Critical micelle concentration

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In colloidal and surface chemistry, the critical micelle concentration (CMC) is defined as the
concentration of surfactants above which micelles form and all additional surfactants added to the
system go to micelles.[1]
The CMC is an important characteristic of a surfactant. Before reaching the CMC, the surface tension
changes strongly with the concentration of the surfactant. After reaching the CMC, the surface tension
remains relatively constant or changes with a lower slope. The value of the CMC for a given
dispersant in a given medium depends on temperature, pressure, and (sometimes strongly) on the
presence and concentration of other surface active substances and electrolytes. Micelles only form
above critical micelle temperature.
For example, the value of CMC for sodium dodecyl sulfate in water (no other additives or salts) at 25
C, atmospheric pressure, is 8x103 mol/L.[2]
The study of the aggregation of lipids (amphiphiles) is known as lipid polymorphism.
Description[edit]

Top to Bottom: Increasing concentration of surfactant in water slowly forming a layer on the surface
and eventually forming micelles at or above the CMC. Notice that the existence of micelles does not
preclude the existence of individual surfactant molecules in solution.
Upon introduction of surfactants (or any surface active materials) into the system, they will initially
partition into the interface, reducing the system free energy by:
1. lowering the energy of the interface (calculated as area times surface tension), and
2. removing the hydrophobic parts of the surfactant from contact with water.
1

Subsequently, when the surface coverage by the surfactants increases, the surface free energy (surface
tension) decreases and the surfactants start aggregating into micelles, thus again decreasing the
system's free energy by decreasing the contact area of hydrophobic parts of the surfactant with water.
Upon reaching CMC, any further addition of surfactants will just increase the number of micelles (in
the ideal case).
There are several theoretical definitions of CMC. One well-known definition is that CMC is the total
concentration of surfactants under the conditions: [3]
if C = CMC, (d3F/dCt3) = 0
F = a[micelle] + b[monomer]: function of surfactant solution
Ct: total concentration
a, b: proportional constants
The CMC generally depends on the method of measuring the samples, since a and b depend on the
properties of the solution such as conductance and photochemical characteristics. When the degree of
aggregation is monodisperse, then the CMC is not related to the method of measurement. On the other
hand, when the degree of aggregation is polydisperse, then CMC is related to both the method of
measurement and the dispersion.
The common procedure to determine the CMC from experimental data is to look for the intersection
of two straight lines traced through plots of the measured property versus the surfactant concentration.
This visual data analysis method is highly subjective and can lead to very different CMC values
depending on the type of representation, the quality of the data and the chosen interval around the
CMC.[4] A preferred method is the fit of the experimental data with a model of the measured property.
Fit functions for properties such as electrical conductivity, surface tension, NMR chemical shifts,
absorption, self-diffusion coefficients, fluorescence intensity and mean translational diffusion
coefficient of fluorescent dyes in surfactant solutions have been presented. [5][6][7] These fit functions
are based on a model for the concentrations of monomeric and micellised surfactants in solution,
which establishes a well-defined analytical definition of the CMC, independent from the technique.
The CMC is the concentration of surfactants in the bulk at which micelles start forming. The word
bulk is important because surfactants partition between the bulk and interface and CMC is
independent of interface and is therefore a characteristic of the surfactant molecule. In most situations,
such as surface tension measurements or conductivity measurements, the amount of surfactant at the
interface is negligible compared to that in the bulk and CMC can be approximated by the total
concentration.
There are important situations where interfacial areas are large and the amount of surfactant at the
interface cannot be neglected. For example if we take a solution of a surfactant above CMC and start
introducing air bubbles at the bottom of the solution, these bubbles, as they rise to the surface, pull out
the surfactants from the bulk to the top of the solution creating a foam column thus bringing down the
concentration in bulk to below CMC. This is one of the easiest methods to remove surfactants from
effluents (foam flotation). Thus in foams with sufficient interfacial area there will not be any micelles.
Similar reasoning holds for emulsions.

The other situation arises in detergency. One initially starts off with concentrations greater than CMC
in water and on adding fabric with large interfacial area and waiting for equilibrium, the surfactant
concentration goes below CMC and no micelles are left. Therefore the solubilization plays a minor
role in detergency. Removal of oily soil occurs by modification of the contact angles and release of oil
in the form of emulsion.
Zeta potential

Diagram showing the ionic concentration and potential difference as a function of distance from the
charged surface of a particle suspended in a dispersion medium.
Zeta potential is a scientific term for electrokinetic potential[1] in colloidal dispersions. In the
colloidal chemistry literature, it is usually denoted using the Greek letter zeta (), hence -potential.
From a theoretical viewpoint, the zeta potential is the electric potential in the interfacial double layer
(DL) at the location of the slipping plane relative to a point in the bulk fluid away from the interface.
In other words, zeta potential is the potential difference between the dispersion medium and the
stationary layer of fluid attached to the dispersed particle.
The zeta potential is caused by the net electrical charge contained within the region bounded by the
slipping plane, and also depends on the location of that plane. Thus it is widely used for quantification
of the magnitude of the charge. However, zeta potential is not equal to the Stern potential or electric
surface potential in the double layer,[2] because these are defined at different locations. Such
assumptions of equality should be applied with caution. Nevertheless, zeta potential is often the only
available path for characterization of double-layer properties.
The zeta potential is a key indicator of the stability of colloidal dispersions. The magnitude of the zeta
potential indicates the degree of electrostatic repulsion between adjacent, similarly charged particles
in a dispersion. For molecules and particles that are small enough, a high zeta potential will confer
stability, i.e., the solution or dispersion will resist aggregation. When the potential is small, attractive
forces may exceed this repulsion and the dispersion may break and flocculate. So, colloids with high
zeta potential (negative or positive) are electrically stabilized while colloids with low zeta potentials
tend to coagulate or flocculate as outlined in the table. [3][4]

Zeta potential [mV]

Stability behavior of the colloid

from 0 to 5,

Rapid coagulation or flocculation

from 10 to 30

Incipient instability

from 30 to 40

Moderate stability

from 40 to 60

Good stability

more than 61

Excellent stability

Measurement of zeta potential[edit]

Zeta potential is not measurable directly but it can be calculated using theoretical models and an
experimentally-determined electrophoretic mobility or dynamic electrophoretic mobility.
Electrokinetic phenomena and electroacoustic phenomena are the usual sources of data for calculation
of zeta potential.
Electrokinetic phenomena[edit]
Main article: Electrokinetic phenomena
Electrophoresis is used for estimating zeta potential of particulates, whereas streaming
potential/current is used for porous bodies and flat surfaces. In practice, the Zeta potential of
dispersion is measured by applying an electric field across the dispersion. Particles within the
dispersion with a zeta potential will migrate toward the electrode of opposite charge with a velocity
proportional to the magnitude of the zeta potential.
This velocity is measured using the technique of the Laser Doppler Anemometer. The frequency shift
or phase shift of an incident laser beam caused by these moving particles is measured as the particle
mobility, and this mobility is converted to the zeta potential by inputting the dispersant viscosity and
dielectric permittivity, and the application of the Smoluchowski theories (see below). [5]
Electrophoresis[edit]
Main article: Electrophoresis
Electrophoretic velocity is proportional to electrophoretic mobility, which is the measurable
parameter. There are several theories that link electrophoretic mobility with zeta potential. They are
briefly described in the article on electrophoresis and in details in many books on colloid and interface
science.[6][7][8][9] There is an IUPAC Technical Report[10] prepared by a group of world experts on the
electrokinetic phenomena.
From the instrumental viewpoint, there are two different experimental techniques:
microelectrophoresis and electrophoretic light scattering. Microelectrophoresis has the advantage of
yielding an image of the moving particles. On the other hand, it is complicated by electro-osmosis at
the walls of the sample cell. Electrophoretic light scattering is based on dynamic light scattering. It
allows measurement in an open cell which eliminates the problem of electro-osmotic flow for the case
of an Uzgiris, but not a capillary cell. And, it can be used to characterize very small particles, but at
the price of the lost ability to display images of moving particles.

Both these measuring techniques may require dilution of the sample. Sometimes this dilution might
affect properties of the sample and change zeta potential. There is only one justified way to perform
this dilution - by using equilibrium supernatant. In this case the interfacial equilibrium between the
surface and the bulk liquid would be maintained and zeta potential would be the same for all volume
fractions of particles in the suspension. When the diluent is known (as is the case for a chemical
formulation), additional diluent can be prepared. If the diluent is unknown, equilibrium supernatant is
readily obtained by centrifugation.
Electroacoustic phenomena[edit]
Main article: Electroacoustic phenomena
There are two electroacoustic effects that are widely used for characterizing zeta potential: colloid
vibration current and electric sonic amplitude, see reference.[8] There are commercially available
instruments that exploit these effects for measuring dynamic electrophoretic mobility, which depends
on zeta potential.
Electroacoustic techniques have the advantage of being able to perform measurements in intact
samples, without dilution. Published and well-verified theories allow such measurements at volume
fractions up to 50%, see reference. Calculation of zeta potential from the dynamic electrophoretic
mobility requires information on the densities for particles and liquid. In addition, for larger particles
exceeding roughly 300 nm in size information on the particle size required as well.
Calculation of zeta potential[edit]
The most known and widely used theory for calculating zeta potential from experimental data is that
developed by Marian Smoluchowski in 1903.[11] This theory was originally developed for
electrophoresis; however, an extension to electroacoustics is now also available.[8] Smoluchowski's
theory is powerful because it is valid for dispersed particles of any shape and any concentration.
However, it has its limitations:

Detailed theoretical analysis proved that Smoluchowski's theory are valid only for a
sufficiently thin double layer, when the Debye length, 1/, is much smaller than the particle
radius a:

The model of the "thin double layer" offers tremendous simplifications not only for
electrophoresis theory but for many other electrokinetic and electroacoustic theories. This
model is valid for most aqueous systems because the Debye length is typically only a few
nanometers in water. The model breaks only for nano-colloids in a solution with ionic
strength approaching that of pure water.

Smoluchowski's theory neglects the contribution of surface conductivity. This is expressed in

modern theories as the condition of a small Dukhin number:

The development of electrophoretic and electroacoustic theories with a wider range of validity was a
purpose of many studies during the 20th century. There are several analytical theories that incorporate
surface conductivity and eliminate the restriction of the small Dukhin number for both the
electrokinetic and electroacoustic applications.

Early pioneering work in that direction dates back to Overbeek [12] and Booth.[13]
Modern, rigorous electrokinetic theories that are valid for any zeta potential and often any a, stem
mostly from Soviet Ukrainian (Dukhin, Shilov and others) and Australian (O'Brien, White, Hunter
and others) schools. Historically, the first one was Dukhin-Semenikhin theory.[14] A similar theory was
created 10 years later by O'Brien and Hunter. [15] Assuming a thin double layer, these theories would
yield results that are very close to the numerical solution provided by O'Brien and White. [16] There are
also general electroacoustic theories that are valid for any values of Debye length and Dukhin
number.[8][9]
http://www.funsci.com/fun3_en/exper2/exper2.htm

PRESENTATION
In this article, we collect a series of laboratory experiments which mainly concern surface phenomena
and colloidal systems. Due to their number, these experiments will be briefly described. As you know,
our articles do not intend to supply an exhaustive explanation of the topics we deal with, but rather to
give rise to a curiosity toward them and to give young people exposure to interesting categories of
natural phenomena.

INTRODUCTION
TO
SURFACE
PHENOMENA
Why do some insects succeed in skating on water instead of sinking? Why in some cases, does the
water sprinkled on a glass surface collect into drops and in other cases spread like a thin film? Why
does water climb up a thin tube? Why can you make bubbles with soapy water and not with tap
water? For reasons we will see later on, the surface of a substance has special properties. These
surface properties are what allow these strange phenomena we have mentioned. Not only that, but the
surface is also the place of contact among different substances. In short, the properties of surfaces are
so special and important that there is a branch of science, the physics of surfaces, devoted to the study
of surface phenomena.
SURFACE TENSION
A molecule of a liquid attracts the molecules which
surround it and in its turn it is attracted by them
(figure 2). For the molecules which are inside a liquid,
the resultant of all these forces is neutral and all them
are in equilibrium by reacting with each other. When
these molecules are on the surface, they are attracted
by the molecules below and by the lateral ones, but
not toward the outside. The resultant is a force
directed inside the liquid. In its turn, the cohesion
among the molecules supplies a force tangential to the
surface. So, a fluid surface behaves like an elastic
membrane which wraps and compresses the below
liquid. The surface tension expresses the force with
which the surface molecules attract each other. A way
to see the surface tension in action is to observe the
6

efforts of a bug to climb out of the water. On the

contrary, other insects, like the marsh treaders and the
water striders, exploit the surface tension to skate on
the water without sinking. Here are some simple
experiments using surface tension:
1 -The floating needle.
Carefully place a needle on the surface of a glass of
water. If the water does not completely wet it, you will
see the needle float. To avoid your fingers disturbing
the surface as you place the needle, you can make a
small cradle from wire to hold the needle as you lower
it gently on to the surface of the water. Another way to
make it easier to float an object heavier than water
using only the surface tension is to first float a strip of
tissue paper and lay the needle on it. Slowly, the water
will soak the strip, which will eventually sink, while
the needle will remain on the surface.
Figure 3 - Floating needle. At the bottom of the pot you
can see the sunken strip of tissue paper.

2 - Make sulfur powder sink. Sprinkle some sulfur powder over a glass of water (You can buy sulfur
in a hardware store). Sulfur is hydrophobic enough to float on the water. Add a drop of detergent and
you will see the particles of sulfur sink. This experiment also works with talcum powder which you
probably
already
have
in
your
home.
http://www.ilpi.com/genchem/demo/tension/ has a short movie on this experiment and a description of
the properties of surfactants.
3 - Launch of the needle. With some steel wire, make a ring. Place a needle on the ring and submerge
in soapy water. When you extract the ring, two membranes will be formed: one at the left side of the
needle and the other at the right side. Now, with a finger burst one of these membranes. The needle
will be thrown away by the surface tension of the remaining membrane, which quickly contracts, in
an effort to achieve the smallest possible surface area.
4 - The strength of the soap films.
With some iron wire, make a "U" frame and a slider, as shown by the
figure 4. Plunge the frame in soapy water. When you extract it, you will
see that the slider will be drawn toward the bottom of the frame by the
surface tension of the soap membrane. By holding the slider still with
your fingers, you can feel the force of the membrane.
Figure 4 - U-shaped frame with slider. The surface tension of the
membrane draws the slider toward left.

5 - Measuring the surface tension. In order to measure the surface tension of a liquid, you can use
an equal-arm analytical balance. As shown by the figures 5 and 6, hang a U-shaped steel wire under
one of the two weighing pans (A). By lowering the A arm and then by lifting it up again, make a
membrane to form in the U-shaped frame. Balance it with some masses on the weighing pan B. At
this point, break the film. The balance will go down by the B side, therefore restore the equilibrium
placing some masses on the side A. The value of these last masses (F) corresponds to the force with
which the membrane tends to close into the liquid. The surface tension (T) is given by the force (F)
divided by the width (W) of the membrane, divided again by two because it is necessary to keep into
account the membrane possess two surfaces. So, T = F/2W. The value of the surface tension of the
distilled water is 7,42 g/m at 20C and that of ethyl alcohol is 2,27 g/m always at 20C. We supply to
you these values because you will be allowed to compare with them those you obtain through
experimentation. If you do not possess an analytical balance, you can build one of them. It will not be
as exact, but it will allow you to do these measures. Given the forces which play in this experiment,
the balance should have an accuracy of a hundredth of a gram at least.
http://www.pvri.com/sp/BalBuild.htm How to build a no cost sensitive balance (by Salvatore
Previtera)
http://userpages.prexar.com/dwilliamsmaine/scale/scale.html A Home-made Balance Scale (by Dan
Williams)

6 - Other method to measure the surface tension. To measure the surface tension of liquids, you
can use a metal wire ring of the diameter comprised between 3 and 4 cm, instead of the "U" frame we
have described. This wire should be made of platinum, anyway, as this material is costly and not easy
to find, use a stainless steel wire which you can buy in a welding shop or in a hardware store. If you
have difficulty finding a wire of this material, use an iron wire. Its diameter should be of 1 - 2 mm.
Even
in
this
case
you
should
use
an
analytical
balance.
Dip the ring just under the surface of the liquid of which you want determine the surface tension.
Level the balance in these conditions. Add some masses on the opposite arm until the ring detaches
from the liquid. The surface tension (T) of the liquid will be given by the detachment force (F) you
have measured divided by two times the mean circumference (crf) of the ring: T = F/2crf. This factor
2 takes into account the two surfaces of liquid: the internal one and the external one to the ring (figure
8). For reasons of clarity, in the figure the ring has been drawn with the diameter greater than the
actual
diameter.
http://www.tensiometry.com/STMethods.htm Other methods to measure the surface tension.
7 - With distilled water, verify the good working order of your experimental system.
8
Determine
the
surface
tension
of
the
tap
water.
9 - Determine the surface tension of the tap water to which you have added a little detergent. You will
notice that small amounts of surfactants are sufficient to lower the surface tension of the water a lot.
10 - Relationship between the weight of the drops and the surface tension. By a dropper, slowly
drop some water of the test 8 and determine the mass of a certain number of drops (ie 30). Do the
same thing with the water of the experiment n 9. Verify if there is a relationship between the mass of
the drops and the surface tension of the solutions. Answer: The mass of the drops is proportional to
the surface tension of the liquid: M = T/K, where K is a constant which you can determine using
distilled water at 20C of which you know the surface tension. This constant is valuable only for this
dropper. Determine the mass of a given number of drops is a method to measure the surface tension of
a liquid. In these tests, to obtain a better precision, calculate the mean of a series of measures. Verify if
the following relationships are valuable: T1:M1 = T2:M2.
11 - Surfactant powered boats. From a thin wooden or cardboard sheet, cut three little "boats" like
those indicated in the figure 9. They must have an opening with a seat for a bit of soap. Place a bit of
soap in the seat of a boat and put it in a small basin with water. You will see the boat move quickly
forward. With the opening on a side or off-center, the boat will turn. The movement of the boat can be
explained by the quick scatter of surfactant molecules on the water surface, so this little boat would
move by reaction. Another explanation recalls Marangoni's effect, according to which, in case of a
9

gradient of surface tension from one zone of a liquid to another,

there will be established a flow from the zone of low surface
tension toward the one of high surface tension. In this case, the boat
will be dragged by the movement of the water surface. This
amusing experiment can also be done using substances other than
soap, provided they have surface active properties. For example,
you could place a little drop of detergent on the carving. If you will
use a bit of camphor, your boat will sail more quickly and longer. If
the stretch of water in which the boat moves is small, like a dish or
a small basin, quickly the water surface will be covered by a layer of surfactant molecules and the
boat will stop and you will need to change the water to restart the boat. If instead you do these
experiments in a pond, you will not have this problem. Try different shapes of boat and of carving, try
hot and cold water, different types of soap, etc. The water will quickly soak through the wood or
especially the cardboard of your boat and will disable it. Some boards will even sink. To save your
fleet, make the little boats waterproof with acrylic paint or flatting. When the paint dries, you will be
able to restart the races.
http://hyperphysics.phy-astr.gsu.edu/hbase/surten.html
Surface
Tension
***
http://teachers.net/lessons/posts/224.html
Surface
tension
on
coins
http://www.online-tensiometer.com/oberfl/ Some experiments on the surface tension
http://www.biologylessons.sdsu.edu/ta/classes/lab1/TG.html
Properties
of
Water
http://www.ed.gov/pubs/parents/Science/soap.html Have you ever tried using soap to power a boat?
Internet keywords: surface tension, surface phenomena, surface tension boat, soap boat.

WETTABILITY
Why does one fabric absorb water well while another seems to refuse it? Why does water collect into
large drops on a greasy surface and instead form an adherent film on a clean surface? According to the
nature of the liquid and the solid, a drop of liquid placed on a solid surface will adhere to it more or
less. To understand this phenomenon it is necessary to take into account the fact that molecules of a
liquid are subject to a cohesive force which keeps them united to one another, but there is also an
adhesive force which is the force with which the molecules of the liquid adhere to the surface of
materials that they contact. When the forces of adhesion are greater than the forces of cohesion, the
liquid tends to wet the surface, when instead the forces of adhesion are less by comparison to those of
cohesion, the liquid tends to "refuse" the surface. In this people speak of wettability between liquids
and solids. For example, water wets clean glass, but it does not wet wax.
1 - Measuring the contact angle. Place a drop of a liquid on a smooth surface of a solid. According
to the wettability of the liquid in relationship to this solid, the drop will make a certain angle of
contact with the solid. With reference to the figure 10, if the contact angle is lower than 90, the solid
is called wettable, if the contact angle is wider than 90, the solid is named non-wettable. A contact
angle equal to zero indicates complete wettability. To measure the contact angle use a protractor and a
ruler. Taking a picture of the outline of the drop will make easier and more exact the measurement.

10

2 - Prominent drops, flat drops. Lay a water drop on a dirty glass plate. For example a glass with a
lot of fingerprints. Measure the contact angle. Now wash the plate with water and detergent, then rinse
it with care and dry it. Make the test again and compare the contact angle in the two cases.
3 - Misted plate. Breathe on a glass plate which has been washed, but not very well. You will see the
plate become misted, this is due to the formation of a myriad of tiny water drops on the surface of the
glass.
4 - Water film. With water and detergent, wash a plate of glass well, then rinse it a first time with tap
water and then with distilled water and leave it to dry in a place devoid of dust. Now, breathe on it. If
the plate of glass is very clean, it will not mist because the water will arrange on the surface as a thin
and continuous film of water. This happens because the water has complete wettability toward a clean
glass. If the cleaning method above has not cleaned the plate well enough, wipe it with a cotton cloth
with some pure acetone in it. Use caution because acetone is inflammable and toxic, so do this
operation outdoors and with care.
By studying plants, a German scientist discovered a method to keep surfaces clean or to clean them
with less water. You have to cover the surface with a thin layer of wax. This substance has a very low
wettability toward the water. It tends to keep clean and it is commonly used to enhance the cleanliness
and appearance of buildings and vehicles.
http://www.fys.uio.no/~eaker/thesis/node9.html
http://www.ksvinc.com/contact_angle.htm
Contact
Internet keywords: wettability, interfacial tension, IFT, contact angle

Wettability
Angles

11

CAPILLARITY
Let us stay in the field of the wettability. Surely
you have noticed that water tends to rise near the
walls of a glass container. This happens because
the molecules of this liquid have a strong tendency
to adhere to the glass. Liquids which wet the walls
make concave surfaces (eg: water/glass), those
which do not wet them, make convex surfaces (eg:
mercury/glass). Inside tubes with internal diameter
smaller than 2 mm, called capillary tubes, a
wettable liquid forms a concave meniscus in its
upper surface and tends to go up along the tube
(figure 11). On the contrary, a non-wettable liquid
forms a convex meniscus and its level tends to go
down. The amount of liquid attracted by the
capillary rises until the forces which attract it
balance the weight of the fluid column. The rising
or the lowering of the level of the liquids into thin
tubes is named capillarity. Also the capillarity is
driven by the forces of cohesion and adhesion we
have already mentioned.

1 - The rise of water along a capillary. Immerse a capillary in a glass containing tap water and
measure the height (h) of the water column inside it.
2 - Effect of the surfactants. Add a few drops of detergent to the water and measure again. Compare
the variation in the height of the water column. You will be able to notice that even small amounts of
surfactants produce important effects on the level reached by the water in the capillary.
3 - Effect of the diameter of the capillary. With a tube of glass and a Bunsen burner, make a series
of capillary tubes having different diameter. Verify the relationship between the height of the water
column and the internal diameter of the capillary. (Answer: the height of the column is described by
this formula h=k/r, where h is the height of the column, k is a constant which depends on the surface
tension of the liquid and on the contact angle between the liquid and the wall, r is the internal radius
of the capillary tube. So, with the same liquid and material of the capillary tube, the height of the
column is in inverse proportion to the diameter of the capillary tube. You can determine the value of k
for water using distilled water at 20C.
4 - Try other liquids. Make some other tests with liquids other than water, such as alcohol, oil, etc.
and measure the height of the liquid column. This height depends by a number of factors such as the
surface tension of the liquid, the contact angle liquid/capillary, the radius of the capillary, the density
of the liquid, the acceleration of gravity. In fact, the column attains the height of equilibrium between
the ascensional forces and its own weight. Oily substances tend to contaminate inside the capillary, so
when changing from one liquid to another, clean the capillary well or replace it. The vegetable world
exploits capillarity and osmosis to bring water up to the higher parts of plants. In this way, some trees
succeed in bringing this precious liquid up to 120 meters above the ground.
5 - An emergency plant watering system. It is summer and you are going on vacation. You are
worried about your potted plants, which risk to remain without water. In fact, even if you have asked
your neighbor to water them, you know by experience that after the first day, he will forget, that's just
the way he is. Then, try this emergency watering system. It bases itself on the fact that a string is able
to carry water among its fibers by capillarity. Place a tank on some bricks and fill it with water. Place
12

the pots round the drum. Cut some pieces of string long enough to reach the bottom of the tank and to
be inserted into a pot. Immerse all strings in the water to soak them well. Tie all the strings together at
one end and sink this knot to the bottom of the drum with a stone or weight. Now, one at the time, put
the free end of each string into a different pot. Each pot has to be served by a string. Test the system
before you go on your vacation. You have to verify if it works well, to find the suitable type of string
and to proportion the amount of water in the tank to the length of your absence. Try strings made up
of fibers of different dimension, of different materials, even in plastic. If the string tends to become
encrusted with mineral deposits, add some vinegar to the water. Also try to insert each string in a thin
plastic tube. If the water flow is too fast, use a thinner string. Check the effect of some drops of
detergent on the flow.
http://www.svce.ac.in/~msubbu/FM-WebBook/Unit-I/Capillarity.htm
Internet keywords: capillary, capillarity.

Capillarity

SOAPS
AND
DETERGENTS
How do soaps and detergents work in removing dirt? Soaps and detergents are formed by special
molecules, which have a hydrophilic head, which therefore loves to remain in water and a
hydrophobic tail, which avoids water and loves fat substances (figure 12 A). Because of their
hydrophobic tail, a part of the molecules of detergent collects to the water surface forming a
monomolecular layer (figure 12 B), it lowers the surface tension of the water and makes easier its
penetration into the fabrics to be cleaned. Within the water, the molecules of detergent collect
themselves in micelles and membranes, little aggregates of molecules united by their hydrophobic tail
(figure 12 B). When they meet dirt, these molecules surround the particles and insert their tail in them.
The hydrophilic heads attract the dirt toward water and with the agitation of the liquid they contribute
to remove the dirt from the fabric (figure 12 D). The crown of hydrophilic heads carries the particles
of dirt in the water (figure 12 D), where they end up in suspension and then they are rinsed away.
Hence, the dirt water contains also greasy particles which have been emulsified. For the same reason,
the detergents aid the formation of emulsions. The substances which lower the surface tension of a
liquid are called surfactants (from: surface-active agents). The lowering of the surface tension of the
water allows the formation of soapy membranes (figure 12 C), foam and soap bubbles. Notice the
special arrangement of the surfactant molecules in these membranes.

13

The phospholipids are molecules like surfactants, they also have a hydrophilic head and this time two
hydrophobic tails. These molecules are the main components of the membranes of cells. In fact,
usually the membranes of cells are made up of two layers of phospholipids, with the tails turned
inward, in the attempt to avoid water. As we know, the external membrane of a cell contains all the
organelles and the cytoplasm. Liposomes are empty cells which are manufactured by some industries.
They are microscopic vesicles or containers, formed by the membrane alone. They are widely used in
the pharmaceutical and cosmetic fields because it is possible to insert chemicals inside them. You can
use liposomes to contain hydrophobic chemicals such as greasy or oily substances so that they can be
dispersed in an aqueous medium by virtue of the hydrophilic properties of the membrane of the
liposomes.
http://cellbio.utmb.edu/cellbio/membrane_intro.htm
Membrane
Structure
and
Function
http://ntri.tamuk.edu/cell/membranes.html
Architecture
of
membranes
Internet keywords: phospholipids membrane, cell membrane
1 - Comparison of the ability of different detergents. Try the efficacy of different detergents for
glass or dishes. Soil some microscope slides with the same type of fat. If you do not have microscope
slides, use glasses or even ceramic dishes. Clean all the slides with a different detergent, rinse them
well and dry them. You can check the level of cleanliness by measuring the contact angle of water
drops placed on them. Another method is to measure the reflected light by each slide in the same
conditions of illumination by means of an exposure meter: the cleaner slide reflects less light.

SOAP
BUBBLES
As long as there has been soap, making soap bubbles has been an amusement for children. Everybody
has played with soap bubbles as a child. A straw and a glass with soapy water is all that is needed to
amuse a child for hours. One child blows bubbles and others run after them and play with or pop
them. What astonishes the children is the spherical and perfect shape of the bubbles, their colors, their
transparency, their lightness which competes only with that of the butterflies and fairies. By means of
thin membranes of soapy water, it is possible to do interesting experiments and amusing games, such
as to blow bubbles of different sizes, concentric bubbles, helical bubbles, "solids" supported by
frames in metal wire, it is possible to observe and to study the coloured interference figures on the
membranes of soapy water, to obtain membranes so thin that they lose all color and become invisible,
to obtain membranes measuring some square meters of surface and bubbles of some cube meters of
volume, so that you can to trap a friend. And then you will learn to blow cubic bubbles... by using a
square straw, of course! No, just kidding! :)
HOW
DO
THE
SOAP
BUBBLES
FORM?
As Grownups, we pose questions like these: "How do soap bubbles form? Why does soapy water
produce foam while pure water does not?". When water sprays from a tap in a small basin, you can
see bubbles form, but they burst very soon. This is due to the fact that the surface tension of the
normal water is high and it tends to draw the water molecules into the main body of the water, to the
point where the thickness of the bubble wall is too thin to remain intact and quickly bursts. Instead,
the surface tension of the soapy water is much lower: about a third of the pure water, so the molecules
of the bubble are less stressed and it can last longer. Soap and detergents lower the surface tension of
water and, as we have said, they are called surfactants. As we have said in the paragraph on the soaps
and detergents, the molecules of surfactants have a hydrophilic head and a hydrophobic tail. When
these molecules are dissolved in water, they tend to collect on the surface with the tails outward,
forming continuous layers (figure 12 B). The membranes of soapy water are made up by three layers:
the external two are formed by surfactant molecules and the internal layer is formed by soapy water
(figure 12 C). These layers of surfactant molecules are very elastic and they deform easily without
breaking. They also slow the evaporation of the water film and so extend the life of the bubbles.
RECIPES
Water is an important ingredient to our recipes. Usually, to produce soap bubbles, people used a
14

mixture of tap water and soap. Unfortunately, the mineral salts which make hard water subtract a part
of soap with negative consequences on the formation of the bubbles. In fact, soap reacts with the
calcium and magnesium salts, which are in the tap water, forming an insoluble precipitate which
subtracts surfactant molecules from the solution. Instead, the detergents react with the mineral salts of
the water producing soluble compounds, so detergent are less influenced by the hardness of water. If
your tap water is soft, it is OK to use for bubbles. In any case, you will obtain the best results with
distilled water.
After the water, the most important ingredient is the base surfactant. There are a lot of surfactants
which can be used as detergents and to blow bubbles. Therefore, try some different brands of
detergent until you find the best one. Dawn and Joy brand liquid detergents for dishes supplied good
results, but try other products if you like.
The presence of water in a soapy film is important to make it last a long time. As time goes by, a part
of the water migrates by gravity and reaches the bottom of the film or of the bubble and another part
evaporates. In this way, the membrane grows thin, weakens and in the end bursts. To extend the life of
bubbles, people add substances which make the water more viscous, slowing its descent toward the
bottom. Other substances are added to slow the evaporation of the water. Substances which have these
effects are: sugar, honey, glycerin, gelatin, arabic gum, viscous liquid soap. You will have best results
if you let the soapy solution rest for a couple of days, but if you are impatient, you can use it
immediately. A cold solution makes longer lasting bubbles. For various bubble recipes, look at the
links we have put at the end of this section on bubbles.
1 - How to find the basic surfactant.
To find the main component of your recipe, the base surfactant, obtain
some dishwashing detergents, shampoo, bath soap, etc. With water, make
a solution in the ratio of 1 to 10 for each surfactant. In a place without
wind, blow a bubble of about 7 cm in diameter. Keep it on the straw
(figure 13) and measure its duration. Repeat the test 5 times for each
detergent so to obtain a more reliable mean value. Obviously, the best
detergent is the one which produces bubbles which last longer.
Figure 13 - How to keep the bubbles during the test of duration.

2 - Adjusting the secondary ingredients. A second series of tests will have the purpose of adjusting
the recipe in its secondary components, those destined to reduce the evaporation and the fluidity of
the water. Follow the same method as you did in point 1.
3 - Blow some bubbles. When the solution is ready, you will be allowed to pass to the further
experiments. In the meantime, blow some bubbles and watch them fly, carried by the wind.
4 - How to make bigger bubbles. With some thick iron wire, make a ring of about thirty cm
diameter. Immerse it in bubble solution that you have put in a small basin. Moving the ring quickly in
the air, you should be able to obtain quite large bubbles.

15

5 - Again on the force of the surface tension.

Knot a heavy cotton thread with a slipknot to the ring of the experiment
4. After you have wet the ring in the soapy solution, the ring will be
closed by a film. If you burst the membrane inside the loop, you will see
it take a circular shape (figure 14). This happens because of the surface
tension of the remaining part of the soapy film.
6 - A support for bubbles. To comfortably observe bubbles, it is
important they are steady. With some iron wire, make some rings on
which to put the bubbles. Leave a stem to each ring so you can insert it
into an object or you can shape as a pedestal. To avoid bursting the
bubbles you put on it, wet the ring with bubble solution. Wood or velvet
can support bubbles for a long time without bursting them, but are harder
to fashion into a ring shape.

7 - Study the contact surface among bubbles. On a clean glass or a rigid plastic sheet soaked with
solution, place two bubbles in contact each other. Observe the surface of contact. You will see the
smaller bubble of the two will tend to bulge into the bigger one. This happens because of the internal
pressure of the little bubble is higher than the pressure of the large ones. This also means that two
bubbles of equal diameter have a flat contact surface. After having made some bubbles in contact with
each other, produce some foam and observe it. Observe that sometimes the shapes of the foam
bubbles are the same as that of cells of biological tissues, in other cases the shapes of the cells are
different because they have to increase their surface of contact or for other reasons. Note also that the
crystals of metals often have the same shape as the foam bubbles. After all, during the solidification of
a metal, they are deformable spheres very close each other and which cannot leave empty spaces.

Figure
15
- Figure
16
- Figure
17
- Figure 18 - Figure 19 - TubeMembranes on a Membranes on a Membranes in a Membranes shaped
membrane
cubic frame. These cubic frame. The pyramidal
frame between two between two rings. It
membranes do not cubic central bubble (tetrahedron). Place rings
and has been obtained by
arrange on the faces has been placed with a bubble in the having a film breaking the film in
of the cube, but they a straw.
center.
in common. common.
are in contact each
other.
8 - Solid figures made on suitable frames. With some frames made with metal wire, you can create
flat, helical films or with many other forms. You can also create quite complex solids (figures 15, 16,
17, 18, 19, 20). To do this you have to dip a suitable frame into the soapy solution. When you will
have withdrawn it, you will see the membranes. Usually, people expect these films to form on the
faces of the solid, but this does not happen because they tend to keep into contact with each other and
16

to form figures of minimum surface area. Remember that soapy films tend to keep the shape of
smallest energy. So, if you will make a tube-shaped membrane, do not be surprised if its diameter will
reduce in the middle.
9 - Helical films. To obtain helical films (figure 20), make a helix with a few coils made up of iron
wire (like a normal spring), place a piece of wire along the axis of the helix and solder it to the two
extremities of the helix.
10 - Regular polyhedral bubbles. What shape frames are necessary to obtain central bubbles with
the shape of an octahedron, a dodecahedron, an icosahedron? It is possible fabricate them?
http://www.enchantedlearning.com/math/geometry/solids/
http://wwwalu.por.ulusiada.pt/21575200/
Internet keywords: regular polyhedra

Figure 20 - Helical film.

Figure 21 - Frames on metal wire to study the soapy

membranes.

The figure 21 shows some frames of metal wire which can be made to study the soap films and to
measure the surface tension of liquids. To build them, we have used galvanized iron wire, cut in
segments which then we have soldered with tin. You can also try plastic coating these frames by
dipping them into tool handle coating products which are sold at hardware stores.
"Why are soap bubbles colored?". The membrane of the soap bubbles are formed by three layers.
The external two are both formed by a layer of surfactant molecules with the polar head turned
inward, the inner layer is formed by soapy water (figure 12 C). The light which crosses a soap film is
in part reflected by the front surface of the membrane and by the back one. The waves of light
reflected emerge out of phase, they sum algebraically (interference), giving rise to variations of color.
The emerging hue depends on the thickness of the film. These colors are very fine and create beautiful
shapes formed by the zones of different color when turbulence is present within the film. In fact, if
you gently blow on a film, you can create magnificent designs (figures 1, 22, 23, 24). Over time, due
to evaporation or the descent of the water toward the bottom, the thickness of the membrane will have
17

become very thin, the two reflections will fade completely and the bubble will become black against a
black background: it will not show colors any more and will become invisible. In that condition, the
film will be also very unstable and near bursting.

Figure 22 - The interference Figure 23 - By gently blowing Figure 24 - By blowing again,

fringes which form as the water on the film, you can create the figures become more
flows down by gravity. As the beautiful turbulence zones which complex and rich with details.
film gets thin at the top it can be observed and studied.
becomes black because its Notice on the top the black zone
thickness is less than the has widened.
wavelength of the visible light.
11 - Colors and shapes of the figures of interference on soap films. The soap membranes are well
suited to observe the colors and the turbulences which are created by light air currents. So, by means
of a ring on iron wire, make a soap film and examine its colors. Blow lightly on the film to observe
the turbulence on its surface (figures 23 and 24). To better see the colors of the membrane, it is
worthwhile to observe it against a black background and illuminate it with bright white light. If you
keep the frame vertical, you will see the colors change as the film grows thinner. Usually, shortly
before bursting, a part of the film will become black. Here some other figures of interference: figure
31, figure 32.
12 - To cross a membrane without bursting it. If you touch a film with a dry finger, the membrane
will burst. If you will wet the same finger with the soapy solution, the film will not burst and you will
be able to penetrate it.
13 - Plays on the water. Make bubbles in a small basin of water. Look for the conditions which allow
to the bubbles to bounce or to alight on the surface without adhere to it. Place a drop of oil on the
surface of the water, which will arrange itself on the surface as a monomolecular layer, (eg. stearic
acid) and repeat the test. Also an oily hair can deposit a thin, oily layer on the waters surface, when
slowly immersed in it.

18

OSMOSIS
If you place two solutions of different
concentration side by side, keeping them
separated only by means of a membrane, you will
see the level of the more concentrated solution
increase (figure 25). This happens because the two
solutions try to attain the same concentration by
diffusion.
The
membrane
has
to
be
semipermeable, that is it has to allow the passage
of the solvent but not of the solute. The molecules
of the solvent have to be smaller than those of the
dissolved substance. In practice, this condition is
very frequent given that the molecules of water
are very small. It is necessary to remember that it
is possible to make solutions with other liquids
also. Osmosis is the tendency of the system to
reach the same concentration in both solutions. It
is a phenomenon of great importance in biology
and which is also the basis of the function of the
kidney, of the absorption of water by plants and
which is used by industries to concentrate or to
purify solutions. In fact, applying a pressure on
the side of the more concentrated solution, it is
possible to reverse the process and cause the
solvent to pass to the less concentrated solution.
This is the process of the reverse osmosis. It is
used also to purify water, to concentrate solutions,
etc.

In order to do experiments with osmosis, you need to obtain a semipermeable membrane. For this
purpose, you can use cellophane, which is a thin transparent film, essentially made up of cellulose and
which is often used to pack wrap flowers and gifts. Sometimes, florists also use a plastic which is very
like cellophane, but, instead is completely impermeable to the water and which is not suitable for
these experiments. How can you distinguish between these two materials? Putting some water on
cellophane, you will see it soften, dilate and even the opposite side of the sheet will become moist.
This does not happen with the transparent plastic sheet. You can obtain cellophane in a stationery
shop. Unfortunately, this material is often covered with a thin layer of water repellent nitrocellulose
which prevent the passage of the water. This layer can be removed by immersing the cellophane in a
solvent for varnish or perhaps in acetone. Use caution because these solvents are inflammable and
toxic.
Another possible source of semipermeable membrane can also be found in certain plastic bags. The
plastic is made from starch and is used to produce biodegradable plastic bags for recycling. In some
European cities, these plastic bags are used to collect organic wastes. When touched, this plastic is
flabby, quite elastic and near rubbery. You can also try the membrane of a chicken egg and other
membranes you will find or you are able to fabricate.
Water flows slowly through the membrane. If you limit yourself to closing the bottom of a tube, it will
take days to see the level of the inner liquid increase. To accelerate the flow, it is necessary to widen
the surface of exchange. It would be necessary to have special flared tubes, which are difficult to find.
Instead, you can use a small funnel, which is much easier to obtain.

19

1 - Diffusion by osmosis. For the first experiment, use distilled water, some sugar, a semipermeable
membrane, a beaker, and a support for pipettes. Obtain a flared tube of glass or transparent plastic. Or,
as an alternative, a little transparent funnel. The internal diameter of this tube has to be at least one
cm. With a rubber band or clamp, attach a piece of membrane on the flared bottom of the tube and
then pour the concentrated solution of sugar in the tube. Insert the tube in a beaker and put water into
it until you attain the same level of the solution in the tube. After some hours, you should see the level
of the liquid in the tube is increased (figure 25). After some time, the level will attain a maximum. If,
instead of tap water, you will use distilled water, the phenomenon will be more evident. To render
more visible the concentrated solution, you can add a drop of ink or some watercolor. Why does the
more concentrated solution rise? As we said, there is a tendency of the two solutions in contact via a
semipermeable membrane to reach the same concentration. The more concentrated solution absorbs
solvent from the more diluted. In these experiments, the level of the liquid in the tube increases, but
not to infinity. It goes up until the pressure of the liquid column attains the equilibrium with the
osmotic pressure. The equilibrium pressure between a solution and its solvent is the osmotic pressure
of that solution.
2 - Osmotic pressure and density of the solution. Determine the osmotic pressure of some solutions.
Verify if it is proportional to the amount of molecules per volume of the solution.
3 - When the dissolved particles are very small. If, instead of the sugar, you will use salt, the
osmotic pressure will result very low. This happens because in water the salt dissociates itself into the
Na+ and Cl- ions, which are smaller than the molecules of water and they easily pass through the
semipermeable membrane.
4 - Osmotic pressure and microorganisms. Place under the microscope a slide with a small drop of
water rich in protists, then add a pair of drops of distilled water. At the beginning, the protists will
swell and you will see their vacuoles work very hard in the attempt to expel the excess water from
their cytoplasm, then you will see their cellule explode, pouring their organelles outward. The cilia of
the mouth will continue to beat for long time, even if they are not connected to the body any more.

INTRODUCTION
TO
THE
COLLOIDAL
SYSTEMS
Let us leave the surface phenomena to enter into the mysterious world of the colloids. A first example
of a colloid is gelatin, a strange substance: neither liquid nor solid. It is very elastic and if deformed it
returns to its previous shape. Goofy, the friend of Mickey and Donald, learned something about it
when, in the Disney film: Mickey and the Beanstalk, he was "walking" on a pudding of the Giant. The
emulsion of oil in water is another substance with unusual properties. Unusual are also substances
such as foams, aerosols, smokes and fogs, not to mention the solid emulsions and foams. What do all
these curious substances have in common? That is what we will see before long. These substances are
called colloids and they are in some ways related to the solutions and to the mixtures, even if they do
not belong to the former nor latter. To understand what colloids are, it is necessary to know what
solutions and mixtures are.

SOLUTIONS
A solution is a homogeneous mixture of two or more substances. When placed in water, many
substances dissolve and are called soluble, others do not dissolve and are called insoluble. Salt and
sugar easily dissolve in water. If instead you put sand in water, you can mix for as long as you want,
but you will not succeed in dissolving the sand. In fact, sand is insoluble in water. In a solution, the
material present in greater quantity is defined solvent and that in smaller quantity solute. What does it
mean to say that a substance is soluble in another? It means that the molecules of the solute separate
each other and they disperse among those of the solvent. Instead, the insoluble substances keep
themselves compact and their molecules do not disperse into the solvent. As solvent, we have used the
example of water because many solids are soluble in water, but nearly every liquid can be a solvent.
20

And then, why we should limit ourselves to the liquids? Let us generalize the concept of solvent and
concede to all substances, solid or liquid or gaseous the possibility to be a solvent. At this point, even
the solutes can belong to all of these three states of matter. For example, some solid solutions are the
metal alloys such as steel (Fe+C), brass (Cu+Zn), bronze (Cu+Sn). Finally, all gases are completely
soluble among each other. Also common are solutions of gases in liquids. For example, carbon
dioxide is added to many beverages to make them fizz. In the water of ponds, rivers and seas, gases
like oxygen, carbon dioxide and others go into solution in a natural way. The presence of these gases
in the water make possible the life of the aquatic organisms.
The solubility of a substance is measured as the maximum amount, in grams, which can be dissolved
in 100 g of solvent. When the solute does not dissolve any more, but a deposit is formed on the
bottom, the solution is defined saturated.

CATEGORIES OF SOLUTIONS

SOLUTE

SOLVENT EXAMPLE

Gas

Gas

air (nitrogen, oxygen, etc.)

Liquid

Gas

moist air (water vapor in air)

Solid

Gas

atmospheric dust

Gas

Liquid

CO2 in water (sparkling water)

Liquid

Liquid

wine (water + alcohol)

Solid

Liquid

marine water (salt in water)

Gas

Solid

gas in silicates (pumice stone)

Liquid

Solid

dental alloys
cadmium)

Solid

Solid

metal alloys (steel, bronze)

(mercury

in

1 - Saturated solution. Determine the content of salt in a saturated solution. In order to not waste too
much salt, use only a little water.
2 - To grow crystals. Determining the density of sugar in a saturated solution is not easy because
sugar continues always to dissolve. Anyway, make a heavy sugar solution and a saturated solution of
salt in water. Put a cotton thread in each of them and wait some days for some crystals to grow.
Describe the shape of these crystals. If you like to grow crystals, it is possible to find packets of salts
specially chosen to this purpose. Also search the Internet with the words: growing crystals.
3 - Where does sugar go? Put a beaker on a magnetic stirrer, insert the stir bar and fill the container
with water up to the top. Slowly, add grains of sugar so they are dissolved by the stir bar as it rotates.
Note the amount of sugar you will have put into the water before it overflows. Do the same thing with
salt and then with sand. Compare the results and explain the different behaviors.
4 - How to separate salt from sand? Solve this problem: A day, a child who lived on the border of
the desert was sent to buy some salt. While he was coming back and he was playing with friends of
his own, the bag broke and the sand shed on the sand. For these people the sand was important and
costly, so that child would be scold by his parents. How would have you done to recover the precious
salt, separating it from the sand?
21

MIXTURES
As we have seen, by mixing sugar with water, a solution is obtained. If instead we mix sand into
water, we obtain a mixture. Also by mixing bits of coal and iron filings we obtain a mixture. With a
pair of thin tweezers it is possible to take away sand grains from the water or pieces of coal from the
filings, but it is not possible to take away singly molecules of sugar from the water because they are
too much small. Hence, what distinguishes a mixture from a solution? In a mixture the particles are
enough large to be separated by mechanical means such as tweezers or sieves, in a solution this is not
possible because the particles which form it are so small that they cannot be seen even with an
electron microscope. To separate the components of a solution it is necessary to use physical method
like distillation. So, mixtures are formed by quite big particles, solution are formed by very small
particles.
1 - A mixture. Make a mixture, for example by using sand and wood sawdust. How could you
quickly separate the two components?
2 - Sedimentation speed and size of the particles. As indicated in the experiment on the analysis of
the soil composition in the article on the experiments on environmental education and biology, put
some water and a sample of earth in a glass or transparent plastic jar. Close the pot and shake it until
all the earth is dissolved. Place the jar at rest and observe the different layers of materials. On the
bottom, there will be stones and gravel, then thick sand and fine sand. Silt will require half an hour to
be deposited, clay will demand 24 hours. Very small particles will remain in suspension, some of them
will deposit very slowly, the finest ones instead will never deposit. Some other substances will have
gone into solution. It seems the Etruscans collected the very fine clay which deposited after some
days to obtain the black color of their earthenware.
3 - To separate particles according their grain size. If you want to separate the thick sand from the
finer sand, you can use a sieve. If you want to clean sand from silt and clay, you can use flowing
water. With a plastic tube, make water flow into the container of the sand. The water will carry away
the smaller particles, while the larger ones will remain in the container. This method exploits the
different sedimentation speeds to separate the particles of different grain size. Usually, the sand
destined to be put in aquariums is cleaned to avoid water contamination. By using a sieve and with
sedimentations and cleanings, produce 100 g of thick sand, 100 g of thin sand, 100 g of silt and 100 g
of clay. Remove the water in excess and let all components dry to obtain moist sands, soft silt and
clay. Compare the properties of these materials.
4 Observe under the microscope the finest particles. With a microscope, try to measure the size of
the particles of silt, clay and of those which remain in suspension in water during your experiments of
sedimentation.

COLLOIDS
We have seen that in the solutions, the molecules of the solute separate each other and disperse among
those of the solvent. In the mixtures instead, the molecules do not separate and the particles remain
compact. From the point of view of the sizes, solutions are formed by very small particles (single
molecules) and the mixtures by quite large particles. In an intermediate position, between mixtures
and solutions, there are the colloids. They are dispersions of small particles, but not molecule sized.
What distinguishes mixtures from colloids and from solutions is therefore the size of the particles
which form them. By convention, a colloid is a dispersion of particles which size is comprised
between 0.2 and 0.002 m (a micrometer, or micron, = 10 -6 meters). If the particles are larger than 0.2
m, we have a mixture, if they are smaller than 0.002 m, we have a solution. In general, the
components of a colloid are formed by small aggregates of molecules, while the components of a
solution are single molecules. Anyway, if these molecules are large enough, as it is the case of many
macromolecules, their solution will give a colloid. So, the criterion of distinction between colloids and
22

solutions cannot be the presence of single molecules, but as we were saying, the size of the particles
which form them.

MIXTURES

COLLOIDS

SOLUTIONS

large particles

mean particles

thin particles

> 0.2 m

0.2 - 0.002 m

< 0.002 m

According to the dispersing phase, colloids are distingued in gaseous, liquid and solid suspensions.
Gaseous suspensions, or aerosol, are smokes and fogs. Smokes are suspensions of solid particles in a
gas. Fogs are suspensions of liquid particles in a gas. Sols, gels, emulsions, foams are liquid
suspensions. Oily rocks, pumice stones are solid suspensions.

TYPES OF COLLOIDS

DISPERSED
PHASE

DISPERSANT
PHASE

NAME

Solid

Gas

Smoke - Aerosol Smoke

Liquid

Gas

Fog - Aerosol

Fog

Solid

Liquid

Sol, Gel

Paint, Gelatin

Liquid

Liquid

Emulsion

Milk

Gas

Liquid

Foam

Beer foam

Solid

Solid

Solid suspension Amethyst

Liquid

Solid

Solid emulsion

Oily rocks

Gas

Solid

Solid foam

Pumice stone

EXAMPLE

The term colloid refers to substances with a glue-like consistency, in which the dispersant phase is
therefore liquid. However, do not forget that even substances such as smokes and aerosols, in which
the dispersant phase is aeriform and which we can also call gaseous suspensions, are colloids. Finally,
even some solid substances, in which the dispersant phase is solid and which we can also call solid
suspensions, are colloids too.
Colloids have unusual properties, for example gelatin. Colloidal systems have a high ratio
area/volume among the surface of the particles and their volume. In other words, as in the colloids the
amount of dispersed particles is very large, their overall surface is very large too and by consequence
the interaction of the two phases is important. For example, a cube of 1 cm a side has a surface area of
6 cm2, the material of the same cube divided into little cubes of 0.002 m of side, has a surface area of
3000 m2. Because of the wide surface of contact between the two phases, often the colloids are
studied with the surface phenomena and the discipline which studies them is called surface and
colloid science.
23

SOL
A sol is a dispersion of very thin solid particles in a liquid. It has a liquid consistency and resembles a
true solution. An aqueous sol appears clear, very similar to common water. Anyway, if you shine an
intense beam of light across it, a part of the light will be diffused from the particles which are in
suspension. These particles are very small, but they are still enough large to obstruct the light and
diffuse it. This phenomenon is called Tyndall effect. You can observe it with sols, but not with true
solutions.
1 - Tyndall effect. In a transparent jar, put some clayey earth 1/4 of the volume and water until attain
3/4 of the container. Close the jar with its cap and shake until all the earth is "dissolved". Leave the
pot to rest for a day to allow the clay particles to settle. The liquid which is above the sediment should
have become clear. Shining an intense bundle of light through the jar, you should see the Tyndall
effect. Do the same thing with a glass of pure water and compare the results.

GEL
A gel is a dispersion of very thin solid particles in a liquid and it has a gelatinous consistency.
Increasing the concentration of the particles, a sol can pass to the state of gel. On the contrary, by
diluting a gel you will obtain a sol. So, what makes a sol different from a gel is its fluid or gelatinous
consistency. Also the temperature can determine the passage from sol to gel and vice versa. For
example, broth gelatin is gelatinous at room temperature, but it becomes liquid when it is heated.
Animal gelatin is a reversible gel because depending on the temperature it can pass from gel to sol
and vice versa The albumen of eggs instead is not reversible because when heated it coagulates and it
does not come back to the state of sol. Silica gel absorbs moisture and keeps its properties with broad
concentrations of water. Because its affinity for water it is used as dehumidifier. When left to rest, a
sol can spontaneously jell and come back to the state of sol simply by mixing it (eg: aqueous
suspensions of kaolin).

1 - Making gelatin. Buy some dry gelatin. Dissolve it in warm water and, with subsequent dilutions,
determine what is the minimum concentration of dry gelatin necessary to obtain a normal gelatin at
room temperature. Do not keep gelatins a long time because they easily become cultures of bacteria.
Store them in a refrigerator and, after a day, throw them away.
2 - Reversibility of the gelatin. By means of the temperature, make some gelatin pass from the gel to
sol states and vice versa.

24

3 - Experiments with vegetable resin. Resins are gels and they possess useful properties. Often,
fruit-bearing plants produce gelatinous spheroids which diameter can attain some centimeters.
Conifers are important producers of resins and often you can collect drops of resin which hang from
their trunk. You can also make an incision on a trunk to obtain some resin. Canada Balsam is a very
important resin in optics and in microscopy. It is extracted from the Abies balsamea, a conifer of
North America and it is used to glue lenses and to make permanent microscope slides. For their
adhesive properties, resins take part to the composition of paints. Collect resin from trees, observe
under the microscope the particles which are suspended in it. Dissolve the resin of a fruit-bearing tree
in warm water and try to obtain a glue. Dissolve the resin of a conifer in turpentine and assess their
adhesive properties.
4 - Experiments with polysaccharides. Polysaccharides are resinous gums soluble in water. They are
used in the fabrication of cosmetics, paper and in a lot of other applications. Some polysaccharides are
edible and are added in creams, yogurts and in other foods. You can obtain some polysaccharides and
experiment with their properties. In particular, add to them some water and check the consistency,
viscosity
and
adhesiveness
of
the
substance
you
will
obtain.
Absolutely do not eat polysaccharides, do not inhale their powders and do not use them in
recipes for food. If eaten dry, these substances will swell and risk obstruction of the digestive tract. If
inhaled, they will swell and risk obstruction of the respiratory airways, causing dangerous problems in
breathing. Do not use them in food recipes, but only in experiments. Keep in mind that some
polysaccharides are not edible. When hydrated, these substances become culture medium for bacteria,
so use them for a short time and then throw them away. An adult must be always present during these
tests.
http://saps1.plantsci.cam.ac.uk/worksheets/ssheet22.htm Some Gum Fun (experiments with
polysaccharides).
http://food.orst.edu/gums/foegeding.html
Hydrocolloids,
Vegetable
Gums
References.
http://class.fst.ohio-state.edu/FST605/lectures/lect20.html Gums and stabilizers (formula and other
information).
Internet keywords: polysaccharides, hydrocolloids, experiments, recipes.
5 - Making photographic gelatin. Photographic gelatins have a suspension of silver halide salts,
which are sensitive to the light. When they are still warm, these gelatins are spread on a transparent
plastic film to obtain a photographic film, or on a card to obtain paper for photographic prints. As
shown through the history of photography, there are many methods to produce photosensitive
surfaces, and many of them do not use silver salts. In the Internet you can find recipes to make
photosensitive films and paper by many techniques. These preparations require the use of substances
and procedures which can be dangerous. Read information on the caution needed. Children must be
guided
by
an
adult
who
is
expert
in
chemistry.
EMULSIONS
An emulsion is a dispersion of an insoluble liquid in another liquid. For instance, the oil is not soluble
in water. If you pour some oil in a container with water, it will float it and keeps separate from the
water. Instead, if you vigorously shake the container, you will obtain a dispersion of small drops of oil
in water, however these drops quickly join together, so that in a short time nearly all the oil will return
as before. To make the emulsion more stable, before shaking the container, add some detergent. The
surfactant molecules will arrange on the surface of the oil drops with the heads outward. As these
heads have an electrical charge and as this charge is always the same, the oil drops will repel each
other and be unable to return to the homogeneous layer as before. So, surfactants can help you to
obtain more stable emulsions. There are special surfactants for emulsions, endowed of a higher
capability to stabilize the oil drops than the detergents. There are also emulsifying agents for
alimentary use such as lecithin and emulsifiers for industrial purposes which are not edible. Butter is
formed by small water drops suspended in fat. Cheese and mayonnaise too are considered emulsions.
A lot of creams used both in pharmacy and in cosmetics are emulsions. Fuels emulsified with water
have been produced. Emulsified oils are used in machine working to make it easier to cut metals with
25

machine tools. In fact, metal cutting can create an intense heat, which has to be removed if you want
to avoid burning the tools. The oil and water in the cutting fluid help remove the heat and make it
possible to cut metals efficiently. Milk is another emulsion made up by small greasy drops in an
aqueous phase.
1 - Stability of the emulsions.
Fill two plastic bottles halfway with water,
then put 5 cc (about a spoonful) of vegetable
oil in each. Only in one of these bottles, put
0.5 cc (about 20 drops) of liquid detergent for
dishes. Close the bottles and shake them for a
couple of minutes to emulsify the oil, then
place them on a table and observe them. The
drops of oil will try to reassemble and to
surface. By comparing the two emulsions, you
will see that the one with detergent will be
much more stable (figure 28). In fact, even
after a month, the white color of this emulsion
indicates that there is a great deal of small oil
drops in the liquid, while in the other bottle the
liquid is become nearly transparent, this is a
sign that near all the oil drops have fused
together and surfaced.
2 - Vinegar and vegetable oil. Using a kitchen
whisk, emulsify a teaspoon of vinegar with
125 cc of peanut oil or olive oil. The emulsion
will result instable.

Figure 28 - The two emulsions of the experiment 1

after 24 hours of rest. In the right bottle, some
detergent has produced a more stable emulsion.

3 - Mayonnaise. To the ingredients of the test 2, add an egg yolk and emulsify again. The emulsion will be
much more stable. Add some salt and if you want some pepper and you will have obtained a good mayonnaise.
If you prefer, you can replace the vinegar with lemon juice. Why is the emulsion stable with the egg yolk? This
is due to the presence of lecithin in the egg yolk. Lecithin is a surfactant and the molecules spread on the surface
of the oil drops with the hydrophilic head outward. As these heads are electrically charged, the oil drops will
repel and their merging is prevented. Lecithin is a phospholipid and it has a structure like that of the
phospholipids which form the membranes of cells. Another well known lecithin and which you can find on the
market is soy lecithin.

FOAMS
Foam is a dispersion of a gas in a liquid (liquid foams) or in a solid (solid foams). Among the liquid
foams, we have the ones produced by soaps and detergents, and various foods such as wine, beer and
many others. Among the solid foams we have Pumice stone, earthenware, sponges, expanded plastics
like expanded polystyrene and expanded polyurethane. By dispersing helium in a liquid which
produced bubbles with very thin walls and which then solidified, some researchers succeeded in
fabricating a solid foam lighter than air.

26

1 - Foam and shape of the bubbles in contact. With a drop of liquid detergent in a small basin of
water, make a foam. Observe the shape of the bubbles which are in contact each other. With a
microscope, observe a thin section of elder pith and compare it with the foam.
2 - Make a solid foam. Beat egg whites and some sugar, then cook it so to obtain its solidification:
you will have obtained a meringue, just an edible solid foam.

OTHER EXPERIMENTS WITH SURFACTANTS AND COLLOIDS

1 - Who can guess more colloids? List the colloids you have in your home or which you know by experience:
(milk, mayonnaise, resin, paint, ink, expanded polystyrene, cell cytoplasm, blood serum, etc.).
2 - A half-solid fluid. Put in a cup four spoons of corn starch. Add some water until you have obtained a creamy
substance. While mixing, you will notice that this substance has an odd property: if you slowly mix it, it behaves
like a liquid, but if you try to mix it fast, it seems solid. By quickly lifting it on a side, you will be also able to
remove this cream from the cup, but you will have some difficulties in keeping it in your hands because, even if
it moves slowly, it will escape from all sides like a liquid. Liquids which change viscosity with the mixing speed
are called dilatant fluids. Also wet sand behaves as dilatant fluid. Sold in the US as a childs toy under the name
of Gak or Goo, you can make your own by dissolving 1/2 cup of white glue with 1/2 cup of water, then adding 3
tablespoons of Borax, while stirring well. You will obtain a substance which is apparently solid, but which loses
its shape within some minutes, becoming like a liquid puddle... which however you will able to lift it as if it was
a carpet.

ATOMIZER
FOR
AEROSOL
How do atomizers work? There are many models of atomizers or of sprayers like those of pressurized spray
paint cans, or those provided with a small pump that you press with a finger, those that work by mean of a
rubber syringe or, for industrial uses, by a compressor.
1 - Anatomy of an atomizer.
Disassemble a trigger spray bottle. Often, these devices
breaks so, if you have one of them broken, dismantle it to try
to understand why it does not work any more and try to
repair
it.
http://www.howstuffworks.com/question673.htm
Trigger
spray bottle.
2 - Build an atomizer. To build a small atomizer, take two
thin straws and fix them as shown in figure 30. At the end of
the horizontal straw, insert a plug with a hole of one mm of
diameter. Under the vertical straw, mount a small bottle with
water. Now, blow with force in the horizontal straw. The air
jet which comes out of the hole will cause an area of low
pressure above the vertical can which will draw some water
up the straw and blow it away atomizing it. To produce an air
jet, you can also use a rubber syringe. Usually, this type of
atomizers is used for perfumes, but you can use it also to
humidify the leaves of a house plant.
Instruments
Since our research is strongly experimentally oriented, we maintain a substantial instrumental park in
our laboratory. These instruments can be classified in three main groups, namely light scattering,
atomic force microscopy, and surface sensitive techniques. We also operate various standard

27

laboratory equipment, such as, refractometers, viscometers, titrators, pH sensors, conductivity

meters, or water purification systems.
General course objectives:
This introductory master course presents colloid and surface chemistry. The course deals
with important principles and phenomena related to colloid systems and surface
chemistry. These subjects are fundamental to the understanding and design of a range of
processes like e.g. adhesion, lubrication, cleaning, oil recovery, water and air purification.
Furthermore the subjects are essential for the application and design of a number of
chemical products like e.g. paint, glue, detergents, cosmetics, drugs and foods. Finally,
the course offers understanding of several naturally occurring phenomena like e.g. fog,
rain drops, the capillary effect the red sunset, the blue sky and the rainbow, and beer
foam.
Learning objectives:
A student who has met the objectives of the course will be able to:

evaluate and describe colloidal nano-technological and chemical systems,

processes and products

use different theories to calculate surface and interfaces tensions and use this to
estimate e.g. wetting and other system characteristics

identify mechanisms for adhesion between surfaces and materials and use
different methods to estimate this

describe the most important and fundamental theories in surface chemistry

explain micellation of surfactants, know how to measure this and calculate

dependencies of salt concentration, system temperature and surfactant chain
length

compare and understand adsorption in gas-liquid and solid-liquid surfaces and

perform quantitative adsorption calculations

calculate molar mass and molecular shape of colloid particles and polymers based
on experimental data

describe the interactions between colloidal particles and identify similarities and
differences for the governing molecular forces and interactions

explain the most important parameters for the theories of colloidal interaction and
perform calculations using the theories

describe the conditions for stability of colloidal systems and discuss and compare
different mechanisms for stabilization

describe mechanisms for stabilization of emulsions and foam, and design

emulsions and foam by using various semi-empirical methods

Content:
i. Common presentation of colloidal and surface phenomena
ii. Theories for calculating surface tension (in air), liquid-liquid interfacial tensions as well

28

as interfacial tensions for solid surfaces

iii. Fundamental theory (Young-Laplace, Kelvin equation, Youngs equation for contact
angle and Gibbs adsorption theory)
iv. Surfactants detergents: micellation (critical micellar concentration, CMC) adsorption
of surfactants on surfaces
v. Adsorption at gas-liquid, liquid-liquid and solid-liquid surfaces. Langmuir and BET
theories
vi. Wetting and adhesion mechanisms and calculations including Zisman's plot
vii. Kinetic, optical and electric properties of colloidal particles
viii. Experimental metods for characterising colloidal particles estimation and
measurement of structure, size and shape
ix. Intermolecular og interparticle forces: van der Waals and double-layer forces (zeta
potential, Debye thickness, Hamaker constant)
x. Stability of colloidal systems. DLVO theory and steric stabilization
xi. Emulsions and foam, (HLB, Bankroft-rule, etc.)
Colloids Applications
A colloid is typically a two phase system consisting of a continuous phase (the dispersion medium) and
dispersed phase (the particles or emulsion droplets). The particle size of the dispersed phase typically ranges
from 1 nanometer to 1 micrometer. Examples of colloidal dispersions include solid/liquid (suspensions),
liquid/liquid (emulsions), and gas/liquid (foams). A more complete range of colloidal dispersions is shown in the
table below.

Particle Interactions
As particle size decreases, surface area increases as a function of total volume. In the colloidal size range there
is much interest in particle-particle interactions. Most colloidal commercial products are designed to remain in a
stable condition for a defined shelf life. Milk is an example where homogenization is used to reduce droplet size
to delay the onset of phase separation (i.e., creaming with the fat rising to the surface). Commercial suspensions
may be formulated to keep particles in suspension without sedimenting to the bottom. Examples of phase
separation mechanisms are shown below.

29

Colloidal Stabilization
Stabilization serves to protect colloids from aggregation and/or phase separation. The two main mechanisms for
colloid stabilization involve steric and electrostatic modifications. Electrostatic stabilization is based on the
mutual repulsion of like electrical charges. By altering the surface chemistry to induce a charge on the surface of
particles it is possible to enhance the stability of the colloidal dispersion.

Zeta Potential
Zeta potential refers to the potential in the interfacial double layer (DL) at the location of the slipping plane
versus a point in the bulk fluid away from the interface. In other words, zeta potential is the potential difference
between the dispersion medium and the stationary layer of fluid attached to the dispersed particle. A classic
example of colloid chemistry is to measure zeta potential vs. pH to determine the conditions where the zeta
potential reaches zero, known as the isoelectric point.
Download the application note on Isoelectric Point Determination (You need to be logged in).

Instrumental Techniques
Scientists working to improve colloidal stability measure particle size, zeta potential, or both. Various
techniques are now capable of measuring particle size into the colloidal region including dynamic light
scattering (DLS) and laser diffraction. The SZ-100 nanoPartica DLS system can measure particle size and zeta
potential of colloidal dispersions and has the option of an automatic titrator for zeta potential vs. pH studies. The

30

LA-960 laser diffraction particle size analyzer is the best choice when particles above 1 micron may also be
present in the particle system.
Learn how dynamic light scattering measures particle size.
Watch Webinar TE012: Introduction to Dynamic Light Scattering (You need to be logged in)
Learn how electrophoretic light scattering measures zeta potential.
Watch Webinar TE013: Introduction to Zeta Potential Technology (You need to be logged in)

More Information about Colloids

Nanoparticles

Colloidal Silica

Gold Nanoparticles

Metal Nanoparticles

Colloid Analyzers

SZ-100 - Nanopartica Series Instruments

Industry's widest range and highest precision measurement instrument for Nanoparticle characterization.

LA-960 Laser Particle Size Analyzer - High Performance Laser Diffraction

Analyzer
The LA-960 uses Mie Scattering (laser diffraction) to measure particle size of suspensions or dry powders. The
speed and ease-of-use of this technique makes it the popular choice for most applications

Colloidal Stability in Aqueous Suspensions

Why too much dispersant causes problems.
Abstract
Zeta potential in aqueous suspensions is a function of two variables: charge at the shear plane and
free salt ion concentration. [Free here means not attached to the particle surface.] If a dispersant is

31

added to increase the surface charge density (increase stability) and it's too concentrated, the
contribution it makes to the free salt ion concentration is counterproductive (promotes instability).
Introduction
Colloidal suspensions are stabilized in one of two ways. Surface charge, naturally occurring or added,
enhances electrostatic stability. Adsorption of non-polar surfactants or polymers enhances stability
through static stabilization. Electrostatic stabilization gives rise to a mobile, charged, colloidal particle
whose electrophoretic mobility can be measured. Zeta potential is calculated from mobility.
The square of the zeta potential is proportional to the force of electrostatic repulsion between charged
particles. Zeta potentials are, therefore, measures of stability. Increasing the absolute zeta potentials
increases electrostatic stabilization. As the zeta potential approaches zero, electrostatic repulsions
becomes small compared to the ever-present Van der Waals attraction. Eventually, instability
increases, that can result in aggregation followed by sedimentation and phase separation.
Electrostatic Potential Differences: Surface Potential Defined
Imagine that you had two, infinitesimally small metal probes attached to a voltmeter. Now imagine one
probe is attached to the surface of a colloidal particle and the other one is in the liquid in which the
particle is suspended. The reading on the meter is the electrostatic potential difference between these
two points. It is called the surface potential o. See Figure 1 where o = +80 mV.
The y-axis in this figure also represents the solid-liquid boundary. The x-axis, in nanometers, is the
distance from the surface out into the liquid, it being assumed there is no other particle close by.
There are two idealizations in a figure like this one. First, real solid particles are not smooth at the
atomic level. They are more like low lying, rough hills on the atomic level. Second, the charge density
on the surface is not typically uniform, but often patchy. The surface has lots of hydrophobic spaces
characterized by no charge and lots of hydrophilic spaces characterized by charge.
Therefore, if we could attach a tiny voltmeter probe at specific surface locations, the surface potential
would vary from place to place. But we can neither freeze the particle motion in a liquid nor are there
probes small enough. Thus, a cartoon like this one arises when we average spatially (vertically) over
the rough surface to define an imaginary plane to call the surface.

Figure 1: Electrostatic potential vs. distance in nanometers from colloidal particle surface.
(Courtesy of David Fairhurst)
In addition, we are averaging temporally over the rotational diffusion time of the particle that is much
faster than the time to make an electrostatic measurement. Still, these idealizations work well and
have been the basis for using zeta potential determinations to describe colloidal stability for more than
50 years.
Before describing the zeta potential, it is wroth nothing a few special features of the curves in Figure
1. If nothing is specifically adsorbed onto the surface, the corresponding anions (the suspensions

32

much be neutral overall), or the anions from added salts (or surfactants) preferentially gather near the
positive surface. Thermally-driven diffusion increases the randomization of all ions as the distance
from the surface increases. The electrostatic potential difference thus decreases. Far enough away
from the surface, if the voltmeter probes are placed in the liquid; the electrostatic potential difference
is zero since the average charge density is constant.
Depending on the sophistication of the theory to describe what takes place close to the surface, a
variety of imaginary, but theoretically useful planes or layers are defined. Here, the simplest is shown.
It is called the Stern plane. The electrostatic potential difference is called ?d. It represents the average
position of the counter-ions that move with the surface.
Zeta Potential Defined
Any molecule covalently bonded to the surface move with the particle when it diffuses or is induced to
move electrophoretically in an applied electric field. When wetting, dispersing or stabilizing agents are
strongly adsorbed onto the surface, they too move with the particle. Counter-ions very near the
surface, perhaps within the first nanometer or two also move with the particle. Finally, solvent
molecules are sometimes also strongly bound to the surface.
However, at some short distance from the surface, the less tightly bound species are more diffuse and
do not move with the particle. So another imaginary yet useful theoretical layer is defined: the shear
plane. Everything inside the shear plane is considered to move with the particle; everything outside of
the shear plane does not. In other words, as the particle moves it shears the liquid at this plane.
The zeta potential is defined to be the electrostatic potential difference between an average point on
the shear plane and one out in the liquid away from any particles.
Zeta potential is important because, for most real systems, one cannot measure the surface potential.
One cannot measure the zeta potential directly either; however, one can measure the electrostatic
mobility of the particles and calculate zeta potential. Though strictly incorrect, it is common to hear the
zeta potential spoken of as a substitute for the surface potential. The surface potential is a function of
the surface charge density. The zeta potential is a function of the charge density at the shear plane.
The magnitude of the zeta potential is almost always much smaller than the surface potential. Even
the sign of the zeta potential can be different.
Figure 1 also shows the case of specific adsorption of an anionic dispersing agent onto the positively
charged surface. This may occur if the hydrophobic, patchy surfaces that are uncharged can firmly
anchor the non-polar tail of a sufficiently long, anionic surfactant. The shear plane is shifted further out
(for simplicity, not shown here) and is now negative. The zeta potential is now negative; whereas, the
original zeta potential is positive.
Whether or not the sign of the zeta potential is the same as that of the surface potential, it is clear that
the zeta potential is a measure of the charge density ultimately arising from the surface or species
attached to it. There is another contribution to zeta potential that is too often ignored when trying to
properly interpret colloidal stability.
Effect of Salt on Zeta Potential
Theories describing how the charge density around a particle varies with distance always use the
concept of the diffuse double layer. In the simplest theory, the electrostatic potential decays
exponentially with distance away from the shear plane. The inverse of the decay constant is a
distance called the Debye double layer thickness. It is a function of free salt ion concentration (as
embodied in the value of the ionic strength): the higher the concentration, the faster the decay, the
smaller the double layer thickness. At high enough salt, the double layer collapses to the extent that
the ever-present attractive van der Waals forces overcome the charge repulsion. This is one example
of the so-called "salting out" effect. Electrostatically stabilized colloidal suspensions will become
unstable with the addition of enough salt.

33

Figure 2: Effect of salt concentration on zeta potential. (courtesy of David Fairhurst.)

See Figure 2. The zeta potential decreases when the concentration of free salt ions increases. In the
figure, c is the free salt ion concentration. Since c2 > c1 it follows that ?2< ?1. (For simplicity, the shift
in the position of the shear plane was not shown.)
Too Much Dispersant
Oxide surfaces often have an affinity for phosphates. Phosphate ions can increase surface charge
density, resulting in higher absolute zeta potential. An example is shown in Figure 3. Colloidal silica,
SiO2, catalog no. 421552, obtained from the Sigma-Aldrich Company is 30% v/v aqueous suspension
as received. It was diluted about 100:1 for these measurements. All measurements were made with a
Brookhaven NanoBrook ZetaPALS zeta potential analyzer. The zeta potential is approximately -30
mV diluted in just DI water.
When tetrasodium pyrophosphate, TSPP, is added to water, it hydrolyzes completely to form
phosphate. The hydrogen phosphate hydrolyzes a little bit to form dihydrogen phosphate plus
hydroxide ion. For this reason, solutions of TSPP are basic with pH around 10, depending on the
initial concentration of TSPP.

Figure 3: Zeta potential of SiO2 vs. Concentration of added TSPP.

With the initial addition of TSPP, the zeta potential decreases. This suggests that the hydrogen
phosphate, the phosphate species in highest concentration, adsorbs at the silica surface. The
negative surface charge density is increased, and the zeta potential decreases to approximately -70
mV, a substantial change towards greater electrostatic stability.However, TSPP is a 4:1 electrolyte and

34

for every mole of TSPP added, the ionic strength increases by a factor of 10. A lot of free ions are
created that begin to decrease the double layer.Initially, the decrease in the double layer thickness
that would result in a higher zeta potential is insignificant compared to the effect of the hydrogen
phosphate adsorbing at the surface. Yet, there is a competition and the two effects strike a balance
from 0.01 to 0.1% wt/vol. Beyond 0.1% the particle surface is saturated and additional TSPP now
works against stability by collapsing the double layer resulting in a significant decrease in the zeta
potential.Clearly, for this particular distribution of SiO2 surface areas, somewhere between 0.01 and
0.1% wt/vol is optimum for stability. Adding more is counterproductive. Since the concentration of
SiO2 in this case was 0.6% w/vol, the optimum TSPP concentration varies from 1.7% to 17% of the
solids concentration. A rule of thumb is 10% of the solids concentration for the dispersant. Clearly, that
rule depends on the particle size distribution as that determines surface area and coverage
requirements. Yet, here, it held up reasonably well.
Ionic dispersants can help stabilize oxide surfaces by adding surface charge density. Zeta potential is
a measure of the success of the addition. However, too much dispersant can be counterproductive
when the surface is saturated and the ionic strength rises too much.
Colloid
Properties of Colloids
One property of colloid systems that distinguishes them from true solutions is that colloidal particles scatter
light. If a beam of light, such as that from a flashlight, passes through a colloid, the light is reflected (scattered)
by the colloidal particles and the path of the light can therefore be observed. When a beam of light passes
through a true solution (e.g., salt in water) there is so little scattering of the light that the path of the light cannot
be seen and the small amount of scattered light cannot be detected except by very sensitive instruments. The
scattering of light by colloids, known as the Tyndall effect, was first explained by the British physicist John
Tyndall. When an ultramicroscope (see microscope) is used to examine a colloid, the colloidal particles appear
as tiny points of light in constant motion; this motion, called Brownian movement, helps keep the particles in
suspension. Absorption is another characteristic of colloids, since the finely divided colloidal particles have a
large surface area exposed. The presence of colloidal particles has little effect on the colligative properties
(boiling point, freezing point, etc.) of a solution.
The particles of a colloid selectively absorb ions and acquire an electric charge. All of the particles of a given
colloid take on the same charge (either positive or negative) and thus are repelled by one another. If an electric
potential is applied to a colloid, the charged colloidal particles move toward the oppositely charged electrode;
this migration is called electrophoresis. If the charge on the particles is neutralized, they may precipitate out of
the suspension. A colloid may be precipitated by adding another colloid with oppositely charged particles; the
particles are attracted to one another, coagulate, and precipitate out. Addition of soluble ions may precipitate a
colloid; the ions in seawater precipitate the colloidal silt dispersed in river water, forming a delta. A method
developed by F. G. Cottrell reduces air pollution by removing colloidal particles (e.g., smoke, dust, and fly ash)
from exhaust gases with electric precipitators. Particles in a lyophobic system are readily coagulated and
precipitated, and the system cannot easily be restored to its colloidal state. A lyophilic colloid does not readily
precipitate and can usually be restored by the addition of solvent.
Thixotropy is a property exhibited by certain gels (semisolid, jellylike colloids). A thixotropic gel appears to be
solid and maintains a shape of its own until it is subjected to a shearing (lateral) force or some other disturbance,
such as shaking. It then acts as a sol (a semifluid colloid) and flows freely. Thixotropic behavior is reversible,
and when allowed to stand undisturbed the sol slowly reverts to a gel. Common thixotropic gels include oil well
drilling mud, certain paints and printing inks, and certain clays. Quick clay, which is thixotropic, has caused
landslides in parts of Scandinavia and Canada.
colloid (kloid) [key] [Gr., = gluelike], a mixture in which one substance is divided into minute
particles (called colloidal particles) and dispersed throughout a second substance. The mixture is also
called a colloidal system, colloidal solution, or colloidal dispersion. Familiar colloids include fog,
smoke, homogenized milk, and ruby-colored glass.

35

Formation of Colloids
There are two basic methods of forming a colloid: reduction of larger particles to colloidal size, and
condensation of smaller particles (e.g., molecules) into colloidal particles. Some substances (e.g., gelatin or
glue) are easily dispersed (in the proper solvent) to form a colloid; this spontaneous dispersion is called
peptization. A metal can be dispersed by evaporating it in an electric arc; if the electrodes are immersed in water,
colloidal particles of the metal form as the metal vapor cools. A solid (e.g., paint pigment) can be reduced to
colloidal particles in a colloid mill, a mechanical device that uses a shearing force to break apart the larger
particles. An emulsion is often prepared by homogenization, usually with the addition of an emulsifying agent.
The above methods involve breaking down a larger substance into colloidal particles. Condensation of smaller
particles to form a colloid usually involves chemical reactionstypically displacement, hydrolysis, or oxidation
and reduction.
Colloids, Solutions, and Mixtures
The Scottish chemist Thomas Graham discovered (1860) that certain substances (e.g., glue, gelatin, or starch)
could be separated from certain other substances (e.g., sugar or salt) by dialysis. He gave the name colloid to
substances that do not diffuse through a semipermeable membrane (e.g., parchment or cellophane) and the name
crystalloid to those which do diffuse and which are therefore in true solution. Colloidal particles are larger than
molecules but too small to be observed directly with a microscope; however, their shape and size can be
determined by electron microscopy. In a true solution the particles of dissolved substance are of molecular size
and are thus smaller than colloidal particles; in a coarse mixture (e.g., a suspension) the particles are much larger
than colloidal particles. Although there are no precise boundaries of size between the particles in mixtures,
colloids, or solutions, colloidal particles are usually on the order of 10 - 7 to 10 - 5 cm in size.
Classification of Colloids
One way of classifying colloids is to group them according to the phase (solid, liquid, or gas) of the dispersed
substance and of the medium of dispersion. A gas may be dispersed in a liquid to form a foam (e.g., shaving
lather or beaten egg white) or in a solid to form a solid foam (e.g., styrofoam or marshmallow). A liquid may be
dispersed in a gas to form an aerosol (e.g., fog or aerosol spray), in another liquid to form an emulsion (e.g.,
homogenized milk or mayonnaise), or in a solid to form a gel (e.g., jellies or cheese). A solid may be dispersed
in a gas to form a solid aerosol (e.g., dust or smoke in air), in a liquid to form a sol (e.g., ink or muddy water), or
in a solid to form a solid sol (e.g., certain alloys).
A further distinction is often made in the case of a dispersed solid. In some cases (e.g., a dispersion of sulfur in
water) the colloidal particles have the same internal structure as a bulk of the solid. In other cases (e.g., a
dispersion of soap in water) the particles are an aggregate of small molecules and do not correspond to any
particular solid structure. In still other cases (e.g., a dispersion of a protein in water) the particles are actually
very large single molecules. A different distinction, usually made when the dispersing medium is a liquid, is
between lyophilic and lyophobic systems. The particles in a lyophilic system have a great affinity for the
solvent, and are readily solvated (combined, chemically or physically, with the solvent) and dispersed, even at
high concentrations. In a lyophobic system the particles resist solvation and dispersion in the solvent, and the
concentration of particles is usually relatively low.

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