Surface Chemistry

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Surface Chemistry

(Adsorption, Colloidal solution, Catalysis)

Surface chemistry is that branch of chemistry which deals with the study of the phenomenon occurring
at the surface of interface, i.e., at the boundary separating two bulk phases.

Adsorption
The phenomenon of attracting and retaining the molecules of a substance on the surface of a liquid or a
solid resulting into a higher concentration of the molecules on the surface is called adsorption.

Adsorbate & Adsorbent

The substance thus adsorbed on the surface is called the adsorbate and the substance on which it is
adsorbed is called adsorbent.

Why adsorption takes place at the surface of solid or liquid substance

Due to unbalanced inward forces of attraction or free valencies at the surface, liquids and solids have
the property to attract and retain the molecules of a gas or a dissolved substance onto their surfaces
with which they come in contact.

-----------

----------- − NI – NI −

----------- − NI – NI –

(A) (B) (C )

Desorption

The removal of the adsorbed substance from the surface is called desorption (which can be brought
about by heating or reducing the pressure).

Sorption : when both adsorption and absorption both will take place simultaneously and therefore
sometimes it is difficult to distinguish between the two processes then this is called sorption.

Occlusion

The adsorption of gases on the surface of metals is called occlusion.


Examples of adsorption, absorption and sorption.

(i) If silica gel is placed in a vessel containing water vapours, the latter are adsorbed on the
former. On the other hand, if anhydrous CaCl2 is kept in place of silica gel, absorption takes
place as the water vapours are uniformly distributed in CaCl2 to form hydrated calcium
chloride (CaCl2 . 2H2O).
(ii) Ammonia gas placed in contact with charcoal gets adsorbed on the charcoal whereas
ammonia gas placed in contact with water gets absorbed into water, giving NH4OH solution
of uniform concentration.
(iii) Dyes get adsorbed as well as adsorbed in the cotton fibres, i.e., sorption takes place.

Positive and Negative Adsorption

When the concentration of the adsorbate is more on the surface of the adsorbent than in the bulk, it is
called positive adsorption.

If the concentration of the adsorbate increases in the bulk after adsorption, it is called negative
adsorption.

For example, when a concentrated solution of KCl is shaken with a dilute solution of KCl, it shows
negative adsorption.

Factors Affecting Adsorption of Gases by Solids


Almost all solids adsorb gases to some extent. However, the exact amount of a gas adsorbed depends
upon a number of factors, as briefly explained below:

(i) Nature and Surface area of the adsorbent


Greater the surface area of the adsorbent, greater is the volume of the gas adsorbed. It is
for this reason that substances like charcoal and silica gel are excellent adsorbents because
they have highly porous structures and hence large surface areas.

(ii) Nature of the gas being adsorbed.


Different gases are adsorbed to different extents by the same adsorbent at the same
temperature.

This is illustrated in which the volumes of different gases (reduced to N.T.P. conditions) adsorbed by one gram of
charcoal at 288 K have been given. The critical temperatures of the gases are also included in the Table.

Gas H2 N2 CO CO4 CO2 HCl NH3 SO2

Volume adsorbed (cc) 4.7 8.0 9.3 16.2 48 72 181 380

Critical temp (K) 33 126 134 190 304 324 406 430
It may be seen that higher the critical temperature of a gas, greater is the amount of that gas
adsorbed. In other words, a gas which is more easily liquefiable or is more soluble in water is more
readily absorbed.

Effect of Temperature:

It is observed that the adsorption decreases with increase of temperature and vice versa. For example,
one gram of charcoal adsorbs about 10 cm3 of N2 at 273 K, 20 cm3 at 244 K and 45 cm3 at 195 K.

Explanation:

Like any other equilibrium, adsorption is a process involving a true equilibrium.

Gas (adsorbate) + Solid (adsorbent) ⇌ adsorption + heat

Applying Le Chatelier’s principle, it can be seen that increase of temperature decreases the adsorption
and vice versa.

Types of Adsorption

1. Physical adsorption
2. Chemisorption

Distinction between physical adsorption and chemisorption

PHYSICAL ADSORPTION CHEMISORPTION

1. The forces operating in these cases are weak 1. The forces operating in these cases are similar
vanderwaal’s forces. to those of a chemical bond.
2. The heats of adsorption are low, viz., about 20- 2. The heats of adsorption are high, viz., about
40 kJ mol−1. 40−400 kJ mol−1.
3. No compound formation takes place in these 3. Surface compounds are formed.
cases. 4. The process is irreversible. Efforts to free the
4. The process is reversible, i.e., desorption of the adsorbed gas give some definite compound.
gas occurs by increasing the temperature or 5. It requires activation energy.
decreasing the pressure. 6. This type of adsorption first increase of
5. It does not require any activation energy. temperature. The effect is called activated
6. This type of adsorption usually takes place at adsorption.
low temperature and decreases with increase 7. It is specific in nature and occurs only when
of temperature. there is some possibility of compound
7. It is not specific in nature, i.e., all gases are formation between the gas being adsorbed
adsorbed on all solids to some extent. and the solid adsorbent.
8. The amount of the gas adsorbed is related to 8. There is no such correlation.
the ease of liquefaction of the gas. 9. It forms unimolecular layer.
9. It forms multimolecular layer.
What is adsorption isotherm

A graph between the amount (x/m) adsorbed by an adsorbent and the equilibrium pressure (or concentration 1
for solution) of the adsorbate at a constant temperature is called the adsorption isotherm.

Freundlich’s Adsorption Isotherm

It is an empirical equation expressing the relationship between the extent of adsorption and pressure
which is graphically represented as

T = Constant
𝑥
𝑚
= Kpo

𝑥 𝑥
𝑚 𝑚
= Kp n

SATURATION PRESSURE, Ps
𝑥
𝑚
= Kp

 At low pressures, the graph is straight line. So x/m α p or x/m = kp



At high pressures, the graph becomes independent of pressure. So x/m= kpo
 At intermediate pressure, x/m varies with the power of the pressure lying between 0 and 1.
Therefore x/m α p1/n

Adsorption Isobars

A graph drawn between the amount adsorbed (x/m) and temperature ’t’ at a constant equilibrium
pressure of adsorbate gas is known as adsorption isobar.

The physical adsorption isobar shows a decrease in x/m throughout with rise in temperature, the
chemisorptions isobar shows an initial increase with temperature and then the expected decrease. The
initial increase is because of the fact that the heat suppied act as activation energy required in
chemisorptions (like chemical reaction).
𝑥
P = CONSTANT 𝑚
P = CONSTANT

𝑥
𝑚

t t

(a) (b)

Applications of Adsorption

Adsorption finds extensive applications both in research laboratory and in industry. A few applications
are briefly described below:

(i) In preserving vacuum.


In Dewar flasks, activated charcoal is placed between the walls of the flask so that any gas
which enters into the annular space either due to glass imperfection or diffusion through
glass is adsorbed.

(ii) In gas masks.


All gas masks are devices containing suitable adsorbent so that the poisonous gases present
in the atmosphere are preferentially adsorbed and the atmosphere are preferentially
adsorbed and the air for breathing is purified.

(iii) In clarification of sugar.


Sugar is decolorized by treating sugar solution with charcoal powder. The latter adsorbs the
undesirable colours present.
(iv) In catalysis.
The action of certain solids as catalysts is best explained in terms of adsorption. The theory
is called adsorption theory. According to this theory, the gaseous reactants are adsorbed on
the surface of the solid catalyst. As a result, the concentration of the reactants increases on
the surface and hence the rate of reaction increases. The theory is also able to explain the
greater efficiency of a catalyst in the finely divided state, the action of catalytic promoters
and poisons.

(v) In removing moisture from air in the storage of delicate instruments.


Such instruments which may be contact with the moist air, are kept out of contact with
moisture using silica gel. Silica gel is the most commonly used dehumidizer, i.e., to adsorb
humidity or moisture from the air.

Assignment

1. How is the adsorption of gas related to its critical temp.?


2. In case of chemisorptions why adsorption first increases and then decreases?
3. Which will be adsorbed more readily on the surface of charcoal and why –NH3 or CO2.
4. How can the constants K and n of the Freundlich adsorption equation be calculated?
5. What is the difference between physical adsorption and chemisorptions?
6. Give reason why a finely divided substance is more effective as an adsorbent?
7. What do you understand by activation of adsorbent? How is it achieved?
8. What role does adsorption play in heterogeneous catalysis?
9. Define specific surface area.
10. Define dehumidizer. Give an example.
Colloidal state of matter

Dispersed phase and Dispersion medium

Just as in true solution, the substance dissolved is called the solute and the medium in which it is
dissolved is called the solvent, similarly in a colloidal system, the terms solute and solvent are replaced
by the terms dispersed phase and dispersion medium respectively.

Thus dispersed phase means the substance distributed in the dispersion medium in the form of
colloidal particles and the dispersion medium means the medium in which the substance is dispersed
in the form of colloidal particles. The colloidal system thus obtained is sometimes called a colloidal
dispersion or a disperse system.

Classification of Colloids
Colloids are classified in three different ways as follows:

(A) Based on physical state of dispersed phase and dispersion medium.


Depending upon whether the dispersed phase and the dispersion medium are solids, liquids or
gases, eight types of colloidal systems are possible. A gas mixed with another gas forms a
homogeneous mixture and not a colloidal system.

Types of colloidal systems (or colloidal dispersions)


S. No. DISPERSE DISPERSION NAME EXAMPLES
DPHASE MEDIUM

1. Solid Solid Solid sol Some coloured glasses, gem stones

2. Solid Liquid Sol Some paints, cell fluids, muddy water

3. Solid Gas Aerosol Smoke, dust

4. Liquid Solid Gel Cheese, butter, jellies

5. Liquid Liquid Emulsion Milk, hair cream

6. Liquid Gas Aerosol Fog, mist, cloud

7. Gas Solid Solid foam Pumice stone, foam rubber

8. Gas Liquid Foam Froth, soap lather


Dispersion medium Name of the sol
Water Aquasol or Hydrosol

Alcohol Alcosol

Benzene Benzosol

Gases aerosol

(B) Based on nature of interaction between dispersed phase and dispersion medium.

On this basis, colloidal sols are divided into two categories, namely, lyophilic and lyophobic. If
water is the dispersion medium, the terms used are hydrophilic and hydrophobic.

1. Lyophilic colloids.

Lyophilic means liquid- loving. Substances like gum, galatine, starch, rubber etc. which
when mixed with a suitable liquid as the dispersion medium directly form the colloidal sol
are called lyophilic and the sols thus obtained are called lyophilic sols. As they form the
colloidal sol directly, they are also called intrinsic colloids.

These sols are also called reversible sols i.e. if the dispersed phase is separated from the
dispersion medium (say, by evaporation), the sol can be made again by simply remixing with
the dispersion medium and shaking.

These sols are quite stable and cannot be easily precipitated.

2. Lyophobic colloids.

The word ‘lyophobic’ means liquid-hating. Substance like metals, their sulphides etc. when
simply mixed with the dispersion medium do not form the colloidal sol. Their colloidal sols
can be prepared only by special methods (as discussed later). As their colloidal sols have to
be prepared by indirect methods, they are also called extrinsic colloids.

These sols are readily precipitated (or coagulated) and hence are not stable.

Further, once precipitated, they do not give back the colloidal sol by simple addition of the
dispersion medium. Hence, they sols are also called irreversible sols.

The greater stability of the lyophilic colloidal sols than the lyophobic colloidal sols is due to
the fact that the former are highly hydrated in the solution.
Points of difference between lyophilic and lyophobic sols
S.No. PROPERTY LYOPHILIC SOLS LYOPHOBIC SOLS

1. Ease of Prepared easily by directly Cannot be prepared directly.


preparation mixing with the liquid Prepared by special methods
dispersion medium. only.

2. Stability They are quite stable and are They are easily precipitated by
not easily precipitated or addition of a small amount of a
coagulated. suitable electrolyte.

3. Hydration They are highly hydrated They are not much hydrated.

4. Nature of These sols are usually formed These sols are usually formed by
substance by the organic substances the inorganic materials like
like starch, gum, proteins etc. metals, their sulphides etc.

5. Viscosity Their viscosity is much higher Their viscosity is almost the


than that of the medium. same as that of the medium.

(c) Based on the type of particles of the dispersed phase. (Multimolecular, Macromolecular and
Associated Colloids)
Depending upon how the different substances may have size in the range of the colloids, the
various types of colloids or colloidal dispersions may be divided into the following three
categories:

(1) Multimolecular colloids.

When on dissolution a large number of atoms or smaller molecules of a substance (with


diameters less than I nm) aggregate together to form species having size in the colloidal
range, the species thus formed are called multimolecular colloids.

The dispersed phase in this type of colloidal systems may contain large aggregates of atoms
or molecules formed as a result of aggregating properties of the dispersed particles.
For example, a gold sol may contain particles of various sizes having several atoms. Sulphur
sol consists of particles containing a thousand or so of S8 sulphur molecules. These are held
together by vanderwaal’s forces.

(2) Macromolecular colloids.


When certain substances having big size molecules, called macromolecules, having large
molecular masses are dissolved in a suitable liquid, they form a solution in which the
molecules of the substance, i.e., the dispersed particles have size in the colloidal range. Such
substances are called macromolecular colloids.

These macromolecular substances are usually polymers with very high molecular masses.
Examples of naturally occurring macromolecules are starch, cellulose, proteins, enzymes
and gelatin.
(3) Associated colloids – Micelles.
The substances which when dissolved in a medium at low concentrations behave as normal,
strong electrolytes but at higher concentrations exhibit colloidal state properties due to the
formation of aggregated particles are called associated colloids. The aggregated particles
thus formed are called micelles.
The formation of micelles takes places only above a particular temperature called Kraft
temperature (Tk) and above a particular concentration called Critical Micelle Concentration
(CMC).
The most common example of associated colloids is that of surface active agents such as
soaps and synthetic detergents. For soaps, the CMC is 10−4 − 10−3 mol L−1 each micelle
contains at least 100 molecules.

Mechanism of micelle formation.

Let us take the example of soap solution.


Soap
Soap is sodium salt of higher fatty acid and may be represented as RCOONa, e.g., sodium
stearate viz CH3 (CH2)16COO−Na+ or sodium palmitate, viz., CH3 (CH2)14COO−Na+ when
dissolved in water, it dissociates into RCOO− and Na+ ions. The RCOO− ions, however, consist
of two parts, i.e., non-polar long hydrophobic (water repelling) and the polar group COO-,
called the head, which is hydrophilic (water loving).

The RCOO- ions, are therefore, present on the surface with their COO- groups in water and
the hydrocarbon chains R staying away from it and remain at the surface.
At higher concentration, these ions do not remain on the surface but are pulled into the
bulk of the solution. As a result, at higher concentration, the RCOO- ions form an oily
aggregate with their hydrocarbon chains (represented by wavy lines) pointing towards the
centre and the COO- part (represented by solid circle) outwards, as shown above. An
aggregate thus formed is known as “ionic micelle”. Each of these micelles may contain upto
100 ions.

Polar Head
+
Na
Na+ COO− Na+
NON-POLAR TAIL
+ +
Na Na

Na+ Na+

Na+
Na+
Na+ Na+

Na+

Aggregation of RCOO− ions to form an ionic micelle

Similarly, in case of detergents, e.g., sodium lauryl sulphate, viz, CH3 (CH2)11 OSO-3 alongwith
the long hydrocarbon chain. It is an example of an anionic detergent as anions associate
together to form an ionic micelle, similar to that of soap. A well known example of a cationic
detergent forming an associated colloid is that of cetyl trimethyl ammonium bromide,
CH3(CH2)15(CH3)3N+Br-.
Comparison of some important characteristics of multimolecular, macromolecular and
associated colloids.

Multimolecular colloids Macromolecular colloids Associated colloids

1. They are formed by the They are molecules of large They are formed by of
aggregation of a large number size, e.g., polymers like rubber, aggregation of a large no. of
of atoms or molecules which nylon, starch, proteins, etc. ions in concentrated solution,
generally have diameters less e.g., soap sol.
than 1 nm, eg. Sols of gold,
sulphur, etc.

2. Their molecular masses are They have high molecular Their molecular masses are
not very high. masses. generally high.

3. Their molecular are held Due to long chain, the van der Higher is the concentration,
together by weak van der Waal’s forces holding them are greater are the van der
Waal’s forces. comparatively stronger. Waal’s forces.

Preparation of Colloidal Sols


As discussed earlier, the lyophilic sols can be prepared directly by mixing the substance with the
dispersion medium. For example, colloidal sols of starch, gelatin, gum Arabic, soaps etc. are prepared by
simply dissolving these substances in warm water.

Similarly, a colloidal sol of cellulose nitrate is obtained by dissolving it in an organic solvent such as ethyl
alcohol. The product obtained is called collodion.

However, the lyophobic sols cannot be prepared directly. Hence, the following two types of methods
are employed for obtaining the lyophobic sols.

A. Dispersion or Disintegration methods.

These methods involve the breaking of the bigger particles to colloidal size.
The methods generally employed for this purpose are briefly described below.
(1) Mechanical disintegration.
The mechanical disintegration is carried out in a colloid mill which consists of two steel discs
with a little gap in-between and capable of rotating in the opposite directions at high speed
(7000 revolution per minute).
A suspension of the substance in water is introduced into the mill. The size of suspension
particles is reduced to that of colloidal size.
Suspension

Hollow shaft
Driving belt

Discharge Discharge

Steel discs rotating in


Opposite directions

2. Electro-disintegration (Bredig’s method).


This method is employed for obtaining colloidal solutions of metals like gold, silver, platinum
etc. an electric arc is set up between two metallic electrodes suspended in a trough of
water.
The intense heat of the arc converts the metal into vapours which are condensed
immediately in the ice cold water bath resulting in the formation of particles of colloidal
size.
METAL
ELECTRODES

-------------
------------
ICE -------------
-------------

DISPERSION
MEDIUM

3. Peptization.

Peptization is a process of converting a precipitate into colloidal


particles on adding suitable electrolyte. The electrolyte added is
called peptizing agent.

EXAMPLE: A reddish brown coloured colloidal solution is obtained by adding small quantity
of ferric chloride solution to the freshly precipitated ferric hydroxide.

Cause of peptization.

As the electro;yte is added to a freshly precipitated substance, the particles of the


precipitate preferentially adsorb one particular type of ions of the electrolyte and get
dispersed due to electrostatic repulsions. This gives particles of colloidal size.

Freshly prepared precipitates are preferred as they are easily peptized.

+ FeCl3 + + + + + +
Fe(OH)3 + + + + + +
+ + + + + +
COLLOIDAL PARTICLES
FRESHLY OF Fe (OH)3
PRECIPITATED Fe (OH)3

B. Condensation or Aggregation methods.

These methods involve the joining together of a large number of smaller particles to form
particles of colloidal size. The methods generally employed for this purpose are as follows:

(1) By chemical reaction:


(i) By double decomposition: when H2S is passed through a dilute solution
of arsenious sulphide is obtained.
As2O3 + 3H2S → As2S3 + 3H2O
colloidal solution

(ii) By reduction :

gold, silver, platinum, etc. are obtained in colloidal form by reduction of very dilute
solutions of their salts with a suitable reducing agents e.g.
2AuCl3 + 3SnCl2 → 2Au + 3SnCl4
gold sol
Gold sol can also be obtained by reduction of AuCl3 solution with formaldehyde and tannic
acid or with hydrazine
2AuCl3 + 3HCHO + 3H2O → 2Au + 3HCOOH + 6HCl
gold sol.

Or 4AuCl3 + 3NH2NH2 → 4Au + 3N2 + 12HCl


Hydrazine gold sol.

(iii) By oxidation:

sulphur is obtained in the colloidal form when H2S is bubbled through the solution
of an oxidizing agent like nitric acid, bromine water, etc.
H2S + Br2 → S + 2HBr
H2S + 2HNO3 → 2H2O + 2NO2 + S

(iv) By hydrolysis:

Fe(OH)3 and Al(OH)3 sols are obtained by boiling solutions of their corresponding
chlorides.
FeCl3 + 3H2O → Fe(OH)3 + 3HCl
Purification of Colloidal Solutions

When a colloidal solution is prepared, quite often it contains certain impurities of electrolytes which are
crystalloidal in nature and tend to destabilize the solution. Hence, their removal is very essential.

(1) Dialysis.

The process of separating the particles of colloids from those of crystalloids by diffusion of
the mixture through a parchment or an animal membrane is known as dialysis.

Principle

The separation of crystalloids from the colloids is based upon the principle that the particles of
the crystalloids pass through parchment paper or cellophane membrane whereas those of the
colloids do not.
The apparatus used is called a dialyser.
 = CRYSTALLAOIDS
O = COLLOIDS

ADDITION OF
IMPURE SOL
WATER

DISTILLD
WATER
FUNNEL
---------- --------------
SOLUTIO ---- --- ------ ------
OF ---- --- ----- -----
CRYSTA. ---- ----- ------ -----
-----------------------------

CELLOPHANE BAG

Process

A cellophane paper is turned into a bag with a funnel tied in the mouth of the bag. The impure
sol is filled into the bag which is then suspended into a vessel containing distilled water. After
some time whole of the crystalloid in solution passes out leaving the colloid behind. The distilled
water is renewed frequently to avoid accumulation of the crystallids as otherwise they may start
diffusing back into the bag.
The above process can be quickened if an electric field is applied around the membrane (the
process is then called Electro-dialysis).

Note.

The most important application of dialysis is in the purification of blood in the artificial kidney
machine. The dialysis membrane permits small particles of the excess ions and waste products
to pass through whereas colloid-sized particles such as haemoglobin do not pass through the
membrane.

CELLOPHANE TUBING
BLOOD FROM BLOOD TO OTHER DIALYSIS MEMBRANE
ARTERY VEINS

----- -----
---- ------
- - - - ----- - - - - - - - - - - - - - - - ------ - - - - -
- - - - - --- - - - - ESSENTIAL - - - - - - - - - -
- - - - - - - - - - - IONS - - - - - - - - - - - - -
- - - - - ------ - - - - - - - - - - - - - - ------ - - - - - WASHING
- - - - - ------------------------------------ - - - - -- SOLUTION
-------------------------------
- - - - - - - - - - - - - EXCESS IONS - - - - - - - -
- - - - - - - - - - - - & WASTE PRODUCTS- - - -

(2) Ultrafiltration.

Ordinary filter paper is permeable to colloidal dispersions (pores being of colloidal size) as well
as to true solution, and thus cannot be employed for filtering sols.

Ultrafilter and Ultrafiltration

A filter paper treated with collodion or gelatin solution followed by hardening by dipping in
formaldehyde solution serves the purpose. Due to this treatment, the pore size of the filter
paper is reduced. The filter paper so obtained is called ultrafilter and the filtration device using
such a filter paper is called ultrafiltration.
The sol is poured over the ultrafilter which permits solution of electrolytes to pass through but
retains the colloidal particles in the form of slime.

(3) Ultra-centrifugation.

In this method, the impure sol is taken in a tube which is placed in an ultracentrifuge. In this
machine, the tube is rotated at a very high speed. As a result, the colloidal particles settle down
at the bottom of the tube whereas the crystalloids and other soluble impurities remain in the
solution. This solution is decanted off and the colloidal particles are remixed with the dispersion
medium to give the pure colloidal sol.

Properties of Colloidal Solutions

1. Physical Properties

(a) Colloidal solution are heterogenous in nature.


(b) Colloidal solution are stable in nature.
(c) Filterability:
Ordinary filter paper cannot be used for removing the dispersed phase because size of pores
of filter paper is bigger than the size of colloidal particles which can easily pass through the
pores of the ordinary filter paper.
Animal membrane or parchment paper does not allow the colloidal particles to pass through
it. This forms the basis of separating the particles of the colloid from those of the crystalloids
in the process called dialysis, discussed earlier.

(d) Visibility:

The particles in colloidal solution are not visible to naked eye or under ordinary microscope.

Note : In fact, a particle is not visible if its size is less than half the wavelength of the light used to see it. Since the minimum
wavelength of the visible light range is 3600 Ao, therefore, with visible light, a particles of size less than 1800 Ao cannot be seen.
As the maximum size of the colloidal particles being less than 1800 Ao, these are not visible.

2. Colligative properties-Osmotic pressure.


Measurment of osmotic pressure has been used to determine the average molecular masses of
colloidal particles
Why: Colloidal particles have very high average molecular masses, and hence the number of moles
present in solution will be extremely small. Thus, the value for any of the colligative properties for a
particular substance will be smaller as compared to its value when it is a part of true solution. However,
some colloids have measurable osmotic pressures which have been determined with a reasonable degree
of accuracy.
3. Mechanical Properties-Brownian movement.

Brownian movement may be defined as continuous zig-zag movement of the colloidal particles
in a colloidal sol.

Cause of Brownian movement.


The explanation of the phenomenon is that the molecules of dispersion medium due to their
kinetic motion strike against the colloidal particles (dispersed phase) from all sides with different
forces causing them to move.

(a) (b)

Brownian movement

Importance of Brownian movement.

(i) Brownian movement opposes the force of gravity and does not allow the colloidal
particles to settle down. Thus, it is responsible for the stability of the colloidal solution.

(ii) It has also helped in the determination of Avogadro’s number.

4. Optical Properties-Tyndall-effect.

Tyndall effect may be defined as the scattering of light by the colloidal particles present in a
colloidal sol.
How can we observe Tyndall effect
If a strong converging beam of light is passed through a colloidal solution placed in a dark room,
the path of beam gets illuminated with a bluish light. The path of the light is made visible by the
scattering of light by the colloidal particles. The phenomenon was observed by Tyndall in 1869
and is called Tyndall effect

The illuminated path of beam is called Tyndall cone.

The phenomenon is also observed when a beam of light is projected in a cinema hall and it
becomes visible due to the scattering by colloidal dust particles in the air of the room.

SLIT MICROSCOPE

-------------
-------------
-------------
-------------
ARC Tyndall - - - - - - - - - - - - -

LAMP Cone Cell Containing Sol

------------- -------------
------------- -------------
------------- ---- -------------- ----
-------------
------------------------------------
Torch - - - - - - - - - - - - - -------------
------------- -------------
True Solution Colloidal Sol
(No Scattering of Light) (Scattering of Light) Screen

The Tyndall effect has been used to devise an instrument called ultramicroscope in which the
light scattered by the colloidal particles can be seen through a microscope.

The importance of Tyndall effect lies in the fact that it has helped to confirm the heterogeneous
nature of the colloidal solution.
5. Electrical Properties. (a) Stability of colloidal sols-Electrical charge on colloidal particles.

The stability of a colloidal solution is due to the fact that the colloidal particles in the sol are
electrically charged. The particles, therefore, repel one another and do not coalesce (come close
together) to form large non-colloidal particles.

Colloidal particles carry either positive or negative charge. All the dispersed particles in a
colloidal solution carry the same charge while the dispersion medium has an equal and opposite
charge.
For example, arsenious sulphide particles are negatively charged whereas the dispersion
medium (water) is positively charged. Ferric hydroxide particles are positively charged whereas
the dispersion medium (water) is negatively charged.

Using water as the dispersion medium, the charge on the particles of some common sols is as given in
Table.

NAGATIVELY CHARGED POSITIVELY CHARGED

Metallic particles Metal hydroxides like


Starch Fe(OH)3 , Al(OH)3 ,
Clay Cr(OH)3 , Ca(OH)2
Silicic acid Oxides like TiO2, etc
Metal sulphides like Haemoglobin
As2S3 , CdS, etc. Basic dyes like
Acidic dyes like congo Methylene blue
Red, eosin etc. Prussian blue

Origin of electrical charge on colloidal particles.


The various reasons for the origin of electrical charge on the colloidal particles are as follows:

(i) Frictional electrification caused by the mutual rubbing of the colloidal particles with
molecules of the dispersion medium.
(ii) Electron capture by particles from air and during electro-dispersion in Bredig’s arc
method.

(iii) Preferential adsorption of ions from solution. An ionic colloid adsorbs ions common to
its own lattice during the preparation of the colloidal sol.

For example, if colloidal sol of Agl is prepared by adding Kl solution to AgNO3 solution till
Kl is in slight excess, iodide ions (I-) will be adsorbed on the surface of AgI particles
thereby giving them a negative charge
AgI + I- → AgI ⋮ I-
(From KI) Negative sol.

On the other hand, if the colloidal sol of AgI is Prepared by adding AgNO3 solution to KI
solution till AgNO3 is in slight excess, Ag+ ions will be adsorbed thereby giving positive
charge to the colloidal particles

AgI + Ag+ → AgI ⋮ Ag+


(From AgNO3) Positive sol

In either case, the left out ions will remain in the dispersion medium (e.g., K+ ions in the
first case and NO-3 ions in the second case) thereby giving equal and opposite charge to
the dispersion medium.

K+ K+ NO−3 NO−3

Ag+

Ag+

K+ K+ NO−3 NO−3

K+ K+ NO−3 NO−3

(b) Electrophoresis or cataphoresis.

The movement of colloidal particles under the influence of an electric field is called electrophoresis or
cataphoresis.
− + COLLOIDAL SOL − +

-.-.-. ‘ .- .-. - - -- .‘.’.’..’


---- ---- ---- ‘.’.’.’.
- - - - - - .- . .-
- .-. - . .. ;.
- .-.-. .-..- . --- .;-;;.;
-.-.- -.-.-.. - - -- ----
-.-. -. -.-.-.- ---- ----
- .- . .-.- .- - - -- ----
-.-..- - .-.-.-. --- ----
-.--.-.-. -. - .-.. - - - - -- ------
- -.-.-.- -.- -.-..- - -----------

(a) (b)

(a) Before electrophoresis


(b) After Electrophoresis

Note : As soon as the colloidal particles reach the oppositely charged electrode, they get neutralized and
coagulated.
Electrophoresis can be used to find out the nature of the charge that the colloidal particles carry.

Eariler the term used was ‘cataphoresis’ because most of the colloidal sols studies at the time contained
positively charged colloidal particles and thus migrated towards cathodes.
(c) Electro-osmosis.

Electro-osmosis may be defined as a phenomenon in which the molecules of the dispersion


medium are allowed to move under the influence of an electric field whereas colloidal particles are
not allowed to move.
WATER COLLOIDAL WATER
‘. SOL
\ \ \ - - - - --- -- - - | -.-.’;-.-. . | - - - - - - -- - - - \ \ \ \
\ \ \ \ \ \ - - - - - - - | -.-.-.-… | - - - - - - - - -\ \ \ \ \ \ \
\ \ \ \ \ \ - - - - - - - | -.-.-.-.- | - - - - - - - - - \ \ \ \ \ \
+ \ \ \ \ \ \ - - - - - - - | .-.-.-.-.- | - - - - - - - -- \ \ \ \ \ \ \ −
\ \ \ \ \ \ - - - - - - - | -.-. -.-. | - - - - - - - - -\ \ \ \ \ \
\\\ ---------- | ----- | ------------ \\\

SEMIPERMEABLE MEMBRANE

(d.) Coagulation or Flocculation:

Coagulation is a process of aggregating together the colloidal particles so as to change


them into large sized particles which ultimately settle as a precipitate.

Coagulation is generally brought about by the addition of electrolytes . When an electrolyte


is added to a colloidal solution, the particles of the sol take up the ions which are oppositely
charged and thus get neutralized. The neutral particles then start accumulating to fro
particles of larger size which settle down.

Flocculation and coagulation

When a small amount of the electrolyte is added, i.e., when the concentration of the electrolyte
added is low, the process is called flocculation. It can be reversed on shaking.

However, at higher concentration, coagulaton takes place and the process cannot be reversed
simply by shaking.

The minimum amount of an electrolyte (millimoles) that must be added to one litre of a colloidal
solution so as to bring about complete coagulation is called the coagulation or flocculation or
precipitation value of the electrolyte. Thus, smaller is the coagulation value of an electrolyte; greater
is its coagulating or precipitating power:

Hardy Schulze Law.

Acc. to this

(i) The effective ions of the electrolyte in bringing about coagulation are those which carry
charge opposite to that of the colloidal particles.
(ii) Greater is the valency of the oppositely charged ion of the electrolyte being added, the faster
is the coagulation.
(iii) The coagulating power of an electrolyte is directly proportional to the fourth power of the
valency of the effective ion i.e. ion having charge opposite to that of the colloidal particles.

Example: For coagulation of negative charged arsenious sulphide sol., trivalent cations (Al3+)
are far more effective than divalent (Ba2+) cations which in turn are more effective than
monovalent (Na+) cations.
Similarly, for coagulation of positively charged ferric hydroxide sol, tetravalent [Fe(CN)6]4-
anions are more effective than trivalent anions (PO43- ) which are more effective than
divalent (SO42-) anions which in turn are more effective than monovalent (Cl-) anions.

As coagulating power is inversely proportional to coagulation/flocculation value, to compare the relative


coagulating powers of two electrolytes for the same colloidal sol, we have

Coagulating power of electrolyte 1 Coagulation value of electrolyte 2


Coagolating power of electrolyte 2
= Coagulation value of electrolyte 1

For a negatively charged sol, like that of As2S3 the coagulating powers of the cations are in the order:

Al3+ > Ba2+ > Na+.

For a positively charged sol like that of Fe (OH)3, the coagulating powers of the anions are in the order:

[Fe(CN)6]4- > PO3-4 > SO2-4 > Cl−

Coagulation can also be caused by the following methods:

(i) By electrophoresis.
(ii) By mutual precipitation.
(iii) By prolonged dialysis.
(iv) By heating or cooling.

Protective Action of Lyophilic Colloids and Gold Number

It has already been explained that lyophobic sols like those of metals (Au, Ag, Etc.) are unstable and are
easily precipitated by addition of electrolytes. However, it is observed that the addition of certain
lyophilic colloids (like a metal sol) render lyophobic colloids difficult to coagulate by the addition of
electrolytes∗. The process is known as ‘protection’ and the lyophilic colloids are termed as protective
colloids.
It is believed that the protective action of the lyophilic colloids is due to the covering up of the particles
of the lyophobic colloid by those of the lyophilic colloid

Lyophilic Particles

(Protecting Particles)

Lyophobic Particles

(Particles Being Protected)

The exact mechanism of protection is not clear.

To compare the protective action of different lyophilic colloids, Zsigmondy (in 1901) introduced a term
called Gold number. It is defined as follows:

Gold number of a protective colloid is the minimum weight of it in milligrams which must be added to
10 ml of a standard red gold sol (containing 0.5 to 0.06 g of gold per litre) so that no coagulation of
the gold sol (i.e. the change of colour from red to blue) takes place when I ml of 10% sodium chloride
solution is rapidly added to it.

Evidently, smaller the gold number of a protective colloid, the greater is its protective action.

Emulsions

An emulsion is a colloidal dispersion in which both the dispersed phase and the dispersion medium are
liquids.

Method of preparation.

An emulsion is prepared by shaking strongly the mixture of the two liquids or by passing the mixture
through a colloid mill, called the homogenizer. The emulsions thus prepared from the pure liquids are
usually not stable and the two liquids separate out on standing. To get a stable emulsion, small
quantities of certain other substances are added during preparation.

The substances thus added to stabilize the emulsions are called emulsifiers or emulsifying agents. The
substances commonly used as emulsifying agents are soaps of various kinds, long chain sulphonic acids
or lyophilic colloids (proteins, gum, ager etc.).

Role of emulsifier.

The role of emulsifier can be explained taking the example of soap as an emulsifier. If a drop of oil is
surrounded by soap solution, the R – part of the soap remains in the oil and the COO−Na+ part remains in
water as shown in Fig.

Thus, soap molecules are concentrated over the surface of the drop of oil. As a result the interfacial
tension between oil and water decreases and hence they are intermixed into each other to form the
emulsion.

Some other commonly used stabilizing agents are proteins, gums and agar.

--------------------------
- - WATER- - - - - - - - - - - - - - - - - - Solid Circle
------------------------- Represents
--------- -------- Polar Group (COO−Na+)
------- ------- Wavy Line ( ↭ )
------- OIL ------- Represents
-------- -------- Non-Polar
--------- --------- Group (R-)
--------------------------
--------------------------
--------------------------
--------------------------

Role of soap as an emulsiner

Types of Emulsions.

Types of emulsion (a) oil in water (b) water in oil

OIL DROPLETS WATER DROPLETS

----------------- -----------------
----------------- -----------------
----------------- -----------------
----------------- -----------------
----------------- -----------------
----------------- -----------------
----------------- -----------------

(a) WATER (b) OIL

Emulsion of oil-in-water in which oil is the dispersed phase and water is the dispersion medium.

Emulsion of water-in-oil in which water is the dispersed phase and oil is the dispersion medium.

Evidently, the type of emulsion depends upon the relative amounts of the two liquids. If water is in
excess, it is oil-in-water emulsion.

The type of emulsion formed also depends upon the nature of the emulsifying agent. For example, the
presence of soluble soaps as the emulsifying agents generally favours the formation of emulsions soaps
(containing non-alkali metal atoms) favours the formation of emulsions of water-in-oil.

Examples of emulsion. The two well known examples of emulsions are:

(i) Milk in which the particles of the liquid fat are dispersed in water.
(ii) Cod liver oil emulsion in which water is dispersed in the oil.

Note: Emulsions can be separated into their constituent liquids by boiling, freezing, centrifuging, electrostatic precipitation by
adding large amounts of the electrolytes to precipitate out the dispersed phase or by chemical destruction of the emulsifying
agent. The separation of cream from milk is a well known example of centrifuging.

CATALYST AND CATALYSIS

Definition

Catalyst is a substance which can change the speed of a chemical reaction without being used up in that
reaction and the phenomenon is known as catalysis.

Positive Catalysis
If a catalyst increases (accelerates) the speed of a reaction, it is called a positive catalyst and the
phenomenon is called positive catalysis. For example, oxidation of SO2 to SO3 in presence of NO (lead
chamber process) or in presence of V2O5 (contact process) are examples of positive catalysis.

Negative Catalysis

On the other hand, if a catalyst decreases (retards) the speed of a reaction, it is called a negative catalyst
and the phenomenon is called negative catalysis.

Decomposition of H2O2 in presence of phosphoric acid and oxidation of chloroform in presence of


alcohol are examples of negative catalysis.

How does a catalyst work?

A catalyst lowers the activation energy for the forward reaction as well as for the backward reaction.
As a result, the reaction follows an alternate path and the rate of forward reaction as well as that of the
backward reaction are accelerated to the same extent.

In the presence of catalyst, the equilibrium is attained quickly

--------------------------------------------- Without catalyst

E’a,f -------------------------------- With catalyst

------------------------ E’a,b Ea,b

Energy Reactants △H

f=forward
b=backward
--------------------- Products

PRODUCTS COORDINATE

Types of Catalysis
There are two types of catalysis

(1) Homogeneous Catalysis


(2) Heterogeneous Catalysis
(1) Homogeneous Catalysis.

If the catalyst is present in the same phase as the reactants, it is called a homogeneous catalyst
and this type of catalysis is called homogeneous catalysis.

(i) Oxidation of sulphur dioxide to sulphur trioxide in presence of nitric oxide as catalyst (in
lead chamber process for manufacture of H2SO4).

2SO2 (g) + O2 (g) NO (g) 2SO3 (g)

Here, all substances are present in the gaseous phase.

Theory of Homogeneous Catalysis.

Intermediate compound formation theory.

According to modern views, a catalyst enters into chemical combination with one or more of the
reactants forming an intermediate compound which then decomposes or combines with one of the
reactants to produce the product and the catalyst is regenerated.

The involvement of the catalyst in the reaction lowers the free energy of activation and hence
accelerates the speed of the reaction. In other words, a new more efficient path is followed.

For example, the oxidation of SO2 to SO3 in presence of NO takes place as follows:

O2 (g) + 2NO (g) 2NO2 (g)

Reactant Catalyst Intermediate

SO2 (g) + NO2 (g) SO3 (g) + NO (g)

Reactant Intermediate Product Regenerated catalyst

(2) Heterogeneous Catalysis.

If the catalyst is present in a different phase than that of the reactants, it is called a
heterogeneous catalyst and this type of catalysis is called heterogeneous catalysis.

The catalyst in heterogeneous catalysis is generally solid and the reactants are mostly gases and
sometimes liquids. In heterogeneous catalysis the reaction starts at the surface of the solid
catalyst. That is why it is also known as surface catalysis.
Some of the important examples of heterogeneous catalysis which are of commercial or
technological importance are given below:

(i) Manufacture of ammonia from N2 and H2 by Haber’s process using iron as catalyst.
(ii) Synthesis of methyl alcohol (CH3OH) from CO and H2 using a mixture of Cu, ZnO and
Cr2O3, as catalyst.

Some important features of solid catalysts (or heterogeneous catalysis)

Some important aspects of heterogeneous catalysts are briefly described below:

(1) Activity.
By activity of the catalyst we mean its capacity to increase the speed of the chemical reaction.

Note: In certain cases, the extent to which speed of the reaction is increased is as high as 1010 times.

Combination of H2 and O2 in the presence of platinum (catalyst) to form water with explosive
violence is an excellent example of catalytic activity. In the absence of the catalyst, platinum, H2
and O2 do not combine and can be stored as such for an indefinite period.

Pt
2H2 + O2 2 H2O

(2) Selectivity.
By selectivity of a catalyst we mean its ability to direct the reaction to form particular products
excluding others.
For example,
(i) CO and H2 react to form different products in presence of different catalysts as follows:

Cu
CO (g) + H2 (g) HCHO (g)

Cu/Zno-Cr O
CO (g) + 2H2 (g) 2 3 CH3OH (g)

Ni
CO (g) + 3 H2 (g) CH4 (g) + H2O (g)

(ii) Acetylene on reaction with H2 in presence of platinum as catalyst gives ethane while in
the presence of Lindlar,s catalyst (palladium + BaSO4 poisoned with quinoline or
sulphur) gives ethylene.
H H
Pt
H–C–C–H

H H
H – C≡C – H + H2 Ethane
Acetylene H H
(Ethyne) Lindlar’s
H–C=C–H
Catalyst Ethylene
(Pd+BaSO4+quinoline)

(3) Specificity.
Action of a catalyst is highly specific (selective) in nature, i.e., a given substance can act as a
catalyst only in a particular reaction and not for all reactions. It means a substance which acts as
a catalyst in one reaction may fail to catalyse other reaction.

Zeolites
What are Zeolite?

1. Zeolites are aluminosilicates∗ with the general formula Mx/n [(AlO2)× (SiO2)y] . z H2O. (where n is the
change on the metal cation Mn+, which is usually Na+, K+ or Ca2+ and z is the number of water molecules of hydration
which is highly variable).
2. They are three-dimensional net work silicates in which some silicon atoms are replaced by
aluminium atoms. They are found in nature as well as synthesized in the laboratory or industry.
They form an important class of oxide catalysis.
3. How are they used and act as shape selective catalyst?
Zeolites to be used as catalysts are heated in vacuum so that the water of hydration is lost. As a
result, zeolite becomes porous, i.e., the cavities in the cage-like structure which were occupied
by the water molecules become vacant. The size of the pores generally varies between 260 pm
and 740 pm. Thus, only size is small enough to enter these cavities and also leave easily. It will
not adsorb those molecules which are too big to enter. Thus, zeolites act as selective adsorbents
and hence as ‘molecular sieves’.
For example, the zeolite, sodium alumina silicate, can absorb straight chain hydrocarbons and
not branched chain or aromatic ones.

Define shape selective catalysis.

The reaction taking place in zeolites depends upon the size and shape of reactant and product
molecules as compared to those of the pores and cavities of the zeolite. That is why these types
of reactions are called ‘shape-selective catalysis’.

Uses of Zeolite

1. Zeolites are being very widely used as catalysts in petrochemical industries for cracking of
hydrocarbons and isomerization. An important zeolite catalyst used in the petroleum industry is
ZSM – 5∗ (Zeolite sieve of Molecular Porosity 5). It converts alcohols directly into gasoline
(petrol) by first dehydrating them so that a mixture of hydrocarbons is formed.
ZSM−5
Alcohols Dehydration
Hydrocarbons

2. Hydrated zeolites are used as ‘ion-exchangers’ in softening of hard water.

Mechanism of Enzyme Action

Lock and key model.

Enzymes are highly specific in their action. The specificity of the enzymes is due to the presence
of some specific regions, called the active sites, on their surface. These active sites are
associated with some functional groups which form weak bonds such as H-bonds, van der Waals
attraction, with the substrate (reactant) molecules.

The shape of the active site of any given enzyme is such that only a specific substrate can fit
into it, in the same way as one key can open a particular lock.

1. Specific substrate binds at the active site of enzyme to form enzyme substrate complex.
2. At the active site Substrate molecules react to form the products.
3. Since the product molecules do not have any affinity for the enzyme surface, they at once
leave the enzyme surface making room for the fresh substrate molecules to bind to the
active sites.

The whole sequence is diagrammatically represented in Fig.

Substrate

; ;‘ ; ; Active Site ; ; ; ; ; ;; ;

; . ;; . ; ; ; ; ; Step 1 ;; ; ; ; ; ; ; ; ; ; ;

. ‘ .; .; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;
;; ; ;; ; ; ; ; ; ; ;; ; ; ; ; ; ;;

Enzyme-substrate

Products Complex

Step 2

;;; ;;; ;; ;;;;;;; ;;;;

; ; ;; ; ; ; ; ; ; ; ; ; ; ; ; ; Step 3 ;; ;;;;;;; ;; ;;;;;;

;;;;;;;;;;;;;;;;;;; ;;;;;;;;;;; ;;;;;;

;;;;;;;;;;;;;; ;;;;;;;;;;

Enzyme Enzyme-Products

association

Lock and key mechanism of enzyme action

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