Surface Chemistry

Introduction: Surface chemistry is the study of processes that occur at the interface of two bulk
phases. The bulk phases can be of the type solid-gas, solid-liquid, liquid-gas and liquid-liquid.
There is no interface between gases because of their complete miscibility. The bulk phase can be
solutions or pure compounds.
The interface is usually a few molecules thick. One of the most important feature of the interface
that affects processes is the surface area of the interface. The area of the interface depends on the
size of the particles of the bulk phases.
Many processes occur at the interface. They range from simple physical processes such as
dissolution and evaporation to chemical reactions such as corrosion, heterogeneous catalysis and
electrode processes. Surface processes such as filtration, adsorption on activated carbon, ionexchange and reverse osmosis are used in water and waste water treatment. Hence, surface
chemistry studies are important since they have many applications.
In this chapter, features pertaining to surface phenomena are discussed. Features such as
adsorption, catalysis, formation of colloids, emulsions and micelles and their uses are discussed.
Adsorption: Adsorption is a surface phenomenon. In this process, accumulation or
concentration of a substance takes place at the surface or interface as compared to the bulk
phases. This happens because the molecules of the bulk phase at the surface are attracted
only from below and from the sides as compared to the molecule inside the bulk of the
phase. In the interior, molecules experience forces of attraction from all sides.
fig 7.1 - Molecules at the surface of a liquid experience a net
attraction downward
Hence, the molecules at the surface experience a net attraction
downward and tend to move towards the interior to increase
attractions. On account of the unbalanced forces, the surface of a
liquid or solid is in a state of strain. This implies that the surface
molecules have higher energy than those present in the interior. So,
when the surface of liquid or solid attracts, other molecules, this
energy is reduced. In other words, adsorption results in decrease of surface energy.
The substance, which accumulates on the surface is called adsorbate and the adsorbing phase is
called adsorbent. The process of removal of an adsorbed substance from the surface on which it
is adsorbed is called desorption.
The phenomenon of adsorption in solid adsorbents is enhanced when finely divided solid
particles are used. This is because the surface area increases tremendously with the use of finely
divided particles. Very good adsorbents such as charcoal, silica gel, alumina gel and clay have
large surface areas due to their porous structures. Similarly, colloids posses enormous surface
area per unit mass and are very good adsorbents.
Difference between Absorption and Adsorption
In the process of absorption molecules of one phase interpenetrate uniformly among those of
another phase to form a solution with the second phase. In adsorption, molecules of one phase
are present in higher concentration at the surface of the second phase. Water vapor is absorbed by
calcium chloride while it is adsorbed by silica gel. In the same manner, ammonia is absorbed by
water and is adsorbed by charcoal.
Sorption, which includes both absorption and adsorption is a process in which a substance moves
from one phase to be accumulated in another phase. The difference between adsorption and
absorption is illustrated graphically as shown in below figure, for the case where a substance
moves from a liquid phase to a solid phase.

fig 7.2 - Types of sorption separations

In the figure, m is the amount of the
substance that has moved across the interface.
In adsorption, the process is rapid in the
beginning and slows down near equilibrium
while absorption takes place at uniform rate.
Types of Adsorption
Depending on the nature of attractive forces
existing between the adsorbate and adsorbent,
adsorption can be classified as:
i) Physical adsorption
ii) Chemical adsorption

i) Physical adsorption (Physisorption): Here, the forces of attraction between the molecules of
the adsorbate and the adsorbent are of the weak van der Waals' type. Since the forces of
attraction are weak, the process of physisorption can be easily reversed by heating or
decreasing the pressure of the adsorbate (as in the case of gases).
ii) Chemical adsorption (Chemisorption): In chemisorption, the forces of attraction between
the adsorbate and the adsorbent are very strong; the molecules of adsorbate form chemical
bonds with the molecules of the adsorbent present in the surface.
The differences between physisorption and chemisorption are summarized in the below table.
Comparison between Physisorption and Chemisorption
Physisorption

Chemisorption

Forces of attraction are vander Waals forces

Forces of attraction are chemical bond

forces

Low enthalpy of adsorption (20 - 40 kJ/mole)

High enthapy of adsorption (200 - 400

kJ/mole)

This process is observed under conditions of low

temperature

This process takes place at high

temperatures

It is not specific

It is highly specific

Multi-molecular layers may be formed

Generally, monomolecular layer is formed

This process is reversible

This process is irreversible

Adsorption of Gases on Solids

Adsorption of gases on solids depends on the following factors:
i) Nature of the gas (adsorbate) (ii) Nature of the solid (adsorbent) (iii) Specific area of the solid
iv) Pressure of the gas
(v) Temperature
(vi) Activation of adsorbent.
(iv)Pressure of the gas - Adsorption Isotherms
The extent of adsorption of a gas on a solid generally increases with pressure. The extent of
adsorption is given by x/m, the ratio of the mass (x) of the adsorbate and the mass (m) of the
adsorbent when dynamic equilibrium has been attained. The plot of extent of adsorption versus
pressure of the gas at a given temperature is called the adsorption isotherm. Adsorption isotherm
of different shapes have been observed for various experiments, that is different adsorption

isotherms are usually described by different empirical equations. Here, the two most common
adsorption isotherms namely, Freundlich isotherm and Langmuir isotherm will be discussed.
Freundlich Adsorption Isotherm
This type of isotherm is described by the equation

where K and n are the parameters of the equation which depend on the nature of the gas, and P is
the pressure.
At equilibrium, pressure Ps, x/m reaches its maximum value, that is, no further adsorption takes
place even if the pressure is increased. A saturation state has been achieved. The adsorption
isotherm which conforms to Freundlich equation is shown in below figure.
fig 7.3 - Freundlich adsorption isotherm
Since n is greater than one, qualitatively, it
can be said that the extent of adsorption x/m
does not increase rapidly with increase in
pressure as shown in the above figure.
Freundlich equation can be transformed into a
linear form by taking the logarithms on both
sides of the equation 1.

Hence, if the plot of log(x/m) versus log P

yields a straight line, it implies that the
adsorption process conforms with Freundlich
isotherm. From the intercept, the parameter K
is obtained, while the slope is equal to (1/n).
Adsorption from Solutions
Adsorption of solutes from solutions also takes place on solids. Process of adsorption is used to
reduce colors from solution. For e.g., raw sugar solution is decolorised by charcoal.
Chromatographic separation of a mixture of compounds in solution happens due to the different
adsorption tendencies of the compounds on to the solid phase. Chromatographic methods are
used in the analysis of environmental pollutants as well as in the pharmaceutical industry. As
mentioned earlier, activated carbon is used extensively in water and waste-water treatment.
Freundlich and Langumir adsorption isotherms are also applicable to adsorption processes in
solutions. In place of equilibrium pressures, equilibrium concentrations of the adsorbates are
used and the isotherms are expressed in the forms,
where 'c' is the concentration of the solute in
solution.
Catalysis: A catalyst is a substance that increases the rate of a reaction by providing an alternate
path of lower activation energy. Since catalysts are not consumed in a reaction, very small
quantities of catalyst are required to enhance a reaction rate.
Types of Catalysis: Catalytic reactions are classified as homogeneous catalysis or heterogeneous
catalysis. When a catalyst mixes homogenously with the reactants and forms a single phase
it is called a homogenous catalyst. When a catalyst exists in a different phase from that of
the reactants it is called a heterogeneous catalyst. Catalysts are used in numerous industrial
processes. In nature, thousands of biological catalysts called enzymes are used to speed up
cellular reactions inside and outside the living cells.
Some examples of homogenous catalysis are given below.

1) Oxidation of SO2 in presence of NO catalyst.

2) Catalytic decomposition of ozone by chlorine atoms.

3) Hydrolysis of sugarcane solution in the presence of dilute sulphuric acid.

4) Formation of diethyl ether from ethyl alcohol using concentrated sulphuric acid as catalyst.
5) Hydrolysis of esters in the presence of H2SO4 catalyst.

In heterogeneous catalysis, the catalyst is generally a solid while the reactants are gases, although
sometimes liquid reactants are used. Heterogeneous catalysis is also called surface catalysis since
the reaction starts from the surface of the solid catalyst. In heterogeneous catalysis, first, the
chemical adsorption (chemisorption) of the reactants onto the surface of the catalyst takes place.
The catalysts provide enormous surface areas (1 to 500 m2/g) for contact.
Some examples of heterogeneous catalysis which are important industrial processes are listed
below.
1) Haber's Process: Manufacture of NH3 from N2 and H2 using iron as catalyst.

2) Manufacture of methyl alcohol from CO and H2 using (ZnO+Cr2O3) as catalyst.

3) Preparation of sulphuric acid by contact process where V2O5 is the solid catalyst.
4) Oxidation of NH3 using Platinum as catalyst (Ostwald process)

5) Oxidation of CO in automobile exhaust by platinum catalyst

6) Addition of H2 to C=C bonds of organic compounds to form C-C bonds (catalytic
hydrogenation).
Catalytic hydrogenation is frequently used in petroleum, plastics and food industries. The
conversion of vegetable oil into margarine is an example of catalytic hydrogenation process. One
of the simple hydrogenation process is the conversion of ethylene to ethane in the presence of
platinum catalyst. The mechanism of this hydrogenation reaction is illustrated in the figure.
fig 7.6 - The proposed mechanism of catalytic hydrogenation of C2H4
The overall hydrogenation reaction is given by

In the 1st step (A), ethylene and hydrogen

molecules diffuse to the catalyst (Platinum)
surface. In the 2nd step (B), the reactants are
chemisorbed. The pi electron of ethylene form
bonds with the platinum metal, and hydrogen
molecules split into hydrogen atoms that bond to
the metal. 3rd, the hydrogen atoms migrate to an
ethylene molecule bonded to the catalyst, where
they react to form ethane. Then the ethane
molecule which is formed diffuses away as it
does not bond to the metal. The metal is
regenerated in this step.
In heterogeneous catalysis, the reactants are
adsorbed onto the surface of the catalyst. This
adsorption facilitates the reaction in the
following ways:
i) Adsorption of a reactant molecule makes the attack of another molecule on it more probable
because the adsorbed species is not free to move about and escape collisions.
ii) An adsorbed molecule may be oriented properly for effective collision with another reactant
species.
iii) Most chemisorptions are accompanied by large amounts of heat production. This may supply
some of the energy of activation required for the reaction.
iv) In the process of chemisorption, some adsorbed molecules may dissociate to form reactive
atoms or free radicals, as seen in the case of catalytic hydrogenation of unsaturated organic
compounds where the hydrogen molecules splits up into atoms at the surface of the metallic
catalyst.
Nature of Solid Catalyst
Heterogeneous catalysis is extensively used in chemical industry. Hence, development, selection
and application of solid catalysts forms an important area in surface chemistry studies. The
nature of the solid catalyst has profound effects on heterogeneous catalytic reactions. Solid
catalysts can be metals, semiconducting oxides and sulphides, insulating oxides and acids. These
substances can be used in the pure form or in the form of mixtures. The catalysts can be
crystalline, microcrystalline or amorphous.
Properties of Catalysts
Catalyst

Examples

Function

Metals

Fe, NI, Pt, Ag

Hydrogenation Dehydrogenation

Semiconducting oxides and

sulphides

MO, ZnO, MgO, Si2

O3/MoO3, MoS2

Oxidation Desulphurization

Insulating oxides

A12O3, SiO2, MgO

Dehydration

Acids

SiO2/Al2O3 Zeolites

Cracking Polymerization
Isomerization

The two important aspects of solid catalysts are (i) activity and (ii) selectivity.
1) Catalytic Activity: The activity of a catalyst depends on the strength of chemisorption. To be
active, the surface of the catalyst should be extensively covered by the adsorbate, that is, the
chemisorption should be strong. However, if the strength of the adsorbent-adsorbate bond
becomes too strong then the activity of the catalyst declines because other reactant molecules

cannot react with the adsorbate or because the adsorbate molecules become immobilized on the
surface. It has been observed that the catalytic activity increases from group 5 metals to group 11
with maximum activity shown by group 7-9 elements of the periodic table.
Many metals are suitable for adsorbing gases and the general order of adsorption strengths
decrease along the series O2, C2H2, C2H4, CO, H2, CO2 and N2. Metals such as Fe, V and Cr show
strong activity towards all these gases but Mn and Cu do not absorb N2 and CO2.
2) Selectivity: The selectivity of a catalyst is its ability to make a reaction proceed in a
particular direction to yield a particular product. This aspect of a catalyst can be well
understood with examples.
Example 1: The reaction of CO with H2 yields different products when different catalysts are
used i.e.,
a)
b)
c)
Example 2: The reaction of acetylene C2H2 with H2 results in different products, ethane and
ethylene, when different catalysts are used.
a)
b)

These two examples illustrate the point that a catalyst is highly selective, that is, a given catalyst
can be active only in particular reactions and not in all reactions.
Zeolites - Shape-Selective Catalysis: are those reactions that depend on the pore structure of
the catalyst and the size of the reactant and product molecules. In such reactions, zeolites
are used as catalysts. Zeolites are microporous aluminosilicates of the general formula
Mx/n [(AlO2)x (SiO2)y].z H2O where n is the charge of the metal cation, Mn+. M is usually
Na+, K+ or Ca2+ and z is the number of moles of water of hydration, which is highly variable.
The characteristic of zeolites is the openness of the [(Al2)O2]n framework. In this framework,
some of the silicon atoms are replaced by aluminium atoms. Zeolites are found in nature and
they are also synthesized for catalytic selectivity. Because of the three dimensional cage
like structure, zeolites can be used as ion-exchange materials and selective adsorbents.
Zeolites as ion-exchange materials have been replaced by synthetic cationic and anionic
exchange resins, but their use as selective adsorbents for gases or liquids is extensive. The
zeolites act as molecular sieves for the reactants. To achieve this, zeolites are heated in vacuum
so that the water of hydration is lost. Once the water is removed, the zeolite structure becomes
porous. The pore size in zeolites is generally in the range 260 - 740 pm. The size of the porous
cavities influences the catalytic activity of the catalyst. Only those molecules can be adsorbed in
the pores whose sizes are small enough. This facilitates the molecules to enter the cavities and
leave easily. Hence, zeolites act as selective adsorbents. Depending on the size of the reactants
and product molecules relative to the sizes of the cavities of zeolites, reactions occur in a specific
manner. For e.g., alcohols are converted into gasoline using a zeolite catalyst ZSM-5 (Zeolie

Sieve of Molecular Porosity-5). The formula of ZSM-5 is Hx[(AlO2)x(SiO2)96-x].16 H2O. The

alcohol is dehydrated in the cavities by the protons and this results in gasoline. Zeolites are used
in cracking long-chain hydrocarbons in the petrochemical industry.
Enzyme Catalysis: Enzymes are macromolecules, usually proteins, produced in living systems,
which act as catalysts in physiological reactions. The striking characteristics of enzymes are
their catalytic power and specificity. Enzymes have immense catalytic power. They
accelerate reactions by factors of at least a million. Most reactions in living systems do not
occur at perceptible rates in the absence of enzymes. A simple reaction like hydration of CO2
is catalyzed by the enzyme carbonic anhydrase and is called as enzyme catalyzed reaction.
The transfer of CO2 from tissues into the blood and then to the alveolar air would be very
slow in the absence of this enzyme. The enzyme can hydrate 105 molecules of CO2 per
second, which is 107 times faster than the unanalyzed one.
This example illustrates the fact that enzymes have immense catalytic power. Enzymes increase
at the rate of 106 to 1020 times. The catalytic power of proteins comes from their capacity to bind
substrates (reactant) molecules in precise orientations and to stabilize transition states in the
making and breaking of bonds.
Enzymes are highly specific. An enzyme usually catalyses a single chemical reaction or a set of
closely related reactions. For e.g., urease catalyses the hydrolysis of urea only.
Other examples of enzyme catalyzed reactions are as follows:

The remarkable specificity of enzymes comes from the ability of the enzymes to bring the
substrates into a favorable orientation in the enzyme-substrate (ES) complexes such that the
substrates are bound to specific regions of the enzymes. Each enzyme has a specific active site.
The active site of an enzyme binds the substrate and contains the residues that directly participate
in the making and breaking of bonds. Some key features of the active site are:
1. The active site takes up a relatively small part of the total volume of an enzyme.
2. The active site is a three dimensional entity formed by groups that come from different
parts of the linear amino acid sequence.
3. Enzymes bind the substrate by multiple weak interactions. These weak interactions are
electrostatic bonds, hydrogen bonds, van der Waals' forces and hydrophobic interactions.
van der Waals' forces become significant in binding only when many substrate species
can come simultaneously close to many enzymes species. Hence, the enzyme and
substrate should have complementary shapes. The directional nature of hydrogen bonds
between substrate and enzyme brings about a high degree of specificity.
4. Active sites are clefts and crevices. Substrate molecules bind to the clefts or crevices.
5. The specificity of binding of a substrate depends on the precisely defined arrangement of
atoms in the active site. To fit into the active site the substrate must have a matching
shape, just like how a key fits into a lock.

This is the Lock and Key model of the interaction of

substrate and enzyme. The active site of the
enzyme alone is complementary in shape to
that of the enzyme
This model was proposed in the late 19th century. Since
then, modern X-ray crystallographic and spectroscopic
methods have revealed that in many cases, enzymes are markedly modified by the binding of
substrate. The active sites of these enzymes have shapes that are complementary to that of the
substrate only after the substrate is bound. Such enzyme-substrate interaction are described by
induced fit model.
This is the Induced-fit model of the interaction of
substrates and enzymes. The enzyme
changes shape upon binding substrate. The
active site has a shape complementary to
that of the substrate only after the substrate
is bound
In enzyme catalyzed reaction, the rate of enzyme
catalyzed reaction varies with the concentration of
the substrate in the manner as shown in figure.
RHS fig. is the representation of the rate of
enzyme catalyzed reaction graph.
At a given concentration of enzyme, the
rate of reaction is almost linearly
proportional to [S] when [S] is low. At high
[S], r is nearly independent of [S]. To
account for such behavior, Leonor
Michaelis and Maud Menten proposed the
following steps in enzyme catalyzed
reactions.

The formation of ES complex is fast and reversible, while the formation of the product (step 2) is
the slow, rate determining step. The rate of enzyme catalyzed reaction changes from first order to
zero order as the concentration of the substrate is increased.
Characteristics of Enzymes:
Enzymes are proteins involved in all the biochemical conversions in the plant and animal
cells. Enzymes act as biochemical catalyst and accelerate the chemical conversion but
remain unmodified themselves. The enzymes work by decreasing the activation energy
required for the reaction.
The reactant in a biochemical conversion is called a substrate. The site in the enzyme
molecule where the substrate binds and the reaction takes place is called the active site. It
is usually a small pocket like cleft found deep inside the enzyme molecule.
Enzymes are selective in terms of the substrate and act upon closely related molecules.
On one hand, certain enzymes act on only one substrate thus displaying absolute

selectivity while others recognize only the bond that they act on and are not affected by
the type of the molecule containing the bond.
Being protein in nature, enzymes require specific conditions for pH and temperature for
optimal activity. At high temperatures and non-optimal pH the enzymes lose their tertiary
structure (are denatured) which is critical for its activity.

Colloids: It is well known, that solutions are homogenous systems while suspensions are
heterogeneous systems, i.e., they consist of more than one phase. In between the extremes
of suspensions and solutions lies the colloidal system.
Colloids appear homogenous like a solution, but they consist of comparatively large particles of
one substance dispersed throughout another substance (dispersion medium). The essential
difference between a solution and a colloid is one of particle size.
1) In a solution, the particles are ions or small molecules.
2) In a colloidal system, the dispersed phase may consist of particles of a single macromolecule
or an aggregate of many atoms, ions or molecules. Although colloidal particles are larger than
simple molecules, they are small enough to remain suspended. Colloidal particle sizes range
from about 10Ao to about 1000 Ao i.e., 1nm to 1000 nm.
Types of Colloids: Colloids are characterized
a) according to the state of the dispersed phase and the state of dispersion medium.
b) nature of interaction between dispersed phase and dispersion medium.
c) types of particles of the dispersed phase.
Classification Based on the State of the Dispersed Phase and Dispersion Medium
The below table lists various types of colloids with various examples.
Types of colloids
Dispersion
Medium

Dispersed
Phase

Type of colloid

Example

Gas

Liquid

Aerosol

Fog, mist

Gas

Solid

Aerosol

Smoke

Liquid

Gas

Foam

Whipped cream

Liquid

Liquid

Emulsion

Mayonnaise, hair cream

Liquid

Solid

Sol

Paints, cell fluids

Solid

Gas

Foam

Pumice, plastic foams

Solid

Liquid

Gel

Jelly, cheese

Solid

Solid

Solid Sol

Ruby glass (glass with dispersed

metal)

Fog and smoke are aerosol which are liquid droplets or solid particles dispersed throughout a
gas. When liquid droplets are dispersed throughout another liquid phase this results in emulsion,
as in the case of butterfat dispersed throughout homogenized milk. A sol consists of solid
particles dispersed in a liquid. Foam consists of gas being dispersed in a liquid phase as in the
case of whipped cream.
Out of the various types of colloids, sols, gels and emulsions are very common. In the later
sections 'sols' and 'emulsions' are discussed in some detail.

Classification Based on the Nature of Interaction Between Dispersed Phase and Dispersion
Medium: Colloidal systems, depending on the nature of attraction between the dispersed phase
and the dispersion medium are classified into lyophobic (solvent hating) and lyophilic (solvent
loving). If water is the dispersion phase is water, then the colloids are either hydrophilic or
hydrophobic.
1) Lyophilic colloids: In this type of colloids sols, the dispersed phase has great attraction for the
dispersion medium. In such colloids, the dispersed phase does not precipitate easily and the
sols are quite stable. If the dispersion medium is separated from the dispersed phase, the
sol can be reconstituted by simply remixing with the dispersion medium. Hence, these sols
are called reversible sols. Examples of lyophilic sols include sols of gum, gelatine, starch,
proteins and certain polymers in organic solvents.
2) Lyophobic colloids: In this type of colloidal sols, the dispersed phase has little affinity for the
dispersion medium. These colloids are easily precipitated on the addition of small amounts
of electrolytes, by heating or by shaking and therefore are not stable. Once precipitated, it
is not easy to reconstitute the sol by simple mixing with the dispersion medium. Hence,
these sols are called irreversible sols. Examples of lyophobic sols include sols of metals
and their insoluble compounds like sulphides and oxides. Lyophobic sols need stabilizing
agents to keep the dispersed phase from precipitating out.
Hydrophobic sols are often formed when rapid crystallization takes place. With rapid
crystallization, many centres of crystallization called nuclei are formed at once. Ions are attracted
to these nuclei and very small crystals are formed. These small crystals are prevented from
settling out by the random thermal motion of the water molecules.
Classification of Colloids Based on Type of Particles of the Dispersed Phase
1) Multimolecular colloids 2) Macromolecular colloids 3) Associated colloids.

Multimolecular colloids: In this type of colloids the colloidal particles are aggregates of atoms
or small molecules with molecular size less than one nanometer (1 nm). For e.g., gold sol
consists of particles of various sizes which are clusters of several gold atoms. Similarly,
sulphur sol consists of colloidal particles which are aggregates of S8 molecules. The
molecules in the aggregates are held together by Van der Waal forces.
Macromolecular colloids: Macromolecular colloidal particles are formed when on dissolution
in a suitable solvent, the macromolecules have sizes which are in the colloidal range.
Naturally occurring macromolecules are starch, proteins and cellulose. Man made
macromolecules are polymers such as polyethylene, nylon and polystyrene. These colloids
are quite stable and resemble true solutions in many respects.
Associated colloids (Micelles): Certain substances behave as strong electrolytes at low
concentration but at higher concentrations these substances exhibit colloidal characteristics
due to the formation of aggregated particles. These aggregated particles are called micelles.
Micelles are called associated colloids. The formation of micelles takes place only above a
particular temperature called Kraft Temperature (Tk) and above particular concentration
called the Critical micelle concentration (CMC). On dilution, these colloids revert back to
individual ions. Surface active molecules such as soaps and synthetic detergents form
associated colloids in water. For soaps, the CMC is about 10-4 to 10-3 mol L-1. Micelles
have both a lyophilic and lyophobic parts. Micelles may consists of more than 100
molecules.
Mechanism of Micelle Formation
Micelles are formed by specific molecules which have lyophilic as well as lyophobic ends.
Ordinary soap which contains sodium stearate (C17H35COONa) forms micelle in water. The
stearate ion has a long hydrocarbon end that is hydrophobic (because it is nonpolar) and a polar
carboxyl group (COO-) that is hydrophilic.

When the concentration of sodium stearate is below its CMC, then it behaves as a normal
electrolyte and ionizes to give Na+ and C17H35COO- ions. As the concentration exceeds the CMC,
the hydrophobic end starts receding away from the solvent and approach each other. However,
the polar COO- part interacts with water. This leads to the formation of a cluster having the
dimensions of a colloid particles. In each cluster a large number of stearate groups clump
together in a spherical manner such that the hydrocarbon parts interact with one another and the
COO- groups remains projected in water.
fig 7.9 - Aggregation of RCOO- ions to form a
micelle
Cleansing Action of Soaps
The cleaning action of soap occurs when oil and
grease are absorbed into the hydrophobic
centers of soap micelles and are washed away.\

fig

7.10

Cleansing action of soap: Sodium lauryl sulphate is a synthetic detergent present in laundry
soaps, toothpastes and shampoos. The formula of sodium lauryl sulphate is CH3(CH2)11SO4- Na+.
It has a hydrophilic sulphate group and a hydrophobic
dodecyl (C12H25) group. These detergent molecules
are called 'anionics' because they have negative
charge at the hydrophilic end. There are detergents
which are 'cationics' that is they have positive charge
at the hydrophilic end. For e.g.,
which is a quarternary ammonium compound.
Many cationic detergents have germicidal properties and are therefore used in hospital
disinfectants, mouthwashes and certain eyewetting solutions.
Preparation of Colloidal Sols
For the preparation of lyophilic and lyophobic sols different methods are used.
Preparation of Lyophilic Sols: Since lyophilic sols are quite stable, they can be easily prepared
by shaking the lyophilic substance with the dispersion medium.
Examples are: Colloidal sols of gum, starch, gelatine and egg albumin.
Preparation of Lyophobic Sols: Lyophobic sols are prepared by two methods. They are:
1) Condensation methods
2) Dispersion methods.
Condensation methods: In condensation methods particles of atomic or molecular size are
induced to combine to form aggregates of colloidal dimensions. To achieve this, chemical
as well as physical methods are employed.
a) Chemical methods: Colloidal sols can be prepared by chemical reactions, which involve
double decomposition, oxidation, reduction and hydrolysis. Examples of sols made by
these methods are given below:
i) Double decomposition
ii) Oxidation
iii) Reduction
iv) Hydrolysis

Sols of silver halides are prepared by mixing dilute solution of silver salts with alkali halides in
equivalent amounts. Similarly, silica gel sol is prepared by mixing dilute solutions of sodium
silicate and HCl.
Dispersion methods: In dispersion methods, colloidal particles are obtained by breaking large
particles of a substance in the presence of a dispersion medium. Since the sols formed are
unstable, they are stabilized by adding stabilizing agents. Some of the dispersion methods
are:
a) Mechanical dispersion
b) Electrical disintegration c) Peptization.
b) Electrical disintegration or Bredig's Arc Method: In this method, an electric arc is struck
between electrodes of the metal immersed in the dispersion medium.
fig 7.12 - Bredig's arc method The intense heat produced by the arc vaporizes the metal, which
then condenses to form particles of colloidal
size. By this method, sols of metals such as
gold, silver and platinum can be prepared.

c) Peptization: The process of converting a precipitate

into a colloidal sol by shaking it with the dispersion medium, in the presence of a small
amount of electrolyte, is called peptization. The electrolyte used is called the peptizing
agent. This method is used to convert a freshly prepared precipitate into a colloidal sol.
In the process of peptization, the precipitate adsorbs one of the ion of the electrolyte onto its
surface. The ion adsorbed on the surface is generally common with those of the precipitate.
Adsorption of ion results in the development of positive or negative charge on precipitates and
which ultimately break up into colloidal size particles. For e.g., a precipitate of silver iodide
already formed can be dispersed by the addition of potassium iodide. Here potassium iodide is
the peptizing agent.
Purification of Colloidal Sols
The colloidal solutions prepared by various methods usually contain electrolytes and other
soluble substances as impurities. These impurities if not removed can destabilize the sols.
Impurities are removed by the following methods:
1) Dialysis
2) Ultra-filtration
3) Ultra-Centrifugation.
Dialysis: Removal of soluble impurities from sols by the use of semipermeable membrane is
known as dialysis.
Solutes present in a true solution can pass through a semipermeable membrane such as
parchment paper or cellophane. However, sol particles cannot pass through such membranes.
When a bag made up of such a membrane is filled with the colloidal sol and then placed in fresh
water, the soluble particles such as electrolytes pass through the membrane and go into the water
leaving behind the colloidal sol.

The movement of the ions across the membrane can be enhanced by applying electric potential
across two electrodes. This is known as electrodialysis.
fig 7.13 - An apparatus for electrodialysis
The most important application of dialysis is in the
purification of blood with the aid of an artificial kidney
machine. The dialysis membrane permits excess ions and
waste products like urea molecules to pass through and
does not allow the colloidal particles of haemoglobin to
pass through.

Ultra-Filtration: In this method, colloidal sols are filtered through graded filters called ultrafiltrers. These filters allow the electrolytes to pass through but not the colloidal particles.
These ultra-filters are made from ordinary filter papers by impregnating them with
colloidal particles. Filtration is usually carried out by either by applying pressure or by the
use of suction.
Properties of Colloidal Sols : Colloidal sols are biphasic in nature. It consists of the dispersed
phase and the dispersion medium. In the colloidal solution, each particle is contained within
its own surface boundary and therefore has a separate existence from the dispersion
medium.
Colligative properties: Colloidal particles have high average molecular masses.
Therefore the mole fraction of the dispersed phase is very low. Hence, in colloidal
solutions the relative lowering of vapor pressure, elevation in boiling point, depression in
freezing point and osmotic pressure is very low. However, osmotic pressure
measurements are used in determining the molecular masses of the polymers.
Optical properties: Although a colloidal solution appears to be homogenous because the
dispersed particles are too small too be seen, it can be distinguished from a true solution
by its ability to scatter light.
The scattering of light by colloidal sized particles is called
the Tyndall effect. This effect was first observed by Tyndall
in 1869. A strong beam of light was passed through a
colloidal sol placed in a dark place. The path of the beam got
illuminated. The illuminated path of the beam is called
Tyndall cone.
fig 7.14 - Demonstration of Tyndall effect

Brownian movement: Brownian movement was first discovered by Robert Brown, a

botanist, in 1827. He observed that pollen grains in water do not remain at rest but move
about continuously and randomly. This random continuous movement (Brownian
motion) was observed in colloidal sol when the sol was viewed under a ultra microscope.
Brownian motion in colloidal sols arises due to the impact of the molecules of the
dispersion medium with the colloidal particles. It has been postulated that the impact of
the molecules of dispersion medium on the colloidal particles are unequal. This leads to
the zig-zag (random) motion of the colloidal particles.
fig 7.15 - Zig-zag or Brownian motion
This random movement decreases as the size of the particles
increases because the effect of the impacts average out. When the
size of the dispersed particles increases beyond the colloidal range,
Brownian motion stops, i.e., no Brownian movement is observed.
The significance of Brownian movement is that
i) it provides a direct demonstration of ceaseless motion of
molecules as postulated by kinetic theory.
ii) It counters the force of gravity acting on colloidal particles and
hence helps in providing stability to colloidal sols by not allowing them to settle down.
Electrophoresis: The colloidal particles are electrically charged and they carry the same
type of charge, that is, either the colloids are negatively charged or positively charged.
The dispersion medium has an equal and opposite charge making the system neutral as a
whole. Since the colloids carry the same type of charge, they repel each other and do not
combine to form bigger aggregates. This is the reason why a sol is stable. The existence
of charge on the colloidal particles is inferred from the observation that the colloidal
particles move either towards the cathode or anode when the colloidal sol is placed in an
electric field. This phenomenon of charged particles moving towards the oppositely
charged electrodes in the presence of an electric field is called electrophoresis.
Electrophoresis is carried out by placing the
colloidal solution in a U tube which is fitted with
platinum electrodes.
fig 7.16 - Apparatus for electrophoresis
When electric current is passed, the charged
colloidal particles move towards the oppositely
charged electrode. A colloidal sol of AS2S3, which
is
negatively charged will move towards the anode
when placed in an electric field.
Coagulation or Flocculation:
Coagulation is the process by which a colloid precipitates out of a solution. The precipitation is
brought about by induced aggregation. For e.g., an iron (III) hydroxide sol can be made to
aggregate by addition of an ionic solution. A positively charged particle of iron (III) hydroxide
gathers a layer of anions around it. The thickness of this layer is determined by the charge on the
anions. The greater the magnitude of the negative charge, the more compact the layer of charge.
For e.g., phosphate ions gather more closely to the positively charge iron (III) particle than do
chloride ions.

fig 7.11 - Layers of ions

surrounding a charged particle of
iron (III) hydroxide.A: Fe(OH)3
surrounded by Cl- ionsB: Fe(OH)3
surrounded by PO43- ions

If the ion layer is gathered close to

the colloidal particles, the overall
charge is effectively neutralized and
two colloidal particles can approach
close enough to aggregate and
precipitate out. The coagulation of colloids by an electrolyte takes place only when the
electrolyte has a certain minimum concentration.
The minimum concentration of electrolyte in millimoles that is added to one liter of the colloidal
sol to bring about complete coagulation is called the flocculation value of the electrolyte for the
sol.
Different electrolytes have different coagulation values. Smaller the coagulation value of the
electrolyte, larger is its coagulating power. According to Hardy and Schulze, coagulation of
colloids by electrolytes is governed by two factors, namely
i) Ions carrying charge opposite to that of the colloidal particles are effective in bringing about
coagulation.
ii) Coagulation power of an electrolyte is directly proportional to the valency of its ions.
These two observations made by Hardy and Schulze are called the Hardy Schulze rule. On the
basis of this rule, it is possible to predict that for colloidal sols consisting of negatively charged
particles such as (AS2S3)Al3+ ions are more effective than Ba2+ or Na+ ions. For positively
charged colloidal particles, PO43- is much more effective than Cl- to bring about coagulation.
Coagulation of Negatively Charged Colloids As2S3 Coagulation Positively Charged Colloids Fe(OH)3

Colloidal sols can be coagulated by mutual precipitation, electrophoresis, repeated dialysis and
heating. Some examples of coagulation which occur in nature are:
1) Curdling of milk: Milk is a colloidal suspension in which the particles are prevented
from aggregating because they have electric charges of the same sign. When milk
sugar (lactose) ferments, ions responsible for curdling are formed.

2) When river water meets the concentrated ionic solution of an ocean, coagulation of the
colloidal suspension of the soil in river water occurs.
Emulsions : Emulsions are colloidal solutions in which both the dispersed phase and
dispersion medium are liquids. Emulsions are broadly classified into two types.
i) Oil-in-water emulsion
(ii) Water-in-oil emulsion.

i) Oil in water emulsion: In this type of emulsion oil is the dispersed phase, while water is the
dispersion medium. Examples are milk and vanishing cream.
ii) Water in oil emulsion: In this type of colloidal system water is the dispersed phase and oil
acts as the dispersion medium. Examples of water in oil emulsions are butter, cold cream
and cod liver oil.
Identification of Emulsions: The two types of emulsions can be identified by the following
methods.
Dye test: When some oil soluble dye is added to the emulsion, the background becomes colored,
it implies that the emulsion is water-in-oil type. If the droplets become colored, the
emulsion is oil-in-water type.
Dilution test: If the emulsion can be diluted with water, this indicates that water is the dispersion
medium and the emulsion is of oil-in-water type. If water forms a separate layer, the
emulsion is water-in-oil type.
Preparation of Emulsions: Emulsification is the process of making emulsions. Emulsions are
made by shaking the dispersed phase and dispersion medium vigorously and then stabilizing
the emulsion with an emulsifier. Most often soaps and detergents are added to stabilize
emulsions. Stabilization is obtained by the coating of the drops of an emulsion by the
stabilizer. This prevents the drops of the emulsion from combining together and separating
out as a separate layer. Other common stabilizing agents are proteins, gum and agar.
Applications of Colloids: Colloids have uses in our daily life as well as in various industrial
processes. Some of the applications where colloids are present are listed below.
1) Pharmaceutical industry makes use of colloidal solution preparation in many medicines. A
wide variety of medicines are emulsions. An example is Cod Liver Oil.
2) Paint industry also uses colloids in the preparation of paints.
3) Asphalt emulsified in water is used for building roads.
4) In metallurgical operations the metal ores are concentrated by froth-flotation process which
involves the treatment of the pulverized ore in emulsion of pine oil.
5) The negatively charged rubber particles from rubber sol are deposited on wares and handles of
different tools. Rubber gloves are formed by rubber plating on a suitable templates.
Presence of colloids in certain cases causes problems especially, related to health of human
beings and other creatures untreated sewage and smoke are harmful to health. Removal of the
colloidal particles in these cases is essential. In sewage disposal, the colloidal particles are
removed by discharging them at the electrodes. Sewage water
is passed through a tunnel fitted with metallic electrodes, which
are maintained at high potential difference. The particles move
to the oppositely charged electrodes and coagulated. The
coagulated matter is used as manure and the cleaned water is
used for irrigation.
Smoke is a dispersion of negatively charged colloidal particles
of carbon in air. To remove the carbon in air, smoke is passed
through a Cottrell Smoke Precipitator.
fig.7.17 - Schematic diagram of Cottrell smoke precipitator
The precipitator consists of two metal discs charged to a high potential. The charge on the
unburnt carbon gets discharged. Consequently, the carbon particles aggregate and precipitates to
the bottom. Cottrell smoke precipitator is usually used in the chimney of an industrial plant.