(Refer Slide Time: 04:14)

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So we will think a little bit about deriving the Poisson equation to begin with. I am sure all of
you know this. But we will try and give some very simple arguments. To show that you know,
you can actually derive Poisson equation because this is a starting step for looking at electrical
double layer model. I thought it would be nice to do it. Again this is in the textbook that I am
following. So this is a point charge plus q minus q.

And the distance of separation is r. And the force is acting between the 2 charges is given by
this, it is, the coulombs law, 1 / 4 pi epsilon 0 q 1 q 2 or q square / epsilon r you know r into r
square that is the coulombs law. Now, if I you know somehow take this guy out if I take this out
and ask a question as to if I have a positive charge q. And I ask a question as to what is the
electric field that is generated at some you know distance r from this plus charge q. So, that
electric field is given by FC / q which is 1 / 4 pi epsilon 0, q / epsilon r, r square we know that.
(Refer Slide Time: 05:42)

383
Now, it turns out that, so, the expression that we wrote earlier there are for point charges. Now,
this expression holds good not only for point charges for however, for any distribution of
charges such that the total charge is q. So, what I mean by that is if I imagine that you know I
am going to enclose this in a sphere of radius r, I will consider some distribution of charges.

Now, if I have a distribution of charges, I can define again a charge density I can define a
charge density q that is the number of charges or the charges per unit volume multiplied by the
volume if rho star is the charge density. So, what we are doing is we are considering a sphere of
radius r which contains q units of charge which are uniformly distributed such that the charge
density is rho star therefore, this q I can relate that to the volume of the sphere and the surface
charge density.

Instead of a point charge if I replace that with a sphere with certain distribution, but as long as
the total charge is q in this case as well as this case, the same expression would hold good that is
what I am trying to you know mention.
(Refer Slide Time: 07:27)

Now that we have this that is the electric field that is generated at some distance and at some
distance r from a distribution of charges, which has a charge density rho star. So, what we can
do is I can take this expression, so, I have E here 1 / 4 pi epsilon 0. So, I have epsilon r into r
square here instead of q, I am going to replace q with this, instead of q I am writing this in terms
of the surface charge density and the volume is that just comes from the definition itself.

384
So, we had done this here I mentioned that the electric field that is generated because of the
point charge in this expression gives you the electric field that has generated because of the
point charge which has a charge plus q or the same expression would also hold good if I replace
the point charge by certain distribution of charge such that the overall charge is q that is given
by the volume multiplied by the surface charge density or the charge entity itself instead of q I
am replacing that with 4 / 3 pi r cube into rho star is it okay?
“Professor-student conversation starts”
Now, that is; yeah, go ahead. What is volume density rho? So, this is rho is what is called the
charge density. This is the, if I say that there are 100 charges, which are uniformly distributed
100 ions for example. Is it uniformly distributed? Yeah uniformly distributed there is an
assumption. And then you know the charge density is going to be 100 multiplied by 1.6 into 10
power - 19 coulombs divided by the volume otherwise the center of charge? We have to worry
about. So if the distribution is not uniform then you know, we are assuming as uniform? It is a
uniformly distributed charge.
“Professor-student conversation ends”
So, therefore, your I can cancel r square with here that leaves me r in the numerator and the rho
star here and the 4 4 gets cancelled, the pi pi gets cancelled what you have here is a 3 that comes
from here and epsilon, where epsilon is epsilon 0 into epsilon r therefore E, therefore this E
becomes r rho star given by 3 times epsilon. Now, what I can do is I can write, I can take this
expression I can multiply by r square on both sides and then I am going to differentiate that with
respect to r, d / dr.

So, therefore, this d / dr of r cube into rho star / 3 epsilon, so, therefore, this becomes 3 r square
into rho star / 3 epsilon, this this gets cancelled. So, essentially I am left with r square into rho
star / epsilon.
(Refer Slide Time: 11:31)

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So, therefore, now that I know that there exists a relationship between the electric field and the
surface potential left hand side is going to remain the same d / dr of r square into epsilon that
comes from here, and the right hand side is going to be r square rho star into epsilon, that is
what we just derived. Now, instead of epsilon E, I am going to replace that with d psi / dr. I am
going to replace that with d psi / dr.

And because I have a negative sign here, so, I am going to get minus on the right hand side or
left hand side depending on how you want to do it. So, therefore, essentially I end up with d / dr
of r square d psi / dr = - r square into rho star / epsilon I can get this r square to the other side
therefore, 1 / r square d / dr of r square d psi / dr = - rho star / epsilon that is what you so, that is
essentially so, now in this case what was assumed is that the charge it the very so you if that is a
so.

I want to go from if you look at this the same thing is written in a partial derivative form so
because you know you could have a case where you know psi need not be varying only with
respect to r, you could also have a case where the psi the surface potential can be a function of
both theta, phi as well as r. So, what we derived is the first term in the equation similarly if you
assume a variation only in theta or variation in only in psi.

And if I take a general case where psi is a function of both r, theta and phi so, you end up with
this expression, the left hand side can be written as del square psi and the right hand side is
essentially minus rho star / epsilon this is what is called a Poisson equation what this equation

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essentially tells you is that if I have a surface which is charged, how does the potential vary with
distance, in different directions? That is what this expression essentially tells you about.
(Refer Slide Time: 14:36)

So, now, with this Poisson equation as a starting step, we would like to look at potential near a
planar charge surface. So what we derived was a case where I have a spherical surface and what
is the variation of surface potential with r, theta and psi is what we looked at but if I look at it,
because the calculations are much more easier if you work with a planar charge surface.

We would like to look at derive you know start we would like to start with Poisson equation in
the case of a planar surface the Poisson equation becomes del square psi / del x square + del
square psi / del y square + del square psi / del z square = - rho star / epsilon. And so, basically
the Poisson equation essentially tells you something about the variation of potential with
distance from a charged surface it could be for any arbitrary you know surface that is what is
described by the Poisson equation and this del square is what is called Laplace operators you
know a little bit about it.
(Refer Slide Time: 15:53)

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Now, what we would like to do is we would like to solve this because if I want to find out what
is the variation? You know how does you know this, we know that you know this psi is a
function of x, y, z I would like to look at the variation of size a function of x, y and z. So, for
that we would have to solve Poisson equation. And what we are going to do is so epsilon is
epsilon r multiplied by epsilon 0 which account for the presence of the medium and rho star is
the charge density units are coulomb per meter cube.

And of course, psi is a function of x, y and z. So, the objective is to find a potential that satisfies
the Poisson equation and with the boundary condition that at x = 0, sorry at x is equal to
infinity, when x is tending to infinity, psi is going to be 0. If I have a charged surface, if I look
at the distance very, very far away from the surface, the potential is going to be 0 that is one of
the boundary condition. And the potential at the interface that is when x = 0.

The potential is going to psi 0, these are the 2 boundary conditions that we are going to use at x
= 0 the potential is psi 0 at x is equal to infinity psi 0 is 0. So, we therefore, we would like to
obtain an expression for the potential that satisfies the Laplace equation with these 2 boundary
conditions. Is that okay?
(Refer Slide Time: 17:55)

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So, now, so, how do we do that? So I want to solve this so, we are going to. So, what you
looked up here is an expression where we see that the potential varies with x as well as y as well
as z, we are going to take even simpler case, we will only talk about the 1 dimensional case in
which the potential varies only with x. So, therefore, I can write this as d square psi / dx square,
that is equal to minus rho star / epsilon.

So, what we are looking at is a if we consider a planar solid surface with homogeneously
distributed electric charges, such that density is rho star that is in contact with a liquid. And as a
result of the charges on the surface, the surface generates a potential which is what is called
which is represented as psi. And this psi would vary with distance in some particular way. We
are after calculating what this function is?

We would like to find out whether psi of x is it, you know, an exponential function. Does it vary
exponentially as a, you know as a as we move away from the surface, or does it vary linearly?
Does it have any other functional form that is what we would like to look at the objective is to
obtain an expression for the potential distribution. So for that, we are going to consider a 1
dimensional Poisson equation.

Now, in order to do this, so psi is a permittivity. So, that is going to be if I were to do an

experiment in a liquid which is maintained at a particular temperature and if the medium I know
everything about the medium your epsilon is going to be a constant, but however the sigma star.
So, in order to actually solve this, I should somehow express rho star in terms of the potential

389
itself that is when I can solve this expression to solve this expression, the charge density that is
rho star has to be expressed as a function of potential only then you know.

If I have a way of writing like rho star you know, I would like to express rho star as a function
of psi itself, then I can substitute for rho star I can go ahead with solving this. So, to do that,
what we do is we use something called a Boltzmann factor.
(Refer Slide Time: 21:25)

So, what is written here is n i is the number of ion types, i is the type of the ion that I am
considering number of ion types per unit volume. So, units of this, is going to be number per
volume near the surface. And n i infinity is the concentration of the ions at a distance very far
away from the surface, again, this is going to have units of again number per unit volume and is
that z i is the, the valency of the ions and i sorry, E is the charge of the electron psi is the
potential and kBT is the a thermal energy, so that is the Boltzmann factor.

So, what this expression essentially tells you is that so, this tells you something about given that
I have a surface potential whose potentially is psi, what is the probability of finding an ion? So,
there will be several ions in the solution, there is going to be several ions in solution. Now, so, if
you look up this so, let me just go through this. So, what this tells you is that you know, the
work required to bring an ion from infinity to a position at which the potential is psi, so, say that
I have ion say n i, at a distance very, very far away from the surface.

Now, for to move this ion from a very large distance away from the surface into a region very
close to the surface and I have do some work. Is that is does it make sense? I would have to

390
essentially do some work to move any ion from one location to the other how of work that I
have to do depends on from where to where I want to move. If I want to move more to a
distance very close to the surface, and am I have to spend more energy.

But if I am okay to move to a location, which is slightly away from the surface, I will have to
spend less energy. So, this energy this work that has to be done in moving the surface in moving
an ion is actually essentially given by zi times e times psi, this psi would be the, the potential at
any location where you want to move it, the psi is the potential at a location where you want to
move the charge.

And it will depend also on the, the valancy of the ions itself. If z i, that I have a monovalent ion
or a divalent ion, it also depends on that. So the probability of finding an ion at this position is
related to the ion concentration at infinity. This is the ion concentration at infinity through this
Boltzmann factor. Think a little bit about this. So we will again discuss the Boltzmann factor in
the next lecture. And then we will try and proceed with obtaining a solution for 1 dimensional
Poisson Boltzmann equation Poisson equation, we will try into the next class, thanks.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology – Madras

Lecture – 31
Potential Distribution Near Planar Surfaces: Derivation of the Poisson - Boltzmann
Equation

(Refer Slide Time: 00:14)

(Refer Slide Time: 00:19)

So, we will continue with the models for electrical double layers. So, what we were trying to
do in the previous lecture was looking at potential distribution near a planar surface. We took
a 1 dimensional case that means we are trying to solve 1 dimensional Poisson equation and
this is what the expression is, and we would like to solve this at the boundary conditions that
at x = 0 potential at the surface itself.

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And x is equal to infinity, the potential is going to be 0. The potential would be 0 to infinity
because either the concentration of ions at infinity is 0 or it is such that the concentration of
positive ions and negative ions is equal such that the overall potential gets canceled. That is
the reason why at x is equal to infinity, psi going to be 0. And we said that if you really want
to solve this, I would somehow want to express rho star in terms of psi.

So, the way to do this would be, we know that the rho star which is the charge density, the
charge density would be related to again the concentration of ions that you have the solution.
And we had said that this n i is related to n i infinity that is the concentration of i th type of
ions in solution. It depends on what is the concentration of the same species at infinity
multiplied by a factor, which is exponent of – z i e times psi divided by kBT. That is what we
mentioned. And if I know n i star, I can get rho star because you know, n i is related to psi
therefore, I am able to express rho star in terms of psi that is what we are trying to do.
(Refer Slide Time: 02:39)

So, in this Boltzmann factor, this quantity z i e psi tells you something about what is the work
that has to be done to bring any specific ion. In this case, we are considering n i to bring it
from infinity to a position where the potential is psi.
(Refer Slide Time: 03:45)

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And that work that has to be done is given by z i times e times psi. rho star is also a function
of x. So, when I said this psi is actually also a function of x. We defined rho star. Let us go
back. The way the rho star was defined here. We defined it as a charge density. So, basically
it depends on the distribution of ions in the solution.
(Refer Slide Time: 04:12)

If you look at a charge surface, we know that the concentration of counter ions in solution, if
you look at the concentration, let us go back to this model, If we look at this model, let us
take you know, finite volume here and finite volume somewhere there and find out what the
distance, very far away distance. Now, if you look at, you know, the fact that you know, the,
the concentration of counter ions is going to be higher here.

And, if you go to account for the polarity, everything. There will be some, you know, rho star
that you can calculate, which basically is the number of ions that you have per unit volume

394
that I am taking. If I take a finite volume. However, if I go to a very far, if I look at, you
know, I mean let us say, I am taking a similar volume here. The fact that you know, I have,
you know, both positive and negative and if there an equal number your rho star is going to
be 0.

Because you know, there is a contribution that comes from the positive ion and there is also a
contribution that comes from negative ion, so if you can say that overall charge density, even
though it is number. I mean, this is the total charge per unit volume. The total this is not the
number. It is not the number density it is the charge density that means if I have ion whose
valence is i multiplied by e, multiplied by the total is a number as well.

The total charge divided by the unit volume. So, if I go to a very far away distance, the fact
that you know you will have a equal probability of finding both positive and negative ions, so
I am going to have charge density which could be – z i times e divided by volume times the
number. For example and + z i times e multiply by number by volume. Therefore, that
becomes essentially 0. So, this is actually rho star is actually spatially varying when you think
about, the total charge in the whole system is going to be electrically neutral.
(Refer Slide Time: 06:13)

So, we were talking about the Boltzmann factor. So, this essentially tells you what is the
work that is required to bring an ion of a specific type from infinity to. So, now, if you look at
this expression. So, the work that one has to do depends on what is a local psi? That means,
we know that you know psi varies in a particular way, if I look at some position here and
some position here or some position very very far away for example.

395
So, that means I would have to spend less work to bring an ion to this location, but however,
if I want to go closer to this, you know, to the charge surface, because of the fact that psi is
going to be higher psi is going to be highest at the surface that is psi not. Therefore, if I want
to move any ion to a location much closer to the charge surface, I would have to do more
work.

And so, this quantity is esentially telling you what is the probability of finding an ion at this
position, at any location that I am looking at, what is the probability of finding an ion of that
type at a particular location is what this quantity essentially gives you. Where n i is the
number of ions per unit volume, at any location. Need not been near the surface if at any
location in the vicinity of the charged surface, and n i infinity is the concentration of ions far
away from the surface.

That is, you can think about if I have added if I have taken a charge surface, and say it is
positive or negatively charged, if I have added say 1 milli molar salt concentration to the
solution, this n i you know n I infinity can be considered as the bulk concentration, it can be
considered as the concentration of the electrolyte that I have added. And z i of course is the
valency of the ions. So, depending upon whether you are talking about you know,
monovalent ions or divalent ions and you know z i can be, + 1 or – 1 or + 2 or – 2 depending
upon you know, what kind of ions that you are working with.
(Refer Slide Time: 08:38)

So, you can actually think about this Boltzmann factor, you can actually derive an expression
from Boltzmann factor if you know a little bit about you know, chemical equilibria of

396
electrolyte solutions. So, we know that in solution thermodynamics, we talk about chemical
equilibrium mu i which is the chemical potential is equal to mu i 0, which is the chemical
potential of any species or any chemical in the standard state.

+ RT ln a i, where a i is what is called as activity coefficient. Now, when you are working
with ideal solution, you can replace activity coefficient with you know, mole fraction or
molar concentration of you know, ions in solution therefore, mu i becomes mu i not + RT ln
x i. Now, the condition for you know, a solution to be in a thermodynamic equilibrium is that
d mu i is going to be 0.

Therefore, so a d mu i is going to be df mu i 0 + dF RT ln x i. And because d mu i 0 is the

chemical potential in the standard state, that is going to be 0 therefore d mu i becomes RT
into d because you know, if I am working with the constant temperature I can take RT out.
So, d mu i essentially becomes RT d ln x i. So, which essentially tells you that and because of
the fact that you know this chemical potential is 0.

Therefore RT d ln x i = 0 or d ln x i = 0 which tells you that you know this ln of xi should be

constant which gives you that x i = x i infinity that means, if for any solution to be in
chemical equilibrium, the concentration of species at any location is same everywhere. That
means if I have a container and like say for example, I have NaCl for example, of course this
is an ionic state but I know I can take a mixture of 2 species for example.

That means, if I go to some location I look at the concentration of say species A and B in 1
location and if I look at the concentration of A and B in another location, the concentration
here and here is going to be exactly same. That is what this expression essentially tells you.
That is when you talk about chemical equilibrium.
(Refer Slide Time: 11:23)

397
However what we are looking at is a case where you have charged species, when we talk
about charged species I have an electrolyte solution, similar to chemical potential, you can
define something called as a electrochemical potential. Which is mu E, that is the
electrochemical potential, which is summation of the contribution that comes from the
chemical potential plus an additional term.

In this additional term again z i is the valency of the ions, F is what is called as the Faraday
constant and psi is what is called as a local electrostatic potential. And this Faraday constant
is equal to the charge of the electron multiplied by NAV, that NAV is the Avogadro number.
So, therefore, when you talk about electrochemical potential you can say that there is for each
ionic species in solution, there is a electrochemical potential at any given location.

It depends on you know the constituents of the electrolytes at any given location in the
solution there is a electrostatic potential which tells you something about how easy or how
difficult it is to add more of that species into the solution at that location. Or the other way of
thinking about this would be that if I want to add a particular species into a particular
location, in this in the electrolyte solution, I would have to do some mechanical work.

And that mechanical work which is required to bring 1 mole of an ion from a standard state to
a specified concentration and a chemical potential. That means if I have a solution, and if I
want to add some species at that location. So, the amount of work that I have to do depends
on what is the local concentration of ions at that location and what is the electrochemical
potential because of the charge species of a particular ion that is present at that location.

398
So, again, of course at a chemical you know, if you say that there is something if the solution
as a whole is in electrochemical equilibrium, again d mu i should be equal to 0 that means, I
mix some electrolyte in solution and waited for enough time, let the system equilibrate at
equilibrium, d mu E is going to be 0 therefore, d mu i + z i into F into d psi is going to be 0.
This d mu i we have already shown that it is RT d ln x i.

From the previous case, + z i F d psi = 0. Therefore, I can write d ln x i. If I take this term to
the hand side, so, – z i F divided by RT, RT times d psi. Therefore, I can just say If I integrate
this out I get ln of x i = – z i F by RT into psi plus constant.

(Refer Slide Time: 15:14)

399
That is what you get and of course, if I substitute the limits that you know at psi is going to be
0 at x i = x i infinity you know if I do all of that, so, therefore, I get an expression which lets
x i which is the concentration of a particular ionic species, at any given location, you know is
equal to x i infinity, which is the concentration of the same species at infinity times exponent
of – z i, F by RT into psi.

And, and we know that F is e times NAV. We are substituting for F as e times NAV and RT is
related to the Boltzmann constant as R = kB times NAV. So, if I replace instead of R, if I put
NAV times kB, this NAV gets cancelled. Therefore, I have kBT in the denominator and z i into e
is in the numerator. Therefore, x i essentially is equal to x i infinity into exponent – z i e
divided by kBT times psi.

So, this essentially is the Boltzmann factor. So, either you can define it or you can actually go
through this route of electrochemical potential and invoke the fact that when you have an
electrolyte solution in equilibrium, the electrochemical potential is 0 and you can actually
essentially derive the Boltzmann factor.
(Refer Slide Time: 17:01)

400
So, that is what we have. So, we would like to solve this 1 D Poisson equation you would like
to solve that. This rho star is summation of summation z i e n i because, you know, I would
have to you know, I could have a you know case where I have a charged species, you know,
it is not necessary that if I have a charge species I said that, you should always think about
counter ions being in solution.

This is the most ideal case. I only have the charge surface and the counters which come only
because of dissociation of charges on the particle surface. However, in general, so, if I have a
case like this, my rho star is only going to be just z i e n i, that is it. In this case, the counter
ions being negative, so it is going to be – 1 times e and n i is going to be the concentration of
ions in solution.

If I say that there are 100 you know ions for example, is going to be multiplied by 100
multiplied by 1.6 into 10 to power –19 coulomb divided by the volume of the solution that
gives me what is rho star. This is the charge density, the charge per unit volume, that is how
you get rho star but however, in several cases, what you will do is you will have counter ions
because of the dissociation plus additionally we will also add a lot of salt.

You always hear terms like you know, I have a choice stabilized dispersion I have added 1
milli molar salt to the dispersion or I have added 10 milli molar salt to dispersion. When you
have a case like this, I would have both co-ions as well as counter-ions in solution. Therefore,
if you want to calculate rho star, I would have to sum up all the ions present. That is
summation of z, for example, if I have NaCl for example, only NaCl.

401
Then what are we going to have is for Na is going to be + 1 times e, again the concentration
of the concentration is say 1 milli molar. For example 1 milli molar divided by, of course you
to convert a number by using, you know, have a Avogadro number all that. But anyway plus,
I would have – 1 that is because of Cl –, plus multiply by e n i. So therefore, this rho star, you
would have sum up all the ions present in the solution both co ions, counter ions.

You could have case where there could be multiple, you know, ions present to the solution. I
would have to sum all of them up. This rho star has given as sigma i z i times e times n i.
Now, z i e I am going to keep it the way it is and the for n i, I am going to substitute for the
Boltzmann factor. And because e and epsilon, if I am working with a particular solution I
mean, if the dielectric constant the medium that I am using is like say for example water you
know to particular conditions.

I can you know, your epsilon is essentially going to be constant. So, I can take – e divided by
epsilon out sigma I have z i, I have n i infinity exponent – z i e psi divided by kBT. This
expression is what is called as a Poisson Boltzmann equation. Because we started with the
Poisson equation and then we use a Boltzmann factor. You know, and then we obtain an
expression for how does the potential vary as a function of you know, a differential equation.
That counts the variation of the potential as a function of separation distance. That is what is
called the Poisson Boltzmann equation.

402
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology – Madras

Lecture – 32
Potential Distribution Near Planar Surfaces: Solution to the Linearised Poisson –
Boltzmann Equation

(Refer Slide Time: 00:16)

Now, I would like to solve this. So, what I have is this now I would like to solve this. So, we
can either obtain a solution of this equation it depends on at what level you want to, you
know, solve the problem, Either I can simplify and I can take some specific cases, or I can
solve it for a very general case, you know, what I am trying to say is that, I can solve this I
can simplify this equation and obtain a much simpler.

You know differential equation, which I can solve if I assume that I am working with low
potentials or, I can take a case where I am working with z is to z electrolyte, that means I am
working with symmetric electrolyte z is to z for example, NaCl is an example of a symmetric
electrolyte, you know, that is z is to z, 1 is to 1 electrolyte. So, for cases like that, I think you
can solve this, you know, expression fairly simply, but if you look at very complicated cases,
where the potential is very high, you know, or when you are working with non-symmetric
electrolyte this is know the solution is much more involved.
(Refer Slide Time: 01:38)

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So, we will take a simple case of low potential. We will come back a little bit and then tell
you what that low potential is. But for the sake of simple, you know, what we will do is. So, I
have this expression, let me write that up. So, this is d square psi / dx square = – e by epsilon
sigma n i infinity into z i exponent – z i, e psi divided by k B T. That is what we derived. So,
now, so, when I say if you look at the right hand side, when I say it is a low potential, this rho
star we were expressing it as sigma summation of I you know.

For all the species z i times e n i, and n i infinity I we used to represent it in the form of
Boltzmann factor and Boltzmann factor had this exponent – z i e psi / k B T term. So, the
moment I say low potential, I can take an exponential term. For a low potential I can write
this as 1 – z i e psi / k B T. So, it means you have a e power – 6 for example, we know that I
can write it as 1 – x + x square by you know, that is a series.

I can you know, kind of omit all the higher order terms, I can restrict only to the, the first
term, therefore, I can actually write e power – x as 1 – x. Therefore, this exponent – of z i e
psi / k B T. I am writing it as 1 – z i e psi / k B T. No. So if you look at this, so I am only talk
about this term. I am only talking about that rho star. I have only rho star, rho star, we wrote
it as sigma i z i, e, n i, n i infinity, I am supposed to write in terms of the Boltzmann factor.
And there is an exponent – z i e psi by kBT term.

I am going to write that as 1 – that I E, psi / kBT. That is all we have done. So therefore, I can
simplify this as sigma z i e n i infinity times 1, this term, multiply by – sigma z i e n i infinity
at the next term, z i e, psi divided by kBT. Now, if you look at this term, what can you say

404
about this term? So anyway it is rho star infinity, Anyway rho star infinity, and rho star
infinity is actually 0, because if I look at.
(Refer Slide Time: 05:25)

So what you should imagine is this right? Whenever I talk about a distribution of ions in
solution, so imagine that I have an electrolyte solution, Na + and Cl –. So we know that at
equilibrium, there will be some distribution of ions in solution. And there is a, because it is a
symmetric electrolyte, there is an equal probability of finding an Na + and Cl – everywhere in
the solution. If you have a homogeneous solution, now, what I do is I bring in a charged
species now.

Whatever distribution that I had earlier, is going to be disturbed, there is going to be a lot of
restructuring of ions and the leaps restructuring of ions will essentially lead to a electrical
double layer formation. That means the concentration of counter ions close to the charge
surface is going to be higher, but if I go to a sufficiently far away distance, then you will have
again the distribution of ions it is going to be very similar. I am talking about one plate for
example.

I am talking about when I say infinite distance that means it is sufficiently far away from the
charged surface. And you will learn a little bit later, when I say sufficiently far away distance.
We are talking about a distance called the thickness of the double layer. That means if you go
to a distance which is farther than the double layer thickness, you know, there will be equal
probability of finding the positive ions and negative ions in solution.

405
In such a case, this rho star infinity is going to be 0 because if I am working with like a
simple case of, you know, Na + and Cl – this term is going to be + 1, e n i infinity – 1.
Because of the Cl – E, n i, infinity, because if I add one milli molar NaCl solution, I am
actually adding the same concentration of Na + and same concentration of Cl – ions.
Therefore, it was even otherwise.

No, I am only talking about the only thing is if I take for example, CaCl 2, is going to be + 2
times whether there will be 2 times – . So, essentially, this is applicable irrespective of, you
know on an average, the total charge there is 0. Therefore, the total potential will be 0.
(Refer Slide Time: 08:15)

So therefore, the first term becomes 0, therefore, this term becomes 0, I am only left with the
second term, therefore, I have z i here another z i there, therefore, there is a z i square that
comes in. And you have e e therefore, you have e square and there is psi divided by kBT. So,
which I can express it as. So, there is a minus there. So because I had, so there is a rho star.
So this is rho star and because I had d square psi / d x square = – rho star / epsilon, there is a
minus, minus gets cancelled.

Therefore, I am left with and of course, another epsilon comes in because I had epsilon in the
denominator. So therefore, d square psi / dx square = e square / kBT and epsilon and
summation of all the ions in the solution sigma i n i infinity into z i square, multiply by psi.
(Refer Slide Time: 09:43)

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(Refer Slide Time: 09:59)

Now, let’s think a little bit about what is this you know, we said that, so this expression, I
said this is a Poisson Boltzmann equation, now this expression is what is called a linearized
Poisson Boltzmann equation, which is applicable only for the case of low potential, what do I
mean by low potential is z i e, time psi must be much less than kBT. So now you can put in
some appropriate numbers.

So let us say that you know, so let us look at the limiting case. So z i e psi must be less than
kB T for me to assume for me to say that I am working with the low potential case, So, if I
take e psi = kB T, that means, you know, I am talking about again, you know, if z i = 1,
therefore, e time psi = kB T. I know what is kB T the thermal energy so 1.3 10 power – 23
joules per Kelvin multiply we are working with you know 298 Kelvin and e is the charged
electron the psi you know.

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Comes out to be something like 25.7 milli volts, so you can say that if you are working with
charged particles you know at 298 Kelvin at room temperature, if the potential if the zeta
potential of the particle that you are measured. If that potential is 25.7 or lower, I can assume
that the particle charges low. So, that is so, you can kind of get an estimate as to what do I
mean by a low potential or high potential by this simple approximation.

So, this psi if you work with you know, if I work at 25 degrees centigrade, if you have
potential can be regarded as either low or high depending upon, whether the charge surface
that you are working with has a potential that is less than 25 millivolts are more than you
know 25 millivolts. This number is important, because you know, sometimes you may be
working with like say a charge stabilize dispersions say that it is charged positively charged
particles.

You and somebody measures the charge on the particles and they say that it is 15 millivolts
or you know, somebody works with the case where the charge is say – 100 millivolts. So, we
know that definitely a higher charge means you know, it is more stable. But however, if you
look at you know, this the case in even the case where the charges 15 milli volts or the
surface potential is 15 milli volts there would still be electrostatic repulsion, however, it may
not be sufficient right to know for the particles to be stable.

So, of course, the more closer to 0 it is that means you know, your charge interactions may
not be very important at all. So, therefore, you can keep this 25 millivolts in mind that if the
surface charge is such that the surface potential is 25 millivolts or lower you know, such
systems exhibit very limited stability because of the electrostatic effects.
(Refer Slide Time: 13:53)

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So, now you have this linearized Poisson Boltzmann equation and of course, if I so, this is a
quantity of which you have control over that means, you know some of them are constants in
the equation, so, is e square is constant epsilon you know is related to the medium in which
the particles are dispersed. So, you will typically know those values and of course, kB T is the
thermal energy and if you work with finite temperature.

And of course, you have control over the concentration of the ions are in solution and also
you will know their valence everything therefore, I can plug all these constant together into
and say it is kappa square, it is kappa square times psi, therefore, d square psi / dx square
becomes kappa square into psi. That is your linearized Poisson Boltzmann equation and of
course I can solve this so you have if I use a boundary conditions that at for x tends to 0, psi
becomes psi not.

And as x tends to infinity, psi becomes 0, if I use these boundary conditions, so it turns out
that psi becomes psi goes as psi not into exponent – k times x. you know how to do this. So,
you will have psi, you can dial it as A times e exponent of – k x + B times exponent + k x.
That is the solution and if I substitute the boundary conditions, you will essentially get this.
So that is the solution for Poisson equation, in 1 dimension.

So, essentially, what this tells you is that if I have a charge surface with you know, some
counter ions in solution. So, this potential essentially decays as an exponential function. So,
now I with this given if I know what is kappa. I will be able to calculate what is the potential
at every location, how does that vary as a function of separation distance and I should be able

409
to calculate that given that I know what a sign not and what is kappa if I know that I can
know what is the variation of potential with distance.

That is what we were after, no, it is kappa. So, psi = psi not exponent – k times X, you can
work it out. So, you can write this as d square psi = kappa square psi d square – k square you
know is equal to psi = 0. So, you can do that. So, what we have done is a case where we are
trying to think about a potential distribution near a planar surface.

You can and this particular assumption that low potential it is what is called as a Debye
Huckel approximation. So, what is called as a Debye Huckel approximation and Debye
Huckel the 2 people who developed solution you know for the Poisson linearized Poisson
Boltzmann equation which is applicable for low potential cases, that is why this particular
solution that we are looking at is what is called Debye Huckel, you know, approximation.
(Refer Slide Time: 18:20)

You can do a similar calculation for planar you know, other kind of geometries as well,
instead of spherical, instead of planar surface, if I am working with spherical surfaces, I can,
again do a similar kind of formulation and only thing at do is I am going to consider, again if
you look at, you know, the spherical coordinate system, Again, going to assume that psi is a
function of only r, it only varies as a function of r is only a function of r.

Therefore, I will take the only the first term that is 1 over r square d / d r of r square into d psi
/ r. That is the the first term in the general expression in the general poisson equation.
Because I am only worried about how does psi vary with r that is the first term. And again, I
can the right hand side again, I am going to linearize it. Therefore, I essentially end up with,

410
again the linearized Poisson Boltzmann equation in the cylindrical in the spherical coordinate
system. So that is going to be the starting point. And I can of course, solve this as well.

It is a fairly simple derivation, so you should be able to work it out. So what we will do is
into in the next lecture, we will try and solve Poisson Boltzmann equation for the spherical
surfaces case. And then we will talk a little bit about you know, what is the importance of this
kappa square, You know, because this quantity is very, very important because in any
calculations where you want to extract the electrical double layer interactions, you should
know how to calculate that.

And we will talk a little bit about what is the importance of and how does it depend on the
salt concentration how does it vary; we will discuss some of those things in the next lecture.
Thanks.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology – Madras

Lecture – 33
Potential Distribution Near Spherical Surfaces: Solution to Linearised Poisson –
Boltzmann Equation

(Refer Slide Time: 00:14)

So we are, you are still looking at electrical double layer models. So, what we have done in
the last class was to look at working out solution for a case where you have a planar surface
that is charged, that is, you know, in a bath of electrolyte. We are trying to look at how does
the potential varies function of separation distance x. And then we found that psi goes as psi 0
exponent - kappa x. That is what we derived.

That is we took a case of planar you know, surface. So what we are going to look at today is a
case where, instead of a planar surface, I have a curved surface, if I have a spherical particle,
for example, and if that is, you know, charged, we will think a little bit about how do we
derive an expression for how does the potential fall with distance from the spherical surface.
And then we will talk about a parameter that comes out of all the analysis that we have done,
it is what is called as Debye Huckel parameter.

And finally, we will try and compare, we looked at capacitor model, which I said is one of
the most simple model that people have developed, we try and compare that with diffuse

412
double layer model. And by that comparison, you can actually draw some nice inferences. So
we will discuss a little bit about that.
(Refer Slide Time: 01:43)

So, briefly as mentioned this yesterday, this is now the linearized Poisson Boltzmann
equation. But in the case, where I have a spherical surface that is charged, and I would like to
look at the variation of psi with r and so to do so we start with the linearized PB equation.
And we can do some simple modifications. I can, if I substitute for x as r time psi, there is
just a simple steps because we would like to have an next have a differential equation.

Which I can eventually solve and then get an expression for how does psi vary as a function
of r i that is what we are after. So we do a simple substitution, if you substitute x = r psi, that
is this term here, I keep it the same, I will take r square to the right hand side. So therefore I
have r square and this we know is kappa square. That is how we defined yesterday that has
kappa square and you have psi. So therefore, I am going to keep the left hand side same the
right hand side, instead of r time psi, I am going to replace it with x.

r time psi is going to be x, and I am going to retain 1 r and kappa square, that is what we
done. This term d / dr of r square d psi / dr, I can actually write it as d / dr of r square instead
of psi, I can replace it with x / r. Therefore, this become d / dr of r square into 1 - r, 1 / r into
dx / dr. So, this is basically you know, if you have know d / dr of uv. It is u into dv / dr + v.
So we are going to use a chain rule. That is how this is done therefore, this becomes d / dr of r
square into 1 over r into dx / dr - x into 1 over r square - 1 over r square therefore, you get
the right hand side.

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(Refer Slide Time: 04:10)

So that is what is written here, this is what we essentially obtained. Now, because I have r
square you know, I can multiply you know, I can take the r square inside therefore, this
becomes multiplied by r square, multiply by r square and this r square is as we get cancelled.
So, I have x here and this becomes r into dx / dr, just a simple manipulation. Therefore, d / dr
of r square d psi / dx dr essentially is d / dr of r times dx / dr - x.

I can further expand this I can write this as d / dr of if I so, I can write this as dr. Again again
I use the product rule. So d / dr of r into dx / dr + r into d square x / dr square - dx / dr. dx / dr
and dx / dr gets cancelled essentially you are left with r into d square x / dr square.
(Refer Slide Time: 05:33)

So, therefore, essentially what we have done is, so, therefore, this is the equation that we
started off with, it ultimately becomes with the simple manipulation becomes r into d square

414
x / dr square is equal to the right hand side that we had right? r into k kappa square into x.
Because, again we are defined x as r time psi. Therefore, I mean that is what we define.
Therefore, d square x / dr square becomes kappa square into x because you know your x r and
r gets cancelled here.

So essentially I have a simple differential equation now, which I can solve, I know that the
solution for this particular differential equation is x is A exponent - kappa r + B exponent
kappa r. That is the, this solution. And therefore, but because I know that x and psi are
related, therefore, psi becomes A exponent - kappa r / r + B exponent kappa r / r. That is the
solution of this differential equation. And of course, you would have to solve it. I mean, I
have to get these constants A and B. For that I am going to use the boundary conditions.
(Refer Slide Time: 07:02)

The boundary conditions, that we have is that psi tends to 0 as x tends to infinity. And if you
look at this expression, this condition will only be satisfied if B = 0. The fact that psi you
know tends to 0 if x tends to infinity, are r tends to infinity is only satisfied if B = 0 therefore,
the solution becomes psi = A exponent of - kappa r / r. And if I use the other boundary
condition, that is at the surface of the spherical particle, for example, if the size of the
spherical particle that I am considering is Rs.

There is a radius of the spherical particle at r = R s, psi has to be psi 0. Where, R s is the
radius of the spherical particle. If I substitute for that, then I can get the constant A out,
therefore, psi goes as psi 0 r / capital Rs / r exponent of - kappa into r - capital R s. That is
the solution we get. So again, like similar to the case of spherical linear, you know, for the

415
case of flat surfaces, the potential in the case of spherical surfaces also, you know, falls
exponentially with distance that is all this captures.

The functional form, whether it is a planar surface, or the spherical surface is very much
similar. That is also because of the fact that we are considered a linearized version of the
model. So that is the that is how you this is an expression that tells you something about the
potential distribution around a spherical surface again, this is a Debye Huckel approximation
because we are consider the case of low potential that is when we can have a linearized
version of the Poisson Boltzmann equation.
(Refer Slide Time: 09:08)

So that is. That is just a comparison. That is for the planar surfaces. That is for curved or
spherical surfaces. So, a couple of things to keep in mind when you are looking at these
expressions are these are strictly applicable in low potential cases. That is what we have
assumed throughout this derivation that is very important. And so, this result is a limiting
case to which all equations that are more general must reduce to at low potential that means if
I if I have a way of.

You know, deriving a similar expression for how psi varies with distance for more general
case you know what I mean by more general case is you could have the potential need not be
low if we have a very high potential case or if you have cases where I have variation both in x
y and z direction. So, if you have a very general expression like that, and if I take that
expression and then put in the condition that look.

416
I have an expression which is a general expression. Now I am going to apply the condition
there is a low potential. So, if you use that all these equation that you develop should
basically give rise to these limiting equations.
(Refer Slide Time: 10:50)

No, when I say see, this is, let me go back to that. So, what do I mean by low potential. So,
when we wrote so, I said this was an exponential term. This was actually exponent - z i e psi
/ kB T, I can write this in this form only when z i e psi is < kB T.
(Refer Slide Time: 11:22)

So that is how the low potential was derived that was thought of, and then we said that if I am
working with the monovalent because you know this there was z i here, if I assume that I am
working with a monovalent ions, z i is going to be 1. So, this limiting, you know, so,
basically, I can estimate a potential, if I know what is the charge of the electron and the
thermal energy, that potential turns out to be something like this.

417
And, and this is the limiting potential, below which I can say that the potentials are low
potential. So, typically, a potential like this, I can say that the particles are reasonably less
charged, you know, compared to cases, if I have like 100 millivolts, as a potential surface
potential, for example, or zeta potential, that would be really highly charged, Whereas, if I
have potentials, which are 20, 25 millivolts, or even lower than that, you know, you can take
these cases to be low potential cases where I can.

You know, use this linearized solution of linearized Poisson Boltzmann equation to really
understand the potential variation with separation distance. And, and as we are going to do,
as we go to discuss later, how this potential varies with distance is really important. I do not
have a solution here. So, let me just go back.
(Refer Slide Time: 12:53)

So, how this potential varies with separation distance is really important, because that is what
is going to determine the electrical double layer repulsion between the particles, we will
discuss a little bit of that in the next you know, maybe a few lectures. So, again to recap, so,
they are certainly applicable for low potential and this is a limiting case to which all the more
general solutions should reduce to when we invoke the condition of low potential case and so,
these expressions.

So, what these expressions also capture is the effect of electrolyte concentration and the
valency. So, let me put it this way. So, these expressions, they capture the fact that psi varies
in a particular way, when you have when the concentration of electrolyte in the solution

418
changes or when the valency of ions in the solution changes. So, that means, if I have like
say, let me put it this way.

So, if I have potential if this is psi 0 say that you know, the potential varies in this particular
way with if I use say 1 is to1 electrolyte. Now, if I use the same electrolyte, but I go for a
higher concentration. So, they say this is concentration 1. So, this is again 1 is to 1 the
concentration to where concentration 2 is greater than concentration 1. So, there is a
particular way, this potential will vary with distance as you change the concentration of the
salt or as you change the valency of the ions that you have put in the solution.

So, these in the limiting cases, still capture the variation of psi 0 with separation distance, in a
consistent way. We which is also captured by more rigorous calculation, the only thing is the
magnitude may be slightly off, but the way psi varies with electrolyte concentration and
valency is still qualitatively very similar, whether you use a rigorous model or these limiting
cases, that is the point is that mean.

So the effect of electric concentration and valency in this approximation, or qualitatively

consistent with the results of more rigorous calculation, there may be quantitative mismatch,
because you have invoked the low potential case. However, in terms of the nature of
variation, they are qualitatively they are similar to the more rigorous calculations.
(Refer Slide Time: 15:52)

Now, in these expressions, this kappa square, we had taken it as it turns out, during the inner
simplification kappa square comes out as epsilon square divided by e square divided by

419
epsilon kB T multiplied by summation of n i infinity z i square. Let us look at what is the unit
of what is the unit of kappa? I will go by a simpler way of doing this. You look at this
expression psi is equal to psi 0 exponent - kappa x x will have units of length therefore,
kappa should have units of length inverse.

So, the parameter kappa should have a unit of meter inverse or k inverse should have a length
unit of length. This kappa inverse is what is called as Debye Huckel parameter. That is
because this comes out when you are looking at Debye Huckel approximation, the low
potential case that is why it is called a Debye Huckel parameter and people often refer to k
inverse as the thickness of the double layer.

Thickness of the double layer people also call this parameter as Debye Huckel. So, k inverse
which has units of length is called as Debye length and k which has units of meter inverse is
called inverse Debye length and stuff. So, but these are the names that people use
interchangeably depending upon you know, different textbook and different. And so, like we
mentioned that we always kind of compare the interaction potential U or phi, we always kind
compare and they say something about what is the potential with respect to kB T.

I mentioned that whenever you do any interaction potential calculation is always a good idea
to scale your interactions with the thermal energy. Because that will give you a kind of a
magnitude which you can easily connect to or similarly, all distances within the double layer
are judge with respect to the double layer thickness. So, in many you are working with
electrical double layer interactions in charge dispersions.

You will always ask a question is to what is the size of the particle compared to k inverse,
what is the distance between the particles compared to k inverse. So therefore, so all the
distances within the double layer, and, you know, all the interactions, the range of interaction
that you talk about in electrical double layer interactions, you can people always try their
judge with respect to the distance of the thickness of this double layer.
(Refer Slide Time: 19:34)

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Now, this n i infinity is the concentration of ions, that is, that is the number of ions per unit
volume. That is what we had mentioned. You can express, you can actually kind of, just
rearrange this expression and then express K square in terms of more measurable you know
quantity. So, I can this n i infinity which is the concentration of ions in the solution, you
know, you can express this in terms of the molarity of the salt that is added.

Because molarity will have units of moles per liter and because I want to convert that into
moles per meter cube, i multiplied by 1000 and because I have moles, I would like to convert
that into the number of, I would like to convert that into number of ions, therefore, I am
multiplying by Avogadro number. Therefore, kappa square becomes e square divided by
epsilon k B T, I can replace n i infinity with 1000 Mi NA and z i square and NA being a
constant.

I can just take it out and 1000 also I can take it out therefore, kappa becomes thousand a
square NA divided by epsilon kB T summation of I Mi z i square to the power half. So, I have
list out so, that is kappa. This so far we are writing kappa square. So, the kappa essentially is
the entire thing to power half.
(Refer Slide Time: 21:37)

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So, this is some typical values. What is this is a table that I have taken from the book this is
the molarity of the salt different salt concentration 0.001 molar 0.01 molar 0.1 molar and this
is a z is to z electrolyte, This is for symmetric electrolyte 1 is to 1, 2 is to 2, 3 is to 3 these are
all symmetric electrolytes. The next few columns are for asymmetric electrolyte, that is again
z is to z but you could have 1 is to 2 or 2 is to 1 electrolyte or 3 is to 1 or 1 is to 3 these are
asymmetric electrolyte.

And these are kappa values, that is a Debye Huckel parameter and this is kappa inverse that is
the inverse you know or the double layer thickness, which has units of meter. And what is
interesting to note is that all these numbers, if you look at all these numbers, they are again of
the order of nanometers they are of the order of nanometer that is again important to keep in
mind whenever you do any calculation, where you are being asked to calculate kappa inverse.

If you get values which are microns are really large that means there is something wrong with
your calculation because kappa inverse values are supposed to be in the nanometer size
range. And so, if I look at these numbers if I look at these numbers one comment that I can
make is that the thickness of the double layer is about the same magnitude as the prediction
based on the capacitor model if you remember the calculation that we made if we took a
simple case and we showed that the thickness delta.

The delta there is a separation distance between the plates of the capacitor we said it was
coming to be somewhere 4.4 nanometers or something like that. So, if you look up these
numbers, the thickness of the double layer is of the same magnitude as that predicted with a

422
capacitor model. However, the diffuse model captures the dependence of double layer
thickness on the concentration and the valence of the ions, which is not there for the capacitor
model.

For the capacitor model, delta was fixed by the potential drop, it was fixed with a potential
drop. It was fixed by the dielectric constant the medium it was fixed by the sigma star, which
is the surface charge density, because we had something like del psi / delta was going as
sigma star divided by epsilon, epsilon 0. Epsilon r epsilon 0, I think that is what that was the
expression that we had. So, this delta is fixed by the potential drop, the surface charge density
and the permittivity.

You know, constant of the medium that you have between the plates. However, so the
capacitor model did not capture the variation of delta with the concentration and the valency
of ions is the solution. However, the diffused double layer model does you know capture that
that is one of the differences.
(Refer Slide Time: 25:12)

So, the other influence that you can draw if you go back and look at you know, this
expression is that k the kappa. It varies as M power half you know and it varies as
proportional to z or kappa inverse is inversely proportional to M, the concentration of the
electrolyte to the power half or kappa inverse is inversely proportional to z. So, that again is
kind of. So, if you look at these values. So, this is a case where I have like if you look at some
typical numbers are given.

423
So, this statement we already made the thickness of the double layer that is kappa inverse it
varies inversely with Z that comes straight away from the expression that you had it varies
inversely with M power half again I can make the statement only for z is to z electrolyte. So,
that is again here it goes as inverse z kappa inverse goes as 1 over z and m power half minus
half. But however, for the non-symmetric electrolyte is a little bit more complicated.

And the double layer thickness equals to about 1. If you look at this expression, so, I take
0.01 molar. And for 3 is to 3 electrolyte, the double layer thickness is about 1 nanometer.
However, if I take 0.001 molar electrolyte and if it is 1 is to 1 electrolyte, the double layer
thickness is about 10 nanometre, so you can get these numbers and think a little bit about how
does so, essentially, what I am trying to tell is that if I compare for the so let us think about.

So, 3 cases 0.001, 0.01 and 0.1. Let us stick to 1 is to 1 electrolyte. I am keeping the same
type of electrolyte 1 is to 1, but however, we are changing the concentration. Therefore, in
one case, the double layer thickness is about 10 nanometer and I increase the salt
concentration the double layer thickness becomes 3 nanometer, I increase the concentration
further the double layer thickness becomes over 1 nanometer about this 9.61 10 power - 10 is
0.9.

So, therefore, if I keep the type of electrolyte same if I increase the concentration from 0.01
to 0.01 the double layer thickness goes from about 10 to about 3 to 1, it was 10 nanometer
here is 3 nanometers there and it is about 1 nanometer here. So, basically this basically the
formalism that we have done the Debye Huckel approximation essentially captures. How
does both the potential vary with distance.

And how does it vary with the electrolyte concentration, how does it vary with the type of
electrolyte that you have used these are the you know. So, this is a again a just a plot
whatever I mentioned you know the previous last few seconds So, similar so what you are
what is plotted is a scaled potential. So, I can divide this by psi 0, I can get this that is what is
you know, on the y axis x axis is your separation distance, that is for 1 is to1 electrolyte.

And all that has been done is the salt concentration is systematically increased. That means
you get a more steeper, more steeper drop in the, the potential with separation distance when
you have a higher salt concentration and the fall becomes more gradual, if you have low salt

424
concentration. So, in this case, the type of electrolyte is fixed and the concentration is change.
However, if I fix the concentration of the electrolyte, and change the type of electrolyte 1 is
to 1, 2 is to 2, 3 is to 3.

Again, symmetric light you will again see that the, the potential decrease becomes more and
more gradual. If you change the electrolyte from 3 is to 3 to 2 is to 2 to 1 is to 1. So therefore,
these potential, the plot of how the potential varies, they drop off more rapidly for higher
concentration or higher values of higher willingness of the electrolyte. What do you think is
implication of this?

What do you think is the implication of the fact that the potential drops off more gradually or
more rapidly? What consequences do you think this has on the electrical double layer
interactions? Take a little bit about this question. So, I will come back and we will come back
and make a point.

425
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology – Madras

Lecture – 34
Comparison of Capacitor model and Diffuse double layer model

(Refer Slide Time: 00:14)

Now, what I want to do is a simple exercise where we would like to compare the capacitor
model and the diffuse double layer model. So, this is what we derived earlier that is d psi / dx
= delta psi divided by delta is equal to sigma star / epsilon not epsilon r where delta psi is the
potential drop between the plates. Now, I would like to take you know the psi = Psi 0
exponent - kappa x and d square psi / dx square - rho star / epsilon.

These are the this was a basic equation that we use for obtaining how the potential varies with
separation distance that is the now, I would like to use these expressions and then express this
in a way I can compare with the capacitor model.
(Refer Slide Time: 01:47)

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So, for that what we will do is so, I have written a expression here which tells you the sigma
star which is the surface charge density that we had in the capacitor model this rho star is the
charge density but that is charged per unit volume in this case. Now, if you assume that I do
not have any other added electrolyte I only have the charges because of I only have the
counter ions that come because of the dissociation of charges on the particle surface.

Then what I can do is I can say that because of the electro neutrality I can say that the charge
density at the 2 phases must be equal when I say 2 phases one I am talking about the charged
surface at the 2 phases, this was not 2 phases 2 phases, because of the electron neutrality the
charge density in the 2 phases must be equal when I say 2 phases one is the charge surface
and the counter ion sub phase. The other way of saying the same thing would be.

So, the total charges contained in a volume element of a solution across you know so I can
put this way let us say this. So, I can define sigma star. Then what you do is I consider the
total charge that is contained in a volume element. And I am going to count all the ions that
are present from the wall to infinite distance away from the wall. The total charge that is
contained, determined in that way must be exactly equal to the charges on the particle
surface.

However, they should be opposite in sign. Is it okay? So we are talking about in this case. So,
imagine that I have a diffused double layer now. We will come back. When one other phase
contains diffuse layer that means this is a charged surface. And I have a diffuse layer when
one of the phases contained diffuse layer. The total charge contained in a volume element of

427
a solution across the cross section extending from wall to infinity must contain the same
amount of charge, although opposite in sign as the unit area of the wall contains.

So that is what this expression essentially says. You have a question. So, that is a good point.
So, sigma star corresponds to the charge density of the surface, if I have a charged surface.
So, we what we defined is sigma star was q /A. The total charge on the particle surface
divided by area that is how it was defined and in this case, rho star is a charge in the solution.

So, we are talking about equating the charges on the particle surface and the charges in
solution. And because of the fact that the electro neutrality you know must be preserved, the
total charges that are in the solution on the particle surface should be same as the charges in
the solution, however, they should be of opposite sign. Think a little bit about this, you know,
we can discuss this further as well.

So, now, I have rho star I can instead of sigma star is a rho star, what I can do is I know that
rho star / epsilon, is minus d square psi / dx square, so, we will replace with that instead of
rho star and we could have d psi / dx, and I would have epsilon that comes here and there is a
– 1 minus here minus here it becomes plus. So, therefore, sigma star is epsilon 0 to infinity d
square psi by dx square into dx.

And I would have to sum up all the charges all the way from distance is equal to 0 to infinity.
Therefore, sigma star if I integrate this I can write this as sigma star is equal to epsilon into d
psi / dx at infinity - d psi / dx at 0 that is at the surface of the charged body and that is at a
distance very far away from the charge surface.
(Refer Slide Time: 07:42)

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And we know that we know that d psi / dx at infinity is going to be 0 because we know that
psi itself is 0 at you know x is equal to infinity therefore, the first term is going to be 0 then
you are left with epsilon times 0 - d psi / dx at 0 therefore, sigma star is - epsilon d psi / dx 0
and because we know that the potential varies in a false and you know in an exponential way
I can get what is d psi / dx at 0.

Therefore, d psi / dx = 0 will be psi not exponent - kappa x times - k and because for
extending to 0 this term becomes 1. So, I have - k times Psi 0. Therefore, sigma star which is
equal to - epsilon d psi/ dx at 0 will be equal to epsilon kappa Psi 0.
(Refer Slide Time: 08:53)

And therefore, I can rearrange this to get sigma star is equal to epsilon into Psi 0 divided by
kappa inverse and if you look at the capacitor model the expression was sigma star is equal to
epsilon delta Psi 0/ delta. So, we are able to express sigma star you know obtained from the

429
Debye Huckel approximation in a you know is an equation which is analogous to the
capacitor model.

So, what you can infer from this is that these results they essentially show that the diffuse
double layer at low potential you know you can think about it behaves like you know
capacitor model however, the separation distance is replaced by k inverse. Instead of delta
you have kappa inverse. But of course it this model captures the you know some really
important features for example, the distance over which significant potential exist decrease
with increasing electrolyte concentration.
(Refer Slide Time: 10:25)

What I mean by that if I look at this expression what do you understand by the statement the
distance at which the significant potential exists decrease with electrolyte concentration. So,
if I look at these expressions of course, if I go to a very far away distance potential is going to
be 0. Now, what is important when you worry about electrical double layer interaction is that
when the 2 surfaces charged surfaces come closer if the potential when they approach if the
potential is very, very high that means the repulsion is also going to be high.

So, if I look at a particular let us look at this potential which is this prediction rate it occurs at
may be separation distance of 10 nanometer, let’s go back and look at a same potential occurs
at a much lower separation distance the same potential occurs at whatever 3.5 nanometers
something like that. Now, if I go here, the same potential occurs at even lesser separation
distance. That is what the first statement essentially means, the distance over which
significant potential exist decreases with increase in the electrolyte concentration.

430
That was actually demonstrated by here. Because this is a case where the electrolyte
concentration is changing, the electrolyte concentration is changing when the electrolyte
concentration is 0.001 this particular potential occurs at 10 nanometer, but the same potential
occurs at a lower distance, when I have a higher concentration of salt, if I go for even higher
concentration of salt, the distance at which the same potential exists even decreases.

That is the first statement the distance or which significant potential exists decreases with
increasing electrolyte concentration. And the second point, the range of electrostatic potential
decreases as the valency of the ions in the solution increases. This is right that we can draw
from the second point. Can I make this so I am going read that again .The range of
electrostatic potential decreases as the valence of the ions in the solution increases.

So, there I mean, now you have a statement about the range of interaction. Now, the range of
interaction electrical double layer interaction essentially depends on how does this potential
vary with distance, if the potential falls off steeply, the range over which the electrical double
layer interactions become important is smaller. However, if you have a case, where the
potential decreases more gradually.

That means, the range over which the electrical double layer interactions are important or the
electrostatic interactions become important over a larger range of separation distance. Do you
get that point? Or do you have to explain? So, you can think about it, you can in a way, think
about k inverse or 1 over k as a distance over which the electrical double layer interactions
are become important. If you go by that so the more the kappa inverses, more will be the
range.

Now, because I am able to decrease kappa inverse by adding a higher concentration of salt or
by increasing the valency of the ions I have put in. Therefore kappa inverse is going to go
down. Therefore, the range of over which the electrical double layer interactions become
important is also going to go down, that is the point. I think a little bit about it.
(Refer Slide Time: 15:08)

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So that is about what I want to speak today. So we will what we will do the next class is to
look at more general solution. Instead of looking at linearized Poisson Boltzmann equation,
we will just look at a more general case for a symmetric electrolyte and then we will try and
look at it how does a potential vary with separation distance and then discuss again, the
implications.

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 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology, Madras

Lecture – 35
Models of Electrical Double Layer: Gouy Chapman Theory - 1

So we will continue with module 4. In today’s lecture we will try and look at 2 aspects, one is
models for double layers looking at Gouy Chapman theory and hopefully if we have some
time we will also look at structure of electrical double layers.
(Refer Slide Time: 00:33)

So what we have done so far is to look at potential distribution near a planner charge surface.
In that context, we have looked at solution of Poisson Boltzmann equation. However, with
the limitation that we are only considering the low potential case which is what is called as a
Debye Huckel theory. In which we started off with one dimensional Poisson Boltzmann
equation. And then we showed that psi essentially goes as psi naught exponent minus Kappa
x, where Kappa is given by this particular expression.
(Refer Slide Time: 01:24)

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So now what we want to do today is to essentially take out this limitation of low potential that
means, we would like to obtain a solution of the Poisson Boltzmann equation without the low
potential limitation that is what we would like to do. Again the starting expression is going to
be one dimensional Poisson Boltzmann equation, because we are assuming that psi varies
only in the x direction. That is we are only considering that psi is a function of x alone.
(Refer Slide Time: 02:05)

And the solution for this particular case is given by what is called as a Gouy Chapman
Theory. So for that we will again solve one dimensional Poisson Boltzmann equation and it
turns out that for z is to z electrolyte again the dependence of potential with separation
distance is still going to be exponential and is given by gamma = gamma naught exponent
minus Kappa x, where gamma is exponent z e psi / 2 kB T - 1 divided by exponent z e psi 2
kB T + 1.

434
And similarly, gamma naught is same as it takes the same similar functional form as gamma
with psi replaced by a psi naught. So that is what we are going to derive in today’s lecture.
(Refer Slide Time: 03:00)

So again we will start with Poisson Boltzmann equation one dimensional case. And if you
remember this, so we had d square psi / dx square = - rho star divided by epsilon, instead of
rho star, we have used the Boltzmann factor and then we have written an expression for rho
star, which essentially is a summation for all the species that I have in the solution, I would
have to sum up the contribution from all the ions that I have in the solution.

Which is essentially is e times zi times ni and with ni being given by the Boltzmann factor. So
what we will do is we will start with this expression. And we will do some simple
manipulations so we are going to multiply both the sides of this equation by 2 times d psi /
dx, so that is what we have on the left hand side. And that is what we have on the right hand
side as well.

Now if you look at the left hand side, I can write this as d / dx dx of d psi / dx whole square.
So if I differentiate this function, so what I will get is, I get 2 times that is 2 here, times d psi /
dx, multiplied by d square psi / dx square. So that is the left hand side term, and the right
hand side term, I can write this as d / dx of 2 times k B T divided by epsilon into sigma i ni
exponent of minus zi e psi / k B T.

435
So if I differentiate this term, so the first term remains the same kB T divided by epsilon, and
what you have here, so I am going to have sigma i ni infinity, and if I am going to replace,
differentiate this term is still going to be exponent minus zi e psi / kB T multiplied by, so it is
going to be multiplied by zi e divided by kB T. And this kB T, kB T gets cancelled, and so
therefore and you have e here that is the e there and I have psi sorry epsilon. So I have e /
epsilon and zi is here zi ni infinity that is this term.

And of course, this term is as it is. And of course I have 2. So essentially, this by this simple
manipulation, I can write the one dimensional Poisson Boltzmann equation as d / dx of d psi /
dx whole square is equal to d / dx of 2 kB T divided by epsilon summation i ni infinity
exponent of minus zi psi divided by kB T.
(Refer Slide Time: 06:12)

So now if I can integrate this expression, so I can integrate this on both the sides. So what I
will be ending up with this d psi / dx whole square is equal to this plus a constant term. So we
can evaluate the constant fairly easily.
(Refer Slide Time: 06:32)

436
We know that psi = 0 at x = infinity and d psi / d x. Therefore, because psi = 0, you can also
say that d psi / dx = 0 at x = infinity. So, if I substitute for these conditions, so this is you
know 0 and if I substitute psi = 0, this term becomes 1. Therefore, essentially I have 2 kB T
divided by epsilon summation i ni infinity and plus constant is equal to 0. Therefore the
constant essentially becomes minus 2 kB T divided by epsilon summation i ni infinity. So
therefore, we have been able to evaluate the constant. I can substitute for the constant.
(Refer Slide Time: 07:28)

So therefore, I could write d psi / dx whole square as the first term minus the constant term
and because I have 2 kBT by epsilon summation i n i infinity as a common I can take it out.
Therefore, in the parenthesis I will have exponent minus zi e psi divided by kB T - 1. Now I
can simplify now because we are considering a specific case of z is to z electrolyte, what I

437
can do is I can take this term and then whenever I have z is to z electrolyte there is going be z
plus and z minus type of ions.

Therefore, there so because it is taking a symmetric electrolyte case, what I can do is I can
wherever I have z in, I can substitute for plus 1 as well as z = -1. So that I count for both the
co ions and the counter ions in the solution. Therefore, the first term remains the same and
exponent of if I substitute zi as plus z therefore, the first term is going to be exponent of
minus z e psi divided by kB T - 1.

And the next term if I substitute for zi to be minus z, so therefore, the next term essentially
become the exponent of z e psi divided by kB T. So, the substitution of z = +1, z = -1 is
specifically for 1 is to 1 electrolyte. If you have a 2 is to 2 electrolyte, I would have to
substitute z = +2 and z = -2, but because we are considering the case of a general z is to z
electrolyte.

Therefore, it makes sense to replace zi with minus zi and zi with plus zi. Therefore, d psi / dx
whole square essentially becomes 2 kB T and infinity divided by epsilon into exponent minus
z e psi divided by kB T - 1 + exponent Z e psi divided by kB T - 1. The reason why we have
taken ni infinity out of the summation sign is because for a given concentration ni for both
plus z and for minus z ions is essentially the same. Therefore, I can actually take it out of the
summation term and it will become n infinity.
(Refer Slide Time: 10:17)

438
So, now that we have this. So, what I can do is so this is what we had earlier. So, there is
minus 1 here and minus 1 that becomes minus 2 and in the parenthesis you have exponent of
minus z e psi divided by kB T + exponent of z e psi / kB T. If you look this up, you can write
this as exponent minus z e psi divided by 2 KB T - exponent z e psi divided by 2 KB T whole
square.

These are the form a - b whole square, which is same as a square + b square - 2ab, therefore I
can recover this expression. So that I have the first term whole square that is this. So, if you
look at this expression, so I have exponent z e psi divided by 2 kB T whole square. Now, I can
simplify this. I can take the 2 in the numerator, this, this gets cancelled essentially I have the
first term.

Similarly, that is this term similarly, so I have again I can take the 2 in the numerator, so I can
this, this gets cancelled. So, I essentially have the first term here and the second term there.
And if you look at this, this essentially is minus 2 times exponent - z e psi divided by 2 kB T
+ z e psi / 2 kB T essentially it is exponent of 0 which is 1. Therefore, I recover the minus 2.
(Refer Slide Time: 12:09)

So therefore, so I can express this particular expression as d psi / dx whole square is 2 kB T n

infinity divided by epsilon into exponent - z e psi by 2 kB T - exponent z e psi divided by 2 kB
T the whole square. Now again, we are going to do some more manipulation. So we are going
to assume or we are going to put z as z e psi divided by kB T, this is a simple substitution. So
therefore, from this what I get is I get psi to be y kB T divided by z e.

439
So therefore, I can replace for psi in terms of y, so I have d / d x, instead of psi, I am going to
replace it with y kB T divided by z e, that is this term multiplied by y, and the right hand side
becomes 2 kB T an infinity / epsilon into exponent - y / 2 - exponent of y / 2, because we are
substituted this to be y, therefore I have y here and I have 2 in the denominator, the same
thing is also true for this case.

So therefore, and because for a given electrolyte and given temperature kB T divided by z e is
constant. I am going to take kB T square divided by kB T divided by z e whole square outside.
So I have dy / dx whole square = 2 kB T n infinity / epsilon multiplied by this term.
(Refer Slide Time: 13:50)

That is of course which is valid only for a z is to z electrolyte and at a given temperature. So
and what I can do is I can take the square root on both the sides of this expression, so I will
end up with dy / dx on the left hand side and this term raised to the power one and a half and
this and the square gets cancelled, I have exponent of minus y divided by 2 - exponent of y
divided by 2.
(Refer Slide Time: 14:25)

440
Now, if you look at, if you take a closer look at this expression, it turns out that you can relate
that to the Kappa. So what we know from the definition of Kappa is that Kappa square = e
square divided by epsilon kB T multiplied by summation of i ni infinite into zi square. Now
because we are considering z is to z electrolyte, I can write this as n infinity times plus z
whole square plus n infinity into minus z whole square.

Therefore, I will have 2 times z square into n i infinity that comes from the term in the
parenthesis and I have of course, e square divided by epsilon kB T. So, now if you look at this
expression and compare it to this, so what you essentially have is, if I take the square on both
sides, I have what I have is Kappa is same as this term to the ratio of one and a half. So
therefore, so this particular expression which is valid for z is to z electrolyte.
(Refer Slide Time: 15:41)

441
I can write it as dy / dx is equal to Kappa times exponent of minus y / 2 - exponent of y / 2.
Now I can separate the variables. So I have dy the terms with y on the one on one side I can
just rearrange this you know a bit. So therefore, I end up with dy divided by exponent of
minus y / 2 - exponent minus y / 2 = Kappa times d x.
(Refer Slide Time: 16:14)

And which if you want to evaluate this further, again we are going to substitute for u as e
power y / 2 therefore, du / dy is e power y / 2 divide multiply by one and a half. So therefore,
2 times du, I can cross multiply them, 2 times du is e power y / 2 times dy, therefore dy
essentially becomes 2 e power -y / 2 into du. So therefore for dy, we are going to substitute it
as 2 times e power -y / 2 into du.

And this because we are substituted, so therefore exponent of minus y / 2 - exponent of y / 2

they remain the same, so therefore now what I can do is we could take this term to the
denominator. Therefore I have 2 dy multiplied by e power y / 2 multiplied by e power -y / 2 -
e power y / 2. So, if I take e power y / 2.
(Refer Slide Time: 17:32)

442
Again inside the parenthesis so I essentially have e power y / 2 - y / 2 - e power y / 2 + y / 2.
So, this becomes 1 and e power y / 2 + y / 2 essentially is e power y itself. So therefore, dy
divided by exponent of minus y / 2 - exponent y / 2 becomes 2 times du divided by it was
actually 1 - e power y and because u is e power y / 2 essentially this becomes 1 - u square
which I can write it as du divided by 1 plus u + du divided by 1 - u. So therefore, if I sum, if I
simplify this it becomes du times 1 + u + 1 - u divided by 1 - u square this gets cancelled,
essentially you end up with what you had earlier.
(Refer Slide Time: 18:36)

So therefore, if you have been able to simplify this, we have been able to recast this
expression as du / 1 + u + du divided by 1 - u is Kappa times dx. So, I can integrate this
easily. So, if I integrate this what I essentially end up with is ln of 1 + u - ln of 1 - u = Kappa
x + constant. Therefore, ln of 1 + u divided by 1 - u = Kappa times x + constant.

443
(Refer Slide Time: 19:14)

So, I can integrate again, evaluate the constants we have substituted u as e power y / 2 and
therefore, y becomes z e psi divided by kB T that is what we have done. So, if you go back so
it is u = e power y / 2 and so therefore, we substituted y to be z e psi divided by kB T. So
therefore, so this is comes from the substitution that we have done. Therefore, u essentially
becomes e power instead of y I am going to have z e psi divided by kB T and of course, I have
the one over 2 term there.

Therefore, u becomes e power z e psi divided by 2 kB T. We know that at x = 0 that means; if

I have a charged substrate and if this is how the x varies from the surface at x = 0, the
potential is psi naught. So, if we have that, so now and therefore at x = 0 y naught becomes z
e psi naught divided by kB T and u naught becomes e power y naught divided by 2. So, we
are essentially re evaluating all the initial conditions and the boundary conditions in terms of
y naught and u naught. So therefore, if I substitute for x = 0, so this term goes away and what
I end up with this the constant = ln of 1 + u naught divided by 1 - u naught.
(Refer Slide Time: 21:15)

444
So therefore, we end up with ln of 1 + u divided by 1 - u = Kappa x + ln of 1 + u divided by 1
- u. I can take this on to the other side and if I again use the condition that ln of x - ln of y =
ln of x / y. So therefore, I have this term here and because it is y divided by y, so this you
know is, you can notice 1 - u is in the numerator and 1 + u is in the denominator. So, what we
can do here is that I can if you look at these terms, I can write this as minus of u naught - 1. I
can write this as minus of u - 1 this gets cancelled.

Therefore, what I end up with this 1 + u or u + 1 that remains as it is and 1 - u I can write it as
u naught - 1 and 1 - u I can write it as u - 1. So therefore, ln of u + 1 divided by u naught - 1
whole divided by u - 1 multiplied by u naught + 1 is Kappa x.
(Refer Slide Time: 22:46)

445
And, and so of course, we would have to obtain an expression in terms of psi and psi naught.
Therefore, we could do again substitute back. So, because u is e power y / 2 and y is z e psi
divided by kB T, I can write this u as e power y / 2 + 1 times e power y naught / 2 - 1 whole
divided by, so maybe let me just do a better job. So, I can substitute, I can write this as ln of e
power y / 2 + 1 multiplied by e power y naught / 2 - 1 divided by e power y / 2 - 1 times e
power y naught / 2 - 1.

And because y is z e psi divided by kB T, I can substitute again for y here. So, essentially I
end up with ln of exponent of z e psi divided by 2 kB T + 1 times z e psi naught because you
have y naught here, I have z e psi naught divided by 2 kB T - 1 whole divided by exponent of
z e psi / 2 kB T - 1 and that will be equal to Kappa x.
(Refer Slide Time: 24:19)

So, again some simple rearrangements I can put together all the psi terms together and all the
psi naught terms together. Therefore, gamma divided by gamma naught is exponent of minus
Kappa x. Therefore, gamma = gamma naught exponent - Kappa x.
(Refer Slide Time: 24:42)

446
Where gamma and gamma naught are given by these expressions, so therefore, we have been
able to show, we have been able to obtain what is called as a Gouy Chapman theory or Gouy
Chapman expression that was derived by Gouy and Chapman for how the potential varies
with separation distance without limiting to the case of low potential that means this
expression is valid for any situation except for the fact that we will still have to consider the
symmetric z is to z type of electrolytes.

447
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology, Madras

Lecture - 36
Models of Electrical Double Layer: Gouy Chapman Theory - II

(Refer Slide Time: 00:15)

So now what we will do is we will try and look at simplifying this general expression to some
specific cases.
(Refer Slide Time: 00:23)

448
What we know is that z gamma is gamma nought exponent - kappa x is valid for any potential as
long as the electrolyte is z is to z. Now so we know that this expression should can be simplified
to psi = psi naught exponent - kappa x.
(Refer Slide Time: 00:55)

Of course, for the case of low potential, so, let us look at how we do that. So, that is the Gouy
Chapman solution. And we know that gamma is exponent of z psi divided by 2 kB T - 1 divided
by exponent of z e psi divided by 2 kB T + 1, that is what, that is a gamma naught. That is a
gamma That is what was here So that is, what is here Now, if we assume the low potential case,
so what I can, what one could do is this exponent term, I can write as a, I can neglect the higher
order term.

And I can write exponent of z e psi divided by 2 kB T as z e psi, divided to kB T + 1, and I am

going to neglect all the higher order terms. Similarly, denominator also the same thing I am
going to only retain the first 2 terms in the series expansion of exponent of z e psi divided by 2
kB T. So, therefore, gamma becomes so I can cancel these 2 in the numerator, I have z e psi
divided by 2 kB T divided by in the denominator I have z e psi divided by 2 kB T + 2 because we
are taking low potential case, we had.

So, the low potential case is when z e psi divided by kB T is less than 1. And because at e psi
divided by kB T is less than 1 and that divided by 2 is going to be even further less than 1
therefore, I can neglect this term. So, denominator essentially will be just 2 therefore, gamma

449
becomes z e psi divided by 4 kB T. I can do a similar simplification also for gamma nought as
well, which again turns out to be z e psi nought divided by 4 kB T and this this gets cancelled this
this gets cancelled and you end up with the expression for the low potential limit.

Therefore, the general Gouy Chapman solution you know simplifies it is to the Debye Huckel
approximation for the case of low potential.
(Refer Slide Time: 03:56)

So, the other simplification one can do is that is a special case 2 this is for large value of x at
which the potential has fallen to small values regardless of its initial potential. Now, we know
that potential varies with distance if you go away from if this is psi nought is initial potential and
as we go away from the charge surface, we know that the potential is going to decrease. Now, if
we take some distance, that is x such that it is very large that the potential has fallen to a very
low value regardless of this initial potential.

So, in such a case, what I can do is I can simplify gamma as z e psi divided by 4 kB T because
again I can invoke the condition that at a very large separation distance the potential is low I can
again only consider the first 2 terms neglect the higher order terms. So, therefore, gamma
becomes z e psi divided by 4 kB T. However, because psi could be larger psi could be any
potential. Therefore, I will have to continue to retain gamma nought as it is because I cannot
invoke the low potential case like we did for the earlier case.

450
Because now, gamma could be gamma nought could be significant or gamma nought psi being
could be any value. Therefore, I am going to retain gamma as gamma nought therefore, for the
case where for a very large value of x such that the potential has fallen to a very small value
regardless of the initial potential, I can simplify the Gouy Chapman theory to be to take the form
z e psi divided by 4 kB T that is on the left hand side the right hand side remains the same.
(Refer Slide Time: 06:34)

If you take the third special case again this is for a very large value of x such that the potential
has fallen to a low value. Therefore, the simplification that we have done in terms of writing
gamma nought as z e psi divided by 4 kB T will still hold and on the right hand side you had
gamma nought exponent - kappa x. What do you see here is a table where gamma nought is
tabulated as a function of psi nought that is psi nought in millivolts.

This is gamma nought if you look up this table it turns out that if you look at very large values of
psi nought gamma nought essentially is very close to 1 therefore if the surface potential if the
initial potential is very large gamma nought will you can it is approximately equal to 1 that is
from this table therefore, z e psi divided by 4 kB T becomes exponent of - kappa x itself because
gamma nought = 1. Therefore, from this I can write psi as 4 kB T divided by z e into exponent of
- kappa x. So, these are the 3 simple you know special cases one could derive from starting with
the Gouy Chapman theory.
(Refer Slide Time: 08:13)

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What is plotted here is a potential in millivolts and that is the separation distance and if you look
at this plot, there are 4 expressions there are 4 lines a continuous line, a dashed line and dashed
and dotted line, there are essentially 4 there are essentially different solutions that is the Debye
Huckel approximation. That is the Gouy Chapman theory and this is for the case where the
potential has fallen to a very low value regardless of the initial potential and this is the case
where the potential is fallen to a low value regardless of the initial potential.

And the initial potential being very high so, if you look at the solution that is plotted for specific
case, psi nought is 77.1 millivolts. This is a significant potential, this is not the low potential
because we said that the potential has to be of the order of 25 millivolts for one to consider the
potential to be the low potential case. So therefore, psi nought = 77.1 is a not a low potential
case. And kappa is given by this. So kappa inverse is marked here. That is a kappa inverse
corresponding to this kappa value.

And this is the kappa value that you have is for 0.1 molar solution of electrolyte and so, the best
expression that one could use to predict the variation of potential with separation distance in this
particular case is going to be this expression because this is the Gouy Chapman theory, which is
valid for the symmetric electrolyte 1 is to 1 in this case and we know that it is applicable for you
know any potential because we are not invoking the low potential limit case.

452
Therefore, this particular line that is this line that I am tracing now, that is the solution that
corresponds to the Gouy Chapman theory, but however, if you look at the other 2 lines, that is
this line, as well as this line, these are one is for the low potential limit and the other one is for
the case, where the potential is fallen to a low value regardless of what is the initial potential, we
know that these 2 also do a reasonably good job that means, both that means though the potential
is best described by the Gouy Chapman theory that is this expression.

This as well as this still do a very good job of predicting what is the variation of potential with
the separation distance. However, because of the fact that the potential that we are considered is
77.1 millivolts, that means, it is not significantly large to take gamma nought = 1 as it is evident
63 the expression is equation 68 that is the case corresponding to the special case for large value
of x and large value of initial potential, it is does not do a good job of predicting how the
potential varies with separation distance. Therefore, depending upon the situation, you should be
able to use one of these expressions to find out how the potential varies with separation distance.
(Refer Slide Time: 12:36)

Now, that we know how the potential varies with separation distance, we can also look at the
variation of the concentration of co-ions and the counter ions as well you know, in the vicinity of
the charge surface. So, we know how the potential varies with separation distance, but however,
if you want to know how does the concentration of in this case you have positively charged
surface therefore, the negatively charged ions are going to be the counter ions. Of course, I could

453
also have positively charged ions as well in the solution, which are going to be coins and how
does their concentration vary with separation distances is also of interest?
(Refer Slide Time: 13:22)

So, for that what we are going to do is to again start with the Boltzmann factor. So, we know that
n i divided by n i infinity is exponent of minus z e z i e psi divided by kB T and this ni is not a
constant and n i infinity is fixed by the concentration of the electrolyte in the solution that is a
fixed quantity for a given concentration and this is a constant this as well and zi is the valence of
the ions. So, once that is fixed, so, everything is a constant here except for psi and n i varies with
separation distance, we know that psi also varies with separation distance.

Now, because we have derived how does psi you know depend on various with separation
distance? We can substitute relevant expression for psi. So, if I assume the low potential case, I
can replace psi to be psi nought exponent of - kappa x. Therefore, now, that I know how psi
varies with separation distance I should be able to also calculate what is how does the
concentration of the ion varies with separation distance.
(Refer Slide Time: 14:45)

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So, therefore, from this approach, I can actually calculate what is the concentration of the counter
ions? And what is the concentration of the co-ions? In this case both of them are scaled with n
infinity which is the concentration of the electrolyte that I have in the solution. How does the
concentration of the counter ion decreases as you go away from the separation distance and how
does the concentration of the co-ions again varies with separation distance one could calculate
from this approach.
(Refer Slide Time: 15:15)

What would also be interest would be what is called as the distribution of excess ion
concentration that will be given by n minus minus n plus that is the difference in the
concentration of the co-ions and the counter ions and how does that vary with seperation distance
one we should be able to calculate all of this from this simple formulations.

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 Colloids and Surface
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 37
Structure of Electrical Double Layer

So, in today’s lecture so we will start with discussing the summary of electrical double layer
models followed by structure of double layer and then we will move on to think about what
happens when there is overlap of the double layers? We will calculate what is the force? And the
potential of interaction between the particles when there is overlap of the double layers. Then
something called as a DLVO potential followed by how does the DLVO potential varies for
different cases that is what we are going to do today.
(Refer Slide Time: 01:06)

So, what we have discussed in the model for double layers is that one of the simplest models was
capacitor model or the Helmholtz double layer model in which it was assumed that if you have
any charge surface in the immediate vicinity of the charge surface. You have a layer of counter
ions, which are tightly bound to the charge surface and the way the potential varies with this
distance it in a very much resembles this line that is there is a linear variation of the potential
with distance in the double layer.

And the next model that we looked up was what are called as a class of model called a diffuse
double layer model in that we have looked at Debye Huckel formulation and Gouy Chapman

456
formulation in which it is assumed that the correct picture of the distribution of charges in the
solution are considered. So the idea is that the fact that the counter ions and the co-ions that you
have in the solution; you know they do have thermal energy.

And because of this thermal energy there is a more diffuse distribution of counterions in solution
that is the charge density varies with distance from the surface. So, that gave us the fact that the
potential psi goes as psi 0 exponent - kappa x or gamma = gamma 0 exponent - kappa x. That is
what we are derived for the two diffused double layer models. However in one could also think
about a more elaborate model in which you can combine both the aspects of the capacitor model
and the diffused a double layer model.

And then we can say that look in the region very close to the charge surface, you still have a
linear variation that is captured by the capacitor model and however it is at a distance x greater
than x1 you can have a diffuse double layer kind of model. So, one could combine both the
capacitor model and the diffuse double layer model to come up with a better or a more elaborate
model and because we know how the potential varies in the two regions. And one could think
about exploiting this fact to come up with a more general description of the electrical double
layer model and this is the situation which is more close to reality.
(Refer Slide Time: 04:14)

So, we will talk a little bit more details about electrical double layer itself so, what is plotted is
there is a picture here, a schematic in which what you have is a negatively charged particle and

457
these are the negative charges that are represented on the particle surface and as you can see that
you know it is a real surface. Therefore you see that there you know it kind of exhibits these
undulations these.

So, this is because if you look at any particle at a nano scale is not homogeneous there could be
some heterogeneities on the surface. So, that what this essentially depicts and so, what is plotted
here is this is a potential and that is a separation distance r and of course we know that the force
of you know interaction is related to the potential of interaction through this particular formula
that is F of r is the negative gradient of the potential.

So, what you are seeing is a schematic of a simplified double layer model in solution at the
surface of the colloidal particle that is colloidal particle that we are considering and at the surface
how does the psi r vary with distances what is shown. So, psi r is the electrostatic potential and it
is plotted as a function of distance from the particle surface that is this line and that is the yellow
line that you know is marked here.
(Refer Slide Time: 06:03)

So, what is also marked here in this picture of electrical double layer is something called as a
stern layer, the innermost layer of ions that is we are talking about now because the particle is
negatively charged. So, these positive charges that you see these are the counter ions now in the
immediate vicinity of the charge surface, the innermost layer of the ions is adsorbed to the
surface and the rest of the counter ions are in the solutions.

458
That is the inner layer of ions, counter ions and of course, there are some other counter ions as
well and the whole system, the entire system as a whole is electro neutral because they will be
equal number of positive and negative charges in the solution. If you look at the region that is a
solution region that is marked here, you see that the intensity of the shading decreases as you
move away from the charge surface.

The shading denotes the density of the counter ions and the counterions concentration is high
closer to the charge surface that is the density of the counterions is high close to the particle
surface and it falls when we move away from the surface. Of course there could be additional
cations and anions in solution that may arise because often what is done is to dispersion of
charged particles will add some additional electrolyte or some buffers.

Because of which there could be additional cations and anions in the solution and of course they
will also be distributed in a particular way in the solution and so this innermost layer of ions that
is adsorbed close to the surface that the region that corresponds to this innermost layer of ions is
what is called as a stern layer.
(Refer Slide Time: 08:18)

So, the ions in the stern layer can be considered to be immobile that means for all practical
purposes, they are adhered strongly onto the particle surface and therefore the this region
essentially acts more like a capacitor over which the potential varies linearly with separation

459
distance that is what is shown here. If you look at this, how this yellow line varies in this stern
layer region there is a linear fall of potential with separation distance.

The outermost limit of the stern layer is associated with what is called as a plane of shear and so
this essentially signifies that beyond this plane of shear that is I am going to draw a vertical line
here so maybe here I am going to draw a dotted line that is the plane of shear beyond which the
liquid around a moving particle is no longer trapped to move with the particle. So, if you look at
the configuration of the charged particle and the solution next to it there is a stern layer where the
counter ions are strongly bound charge surface.

And of course there will be also be some liquid as well in the stern layer. Now, when the particle
moves whatever liquid that is trapped in the stern layer will also move along with a particle.
However, beyond this boundary the liquid moving around a particle is no longer trapped to move
with the particle. So, therefore, this boundary essentially tells you whether the liquid next to the
particle is moving along with a particle or not moving with the particle.

The potential at this point is often considered to be the zeta potential and this is a zeta potential is
a parameter of practical significance. Because depending upon the zeta potential of the particles
in the dispersion you know, you can comment on the stability of colloidal particles in the
solution and it is determined by a technique called electrophoteric mobility measurements which
we will discuss in the in the next few classes.

So, just to sum up there is a stern layer in which the counterions are strongly bound to the
particle surface and the outer limit of this stern layer is what is called as a plane of shear beyond
which the liquid around the moving particle is no longer trapped to move with the particle that
means, the liquid has the kinetic independence beyond the plane of shear. However, within the
stern layer the liquid does not have kinetic independence because it moves along with a particle
when the particle is set into motion.
(Refer Slide Time: 11:43)

460
So, that is again the similar picture depicted here so you have a positively charged particle
surface and the stern layer very next to it and there is a plane of shear and of course if you look at
there is a certain structure in which the counter ions and the co-ions are arranged in the solution
that is what is called as a diffused layer. So, therefore if you look at the stern layer, the linear fall
of potential is evident and in the diffuse double layer, the potential falls more like a exponential
way.

And the potential at the surface is psi 0 and the potential at the plane of shear is the zeta potential
and what is also marked as k inverse, which is the Debye screening length and at k inverse the
potential typically is denoted as psi d that is the potential at the diffuse layer boundary and it
turns out that this potential diffuse layer boundary is important because when the two particles
start approaching each other.

When the potential is larger than when the potential at the overlap becomes larger than psi d that
is when the repulsion between the particles become significant and this k inverse that is the
Debye screening length, it provides a good first estimate of the distance beyond which the
Coulomb interactions can be essentially ignored. That means if we are considering two particles
in solution if the distance between the particles is larger than k inverse. So, we can ignore the
electrical double layer interactions and one has to worry about the other kind of interaction that
may be present in the system.
(Refer Slide Time: 14:04)

461
So, with that picture we will we would like to talk about overlap of electrical double layers and
how does that manifest into inter particle repulsion. So, for that what we are going to do is we
are going to consider two plates and say that both the inner you can think about them as infinite
you know plates. So, in which both the surfaces of the particle are charged so, it is a substrate of
some finite thickness t and they have an area A.

And now, so, we know that there will be some potential psi 0 associated with each of these
surfaces and because we are assuming that both this surface and this surface are homogeneous in
terms of surface chemistry the material you know they are made of therefore, we can assume that
the potential of the surface on either side is essentially the same and of course we know how the
potential varies with distance now because we have developed if we have developed expressions
for how the potential varies with separation distance.

Now, if the distance between the plates that is h if it is greater than or far far greater than kappa
inverse as I mentioned earlier though there would not be any overlap of electrical double layers
therefore, in such cases the inter particle repulsion will not exist. So, what we are going to
consider is the case where when h becomes less than kappa inverse that means when there is a
overlap of the double layers. We will we would like to calculate what is the repulsion between
the two particles?
(Refer Slide Time: 16:31)

462
So, therefore, the objective is to calculate the force per unit area or the pressure that operates on
the two charged surfaces as a result of overlap of doubles layer. So, you have a schematic here
this is a schematic of two plates that is a plate 1 and that is plate 2 and these are two plates of
constant thickness and they are separated by a distance h that is the distance between the two
plates and the plates are immersed in infinite reservoir of electrolyte that is the bulk
concentration of the electrolyte is n infinity.

Because once so, you should imagine that so, these plates are immersed you know a bath of
electrolyte and the concentration of the electrolyte is fixed and so essentially n infinity there is a
concentration electrolyte in the bath is fixed and the potential at the surface is psi 0. So, whether
you take the inner surface or the outer surface because they are chemically homogeneous. So, the
potential of the surface is psi 0 and that in other words we can say that the charge density at the 2
surfaces is exactly the same.

So, now so, what is shown here is that so, there is a region that has between the two plates and
there is a region outside. So, we are going to name two regions the outer region in this region the
potential in this region is influenced by only one of the phases. So, that is the region outside the
two plates that means so, that is the interior region, the inner region where the there is a region
between the plates, where the potential in this gap is influenced by both the surfaces. However,
in the outer region, the potential is influenced by only one of the phases.
(Refer Slide Time: 19:03)

463
I have already made this point but I would like to go through it again when the distance between
the plates is large and when I say large, we always talk about distances in terms of some
characteristic length scales. So, in this case the distance h when I say it is larger it is larger than
kappa inverse. The potential from the inner and the outer face will drop in a similar fashion that
is when they are sufficiently far apart, whether you look at how the potential varies in the outer
region from outer face or the inner face.

The potential would fall in a similar fashion and it could be Gouy Chapman way that is capital
gamma = gamma 0 exponent – kappa x or it could be Debye Hackle way if we are considering
the case of low potential. The potential drop in the outer region when the distance between the
plates is large is given by the solid line. This line essentially captures how the potential falls with
distance when the distance between the plates is larger.

Now so, there are some dashed lines in between so if you look at this line that is a dashed line
this as well. The potential drop in the inner region when the distance between the place is large
that means, when they are sufficiently far apart so, that the way the potential varies in the outer
region is exactly same as the way the potential varies on the other face and that is captured by
this dashed line and what you in the schematic is this line.

So, that is when this again is a potential variation, when the distance between the particles, start
decreasing that means when the particles are sufficiently close such that now, h is less than

464
kappa inverse. The potential from each of the inner face they begin to overlap the net potential
takes the shape of a solid line that is shown here. However the potential in the outer region
remains unaffected because in the outer region, the potential is only influenced by the outer face.

However, because of the overlap both the inner face of both the particle 1 and the particle 2 will
influence how the potential varies within the gap and that is essentially captured by this solid line.

465
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 38
Force of Repulsion between Interacting Surface

(Refer Slide Time: 00:14)

So, now of course you have some fluid in between the plates, because you know these two
plates are immersed in a bath of electrolyte there is fluid you know in the outer region as well
as inner region. And if we assume that the plates are in equilibrium what you could do is you
can consider you can think about doing a force balance so, you can consider a volume
element of fluid that is parallel to the face of the plates that are considered.

And you could do a force balance it turns out that there are two forces that are acting on the
volume element first is what is called as osmotic pressure force. And this arises because if
you look at the region within the two plates there is certain concentration of electrolyte and
because of the fact that there is a concentration of you know the counter ions close to the
surface is higher. So, the concentration in this region would be very different from the
concentration in a region that is in the region outside the gap.

That is the concentration of the if I am going to think about the concentration of the
electrolyte in the region as C1 and if I say that the concentration of the electrolyte in the
region outside the plates is C2, this C1 would be greater than C2 because of the fact that the

466
gaps are low and the if you look at the number density of ions the in the gap would be larger
compared to what you have in the region outside.

Because of which because of this difference in the concentration of ions in the region
between the plates and that outside there is going to be an osmotic pressure force term that is
going to be important. And the second force will arise because of the fact that you have
particles that are charged. And because of this there is going to be an electrostatic force that
will also come into the picture.

So, what we are going to do is we are going to consider the x component of the two forces the
x component of the automatic pressure force is given by - dp / dx that is because we are only
considering a 1 dimensional case of how the force varies with distance in the x direction. And
F x is given by - dp / dx and the electrical force per unit volume is given by the product of
charge density times the field strength.

That again comes from the electrostatic concept that electric field E is force times q and E
again is - d psi / dx sorry this is F times q so, this F is E times q and therefore I can write F as
q times E that is q times - d psi / dx and there is a minus sign here. So, therefore one could
write the electric force per unit volume that is acting on a fluid element that is considered is
given by the charge density rho star times the gradient in the potential and because the plates
are in equilibrium the summation of all the forces should be equal to 0.

That is Fp in this case Fx + Fel should be equal to 0 therefore dp / dx + rho star times d psi / dx
is going to be 0 you can arrive at a similar expression for the force balance if you start with
Navier Stokes equation as well. And this is the term that comes if you have flow in the
solution. However because we are talking about a case where you have particles immersed
you know infinite bath of electrolyte and there is no bulk flow the velocity u is going to be 0
therefore this term is going to be 0.

And we are going to assume that the gravitational effects are not important therefore that
term again would be 0 and you have the charge density here times E that is the strength of the
electric field and that we know it is - d psi / dx and you have delta p here and because we are
only worrying about the pressure gradient in the x direction therefore this del p essentially
would be dp / dx.

467
So, whether you identify the different forces acting on the volume element and then do a
force balance or you start with Navier Stokes equation and then cancel out or neglect the term
that are not relevant you end up with the same expression that this Fx + Fel = 0.
(Refer Slide Time: 06:15)

So, therefore the criteria for the equilibrium is Fx + Fel = 0. Therefore dp / dx + rho star times
d psi / dx = 0 and we know this from the Poisson equation; the Poisson equation 1 dimension
is d square psi / d x square = - rho star / epsilon. So, I can instead of rho star I can replace so,
that is the dp / dx term instead of rho star I can replace that with epsilon times d psi / dx and d
square psi / dx square times d psi / dx.

Since, we know that d square psi / dx square times d psi / dx = 1/2 d / dx of d psi / dx whole
square so, if I simplify this what I get is 1 over 2 times d / dx of d psi / dx whole square is 2
times d psi / dx times d square psi / dx square this, this gets cancelled we essentially end up
with the same term. So, therefore dp / dx - epsilon times d square psi / dx square times d psi /
dx I can write this as dp / dx - epsilon / 2 times d / dx of d psi / dx whole square.

So, if I take d / dx is common so, therefore this becomes p - epsilon / 2 times d psi / dx whole
square = 0. Now, if I integrate this so what I end up with this p that is this - epsilon / 2 d psi /
dx whole square is equal to constant. And therefore the criteria for equilibrium now becomes
p - epsilon / 2 d psi / dx whole square is equal to constant and now if you look at this
expression this is the contribution that comes from the osmotic pressure and this is a
contribution that comes from the electric field.

468
So, what this expression is it tells you is that if you look at not only for the volume element
like say at the central location if you look at volume element at any location this equation
would be satisfied because of the fact that we are assuming that the entire system is in
equilibrium and the electric field contribution to the pressure is what is called the Maxwell
pressure or the Maxwell stress which comes into picture.

Whenever you have flow or maybe a flow coupled with electric field effects in the solution or
any case where you have pressure contribution comes from things like osmotic pressure or
flow and then there is a coupled effect along with the electric field present in the system.
(Refer Slide Time: 10:16)

So, therefore this expression that we have derived which is the condition for equilibrium is
valid at all location within the plates. So, of course we will be interested to find out what is
the integration constant one of the way to think about obtaining the integration constant is to
look at how does this potential because of the overlap varies with the distance. So, if you look
at this I can say that at the midpoint so if h is the distance between the plates.

And that is the dashed line that is drawn that is the mid plane that is at the distance h / 2 at the
midpoint you can say that d psi / dx = 0 at h / 2 and pressure at h / 2 is ph/2. So, therefore if I
substitute these conditions this term becomes 0 therefore constant essentially becomes p at h /
2. Now, if you look at the overlapping electrical double layers so, even though the surface
potential is psi 0.

469
When the overlap occurs, let us say that this is the potential with respect to one plate and say
that this is the potential with respect to other plates. So, the repulsion between the particle
does not depend on what is psi 0 however what is the potential at the overlap therefore psi h /
2 is the potential that governs the repulsion between the surfaces not psi 0.
(Refer Slide Time: 12:41)

So, therefore now we would like to express the potential you know the so, what we will do is
we will again do some simplifications. So, that is the force balance and therefore I can write
recast this as dp = - rho star multiplied by d psi and we know that the charge density in
solution can be written as summation i zi e times ni. So, all that we are doing is we are
summing up the charge contribution because of different types of ions in solution.

So, zi is the valency and e is the charge on the electron and ni is the concentration of the i th
type of ions in solution. So, I can bring in the Boltzmann factor so, zi e times the Boltzmann
factor that is rho star and when you have z is to z electrolyte is a zi takes the value of + z or -
z therefore I can expand this term I can write 2 terms one for the + z case and the other one
for the - z case. Therefore dp becomes - z e n infinity times.

And now note that ni infinity I am replacing that as n infinity itself because the concentration
of both the cations and the anions is exactly same. And I can denote that as n infinity. So,
therefore I can take this out that is a common factor. So, you have exponent minus is z e psi /
kBT sorry z e n infinity times exponent – z e psi/ kB T - exponent of z e psi / kB T. So, that is
what you end up with. And we can use the fact that exponent x - exponent - x is 2 sin
hyperbolic x therefore I could write this as dp. So, I think there is a mistake here. So that is

470
should be positive. Therefore dp is = 2 times z e n infinity times sine hyperbolic z e psi/kB T
times d psi.
(Refer Slide Time: 15:36)

I could integrate this and use the boundary condition that at a in the so, when we consider that
the potential is at a very large separation at a very large distance from the surface we know
that the potential would be 0 that is size equal to 0 and at that location we say that the osmotic
pressure which is proportional to the concentration of ions that you have at that location is p0.
And at h / 2 the potential is psi h / 2 and correspondingly the osmotic pressure p is p at h / 2.

Therefore once I integrate and then substitute these conditions end up with ph/2 - p0 = 2 times
kBT n infinity and you have a cos hyperbolic z e psi h / 2 / kB T - 1. So, this expression
essentially gives the excess pressure that is p h / 2- p 0; p 0 is the osmotic pressure when were
psi is 0 and the difference between p at h / 2 - p0 essentially gives you what is the excess
pressure at x = h / 2.

And it represents the force per unit area with which is the plates are pushed apart because of
the overlap therefore ph/2 - p essentially is FR that is the force of repulsion and that is the force
of repulsion per unit area and that is what given by this. So, therefore what we are trying to
do here is that if you look at this expression FR which is a force of repulsion it is expressed in
terms of the potential at the midpoint that is it is expressed in terms of psi at h / 2 that is the
potential at the midpoint between the 2 plates and of course this is an unknown quantity what
we know is psi 0 however psi at h / 2 is not known.
(Refer Slide Time: 18:27)

471
And you can do some approximations to find out to evaluate what is psi at h / 2. So, that is
the excess pressure FR. Now, we did think about some special case of Gouy Chapman
expression which is applicable for z is to z type of electrolyte for any surface potential. So,
now if you look at this expression we derived this for a case where the potential has fallen to
a low value that means we are talking about a distance at a distance that is sufficiently.

So, we are talking about the case where we are looking at a distance, a very large distance
from the charge surface such that the potential is fallen to a low value. So in such a case we
can simplify a gamma = gamma 0 exponent - kappa x as psi = 4kB T / z e gamma 0 times
exponent of - kx. So, what we are going to do so, because we have two plates plate 1 and
player 2.

So, therefore there is going to be psi 1 that is contribution that comes from the plate 1 and psi
2 there is a contribution that comes from the psi 2. So, we are going to say that psi at h / 2 is
summation of psi 1 + psi 2 therefore psi h /2 becomes 2 times 4kB T / ze gamma 0 exponent
of -kappa h/2. So, this particular approximation is what is called as a superposition
approximation which is valid only when the surfaces are sufficiently far apart.

That is what I mentioned that the Gouy Chapman theory was simplified to give this
expression which is applicable for any psi 0 the psi 0 could be very high. However which is
valid only when the surfaces are sufficiently far apart that is we are considering a case where
the overlap of the double layers is moderate.
(Refer Slide Time: 21:11)

472
So, therefore psi h/2 we have derived that and so, this result that we have used it applies well;
away from the surface where the potential is low. So, and we can of course consider the fact
that the cos hyperbolic that you have here. So, if you look at the expression for the excess
force I have a cos hyperbolic term and you know I can consider a series expansion of the cos
hyperbolic term.

And the excess pressure now I can write this in terms of I can neglect the higher order terms
and therefore so, instead of cos hyperbolic what I can do is I have 2 times kBT this term
instead of cos hyperbolic h / 2 / 2 kBT - 1 what I will do is I can take this it is cos hyperbolic
x – 1 = x square / 2 factorial and I am going to neglect the higher order terms therefore so, I
can write this as this divided by 2 therefore this, this gets cancelled.

So, I essentially end up with this expression. So, therefore FR which is the force of repulsion
goes as kBT times n infinity is z e psi at h / 2 / kBT whole square. So, I can take z e / kBT
outside and I have psi h / 2 square here I can replace for psi h / 2 I can replace this expression
now therefore FR that is the force of repulsion essentially becomes kBT n infinity. So, I have 8
gamma 0 exponent of – k h/2 whole square that means the force of repulsion essentially
becomes FR = 64 kB T n infinity gamma 0 square exponent of - h / k inverse.

473
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology, Madras

Lecture – 39
Potential Energy of Repulsion between Planar Double Layers and DLVO Theory

(Refer Slide Time: 00:14)

So, far we have derived an expression for repulsive force between two interacting surfaces,
when we say interacting surfaces it means that there is a overlap of electrical double layer and
the expression that we been able to obtain is this that is the excess pressure or the force per
unit area with which the particles are the two surfaces that we are considering that is this and
this are pushed apart as a result of overlap of electrical double layer is given by this.

FR = 2 kBT n infinity cos hyperbolic z e psi at h / 2 / kB T - 1 and because we can express cos
hyperbolic x as a series expansion in this form instead of cos hyperbolic x - 1 I can substitute
for cos hyperbolic x - 1 = x square / 2 factorial and I can neglect the higher order terms. So, if
I do that, in the end the expression for repulsion becomes something like this 64 kBT n
infinity gamma not square exponent of - h / kappa inverse that is what we have derived so far.
(Refer Slide Time: 01:37)

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Now, if you look at this expression, if we what we would like to do now is to look at a case
where the distance of separation between the two plates is fixed that is, h is fixed and because
we know that kappa square you know depends on you know the permittivity temperature and
iron concentration in a particular way therefore, kappa varies as n infinity power of half
kappa square goes n infinity therefore, kappa varies as n infinity to the power of half.

So, that is essentially is so, if this is kappa, therefore, kappa goes as if I take square on both
sides, they essentially kappa goes as n infinity to the power of half. So, I can so, this is a
constant for a given because if you are working at a given temperature, this is constant and if
the surface potential is fixed, this gamma not square would also be fixed therefore, I can write
the expression for the force of repulsion as some constant C1 times n infinity exponent minus
some constant multiplied by n infinity to power of form 1 half.

Therefore, from this expression what we can conclude is that, the force of repulsion decreases
with increase in electrolyte concentration between the 2 surfaces compared at same distance,
that means for a given distance, because you have there is a pre exponent term and there is an
exponent term because of the fact that this decreases much more drastically with increasing
the electrolyte concentration.

Therefore, the overall effect is essentially governed by this term. Therefore, the force of
repulsion decreases with increase in the electrolyte concentration. And the other point that we
can make is that the addition of the other way of saying this same point would be the addition

475
of electrolyte to dispersion in many cases is known to induce that coagulation of colloids that
means, if you have the particles nicely dispersed.

The addition of electrolyte like salt for example, it gives rise to the coagulation or
aggregation of particles that arises because of the fact that increase the electrolyte
concentration leads to a reduction in the repulsive forces, which will make a colloid to go
from a stable state to a destabilized or unstable state.
(Refer Slide Time: 04:36)

Since we know that, the potential is given by the force times distance through which it
operates, for change for an increment the change or the increment in the potential arising
from a change in the separation distance, you can actually calculate by knowing F of R
therefore, because d phi of R goes as – FR time dh therefore, one could integrate this
expression to obtain an expression for the potential of repulsion between the two charge
surfaces.

And if I use the boundary condition that the potential becomes 0 when the distance of
separation is very very large at a separation distance which is much larger than k inverse or if
you consider the distance of separation to be very very high, the force of repulsion would be
0 therefore, phi of R essentially goes as 64 kBT n infinity kappa inverse is a factor that comes
when you integrate this term and of course, you going to have the exponent - h / kappa
inverse term intact.

476
So, therefore, now, what you have is that so, if you look at n infinity here n infinity goes as
let us go back to the previous expression. So, you have a kappa inverse here. So, therefore,
you had kappa which goes as n infinity power half n infinity power half and you have kappa
inverse which goes as n infinity power of minus half so, because you have n infinity here and
kappa inverse goes as n infinity power of minus half.

So, let me just quickly so, you have n infinity to the power of 1 that is this term and kappa
inverse goes as n infinity power minus half therefore, overall this phi R the energy of
repulsion or the interaction potential goes as some constant times n infinity to the power of
half and exponent of minus C2 some other constant times n infinity to the power of half and
again this expression is written for a given separation distance of course, this expression is
again valid when the distance of separation between the surfaces are large.

Again the same conclusions can be drawn that the potential energy of repulsion decreases
with increasing electrolyte concentration because of a strong dependence of the exponential
term on the concentration of the electrolyte that are being considered.
(Refer Slide Time: 07:54)

So, we have been able to derive this expression for the overall potential or the total electrical
double layer potential if we were able to do it or it was possible to obtain this expression
because of the relatively simple approximation for the potential at the midpoint. So, we said
that it is not the potential at the surface, but the potential at the mid plane, the potential that
h/2 is what governs the electrical double layer repulsion.

477
And of course, we did use a superposition approximation to say that psi at h/2 = psi 1 + psi 2.
So, we essentially used this approximation to obtain how the phi of R quantitatively depends
on the several parameters in what however, general method for the evaluation of the potential
energy of repulsion, it was derived by or it was put forward by Verwey and Overbeek in
which a numerical simulation was used to capture.

How does the potential energy of repulsion varies with separation distance for any charge
stabilized colloidal system for a very general case of the conclusions from these numerical
integration procedure or that the potential energy of repulsion may extend appreciable
distances from surfaces, but its range is compressed by increasing the electrolyte
concentration of the system.

So, when we say that the electric potential energy of repulsion can extend to appreciable
distances from the surfaces, we are talking about distances of the order of kappa inverse are
less or of the distances of that order and however, the strength of the repulsion is reduced or
compressed or decreased by decreases by increasing the concentration of electrolyte in the
system.

The second point is the condition under which approaching particles first influence one
another are at large separation distance for which the approximate relationship is given by
this. So, therefore, the general solution that has been developed by numerical integration it
kind of reduces to this particular expression when we are considering a moderate overlap or
when the overlap is such that the distance between the particles is sufficiently larger.

The sensitivity of aqueous hydrophobic colloids to electrolyte concentration is due to the

dependence of the inter particle repulsion on this concentration. So, there are several systems
where lyophobic that means, the colloidal particles which do not disperse well in solutions
are considered and the colloidal stability of such particles and the dependence of the stability
on the electrolyte concentration is kind of captured by this particular theory. So, that is about
the overlap of electrical double layers and how does that manifest into the repulsion between
the particles.
(Refer Slide Time: 11:46)

478
So, now, we will move on to looking at colloidal interactions in charge stabilized
suspensions. So, what we are have is a schematic 1 and 2 in which what is considered is you
have a dispersion of and negatively charged particles and a dispersion of positively charged
particles in a fluid medium and whenever you have a system of charge stabilized colloidal
system.

So, you have to think about the attractive interactions between the particles and that comes
from the contribution of the Van der Waals forces, which were discussed in module 2 and the
repulsive interactions, which come about because of the overlap of electrical double layers
which has been discussed in this module or the module 4. So, in such a system of charge
stabilized colloids. The total interaction as a function of separation distance d is given by the
summation of the Vander Waals contribution and the electrostatic or the electrical double
layer contribution.
(Refer Slide Time: 13:04)

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And this fact that the total interaction energy is the summation of the Vander Waals forces
and the electrical double layer forces is what is called as a DLVO theory which is named
after Derjaguin Landau, Verwey and Overbeek and this theory was put forward to explain the
stability of charge stabilized colloidal dispersions. So, and what you see here is a plot of how
the DLVO will potential or the total potential in a charged stabilised suspension scaled with
thermal energy how does that vary as a function of separation distance.

So, you have repulsive contribution that comes from the electrical double layer effect and the
Van der Waals contribution that comes from the Van der Waals the attractive term in the
expression and the continuous line that is drawn here is the DLVO interaction and so,
because you have electrical double layer repulsion and Van der Waals attraction, which are of
opposing tendencies.

So, whenever you add up this term, you are going to have a maxima and depending upon the
extent of this maxima what is the so, what is the energy that is required to overcome this
barrier. So, that attractive interactions become dominant this is what is called as a energy
barrier for aggregation. So, typically, when this energy barrier is of the order of several tens
of kBT one could say that such colloidal dispersions of charge stabilized particles are stable to
aggregation and one could manipulate the strength of this energy barrier by manipulating by
playing with several conditions which we are going to discuss in a while.
(Refer Slide Time: 15:25)

480
So, the contribution of individual interactions that means the contribution of the electrostatic
interactions of electrical double layer interactions and Van der Waals interactions to the total
potential depends on the particle geometry whether we were working with spherical particles
or planar surfaces or you know elliptical particles so, it depends on the particle geometry and
when the particles are you know, not isotropic that is non spherical, any case other than this,
it turns out that what is also important is the orientation effect.

That means, whether in the case of ellipsoids if are the particles when they approach are they
oriented in this particular fashion or are they oriented in the tip fashion or are they oriented
tip to the side. So, therefore, depending upon the orientation of the particles the individual
contribution could vary. The individual contribution also depends on the surface charge, what
is the charge density on the particle surface the concentration of the electrolyte in the solution
and the chemical composition of the particles and many other factors as well.

So, for a planar surface, we have derived this expression for how the potential varies with
separation distance and this expression again we have derived in module 2. That comes from
the Vander Waals forces where kappa is given by e square divided epsilon kBT summation i
zi square and ni infinity.
(Refer Slide Time: 17:08)

481
So, now, if you take particles refer a particular geometry or a given geometry in this case if
you look at planar surfaces, if you look at the phi net or the phi total or phi DLVO you can
say that the total potential depends on several parameters for example, temperature because
you have you know the temperature term in the electrical double layer repulsion therefore,
one could play with the temperature of the solution and then modulate the total potential.

It depends on the permittivity as well. So, if you have kappa inverse here and kappa inverse
depends on again temperature as well as permittivity. So, therefore, you can disperse particles
in fluid of different permittivity and then manipulate the total potential the chemical
composition of the particles also is important because the chemical composition dictates what
is the Hamaker constant of the particle under consideration. And the surface charge whether
the charge density is high, low which will directly affect what is the electrical double layer
repulsion and finally, the concentration of electrolyte as well.
(Refer Slide Time: 18:34)

482
So, we look at particular case and look at how each of these parameters are going to affect so,
what we are going to look at is essentially plotting this expression what we are going to do is
we will consider a case of planar surfaces. So, for which the total potential is given by this
expression and we will look at the effect of first the effect of variation of Hamaker constant.
So, what we will do here is that we take a particular case.

So, we are going to plot phi net which is scaled with kB T and we are going to plot phi net is
the function of separation distance d of course, these expression is for flat blocks or the
planar surfaces. And these plots that you see here, they are actually drawn for different values
of A212 that means, this is A212 that is, this is the blocks of similar chemical composition to
they are interacting via medium 1.

So, therefore, and they are plotted for a constant value of k that is k is 10 power 9 meter
inverse that means, the concentration of electrolyte is fixed concentration of is fixed and they
are also plotted for a case where psi not is equal to 103 millivolts. And of course, the
temperature is also fixed and the medium 1 is medium 1 that is a medium of fixed epsilon.
So, therefore, if you look at the contribution of the electrical double layer and the Van der
Waals forces.

What is kept constant in this plot is that the electrical double layer interactions are kept
constant and the only contribution that has been you know varied is what is the Van der
Waals contribution. So, therefore, what you will see is that so, this is the dotted line that you

483
see if is for the case where A is 2 into 10 power - 19 joules and this is for 10 power - 19 and
this is a 5 into 10 power - 20 and this is for 2 into 10 power - 20 joules.

Therefore, as you move in this direction Hamaker constant A increases. Now, when A
increases that means to say that for a fixed electrical double layer interaction when A is
increasing what happens is the Van der Waals contribution becomes more and more
dominant as A increases therefore, there is some energy barrier for aggregation of the order
of 3 kBT when A is 2 into 10 power - 20 joules.

However, when the value of A increases to 2 into 10 power - 19 joules that is 1 order of
magnitude you know increase you can see that the overall interaction is always attractive if
you look at this case the if I draw this line we can see that the overall interaction in that case
is always attractive that means for given separation distance that we have considered the total
interaction is always attractive. Therefore, this method gives you a way of manipulating the
overall interaction between the colloidal particles by varying the Hamaker constant of the
material being considered.
(Refer Slide Time: 23:08)

So, now, what we can do is we can consider a case where again you have phi net d is phi
electrical double layer + phi Van der Walls. So, what is done in this case is A nought is fixed
there because A nought is fixed the Van der Waals term is fixed that means, the variation of
Van der Waals force of attraction with distance is fixed and also fixed is the concentration of
the electrolyte kappa is 10 power 9 meter inverse.

484
And the temperature is also fixed 25 degrees centigrade and the medium is also fixed
therefore, epsilon is fixed. So, if you look at electrical double layer interaction when the
temperature medium and kappa is also fixed phi electrical double layer depends on what is
the surface potential. So, the so, in this particular case what is varied in the surface potential
is varied and it is varied over a wide range all the way from 103 milli volts to 257 milli volts.

Therefore, you are increasing the surface potential in this particular fashion. So, therefore,
with increasing the potential, so, what will happen is as expected, the electrical double layer
interactions will become more and more dominant therefore, if you look at the repulsive
contribution would increase as you systematically increase the electrical double layer
contraction.

Therefore, for a fixed Van der Waals force of interaction and for a given salt concentration
you can manipulate phi net or the total interactions between charge stabilized collides by
manipulating the surface potential and with the increase in the surface potential the
magnitude of repulsion would increase.
(Refer Slide Time: 25:31)

So, the third way of manipulating the total interaction potential is by varying the electrolyte
concentration. So, in this case phi electrical double layer + phi Van der walls that is phi net or
phi DLVO and again the Van der Waals contribution is kept constant here because A is fixed
at 10 per - 10 millivolts and psi nought is fixed that is the surface potential is fixed at 25.7
million volts.

485
That is the limit of the aah low potential case. And so, in this particular case, what you have
is this is drawn for two spherical particles of radius 100 nanometre that means, we are
considering two spherical particles whose radius is 100 nanometres and we are looking at the
variation of total potential as a function of separation distance and what has changed here is if
you look at the plot there is different values of k that is mentioned.

The different values of kappa and that is achieved by adding different concentration of
electrolyte into the system. So, if you move in this way kappa the value of kappa is increasing
therefore, if you move this particular way kappa inverse is increasing the fact that the kappa
inverse is increasing that means, if you increase in this if you go in this concentration the
concentration of electrolyte decreases kappa is increasing.

So, the concentration of the electrolyte decreases when the concentration of electrolyte
decreases that means, we are if you look at the total contribution to the interactions, so, the
repulsive interactions are becoming more and more dominant because the electrolyte
concentration is decreasing in this particular way. So, therefore, the system such as this so,
therefore, just to conclude a system such as this will have a higher concentration of
electrolyte.

Higher concentration of electrolyte therefore, what will happen is the electrical double layer
contribution to the total potential is weaker however, if you look at a case like this the kappa
inverse is larger that means the electrolyte concentration is lower in this case therefore, the
electrical double layer contribution becomes significant and therefore, the overall interactions
if you look at there is energy barrier that comes into picture.

Because, if you look at this scale, this is kBT at 25 degrees centigrade. So, therefore, there
exists a energy barrier for the particles to aggregate and that happens when the concentration
of electrolyte is lower. However, if you increase electrolyte concentration the Van der Waals
force such become dominant and the overall interactions if we look it up, it is positive. So,
with that we come to the end of module 4.

Where we have been able to look at a system of charged particles so, we started with looking
at the origin of surface charge. Then, we looked at the concept of electrical double layers then
we discussed electrical double layer models. So, followed by, we looked at overlapping

486
double layers and followed by that we talked about the colloidal interactions in a charge
stabilized dispersions, namely the DLVO theory so that that would be it in this module.

487
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology, Madras

Lecture – 40
Electrokinetic Phenomena and Zeta Potential Measurement

We look at new module, module 5, in which we going discuss about what is called as
electrokinetic phenomena, which is a useful tool for measuring what is called as zeta
potential. So, this is going to be the contents for this lecture. So, will briefly again recap, what
is zeta potential and we will look at some examples where zeta potential measurement
becomes important and I will introduce electro-kinetic phenomena in this lecture.
(Refer Slide Time: 00:57)

So, we have looked at what is zeta potential already. So, electrokinetic measurements are
used for measuring zeta potential which is the experimentally determined potential measured
in electrical double layers. So, this is a schematic of electrical double layer and this is how
the potential falls with distance and we have learned that zeta potential is the potential at the
plane of shear which is essentially given by this line that I am tracing.
(Refer Slide Time: 01:39)

488
So, we will so zeta potential depends on several factors the factors that influence are the
surface chemistry and the surface charge density of the particles it does depend on solution
conditions for example, pH of the fluid is important it also depends on the presence of
additives such as electrolytes and electrolytes.
(Refer Slide Time: 02:08)

Now, we look at some salient features of zeta potential for different materials. So, what you
are looking at here is zeta potential measured for two types of particles one is hematite
spheroids that is given by the black line and silica nanoparticles which is given by the red line
and the corresponding SEM micrographs of the particles are given as well. So, you can see
that the certain and what is plotted as a zeta potential as a function of pH in this particular
case, and you will see that under certain pH conditions.

489
The zeta potential is positive and under certain conditions the pH conditions the zeta potential
is negative for hematite particle However, if you look at silica nanoparticles, so, all
throughout the pH window that has been considered the zeta potential is always negative.
And the reason why the silica surface has negative value or the negative zeta potential is
because of the surface chemistry of the particle itself.

There are certain all groups on the surface of silica particles and the dissociation essentially
leads to SiO- group on the particle surface which leads the particle to have a negative charge
on the surface. So, in it is by convention, the zeta potential is positive for the particles that are
positively charged and the zeta potential is negative for the particles that are negatively
charged and you would always come across cases.

Where you will have under certain conditions you could have the zeta potential to be 0 as
well. So, in this particular case concerning hematite particle the pH at which the zeta
potential becomes zero, the potential becomes is called the point of zero charge and this is a
useful quantity because whether a given dispersion of colloids is stable or not depends on
how far you are from the isoelectric point.
(Refer Slide Time: 04:55)

So we will again look at some examples of this in the next few slides. So, what you are
looking at is connecting zeta potential measurements to sedimentation stability these are vials
of images which contain hematite particles, these are iron oxide particles and that is why the
dispersion appears reddish brown in colour. And what is done is this dispersion has been

490
prepared at certain particle concentration and the concentration of particles in all the vials is
exactly the same.

However, the dispersion ph changed from 2.0 all the way up to 12 that means, there are some
dispersions which are acidic in nature and there are some dispersions which are basic in
nature. Now, what you are looking at is again, a time sequence images, where the images of
vials have been taken at different time intervals, this is for 0 hour, this is for 2 hours, this is
after 4 hour, this is after 8 hours.

And as you can clearly see that, at least visually, what one could see is that the dispersion of
these particles at a pH of 12, you do not see any visual changes and so, is also the case if you
look at the pH 2, however, if I look at intermediate pH values, you see that at the end of about
2 hours, at pH 8, there is all the settling of particles and if you look at pH 6 and a half there is
some settling that occurs at about 2 hours.

But however, if you wait for long enough time, there is about 8 hours you see that all the
particles are essentially sedimented at the bottom. So, this example tells us that the charge of
the particular or the zeta potential is one of the important factors that can dictate the
sedimentation stability of the given dispersion and looking at you know the zeta potential plot
here.

So, if you so, the plots corresponding to so, this vials that we are looking at here, it
corresponds to the pH 2, and this corresponds to pH of 12 that has this particular point. And
however, somewhere in between we see that there is the sedimentation therefore, highly
charged particles exhibit a better stability against sedimentation versus less charged or low
charged particles.
(Refer Slide Time: 07:53)

491
The second example that I would like to point out as the application of zeta potential
measurements and how they are important in drying problems so what you are looking at is a
configuration where there is a substrate, and there is a drop and this drop contains particles
and the fluid it would evaporates because you know, if you take like say, if there is a
dispersion in water, you will see that with time, although the fluid will evaporate and the in
the end, what you end up with is that you know, on the glass substrate.

I would have the deposition of particles. So, it turns out that this simple drying problem is
important in several technological important processes, examples are inkjet printing spray
coating, and as well as deposition of pesticides and nutrients, on leaves and so on and so
forth.
(Refer Slide Time: 08:57)

492
So, if we look at the configuration that we had here, so, that is you had a glass substrate or
you had a substrate in which you had particles. So, in such an example of what is important is
the zeta potential of both the dispersed species that is the particles in this case, as well as the
zeta potential of the substrate become important. So, what is plotted here is zeta potential as a
function of pH and like we discussed earlier.

The substrate that is being used is silica surface, therefore, all through the pH window, the
glass is negatively charged. Because the zeta potential is negative, and however, because
these are hematite particles, so we have a pH window where the particles are positively
charged, and there is a pH window where the particles are negatively charged.
(Refer Slide Time: 09:57)

So, we look at some salient so, what happens in a drying problem is that when the liquid
evaporates from the free surface of the drop there is what is called as a capillary flow that is
established and this capillary flow drives the particles to the contact line. What we are
looking at is a movie where there is a dispersion of particles, these are 3 micrometre particles
3 micrometre in diameter, and we are looking at what happens at edge.

This is the boundary or the three phase contact line and with time, what happens is that this
capillary flow dries the particles and it helps in the deposition of particles at the contact line.
So, this is a classic phenomenon called what is called as a coffee-ring effect, that is because,
similar features are found when a droplet of coffee dries.
(Refer Slide Time: 11:11)

493
So, with this in mind, if we deposit or dispersion can containing elliptical particles, that is
hematite particles on a glass substrate, it turns out that there are conditions where we get a
classic coffee-ring effect. And of course, there are conditions where you get a more uniform
deposition of particles to throughout the deposit.
(Refer Slide Time: 11:41)

So, now, one could understand why such different deposition patterns have formed, even
though we have considered dispersions of similar type by the fact that the result that you see
here, this is for a case where the pH is about 2.0 and this is for a case where the pH is about
6.5. And it turns out that in the case of pH 2 the particles are highly charged and the substrate
is weakly charged.

So, in such cases, because of the electrostatic attraction between the highly charged particles
and the substrate, there is a deposition of a layer of particles on the substrate. However, once

494
a layer gets deposited, there is repulsion between the particles in the fluid and the particles
that are already deposited on the substrate. Therefore, there are a lot of free particles in the
dispersion or in the drying drop.

And these free particles are carried to the edge because of the capillary flow that we saw in
the previous video and that leads to the deposition of particles at the edge giving such a
pattern. However, if you look if you look at the case, where the pH is 6 and a half the
substrate is highly charged and the particles are weakly charged. And therefore, there are
many layers of particles deposited on the substrate, because of the fact that the substrate is
highly charged now.

So, it cannot attract more layers of particles even though there is a deposition of particles, one
layer of particles on the surface further deposition is still possible, because of the highly
charged nature of the substrate. Therefore, all the particles are kind of attracted towards the
substrate leaving no particles in the bulk therefore that leads to a more uniform deposit
formation.
(Refer Slide Time: 14:05)

So, therefore, in problems such as drying, of droplets, the fact that pH 2 you get a coffee-ring
effect and pH 6 and a half, you get a more uniform deposition, it can be explained based on
DLVO interactions, which essentially is the fact that the total DLVO interactions is a
summation of the Van der Waals force of attraction and the electrical double layer attraction.
However, in this case, the DLVO interactions have two components.

495
One is the particle-particle interactions and the particle-substrate interactions. Therefore,
depending upon the overall DLVO interaction which is the summation of the DLVO
interaction arising because of the particle presence of particles as well as the particle and the
substrate that is what governs the deposition in such cases.
(Refer Slide Time: 15:06)

So, another example of how one could manipulate the arrangement of particles on the
substrate is again from an example where there is a technique called vertical deposition. In
this technique, what is done is there is a dispersion which contains particles and what you do
is you maintain this dispersion at a certain concentration of particles and you maintain the pH
under certain conditions.

And so, you let the fluid evaporate that is if the fluid is water under normal you know
ambient conditions it would evaporate and as the evaporation of occurs, these particles that
you have the dispersion they are drawn to the three phase contact point and then the particle
start get the particles get deposited on the substrate. Now, what is done in this case is the
conditions are chosen such that the pH is about a 2, 2 and a half. Such that the; particles are
again highly charged and again a condition of pH such that the particles are weakly charged.
(Refer Slide Time: 16:25)

496
So, after the deposition if you look at the glass slides under microscope, you will see that the
sample appears reddish brown because of the fact that these are again iron oxide particles
However, if you look at the microstructure or the arrangement of particles on the substrate, it
looks very different. When the pH is 6 and a half versus when the pH is 2 therefore, when the
pH is 2 because of the fact that the particles are highly charged you have more ordered
arrangement of particles and the substrate.

However, when the pH is 6 and a half that is weakly charged particles, there is a random
arrangement of particles and the substrate therefore, one could use the zeta potential
measurements and the fact that with the change in the zeta potential measurements. The total
interactions or the contribution of the electrical double layer interactions can be manipulated
and those aspects can be exploited to obtain different self-assembly patterns and this different
deposition patterns as well as to control the stability of dispersions or the stability of particles
in a fluid.
(Refer Slide Time: 18:04)

497
So, with that background, so, we will look at what is electro kinetic phenomena electro
kinetic essentially implies a combined effect of motion and electrical phenomena. And such
phenomena are commonly observed in heterogeneous fluids when we say heterogeneous
fluids this is these are fluids containing particles and it is associated with the double layer
charges.

The fact that there is an electrical double layer around charged particles that essentially
manifests in the electro kinetic effects and therefore, such phenomenon is of interest in
studying dispersions containing charged particles and some of the examples of electro kinetic
phenomena or what is called as electrophoresis, electro osmosis, streaming potential and
sedimentation potential. So, we look at each of these aspects.
(Refer Slide Time: 19:09)

498
Before we do that, I would like to give an example of an electro kinetic phenomena that we
all of us know if you look at processes such as electroplating. So, what is done is you use an
externally applied electric current to deposit metal ions on substrate. So that you can obtain a
metal coating. So, these phenomena called electro plating and a schematic that is given to you
here is you have 2 electrodes anode and a cathode and you could have this in a bath of
electrolyte and when you complete the circuit.

When you apply in an electric current, it turns out that there is migration of ions to different
electrolytes the positive ions will migrate towards cathode and the negative ions migrate
towards the anode. So this is an a classic example of electro kinetic phenomena where there
is a combined effect of electric field combined with the motion of ions towards oppositely
charged electrolytes, in a similar way, you instead of ions in the bath, if you have charged
particles, and these charged particles would also migrate and will discuss some of the
phenomena associated with the charged particles.
(Refer Slide Time: 20:54)

So, in the next few slides, so, let us look at the migration of an iron in the electric field. So,
what you have is a we will take a simplest case where or a simple case where you have an
isolated iron you know a fluid and what is being done as an electric field is applied an
isolated electron or an ion in an electric field it experiences a force that force is given by Fel
which essentially is given by the product of the charge.

That the electron has or the ion has multiplied by the strength of the applied electric field and
in and whenever you have an ion, so, it essentially migrates towards the oppositely charged

499
electrolyte electrode because of the force that the isolated ion experiences in the electric field.
And so, whenever you have a motion of any particulate matter or any iron enough in a fluid,
we know that there is going to be some opposing forces.

And this opposing forces arise because we have what is called viscous resistance in the
medium and what this viscous resistance does is it essentially hinders the motion of the
particle and it slows down the ion that is set into motion because of the applied electric field
and this F viscous is given by f times v where f is what is called as the friction factor and v is
the velocity with which the isolated iron is moving in the electric field.
(Refer Slide Time: 22:56)

And although the particle would accelerate when the electric field applied initially, because
of the balance between the viscous forces and the electrical forces, there is going to be an
equilibrium or a stationary state is quickly reached when the equilibrium is established
between the two forces, in the absence of other effects, we can equate Fel to F viscous
therefore.
(Refer Slide Time: 23:46)

500
The velocity with which the electron or the ion is moving is given by q times E divided by f
where f is the friction factor and, because of the fact that the dimension of the isolated ion
that we are considering is very, very small the Reynolds number that is in N Rep that is the
particle number which is given as diameter the particle the velocity which is the particular
moving density of the fluid divided by mu because of the fact that the dimension of the
particle under consideration is very, very small.

That is of the order of sub nanometer. Therefore, this Reynolds number is going to be much
less than 1 therefore, we can assume that the flow is essentially low the low Reynolds number
flows. Therefore, the friction force or the drag force experienced by the isolated iron is given
by F viscous is equal to Fv is equal to 6 pi eta v times Rs where Rs is the dimension of the
spherical object or the dimension of the isolated ion that are under consideration.

So, therefore, the velocity with which the particle is moving or the velocity with which the
accelerated ion is moving is given by q times E divided by 6 pi eta times Rs. So, now I can
rearrange this expression and I can write v divided by E = Q divided by 6 pi eta into Rs and
this quantity v / E that is the velocity per unit field with which the ions are migrating that is
what is called as a electrophoretic mobility this is what is called as.

So, whenever electro kinetic measurements are done, one of the quantity that is really
extracted from electro kinetic measurements is this mobility that is the velocity with which
the particles are moving in the field for a given for a field of given strength and this quantity

501
is what will be used to relate to the zeta potential of the particles and which we will discuss in
the in the next lecture.

502
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 41
Electrokinetic Phenomena

Having discussed zeta potential and the importance of zeta potential measurement in some of
the problems, we will look at electrokinetics further.
(Refer Slide Time: 00:27)

Electro kinetics implies combined effect of motion and electrical phenomena and such
phenomena can be observed whenever you have a heterogeneous fluid that is in case you
have a particle filled fluids and if these particles are charged then you will have an electrical
double layer associated with it. So, whenever you have systems like this the electrokinetics
effects become important and such phenomena is of interest because that will help these
phenomena will help us to study charge stabilized colloids or system in which the colloidal
particles are charged.
(Refer Slide Time: 01:13)

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So, before we talk about electrokinetic phenomena in colloidal system, I would like to
introduce electrokinetic phenomena from a concept that you may already be familiar with if
you look at electroplating process in which what is done is an external electric field is applied
to a solution which contain metal ions the schematic is given here. So, there is an anode and a
cathode and you can imagine that you know there is a bath of electrolyte which contain like
say metal salts.

And whenever electric field is applied, what happens is that there is a migration of ions and
then these metal ions may get deposited on the electrode. So, that you can get a metal coating
on substrates, this is one of the commonly used techniques called electroplating. And, so,
what you see in electrokinetic in electroplating is that there is a migration of ion positive ions
migrate towards the cathode and the negative ions migrate towards anode.

And so, similar to migration of ion, if you have positively charged particles or negatively
charged particles, there will be a migration of colloidal particles similar to either the
migration of ions that we have discussed. Therefore, the electroplating process is an example
of a, phenomena where electrokinetics is observed.
(Refer Slide Time: 02:59)

504
So, there are several examples of electrokinetic phenomena that we are going to discuss, we
will mostly focus about the electrophoresis. However, there are also other techniques called
electroosmosis, streaming potential, sedimentation potential, which are also important in the
context of studying charged surfaces. So, mainly these 4 electrokinetic phenomena can be
subdivided into 2 categories, one category where charged surface is stationary and the fluid is
made to move around, fluid around it is made to move.

So, therefore, so, you could have a case where I have a charged particle for example, then
there is fluid around it. So, if this is a fluid. So, in a class of technique, the charged particle is
stationary or the charge surface is stationary. However, the fluid that is surrounding the
charge surface is made to move in other class of technique, the charge surface is made to
move while the fluid surrounding it is stationary, we will discuss some of these techniques
not in great detail, but just to give an idea of what these methods are in electrophoresis.
(Refer Slide Time: 04:09)

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Electrophoresis is very similar to what we saw in the case of electroplating. Electrophoresis
refers to a movement of a charged particle relative to a stationary fluid due to the application
of an electric field or due to the application of an external electric field. So, you have
particles in a fluid, there is an anode and a cathode. And you have a charged particle that is
depicted here. And there is an electrical double layer that is associated with the charged
particle and whenever you apply an electric field, what happens is that the particle moves this
phenomenon is what is called as electrophoresis.
(Video Starts: 05:02)
So, this is a video of an electrophoresis which is observed. So, what you are looking at is a
video where the circular dots that you see here, these are all the particles and you will notice
that the particles are moving in a particular direction until sometime let me just play the video
again. So, the particles are moving in this direction initially, after a while, you will see that
the particles start moving in the opposite direction that is now they are moving in the opposite
direction.

So, now, this is a case where you have charged particles which are in between two electrodes
and what is applied is an AC electric field and because of the alternating polarity, you will
see that the particles move in 1 direction during you know one cycle and they move in the
opposite direction in the other cycle. And you could of course, have a case where what is
called as a DC electrophoresis.

When you will see that the charged particles depending upon whether positively charged or
negatively charged they will start moving towards one of the electrodes as well. So, this is an

506
example where there are charged particles in a fluid and you set the particle into motion by
applying an external electric field.
(Video Ends: 06:32)
(Refer Slide Time: 06:33)

Now, another class of technique called electroosmosis there are two schematics here. And so,
you could think about this schematic as a case where you have a pore and say that the surface
of the pore is charged in this case it is negatively charged and what is contained between the
charge surface is an electrolyte solution and now, what you could do is that you could apply
an electric field which can be generated by you know having two electrodes and supply and
connecting two electrodes to an external supply.

So, now, when you apply electric field what happens is that the electrolyte solution that is
between the two charge surfaces is set into motion. So, electroosmosis refers to the
movement of the electrolyte surrounding a charge surface and the movement of the
electrolyte is achieved by the application of an electric field. However, the charged surface is
stationary therefore, the electrolyte solution moves with the charge surface being stationary
therefore, there is a relative motion that is set in because of the applied electric field.

The pressure that is necessary to balance the flow that is set up because of the applied
external electric field is what is called as electroosmotic flow and this pressure which is
called the electroosmotic pressure can be easily measured and one could correlate the
electroosmotic pressure to the charged of the surfaces that we know we would like to
investigate. So, therefore, in this technique, what is set into motion is the electrolyte and the

507
motion is set by an applied external field and what is measured is the osmotic pressure and
that can be related to the charge of the stationary surface.
(Refer Slide Time: 09:11)

On the contrary, in what is called as a streaming potential what is done is the electrolyte is
made to move by applying a pressure gradient we know that whenever you have a charged
surface and if there is electrolyte, which is in between these two charge surfaces, I can set up
a fluid motion by applying a pressure gradient. And because of the fact that now you have
charged species in the electrolyte their motion is going to induce an electric field.

And that electric field is what is measured in streaming potential the effective electric field
that has developed is what is called as a streaming potential. So, the difference between the
electroosmosis and the electro and the streaming potential is essentially that the phenomena
are similar that is you have stationary charge surfaces in both the cases and what is moving is
the electrolyte however in the electroosmosis, the electrolyte is made to move by applying an
external electric field. However, in the case of streaming potential the electrolyte is set into
motion by applying a pressure gradient.
(Refer Slide Time: 10:48)

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The last of the electrokinetic technique is what is called as sedimentation potential. So, we
know that if you have a system that contains particles and these particles can sediment to the
bottom of the container either because of gravity or centrifugal force. So, if the fluid density
is like say rho fluid and if the particle density is rho p. So, we know that rho p minus rho f is
an important parameter which will dictate whether there is going to be sedimentation of
particles which is driven by gravity or centrifugal force.

If there is a large difference between the densities of the particle the fluid we can expect that
the gravity settling would be a prominent. However, if the delta rho or the density difference
is small then you know one could you know make the particle settle by the application of an
external field. Now, if these particles are charged let us consider these particles are positively
charged now, because of the fact that you have charged particles now, and the motion of
these charged particles can set up an electric field.

So, now, if you look at individual particles, so, we know that I have a particle that is charged.
Now, every charged particle would have an electrical double layer associated with it, so we
know that there is going to be a counter ions in solution and more counter ions as we go away
from the surface. And of course, there is going to be co-ions as well. Now, because of the so,
when the particles are stationary, this electrical double layer around a charged particles is
symmetric.

However, when the particles move because of the gravity, there is going to be a distortion of
the electrical double layers that means if they are moving in a particular direction you will see

509
that the charged particle is here. Now, the electrical double layer around it is going to be
somewhat distorted with more counter ions in one region versus the other. So, because of
which the system of the colloidal particle and associated double layer looks more like a
dipole.

So, whenever you have charged particles settling, you can imagine that instead of a colloidal
particle, every particle and electrical double layer combination can be imagined like a dipole
and the summation of all these dipoles will lead to an effective electric field and that effective
electric field that has developed is what is called as sedimentation potential therefore, if you
essentially take 2 regions.

For example, region 1 here and region 2 here and if you measure the potential difference,
there is going to be a potential difference that has developed that will depend on the
concentration of the particles that you have the surface charge and the particle and a lot of
other parameters and this potential difference can be measured and that potential is what is
called as a sedimentation potentials therefore, so one could measure sedimentation potential
and of course, this can again be related to the charge of the particle or the zeta potential as
well.
(Refer Slide Time: 15:07)

So, now, we will look at electrophoresis in a little bit more detail. So, before we talk about
electrophoresis of a, colloidal scale particles.
(Refer Slide Time: 15:24)

510
What we will do is? We will consider a simple case of electrophoresis of an ion in an electric
field. So, what you have is a positively charged ion it could be ion with any polarity. So, there
is an anode and there is a cathode now, an isolated electron in a or an isolated ion in an
electric field experiences a force that is directed towards the oppositely charged electrode so,
if you have a positive charge it will move towards cathode and if you have a negative charge
it will move towards anode.

So, that force essentially is proportional to the strength of the electric field that is applied the
strength of the electric field times the q that is the charge of the isolated ion essentially gives
you the force that the isolated ion is experiencing. So, initially the ion could be stationary or
it could be moving about because of the Brownian motion. However, once the external field
is applied, it will move with this force towards the oppositely charged electrode.

So, when the electric field is applied, so, first the ion is going to accelerate, that means there
is going to be a sudden increase in the velocity of the isolated ion. However, this initial
increase is going to die down with time that is because, you have and that is because there is
an opposing forces that comes into pictures. So, because of the fact that whenever there is a
relative motion between the particle and the fluid so, this ion is set into motion.

Now, whenever there is a relative motion between the ion and the fluid that is surrounding it,
there is going to be a viscous force that can come into picture and this viscous force is going
to oppose the motion of the isolated ion and this force F viscous is given by some friction
factor f times the velocity with which the isolated ion is moving.

511
(Refer Slide Time: 18:13)

And soon an equilibrium will be set up between the two forces that are acting on the isolated
ion and that is established when the two forces that are acting on the species are equal
therefore, we could equate the electrical force that has generated because of the applied
electric field and the viscous force that is f times v that is set up because of the drag that the
moving ion experiences in the fluid. So, therefore, so, we could obtain an expression for the
velocity with which the fluid is moving in the, we can obtain an expression for the velocity
with which the ion is moving in the fluid and that is given by q times E/f.
(Refer Slide Time: 19:14)

Now, because we are dealing with species that are very, very small, the dimensions of these
species are going to be you know of the order of sub nanometer. So, whenever you have such
small species, if you calculate the particle Reynolds number, which goes as diameter of the
ion that we are considering, times the velocity with which they are moving times the fluid

512
density divided by viscosity of the fluid because of the fact that the dimension of the species
are very, very small.

This Reynolds number if you calculate it will be much, much less than 1. So, under such
condition these you can refer to this as a low Reynolds number flows therefore, we could use
stokes law and therefore, the friction factor f can be replaced with 6 pi eta times RS this
essentially comes from the F stokes the stokes law for low Reynolds number force therefore,
in v = qE/f we could replace f with qE/ 6 pi eta into RS.

So, therefore, we end up with an expression which is the velocity with which the particles are
moving with which the ions are moving in the field goes as q times E / 6 pi eta times RS. So, I
can rearrange this expression further I can write this as v / E = q / 6 pi eta into RS and this
quantity v / E is what is called as electrophoretic mobility that is the velocity with which the
isolated ion is moving in the presence of an applied electric field of a given strength is what is
called as mobility or the electrophoretic mobility.

And for simple ions, the typical value of electro phoretic mobility would be of the order of 10
power -8 to 10 power -9 meters per second inverse divided by volts per meter. So, if you look
at this expression that E that is the electric field that is applied it is measured in terms of volts
per meter. So, that is because, whenever one does electrophoretic experiments typically you
have an anode and a cathode which are anode and a cathode which are separated by some
distance some known distance like say d.

And so, you can manipulate the electric field that is applied by considering distance different
distance between the electrodes. Therefore, the strength of the electric field that is applied in
an electrophoretic mobility experiment is typically expressed in terms of volts per meter.
Therefore, you will have units of a meter inverse that is from the numerator and E that is
volts per meter, which is the unit in which the applied electric field is measured in
electrophoretic mobility measurements.
(Refer Slide Time: 23:06)

513
So, now, we would like to what we would like to do is to extend the concept that we have
discussed about the electrophoretic mobility of the isolated ions into electrophoretic mobility
of charged particles. We will do that in the next class.

514
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 42
Relation between Electrophoretic Mobility and Zeta Potential - 1

So, far we have looked at mobility of an isolated ion in an applied electric field. So, what we
will do now is, we will extend this concept to understand what is the mobility of isolated
colloidal particle in an electric field?
(Refer Slide Time: 00:30)

So, mobility of the isolated ion is given by u which is the velocity with which the ion is
moving per unit field it depends on the charge of the isolated ion, eta is the viscosity of the
fluid and RS is the dimension of isolate ion that we are considering. If, we want to estimate q
from this expression, that is the charge of the isolated ion which you can relate again to zeta
potential of in the case of a charged colloidal particle.

What we should know is we should know what is the velocity, but however, because the ions
are very, very small in dimension v cannot be measured. Therefore, what one does is you can
actually measure the conductance which is the reciprocal of the resistance and if you know
the conductance and from Faradays constant you can actually calculate what is u. Therefore,
from the calculated value of u I can actually calculate what is the charge of the isolated ion?
That is under consideration.

515
So, we can extend the same concept to essentially obtain the mobility of an isolated particle
in an applied electric field. However by treating that the charged colloidal particles are what
are called as larger ions or the macro ions. Instead of so, if you look at isolated ion so, you
could have ions of different valency they could have z times e, where z is a valency of the
ions multiplied by the charge of the electron is what gives the total charge of the isolated ion.

However, so, we know that z = + 1 or + 2 or + 3 depending upon whether we are considering

a monovalent, divalent or trivalent ions. However, so if we can assume that when you have a
charged particle that is, which has a large number of surface groups on the surface of the
particle, so you can say that, we can still say that q is z times e however, we do not know
what is z, because it depends on the total number of dissociable groups on the surface or the
total number of adsorbed ions on the surface of the particle.
(Refer Slide Time: 03:17)

So, however, when one is dealing with the mobility of isolated particles, the studying
mobility of colloids is much simpler than small ions, because the velocity with which the
particles are moving in a given under the influence of a given external field can be
experimentally measured by direct visualization. So, what I can do is you could have you
know, two electrodes there could be particles in a fluid and I can look at video of the
migration of particles.

Then, you could track these particles in different frames for example, if this is a time t1, these
are the position of the particle, I can say that this would have moved some further location
under the influence of the field. So, therefore, I can calculate what is the displacement of the

516
particle and if I know what is the displacement and the time that the particle has taken for the
movement I can actually calculate velocity directly from simple experiments.

This can be either done by using microscope or one could use light scattering techniques to
detect the position of the particle. So, therefore, once the velocity and the field that is
responsible for the motion of the particles are known, one could actually calculate what is the
mobility directly from experiments? Therefore, studying electrophoteric mobility of particles
is much, much simpler than studying the mobility of ions because we have a chance of
directly visualizing the motion of the particle in the presence of an electric field.

So, for colloidal particles the mobility is known as what is called electrophoteric mobility.
And the phenomena, that is associated with this is what is called the electrophoresis. And one
often combines a microscopy experiment with electrophoresis. Therefore the technique by
which the mobility can be measured when an isolated colloidal particle moves in a field is
what is called as a micro electrophoresis.
(Refer Slide Time: 05:38)

So, now, if you want to calculate, so while u can be readily measured for colloids by doing
simple experiments as we discussed its interpretation is a little bit more difficult than for
simpler ions, because, once you calculate q for an isolated ion, we know that you know it
could, the charge could be either e or 2 times e or 3 times e, depending upon what kind of
ion, one is dealing with.

517
However, the charge carried by colloidal particles is not a known quantity therefore, and of
course, it could vary depending upon the number of charges on the surface and other factors
such as presence of electrolyte in the solution. So, therefore, and moreover if you want to
estimate what is q that is the charge of the, charge carried by the colloidal particle in this
expression RS is again an unknown quantity.

Because RS which is the size of the colloidal particle or the radius of the colloidal particle that
is being investigated is an unknown quantity. So therefore, what one could do is instead of
having an unknown quantity, you could use Stokes Einstein relation and substitute for RS that
is the radius of the particle under consideration in this case, we are specifically considering a
spherical particle. Because the Stokes Einstein equation that has been written up here is valid
for a spherical particle moving in a fluid.

So, therefore, u which is q / 6 pi eta into RS, instead of RS, so what we will do is we will
substitute kBT / 6 pi eta into D. Therefore, so we have 6 pi eta and 6 pi eta get cancelled.
Therefore, the electrophoteric mobility goes as q times D / kB T where D is the diffusivity of
the particle.
(Refer Slide Time: 07:46)

So, therefore, a combination of diffusion experiments which will help us to find what is the
diffusion coefficient of the particle and if you combine that with electrophoresis experiment,
which give us what is the value of the electrophoteric mobility. Therefore a, combination of
these two experiments are necessary to evaluate the charge of the colloidal particle. And of
course, the equation that has been developed here it is valid for situations when the charged

518
particle is considered in isolation from other ions which is of course, which is not the true
case.

Because we know that there are going to be counter ions and there is going to be an electrical
double layer as well. So, all these are going to complicate you know the issues. However, this
expression can be used when we assume that the charged particle under consideration is in
isolation compared to other ions, which is an assumption in developing this expression. And
because of the fact that the charged particles would always have an electrical double layer.

Therefore, the migrating unit that in the electric field is not only the particle plus the
associated electrical double layer along with the particle is what is a migrating unit.
Therefore, one has to exercise caution when one is using these expressions.
(Refer Slide Time: 09:20)

So, now that we know about the mobility of the isolated ions and electrophoteric mobility of
charged particle, what we will do is we will develop expressions for relating electrophoteric
mobility to the zeta potential.
(Refer Slide Time: 09:40)

519
And so, for that what we will do is, we will go back and look at module 4, in which we
looked at potential distribution around charged surfaces. And because we are dealing with
mobility of a charged particle of radius RS, we will consider a case where there is a spherical
particle of radius R and that is being set into motion because of the applied electric field.
Therefore, what we will do is, we will consider a case where we would like to obtain the
potential distribution around a spherical surface.

How does the potential psi varies with distance or from the surface of the spherical particle?
And in specific we will consider the Debye Huckel approximation, which is valid for the low
potential cases. The starting point that we had considered is a linearized Poisson Boltzmann
equation, which is 1 over r square into d / dr of r square d psi / dr = e square / epsilon kBT
sigma i ni infinity zi square times psi, this is kappa square.

So, in order to solve this equation, which is the 1 dimensional Poisson Boltzmann, linearized
Poisson Boltzmann equation in the spherical coordinates, we will introduce a variable x such
that x = r times psi, therefore, I can rearrange this expression as d / dr of r square into d psi /
dr is equal to instead of this term there psi here, instead of so what we will do is, I have taken
there was 1 over r square here, I have taken r to the right hand side.

Therefore, I have r square into kappa square in the right hand side times d psi. I can write this
as d / dr of r square into d psi / dr. Because we have introduced x = r times psi, therefore,
what I can do is, we will rearrange this. I can write this as r times kappa square times r times

520
psi, that is what I have here. So this term, I can write this as r times kappa square into r times
psi, therefore I have r times kappa square times.

Instead of r time psi I have replaced it with x because we have used a new variable x. But, if
you look at the left hand side d / dr of r square into d psi / dr, I can write this as d / dr of r
square into d / dr of x / r, because I am going to replace instead of psi I have x / r now. So
therefore, if I differentiate the term in the bracket, so I what I will get is d / dr = r square into
d / dr of x / r. This term essentially is 1 over r dx / dr - x / r square.
(Refer Slide Time: 13:45)

So, therefore, the left hand side term that is d / dr of r square d psi / dr can be written as d / dr
of r square into 1 over r dx / dr - x / r square. I can take r square, inside the bracket. So
therefore, this essentially becomes d / dr of there is one r and one r gets cancelled. Therefore,
I have only one r there, minus times dx / dr - x. Therefore, d / dr of r square d psi / dr
essentially becomes d / dr of r dx / dr - x which is equal to r into d square x / dr.
(Refer Slide Time: 14:45)

521
So, therefore, what we have done is we have been able to, the left hand side has been
simplified to r into d square x / dr square, that is what we have done here. And the right hand
side is kappa square into x, where x is r times psi. And the general solution of an equation of
this sort is given by x = A times exponent - kappa r + B times exponent kappa r. We can
substitute back for the value of r here. So, therefore instead of, so because we have x here, so
I can replace this with x is r times psi, and I can take r onto the right hand side essentially I
end up with psi = A / r times exponent of - k times r + B / r exponent of k r.
(Refer Slide Time: 15:57)

Of course, we can invoke the condition that the potential psi should go to 0 when x tends to
infinity because if you have any charged surface whether it is positively charged or
negatively charged, we know that if you go to a distance sufficiently far away from the
surface of the particle, so essentially the total potential at a very large distance is going to be

522
0. Because of the fact that the total number of positive co-ions and counter ions in a solution
is going to be essentially same.

Therefore, it turns out that this is true only when B is going to be 0. Therefore, the condition
that psi tends to 0 as extends to infinity gives us a condition that B = 0 that is one of the
integration constant can be left out. Therefore, psi essentially becomes A times exponent of
minus k times r / r. Now, if we consider the limit of infinite dilution, that means we have
added a really large number of salt. In such a case, we know that a potential psi.

So, electric field E is minus d psi by electric field E is q times E is force and therefore, and
because of the fact that E goes as - d psi / dx, d psi / dr in this case, we know that the potential
should be 1 over 4 pi epsilon into q / r this comes from the basic physics. So therefore, as k
tends to 0 that is infinite dilution case equation 1, that we have developed and this expression
should converge.

And that can only happen if, A takes a value of q / 4 pi epsilon. Therefore, the expression for
the potential essentially goes as psi = 1 over 4 pi epsilon into q / r that is the constant that is
derived, that is the constant that is A. So, therefore, psi goes as q / 4 pi epsilon into 1 over r
exponent of minus kappa times r.
(Refer Slide Time: 19:12)

So, therefore, and we know that zeta potential is defined as the potential at the plane of shear.
Therefore, the potential psi tends to zeta when r goes to RS, where RS is the radius of the
spherical particle that we are considering. So, therefore, I can use this condition and write this

523
expression as zeta = 1 / 4 pi epsilon q divided by instead of r, I have RS here, exponent of
minus kappa times RS.

Now, if we invoke the condition of small k times RS. We will talk a little bit about what this
condition essentially means zeta goes as 1 over 4 pi epsilon q divided by RS. So, I can take
this to the denominator, I can write it as 1 over exponent kappa times RS .So therefore, and I
can use a series expansion for exponent k times RS. So, I can write it as 1 + k times RS + k
kappa square RS square / 2 factorial and higher order terms.

And because we are considering a case of small k times RS, we can neglect the higher order
terms, therefore zeta becomes 1/4 pi epsilon into q/RS times 1 / 1 + k times RS and because k
times RS is small, I can write zeta as q / 4 pi epsilon into RS.
(Refer Slide Time: 21:00)

So, therefore, for small k times RS by using linearized Poisson Boltzmann equation for the
spherical particle system, we have been able to show that the zeta potential is given by 1/ 4 pi
epsilon into q / RS. However, we have for the case of an isolated particle moving in a electric
field, we have derived that u goes as q / 6 pi eta into RS. So, I can replace for q from this
expression.

So, I have q, I can write q as zeta times 4 pi epsilon into RS that comes from this expression /
6 pi eta into RS. So, this, this gets cancelled. So I have pi and pi also gets cancelled and
therefore, you end up with 2 / 3 factor multiplied by zeta epsilon / n. Which is what is called

524
as a Huckel equation, which is valid when k times RS is small more specifically, when k
times RS is less than 0.1.
(Refer Slide Time: 22:27)

So, the case that we have considered here is valid for a situation which is what is called as a
thick double layer, because of the fact that you know the k times RS, this expression is valid
for k times RS is less than 0.1. I can rearrange this and I can write this as RS / k inverse, where
k inverse is the thickness of the electrical double layer. Therefore, this condition is met when
k inverse that is the thickness of the double layer is much, much larger compared to the
dimension of the particle.

So, therefore, this Huckel equation can be used to obtain zeta potential from the mobility
measurements when we consider a case where the electrical double layer is thick that will
occur when the concentration of electrolyte in the system is very, very low, that is in the case
of dilute electrolyte conditions.
(Refer Slide Time: 23:30)

525
Now, we would like to look at a case where the other limit that is when k inverse that is the
thickness of the double layer is very, very small that is that will occur when this k times
kappa inverse is very, very small. So, this kappa times RS would be very large, that is larger
than about 100.
(Refer Slide Time: 24:03)

So, for this, what we are going to do is, so we will consider a situation where the thickness of
the electrical double layer is negligible compared to the radius of curvature R of the particle
or any surface that we are considering. And there, so essentially we are considering the thin
electrical double layer limit. So, this derivation that we are going to do, it is applicable for
any geometry as long as the radius of the curvature is large compared to a kappa inverse
which this condition is of course met.

526
When we consider flat place for which the radius of curvature is infinity. So, therefore, that is
very large compared to kappa inverse. And so, this k times RS being large is met when the
concentration of electrolyte is relatively high. That means we have added a very large
concentration of electrolyte in the solution. So, that the electrical double layer is compressed
that means, the dimension of the electrical double layer is very, very small.

Or for case where R that is a RS that is a radius of the particle is much, much larger compared
to much, much larger that will of course, occur if you consider flat particles or when you
have cases where the we are considering slightly curved surfaces. So, therefore, both these
conditions lead to k times RS being very, very large.
(Refer Slide Time: 25:47)

So, whenever a colloidal particle is set into motion in the presence of an electric field, the
fluid element around the particle is also going to move. So, therefore, what we got to do is to
consider a fluid element, which is in the immediate vicinity of the charge surface. And we are
going to do a force balance that we did when we looked at motion of a particle in the fluid.
So, for that what we will do is we will consider a volume element of area A.

And the thickness of the volume element is dx that is what is represented here. That is the
thickness of the volume element and the area is given by A and there is an electric field and
that is applied and because of the electric field that is applied, the particle is going to move in
a particular direction, and it is going to drag the fluid in the immediate vicinity also along
with it.

527
So, what we could do is, we could write an expression for the viscous force that is acting on
the face nearest to the surface of the particle. So, if you consider that the particle is here, so
we can say that at distance x, the viscous force that is acting on the fluid element that we are
considering, is given by eta times A / dv / dx, that comes from the Newton’s law of viscosity
and at a distance x + dx, the force exerted is given by F = eta times A dv dx at x + dx.
(Refer Slide Time: 27:44)

Therefore, the net force that is acting on the volume element is given by which is F viscous is
F at x + dx - F at x, therefore, F viscous becomes eta times A d square v / dx square into dx.
This essentially comes from the definition of the double derivative. And however, we know
that, although the particle will accelerate initially, at some time, there is going to be a
stationary state or a steady state that is going to be achieved.

And that occurs because there is an equal and opposite force that is also exerted on the
volume element. And considering that the volume element in the immediate vicinity of the
charged particle will have ions in the volume element that means we are going to have co-
ions and counter ions present in this volume element. So, there is going to be an electrical
force that will come into picture which is given by q times E.

Now in this case, in the earlier case we looked at q is the charge of the particle. However,
when we are considering a volume element, we are going to write q as the charge density that
is rho star, which is the total charge per unit volume that multiplied by the volume of the fluid
element that we have considered. That will give me what is the total that it gives me the
charge contribution and that times the applied electric field is what gives Fel.

528
So, however, we know that rho star, that is the charge density, it is I can invoke the Poisson
equation again for the variation of potential in 1 direction and the velocity with which the
particles that we are, that is the fluid element that we are considering. So, we are looking at a
plane which is perpendicular to the surface of the particle, therefore the movement of the
particle is only in x direction.

That is perpendicular to the surface so, therefore, because of, I can use the Poisson equation
and write Fel as there is A times dx that is the volume that we had here. And instead of rho
star, I am going to substitute this with E times d square psi / dx square. Of course this is going
to be a negative sign. So, this particular equation that we have written up, this equation
applies to the region very next to the charge surface.

Because we know that if you go to sufficiently far away distance the potential is going to
become 0, therefore this force is not going to be existent at all. So, therefore, F electrical is
equal to - A times epsilon E, d square psi / dy / dx square times dx, is applicable to a fluid
element, which is in the immediate vicinity of the charged surface.
(Refer Slide Time: 31:12)

So, therefore, we will again go back to the force balance, so we had written that F viscous
should be equal to F, electrical when the stationary state is reached. So, that is the expression
for the viscous force that we have developed, and that is the expression for the electrical
force. So, the A on both sides gets cancelled, I can write this as d / dx of eta times dv / dx
times dx = - E times d / dx of epsilon times d psi / dx.

529
If I integrate this, so I will get this term is equal to this term plus an, integration constant. And
because of the fact that if you look at a fluid element that is at a very large distance from the
charge surface, the velocity is going to be 0, because the only the fluid that is in the
immediate vicinity of the particle moves along with the particle. So therefore, v = 0 that
therefore, dv / dx = 0 and of course, the potential is also is 0. Therefore, d psi / dx is also
equal to 0. Therefore, we can invoke these conditions and set C1 = 0.
(Refer Slide Time: 32:42)

So, now that the force balance is given us this expressions I can integrate this expression
further integrating dv eta times integration of dv = - E times epsilon integration of d psi. If
you look at the limits here, so we have used the limits for velocity from v to 0 and when the,
so, if you look at, so the v is the velocity with which the particle is moving and therefore, the
velocity with which the fluid is also moving is also the same.

And if I substitute these integration limits, eta times v becomes minus E times psi times zeta.
Therefore, the electrophotereic mobility u which is given as v divided by the strength of the
applied electric field is equal to epsilon times zeta / eta. So, this expression is what is called
as a Helmholtz Smoluchowski equation for the mobility. We will just look at these limits.

So, we know that, so when, if we assume that this is the fluid element that is very next to the
particle surface. We know that when at the surface of the particle, the velocity of the fluid
and the velocity of the particle have to be same, and that is the velocity v, with which the
particles are moving, at that location the potential is given by zeta. And however, if you look

530
at a very far away distance from the surface that is when the velocity becomes 0 that is the
potential is also 0.

Therefore we have used the condition that when velocity is v the potential is going to be zeta
and when the velocity is 0, the potential essentially is 0. So, therefore, the electrophoteric
mobility which is v / E goes as epsilon times zeta / eta for the case of thin double layers.
(Refer Slide Time: 35:46)

So, therefore, we can both, so we have developed two expressions one which is valid for
kappa times RS less than 0.1 other for kappa times RS greater than 100. So you can write the
expression for the relation between u and zeta in a, as a single expression where u is given by
C times epsilon times zeta / eta and the constant C takes a value 2 / 3 when kappa times RS is
less than 0.1.

And the constant C takes a value of 1 when the kappa times RS is greater than 100. So, this is
the case of thick double layers and this is the case of thin double layers. And the fact that the
coefficient is 2/3 in this case and 1 in this case, you can say that the mobility in the thick
double layer case is smaller than the mobility in the case of thin double layer and that makes
sense.

Because of the fact that whenever you have a thick double layer, there is going to be an
additional drag that will come into picture because of the electrical double layer, thick
electrical double layer around the charged particle and that is going to slow down the motion
of the particle. Therefore, the mobility that is measured is smaller than the case when the

531
mobility is going to be measured when the kappa inverse is very, very small. That is the case
of very thin double layers.

532
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology, Madras

Lecture - 43
Relationship between Electrophoretic Mobility and Zeta Potential - II

So far we have developed what are called as Huckel equation and Helmholtz-Smoluchowski
equation for relating electrophoretic mobility to zeta potential. Now, we will look at what is
called as a Henry's solution for the same before we do that a quick recap of the 2 equations.
(Refer Slide Time: 00:37)

So, one is what is called the Huckel equation, and other one is Helmholtz-Smoluchowski. So,
that is a general expression with C taking a value of 2/3, for Huckel’s limit and C taking a value
of 1 for Helmholtz-Smoluchowski equation. So, and as we have discussed, so, these solutions are
applicable only for certain condition that is when k times R is less than 0.1 or k times R is greater
than 100.
(Refer Slide Time: 01:15)

533
So, just to talk about the need for developing Henry's equation, what you have is a plot of Rs that
is the radius of the spherical particle. And on the x axis you have the concentration of the particle
expressed in moles per liter. And for the concentration that I know, that are given, I can calculate
what is kappa because we know that there is an expression that relates kappa to the concentration
of colloids. So, therefore, I could calculate what is kappa times Rs value?

So, let us take, so, what you see is there are 2 lines, this line is what is called as a that is the
Huckel limit, and this line is what is called as represents the Helmholts-Smoluchowski limit. So,
what I mean by that is, let us take some particular value of kappa. So, if I take kappa value of 10
power 10 and if I take some dimension of the particle to be 10 power - 5 that means, if I go to a
region there, so, therefore, kappa times Rs is going to be 10 power - 6 times 10 power 10
therefore, you are going to have 10 power 4.

So, therefore, kappa times Rs in this case is larger than 100 therefore, one could use the
Smoluchowski limit for you know converting the mobility value that have been measured to
obtain the zeta potential. However, if I take like say a typical value for example, 10 power - 9 is
the particle dimension that is, now we are talking about in this case we are talking about 10
power - 9 meter is the dimension that means, we are talking about nanoparticles the particles are
1 nanometer in size.

534
So, therefore, and if I take a corresponding kappa value to be 10 power 7 therefore, kappa times
Rs takes the value of 10 power - 9 times 10 power 7, so, which is 10 power 0.01. So, therefore,
or 10 power - 2. So, therefore, again what we have considered now, it again falls into the regime
of k times Rs less than 0.1 because, the value of k times R is that we got is 0.01. So, therefore,
so, if I take for any value of Rs and kappa in this range, so, we can use the Huckel limit and for
when you value of R and kappa, which fall into this regime.

So, we could use Helmholtz-Smoluchowski limit and then we can convert the mobility values to
zeta potential. However, there is a large region of particle sizes and the concentration of
electrolyte range where there is a lot of work that occurs both in terms of formulations both in
terms of you know, tuning the stability and causing the destabilization of colloids. So, it so
happens that in the colloidal in the domain of colloidal science, which is of practical relevance.

You will have always have a range of kappa times Rs which is more than 0.1 and less than 100.
So therefore, so we do not have any expression that relates mobility to zeta potential in that
range, and to this end, Henry's solution would develop. So, Henry solution is a general solution
that is, that relates mobility to zeta potential for any value of kappa Rs that is both, it combines
the Huckel limit at one end, and Helmholtz-Solumochowski limit at the other end. And, of
course, it is also applicable for any range of kappa times Rs between 0.1 and 100 as well.
(Refer Slide Time: 05:40)

535
So, the general expression that Henry's developed for the mobility is given by this. And so if you
want to obtain mobility, all you need to know is how does the potential psi varies as a function of
R. And so therefore, this R in this case is the radial distance from the center the particle. And so,
one could simplify this expression to obtain the expression for mobility, if we know how the
potential varies with R, so what we will do is we will take a simple case of Poisson Boltzmann
equation.

And that for a spherical particle, we have derived that psi goes as A times exponent of minus
kappa r divided by r, therefore, now, if I substitute for the fact that the potential becomes zeta
potential add r going to Rs, therefore, I would have there is a mistake here, so, this A should not
be there. Therefore, this A becomes zeta potential, that is here times Rs, that is here multiplied
by exponent of minus is going to be divided by exponent of minus kr or exponent of plus k times
Rs.

So, therefore, if I substitute the value of A back into this expression, we will end up with psi =
Rs into zeta divided by r exponent of - k times r - Rs. So, therefore, now, I know that how the
potential varies with R, therefore, one could substitute the equation back here.
(Refer Slide Time: 07:41)

And then if you do a simple integration, so, you will end up with Henry’s expression for
mobility, which is given by u times 2/3 epsilon zeta divided by n, where eta is the viscosity of
the fluid in which the particles are dispersed and a term f of alpha and f of alpha depends on what

536
is the kappa times Rs value. So, if for kappa times Rs less than 1, it takes this functional form
and for alpha greater than 1, it takes this function form. So, we could quickly cross check that if I
take alpha = k times Rs of the order of 100, that is much larger than 1.

So, therefore, f of alpha becomes 3/2 minus and because we are talking about alpha to be 100,
therefore, you have 9/2 times 1 over 100 time and so, therefore, the all the terms can be
neglected. So, you will end up with f of alpha = 3/2. Therefore, expression u = 2/3 epsilon zeta
divided by eta times 3/2 for kappa times r about 100. Therefore, u becomes epsilon into zeta by
eta. Therefore, we essentially recover the Helmholtz-Smoluchowski limit.

And similarly, if you take the expression that corresponds to alpha less than 1 therefore, if I take
alpha to be very small for example, k times Rs is of the order of say 0.1 then again what will
have is f of alpha will become 1 plus again I can neglect the higher order term. Therefore, in
such a case u becomes 2/3 into epsilon zeta by eta times 1 again we recover back the Huckel
limit. So, therefore, the Henry's expression for mobility is a general solution that is applicable for
obtaining you know, the zeta potential measurements zeta potential values from the mobility
measurements for any given value of kappa times Rs.
(Refer Slide Time: 10:09)

And Henry's expression for mobility is derived by assuming that and as I said that so, it is
applicable for Henry's in a solution is applicable for the entire range of the Rs times kappa value
Rs and values of Rs and kappa that are important from a practical point of view and Henry's

537
expression from mobility is derived by assuming that the external field we know that the external
field that is applied to the colloidal particle in a fluid.

It will also be disturbed by the presence of the particle and of course, this field is also going to
influence the electrical double layer as well and Henry solution is derived by assuming that the
external field is and the field that is developed because of the electrical double layer are additive
and it is applicable for a non conducting particles therefore, if one for inert particles like such as
polystyrene or PMMA or you know particles of that sort in once you know there are particles
that are conducting like gold or any metallic particle.

One has to be careful in using these equations and it is also applicable to cases where the colloids
are present in small concentration that is, so, that the colloid-colloid interactions can be ignored
and in obtaining Henry's solution the diffuse double layer is described by the Gouy Chapman
theory therefore, it is that means, the Henry solution is applicable for symmetric electrolyte. So,
therefore, one has to make sure that appropriate expression for the mobility and appropriate
mobility zeta potential relation is used in order to obtain the correct values of zeta potential.
(Refer Slide Time: 12:26)

And so, what you seeing is a plot where the constant C that is, so, we wrote that mobility u goes
as some constant C times zeta epsilon divided by eta that is what we had developed that is
somewhere here. So, therefore, and we know that C takes a value of 2/3 for the Huckel limit and

538
it plateaus and then takes a value is equal to 1 when the k times Rs values are large. And
however, if you take you can already see that when the k times Rs becomes of the order of 1.

That somewhere here you already see that you know the constant C deviates from this terminal
values. Therefore, that means, the value of constant in the intermediate range deviates from the
values that correspond to the terminal state that is you know of the order of 0.1 and more than
100 and it varies the nature of variation is actually captured by Henry's equation and you will see
that so, what you see in the plot is that the variation of the constant C is plotted for different zeta
potentials.

That is going from very low potential to of the order of 100 millivolts which is a case of a highly
charged particle and this is plotted for 1 is to 1 type of electrolyte and you will see that when the
charge of the particle becomes really large that is when the zeta potential becomes considerably
large you will see that the value of the C that is obtained it deviates significantly from what is
predicted by Henry's equations.

So, therefore, one has to exercise caution as to what is the typical value of the constant that one
should use and that depends on several factors including the zeta potential of the particle or the
surface charge in the particle and the electrolyte that we are considering and other factors as
well.
(Refer Slide Time: 15:11)

539
With that in mind, so, now, we would like to develop an expression for relating the surface
charge q and the zeta potential and, the reason why an expression for q could be useful is that
there are several techniques which are available, where the charge of the particle can be
measured directly by certain technique such example or a couple of example could be
conductometric methods and potentiometric methods and these are titration based method in
which what you do is you consider a colloidal dispersion containing particles.

And you add some additive and monitor, for example, the change in the conductivity and at
certain condition there is there will be an abrupt change in the conductivity and from that you
can back calculate what is the charge. So, now, if there are techniques that are available, which
enable us to get the charge directly, and if there are technicals, there are techniques where zeta
potential can be measured, in order to compare the 2 different techniques you know the
applicability of different techniques.

There should be a relation which will from which I should be able to back calculate one from
other. So, in that context, so, what we will do is, we will try and develop an expression for our
relation between the surface charge q and the zeta potential and for that we will consider the case
of a charged particle charged spherical particle to be more precise, and what we are going to do
is we are going to invoke the condition that the net charge that the particle carries is equal and
opposite to the total charge in the electrical double layer.

And this condition is kind of met when in one works with particles dispersed in like say salt free
solutions, for example. And what we will do is we will consider a thin shell of dimension dr
which is located in distance r. And so, the total charge q or the charge in this thin strip is given
by the charge density that is the number of charges per unit volume multiplied by the volume of
this you know thin shell.

And if you want to calculate the total charge q, you can integrate this expression or the whole
double layer that means, q is given by and you have a negative sign, because the charge on the
particle and the charge in the double layer they are equal and opposite in sign. And therefore, q
can be obtained by integrating this expression for the limits going from Rs to infinity wherein Rs

540
corresponds to the surface of the charged particle and we are accounting for all the ions all the
way up to infinity. So, infinity what we essentially mean is that, we are considering distances
which are larger than double layer thickness.
(Refer Slide Time: 19:22)

So therefore, one could obtain q from this and if I want to integrate this, I should know what is
rho star that is the charge density. And for that we are going to again invoke the Poisson
Boltzmann equation. And we know that for a spherical coordinate system, and if you are
considering the variation of the potential only in the r direction, 1 over r square into d/dr of r
square d psi / dr should be equal to minus rho star times epsilon, I can replace for rho star from
this expression.

Therefore, I have minus epsilon times 1 over r square into d/dr of r square d psi by dr times, this
is the volume term. And with that, this and this get cancelled. So, therefore, I have 4 pi epsilon,
that is the, the constant. And because of the fact that I have one negative sign that was coming
from the, fact that the charges are in the solution are opposite to that of the particles that have
one negative sign there, and there is one negative sign comes from the Poisson Boltzmann
equation therefore, they both get cancelled. So, therefore, I have a positive sign here and times
d/dr of r square d psi by dr at times dr.
(Refer Slide Time: 21:05)

541
So, therefore, now, to obtain the total charge q, I can integrate the expression therefore, q would
be minus I have again so, there is a negative sign here. That is positive. And so, we will just
come back to that. So q essentially goes as 4 pi epsilon r square into d psi / dr at and of course, I
have these 2 limits, therefore, q becomes the constant term multiplied by this term at infinity and
this term at 0 and we know that the potential is 0 at a distance much larger than kappa inverse
that is at infinity. Therefore, this term becomes 0. Therefore, q becomes 4 pi epsilon into r square
d psi / dr at Rs.
(Refer Slide Time: 22:18)

And we know how the potential varies with R for a spherical particle system. So, therefore, I
know that psi is equal to psi naught Rs divided by r exponent of minus kappa times r minus Rs, I
can differentiate this with respect to dr. Therefore, I have the constant term the first term

542
multiplied by the differential of the second term plus the second term multiplied by the
differentiated the first term. So, therefore, d psi / dr at Rs essentially becomes minus zeta that is
because at r is equal to Rs psi becomes zeta.

Therefore, I have a zeta there and times a kappa r + 1 divided by Rs and I can take Rs common
essentially if I take one over Rs common therefore, I end up with my d psi / dr at Rs = minus zeta
divided by Rs times kappa times Rs + 1. So therefore, q becomes 4 pi eta times Rs d psi / dr I can
substitute for r square into d psi / dr. Now, therefore, this is so, d psi / dr you know at Rs so,
therefore, Rs r square at Rs is Rs square capital Rs square and instead of d psi / dr at Rs I have
minus zeta divided by Rs into k kappa times Rs + 1 this and one term gets cancelled.
(Refer Slide Time: 24:22)

So, therefore, what we have is this and this gets cancelled therefore, there is 4 pi epsilon into zeta
times Rs times 1 plus kappa times Rs therefore, so there this is the relation between the charge q
on the particle surface and the zeta potential the size of the particle and the concentration of the
electrolyte that you have in the solution which is which determines what does the kappa values.
So now, once we have a way to relate zeta potential to q one can compare the q that is obtained
by other methods.

And see what is the one to one correlation is it a one to one correlation or other effects that are
neglected in one method or the other, you know can be inferred from such a treatment.
(Refer Slide Time: 25:31)

543
So I would like to talk a little bit about zeta potential measurements and some important
considerations that one should worry about what we should always do zeta potential
measurements under a known salt conditions that is because, you can prepare a colloidal
dispersion and then you know just plug the sample into one of the instrument that measures that
are used for measuring mobility.

So, you may be able to get the value of mobility from the instrument however, to choose an
appropriate method to convert the electrophoretic mobility to zeta potential, we know that kappa
times Rs is a important factor. So, whether you use a Huckel limit or Helmholtz-Smoluchowski
or Henry solution or we are working with 1 is to 1 electrolyte or symmetric electrolyte in general
or asymmetrical electrolyte.

So, depending upon you know the conditions that are being used or the solution conditions under
which the mobility measurements have been made, one should be able to choose an appropriate
relation between the mobility and zeta potential. So, therefore, knowing the salt concentration is
of utmost importance, because, once you know that I can get kappa and of course, I should have
an idea about what is the size of the dimension of the particle.

And therefore, a combination of that is what should be used or what should be calculated in order
to use an appropriate expression for converting mobility to zeta potential. Suppose, if there are if
you do not know the salt concentration, so, one of the method could be that you could measure

544
the conductivity of the dispersion and, because we know that the conductivity can be related to
the ionic concentration of the particle and again from the ionic concentration I can calculate what
is kappa.

So, therefore, if the salt concentrations are not known, one of the nice method could be you
measure the conductivity of the solution and then appropriately convert the conductivity data to
any concentration and then use ionic concentration data to back calculate what is the inverse
Debye screening length that has kappa value and the third consideration is that always use a
dilute concentration of colloids and rule of thumb would be that if you take the dispersion of
particles in a fluid.

For example, if one is working with say latex particles that is say polystyrene particles we know
that they these dispersions appear turbid so, therefore, you use such a low concentration that if
you put a finger on the other side of the turbid that contains the solutions, you know your finger
should be you know visible clearly. So, typical concentration that one uses would be of the order
of you know 0.001 volume percentage or some concentration of that order.

So, therefore, and the reason why this is important is because at higher concentration, the
collateral interactions would become important. So, because whatever theories that have been
developed, they are applicable for conditions where the colloidal particle is assumed to move in
isolation. Therefore, the presence of any other particle in the vicinity is going to affect the
measurements therefore, carry out measurements at as dilute a concentration as possible.

And the last point is the theory that have been discussed how are applicable for spherical
particles so far whatever we discussed and they are also applicable under certain limiting
conditions. So, therefore, if one is interested look at particles of other shapes such as like say rod
like particles or disk shaped particles or elliptical particles one has to look for appropriate theory
there are there have been some developments in the field.

So, one should refer to the latest literature and then use an appropriate solution to calculate zeta
potential from these measurements on also there are several issues that have been omitted in the

545
development that we have discussed one is what is called as a retardation effect. So, what
happens is that, when you have a charged particle that is set into motion by an electric field and
we know that depending upon the charge of the particle is either going to move towards a
negatively charged electrode or a positively charged electrode.

So, however, we should also know that there is going to be the counter ions in solution. So, when
the particle moves in a particular direction, the ions that are present in the electrical double layer
and therefore, the fluid around it will try and move in a opposite direction therefore, the motion
of the particle is hindered that is, there is a retardation force that comes into picture because of
these effects. And one has to be careful about incorporating those things, which have not been
done in the present developments.

So, there are also what are called as relaxation effects and also the surface conductance effects
which also become important under certain conditions. So, therefore, general theory that should
be used should consist should contain all these important features inbuilt in those models
however, for under specific conditions, so, whatever theory that we have developed, it can still
be used to for a meaningful in a measurement of zeta potentials.

So just to conclude, so, what we have done in this particular module is that, we defined zeta
potential and we talked about the important implications of zeta potential in different
applications. Then, we discussed electro kinetic methods and more discussions have been
centered around electrophoresis because it is one of the widely used technique for measuring zeta
potential, then, we discussed the relationship between the mobility and zeta potential.

So, we started with talking about mobility of an isolated ion followed by the mobility of charged
particles assuming that the charged particles can be treated as macro ions. And then, we
developed a relation between the electrophoretic mobility and zeta potential in several cases,
Huckel limit and Helmholtz-Smoluchowski limit as well as Henry's equation which is valid for
the entire range of kappa times Rs value. And, we finally discussed about what are the important
considerations one should think about when measuring zeta potential from any given technique.

546
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology, Madras

Lecture - 44
Colloidal Particles at Interfaces: Introduction

So we are going to start with the module 6 today. And so, this concerns colloidal particles at
interfaces.
(Refer Slide Time: 00:28)

So, far what we have looked at is when we have particles dispersed in a continuous medium, so,
these are the, the solid particles and that is the continuous medium and you have solid particles
dispersed in a fluid medium, fluid medium could be typically water or any other liquid for that
matter or gas. And so, we have looked at colloids in the bulk, as against that, what we are going
to do today is to look at a colloids that are sitting at an interface between two fluids. So what you
are looking at here is immiscible fluid 1 and you know another is immiscible fluid.

So, once you have any combination of immiscible fluids, you will have an interface that
separates the two particles. So, we will deposit particles right at the interface between the two
fluids. And we look at some important consequences of particles at interfaces.
(Refer Slide Time: 01:39)

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Now, before we move on further, I just want to spend maybe a few minutes to talk about how do
we create interfaces with particles or how do we create particle laden interfaces, there are two
typical strategies one could use one is based on what is called as a spontaneous adsorption. So, in
such a case what you do is you consider a system of immiscible liquids. So, this could be like say
water air or like say decane or any other oil in contact with water.

So, then you create an interface now, then what you do is you take dilute dispersion of particles
this portion could be either in the aqueous phase, or the particles could as well be dispersed in
the decane phase as well. But the schematic that you see here, it contains these particles that are
colored blue, and they are disposed in water medium. And so, if you take very dilute dispersions
that is the one of the requirement and we will talk a little bit about why little later.

Then, if the particles are amphiphilic that means they are surface active example could be micro
gel particles or pNIPAM or any micro gel particles which are known to be amphiphilic and in
spite of dispersing these particles in the bulk. If there are sufficient low concentration, you will
see that all the particles migrate to the interface and then they decorate the interface, that is one
way of creating interface with particles and the concentration at which the entire monolayer
entire interface is populated with particles is what is called as critical monolayer concentration.

548
And, for any concentration above that critical monolayer concentration, the particles are going to
be in the bulk as well as at the interface. Therefore, one has to work at sufficiently low
concentration to have particles positioned only at the interface and nothing at the bulk. The
second method of achieving this particle laden interfaces is to use a particle that are effectively
less charged that means, if you have a system like this and if you have the particle that are
disposed in water.

And if the charge density whether if the particles are either positively charged or negatively
charged, and if the surface charge density is lower, and they have a tendency to adsorb
spontaneously at the interface and their adsorption can be tuned by changing solution conditions.
For example, one could consider a pH whether the particles are have a low charge or you could
add a small amount of electrolyte and the fact that the addition of electrolyte reduces the
electrical double layer interaction.

That enables this spontaneous adsorption of particles at interface. In other words, whenever the
particles are trying to approach an interface there is an energy barrier for the absorption and this
energy barrier can be either completely removed or reduced by changing the solution conditions
that as such as manipulation of pH or the addition of salt. So, therefore, the spontaneous
adsorption can be achieved by considering amphilpilic particles in the aqueous phase at
sufficiently low concentration or by using a dispersion where the particles are less charged.
(Refer Slide Time: 06:08)

549
The second method of you know achieving a particle laden interface you know or the interface is
containing particles is by deposition of particles at the interface. So, for that what is done is the
particles must be dispersed in an aqueous alcohol solution. So, what you should do is you should
take a micro syringe for example, and this should contain particles plus if it is an aqueous
dispersion of course, you will have water along with that you would have to add a small amount
of alcohol.

And this alcohol could be isopropanol alcohol, ethanol, methanol or any you know standard
alcohol. And once you have an aqueous alcohol dispersion of particles, so, what you could do is
you can position the micro syringe either in the decane phase or you can position it right close to
the interface. And when you inject these dispersion so, what we will have is you will have small
droplets containing particles that form and the moment these droplets touch the interface.

Because of the presence of alcohol these droplets break and that essentially enables the spreading
of particles the interface and of course, one has to work with very dilute dispersions and another
important consideration is that the fluid that are being used for these experiments have to be
extremely clean and the container also has to be extremely clean. What I mean by that is that it is
a good practice to consider water.

That is double distilled and which does not have any ions present plus the oils that are typically
used you know usually ensure that there are no surface active additives in these oils. For example
decane is passed through a column that contains alumina to remove any surface active impurities
that may be present in the system. The arrangement could be as simple as you consider a burette
and fill the burette with aluminum particles and then you add a small amount of decane.

And then let it pass through this column and then you collect the clean decane at the bottom and
you can use such you know treated oil for further experiments. So, these are couple of different
ways by which one could create interfaces with particles or the particle laden interfaces.
(Refer Slide Time: 09:20)

550
Now, before we discuss further on the particles or interfaces concept, I would like to talk a little
bit about some applications of such systems and the particles or interfaces concept has been used
for stabilization of interfaces, in that means for obtaining emulsions and foams. The schematic
that you see here is a is an example where you have a system of water and an oil and then you
add a little bit of surfactant that is a surface active agent which is designated you know as a
something that is a circular head group and a tail group.

And that is the hydrophilic part of the surfactant and the hydrophobic part of the surfactant and
we know that this effect surface surfactants are surface active and they are known to go and sit at
the interface and you can get what are called as surfactant stabilized emulsions in a similar way.
(Refer Slide Time: 10:54)

551
There has also been a lot of interest in what are called as particle stabilized emulsions, in such a
case the emulsions are prepared by taking an oil and water plus some particles. And these
particles again have a tendency of going and adsorbing at the interface between the 2 immiscible
liquids and then they can act as a as stabilizers.
(Refer Slide Time: 11:20)

This is a an example in which what you are seeing here is this is the aqueous phase and what do
you see at the top which is which appears turbid it is an emulsion layer that has been created by
taking water and decane and what is also present in water is a 1 micro meter particle and these
particles are of silica particles. And, and so you can do microscopy of the emulsion layer that is
formed and he will see that you know, it contains large droplets.

552
And if you focus if you use an optical microscope and if you focus on the droplet surface, you
see that you know there is these droplets are decorated with a single layer or a monolayer of 1
micrometre particle that is present on the surface of these droplets and the presence of these
droplets give a very good stability for the such emulsions.
(Refer Slide Time: 12:49)

One of the advantages of looking at there are several advantages of producing particle stabilized
emulsions, and foams. So, they are the surfactants that are typically used for this purpose, they
can be replaced by less hazardous particles. So, for example, one could look at using inorganic
particles or for example, starch particles of starch, which therefore, one could design edible
Pickering emulsions, you know, without the need of using any hazardous surfactant molecules.

So, the other important consequence of stabilization of emulsions with particles is that solid
stabilized emulsions, they show excellent stability and that is because, once the particles are
sitting at the interface of the two fluids to remove it from the interface to dislodge the particles in
the interface either into the aqueous phase or into the oil phase, it requires a lot of energy and this
energy that is the surface free energy that is required for removing a particle either into the
continuous phase or into the oil phase is given by pi r square.

Where pi r square is the radius of the particles that are being used for stabilization of emulsion
and gamma is the interfacial tension between the two particles, the two fluids that is fluid 1 and
fluid 2 and this term 1 plus or minus cos theta whole square this and that multiply by pi r square

553
will give you what is the area that the particle is replacing when it is at the interface or
essentially if there is a particle that is sitting at the interface.

If the particle is exactly situated the interface is that you know half of the particle is in one phase
and half of the particle is in other phase, then this term becomes pi r square essentially it is what
is called as a contact area that is the area that is obtained by the intersection of the interface and
the particle. So, and the reason why so, this delta G which is the energy that is required to detach
a particle either into the aqueous phase or into the oil phase it goes as the square of the particle
size.
(Refer Slide Time: 16:05)

So, therefore, what you see here is the energy of detachment that is plotted that is a scaled with
kBT and that is plotted as a function of particle radius. Now, if you consider surfactant molecules
which are in a sub nanometer in size, so, if I substitute for r to be sub nanometer it turns out that
this delta G that we calculate it would be of the order of kBT itself that is, you know somewhere
here and now, when the surfactant molecules have energy, which is of the order of kBT.

What they could do was once even though they could be absorbed in interface, they can easily
detach from the interface and go either into the aqueous phase or the continuous phase or into the
oil phase. However, in contrast, if you look at particles that have an energy of radius 1, this is the
radius is in nanometer. Now, if you take particles that are larger in dimension for example, if you
take 1 micrometer particle, so, therefore, if the radius is 1 micrometer.

554
So, let us calculate quickly so, that is pi multiplied by 1 micrometer is 1 to 10 power minus 6
whole square and let us assume that the theta is equal to like say 90 therefore, this term becomes
not important. So, therefore, and if we consider the surface if you consider an oil water interface
with the interfacialtension of say for example, 50 millinewtons per meter. So, therefore, this
becomes 50 into 10 power minus 3 newton per meter, therefore, what we have is pi into 10
power minus 12 and as minus 3 here.

So, that is minus 15 that is approximately 3.14 into 10 power minus 15. That is going to be in
joules. Now, if you divide this by thermal energy at for example, say 298 Kelvin, turns out that
thermal energy kBT at 298 Kelvin, so, is of the order of 4 into 10 power minus 21. So, that is if I
take 298 that is the temperature multiply by 1.38 into 10 power minus 23. So, that is the kBT. So,
therefore, this delta G becomes of the order of 3.14 10 power minus 15 divided by 4
approximately into 10 power minus 21. So, if I say that these are of similar magnitude, therefore,
delta G becomes 10 power minus 15 plus 21 therefore, delta G is of the order of 10 power 6.
(Refer Slide Time: 19:35)

Therefore, the simple calculations show that if you have a 1 micrometer particle of radius 1
micro meter and if that is situated at the interface with the interfacial tension 50 millimeter per
meter. So, the energy that is required to dislodge a particle into one of the phases is of the order
of 10 power 6 kT. And this energy is much larger when you consider a surfactant molecule
which is sub nanometer in size.

555
And of course, this energy decreases with decreasing the particle size. So, what you are seeing
here is you know, a plot of this detachment energy is a function of dimension, therefore, it has
the particle size become smaller and smaller, the energy that is required to dislodge the particle
into one of the phases becomes smaller that means, they can easily escape the interface and such
emulsion would not be highly stable on the contrary, if you use particles which are micrometer in
dimension, the energy of detachment is of the order of 10 for 6 kBT that gives excellent stability
for particle stabilized emulsions.
(Refer Slide Time: 20:50)

And other important aspect of these emulsions is that they are stable under conditions where
surfactant stabilized emulsions, may destabilize that could be they are stable under harsh pH
conditions in the presence of electrolyte as well as when the temperature of the emulsion that are
prepared when they are changed, they still continue to remain stable as well. So, therefore, they
show excellent time stability and they also show excellent stability under various solution
conditions such as changes to pH, electrolyte concentration and temperature.
(Refer Slide Time: 21:43)

556
So, the particles or interfaces concept can also be used to make new colloids and if you look at a
schematic here, what you have is if this is interface, that the blue line and you have two cases
where the particle is immersed more in the water phase and in the second case it is immersed less
in the aqueous phase. And because, and the fact that the part of the surface is in contact with oil
and the part of the surface in is in contact with water.

In this case, it can be exploited to make new type of colloids by what is called as a selective
surface modification of the part of the particle either in contact with water or the one that is in
contact with oil. And what is shown here is an example where a part of the surface that is in
contact with water for example, what is circled here and here they have been coated with gold
particles gold nanoparticles and depending upon how much of the surfaces in contact with water.

I can either have a smaller region coated with gold or a larger fraction of the particle surface
coated with gold and this brings about a novel way of making colloids which are not isotropic
that means, if I take a parent particle for example, say polystyrene surface chemistry would be
same everywhere. However, on the contrary, if you do this treatment, what you have is exactly a
similar particle however, the part of the particle is now coated with gold therefore it this is a nice
way of making new type of colloidal particles.

And such particles which have part of the surface coated with gold, the example of what are
called surface Anisotropic particles because the bulk of the particle is exactly same, what is

557
different is the surface of the particle and there are ways by which one uses what is called as the
fractional surface area that is coated with gold as a method for characterizing such particles.
(Refer Slide Time: 24:36)

And the next application comes in the form of making what are called as colloidosomes again a
new class of materials. So, we are talked about what are called as liposomes and these liposomes
are containers which are stabilized by lipids so, what you are looking at is here his lipid
molecules which have a 1 head group and a 2 tailed group and they are arranged in a particular
fashion to give what are called as surfactant by layers, that is one layer of particle one layer of
surfactant.

And the second layer this is a curved by layer and, these contain fluid inside and this fluid can be
used for as cargo carriers in terms of incorporating either hydrophobic or hydrophilic as well as
complex structures in these containers and they can be used for drug delivery applications. So,
similarly, when you replace lipids with colloidal particles and you make similar structure and
because of analogy with the liposome, they are what are called as colloidosomes. And these
colloidosomes are hollow structures.

So, what you do is you make particle stabilizer emulsion and you can cross link the particle that
means, you know you can join the particular on the surface and you can remove you can
evaporate both the inner fluid and the outer fluid to get a shell like structure called colloidosomes

558
and there is been a lot of interest in making such materials from different particles and exploiting
them in some controlled release applications.
(Refer Slide Time: 26:46)

And just to make a final note, these particles stabilize emulsions. So, what you are seeing here is
a container where you have an oil and aqueous phase with polystyrene particles and this was
emulsified to get you know a particle stabilized emulsion and one could start with such emulsion
as a starting material. And you can use what is called as a colloidal processing route in which
you make a particle stabilized emulsion you induce gelation in such systems gelation of particle
stabilized emulsion.

Which can be simply done by using a higher concentration of colloidal particles you know when
you prepare emulsion and once you have such a gel, what you can do is you can evaporate the 2
fluids that are in the emulsion, both the oil phase and the continuous phase and to obtain a green
body which is which has only the these hollow structures which are with particles and both the
fluids removed. And you can start with this material.

And you can actually sinter it, which is a method of heating this screen body to a temperature
close to the melting point of the particles that are used for making these green body and the
emulsion and you can end up with a porous material. What you are looking at here is a structure
which has a lot of pores and these pores arise because of the oil that was present in the emulsion
and one could use these porous materials in several applications as well.

559
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology - Madras

Lecture - 45
Characterization of Particles

(Refer Slide Time: 00:14)

So that is so that brings us to concluding the fact that there is a lot of interest in looking at
particles at interfaces concept, because there are a large number of applications in the
materials, which have been prepared by exploiting this concept. So now, what we will do is
we will talk a little bit about characterization of particles at interfaces. So, if you look at in
the bulk, we have talked about several techniques and several parameters one need to
characterize the particles.

For example, size, surface charge density, grafting density, you know, several parameters.
Now, when it comes to particles at interfaces, of course, the characterization of all these
parameters is also equally important. And while in the bulk one of the important parameter
which is used to characterize particles in a fluid is what is called as a volume fraction which
is the volume of particles divided by the total volume of the dispersion.

And analogous parameter for colloids at interfaces would be what is called as a surface
fraction that is fraction of the surface that the particles occupy at the interface that is the area
occupied by particles divided by total area of the interface. For example, if one is using a

560
Petri dish for example, and whose size is like say whose radius is capital R then what one
could do is the total area that of the interface is going to be pi R square.

And now, the area that the particles occupy at the interface depends on what is the
concentration of particles at the interface. And typically, when one works with particles at
interfaces, if the particles that are micron in size are used, you can actually do an optical
microscopy and obtain an image which contains particles. Now, if you know the number of
particles at the interface.

And if you know what is the total area that or the area that the particle occupies the interface
that means, the number of particles at the interface multiplied by the area that it occupies, and
that gives you what is called as surface fraction or the fractional area that the particles occupy
at the interface and the typical value of phi could vary from say 0 to about 0.74 if you work
with spherical particles and that 0.74 is when all the particles pack in the form of a crystal
and if the particles are randomly distributed in the fluid you can go to a value as high as 0.64.

However, if you look at spherical particles if they are sitting at the interface and if you
assume that you know they are sitting exactly with half of the surface in the two phases then
one could do a simple calculation and show that if they are arranged in the form of a hexagon
or a HCP or HCP close packing you can just consider a triangular area and then you can
calculate that this phi can be as high as about 0.90 roughly.

So therefore, while the volume fraction when you work with dispersion as a bulk can go from
about phi to 0.74 for spherical particles, the surface fraction can go all the way from about 0
to about 0.90. And the other parameter that one could also use is in the case of you know, the
particles in the bulk, we can talk about number density of particles that is number of particles
per unit volume.

Similarly, in this case one could talk about surface density, which again would be the number
of particles interface divided by the area of the interface. So, these are some additional, you
know, characterization that one has to talk about when one is dealing with particles at
interfaces.
(Refer Slide Time: 05:56)

561
(Refer Slide Time: 06:09)

And another additional characterization that would also be important which is not so much
when you have particles sitting in the bulk is what is called as the position of the particles
with respect to the interface or the contact angle of the particles at the interface. And this is
defined by what is called the Young's equation, which relates the interfacial tension of the
solid.

In this case, the particle that we are dealing with, that is oil that is the interfacial tension of
the solid-oil interface and the solid-water interface and they are related to the interfacial
tension between the oil and water and cos theta and this theta is what is called as contact
angle and that is determined by drawing a tangent that to the particle surface at what is called
as a three phase contact point.

562
So, what is shown here is a location where the fluid 1 and fluid 2 and the solid particle that is
the three phases that come into contact, and at that location, you draw a tangent to the particle
surface and the angle that the tangent makes with the interface gives you what is called as a
contact angle and this contact angle could be less than 90 degree and that is when the particle
is more in contact with the aqueous phase and such particles are termed as what are called as
hydrophilic particles.

And you could have a case where the contact angle theta is greater than 90 when the particle
would like to maximize its contact with the oil phase and such particles are referred to as
hydrophobic particles, and you can have a case where the particle would like to be in equal
contact with both the oil phase and the aqueous phase and such particles are termed as
neutrally wetting.

Therefore, depending upon the type of particles, either the particles could be wanting to be
more in contact with aqueous fluid example of such particles could be several metal oxide
particles for example, hematite particles or SiO2 particles for example, and the examples of
particles which are more prone to being in contact with oil could be several types of
polymeric particles for example.
(Refer Slide Time: 09:31)

And this concept of contact angle is very similar to what is called is a concept of HLB or the
hydrophile lipophile balance, which is defined for a surfactant molecule. So, in the case of
surfactant molecules HLB is defined as it relates the molar mass of the head group to the total

563
molar mass of the surfactant molecule and that is defined as the molar mass of the head group
divided by molar mass of the surfactant.

And, if the molar mass of the head group is large, that means, the out of the total molecular
weight there is a lot of contribution that comes from the head group and such surfactants are
known to be water liking or they have a affinity for being in contact with water. So, and if the
molar mass of the head group is very, very small, that means, the because of the fact that the
surfactant has a tail group.

And a head group in the case where the molar mass of the head group is small, what really
dominates the behavior is the molar mass of the tail group and such surfactants are more oil
soluble in a similar sense, when the particle is sitting at the interface, you could have the part
of the surface that is in contact with oil for example, you can think about analogy with the tail
group of the surfactant and the portion of the particle that is in contact with the water.

And which is a hydrophilic part, you can think about that as an analogy with the head group
of the surfactant molecule and the relative magnitude of the interfacial tension between the
solid and oil, solid-water and the oil-water interfacial tension determined how much of the
surface is in contact with each of the fluids and that is quantified by the contact angle.
(Refer Slide Time: 12:14)

And measurement of the contact angle or the position of the particle with respect the interface
is one of the additional characterization that you know one has to deal with.
(Refer Slide Time: 12:31)

564
And there are qualitative methods to talk about particle wettability or the preference of the
fluid particle to one of the fluids and that is simply done by basically creating taking a
substrate and you deposit the particles of interest you know whose wettability you want to
measure and then you deposit a layer of the fluid for example, an oil or water and look at
what is the contact angle that is again you measure you just draw a tangent at the three phase
contact you know point.

For example, something like this and you measure what is this angle with respect to the
horizontal and you calculate and you find out what this theta value is. So, if the theta value is
close to 0 that means, the fluid that is put on a surface coated with particles it spreads
completely. And therefore, the particles have more preference to that fluid. On the other
hand, if you have a case, where the particles the fluid that is deposited.

If it takes a shape like a perfect sphere, the particles do not have any preference whatsoever to
the fluid and the concentration therefore, depending upon this contact angle, one could come
up with a qualitative way of inferring what is the particle wettability or whether the particle
prefers to be in contact with either oil or water or is it neutrally wetting to both the fluids.
(Refer Slide Time: 14:22)

565
One could do a quantitative estimation of contact angle. Again, we will go back to the
method that we discussed in the context of making new particles wherein, a portion of the
particle surface was coated with gold. So, the experimental setup looks something like this.
So, you create a monolayer that means you deposit particles at the interface and into the
aqueous solution, you add reagents that lead to the formation of gold nanoparticles.

Now, the gold nanoparticles that are there, they can preferentially go and deposit onto the
surface that has in contact with the reaction solution. And that occurs because of the
electrostatic attraction between the particles that are produced as a result of this reaction and
the particles that are sitting at the interface and the fact that the gold nanoparticles are
produced and the particles that are sitting at the interface, they are oppositely charged in this
case, the gold particles are produced.

They are negatively charged and the particles are deposited at the interface they have positive
charge and because of the electrostatic attraction, there is a deposition of gold and once the
gold the reaction is complete, you can transfer these particles onto a substrate and you can
observe these particles under SEM you can calculate what is d that is the area over which the
deposition has occurred.

So, if you look at this, so, if I can fit a circle and I can calculate what is the diameter of the
patch that has been produced? So, I can I have a direct way of measuring d and if we know
what is the diameter of the particle that we started with that is the diameter of the particles

566
that were deposited at the interface calculation and measurement of the small d and capital D
enables the calculation of D.

So, depending upon whether the particle is more in contact with water or less in contact with
water, you know, you can use a different expression which you can actually derive from
simple geometry as well.
(Refer Slide Time: 17:26)

So, therefore, this is a simple and a direct method for measuring the contact angle of the
particle at the interface there are other methods in which what is typically done is that you
deposit particles at an interface between air and aqueous solution or oil and aqueous solution
instead of taking pure water what is done is a small amount of a hydrocolloid is dissolved in
the aqueous phase and the spreading of the particles at the interface is done at a high
temperature.

For example, 50 degrees centigrade in this case and what is done is once you spread the
particles you allow them to reach equilibrium position, you can change the temperature from
25 to from 50 to 25. And when that happens, the aqueous sub phase it solidifies there is a
conversion of a liquid like sub phase into a gel like sub phase and once the gel like sub phase
is formed, the particles are trapped at the interface and they become immobile.

And what you could do is you can pour out the oil because gel is of sufficient strength, I can
pour out the oil and I can replace the top phase with PDMS and along with the PDMS there
will be some cross linking agent which will help the linking of this PDMS molecules to the

567
surface and after a certain curing time, you can peel off PDMS and because of the cross
linking reaction, the particles get embedded in the PDMS.

And that could be observed on an SEM and I can get a micrographs again of what is the
contact diameter that corresponds to the location of the particles with respect to interface and
what is the diameter of the particle and again knowing d and dc one could estimate what is
the contact angle of particles with respect to the interface.

568
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology – Madras

Lecture – 46
Experimental Observations: Concept of Electrostatic Interactions and Stability at
Interfaces

(Refer Slide Time: 00:14)

In this module so far what we have done is we have introduced the concept of particles at
interfaces. And we have looked at several applications, where this concept can be exploited. And
we discussed characterization of particles in the context of when they are at the interface. And
we mentioned that an additional characterization one has to worry about and we discussed about
a contact angle measurements, which is a method of finding out what is the equilibrium position
of particles with respect to the interface.

What we will do in this lecture is that we will look at some important experimental observations
and these experimental observations enable us to make two interesting points. One is that
electrical double layer interactions or the electrostatic interactions are modified when the
particles are at interfaces. And number two is that some of the experimental observations can be
used to discuss what is called as stability of colloids at interfaces. We will discuss some of these
observations and we will think about mathematically deriving some equations which enable us to
make these statements.

569
(Refer Slide Time: 01:54)

And the first result that I am going to show is the seminal work of Pieranski we are looking at the
microstructure of particle laden interfaces. In these experiments, what was done is there is a
small container and that container is filled with a colloidal dispersion what is highlighted now,
and in this container, a very dilute dispersion of particles was placed and this is a dispersion of
polystyrene particles in water and the size of the particle is 245 nanometer in diameter.

And naturally, when you do not have anything at the top as you will have here, therefore, does
not interface between water and air. And what you see here is a schematic of a microscope
objective and you know, you can move this objective up and down. So, that you can focus at the
interface and look at the microstructure of the interface containing these particles. And there are
2 distinct micro structures that can be seen here.

So, if you look at the image, you see these small dots, and these are the, the particles of 245
nanometer diameter. And if you take a closer look, you will see that every particle has its
neighbor, for example, if I look at, let us say a particle here, there is 1 neighbor there 1, 2, 3, 4, 5,
6 right. So, therefore, every particle has 6 neighbors, and it appears that the distance between if I
were to draw a line, you will see that you will see peaks and valleys.

570
And this, the distance between the peaks corresponds to the, the particle position and looks like
they are periodically spaced in figure a and therefore, this microstructure resembles a crystalline
arrangement or an ordered arrangement of particles, on the right, figure b is obtained by doing a
similar experiments, the only difference is that the concentration of the particles at the interfaces
lower.

So, in the context of surface fraction or the fraction of the area that is occupied by the particle, it
is higher in the case of a and it is likely lower for the case of b, and if you look at image b You
know the particles are not as ordered as what you see in a and so, this corresponds to a liquid like
you know microstructure or in this case the particles are disordered. So, these are the
experiments with very tiny particles that are 245 nanometer particles and these are the
microstructure at water air interface.
(Refer Slide Time: 05:25)

And what you are seeing now is microstructure which is obtained by depositing 3 micrometre
polystyrene particles, and they have a zeta potential of minus 85 millivolts they are highly
charged and the fact that zeta potential is minus 85 that means, they are negatively charged
particles and the charge density that is corresponding to this zeta potential is 6.7 micro coulombs
per centimeter square.

And these are deposited at Water-Decane interface, again similar features can be seen the
monolayer is crystalline that means, if I were to draw a line like this, he will see that you know,

571
the inter particle spacing between the particles is very similar and every particle has except for
some small dirt, you know, you see that every particle has 6 neighbors, for example, if I look at
this, so, I can beautifully draw a nice hexagon right. So, therefore, there is a non-closed packed
hexagonal arrangement of particles at the interface.
(Refer Slide Time: 06:47)

Now, the these 2 experiments, the conclusions that can draw that one can draw from these two,
the microstructure that we have discussed So, far is that, so, you have two particles and you can
designate the inter particle separation by this d, the separation distance d what is evident is that
the particle monolayer is homogeneous, what I mean by that is, if I look at any region of the
monolayer whether you are in one corner or in the other.

Or you know, anywhere across the monolayer, the monolayer looks homogeneous that means,
the particles are uniformly distributed all through the available interfacial area. The second
conclusion that one could draw is that inter particle separation distance that is d is much larger
than the diameter of the particles that means, if I look at so, these particles are 3 micrometer in
diameter.

Now, if I look at the inter particle separation distance between the 2 particles, it appears that the
inter particle separation is at least about two times the particle diameter or more depending upon
you know the concentration the particles that one works with and, and the fact that the inter
particle separation is much larger than the diameter of the particle, it suggests that the

572
interactions must be repulsive and that the interactions are a long ranged because of the fact that
the separation distance are at least 2 times the particle radius or larger that suggests that the
interaction between the colloidal particles are repulsive and they are more long range.
(Refer Slide Time: 08:49)

Now, let us look at comparing, you know the particles in the bulk versus particles at interfaces,
what is the difference now, so, we discuss that when you have charged particles dispersed in a
fluid, there is going to be an electrical double layer that is formed the first thing is that the
moment you have a charged particle dispersed in water or any other fluid medium, if there is
going to be dissociation of charges, the particle is going to acquire some charge.

Right and, whatever ions are present in the vicinity of the charged particle, they are going to
rearrange and they are going to give a an electrical double layer, and that electrical double layer
is depicted here. So, you have stern layer and there is a surface of shear and there is an electrical
double layer thickness associated with the thickness of the double layer and you have a stern
layer where the counter ions are closed or tightly bound to the particle surface.

And you have a diffuse layer where the concentration of counter ions varies with the distance
from the charge surface right. And in for such a configuration the interaction between two
spherical particle is given by these two expressions, the first one is for a case where the Gouy
Chapman theory has been used for the overlap of the electrical double layer, and the second one

573
is for the case where we have a Debye Huckle approximation which is valid when the when the
zeta potential is of the order of 25 millivolts.

Now, this is the picture that we have in the bulk that is the overlap of the electrical double layer
it gives rise to electrostatic interactions of the electrical double layer interactions. One thing that
is important to notice is that around the particle since this is a particle around the particle the
electrical double layer is symmetric. Now, if you look at the particles sitting on the interface,
what is shown here is a schematic of particle 1 and particle 2.

And they are sitting at the interface between the two fluids and this is a negatively charged
particle that is the charges that are on the particle surface and you have the counter ions that are
that are depicted here. And one thing that is to notice is that the electrical double layer or the
distribution of counter ions around the charge surface is not symmetric anymore, that is because
the dissociation of the charges occurs only across the surface that is in contact with water.

That means, so, although the particles would also have the surface charge groups you know, in
the on the surface that is in contact with oil, the dissociation of the charges requires a suitable
medium and a charge like say for example, C-O-O-H which would dissociate when it is in
contact with water and under appropriate conditions. And therefore, the dissociation gives rise to
C-O-O minus and H plus only in the region where the particle is in contact with water.

Therefore, there is an asymmetric distribution of counter ions in the case of particles or

interfaces, and this difference is what is giving rise to long range interactions in the case of
particles at interfaces.
(Refer Slide Time: 13:18)

574
Now, this is a schematic, that there is a dissociation of charges only on the water side. Now, what
one could do is that the So, because of the fact that the charges on the particle surface and the
counter ions in solution, the fact that the charge density that is arising because of the in the
charge density corresponding to the dissociation that occurs on the particle surface and the total
number of counter ions in solution are going to be exactly the same.

Therefore, we can associate a charge minus q with the particle surface and similarly, for the for
the ions in the double layer, we can associate a charge plus q and a typical length scale by which
these two charges are separated is of the order of Debye screening length that is Kappa inverse.
Therefore, so for every particle that is at the interface, there is a dipole, that is the dipole
corresponding to particle 1 and that is a dipole that is corresponding to the particle 2.

And these dipoles depending upon what convention you use, they point in the same direction and
they are along the axis that connects the center of the two particles right. So that means if they
will be pointing out in this direction, right maybe I can just redraw. So, they will be pointing in
the same direction and they are along the axis that connect the centers. Now, whenever we have
two charges that are equal in magnitude, but opposite in sign, we can define a dipole moment q
which is given by q times Kappa inverse that is mu.

575
And now, the force of repulsion between the two dipoles is given by if you have two dipoles mu
1 and mu 2 the force of repulsion is given by mu 1 mu 2 divided by 4 pi epsilon naught epsilon r
into r square, where r is the separation distance between the two dipoles and if this expression
can be written if the separation distance r is much greater than Kappa inverse and because the
dipoles are of similar magnitude.

Therefore, the numerator becomes mu square and in the denominator you have 4 pi epsilon
naught epsilon r into r square and because of the fact that so, this is the expression for the force
and the force is the negative gradient of the potential therefore, if you want the repulsion the
repulsive potential or the electrostatic interaction between the two particles, I need phi of r which
I can obtain by integrating this you know from d to infinity and where d is the distance of
separation between the two dipoles and it can vary from d is equal to 0 all the way up to d is
equal to infinity.

So, therefore, if we work this out what you have is mu square 4 pi epsilon naught into epsilon r
integral of 1 over r squared is minus 2 divided by r cube and that goes between the limits infinity
and r is equal to d and because r cube is in the in the denominator the this term at infinity is 0
therefore, phi electrostatic essentially is given by the 2 and the 2 gets cancelled. Therefore, the
final electrostatic is given by mu square divided by 2 pi epsilon naught epsilon r into 1 over d
and because we have defined mu as q times Kappa inverse, I can substitute for mu in terms of q
Kappa inverse.

So, therefore, we can write this as you know q divided by sorry this this is going to be q times
Kappa inverse Kappa - 2 right q this is q times Kappa - 2 in the numerator that is Kappa - 2
therefore, and this charge q would depend on the total number of charges that are dissociated and
you can write this q as z times e where e is the charge in the electron and z can take any value
depending upon the total number of charges that are dissociated.

If for example, if you take a case where you have a particle that is sitting exactly with half of the
surface in contact with oil and water in that case and if the total number of charges on the surface
is like say for example 3000 then this q would become 1500 times e something of that that order

576
So, therefore, phi electrostatic goes as 1 over the distance to the power of 3 as against e power -
Kappa times d for the case of interactions, colloidal interactions in the bulk. So, and this 1 over d
q of dependence is what gives rise to the long range nature of the electrical double layer
interactions compared to the similar interactions in the bulk.
(Refer Slide Time: 20:04)

Now, the other observations are that so, when the particles are trapped at the interface similar to
you know, when they are in the bulk the particles continue to exhibit vigorous Brownian motion
very similar to the particles in the bulk. And it is also observed that once they are at the interface,
if you imagine this to be the interface and if you have, you know, this is a in a petri dish for
example.

So, now, the particles they never penetrate into the bulk that means, once they are sitting at the
interface, once they are absorbed at the interface, they continue to exist at the interface and they
never go back into the, the bulk and moreover, if there is a the particle that is coming in the
vicinity of the interface and experimental observations show that they can be drawn towards the
interface and they can and that means, the transfer from the bulk to interface is possible.

However, the transfer from the interface to the bulk is practically impossible. This suggests that
polystyrene particles are irreversibly stuck at the interface and the fact that they are in
irreversibly stuck points to the fact that the particles are trapped at the interface in an energy that

577
is much deeper than the thermal energy. So, now what we will do is will try and calculate what is
the depth of the energy well, unit in which the particles are sitting at the interface.
(Refer Slide Time: 22:03)

So, we are going to do that by doing a very simple surface energy balance, which is just going to
follow this reference for doing that. So, this is a schematic of like say a polystyrene particle in
this case, which is sitting at the interface between air and water and theta is the, the contact
angle. And so, the, the radius of the particle is R and the center of the particle is at C. And z
refers to the location of it is a vertical distance that will tell us what is the location of the particle
with respect to the interface.

z is equal to if I scale z with R that is the radius of the particle then I will get a z bar and this that
bar is going to be plus 1 when the particle is in is completely in air, and z bar is minus 1 when
the particle is completely in water.
(Refer Slide Time: 23:35)

578
So, now, if you have a configuration like this, now, so, when the particle is at the interface, right
and initially imagine that you know there is a water air interface and you bring a particle either
from you know the upper phase or the lower phase, and then you position them at the interface.
Now, if you look at such a process, wherein you bring in a particle from one of the phases and
position them at the interface.

So, what is done is that we have replaced in this configuration, we have replaced water air
interface, with two new interfaces right. So, if I say that this is the, the water air interface, that
was originally present, and the fact that you have placed the particle interface, you created two
new interfaces, that is the interface between the particle and in this case, air and the interface
between particle and water. We have created two new interfaces and we have removed the water
air interface was originally present.
(Refer Slide Time: 24:59)

579
And therefore, the total surface energy when a spherical particle is at the interface is given by the
summation of the three interfacial energies one is the surface energy of the particle-air interface,
second is the surface energy of the particle-water interface and these are the surface energies that
were newly created and they take the positive sign and however, we have replaced the air-water
interface that is the energy of the missing interface that is negative because that has been lost.
(Refer Slide Time: 25:50)

And so, for and the fact that the surface energy is given by surface area multiplied by surface
tension you can write down the individual contribution to the to the total surface energy and this
term E for the particle- air interface this term is E for the particle-water interface and this is the E

580
term for water interface and if you look at the schematic So, we see that and we said that this
distance is 1 + z bar.

And therefore, the total interfacial area that is available the total particle air interfacial area is
given by 2 pi R square times 1 + z bar that is the particle-air interfacial area that multiplied by
the particle-air interfacial tension or the surface tension will give me the surface energy that is
associated with particle and air interface and the second term this 2 pi R square times 1 - z bar
that this distance.

This is 1 – z bar is this distance that multiplied by 2 pi R square will give me what is the surface
area of the particle-water interface that multiplied by the corresponding interfacial tension will
give us what is the surface energy of the particle-water interface. Now, this pi R square into 1 - z
bar tells us what is the interfacial area that that has been replaced and that multiplied by the
interfacial tension between water and air will give us the contribution of the water-air interface to
the total interfacial energy in this expression the z bar is z / R that is the scaled vertical distance
of the center of the particle C with respect to the air water interface.
(Refer Slide Time: 28:40)

Now, you can divide So, now, if you look at So, you have you know R square term that occurs in
all the terms and because of the fact that gamma water-air is the interfacial tension of the water
of the 2 immiscible fluids that are considered and it does not depend on any particles that one

581
considers therefore, we can scale the total energy as by gamma water-air multiplied by pi R
square.

Therefore, E bar becomes this is the ratio of the particle-air interfacial tension divided by what
are air interfacial tension and this is the particle-water interfacial tension divided by particle
sorry water-air interfacial tension therefore, and if we designate this as a and this as b, this E bar
becomes a multiplied by 2 times 1 + z bar + b multiplied by 2 times 1 - z bar - 1 – z bar whole
square.
(Refer Slide Time: 30:19)

Now, because of the fact that a and b are known, that is, if we take typical these a and b values,
which are the ratio of the interfacial tension of the particle-air with respect to interfacial tension
of air-water and the polystyrene because of the fact that we are considered polystyrene particles,
the polystyrene-air and polystyrene-water interfacial energies are known and, water air
interfacial tension is 72 millinewton per meter.

So, therefore, we know what is the value of a and b and the z bar can go from plus 1 to minus 1.
So, therefore, I can plot this E bar as a function of z bar. And what is interesting in this
expression is that there is a minima at some location, it is a, this variation suggests that there is a
energy well, and, and we can actually calculate the, the positions corresponding to that minima.
So, all you need to do is take this expression that is E bar and we could differentiate this with
respect to z bar.

582
So, that is d E bar divided by d z bar and if you set that equal to 0, so, we get what is z minima
that is the coordinates that correspond to the minimum location that appears to be b - a and
because we know what is the value of b that is 0.14 – a, that is 0.49 therefore, this becomes 0.35
with a negative sign, and the fact that the z bar minimum is negative for the considered case the
particle it tells us that the particle is more in air.

And looking at this value one could make a conclusion as to whether the particle that is
considered is hydrophilic or hydrophobic. So, that means, your z bar minimum if it is equal to I
mean if the minimum occurs at z minimum is equal to 0 that means, the particle is such that the
equal half of the particle are in contact with the two fluids therefore, the particle is going to be in
neutrally wetting. So, therefore, z bar minimum value gives an indication as to whether the
particle resides more in the water phase or more in the air or oil phase.
(Refer Slide Time: 33:37)

Now, and we can we can rearrange this and then write E bar as z bar square + 2 times a - b z bar
+ 2 a + 2 b - 1 and what we could do is we can actually evaluate. So, if you want the because we
know what is the location of the particle with respect to the interface that is we know z bar
minimum I can substitute the value of z bar minimum in this expression and calculate what is the
energy that corresponds to this minimum position that means, I would have to evaluate this
expression however, by replacing z bar with z bar minimum.
(Refer Slide Time: 34:28)

583
And if you substitute for z bar minimum as b - a, it turns out that E bar minimum is 0.14. And
because we have scaled the energy with pi R square into gamma of air-water, if we can calculate
the absolute value of E minimum by multiplying this 0.14 with this pi R square into gamma air-
water and if we take particles that are like say for example 1 micro meter radius therefore, this E
bar minimum becomes 0.14 into pi that is 3.14 multiplied by 1 10 power -6 whole square into 72
into 10 power -3 in SI units and divide.

Therefore, this becomes so, that is 0.14 times, 3.14 times, 72 into 10 power -15 and if we scale
this with thermal energy at 298 Kelvin, which is the order of 4 into 10 power -21 joules
therefore, what we end up with is So, this gets cancelled therefore, typically the number that you
will get would be of the order of 10 power 6 KBT that means, So, if you look at the coordinates
of the minimum the coordinates of the minimum gives us two important parameters.

One is what is the location of the particle with respect to the interface, number two is that what is
the depth of the energy Well, in which the particles are dispersed in which the particles are
trapped and it turns out that for 1 micrometer particle this energy depth is of the order of 10
power 6 KBT and this magnitude of energy magnitude of the energy well is important because
the particles at interfaces are considered as model systems to study colloids in 2 d.

And that can only be said if the depth of energy well is much larger compared to KBT that is, in
this case 10 power 6 times KBT, number two it So, happens that the particles that are trapped at

584
an interface that is 2 dimensional colloidal systems they exhibit very high stability that means, if
you create an interface containing particles and if you ensure that the evaporation of the fluid is
minimized or you know or the condition such that the fluids do not evaporate.

And if you work with the clean fluids or the dust free in environment, it turns out that the
particles at the interface there they continue to remain in the same arrangement for several
months which is which is an indication that the particles once at the interface because of this
very high energy well, they continue to exhibit ultra-high stability an important concept in you
know which helps us to define, you know the particles at interfaces as a nice model system to
look at colloids in 2 dimensions.

585
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology, Madras

Lecture – 47
Implications from surface energy balances and Estimation of energy required for detachment

So far we have looked at some important experimental observations concerning particles located at
fluid-fluid interface. And we have also looked at the hypothesis as well as the theory that has been
put forward to explain these experimental observations. So, which are the facts that the long range
repulsion for the charged particles positioned at the interface arises due to what is called as a dipolar
nature of a dipolar that is associated with every particle at the interface.

And the dipolar-dipolar repulsion is what gives rise to long range repulsive forces. The second
aspect that was also discussed was that the particles are trapped in an energy well and typical you
know the magnitude of this energy well is of the order of 10 power 6 times the thermal energy for 1
micrometer particles and on such a high energy well, in which the particles are trapped is important
in the context of defining colloids at interfaces as a model system to look at particles at interfaces to
study particles at interfaces. What we will do now is to look at some important implications of
surface energy balance that we have done.
(Refer Slide Time: 02:09)

So, what the surface energy balance that we have looked at it provides an estimate of the equilibrium
position of the particle. So, we just plotted the scaled energy that is E bar you know as a function of
the scaled distance and it turns out that, you know, there is a minima in the surface energy plot and

586
that position provides us an estimate of the equilibrium position it will tell us whether the particle is
more residing in the aqueous phase or the water phase.

That is the particle hydrophilic or is it that the particle is residing more in the oil phase or is it that
the particles are hydrophobic and this information is important because, depending upon whether the
particle resides more in the aqua phase or more in the oil phase, one could predict the emulsion type
that is formed when such particles are used for emulsification. For example, what you are looking at
is two pictures where you have a particle that resides more in the water phase.

That is, because, if you look at the portion of the particle that is in water is more such a particles
would give rise to oil in water emulsion, that means, if the particles resides more in a particular
phase, that phase becomes the continuous phase. So, therefore, hydrophilic particles give rise to oil
in water emulsion and typical example of the particles that give all in water emulsion are silica
particles or hematite particles or any particle where the contact angle is less than 90 and the particles
are hydrophobic.

That means, if they prefer to sit in sit more in the oil phase such particles would give rise to water in
oil emulsion and therefore, the surface energy balance can be used to estimate the equilibrium
position of the particle which in turn can be used to predict or a prior check what kind of emulsion
form when such particles are used for emulsification process and the equilibrium position of the part.
Because that is again estimated by surface energy balance is also important.

because of the fact that we know that the dipolar interactions they arise because of the dissociation
of charges on the side of the particle that is in contact with the water and depending upon you know
what is the extent of immersion of particle in the water phase, there could be this is z times q is that
times e and that depends depending upon you know what is the total surface here that is in contact
with water.

This q can be higher if the particles are more hydrophilic and if the particles are hydrophobic, the q
would be lower therefore, the magnitude of the electrostatic interactions would do depend on you
know the what is the location of the particle with respect to the interface and surface energy balance
provides as an estimate of finding out what you know what is the typical area of the particle that is in
contact with ether of the fluids.
(Refer Slide Time: 06:11)

587
Now, so, what is plotted here is the surface energy as a function of scaled immersion depth, so, z is
immersion depth and what you see is two plots one generated for a particle sitting at water-decane
interface and the other generated for a same particle that is sitting at air-water interface. So, these are
ellipsoids you know or prolate ellipsoids and these are having identical charges and size and they are
at two different interfaces.

One is water-decane and water-air and as you can see that the minima in the surface energy plot
occurs at a different location that means, the in one case there you know for example, in this
particular case, this green line corresponds to the case where the particle is sitting at water-decane
interface and this red line corresponds to the case where the particle is sitting at air-water interface in
the equilibrium position. Therefore, such simple surface energy balance can be used to access if
there is a shift in the particle position with respect to the interface when you are doing experiments at
by using particles that are that are of identical charge and size however, at different interfaces.
(Refer Slide Time: 08:07)

588
So, the implication of this shift in the particle position with respect to the interface is that depending
upon whether the particle is you know at water-decane or water-air interface, they can give rise to
very different self-assembly of particles. So, what you are looking at is ellipsoids that have sulfate
groups and the major axis of the ellipsoids is 10 micrometer in both the cases in one case where that
is for the water-decane interface.

You kind of more see linear aggregates that are formed and if you look at water-air interface, you
know the particles are more clustered and they form much larger aggregates. So, therefore, this shift
in the one way to think about this would be that the shift in the position of the particle with respect to
the interface does affect colloidal interactions, and which in turn can lead to different structure at the
interface.
(Refer Slide Time: 09:23)

589
And this is another example, where 3 micrometer silica particles have been placed at the same type
of oil water interface. So, the oil-water interface in this case, oil-water interface in the next case,
however, the contact angle of the particle at the interface is different in one case, the contact angle is
65 or the case a contact angle is 152. In this case, the particle sits more in the water phase, here the
particle sits more in the oil phase and it can we can clearly see that all other condition being same.

The microstructure that you get with the contact angle 65 is very different from the microstructure
that you get at when the contact angle is 150 therefore, we can use the surface energy balance
calculations in a way to understand the influence of various different parameters on the
microstructure of the particle at the interfaces as well as to predict the emulsions that form when
such particles are used in for interface stabilization. Now, what we are going to do now is to kind of
use the surface energy balance that we have done to calculate what is the energy that is required to
detach a particle from the interface.
(Refer Slide Time: 11:02)

So, for that, we will again use this plot of the surface energy that is a scaled total surface energy as a
function of immersion depth that is z bar here and we derived this expression that the scaled surface
energy goes as z bar square times 2 times a - b z bar + 2 a + 2 b - 1 where a is given us the ratio of
the interfacial tension that of particle air to the water-air and particle and b that of particle-water to
water-air.
(Refer Slide Time: 11:47)

590
Now, what we will do is, so, this particular point corresponds to the total energy or the total surface
energy of the particle when the particle is immersed completely in air. So, is this is what the
configuration looks like you have air water interface and the so, in such a case the particle center is
at a distance R you know from the interface therefore, the scaled therefore, z is actually R that is the
location of the particles center with respect to the interface is the radius of the particle itself.

And now, this the equilibrium configuration corresponds to the case where the particle is located at
the interface and we know that the energy corresponding to that is given by E bar minimum and the
energy that corresponds to when the particle is shifted and put completely in the air phase is given by
E bar air and therefore, the energy that is required to detach a particle is given by what is the energy
total surface energy when the particle is in air phase minus what is the energy that corresponds to the
equilibrium position.

Now, and because of the fact that this z is R the scaled height z bar is going to be z r divided by R
that is going to be 1. So, therefore, we can take the total surface energy of the particle that is
corresponding of the system and then if we substitute z bar is equal to 1 we end up with what is the
energy surface energy corresponding to the particle when it is completely in air phase and similarly,
for E bar minimum.

So, I will have to take this expression and then substitute is z bar with z bar minimum that is the
coordinate that corresponds to the minimum position. So, we have already estimated that in the
previous lecture, so, what we will do is, so, we will get E bar air by substituting z bar is equal to 1

591
therefore, you have z bar square that becomes 1 and becausez bar is 1, so, the second term is 2 times
a - b and this term remains as it is.

So, therefore, this this gets canceled, so, you end up with E bar a as 4 times a that means, when the
particle is completely in the air phase, the total interfacial energy or the total surface energy is given
by 4 times a. And similarly, if we substitute for z bar with z bar minima, we know z bar minimum is
given by b - a therefore, this becomes b - a whole square plus you have 2 times a - b multiplied by b
- a and this term is as it is and I can take b - a to be common here.

So, therefore, I end up with b - a + 2 a - 2 b and this remains as it is. So, therefore, this E bar if you
do simplification E bar minimum essentially becomes 2 a + 2 b - 1 - of a - b whole square. So,
therefore, now that we have been able to calculate what is E bar air and E bar minimum.
(Refer Slide Time: 16:01)

So, we can calculate what is the detachment energy which essentially is E bar air - E bar minimum
therefore, this becomes 4 a that is E bar a - E bar minimum term therefore, Ed air that corresponds to
the energy that is required for detaching a particle into the air phase is given by 2 times a - 2 b + 1 +
1 a - b whole square and because we know that a is 0.49 and b is 0.14 we can substitute these values
and we obtain energy that is required for detaching the particle into the air phase is 1.82.
(Refer Slide Time: 16:58)

592
Of course, this is the scale energy if you want the absolute values of the energy, you would have to
multiply this term with pi R square into gamma of air water that is the area that is because we had
scaled that the expression for E bar with pi R square times gamma air-water therefore, if you want
the absolute value of the energy that is required to detach a part into the air phase, you would have to
multiply this with this term.

Similarly, we can calculate what is the energy that is required to move the particle into the water
phase in this case, the equilibrium configuration remains the same and that is given by 2 times a + 2
b - 1 - a - b whole square, but, the now the particle is shifted into the water phase and therefore, the
particle now is such that, it is at a distance again R from the interface. However, because we have
defined z in a particular way.

Therefore, z bar becomes - R divided by R, therefore, z bar becomes - 1 therefore, if you substitute
for z bar is equal to - 1 in the expression for the total surface energy, you end up with the energy of
the total surface energy of the particle when it is in water phase to be 4 b therefore, energy that is
required for detaching the particle into the water phase is given by 4 b that is this term - E bar
minimum and if you substitute for a and b E detachment into water phase turns out to be 0.42.

So, therefore this surface energy balance calculation can also be used to estimate what is the energy
that is required for detaching a particle into one of the phases depending upon the fluid particle
system that no one is dealing with. There are alternate approaches for estimating the energy of
detachment. We will try and take a look at that now.
(Refer Slide Time 19:46)

593
So, what the concept that I am going to discuss is from the book that is edited by you know, these
guys. So, what you are looking at is a schematic where there is a spherical particle of radius a, sorry
radius r and that is the radius of the particle and the contact angle is theta and you have case 1 here
and case 2 and case 1 corresponds to when the particle is at equilibrium configuration.

That means, the spherical particles is positioned at the interface and it is allowed to reach an
equilibrium position and this configuration corresponds to the equilibrium configuration of a
spherical particle of radius r contact angle theta positioned at the interface. Now, this case 2
corresponds to when the particle is removed from the interface and it is positioned in the oil phase
that means, the particles that is positioned the interface that is shifted and then that is placed
completely such that completely in the oil phase and that is shown in this schematic 2.
(Refer Slide Time: 21:50)

594
Now, what we can do is we can write an expression for configuration 1 that is when the particle is in
configuration 1 and we are going to assume that the interface is flat that means, the interface is not
deformed and G of 1 that is the interfacial energy corresponding to the equilibrium position of the
particle which we know that it is the minimum energy configuration and that is essentially given by
the summation of the three interfacial energies.

Where gamma oil-water times A oil-water is the total interfacial energy of the oil-water interface,
particle-water interfacial tension multiplied by the particle-water area is the interfacial energy
corresponding to the particle-water interface. And similarly, there is an interfacial energy
contribution that comes from the particle-oil interface. So, where A oil-water superscript 1 is the
area of the oil-water interface.

Similarly, A pw is the area of the particle-water interface and A po is the area of the particle-oil
interface and if we sum up the interfacial area that is in this the surface here the particle that is in
contact with oil that is this interfacial area and the surface area of the particle that is in contact with
water the summation of the two interfacial areas is equal to Ap which is the total surface area of the
particle which for a spherical particle is going to be 4 pi r square. So, that is the surface energy. So,
this is the surface energy that corresponds to the energy minimum configuration when the particle is
at its equilibrium position.
(Refer Slide Time: 24:28)

Similarly, we can write an expression of the total interfacial energy of the system when the particle
is detached and placed in the oil phase. And in that case, the total interfacial energy is given by there
are only two contribution because the particle is no more in contact with water. Therefore, the

595
interfacial energy conservation that comes from the particle-water interface is essentially 0 now, and
we have only contribution that comes from the oil-water interface and the particle-oil interface.

And in this case A ow superscript 2 is the area of the oil-water interface in state 2 and that is the area
of the interfacial area after the particle is detached that means, so, the particle was occupying certain
area initially now, when it is removed there is only there is the total interfacial area of the oil-water
interface is what is A ow superscript 2 and particle-water interfacial area as we said it is 0.

In this case and A po superscript 2 is the area of the particle-oil interface in state 2 and similarly, we
can write that A pw superscript 2 plus A po subscript 2 should be equal to A p and because of the
fact that this is 0 essentially A particle-oil superscript 2 is going to be A p that is the total surface
area of the particle.
(Refer Slide Time: 26:39)

Now, the energy of detachment it is defined as the energy the total surface energy of the fluid
interface particle system in state 2 minus the this interfacial energy of the system corresponding to
the equilibrium configuration that is G superscript 1. So, therefore, we can substitute the
corresponding terms for each of these terms and because we have A oil-water common. So, we are
going to take that you know outside the parentheses.

This is so, you have A oil-water superscript 2 - A oil-water superscript 1 that is the term with oil,
water interfacial tension and so, we are going to retain this term as it is and because you have a
negative sign here. So, we have to you know basically you have these 2 terms with negative sign and

596
this term will continue to remain the same and because of the fact that a particle-water superscript 2
particle-oil superscript 2.

That is the interfacial area of the particle oil interface we have said that because the particle is only
in contact with oil phase it is same as Ap therefore, we can substitute for Ap instead of A po
superscript 2 and we know that A po is same as the Ap is same as a particle-water in configuration 1
plus A particle-oil in configuration 1 and therefore, these 2 terms gets cancelled. So, this term and
sorry about that.

So, this should be so, you have not the term. We know that this term, this term, that is positive sign
here and this term this negative sign. So, therefore, these 2 terms gets cancelled. So, what we end up
with is particle-oil interfacial tension times A pw 1 minus particle-water interfacial tension
multiplied by A pw superscript 1.
(Refer Slide Time: 29:32)

And because A pw superscript 1 is common, I can take it out of the parenthesis you end up with
gamma particle oil minus gamma particle water term and we can use Young's equation which relates
the interfacial tension of the particle oil interface, particle water interface and oil water interface with
the contact angle so, therefore we can replace this term with the right hand side of Young's equation.

Therefore, we have delta G do is gamma-oil water times A oil water superscript 2 - A oil-water
superscript 1 - gamma oil-water A cos theta times a particle water superscript 1 and this term which
is which is the oil-water interfacial area in configuration 2 – oil-water interfacial area in

597
configuration 1 it is what is called as the contact area c for contact. A c is the area of the oil-water
interface occupied by the particle when it is at the fluid-fluid interface.

Now, if the particle is such that the particle is the half of the particle is in one phase and half of the
particle in the other phase, then the area that the particle occupies at the interface it is essentially pi r
square because the intersection of the particle and the interface at the equilibrium configuration gives
in the area gives a circle whose area is pi r square this would depend on what is the contact angle of
the particle with respect to the interface and this Ac which is A oil-water in configuration 2 – A oil-
water in configuration 1 it is the area of the oil-water interface that is occupied by the particle when
it is at the interface.
(Refer Slide Time: 32:17)

And so, therefore, we can similarly, we can also derive an expression for detaching a particle into the
water phase. So, detaching the particle into oil phase we obtained an expression which is gamma oil-
water into Ac + A particle water you know in configuration 1 multiplied by cos theta that is what we
obtain in the previous you know slide and similarly, we can write the interfacial energy for the
system.

When the particle is in equilibrium position that is again it will still be G1 and when the particle is
completely in the water phase, and we can do a similar surface energy calculation and it turns out
that for detaching a particle into the water phase, the interfacial the energy that is required for
detachment is given by again gamma oil-water the contact area that is the area that the particle
occupies at the interface and minus the particle-oil interfacial area in configuration times cos theta
where theta is the contact angle.

598
(Refer Slide Time: 33:35)

Now, if we are working with spherical particles, so, we know that Ap that is the total surface area of
the particle is 4 pi r square and this Rc it is the radius of the contact line. So, what we mean by that is
that, if you look at the intersection of the interface and the particle, if you see from the top we will
have a circular contact line and the radius this is given by Rc and this Rc is related to the contact
angle theta and R as Rc is equal to r time sin theta.

Therefore, the area that the particle occupies the area of the oil-water interface that the particle
occupies when is the interface is given by pi times Rc square or pi times r sin theta the square and
now that we know the contact angle theta we can do some simple geometry and then show that A
particle water in configuration 1 is 2 pi r square into 1 + cos theta and a particle-oil in configured in
1 is 2 pi r square into 1 - cos theta.

And therefore, the energy that is required for detaching a particle into oil phase, we can obtain in
definite expression, where we are going to replace Ac by the contact area that is pi r square into sine
square theta + A po, it is 2 pi r square into 1 + cos theta multiplied by cos theta because we have pi r
square and as common so, we can take that out. So, we have pi r square times gamma oil water into
sine square theta plus 2 times 1 + cos theta multiplied by cos theta and we can write this as cos
square theta + cos square theta.

This becomes one that is what you have here and 2 times cos theta + cos theta square which is
essentially becomes delta theta delta G detachment into oil phase is pi r square into gamma-oil water

599
multiplied by 1 + cos theta whole square. And similarly, we can show that detachment energy into
the water phase is given by pi r square into gamma oil-water into 1 - cos theta square.
(Refer Slide Time: 36:33)

Therefore, the energy of detachment either into the oil phase or the water phase is given by pi r
square gamma oil-water into 1 + or - cos theta square or 1 - or this you can write it as 1 - mod of cos
theta square. So, therefore, there are 2 approaches to obtaining the energy that is required for
detaching a particle into one of the fluids either by, doing a surface energy balance. We will find out
what is the energy that corresponds to the minimum.

And what is the energy that is when the particle is in one of the phases and the difference between
the 2 or you can both of them of course, you know, you can our analog is so, or you can write an
expression for the total free energy of the system when the particle is in the equilibrium position and
you shift the particle into one of the phases and then write an expression for the total interfacial
energy and the difference of that is the energy.

That is required for detaching the particle into one of the phases and this is an expression you know
a plot of the, the energy of detachment as a function of particle size that we have already seen. And
you will see that the energy of detachment essentially increases with increase in the, the particle
dimension and it goes as radius of the particle to the power 2.

600
 Colloids and Surfaces
Prof. Basavaraj Madivala Gurappa
Department of Chemical Engineering
Indian Institute of Technology – Madras

Lecture – 48
Colloidal Interactions at Interfaces

So now, to end this module, we will start look at again some aspects of colloidal interactions.
(Refer Slide Time: 00:24)

And we have seen several types of colloidal interactions in the bulk, Van der Waals interactions,
electrostatic interactions, steric interactions and other and we saw that the colloidal interactions
at the interfaces in general are modified, when compared to the corresponding interactions and
the bulk is an example of that, we found that we discussed that you know in the case of a charged
particle the electrical double layer around you know a charged particle is symmetric.

And However, when the particles are at the interface, because of the fact that the dissociation
only happens in the region of the particle surface that is in contact with you know one of the
phases depending upon the nature of the dissociable groups, we know that the electrostatic
interactions instead you know being proportional to you know e power - Kappa times the
separation distance they go as 1 over d cube right.

So, this is an example, where the electrical double layer interactions are in the at the interface are
modified in when compared to corresponding interactions the bulk and similarly, the same would

601
also hold although not discuss same would also hold good for the Van der Waals interactions as
well because we know that the permittivity of the medium in which the particles are placed you
know dictate the magnitude of the Hamaker constant.

And hence, the magnitude of the Van der Waals force of interaction now, that the particle is part
in the oil phase, or the air phase, and part in the water phase, you know it will see different fluids
that means different permittivity is you know across the interface and therefore, the Van der
Waals interactions will also be modified in when the particular the interfaces. So, although
certain interactions will get modified when the particles are at the interface.

There are also certain additional interactions that arise when the particles are at the interface.
And these interactions are typically are not present or they are absent in a when we consider
particles in the bulk.
(Refer Slide Time: 03:12)

And these examples of these interactions are what are called as interface mediated interactions or
capillary interactions.
(Refer Slide Time: 03:28)

602
And before we talk about these interactions, I would like to point out to one of the assumption
that we have been we have used in the calculation of the interfacial position and the detachment
energies is that the interface is flat that means, the interfaces unperturbed by the presence of the
particle.
(Refer Slide Time: 03:58)

However, that need not be the case if you have so, the assumption that the presence of the
particle the interface does not deform the interface is will hold good only for a weightless
particle or when the particles are very small. So, what you are looking at is two cases one is a
reference state and that shows the equilibrium configuration of a weightless particle that is the
case where the gravitational forces on the particle can be neglected.

603
And if you have the radius of the particle is R and that is related to the radius of the contact line
and sine of the contact angle by this expression and now, when you have so that is the this is for
a weightless particle right the configuration a now, in b what you have is a particle when the
interface is deformed. So, that is the dotted line that you see that is the equilibrium that is the
location of the interface when we had a weightless particle.

Now we have a force F that is the gravitational force that is acting on the particle and that is
pulling the particles down and because of which the interface is deformed, as shown by these
lines. And what you also see in the figure is that there is this u of r that is the that captures what
is the magnitude of the interface deformation and that is a function of r and this delta h it denotes
what is the shift of the colloid center because of the gravitational forces that is acting on the
particle.

And r is the radial distance from the vertical axis of symmetry that means, you know so, that is
the vertical so, that is the vertical axis of symmetry that coincides with the center of the particle
and r is measured perpendicular to this vertical axis.
(Refer Slide Time: 06:59)

Now, the extent of the shift in the particle position that is delta h and the size of the deformation
which is which is characterized by this u of r it depends on a dimensional parameter epsilon F
which is defined as minus of F divided by 2 pi r times gamma into r naught, where r naught is the

604
radius of the contact line this 2 pi r times gamma times r naught essentially gives us what is the
surface tension force that is acting at the contact line and F is the gravitation force.

So, therefore, this EF is defined as the ratio of the vertical force that is acting on the colloid that
is weight minus buoyancy and the denominator is the surface tension force that is acting at the
contact line right.
(Refer Slide Time: 08:10)

When this epsilon F is very small that means, when the interfacial when this quantity is very
small that means, when the surface tension forces are dominant then the interface deformation is
given by the linearized Young Laplace equation and in this term there are 2 terms. So, this comes
from the hydrostatic pressure contribution and this comes from the Laplace pressure contribution
and so, essentially one could solve this linearized Young Laplace equation to find out the
dependence of u of r with the radial distance r.
(Refer Slide Time: 09:15)

605
And the solution of if we consider the interfacial deformation by a single particle that means,
when there are no particles in the immediate vicinity of the particle or for an isolated particle
sitting at the interface, we can solve the linearized Young Laplace equation to obtain u going as u
naught times ln of lambda / r, where lambda is what is called as a capillary length, which is again
you know defined as the ratio of the interfacial tension contribution to the gravitation
contribution

And this has units of length and typically for if you look at water oil or water air systems this
lambda would be typically of the order of a millimeter in such a case u goes as u naught lambda
ln of lambda / R, when r is much much less than lambda and with u going as u naught going as
minus r naught epsilon F and higher order terms and for the case of r greater than lambda u
essentially, the solution becomes of this form.

And the vertical shift in lambda is minus 2 times r naught epsilon F, if you neglect the higher
order term this u naught is minus r naught epsilon F and which gives rise to delta h being minus
2 times r naught epsilon F therefore, if you know what is the gravitational force that is acting on
the particle and if you know what is the surface tension force we and the radius of the contact
line we can actually estimate what is the shift in the particle position.

And similar to the fact that the electrical double layer interactions originated when the electrical
double layer between the 2 adjacent particles overlap when there is an overlap of the interface

606
deformation that is when the capillary interactions come into picture and U capillary goes as
minus 2 pi gamma, where gamma is the interfacial tension, r naught square, where r naught is the
radius of the contact line, epsilon F square which is the non-dimensional quantity.

That we define which is the ratio of the gravitation force to the surface tension force times ln
lambda divided by d. So, therefore, one could estimate capillary interaction between the particles
when they are sufficiently close such that there is an interface deformation overlap between the 2
particles.
(Refer Slide Time: 12:35)

Now, can we discuss that the interface deformation can occur when the gravitational force acts
on the particle that is true for sufficiently big particles typically, of the order of 10 micrometer
you know are larger however, the interface deformation can also occur due to particle shape what
you are looking at is some results where what is shown is a interferometry experiments, where
the deformation around an elliptical particle under a spherical particle is shown.

And so, yellow region corresponds to negative value of you know the position of the particle
with respect to the interface and positive value corresponds to the positive you know that means
to say that when So, if you look at the fact at this spherical particle case, no matter where we are
around the particle, the interface deformation appears to be symmetric. That means, in this case,
it is always positive value of the z.

607
That means, the interfaces in the case of spherical particles, the interface would either be
elevated or depressed depending upon the nature of the particles that we are considering.
However, if you look at non-spherical particle, there is the interface deformation is that means
the value of the z is positive here and the value of the z is negative here that means, there could
be interface elevations as well as depression around the particle when the particles are elliptical
in shape.
(Refer Slide Time: 14:48)

There are been experiments which capture the interface deformation that it is the interface is
elevated in at the side and the interfaces depressed at the edge of the ellipsoid right and such
interface deformation are what are called as quadrupolar interface deformation.
(Refer Slide Time: 15:19)

608
And these interface deformations have important implications in terms of the self-assembly of
such particles. And whenever, there is an interface elevation you know that is typically referred
to as a capillary negative charge and whenever there is an interface depression by convention it is
referred to as capillary positive charge. And if you look at the nature of the self-assembly of
particles with such deformation.

We see that there is always a tip-tip connection either in in different experiments and that is
because of the rule that the like capillary charges attract therefore, whenever we you would see
an assembly of particles with such quadrupolar symmetry you will all either see or tip-tip
aggregation or side-side aggregation because, these are the only 2 configurations that lead to the
minimization of the total energy free energy of the system and the fact that the like capillary
charges attract lead to such assemblies.
(Refer Slide Time: 16:38)

And in the case where the deformation of the interface is a little bit gravity is negligible, the
distortion of the interface with respect to the planar condition that is h it obeys the Laplace
equation 2 dimension and the solution of this Laplace equation is given by this and the different
terms that you see here are what are called as capillary poles. The first term is what is called a
capillary monopole, the second term is what is called a dipole, and the third one is what is called
as quadrupolar deformation.

609
And we saw an example of that you know earlier and the monopolar deformations are typically
observed when we have spherical particle at the interface. Now, also this is an example where
there is a pin that is located that is positioned at the interface and because of the weight of the
gravity that is acting on the plane you see that the interface is actually pulled up. And if you look
at such monopolar deformation as I mentioned earlier, they will either be interface elevation at a
given our location or they will be interface depression however, in the case of dipoles and higher
order poles you will have both elevation and depression around you know isolated particles.
(Refer Slide Time: 18:29)

And these are examples where higher order poles have been observed this is a case where there
is an octopolar deformation that is that you have 8 regions that is 1, 2, 3, 4, 5, 6, 7, 8 where you
know there is interface elevation and depression occur around a particle this is an example of
again a quadrupolar deformation that occurs when you have elliptical and 2 dimensional rod like
particles.
(Refer Slide Time: 19:10)

610
So, now going further so, the interface deformation can also occur in the case of when the
particles are rough that means, if the particle are have some undulations on the surface and these
undulations can help in pinning of the contact line around the particle surface and because of this
roughness, the interface deformation need not be monopolar anymore and there have been
calculations which showed that for a rough particle.

The interface deformation again is a quadrupolar in nature. So, would also be the case when we
have particles with high surface charge what you are looking at is an example, where we have a
really large particle located at water tetradecane interface and what is plotted is the fact that the
interface these image captures that the interface is not planar anymore, and we can actually
calculate this angle psi and it turns out to be 1.29 case where the particle is charged.

However, when there is a soul effect of gravity, and this angle is given by 0.75 therefore, so, the
difference between the 2 cases is that, so, 12.9 psi is observed when the particle is charged as
against 0.75 when the particle is deformed solely because of gravity, this additional deflection
essentially comes from the fact that the particle is charged and such you know the deformation
are arising because of what is called electro dipping force.

That is in addition to the force of gravity pulling the particle down, there could be contribution
that comes from the charge of the particle and this also essentially gives rise to an additional
deformation. Therefore, there are four different factors that can lead to the interface deformation;

611
one is purely because of gravity that occurs when the particles are sufficiently large. Second,
when we have a particle that is not sphere that is when the particles are non-spherical in shape.

We can either have a quadrupolar or octopolar or you know hexapolara deformation of the
interface, we can also have interface deformation that arise because of the particle roughness and
because of surface charge in the form of electro dipping force.
(Refer Slide Time: 22:21)

So, just to conclude, so, in this module we have looked at we started with discussing how to
position particles at the interface, we looked at some applications of particle at interfaces concept
in the form of using this for emulsion stabilization in the creation of new type of particles and
new materials such as colloidosomes, and also their application in the make in the making of
porous materials as well. We looked at some additional characterization, how to obtain the
equilibrium position of particles with respect to the interface.

We discuss some important experimental observations, which lead to some hypothesis followed
by the development of theory for understanding the structure as well as the stability of particles
interfaces. And we show that we discussed that the surface energy balance calculations have
important implications in terms of understanding the structure of monolayers containing these
particles.

612
We talked about calculation of energy of detachment followed by, how the interactions are
modified, when the particles at interfaces. Finally, we discussed about interface deformation
mediate interactions that arise only when the particles are at the interface compared to the fact
that such interactions are absent when the particles are immersed in the bulk.

613
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