KHANNA CHEMISTRY CLASSES

SURFACE CHEMISTRY
SURFACE CHEMISTRY
Surface chemistry is that branch of chemistry which deals with the study of the
phenomenon occurring at the surface or 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 solid resulting into a higher concentration of the molecules on the
surface is called absorption.
• The substance adsorbed on the surface is called the adsorbate and the substance on
which it is adsorbed is called adsorbent.
• The reverse process i.e. removal of the adsorbed substance from the surface is
called desorption.
• The adsorption of gases on the surface of metals is called occlusion
Example of adsorption :-
(i) When aqueous soln. of raw sugar (yellowish brown color) is shaken with
animal charcoal and then filtered , the filtrate is colourless . This is because
the colouring substances are adsorbed by animal charcoal.
(ii) If silica gel is placed in a closed vessel containing moist air, the air becomes
dry after some time. This is because water molecules are adsorbed the surface of
silica gel.
Mechanism of adsorption :- The situation existing at the surface of liquid or a solid is
different from that in the interior. e.g. a molecule in the interior of liquid is completely
surrounded by other molecules on all sides and hence IMF of attraction are exerted equally
in all direction . While a molecule at the surface of liquid is surrounded by larger number
of molecules in the liquid phase and fever molecules in vapour phase, as a result these
molecule lying at the surface, experience some net inward force of attraction which
causes surface tension, similar inward forces of attraction exist at the surface of solid. In
case of certain solids such as transition metals (like Ni) there are unutilized free
valences at the surface.
Fig.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
Because of the unbalanced inward forces of attraction of free valencies at the
surface, liquids and solids have the property to attract and retain molecules of a gas
or dissolved substance onto their surfaces with which they come in contact.

Adsorption is exothermic :- When adsorption takes place, the residual forces on the
surface of the adsorbent decrease. In other words, surface energy decrease. This appears in
the form of heat called heat of adsorption. Hence adsorption is an exothermic process. i.e.
∆Hadsorption is always negative

Difference between :-
S.No Adsorption Absorption
1. It is a surface phenomenon i.e. it It is a bulk phenomenon i.e. occurs
occurs only at the surface of the throughout the body of material
adsorbent
2. In this phenomenon the concentration In this phenomenon, the
on the surface of adsorbent is concentration is same through out
different from that in bulk the material
3. Its rate is high in the beginning and Its rate remains same through out
then decrease till equilibrium is the process
attained.

e.g. 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 . Dyes get adsorbed as well as absorbed in the cotton
fibers i.e. sorption takes place.
Positive and negative adsorption:- When the concentration of the adsorb ate 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.

Factors Affecting adsorption of gases by solids:-

(i) Nature and surface area of the adsorbent : Same gas is adsorbed to
different extent by different solids at the same temperature. Greater the
surface area of the adsorbent, greater is the volume of gas adsorbed.
Substances like charcoal, silica gel are good adsorbents because they are
highly porous 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 . Higher is the critical
092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
temp. of gas greater is the amount of gas adsorbed . In other words, a gas
which is more easily liquefiable or is more soluble in water is more readily
adsorbed.
(iii) Temperature :- Adsorption decreases with increase in temperature basically,
adsorption is also a process involving a true equilibrium . The two opposing
processes involved are condensation (i.e. adsorption ) of the gas molecules from the
surface of the solid into the gaseous phase Also , the process of condensation ( or
adsorption) is exothermic, so according to lechateliers principle, increase of
temperature decreases the adsorption.
Condensati
 on

Gas (adsorbate ) + solid ( adsorbent ) gas adsorbed on solid + heat
 
Evaporation

• The amount of heat evolved when one mole of the gas is adsorbed on the adsorbent
is called heat of adsorption
(iv) Pressure :- At constant temp the adsorption of a gas increases with increase of
pressure
(v) Activation solid adsorbent :- It means to increase the adsorbing power of an
adsorbent this is done by increasing the surface are of the adsorbent by :-
(a) making the surface of adsorbent rough e.g. by mechanical rubbing or by
chemical action.
(b) Subdividing the adsorbent into smaller pieces or grain:- This method
increases the surface area. But if the adsorbent is broken into too fine particles
that it becomes powder, then penetration of gas becomes difficult and this
obstructs adsorption.
(c) Removing the gases already adsorbed e.g. charcoal is activated by heating in
superheated steam.

Types of Adsorption: - Two types of adsorption – (i) physical adsorption or vander

waal adsorption or Physisorption .
When gas is held (adsorbed) on the surface of solid by vander waal’s forces, without
resulting into the formation of any chemical bond between the adsorbate and adsorbent ,
it is called physisorption
(ii) Chemisorptions or Langmuir adsorption :- When a gas is held on the surface of a
solid by forces similar to those of a chemical bond, the type of adsorption is called
chemisorptions.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY

S.No Physical adsorption Chemisorptions

1. The forces operating in these cases are The forces operating are similar to
weak vander waal’s forces those of a chemical bond
2. The heats of adsorption are low i.e. The heats of adsorption are high
about 20-40 kJ mol-1 about 40-400 k Jmil-1
3. No compound formation takes place Surface compound are formed
4. The process is reversible The process is irreversible
5. It doesn’t require any activation energy It requires activation energy
6. Takes place at low temp and decreases This type of adsorption first increase
with increase of temp. with increase of temp. the effect is
called activated adsorption
7. It is not specific in nature i.e. all gases It is specific in nature and occurs only
are adsorbed on all solids to some when these is some possibility of
extent compound formation between the gas
being adsorbed and the solid
adsorbent.
8. The amount of gas adsorbed is related There is no such correlation
to the ease of liquefaction of the gas
9. It forms multimolecular layers If forms unimolecular layer
Similarities

10. It increases with increase in surface area It also increases with increase in
of the adsorbent surface area of the adsorbent
11. It increases with increases of pressure It also increases with increase of
pressure

Freundlich’s Adsorption Isotherm: - When the adsorbent and adsorbate are enclosed in a
closed vessel, after an initial decrease in the pressure of the gas, gas pressure as well as the
amount of gas adsorbed reach constant values. This is because after the equilibrium is
attained, rate of adsorption becomes equal to the rate of desorption.
The extent of adsorption is usually expressed as x/m, where m is mass of the adsorbent and
x is mass of adsorbate when adsorption equilibrium is attained.

A graph between the amount of gas adsorbed per gram of the adsorbent (x/m) and the
equilibrium pressure of the adsorbate at constant temp is called adsorption isotherm.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
At a value of p of equilibrium pressure, x/m reaches it maximum value and then it remains
constant even though the pressure is increased. This type of adsorption isotherm is
obtained when the adsorbate form a unimolecular layer on the surface of the adsorbent.
• At low values of p, the graph is nearly straight and sloping i.e.
x x
 p1 or  cons tan t xp1 …………………..(i)
m m
x
• At high pressure, becomes independent of p. In this range of pressure,
m
x x
 p° or = constant x p° ………………………….(ii)
m m
• In the intermediate range of pressure, x/m will depend on p raised to powers
between 1 and 0, i.e. fraction
1 1
x x
 pn or  Kp n
m m
Where n is positive integer and n and K are constants depending upon the
nature of the adsorbate and adsorbent at particular temp.
fig.

This relation is known as freundlich adsorption isotherm .

1
x
 Kp n
m
Taking log on both sides
x 1
log  log K  log p
m n
A graph between log x/m against log p.
Fig.

The experimental values, when plotted show deviation from linearity, specially at
high pressure.

Adsorption from solution :-Solid surfaces can adsorb solvents from solution e.g. when a
soln of CH3COOH is shaken with charcoal , some amount of CH3COOH from the solution
is adsorbed on the charcoal and hence the concentration of acid in solution decreases.

The isotherm from the adsorption of solutes from solution ( by solid adsorbents ) is
found to be similar as shown in previous graph . Thus the relationship between x/m and
equilibrium concentration C, of the solute in the solution is also similar , i.e.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
x
 Kc1 / n
m
Taking log of both sides of equation we get
x 1
log  log K  log C
m n
x
This equation implies that a plot of log against log C should be a
m
1
straight line, with slope and intercept log K.
n

Adsorption Isobar’s :- A graph drown between the amount of the gas

adsorbed per gram of the adsorbent (x/m) and temperature, ‘t’ at a
constant equilibrium pressure of adsorbate gas is known as adsorption
isobar.
Fig.

Applications of adsorption :-
(i) In preserving vacuum:- In dewar flasks, activated charcoal is placed between the
wall of the flask, so that any gas which enters into the annular space either due to
the glass imperfection or diffusion through glass is adsorbed.
(ii) In chromatographic analysis :- The selective adsorption of certain substances from
a solution by a particular solid adsorbent helped to develop a technique for the
separation of the components of mixture . This technique is called Chromato graphic
technique e.g. in column chromatography, a long and wide vertical tube is filled with
a suitable adsorbent and the solution of mixture poured from the top and then
collected one by one from the bottom.
(iii) In softening of hard water :- The use of ion exchangers for softening of hard water
is based upon the principle of competing adsorption just as chromatography .

(iv) In froth floatation process . When sulphide ore is shaken with pine oil and water,
the ore particles are adsorbed on the froth that floats and the gangue particles
(silica, earthy matter) settle down in the tank.
(v) In curing diseases:- Some drugs can adsorb the germs on them and hence kill them
and save us from diseases.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY

Colloidal states of matter :-

Colloidal state of matter is, therefore a state in which the size of particles is such
(1 to 1000 nm ) that they can pass through filter paper but not though animal or vegetable
membrane
Characteristies of true solutions, colloaidal solutions and suspensions

S. TRUE
No. PROPERTY SOLUTIONS COLLLOIDAL SUSPENSIONS
SOLUTIONS

Less than 10–9 m

or 1 nm (i.e., < 10 Between 10–9 to 10–
A ) 6
m or 1 nm to 1000 More than 10–6 m
nm or 10000 nm

(i.e., 10 A to 10000 (i.e., > 10000 A ).
1. Particle size Pass through A ).
(diameters) ordinary filter Do not pass
paper as well as pass through through filter
animal ordinary filter paper paper and animal
2. Filtrability membrane. but not through membrane.
animal membrane.
Do not settle. Settle on
Do not settle. standing.
3. Settling
Particles are
invisible. Scattering of light Particles are
4. Visibility by the particles is visible to naked
observed under eye or under a
ultra-microscope. microscope.
Diffuse quickly.
5. Diffusion diffuse slowly. Do not diffuse.

Clear and
6. Appearance transparent. Transluscent. Opaque.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY

Dispersed phase and dispersion medium: - Just as in true solution, we have solute
and solvent, similarly in colloidal system, we have dispersed phase and dispersed
medium.

Dispersed phase: - means the substance distributed in the dispersion medium in the
form of colloidal particles and dispersion medium means the medium in which the
substance is dispersed in the form of colloidal particles.

Classification of colloids:-
(A) Based on physical state of dispersed phase and dispersed medium:-
Depending upon whether the dispersed phase and dispersion medium are
solids, liquids or gases, eight type of colloidal systems are possible.
Depending upon dispersion medium, the solutions are given special names.
Dispersion medium Name of the sol.
Water Aquasol of Hydrosol
Benzene Benzosol
Gases Aerosol

Types of colloidal systems (or colloidal dispersions)

S. No. DISPERSEDDISPERSIONNAME EXAMPLES

PHASE MEDIUM
1. Solid Slid Solid sol Some coloured glasses, gem stones
2. Solid Liqued 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, insecticide sprays
7. Gas Solid Solid foam Pumice stone, foam rubber
8. Gas Liquid Foam Froth, whipped cream, soap father
(b) Based on nature of interaction between dispersed phase and dispersion between
dispersed phase and dispersion medium:- On this basis colloidal solution are divided into
two categories = namely Lyophilic and Lyophobic. If water is dispersion medium, then terms
used are hydrophilic and hydrophobic .

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
(1) Lyophlic colloids: - Lyophilic means liquid loving substance like gum,
gelatin, starch etc. when mixed with a suitable liquid as the dispersion
medium directly form the colloidal sol are called lyophilic and solution thus
formed are called lyophil sols.
(2) Lyophobic colloids :- Lyopbobic means liquid heating substances like metal
, 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. Such substances are called lyopbobic and sols. Formed by them are
called lyophobic sols.

Points of difference between lyophilic and lyphobic sols

S. No. PROPERTY LYOPHILIC SOLS LYOPHOBIC SOLS

1. Ease of Prepared easily by directly Cannot be prepared
preparation mixing with the liquid directly. Prepared by
dispersion medium. special methods only.
2. Stability They are quite stable and They are easily
are not easily precipitated precipitated by addition of
or coagulated. a small amount of a
suitable electrolyte.
3. Hydration They are highly hydrated They are not much
hydrated.
4. Reversible and They are reversible in They are irreversible in
irreversible naturenature, i.e., once nature, i.e., once
precipitated can reform the precipitated cannot form
colloidal sol by simply the colloidal sol by simple
remixing with the addition of the dispersion
dispersion medium. medium.
5. Nature of These sols are usually These sols are usually
substance formed by the organic formed by the inorganic
substance like starch, gum materials like metals, their
proteins etc. sulphides etc.
6. Viscosity Their viscosity is much Their viscosity is almost
higher than that of the the same as that of the
medium. medium.
7. Surface tension Their surface tension is Their surface tension is
usually lower than that of nearly same as that of the
the dispersion medium. dispersion medium.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
(c) Based on the type of particles of dispersed phase:-
(i) multimolecular colloids:- When on dispersion of substance in the
dispersion medium, a large number of atoms or smaller molecules of the
substance (with diameter less than 1nm ) aggregate together to form species
having size in the colloidal range, the species thus formed are called multi
molecular colloids. E.g. a gold sol may contain particle of various size having
several atoms.
(ii) Macromolecular colloids:- When certain substances having big size
molecules, called macromolecules having large molecule masses are dissolved
in a suitable liquid , they form a solution in which the molecules of a the
substance, i.e. dispersed particles have size in colloidal range. Such
substances are called macromolecular colloids. E.g. naturally occurring
macromolecules are nylon, synthetic rubber their colloidal sols. are quite
stable and resemble true solution in many respects.
(iii) Associated colloids – Micelles:- The substances which when dissolved in a
medium at low concentration behave as normal, strange electrolytes but at
higher concentration exhibit colloidal state properties due to formation of
aggregated particles are called associated colloids. The aggregated particles
thus formed are called micelles .
• The formation of micelles takes place only above a particular temp called
kraft temperature (TK) and above particular concentration called critical
micelle contraction (CMC) e.g. surface active agents such as soaps, synthetic
detergents. For soaps, the CMC is 10-4 – 10-3 mol L-1 Each micelles contain
atleast 100 molecule .
Mechanism of micelle formation :- Best examples is soap solution . Soap is sodium salt
of higher fatty acids and can be CH3(CH2)16 COO¯Na+ or
sodium polmitate CH3 (CH2)14 COO¯Na. In water it dissociation to give R COO¯ and Na+
ions. The RCOO¯ further consists of two parts i.e. non polar long hydrocarbon chain R,
called tail which is
Fig.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
Hydrophobic (water repelling) and polar group COO¯ called head, which is hydrophilic
part, i.e. water loving.
• RCOO¯ are therefore present on the surface with their COO¯ groups in water and
hydrocarbon chain R staying away from it and remain at the surface. However at high
concentration , these ions don’t remain on the surface but are pulled into bulk of solution
and form an aggregate of spherical shape with their hydrocarbon chains pointing
towards the centre and COO¯ part (represented by circle ) outwards on the surface of
sphere
• An aggregate thus formed is known as
Ionic micelle.
Fig.

Suppose some grease or oil is stitching to cloth surface. When it comes in contact
with soap solution the stearate ions arrange themselves around it in such a way
that hydrophobic parts of stearate ion are in the oil (or grease) and the
hydrophilic part projects outside the grease, as shown in fig (b) . As hydrophilic part
is polar and can interact with water molecules present around the oil droplet . As a
result the oil droplet is pulled away from the surface of cloth into water to
form ionic micelle, which is then washed away with excess water . Thus a sheath
of negative charge is formed around oil globate which prevents them to come
together and form aggregate.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
Comparison of some important Characteristies of multimolecular.
macromolecular and associated colloids.

Multimolecular colloids Macromolecular colloids Associated colloids

1. They formed by the They are molecules of They are formed by
aggregation of a large large size, e.g., polymers aggregation of a large no.
number of atoms or like rubber, nylon, starch, of ions in concentrated
molecules which generally proteins, etc. solution, e.g., soap sol.
have diameters less than 1
nm, ege. sols of gold,
sulphur, etc.
2. Their molecular masses They have high molecular Their molecular masses
are not very high. masses. are generally high.
3. Their atoms or molecules Due to long chain, the Higher is the
are held together by weak van der waal’s forces concentration, greater are
van der waal’s forces. holding them are the van der waal’s forces.
comparatively stronger.

Preparation of colloidal sols:- Lyophilic sols can be prepared directly by mixing

the substance with dispersion medium e.g. colloidal sols of starch, gelatin, gum
soaps etc. are prepared by dissolving these substances in warm water.

• However Lyophobic sols cant’ be prepared directly two types of methods are
employed for obtaining lyophobic sols.
(A) Dispersion or Disintegration methods:- These method involve breaking of bigger
particles to colloidal size.
(i) Mechanical disintegration:- The mechanical disintegration is carried out in a
colloid mill or bal mill. A colloid mill consists of two steel discs with a little gap in
between and capable of rotating the opposite directions at high speed. (7000 rpm)
Fig.

A suspension of substance in water is introduced into the mill. The size of suspension
particle is reduced to that of colloidal size.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
(ii) Electro Disintegration (Breding’s method) This method is employed for
obtaining colloidal sols of metal like gold, silver , platinum etc. An electric arc is set
up between two metallic electrodes suspended in trough of water. The intense
heat of arc converts the metal into vapour which are condensed immediately in ice
cold water both resulting in the formation of particles of colloidal sign
Fig.

(iii) Peptization: peptization is a process of converting a fresh precipitate into

colloidal particles by shaking it with the dispersion medium in the presence of a
small amount of suitable electrolyte . The electrolyte is called peptizing against e.g.
(i) A reddish brown coloured collidal sols is obtained by adding a small quatity of FeCl3
solution to freshly precipitated ferric hydroside .
(ii) A ppt of Ag I can be peptized by shaking with a dil. soln of AgNO3 or KI
Fig.

As the electrolyte is added to freshly precipitated substance the particles of precipitate

preferentially adsorb one particular type of ions of electrolyte (ions common with the
precipitated substance). As a result they get dispessed due to electrostatic repulsions. This
gives rise to particles of colloidal size.

B. CONDENSATION OR AGGREGATION METHODS

These methods involves joining together of large no. of smaller particles to form particles
of colloidal size
1. By Chemical reaction
(i) By double decomposition
When H2 S is passed through a dilute solution of Arsenious oxide in water a colloidal
solution of Arsenious sulphide is obtained
As2 O3 + 3H2 S → As2 S3 + 3H2 O
(colloidal solution).

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
(ii) By reduction
2 AuCl3 + 3SnCl2 → 2 Au + 3SnCl4
(gold sol)
Gold, silver are obtained in colloidal form by reduction of very dilute solutions of their
salts with suitable reducing agents
2AuCl3 + 3 HCHO + 3 H2O → 2Au + 3HCOOH + 6HCl
(gold sol)
Or 4AuCl3 + 3NH2 NH2 → 4Au + 3N2 + 12HCl
(gold sol)
(iii) By Oxidation
H2 S + Br2 → S + 2HBr
(Sulphur in colloidal form)
(iv) By Hydrolysis
Fe(OH)3 solns are obtained by boiling solutions of their corresponding chlorides
FeCl3 + 3H2O → Fe (OH)3 + 3HCl

2. By Excessive cooling
Colloidal solution of ice in an organic solvent like ether is obtained by freezing mixture of
solvent and water
PURIFICATION OF COLLOIDAL SOLUTIONS
The process of reducing the impurities of the electrolytes to the minimum required level is
known as purification of colloidal solution. Following methods are used for the purification
of colloidal solutions

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
–– The separation of crystalloids from the colloids is based upon the principle that the
particles of crystalloids pass through parchment layer where as those of colloids do not
–– The apparatus used is called dialyser

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY

The impure solution 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 colloids behind. The above process can be quickened if an electric field is applied
around the membrane, the process is then called ELLECTRO – DIALYSIS

2. ULTRA FILTRATION
Through ordinary filter, both colloidal dispersions, as well as true solutions can pass.
However a filter paper treated with colloidal solution or gelatin solution followed by
hardening by dipping in formaldehyde solution, reduces the pore size of filter paper.
The filter paper so obtained is called Ultra filter and the filtration device using such a filter
is called ultra filtration. The solution is poured over the ultra filter, which permits
solution of electrolyte to pass through but retains colloidal particles in form of slime. Slime
in contact with water disperses spontaneously to form a colloidal system.

3. ULTRA – CENTRI FUGATION

In this method, the impure solution is taken in tube, which is placed in ultra centrifuge. In
this machine, the tube is rotated at high speed. As a result, the colloidal particles settle
down at the bottom of tube where as 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 pure colloidal solution.
PROPERTIES OF COLLOIDAL SOLUTIONS
1. Mechanical Property – BROWNIAN MOVEMENT
It may be defined as continuous zig – zag movement of the colloidal particles in a colloidal
solution
– This movement does not depend upon the nature of colloid but depends upon the size of
the colloidal particles and the viscosity of solution. Smaller the size and lesser the
viscosity, faster is the movement of the particles

Cause of Brownian Movement

Molecules of dispersion medium due to their kinetic motion strike against the colloidal
particles from all sides with different forces causing them to move. Colloidal particles
being comparatively heavier, move with slower speed.
Significance / Importance of Brownian Movement

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
(i) B M opposes the force of gravity and doesn’t allow the colloidal particles to
settle down. Thus it is responsible for stability of colloidal solution.
(ii) It has also helped in the determination of Avogadro’s number.
2. TYNDALL EFFECT (Optical property)
If 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 when viewed at right angles to
the direction of the passage of light. The path of light becomes vissible due to scattering of
light by colloidal particles. This is called
TYNDALL EFFECT

– The illuminated path of beam is called Tyndall cone.

This effect is observed only when following two conditions are satisfied
(i) The diameter of the dispersed particles is not much smaller as compared to
the wavelength of the light used
(ii) There is a large difference in the refractive indicies of the dispersed phase and
the dispersion medium
Importance of Tyndall effect
Based on tyndall effect, Zsigmondy, devised an instruments called ultra
microscope which was used to find out the average mass of the particles. Intense
beam of light is focussed on the colloidal solution taken in a glass vessel and then
observed in microscope at right angles to the beam. The light scattered by each
individual colloidal particles appears as a bright star against a dark back ground.
Thus the number of colloidal particles can be converted. Knowing the volume of
solution number of particles per unit volume can be determined. This further
helps to find out average mass of particles.
–– This tyndall effect also helps to confirm the heterogeneous nature of the colloidal
solutions
3. Electrical Properties
a. Stability of colloidal solutions ––
Electrical charge on colloidal particles
Stability of colloidal solution is due to the fact that the colloidal particles in
the solution are electrically charged. The particles, therefore, repel one another and
don’t come close together to form large no colloidal particles. Colloidal particles
carry either positive or negative charge. E.g. As2 S3 particles are negatively charge

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
where as the dispersion medium (water) is positively charged. Fe (OH)3 particles
are positively charged whereas dispersion medium is negatively charged.

POSITIVELY
NEGATIVELY CHARGED
CHARGED
Metal hydroxides
i. Metallic particles i. like
(e.g. Cu, Ag, Au Fe (OH)3, Al(OH)3,
Solutions). Ce (OH)3, Ca(OH)2
Metal sulphides ii. Hydrated metallic
ii. like As2S3, CdS, oxides, e.g.,
etc. Al2O3 . x H2O,
Fe2O3 . x H2O,
Cr2O3 . x H2O etc.
Starch, gum,
iii. gelatin, clay, Oxides like T1O2,
charcoal, silicic iii. etc.
acid solutions.
Acidic dyes like
iv. congo red, eosin iv. Haemoglobin
solutions
Basic dyes like
v. methylene blue,
Prussian blue etc.

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 dispersion medium.
ii. Electron capture –– by particles from air during electro dispersion in Bredig’s arc
method.
iii. Preferential adsorption of ions from solutions.
An Ionic colloidal adsorbs ions common to its own lattice during preparation
of colloidal solution e.g. if colloidal solution of AgI is prepared by adding KI
solution to Ag NO3 solution till KI is in excess, Iodide ions (I–) will be adsorbed on
the surface of AgI particles, there by giving them a negative charge,

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
AgI + I– → Ag I : I–
(from KI) (negative sols.)
On, the other hand if colloidal solution of AgI is prepared by adding AgNO3 solution to KI
solution till AgNO3 is in slight excess, Ag + ions will be adsorbed there by giving positive
charge to the colloidal particles
AgI + Ag+ → AgI : Ag+
(from AgNO3) (positive sol.)
In either case left out ions remain in the dispersion medium, there by giving equal and
opposite charge to dispersion medium.
Similarly,
FeCl3 + H2O (excess) → Fe2O3 . xH2O : Fe3+
(positively charged sol.)
FeCl3 + NaOH → Fe2O3 . xH2O : OH–
(negatively charged sol.)
iv. Dissociation of molecules followed by aggregation of ions
e.g. in case of soap the RCOO– group gets dissociated from Na+ ions and have
tendency to aggregate into a cluster carrying negative charge.

ELECTROKINETIC OR ZETA POTENTIAL

When one type of ions of the electrolyte are adsorbed on the surface of the
colloidal particles it forms a fixed layer. It attracts the counter ions from the medium
forming a second layer which is mobile and is called diffused layer.
The double layer of opposite charges
Fig.

Thus formed is called Helmholtz Electrical double layer.

–– As a results, a difference of potential exists between the fixed layer and the
diffused layer. This potential difference is known as electro kinetic potential or zeta
potential.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY

b. ELECTRO PHORESIS OR CATA PHORESIS

Fig.

The process of Electrophoresis, in volves the movement of colloidal particles towards one
or the other electrode when placed under influence of an electric field. As soon as the
colloidal particles reach the oppositely charged electrode they get neutralized and
coagulated.
Thus electrophoresis can be used to find out the nature of the charge that the colloidal
particles carry.
c. ELECTRO – Osmosis
Fig.

Electro – Osmosis may be defined as a phenomenon in which the molecules of the

dispersion medium are allowed to move under the influence of on electric field where as
the colloidal particles are not allowed to move.

d. COAGULATION OR FLOCCULATION OR PRECIPITATION

Coagulation or Precipitation is a process of aggregating together the colloidal particles so
as to change them into large sized particles which ultimately settle as precipitate.
– Coagulation is generally brought about by addition of electrolyte. When an electrolyte is
added to colloidal solution the particles of solutions take up the ions which are oppositely
charged and thus get neutralized. The ions responsible for neutralization of charge on the
colloidal particles is called the coagulating ion. The neutral particles then start
accumulating to form particles of larger size which settle down.
–– When small amount of electrolyte is added that is when the concentration of electrolyte
added is low, the process is called flocculation.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
–– The minimum amount of an electrolyte (mili moles) that must be added to one litre of a
colloidal solution so as to bring about complete coagulation is called coagulation or
flocculation or precipitation value of electrolyte. Thus smaller is the coagulating value of
an electrolyte, greater is its coagulating power.

HARDY SCHULZE LAW

This law states that –– The quantity of the electrolyte which is required to coagulate a
definite amount of colloidal solution depends upon the valency of the coagulating ion. The
main points of this law are
(i). The effective ions of the electrolyte in bringing about coagulation are those which
carry charge opposite to that of colloidal particles. These ions are called coagulating ion or
flocculating ions.
(ii) Greater is the valency of the ion , grater isits property to bring about coagulation

-For coagulation of negatively charged As2S3 sol, trivalent cations(Al3+)are more effective
than divalent (Ba2+) cations which in turn are more effective than monovalent (Na+) cations
–– Similarly for coagulation of positively charge Fe(OH)3 solution, tetravalent anions [Fe
(CN)6]4– are more effective than trivalent anions (PO43–) which are more effective than
divalent anions SO42– which in turn are more effective than monovalent anions (Cl–)
Coagulation can be caused by following methods
(i) By electro phoresis
(ii) By prolonged dialysis
The stability of colloidal solution is due to presence of small amount of
electrolyte. On prolonged dialysis, the electrolyte is completely removed. As result
the colloidal solution becomes unstable and gets coagulated.
(iii) By heating (boiling) or cooling.
In some cases, heating the sol. result into coagulation, e.g., coagulation of
butter. When a sol is boiled, the adsorbed layer is disturbed because the
number of collisions on them by the molecules of the dispersion medium
increases. Consequently, the charge on the particles decreases. Hence the stability
decreases leading to their setting down as a precipitate.
In some cases, cooling sol results in coagulation, e.g., coagulation of milk, i.e., on cooling
milk, fats start floating on the surface.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
Protective Action of Lyophilic Colloids and Gold Number
Lyophobic sols like those of metals (Au, Ag, etc.) are unstable and are easily precipitated
by addition of electrolyte. However addition of certain lyophilic colloids like gums, soaps,
etc. to lyophobic 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.

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 gof gold per litre) so that no
coagulation.of the gold sol (i.e., the change of colour from red to blue)
takes place when 1 ml of 10% sodium chloride solution is rapidly added
to it.
Emulsion
An emulsion is a colloidal dispersion in which both the dispersed phase and
the dispersed 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 e.g., soaps of various kinds, long chain sulphonic acids or lyophilic colloids
(proteins, agar atc.).
Role of emulsifier: Soap acts as an emulsifiers. Soaps are sodium or potassium salts of
higher fatty acids, e.g., sodium palmitate
(C15H31COONa), sodium stearate
(Cl7H35COONa), etc. A molecule of soap consists of two parts, the hydrocarbon part

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
(C15H31 – and C17H35 –,etc.)which is soluble in oil and the polar group (COO-
Na+) which is soluble in water
R: COO-Na+
Hydrophobic part Hydrophilic part
(Soluble in oil) (Soluble in water)

Thus, 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. Thus,
micelles are formed.
–– Some other commonly used stabilizing agents are proteins, gums and agar.
Types of Emulsions.
(i) Emulsion of oil-in-water (o/w) in which oil is the dispersed phase and water is
the dispersion medium. For example, milk is an emulsion of liquid fat dispersed in
water ,vanishing cream.
(ii) Emulsion of water-in-oil (W/O) in which water is the dispersed phase and oil is the
dispersion medium. For example, cod liver oil is an emulsion of water in oil, or
butter and cream.
––– Type of emulsion depends upon the relative amounts of the two liquids. If water is in
excess, it is oil-in-water emulsion. If oil is in excess it is water-in-oil emulsion.
––– Also depends upon the nature of the emulsifying agent. For example, presence of
soluble soaps as the emulsifying agents generally favours the formation of emulsions of
oil-in-water whereas the presence of insoluble soaps (containing non-alkali metal atoms)
favours the formation of emulsions of water-in-oil.

To test type of emulsion

The type of emulsion can be tested by any one of the following methods :
(i) Microscopic method.
To a small amount of emulsion a few drops of water are added. The water
will mix completely if the emulsion is o/w. Like wise, for w/o emulsion , the
miscibility -with a few drop of oil can be tested. The miscibility can be seen under a
microscope.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY

(ii) Conductance method.

A small amount electrolyte is added to emulsion. If the conductance increases,
the emulsion is o/w type and if there is no significant change, it is w/o type.
(iii) Dye method.
A. small amount of an oil soluble dye is added to the emulsion. If it is w/o
type, it becomes deeply coloured, otherwise it remains colourless
Properties of emulsions.
(i) Emulsion exhibit all the properties like Tyndall effect, Brownian movement,
Electrophoresis, Coagulation on addition of electrolytes, as shown by colloidal
solutions.
(ii) Emulsion can be separated into their constituent liquids by boiling, freezing,
centrifuging or by chemical destruction of the emulsifying agent. The process of
separation of the constituent liquids of an emulsion is called demulsification. e.g.,
separation of cream from milk.
(iii) Emulsion can be diluted by adding any amount of the dispersion medium, i.e., water
for o/w emulsions and oils for w/o emulsions.

Application of Emulsions.
(i) In the metallurgical processes, the concentrations of ore by froth flotation process is
based upon the treatment of the powdered ore with oil emulsion.
(ii) Asphalt emulsified in water is used for building roads without the necessity of
melting the asphalt.
(iii) Several oily drugs are prepared in the form of emulsions.
(iv) Milk which is an important constituent of our diet is an emulsion of liquid fats in
water.
(v) Certain disinfectants such as dettol and Lysol give emulsions of oil-in-water type on
mixing with water.
Harmful effects of emulsions.
In certain cases the formation of emulsion is harmful also for example,
petroleum forms emulsions with water. Thus, in the petroleum wells, we get
the emulsion sometimes instead of petroleum alone. Likewise, in the areas where
small water becomes unfit for use

Applications of colloids.
(i) Medicines. Most of the medicines used are in the colloidal form because in this
form, they aremore easily assimilated due to large surface area and hence are more
effective. For example,
(a) Argyrol is a silver sol used as an eye lotion.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
(b) Colloidal antimony is used for curing kalazar.
(c) Colloidal gold is used as an intramuscular injection.
(d) Milk of magnesia, which is an emulsion, is used as an antacid for reducing acidity in
the stomach.
(ii) Food articles. A number of food articles that we eat are colloidal in nature, e.g.,
milk, butter, ice creams, fruit juices, halwa, etc.
(iii) Fog, mist and rain. In winters, at night, the moisture of the air condenses on the
surface of dust particles forming fine droplets. These droplets are colloidal in size
and hence continue to float in the air in the form of fog or mist. Clouds are aerosols
consisting of small droplets of water suspended in the air. In the upper
atmosphere where the temperature is low, they condense together to form bigger
drops which come down in the form of rain. Rain is also caused when two
oppositely charged clouds meet each other.
(iv) Artificial rain. Artificial rain can be caused by spraying oppositely charged
colloidal dust or sand particles over a cloud. The colloidal water particles present
in [he cloud will get neutralized and coagulate to form bigger water drops causing
artificial rain.
(v) Formation of Delta. River water contains charged colloidal particles of clay, sand
and manyother materials. Sea water is a very big store-house of a variety of
electrolytes dissolved in it. As soon as river water comes in contact with
sea water, the electrolytes present in sea water coagulate the suspended
colloidal particles which ultimately settle down at the point of contact.
Thus, the level of river bed rises. As a result, water adopts a different
course and delta is formed in due course of time

(vi) Blue colour of the sky. This is due to the scattering of light by colloidal dust
particles presentin air (tyndall effect).
(vii) Smoke screen.
In warfare, smoke screens are used which are nothing but colloidal dispersion of
certain substances in the air.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY

B. Industrial applications of colloids

(i) Smoke precipitation. Smoke particles are actually electrically
charged colloidal particles of carbon in the air. Precipitation of smoke
particles is carried out by Cottrell precipitator which is based on the principle
of electrophoresis. Smoke is allowed to pass through a chamber having a
number of metal plates attached to a metal wire connected to a source
of high potential (as shown in the Fig.) Charged particles of smoke get
attracted by oppositely charged electrode, get precipitated after losing their
charge and the hot air passes out through the chimney. The dust particle are
also removed in this process.

(ii) Tanning / leather industry. The process of hardening of leather is known as

tanning. Tanninwhich is obtained from plants, is a mixture of derivatives of
polyhydroxy benzoic acids. It contains negatively charged colloidal particles.
Animal hides are also colloidal in nature and contain positively charged particles.
When they are soaked in tannin, their mutual coagulation takes place and leather
becomes hard
(iii) Purification of water.
The precipitation of colloidal impurities present in water can be done by adding
certain electrolytes like alum etc. The negatively charged colloidal particles of
impurities get neutralized by the Al3+ ions and settle down and pure water can be
decanted off.

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
(iv) Colloidal industrial products. A number of industrial products which we use in our
everydaylife are colloidal in nature, e.g., inks, paints, lubricants, synthetic plastics,
rubber, cement etc.
Catalysis
Catalyst is a substance which can change the speed of a chemical reaction without
itself undergoing any change in mass and chemical composition at the end of the
reaction, and the phenomenon is known as catalysis e.g. The decomposition
takes place at a high temperature in the range of 553-873K .
2KCIO3 →2KCl + 3 O2
However when a small amount of Manganese dioxide (MnO2) is
added, the decomposition not only becomes faster but takes place at a much higher
temperature.
Positive and negative catalysts
if a catalyst increases the speed of a reaction, it is called positive catalyst and on
other hand , if a catalyst decreases the speed of reaction it is called negative catalyst
and the phenomenon is called negative catalysis. For example, oxidation of SO2 to
SO3 in presence of' NO (lead chamber process) or in presence of V2O5(contact
process) arc examples of positive catalysis.
–– Decomposition of H2O2 in presence of phosphoric acid and oxidation of CHCl3 in
presence of alcohol are example of negative catalysis.
Promoters and Poisons
Certain substances like arsenic, CO, etc if present, lower the activity of the catalyst.
These substances are called catalytic poisons. A substance if, present along with the
catalyst, enhances the activity of the catalyst, is called catalytic promoter, e.g.,
molybdenum acts as a promoter for iron catalyst in the manufacture of NH3 by
Haber’s process
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
is calledhomogeneous catalyst and this type of catalysis is called homogeneous
catalysis
(i) Oxidation of sulphur dioxide to sulphur tri oxide 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.
2CO (g) + O2 (g) NO (g)
 2 CO2 (g)

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY

(ii) Decomposition of Ozone in presence of Cl atom, as catalyst

O3 + O 
Cl
2 O2

(iii) Hydrolysis of Ethyl accetate or sucrose solution in presence of dilute sulphuric acid

CH3COOC2H5 (l) + H2O (l) H(aq )  CH3COOH (l) + C2H5OH (l)

C12H22O11 (aq) + H2O (l) H(aq
)  C6H12O6 (aq) + C6H12O6 (aq)
Sucrose Glucose Fructose

Theory of Homogeneous Catalysis

For example, the Oxidation of SO2 to SO3 in presence of NO takes place as follows
O2 ( g )  2 NO( g )  2 NO2 ( g )
Re ac tant Catalyt Intermediate

SO2 ( g )  NO2 ( g )  SO3 ( g )  NO ( g )

Re ac tant Intermediate Pr oduct Re genrated
catalyst

(2) Heterogeneous Catalysis.

If the catalyst is present in a different phase than that of the reactants, it is called
heterogeneous catalyst and this type of catalysis is called heterogeneous catalysis.
For example
(i) Manufacture of ammonia from N2 and H2 by Haber’s process using iron as catalyst
N2 (g) + 3 H2 (g) Fe 
(s )
 2 NH3 (g)
Here reactants are gaseous whereas catalyst is solid.

(ii) Synthesis of methyl alcohol (CH3OH) from CO and H2 using a mixture of Cu (s),
ZnO and Cr2O3, as catalyst
)
CO (g) + 2 H2 (g) Cu( s  CH3OH
ZnO ( s )  Cr2O3 ( s )

(iii) Manufacture of sulphuric acid by the oxidation of SO2 to SO3 using platinised
asbestos or V2O5 as catalyst
SO2 (g) + O2 (g) Pt
(s )
 2 SO3 (g)
Pt
(iv) 4NH3 + 5O2  4NO + 6H2O
800 C

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
Theory of Heterogeneous catalysis (Adsorption theory)
According to modern adsorption theory there are free
valencies on the surface of solid catalysts
(generally metals)and the mechanism involves
the following five steps:
(i) Diffusion of reactant molecules towards
surface of the catalyst (Fig. a).
(ii) Adsorption of the reactant
molecules on the surface of the
catalyst by forming loose
bonds with the catalyst due to presence
of free valencies (Fig.b).
(iii) Occurrence of a chemical reaction
between the reactants and the
catalyst forming an intermediate,
as shown in Fig.c.
(iv) Desorption of the product molecule
from the surface due to lack of its
affinity for the-catalyst surface
(v) Diffusion of product molecules away from
the surface of the catalyst

Advantages of this theory.

(i) Small quantity of the catalyst is sufficient because
the catalyst is regenerated again and again.

(ii) The catalyst takes part in the reaction but is produced back unchanged in mass and
chemical composition at the end of the reaction.
(iii) Catalytic poisons, if present, are adsorbed on the catalyst surface, thereby hindering
the adsorption of the reactant molecules. Hence, they slow down the activity of the
catalyst.

Some Important Features of Solid Catalysts (or Heterogeneous catalyst)

1. Activity. Activity of catalyst means its capacity to increase the speed of chemical
reaction.
Pt
2 H2 + O2  2 H2O

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
2. Selectivity. Selectivity of catalyst means its ability to direct the reaction to form
particular products excluding other for example
Cu
CO (g) + H2 (g)  HCHO (g)
ZnO  Cr O
CO (g) + 2H2 Cu/    CH3OH (g)
2 3

CO (g) + 3H2 (g)  CH4 (g) + H2O (g)

Ni

Acetylene on reaction with H2 in presence of platinum as catalyst gives of ethane

while in the presence of Lindlar’s catalyst (palladium + BaSO4 poisoned with
quinoline gives ethylene.

3. Speceficity. 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 the
reactions.
Zeolites as Shape – Selective catalyst
Zeolites are aluminosilicates with general formula Mx/n [(AlO2)x (SiO2)y]. zH2O where an is
the charge on metal cation Mn + which is usually Na+, K+ or Ca2+ and z is the number of
water molecules of hydration
––– These are three-dimensional net work silicates in which some silicon atoms are
replaced by aluminium atoms giving Al-O-Si frame work. They are found in nature as well
as synthesised in the laboratory or industry. They form an important class of OXIDE
CATASLYSTS.

––– 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
092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY
pores generally varies between 260 pm AND 740 pm. Thus,only those molecules can be
adsorbed in these pores whose size is small enough to enter these cavities and also
leave easily. Thus, zeolites act as selective adsorbents and hence as 'molecular sieves'. For
example, the zeolite, sodium alumino silicate, can adsorb straight chain hydrocarbons and
not branched chain or aromatic ones.-Consequently, 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. Thus these types of reactions are called'shape-
selective catalvsis.

–– 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)

–– Zeolites are used as Ion exchangers in softening hard water

Enzymes as Catalyst
Enzymes are defined as biochemical catalysts .Chemically all enzymes are globular
proteins with high molecular mass rarnging from 15,000 to 1,000,000 g mol- and form
colloidal solution in water .Every biological reaction requires a different kind of enzyme.

Examples of a few enzyme catalysed reactions are given below

S. No. Reaction Enzyme Source
(i) Inversion of canesugar Invertase Yeast
C12H22O11 (aq) + H2O (l)
Invertase
  C6 H12O6 (aq)  C6 H12O6 (aq)
Glu cose Fructose

(ii) Conversion of glucose into ethyl alcohol Zymase Yeast

C6H12O6 (aq) Zymase
 2 C2H5OH (aq) + 2 CO2 (g)
(iii) Conversion of starch into maltose
2 (C6H10O5)n (aq) + n H2O (l) Diastase
 n C12H 22O11 (aq)
Maltose

(iv) Conversion of maltose into glucose

C12H22O11 (aq) + H2O (l) Maltose
 2 C6H12O6 (aq)

Characteristics of Enzymes
(i) Specificity
Each enzyme catalysis only one chemical reaction for example
NH2CONH2 + H2O Urease
 2NH3 + CO2
CH3NHCONH2 + H2O Urease No reaction
N-Methylurea
092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY

(ii) Efficiency
Enzymes are very effective catalysts. They speed up the rate of reaction by factor of up to
1020
(iii) Only small quantity of enzymes can be highly efficient
(iv) Optimum temperature and pH.
Enzyme catalysed reactions have maximum rate at physiological pH of around 7.4
and human body temperature of 37°C (310 K) under one atm. pressure
(v) Enzyme activators (co-enzymes).
The activity of certain enzymes is increased in the presence of certain substances,
called co-enzymes. If a protein contains a small amount of vitamin as the non-
protein part, its activity is enhanced considerably
(vi) Enzyme inhibitors and poisons.

Activity of Enzyme is slowed down in the presence of certain substances. Such

substances are called inhibitors or poisons.

Mechanism of Enzyme Catalysis

The most accepted mechanism of enzyme catalysed reaction is known as Lock and Key
mechanism. Enzymes are highly specific in their action, due to the presence of some
specific regions, called the active sites, on their surface. These active sites are associated
with somefunctional groups such as – NH2, – COOH, – OH, etc. which form weak bonds
such as H- bonds. The safe of active sites of any given enzyme is like a cavity such that
only a specific substrate can fit into it, the same way as one key can fit into a particular
lock. Once the proper orientation is achieved, substrate molecules react to form the
products in two steps.
Thus, the enzyme - catalysed reactions takes place in two steps as follows

092161-60161 www.khannachemistryclasses2.getit.in
KHANNA CHEMISTRY CLASSES
SURFACE CHEMISTRY

Step – 1. Formation of enzyme substrate complex

E + S ↔ ES
enzyme substrate enzyme substrate complex

Step – 2.Dissociation of enzyme substrate complex to form the products

ES  [EP]  E + P
Enzyme product Enzyme product
association (Regenerated)

Process Reactions with catalyst and other conditions

1. Heber’s process for N2 (g) + 3 H2 Finely
 divided
   2 NH3 (g)
iron ( catalyst)
Molybdenum(Promoter)
the manufacture of 200 bar pressure
723 773 Ktemp.
ammonia
2. Ostwald’s process for 4 NH3 (g) + 5 O2 (g) Platinised
  4 NO (g) + 6 H6O (g)
asbestos ( catalyst)
the manufacture of
2 NO (g) + O2 (g) 573   K
 2 NO2 (g)
nitric acid
4 NO2 (g) + 2 H2O (l) + O2 (g) → 4 HNO3 (l)
3. Contact process for 2 SO2 (g) + O2 (g)    2 SO3 (g)
Platinisedasbestos
or V O ( catalyst)
2 5
the manufacture of
SO3 (g) + H2SO4 (l) 673   H2S2O7 (l) → 2 H2SO4
723 K
sulphuric acid
(aq)

092161-60161 www.khannachemistryclasses2.getit.in