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SURFACE CHEMISTRY

Adsorption
Phenomenon of attracting and retaining molecules of a substance on surface of liquid or
solid resulting in a higher concentration at a surface of solid than in the bulk is called
adsorption. The solid substance on the surface of which, adsorption takes place is called
adsorbent. While the substance which gets adsorbed on the solid surface due to
molecular attractions is called adsorbate.Adsorbent may be solid or liquid but adsorbate
may be a gas or a solute in some solution. It is fast in beginnings but become slow
after some time. It is exothermic e.g. adsorption of water on silica gel.
Adsorption is due to the presence of unbalanced forces, believed to have developed
either during crystallisation of solids or due to presence of unpaired, electrons or free
valencies in solids having dorbital. In liquids it is due to surface tension.
Desorption
It is the reverse of adsorption i.e. removal of adsorbed substance from the surface of
adsorbent. This phenomenon is most common in gases adsorbed on solid.
Absorption
When molecule of a substance are uniformly distributed throughout the body of another
substance at uniform rate is called absorption. e.g. absorption of water by CaCl 2, NH3 in
water.
It is assimilation of molecules into a solid or a liquid substance with the formation of a
solution or a compound.
Sorption
Both adsorption and absorption take place simultaneously.
e.g. dyes get adsorbed as well as absorbed on the cotton fibers.
Difference between adsorption and absorption
Sr. Adsorption Absorption
No.
1 Adsorption is a surface phenomenon. The It is a bulk phenomenon. In
adsorbing substance is called adsorbate and absorption the substance
is only concentrated on the surface of penetrates into the bulk of
adsorbent. the other substance.
2 The rate of adsorption is rapid to start with Absorption occurs at a
and its rate slowly decreases. uniform rate
Heat (Enthalpy) of Adsorption
Adsorption is a surface phenomenon and adsorbate molecules are held to the surface of
adsorbent due to attractive interactions. Since energy is always released during
attractive interactions, adsorption is an exothermic reaction.
The amount of heat evolved when one mole of an adsorbate gets adsorbed on the
surface of an adsorbate is called molar heat (enthalpy) of adsorption.
Adsorption in Terms of Gibbs Helmholtz Equation
Adsorption is an exothermic reaction. Therefore, adsorption is accompanied by release of
energy or H is always negative and favours the process. Also absorbate molecules get
lesser opportunity to move about on the surface of adsorbent. Thus, entropy factor
opposes the process. According to Gibbs Helmholtz equation,
G = H T S

Since adsorption does actually take place, H is greater than T S G is negative. As
the adsorption continues, the difference between the two opposing tendencies becomes
lesser and lesser till they are equal i.e., H = TS or G = 0. At this stage, equilibrium
called adsorption equilibrium gets established and there is no net adsorption taking
place at this stage.
Types of Adsorption
There are two types of adsorption.
a) Physical adsorption (or Vander waals adsorption) or physiosorption.
b) Chemisorption
a) Physical Adsorption:
In this type of adsorption, molecules of adsorbate are being held to the solid
surface by weak attractive forces called Vander Waals adsorption. Adsorption of
gases like hydrogen or oxygen on charcoal is an example of physical adsorption. It
displays the features of physical process such as condensation.
Characteristics of Physical and Chemisorption

Physiosorption Chemisorption
1. Adsorption by weak vanderwaals By chemical force (covalent or ionic bond)
forces.
2. Multimolecular layer may be formed Unimolecular layer will be formed
3. Low heat of adsorption viz. about High heat of adsorption viz. about (200
2040 kJ/mol 400 kJ/mol)
4. Easily reversed Not reversed
5. Molecular state of adsorbate on Molecular state may be different. Surface
adsorbent is same. No surface compounds are found.
compounds are found.
6. Usually occurs rapidly at low It occurs at high temperature initially but
temperature and decreases with then decreases.
increase in temperature.

7. It increases with pressure Change in pressure will have less effect


on chemisorptions
8. Not specific Highly specific
9. Extent of adsorption depends on There is no relative between extent of
ease of adsorption depends on ease adsorption and ease of liquefaction of
of liquefaction i.e. surface area, gas.
critical temperature, inversion e.g. Adsorption of H2 on Pt;
temperature Vanderwaals constant decomposition of NH3 in presence of
a, e.g. Adsorption of gases on tungsten, decomposition of Hl on gold
charcoal (zero order)

The difference between physiosorption and chemisorptions is explained by example of


N2 on Iron.
At 83 K it is physiosorbed on Iron surface as nitrogen molecule. At room temperature
there is no adsorption. AT 773 K and above it is chemisorbed on iron surface in the form
of nitrogen atom.
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 is less at
surface relative to its concentration in the bulk, it is called negative adsorption.
e.g. when a concentrated solution of KCl is shaken with blood charcoal, it shows positive
adsorption but with a dilute solution of KCl, it shows negative adsorption.

Factor Affecting Adsorption of Gases on Solids


Nature of Adsorbent
Greater the surface area of adsorbent, greater is the volume of gas adsorbed thus
silica gel,aluminium oxide and clay are best adsorbents. Transition metals act as good
adsorbents for gases due to vacant or halffilled dorbitals and high charge size ratio.
Activated charcoal is a better absorbent.
Specific Area of Adsorbent
Specific area of an adsorbent is the surface area available for adsorption per gram of
the adsorbent. Highly porous substances like silica gel, charcoal are very good
adsorbents since they have larger surface area. Finely divided substances have large
adsorption power.
Nature of Adsorbate
Easily liquefiable gases (with higher critical temperature) like NH 3, HCl, CO2 etc. are
adsorbed to a much greater extent than permanent gases like N 2, O2, H2 etc. Because
easily liqufiable gases have stronger intermolecular forces.e.g. 1 gm activated charcoal
adsorbs more SO2 (critical temperature 630 K) then CH4 (critical temperatures, 190 K)
Pressure
At constant temperature, if pressure is increased, adsorption increases. The increase in
much greater if temperature is low.Freundlich gave the relationship between extent of
adsorption and pressure.
Temperature
Adsorption is an exothermic process having an equilibrium: According to LeChateliers
principle, the magnitude of adsorption should increase with decrease in temperature.
Gas (Adsorbate) + Solid (Adsorbent) Gas adsorbed + heat
The chemisorptions first increases with temperature then decreases. The initial increase
shows that like chemical reaction, chemisorptions needs activation energy.
Activation of Solid Adsorbent
It means increasing the adsorbing power of an absorbent. This is usually done by
increasing the surface area of the adsorbent which can be achieved in any of the
following ways:
(a) By making the surface of the absorbent rough.
(b) By subdividing the adsorbent into smaller pieces or grains.
(c) By removing the gases already adsorbed
Adsorption Isotherms
The amount of a gas adsorbed by a given amount of the adsorbent depends upon both
temperature and pressure. The variation of adsorption with pressure at a constant
temperature is generally expressed graphically. The curves obtained by plotting the
amount of gas adsorbed (a = x/m) against gas pressure at a constant temperature are
called adsorption isotherms.
Adsorption isotherm is a graph between quantities adsorbed under a constant gas
pressure at different temperatures.
Adsorption isostereis the plot of temperature versus pressure for a given amount of
adsorption.
Freundlich Adsorption Isotherm for Physisorption
Amount of the gas adsorbed per unit mass of adsorbent increase linearly with pressure in
the initial stages and then much more slowly attaining a limiting value as the surface
becomes fully covered by gas molecules. The relationship between the magnitude of
adsorption and pressure can be expressed mathematically by an equation:
x
kp1 / n (n 1)
m

The above relationship is commonly known as Freundlich adsorption isotherm. In this


relation, x/m is the amount of gas adsorbed per gram of the adsorbent at the pressure p,
and k and n are the constants depending upon the nature of the gas and adsorbent.

The quantity 1/n is generally less than one. This indicates that the amount of the gas
adsorbed increases less rapidly than the pressure.
x
P1
m
At the lower values of pressure, the graph is nearly a straight line.
At the equilibrium pressure or the saturation pressure (p s), x/m reaches its maximum
value, i.e., no more adsorption takes place even if the pressure is further increased
x
P0
m
.
1
x
Pn
m

At intermediate pressure
1
x
k Pn
m

By taking logarithm, the above equation becomes


x 1
log log k log P
m n

Thus, if we plot a graph between log (x/m) and log p, a straight


line is obtained thus the Frenudlich isotherm is valid. The slope
of the line is equal to 1/n and ntercept on log (x/m) axis will
correspond to log k.
Freundlich isotherm explains the behaviour of adsorption in an approximate manner. The
factor 1/n can have taken value between 0 and 1 (probable range 0.1 to 0.5). Thus, the
above equation holds good over a limited range of pressure.
1 x
0,
n m
When constant, the adsorption is independent of pressure.
1 x x
1, k P, i.e. P,
n m m
When the adsorption varies directly with pressure.
Both the conditions are supported by experimental results. The experimental isotherms
always seem to approach saturation at high pressure. This cannot be explained by
Freundlich isotherm. Thus, it fails at high pressure.
Adsorption from Solution Phase
Solids can adsorb solutes from solutions also. When a solution of acetic acid in water is
shaken with charcoal, a part of the acid is adsorbed by the charcoal and the
concentration of the acid decreases in the solution.
It has been observed that the extent of adsorption:
i) Decreases with an increase in temperature
ii) Increases with an increase of surface area of the adsorbent.
iii) Depends on the concentration of the solute in solution.
iv) Depends on the nature of the adsorbent and the adsorbate.
Freundlichs equation
The precise mechanism of adsorption from solution is not known.
approximately describes the behaviour of adsorption from solution with a difference that
x
k C1 / n
m
instead of pressure, concentration of the solution is taken into account, i.e.,
Application of Adsorption
1. In gas mask:
Finally divided coconut charcoal is used as gas masks for absorbing toxic gases like
CH4, CO, COCl2. It is usually used for breathing in coal mines to adsorb poisonous
gases.
2. In preserving Vacuum:
In Dewar flasks, activated charcoal is placed between the walls of the flask so that
any gas which enters into annular space either due to glass imperfection of
diffusion through glass is adsorbed.
3. Colloidal silica to purify petroleum oil, motor spirit waxes.
4. Fe(OH)3antidot adsorbent in Arsenic poisoning.
5. In clarification of sugar: Sugar decolorized by treating sugar solution with
charcoal powder. The latter adsorbs the undesirable colours present.
6. Heterogeneous catalysis: Adsorption of reactants on the solid surface of the
catalysts increases the rate of reaction. There are many gaseous reactions of
industrial importance involving solid catalysts. Manufacture of ammonia using iron
as a catalyst, manufacture of H 2SO4 by contact process and use of finely divided
nickel in the hydrogenation of oils are excellent examples of heterogeneous
catalysis.
7. In Chromatography: The different chromatographic techniques such as
adsorption, paper or column chromatography which are used for the purification
and the separation of the substances available in small amounts, are based upon
the theory of selective adsorption.

Catalysis
Catalyst is a substance which changes the speed of a reaction, and usually, can be
recovered completely unchanged at the end of a reaction. However it may take part in a
reaction consumed in one step and regenerated in another. This phenomenon is known
as Catalysis.
Example: Potassium chlorate, when heated strongly decomposes slowly giving
dioxygen. The decomposition occurs in the temperature range of 653873 K.
2KClO3 2KCl + 3O2
However, when a little of manganese dioxide is added, the decomposition takes place at
a considerably lower temperature range, i.e., 473633 K and also at also at a much
accelerated rate. The added manganese dioxide remains unchanged with respect to its
mass and composition.
A substance is termed a positive catalyst or simply as catalyst if it accelerates the rate of
chemical reaction. On the other hand, the added substance is termed as negative
catalyst if it retards the rate of a chemical reaction.
Example of Positive Catalysts:
(1) Lead chamber process of H2SO4 using catalyst No.
NO
e.g. 2SO2(g) + O2(g) 2SO3(g)
Mechanism
O2(g) + 2NO(g) 2NO2(g)
SO2 + NO2(g) SO3(g) + NO(g)
MnO
2
(2) 2KClO3 2KCl + 3O2
NO

(3) 2CO + O2 2CO2
Pt( s )

(4) H2O2 2H2O + O2
(5) Hydrolysis of ester in acidic medium.
Activity of a catalyst refers to the ability of a catalyst to accelerate chemical reaction.
e.g. Pt acts as a catalyst in the reaction.
platinum

H2(g) + 1/2O2(g) H2O(l)
Contact process of H2SO4, Where V2O5(s) is used to convert SO2 to SO3.
Example of Negative Catalysts:
i) H2SO4 or acetanilide in the decomposition of H 2O2.
ii) Alcohol in the oxidation of chloroform leading to the formation of phosgene.
iii) Tertraethyllead or nickel carbonyl acting as antiknock material in internal
combustion engines.
iv) Antifreezes like glycerol which retard the rusting of the machines.
Activation Energy in Catalysed Reaction
A catalyst generally increases the rate of reaction. Its
behaviour can be explained on the basis of activation
energy. According to this concept, a catalyst taking
part in a reaction is in a position to lower the height of
the energy barrier for the reaction. In fact, the
reaction is supposed to follow an alternate path in the
presence of catalyst. As a result, the amount of
activation energy for the catalysed reaction decreases
and the height of the energy barrier gets lowered.
This results in increasing the reaction rate or reaction
velocity. In a reversible reaction, a catalyst lowers the
height of the barrier for both the forward and the
backward reactions to the same extent. Therefore,
equilibrium point is not distributed, though the
equilibrium is reached earlier.
Catalytic Promoters
There are certain substances which when added only in small quantity to a catalyst
enhance its activity. This substance itself may not be catalyst. Such substances which
enhance the activity of a catalyst are called catalytic promoters. E.g. Molybdenum is
used as Promoter for Fe catalyst in Habers process.
Catalytic Inhibitors
The rates of some reactions are reduced considerably by the presence of small amounts
of other substances called inhibitors. For example, the oxidation of sodium sulphide
by oxygen gas is inhibited by small amounts of alcohol, aniline and benzaldehyde. Thus,
inhibitor is a substance which when added during the preparation of a catalyst in small
amounts, reduces the catalytic activity to a considerable extent.
The substance whose presence decreases or destroy the activity of a catalyst are called
poison. CO or H2S in hydrogen gas acts as a poison for Fe catalyst in Haber process.
As2O3 acts as a poison for Ptasbestos in contact process for H2SO4.
Theories of Catalysis
Intermediate Compound Formation Theory
This theory explains homogeneous catalysis mainly.
According to this theory, the catalyst combines with one of the reactants to give an
intermediate compound. This compound intermediately reacts with the other reactants
and given the product and regenerates the catalyst in its original form.
Thus the reactants do not directly combine with each other, instead they react through
the catalyst which provides an alternative pathway which involves lesser energy of
activation.
For example, the function of nitric oxide [NO] as a catalyst in the formation of SO 3 is
explained as follows:
2NO + O2 2NO2
Catalyst Reactant Intermediate

NO2 + SO2 SO3 + NO


Intermediate Reactant Product Catalyst
regenerated

Adsorption Theory:
This theory explains the heterogeneous catalysis. The role of a solid catalyst in
enhancing the reaction rate is explained on the basis of this theory in the following steps:
(i) The reactant molecules are adsorbed on the surface of the catalyst at adjacent
point. Adsorption leads to higher concentration of the adsorbed reactant on the
surface of a catalyst.
(ii) As adsorption is an exothermic process, the heat of adsorption provides the
necessary activation energy for the chemical reaction to proceed and enhance rate
of greater.
(iii) The product molecules rapidly leave the catalyst surface to make room for the
other reactant molecules to get adsorbed. Thus the chemical combination between
reactant molecules occurs at the surface of the catalyst at a must faster rate.
e.g. Hydrogenation of ethane in presence of Ni
H H + 2M 2M H
C2H4 + 2M H C2H6 + 2M

Modern Adsorption Theory of Heterogeneous Catalysis


The modern adsorption theory is the combination of intermediate compound formation
theory and the old adsorption theory. The catalytic activity is localized on the surface of
the catalyst. The mechanism involves five steps:
Adsorption of
O O O reacting molecules O O O A
+A+B
O O O Reacting molecuels O O O B

Catalyst surface
having free valencies

Desorption of product O O O A
O O O molecules |
+A-B
O O O B
Product
O O O

Intermedaite
Catalyst

Adsorption of reacting molecules, formation of intermediate and desorption of products

i) Diffusion of reactants to the surface of the catalyst.


ii) Adsorption of reactant molecules on the surface of the catalyst.
iii) Occurrence of chemical reaction on the catalysts surface through formation of an
intermediate.
iv) Desorption of reaction products from the catalyst surface, and thereby, making the
surface available again for more reaction to occur.
v) Diffusion of reaction products away from the catalysts surface. The surface of the
catalyst unlike the inner part of the bulk, has free valencies which provide the basis
for chemical forces of attraction. When a gas comes in contact with such a surface,
its molecules are held up there due to loose chemical combination. If different
molecules are adsorbed side by side, they may react with each other resulting in
the formation of new molecules. Thus, formed molecules may evaporate leaving
the surface for the fresh reactant molecules.
This theory explain why the catalyst remains unchanged in mass and chemical
composition at the end of the reaction and is effective even in small quantities. It
however, does not explain the action of catalytic promoters and catalytic poisons.
General Characteristics of Catalytic Reactions
1. The catalyst is unchanged chemically at the end of the reaction:
The amount of catalyst remains chemically unaffected at the end of a reaction,
though there may be change in physical state such as the particle size or change in
the colour of the catalyst.
2. Only a small quantity of the catalysts in generally needed:
Since the catalyst is not used up, a very small amount of catalyst is required. For
example, hydrogen peroxide can be decomposed by presence of colloidal platinum
at a concentration of 108moldm3 or by a very small quantity of enzyme catalyst.
3. The catalyst does not alter the position of equilibrium in a reversible
reaction
Presence of a small amount of a catalyst does not affect the position of equilibrium.
4. The catalyst does not initiate the reaction
A catalyst simply accelerates or retards a reaction. It does not initiate a reaction.
However, this is not true in all the reactions. Many reactions are known to occur
only in the presence oif a catalyst.
5. The catalyst is generally specific in its action
A catalyst can catalyse only a specific reaction and cannot be used for every
reaction. for example, manganese dioxide can catalyse the decomposition of
potassium chlorate but not that of potassium nitrate or potassium per chlorate.
However, transition metals can catalyse reactions of different types.
6. The catalyst cannot alter the nature of the products of the reaction
Potassium chlorate on decomposition, in presence as well as in absence of
manganese dioxide, gives oxygen.
7. Optimum temperatures
A catalyst has an optimum temperature at which the efficiency of the catalyst is
maximum.
8. A catalyst is poisoned by certain substances
Presence of traces of certain substances such as arsenious oxide, carbon monoxide,
hydrogen cyanide, etc. retards or inhibits the rate of a catalysed reaction to a large
extent. Such substances which retard the activity of catalysts are known as
catalystic poisons.
9. The activity of a catalyst is enhanced by the presence of substances
called promoters:

Types of Catalysis
Broadly, two types of catalysis are known:
(a) Homogeneous catalysis (b) Heterogeneous catalysis
(a) 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) Catalytic decomposition of ozone by chlorine atoms in the gas phase.
O3 O Cl 2O 2

2CO(g) O 2 (g) NO
2CO2 (g)

C12H 22O11 (aq) H 2O(l) H 2SO


4 C6 H12O 6 (aq) C6 H12O6 (aq)
Sucrose Glu cos e Fructose

Lead chamber process of H 2SO4 using catalyst NO (all reactant and products are
gases)
ii) Oxidation of sulphur dioxide into sulphur trioxide with dioxygen in the presence of
oxides of nitrogen as the catalyst in the lead chamber process.
2SO 2 (g) O 2 (g) NO
( g ) 2SO 3 (g)

iii) Hydrolysis of methyl acetate is catalysed by H+ ions furnished by hydrochloric acid.


CH3COOCH3 () H 2O() HCl
() CH3COOH (aq) CH3OH(aq)

b) Heterogeneous catalysis:
In this type of catalysis the catalyst is present in a difference phase than that of the
reactants. In heterogeneous catalysis, catalyst is generally a solid and the reactants
are generally gases but sometimes liquid reactants are also used. It is also known
as surface catalysis. Many reactions that occur on a metal surface such as the
decomposition of Hl on gold and the decomposition of N 2O on platinum, are zero
order because the rate determining step occurs on the surface itself.
Thus, despite an enormous surface area, once the reactant gas covers the surface,
increasing the reactant concentration cannot increase the rate.
The petroleum, plastics and food industries frequently use catalytic hydrogenation.
The catalyzed reaction is believed to take place through the following consecutive
steps.
i) Chemical adsorption of reactants (C2H4, H2) onto the surface of metals.
ii) H2 splits into H atoms which get chemically bound to the solid catalyst i.e. metal
atom
(M) HH(g) + 2M(s) 2M H
iii) The H atoms migrate over the surface of the metal and eventually collide with an
adsorbed C2H4 molecule and the reaction takes place.
C2H4(g) + 2M H C2H6(g) + 2M(s)
iv) Synthesis of methyl alcohol (CH3OH) from CO and H2 using a mixture of copper, ZnO
and Cr2O3 as catalyst.
Cu Cr 2 O 3
, ZnO
CO(g) + 2H2(g) CH3OH(l)
v) Manufacture of ammonia from N2 and H2 by Habers process using iron as catalyst.
Fe
N2(g) + 3H2(g) 2NH3(g)
Important feature of solid catalysts
(a) Activity
It is ability of a catalyst to catalyse a process. The activity of a catalyst depends
upon the strength of chemisorption to a large extent. The reactants must get
adsorbed reasonably strongly on to the catalyst to become active. However, they
must not get adsorbed so strongly that they are immobilized and other reactants
are left with no space on the catalysts surface for adsorption. It has been found
that for hydrogenation reaction, the catalytic activity increases from Group 5 to
Group 11 metals with maximum activity being shown by group 79 elements of the
periodic table.
2H 2 (g) O 2 (g) Pt 2H 2O()

(b) Selectivity
The selectivity of a catalyst is its ability to direct a reaction to yield a particular
product. For example, starting with H 2 and CO using different catalysts we get
different products.
Ni
i) CO(g) + 2H2(g) CH4(g) + H2O(g)
Cu / ZnO Cr2 O 3

ii) CO(g) + 2H2(g) CH3OH(g)
Cu

iii) CO(g) + H2(g) HCHO (g)
Hydrogenation of alkyne with Ni + H 2 or Lindlar catalyst give different product.
Action of a catalyst is highly specific (selective) in nature i.e., a given substance can
act as a catalyst only a in a particular reaction and not for all the reactions. It
means a substance which acts as a catalyst in one reaction may fail to catalyse
other reaction i.e., a catalyst is highly selective in nature.

Shape Selective Catalysis by Zeolites


The catalytic reaction that depends upon the pore structure of the catalyst and the
size of the reactant and product molecules is called shape selective catalysis. The size
of the 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. It will not adsorb those molecule which are too big to enter. Thus they
act as molecular sieves e.g.: Sodium aluminium silicate can adsorb straight chain
hydrocarbons and not branched chain or aromatic ones.
The reactions taking place in zeolites depend upon the size and shape of reactant and
product molecules as well as upon the pores and cavities of the zeolites. That is why
these types of reactions are called shape selective catalysis reaction. Zeolites are
being very widely used as catalysts in petrochemical industries for cracking of
hydrocarbons and isomerisation.
Enzymes are complex nitrogenous compounds which are produced by living plants &
animals.
Selectivity of a catalyst refers to the ability of a catalyst to direct reaction to yield a
particular product (excluding others), e.g. nheptanes selectively gives toluene in
presence of platinum as catalyst.
The catalysis that depends upon the porestructure of the catalyst and molecular sizes of
reactants and product molecules is called shape selective catalysis. e.g. zeolites are
shape selective catalysts due to their honeycomb structure. ZSM5 is used for
converting methanol to gasoline.
Zeolites are microporous aluminosilicates of the general formula M x/n [(AlO2)x (SiO2)y].
zH2O. where n is the charge on the metal cation M n+ which is usually Na+, K+ or Ca2+ and z
is the number of water molecules of hydration which are highly variable. They are three
dimensional network silicates in which some silicon atoms are replaced by Al giving Al
O Si frame work. They exist in nature as well as synthesized in laboratory. They form an
important class of oxide catalyst. Zeolites to be used as a catalyst are heated in vacuum
so that the water of hydration is lost and they become porous.
Enzymes
All biological reactions are catalysed by special catalysts called enzymes. Thus, enzymes
are defined as biological catalysts. Chemically, all enzymes are globular proteins with
high molar mass ranging from 15,000 to 1,000,000g mol 1 and form colloidal solution in
water. However, some enzymes are also associated with some nonprotein component
called the prosthetic group. The prosthetic groups which get attached covalently with
enzyme molecule are known as cofactor& the prosthetic group which get attached at
the time of reaction are coenzymes.
Enzymes are vital for biological processes. Without them, the life process would be very
slow and sluggish. For example, if there were no enzymes in our digestive system, it
would take us 50 years to digest a single meal. Many enzymes can be obtained in pure
crystalline state from living cells.
Properties of Enzymes: Some important properties of enzymes are:
(i) Specificity
Each enzyme catalyses only one chemical reaction. For example, the enzyme
urease hydrolyses urea to NH 3 and CO2 but it does not catalyse the hydrolysis of N
methylurea which is similar in constitution to urea.
(ii) Efficiency
Enzymes are very efficient catalysts. They speed up rate of a reaction by factors of
upto 1020.
(iii) Small quantity
Only small amounts of enzymes can be highly efficient.
(iv) Optimum temperature and pH
Enzyme catalysed reactions is maximum at particular pH called optimum pH, which
is between 57 and temperature of 298310K under one atmospheric pressure.
Under the these conditions, most of the chemical reactions do not occur at
appreciable rates if ordinary laboratory catalysts are used. Human body
temperature being 310 K is suited for enzyme catalysed reactions.
(v) Enzyme activators (Coenzymes)
The activity of certain enzymes is increased in the presence of certain substances
called coenzymes. e.g. if a protein contains a small amount of vitamin as the non
protein part, its activity is enhanced. The activators are generally metal ions like
Na+, Cu+2, Mn+2. Co+2.Amylase in presence of sodium ions are catalytically very
active.
(vi) Influence of Inhibitors and poisons:
Like ordinary catalysts, enzymes are also inhibited or poisoned by the presence of
certain substances. The inhibitors or poisons interact with active functional groups
on the enzyme surface and often reduce or completely destroy the catalytic activity
of the enzymes. The use of many drugs is related to their action as enzyme
inhibitors in the body.
The action of enzymes is controlled by a number of mechanisms and are inhibited
by certain organic molecules called inhibitors.

Mechanism of Enzyme Catalysis


There are a number of cavities present on the surface of colloidal particles of enzymes.
These cavities are of characteristics shape and posses active groups such as NH 2,
COOH, SH-, OH, etc. These are actually the active centres on the surface of enzyme
particles. The molecules of the reactant (substrate), which have complementary shape,
fit into these cavities just like a key fits into a lock. On account of the presence of active
groups, an activated complex is formed which then decomposes to yield the products.
Thus, the enzymecatalysed reactions may be considered to proceed in two steps.
Step 1: Binding of enzyme to substrate to form an activated complex.
E + S ES*
Step 2: Decomposition of the activated complex to form product.
ES* E + P

Mechanism of enzyme catalysed reaction


Colloidal State
The study for this state of matter was initiated by Thomas Graham in 1861.
Substances whose solutions could pass through filter paper and animal membrane,
higher rate of diffusion are called crystalloids.
Substances whose solutions are heterogeneous but looks homogenous can pass
through filter paper but not animal membrane, also, having slower rate of diffusion
are called colloids.
The term colloid does not apply to a particular class of substance but is a
state of matter like solid, liquid and gas. Any substance can be brought
into colloidal state by suitable means.
Mixtures of substances in water, which can neither pass through filter paper nor
animal membrane are called suspensions.
If the solute particles in solutions are in the size range of 1 to 10, the such
particles in solution are called cyrstalloidal particles and the solutions of
crystalloidal particles are called true solutions. These are clear solutions. These
solutions are homogeneous solutions. It is not possible to separate them by
filteration using filter paper or semipermiable membrane.
If the solute particles in solution are of the size in the range of 10 to 1000,
they are called colloidal particles and their solutions are called colloidal solutions.
In suspensions the solute particles are bigger than 1000. Such particles are
visible with naked eyes and due to their greater volume and greater mass have
tendency to settle down under gravity or on long standing.
A colloid is a heterogenous system in which one substance is dispersed (dispersed
phase) as very fine particles in another substance called dispersion medium.
Comparison of Suspensions Colloids and True Solutions
S.N Property True Solution Colloids Suspension
o.
(i) Particle size < 10 10 to 103 > 103
(ii) Visibility Not visible with any Visible with Visible with
of the optical means ultramicroscope naked eye
(iii) Separation
(a) with filter Not possible Not possible Possible
paper Not possible Possible Possible
(b) with
membranes
(iv) Diffusion Diffuses rapidly Diffuses very Does not diffuse
slowly does not
settle
(v) Settling Does not settle but it may settle Settles under
under gravity
Centrifuge
(vi) Nature Hemogeneous heterogeneous Heterogeneous
(vii) Appearance Clear Generally clear Opaque

Colloids and their Classification


A colloidal system is made of two phases. The substance distributed as the colloidal
particles is called Dispersed phase (the internal phase) or the discontinuous phase. The
second continuous phase in which the colloidal particles are dispersed is called
dispersion medium. For example, for a colloidal solution of copper in water, copper
particle constitute the dispersed phase and water the dispersion medium.
They are larger molecules with a diameter range between 1 1000 nm (10 9 to 106 m),
but are small enough to remain suspended.
Colloidal particles have enormous surface area per unit mass as a result of their small
size. Consider a cube with 1 cm side with an surface area 6 cm 2. If the were divided into
1012 cubes, the cubes would be the size of large colloidal particles and have a total
surface area of 60,000 cm2 or 6 m2. This enormous surface area leads to some special
properties of colloids.
Classification of Colloids
Colloids are classified on the basis of the following criteria:
(i) Physical state of dispersed phase and dispersion medium
(ii) Nature of interaction between dispersed phase and dispersion medium.
(iii) Type of particle of the dispersed phase.
(i) Classification Based on Physical State of Dispersed Phase and Dispersion
Medium
Depending on the physical states of dispersed phase or dispersion medium,
colloidal solutions are of eight types:
Disperse Dispersion (appearanc Name (e.g.) alloys
d phase Medium e)
Solid Solid (solid) Solid Sol Coloured glasses, Pearl,
Ruby, alloys, gems
Solid Liquid (liquid) Sol Ag, Sol, Au, Sol., S. Sol.,
Muddy water, gelatin in
water, paint
Solid Gas (gas) Aerosol Smoke, dust, strom
Liquid Liquid (liquid) Emulsion Milk, medicines, oil water,
blood
Liquid Solid (solid) Gel shampoo, jelly, cheese,
butter, all fruits and veg,
polish, curd
Liquid Gas (gas) Aerosol of Cloud, fog, mist, spray
liquid
Gas Liquid (liquid) Foam Soap leather, whipped
cream, shaving cream, soda
water, froath
Gas Solid (solid) Solid foam Styrene foam, Foam rubber
A colloidal dispersion of one gas in another is not possible since the two gases would
give a homogenous molecular structure.
Many familiar commercial products and natural objects are colloids. For example,
whipped cream is a foam, which is a gas dispersed in a liquid. Firefighting foams, used at
emergency aeroplane landings are also colloidal systems. Most biological fluids are
aqueous sols (solids dispersed in water). Within a typical cell, proteins and nucleic acids
are colloidalsized particles dispersed in an aqueous solution of ions and small molecules.
Out of the various types of colloidal given in table the most common are sols (solids in
liquids), gels (liquids in solids) and emulsions (liquids in liquids). If the dispersion
medium is water, the sol is called aquasol or hydrosol and if the dispersion medium is
alcohol, it is called alcosoland so on.
(ii) Classification Based on Nature of Interaction between Dispersed Phase
and Dispersion Medium
Depending upon the nature of interaction between the dispersed phase and the
dispersion medium, colloidal sols are divided into two categories, namely, lyophilic
(solvent attracting) and lyophobic (solvent repelling). If water is the dispersion
medium, the terms used are hydrophilic and hydrophobic.
(a) Lyophilic Sols
Colloidal solutions in which the dispersed phase has considerable affinity for the
dispersion medium, are called lyophilic sols (solventlinking). For example
dispersion of gelatin starch, gum and proteins in water. Such colloidal solutions can
be easily prepared in water and in general and called emulsoids. These solutions
are stable known as reversible colloids since the residue left on evaporating can be
readily transferred back into colloidal state by adding water. These sols are quite
stable and cannot be easily coagulated.
(b) Lyophobic Sols
Colloidal solution in which the dispersed phase has no affinity or attraction for the
dispersion medium are called Lyophobic colloid (solvent hating) solutions. Colloidal
solutions of metals which have negligible affinity for solvents are examples of this
type. Lyophobic colloidal solutions are less stable. On evaporation of solvent the
residue cannot be easily transferred back into colloidal state by ordinary mean.
Therefore, lyophobic colloids are also called irreversible colloids. Lyophobic sols
need stabilizing agents for their preservation. Such sols are readily precipitated on
addition of small amount of electrolytes by heating or by shaking.

Comparison of Lyophobic and Lyophilic sols

SN Property Lyophobic sol Lyophilic sol (Emulsoid)


(Suspensoid)
1 Preparation Cannot be prepared easily, Can be easily prepared by
special methods are required shaking or warming the
substance with solvent
2 Stability are less stable are more stable
3 Reversibility are irreversible are reversible
4 Viscosity Viscosity is nearly same as Viscosity is much higher
that of the solvent than that of the solvent
5 Surface tension Surface tension is almost Surface tension is usually
same as that of solvent low
6 Hydration or These are less solvated as These are highly solvated
solvation the particles have less as the particles have great
affinity for the solvent affinity for solvent
7 Charge The particles carry a The particles have little
characteristic charge either charge or no charge at all
positive or negative
8 Visibility Particles can be seen under Particles cannot be seen
microscope under microscope
9 Coagulation or Precipitated by low Precipitated by high
precipitation concentration of electrolytes concentration of
electrolytes
10 Tyndall effect Tyndall effect is well marked As particles are much
due to appreciable difference solvated so difference
between refractive index of between the refractive
dispersion phase and index of 2 phases is very
medium. less. So tyndall effect is not
well marked.
11 Migration on Migrate towards anode or May or may not migrate.
applying cathode as these carry
electric field charge.
12 General example Mostly inorganic nature. Mostly organic nature

(iii) Classification Based on Type of Particles of the Dispersed Phase


Depending upon the type of the particles of the dispersed phase, colloids are
classified as:

(a) Multimolecular Colloids:


On dissolution, a large number of atoms or smaller molecules of a substance
aggregate together to form species having size in the colloidal range (diameter < 1
nm). The species thus formed are called multimolecularcolloids. For example, a
gold sol may contain particles of various sizes having many atoms. Sulphur sol
consists of particles containing a thousand or more of S 8sulphur molecules.
(b) Macromolecular Colloids
These are formed by macromolecules which have bigger size than the colloidal
particle but as soon as they are put in suitable solvents, they get dissociated to
form smaller particle of the colloidal range. Such systems are called
macromolecular colloids. These colloids are quite stable and resemble true
solutions in many respects. Examples of naturally occurring macromolecules are
starch, cellulose, proteins and enzymes; and those of manmade macromolecules
are polythene, nylon, polystyrene, synthetic rubber, etc.

(c) Associated Colloids (Micelles)


There are some substances which at low concentrations behave as normal strong
electrolytes, but at higher concentrations exhibit colloidal behaviour due to the
formation of aggregates. The aggregated particles thus formed are called micelles.
These are also known as associated colloids. The formation of micelles takes
place only above a particular temperature called krafttemperature (Tk) and
above a particular concentration called critical micelle concentration (CMC).
Conductance of solution decreases at CMC. Shape of micelles changes with change
in concentration. e.g. at high concentration rod shaped micelles are formed while
spherical micelles are formed near CMC. On dilution, these colloids revert back to
individual ions. The importance of micelles and their use is based on the fact that
their hydrophobic interior can dissolve fat or oil etc. while the water soluble part,
makes a hydrophilic surface around this interior, rendering the entire micelle water
soluble. Surface active agents such as soaps and synthetic detergents belong to
this class. For soaps, the CMC is 10 4 to 103mol L1. These colloids have both
lyophobic and lyophilic parts. Micelles may contain as many as 100 molecules or
more.
Mechanism of Micelle Formation
Let us take an example of soap solutions. Soap is sodium or potassium salt of a higher
fatty acid and may be represented as RCOO Na + (e.g., sodium stearate CH3(CH2)16COO
Na+, which is a major component of many bar soaps). When dissolved in water, it
dissociates into RCOO and Na+ ions. The RCOO ions, however, consist of two parts a
long hydrocarbon chain R (also called non polar tail) which is hydrophobic (water
repelling), and a polar group COO (also called polarionic head), which is hydrophilic
(water loving).

Hydrophobic tail and hydrophilic head of stearate ion

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. But at
critical micelle concentration, the anions are pulled into the bulk of the solution and
aggregate to form a spherical shape with their hydrocarbon chains pointing towards the
centre of the sphere with COO part remaining outward on the surface of the sphere. An
aggregate thus formed is known as ionic micelle. These micelles may contains as
many as 100 such ions.

SO 3 Na ,
Similarly, in case of detergents. e.g., sodium laurylsulphate, CH 3(CH2)11 O the

OSO3
polar group is along with the long hydrocarbon chain. Hence, the mechanism of
micelle formation here also is same as that of soaps.
Note: The soaps and detergents form micelles in water only because of the presence of
charge on their molecules. Micelles formation does not occur in solvent like ethyl alcohol
since it is not as polar as soaps. That is why only water is used for the washing of dirty
clothes.

Method of Preparation of Colloidal Solution


Lyophilic sols may be prepared by simply warming the solid with liquid dispersion
medium e.g., starch with water. On the other hand lyophobic sols have to be prepared by
special methods. These methods fall into two categories:

(a) Dispersion methods in which large macrosized particles are broken down to
colloidal size.

(b) Condensation methods in which colloidal sized particles are built up by


aggregating single ions or molecules. This method is also known as condensation
method.

Sr. Dispersion method Aggregation or condensation


No. method
1 Mechanical dispersion 1. Exchange of solvents
2 Electrodispersion 2. Change of physical state
3 Ultrasonic dispersion 3. Chemical method
4 Peptization (a) Double decomposition
(b) Oxidation
(c) Reduction
(d) Hydrolysis

(a) Dispersion Method


1. Mechanical dispersion (e.g. black ink, paint, varnish) dye
Solid material is first finely grounded by usual
methods. It is then mixed with dispersion medium
which gives a coarse suspension. The suspension is
now introduced into the colloid mill. The simplest
form of colloid mill consist of two metal discs held at
a small distance apart from one another and capable
of revolving at a very high speed (about 7000
revolutions per minute) in opposite directions. The
particles are grounded down to colloidal size and are Colloidal mill
then dispersed in liquid. A stabilizer is often added to
stabilize colloidal solution.

Colloidal graphite (a lubricant) and printing ink are made by this method. Tannin is used
as a stabilizer in the preparation of colloidal graphite and gum Arabic in lampblack
colloidal solution (Indian ink)

2. Electrical Dispersion (Bredigs arc Method) (e.g. metal sol.)


This method is suitable for the preparation of
colloidal solutions of metals like gold, silver,
platinum, etc. An arc is struck between the metal
electrodes under the surface of water containing
some stabilizing agent such as a trace of KOH. The
water is cooled by immersing the container in a ice
bath. The intense heat of the arc vaporizes some of
the metal which condenses under cold water.

Note:
(i) This method is not suitable when the dispersion medium is an organic liquid as
considerable charring occurs.
(ii) This method comprises both dispersion and condensation.
3. Peptization
The dispersion of a freshly precipitated material into
colloidal solution by the action of an electrolyte in
solution is termed peptization,the electrolyte used
is called a peptizing agent. During Peptization, the
precipitate adsorbs one of the ions of the electrolyte
on its surface. This causes the development of
positive or negative charge on precipitates, which
ultimately break up into smaller particles of the size
of a colloid.
Few examples of sols obtained by peptization are:
(i) Freshly prepared ferric hydroxide on treatment with a small amount of ferric
chloride solution at once forms, a dark raddish brown solution. Ferric
chloride acts as a peptizing agent.
(ii) Freshly precipitated silver chloride can be converted into a colloidal solution
by adding a small amount of hydrochloric acid or AgNO 3
(iii) Cadmium sulphide can be peptized with the help of hydrogen sulphide. H 2S
is used as peptizing agent for most of the sulphide sol.

4 Hydrolysis
Colloidal solutions of some salts can be prepared by hydrolysis. A colloidal solution
of ferric hydroxide is obtained by boiling a dilute solution of ferric chloride.
FeCl3 + 3 H2O Fe(OH)3 + 3HCl
red sol.
The colloidal solutions of silicic acid is also obtained by hydrolysis of dilute solution
of sodium silicate with 4N hydrochloric acid which is added drop by drop with
constant stirring.
Purification of Colloidal Solutions
Colloidal solutions prepared by above methods generally contain excessive amount of
electrolytes and some other impurities. The purification of colloidal solution is carried out
by the following methods:
Dialysis:
Animal membranes (bladder) or those made of
parchment paper and cellophane sheet have very
fine pores. These process permit ions or very
small molecules to pass through but not large
colloidal particles. Dialysis is a process of
removing a dissolved substance (impurities) from
a colloidal solution by means of diffusions through
semipermiable which is a bag of suitable
membrane containing colloidal solution to be
purified, placed in a vessel (or continuous flow of
water). The ions or molecules of impurities diffuse
through membrane and get dissolved in outer
water and pure colloidal solution is left in the bag.
Blood is a colloidal solution and is purified by
dialysis.
The process of dialysis is a slow process. It can be
made faster by applying an electric field. Two
electrodes are placed in water outside the
membrane bag containing the colloidal solution.
When potential difference is applied across the
membrane, ions in the solution move faster
towards opposite electrode. This process is called
electrodialysis. The colloidal solution is placed in
a bag of suitable membrane while pure water is
taken outside. Electrodes are fitted in the
compartment as shown in figure. The ions present
in the colloidal solution migrate out towards the
oppositely charged electrodes.
Ultrafiltration: Ultrafiltration is the process of separating colloidal particles from
the solvent and soluble solute in the colloidal solution by especially prepared
filters, which are permeable to all substances except colloidal particles. Such filter
are called ultrafilters. e.g. a cellophane membrane. Colloidal particles can pass
through ordinary filter paper because the pores are too large. However, the pores
of filter paper can be reduced in size by impregnating with colloidion solution to
stop the flow of colloidal particles. The usual colloidion is a 4 % solution of
nitrocellulose in a mixture of alcohol and ether. An ultrafilter paper may be
prepared by soaking the filter paper in a colloidal solution, hardening by
formaldehyde and then finally drying it.
Ultrafiltration is a slow process. To speed up the process, pressure or suction is
used. The colloidal particles are left on the ultrafilter in the form of slime. This
slime may be stirred into fresh medium to get a pure sol.
Ultracentrifugation: 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 colloid particles are remixed with the dispersion
medium to give the pure colloidal sol.
Properties of Colloidal Solution
Heterogeneous:
Colloidal particles in a solution differ in sizes and are not homogeneously
distributed throughout the solution.
Visibility:
Colloidal particles cannot be seen with naked eyes or with the help of microscope.
It is a well known fact. No particle is visible if its diameter is less than half the
wavelength of light used. The visible light has greater wavelength than the size of
colloidal particle.
Colour:
The colour of hydrophobic sol depends on the wavelength of the light scattered by
the dispersed particles. The wavelength of the scattered light again depends on
the size and the nature of particles. The colour of colloidal solution also changes
with the manner in which the observer receives the light.
For example, a mixture of milk and water appears blue when viewed by reflected
light and red when viewed by the transmitted light. Finest gold sol is red in colour,
as the size of particles increases, it appears purple, then blue and finally golden.
When light emitted by the setting sun passes through the blanket of dust, the blue
part of the light is scattered away from out eyes and at the same time the red
colour is seen. This sun appears red while setting.

Colour of Ag Particle
Sol diameter
Orange Yellow 6 105 mm
Orange Red 9 105 mm
Purple 13 105 mm
Violet 15 105 mm
Colligative Properties
These properties depend on the number of solute particles in solution. In case of
colloidal solutions, colloidal particles are the aggregates of many ions or smaller
molecules and when compared to true solutions or normal solutions, the total
number of particles of solute in solution are very less and hence these solutions
exhibit colligative properties to lesser extent.
Optical Properties: Tyndalll effect
Sols exhibit Tyndall effect. When a beam of light is passed through a sol and viewed
at right angles.

The path of the light shows up a hazy beam of cone. This was first observed by Farraday
and later by Tyndall and is known as Tyndall effect. It may be defined as the scattering
of light by the colloidal particles in a colloidal sol. The bright cone of the light is called
Tyndall cone. The Tyndall effect is due to the fact that the colloidal particles absorb
light and scatter it in all colloidal dispersion. The phenomenon is also observed when a
beam of light is projected in a cinema hall and it become visible due to the scattering
by colloidal dust particles in the air of the room.
Tyndall effect is observed only when the following two conditions are satisfied
(i) The diameter of the dispersed particles is not much smaller than the wavelength of
light used.
(ii) The refractive index of dispersed phase & the dispersion medium differ greatly in
magnitude.
Some example of Tyndall effect are:
(i) Blue colour of sky and sea water.
(ii) Visibility of tails of comets.
(iii) Twinkling of stars.
The importance of this effect lies in the fact that it has helped to confirm the
heterogeneous nature of the colloidal solutions and is used to distinguish between a
colloidal and true solution.
Zsigmondy, in 1903, used Tyndall effect to set up an apparatus known as ultramicro
scope. An intense beam of light is focused on the colloidal solution contained in a glass
vessel. the focus of the light is then observed with a microscope at right angles to the
beam. Individual colloidal particles appear as bright starts against a dark background.
Ultra microscope does not render the actual colloidal particle visibility but only
observe the light scattered by them. Thus ultra microscope does not provide any
information about the size and shape of colloidal particles.
Kinetic Properties: (Brownian Movement)
When a sol is examined with an ultramicroscope, the suspended particles are seen
as shining speeks of light. By following an individual particle, it is observed that the
particle is in a state of continuous motion in zigzag directions. The continuous
rapid zigzag motion of a colloidal particle in the dispersion medium is called
Brownian movement of motion (first observed by British botanish Robert Brown).

The Brownian movement has been explained to be due to the unbalanced bombardments
of the particles by the molecules of dispersion medium. This motion is independent of
the nature of the colloid but depend on the size of the particles and viscosity of the
solution. Smaller the size and lesser the viscosity, faster is the motion. The Brownian
movement has a stirring effect which does not permit the particles to settle and thus, is
responsible for the stability of sols.
Charge on Colloidal Particles:
Colloidal particles always carry an electric charge. The mutual forces of repulsion
between similarly charged particles prevent them from aggregating and settling
under the action of gravity. This gives stability to the sol. A list of common sols
with the type of charge on their particles is given below.
S Positively Charged Negatively Charged
N
1. Hydrated metallic oxides Metals e.g. copper, silver, gold sols.
e.g.: Al2O3.xH2O, CrO3.xH2O and
Fe2O3.xH2O etc
2. Basic dye stuff example Methylene blue Metallic sulphides like As2S3, Sb2S3,
sol CdS
3. Proteins in acidic medium Hemoglobin Acid dye stuff example Congored
(blood) sols, eosin, albumin.
4. Oxides like TiO2, etc Sols of starch, gum gelatin, clay &
charcoal
The charge on colloidal particles is due to one or more of the following reasons:
(i) The sol particles acquire positive or ve charge by preferential adsorption of +ve or
ve ions from the dispersion medium.
Preferential adsorption of ions is the most accepted reason. The sol particles acquire
positive or negative charge by preferential adsorption of +ve or ve ions. When two or
more ions are present in the dispersion medium, preferential adsorption of the ion
common to the colloidal particle usually takes place. This can be explained by taking the
following examples:
(a) When silver nitrate solution is added to potassium iodide solution, the precipitated
silver iodide absorbs iodide ions from the dispersion medium and negatively
charged colloidal solution results. However, when Kl solution is added to AgNO 3
solution, positively charged sol results due to adsorption of Ag + ions from dispersion
medium.
Agl/l Agl/Ag+
Negatively charged Positively charged
(b) If FeCl3 is added to excess of hot water, a positively charged sol of hydrated ferric
oxide is formed due to adsorption of Fe 3+ ions. However, when ferric chloride is
added to NaOH a negatively charged sol is obtained with adsorption of OH ions.
Fe2O3.xH2O/Fe3+ Fe2O3.xH2O/OH
Positively charged Negatively charged
Having acquired a positive or a negative charge by selective adsorption on the
surface of a colloidal particle as stated above, this layer attracts counter ions from
the medium forming a second layer, as shown below.
Agl/l K+ Agl/Ag+ l
The combination of the two layers of
opposite charges around the colloidal
particle is called Halmholtz electrical
double layer. According to modern views,
the first layer of ions is firmly held and is
termed fixed layer while the second layer is
mobile which is termed diffused layer. Since
separation of charge is a basis of potential,
the charges of opposite signs on the fixed
and diffused parts of the double layer results
in a difference in potential between these
layers. This potential difference between the
fixed layer and the diffused layer of opposite
charges is called the electrokinetic
potential or zeta potential.
The presence of equal and similar charges on colloidal particle is largely responsible
in providing stability to the colloidal solution, because the repulsive forces between
charged particles having same charge prevent them from coagulating or
aggregating when they come closer to one another.
Electrical Properties:
(a) Stability of colloidal sols Electrical charge on colloidal particles: The
dispersed phase particles carry either +ve and ve charge and dispersion medium
has an equal and opposite charge. The particles repel one another and hence do
not coagulate, thus making the colloid stable.
Origin of electrical charge on colloidal particles:
a. Due to frictional electrification
b. due to electron capture by sol particles.
c. Due to preferential adsorption of ions from the solution.
d. Due to dissociation of molecule electrolytes adsorbed on the surface of the
particles.
e. Due to dissociation of molecules followed by aggregation of ions

(b) Cataphoresis or Electrophoresis is the


movement of colloidal particles either towards
cathode or anode, depending on their charge,
under the influence of an electric field.
Electrophoresis is used to determine nature of
charge
Positive sol. Sol Fe(OH)3, Ca(OH)2, Al(OH)3, basic
dye stuffs (methylene blue, methyl violet,
Haemoglobin).
Negative Sol. Metal &sulphides: CdS, As2S3, Cu,
Ag, Pt and dyes (congored, Prussian blue, silicic
acid, gum, charcoal).

(c) Electro Osmosis:


A sol is electrically neutral therefore the dispersion medium carries an equal but
opposite charge to that of dispersed particles. Thus the medium will move in
opposite direction to the dispersed phase under the influence of applied electric
potential if colloidal solution is enclosed within semipermeable membrane. The
movement of dispersion medium under the influence of applied potential is known
as Electroosmosis.
Electroosmosis is direct consequence of the existence of zeta potential between
the sol particle and the medium. When the applied potential exceeds the Zeta
potential, the diffused layer move and causes electroosmosis.

(d) Coagulation or flocculation: [Process of setting of colloidal particle]


We known that the stability of a lyophobic sol is due to the adsorption of positive or
negative ions by the dispersed particles. The repulsion forces between the charged
particles do not allow them to settle. If somehow, the charge is removed there is
nothing to kept the particles apart from each other. In such cases they aggregate or
flocculate and settle down under the action of gravity.
The flocculation and setting down of the discharged sol particles is called
coagulation or the precipitation and can be brought about in following ways:
(a) By addition of electrolyte. (b) By electrophoresis
(c) By mixing two oppositely charged sols. (mutual precipitation)
(d) By boiling (e) Persistent dialysis.
(a) By Addition of Electrolytes:
When an electrolyte is added in excess to a sol, the electrolyte furnishes both types
of ions in solution. The oppositely charged ions get adsorbed on the surface of
colloidal particles. This causes neutralization and thereby the size and mass of
colloidal particle increases and it becomes a suspension particle. Due to greater
volume and greater mass these suspension particles settle down i.e., they
coagulate. The ion irresponsible for neutralization of charge on the particle is called
flocculating ion.
Coagulation or flocculation is the process of bringing colloidal particles closer so
that they aggregate to form larger particle that precipitate and settle down or float
on the surface. It is usually done by addition of an electrolyte. Effective ions or
electrolyte are those which carry charge opposite to colloids.
Hardy Schulze rule states that greater is the valency of the oppositely charged
ion of electrolyte being added, faster is the coagulation: e.g. for a negatively
charged sol, the order is: Al 3+> Ba2+> K+, for a positively charged sol the order is:
Fe(CN)64 PO34 SO 24 Cl

Coagulating value is the minimum amount of electrolyte in milli moles


required to coagulate a 1 lit of solution of sol in two hours. The smaller the
quantity needed, the higher will be the coagulating power of anion.
(b) By Electrophoresis:
During electrophoresis the charged sol particles migrate towards the electrode of
opposite sign. There they deposit their charge and then get coagulated (As the
neutral particles can aggregate and change to suspension particles).
(c) By Mixing Two Oppositely Charged Sols:
The mutual coagulation of two sols of opposite charge can be effected by mixing
them. For e.g. Fe(OH)3 (positive sol) and Arsenioussulphide (negative sol) when
mixed join and coagulate.
(d) By Boiling
Sols such as sulphur and silver halides disperse in water, get coagulated when
boiled, due to increased collisions between sol particles and water molecules, which
remove the adsorbed layer from the sol and therefore the sol particles settle down.
(e) Persistent dialysis:
The stability of a colloidal sol is due to presence of a small amount of the
electrolyte. On prolonged dialysis, the electrolyte is completely removed. As a
result, the colloidal sol becomes unstable and gets coagulated.
Coagulation of Lyophillic Sols:
Lyophilic sols are stable due to charge and solvation of the colloidal particles. When
these two factors are removed, a lyophilic sol can be coagulated. This is done (i) by
adding electrolyte; (ii) by adding suitable solvent.
When solvents such as alcohol and acetone are added to hydrophilic sol, the dehydration
of dispersed phase occurs. Under this condition a small quantity of electrolyte can bring
about coagulation.
Protection of Colloids:
Lyophilic sols are more stable than lyophobic sols
hence they are used as protective colloids to increase
the stability of lyophobic sols, e.g. addition of gums,
gelatin etc. to certain metal sols. These sols are called
Protective colloids.
Protective action of lyophilic sols is explained due to
formation of a thin layer around the lyopobic sol
particles, thus preventing them from coming closer.
Gold number is a term used to compare protective
action of different lyophilic colloids.
Gold number of a lyophilic sol is the minimum amount
of it in milligram, which prevent the coagulation of
10ml gold sol (no colour change from red to blue)
against 1 ml of 10% NaCl solution.
The precipitate of gold sol is indicated by a colour change from red to blue when the
particle size just increases.
Higher the gold number, lesser is the protective power. Gelatin has highest and starch
has lowest protective ability.
Emulsions
Emulsion is a colloidal system involving one liquid dispersed in another, provided both
are immiscible. One of the constituent is oil while the other is water. Normally these are
not expected to be stable because oil and water do not mix. These are therefore
stabilized by the presence of certain substances called emulsifier or emulsifying
agents. Some of the emulsifying agents are soaps, agar, gum etc. the emulsifying agent
forms and interfacial film between suspended particles and the medium.
Some commonly known emulsions are Milk, butter, milk cream, cold cream, vanishing
cream, etc. There are many drugs and medicines which are also in the form of emulsions
e.g. various ointments, cod liver oil etc.
Types of emulsions:
Depending upon the type of proportions in which these constituents are present,
emulsion have been classified into two types.
1. Oil in water emulsions (O/W) are those in which oil is the dispersed phase and
water is the dispersion medium. Milk is a common example in which liquid fats are
dispersed in water. Similarly, if a few drops of nitrobenzene (oil) is added to water,
an emulsion results. Varnishing cream is another example of this type.
2. Water in oil emulsions (W/O) are those in which water is the dispersed phase and
oil is the dispersion medium, Butter is an example of water in oil emulsion in which
water is dispersed in oil. Cod liver oil and cream are the other examples of these
emulsions.

Detection of the types of Emulsions


The nature of an emulsion whether O/W or W/O can be detected with the help of
following tests.
(a) Dilution test. To the emulsion taken in a beaker, add a small amount of water. In
cases it gets diluted, it is an example of oil in water type emulsion. If water forms a
separate layer then the emulsion is water in oil type. Milk, for example, can be
readily diluted with water. It is therefore, oil in water type emulsion.
(b) Dye test. Add a small amount of oil soluble dye to the emulsion. In case, only a
small portion of it gets coloured, it is an example of oil in water emulsion. However,
if the entire background is coloured, it is an example of water in oil emulsion.
Emulsifier and Emulsifying Agents
An emulsifier or emulsifying agent is a substance which helps in stabilizing an
emulsion of oil and water and, thus, prevents them from getting apart. The
commonly used emulsifying agents for O/W emulsion are soaps, detergents,
lyphilic colloids, proteins, gums and agar etc. & for W/O emulsion are heavy metal
salt of long chain fatty acids etc. The preparation of emulsion in the presence of an
emulsifier is known emulsification. The role of an emulsifier in stabilizing an
emulsion can be explained in two ways:

(a) It is believed that an emulsifier gets


concentrated at the oilwater interface i.e.,
the surface at which oil and water come in
contact with each other. It forms a protective
coating around each drop of oil and thus,
prevents the oil drops from coming in contract
with one another. The oil drops remain
suspended in water and are not coagulated.
(b) According to an another view, the role of the emulsifier is the same as that
of lubricant in a machine. Just as a lubricant reduces he friction in the
various parts of machine, an emulsifier also tries to reduce the interfacial
tension between oil and water by suitable means. Thus, oil and water
remain in company of each other and do not get separated. The cleaning
action of soap in washing dirty clothes illustrates the role of emulsifier.
Application of emulsions
The important applications of emulsions in daily life are as follows:
(i) The concentration of the sulphide ore of a metal by froth floatation process involves
the use of some oil such as pine oil. The oil forms emulsion with ore particles. When
air is bubbled through the emulsion, it rises to the surface as foam and is skimmed
off.
(ii) The various drugs available in liquid form such as cod liver oil, Bcomplex, etc., are
emulsions of water in oil type. These are readily adsorbed in the intestines.
Digestive enzymes act on emulsified drugs in order to carry out their metabolic
functions.
(iii) The cleansing action of soap is based upon the formation of oilinwater type
emulsion.
(iv) Milk which is an important constituent of our diet is an emulsion of fat in water.
(v) Cosmetics, lotions, creams and many ointments are emulsions. Several oily drugs
are prepared as emulsions in order to facilitate their adsorption.
Demulsification
It is the process of decomposing an emulsion back into its constituent liquids. The
demulsification can be done by centrifugation, filtration, boiling, freezing and by
some chemical methods such as change in pH. For example, centrifugation
separates cream (fat) from milk which is an emulsion. When water is the
dispersion medium, the presence of a dehydrating agent can result in the
demulsification.
Nature of an emulsion can be distinguished by dilution, viscosity and conductivity tests.
Emulsions show all the properties of colloidal sols.
The process of breaking an emulsion to yield the constituent liquids is known as
demulsification e.g. heating, freezing, centrifuge.
Emulsions are useful as several pharmaceutical preparations, cosmetics, dairy products
etc.
Droplet of emulsion are often negatively charged and can be precipitated by electrolytes

Gels
These are colloidal systems where liquids are the dispersed phase and solids act as
dispersion medium, e.g. curd, cheese etc. When a warm solution of gelatin is cooled it
sets to a semisolid mass which is gel. This process is called gelation.
Applications of Colloidal System
Colloids are widely used in the industry. Following are some examples.
1. Medicines in colloidal form can be easily adsorbed by body tissues & hence are
more effective e.g. colloidal antimony is used in curing kalaazar, argyrols is a silver
sol used as an eye lotion. Colloidal gold is used for intramuscular injection
Neutralization of excess acidity by Al (OH) 3, Milk of magnesia, an emulsion, is used
for stomach disorders, colloidal sulphur germ killer, kalolin used to remove toxins
from intestine. Cod liver oil is emulsion of oil in water. Some ointment, antibiotics,
Penicillin, streptomycin are produced in colloidal form. Colloidal medicines are
more effective because they have large surface area and are therefore easily
assimilated.
2. Food: Gelatin in icecream. It preserve smoothness and prevent ice crystals
formation, protein, milk, cheese are colloids, fruits, jelly, cream, bread is dispersion
of air in baked dough.
4. Purification of water by alums: Water from rivers or lakes are sometimes used
for domestic and industrial purpose after purification. The water from lake or river
is turbid due to the presence of fine clay particles which are negatively charged.
These can be removed by adding potash alum or aluminiumsulphate. Al 3+ ions
from potash alum o aluminiumsulphate neutralize the negative charge on clay
particles. This causes the coagulation of clay particles which settle down leaving
water which is clear of further treatment.
5. Stoppage of bleeding from a fresh cut: The bleeding from a fresh cut can be
immediately stopped by applying a concentrated solution of ferric chloride or
potash alum. Blood consists of colloidal particles of haemoglobins which carry
positive charge on them. When ferric chloride or alum is applied on the cut these
colloidal particles get their positive charge neutralized by the anions available
from these substances in solution. In the absence of the charge, they get
coagulated and the bleeding stops.
6. Delta formation: Formation of delta due to coagulation of colloidal particles of
river water by sea salt. The river water contains colloidal particles of sand and clay
which carry negative charge. The sea water, on the other hand, contains positive
ions such as Na+, Mg2+ and Ca++. As the river water meets sea water, these ions
discharge the sand or clay particles which are precipitated as delta.

7. Photographic plates and films: Photographic plates or films are prepared by


coating an emulsion of the light sensitive silver bromide in gelatin over glass
plates or celluloid films.
8. Fog, mist and rain. In extremely cold weather, the temperature is very low. The
water droplets (moisture) present in air condense on the surface of the dust
particles that are suspended. Since these are colloidal in nature, they float in air in
the form of mist or fog or extremely low, these colloidal droplets grow in size. They
become bigger and bigger and when atmosphere is not in a position to hold them,
they come down as rain.
In the winter season, the atmosphere generally becomes very foggy and visibility
is quite poor. This leads to lot of inconvenience for vehicular movement and result
in major accidents. Farmers are in the habit of burning husk in the open fields. This
results in the release of unburnt carbon particles in the atmosphere. The water
droplets condense on them and they appear as fog. But actually this is smog and
not fog and is extremely injurious to health. This can lead to asthama, lung as well
as throat cancer. It is very essential to educate our farmer community about these
harzards.
9. Purification of Blood: Blood is a colloidal solution. It contains toxic waste
products such as urea and uric acid which pass through the membrane while
colloidal sized particles of blood proteins hemoglobin are retained. Kidney failure,
therefore, leads to death due to accumulation of poisonous waste products in the
blood. Blood is purified by dialysis.
10. Chemical warfare: (Smoke screen): Smoke is a colloidal solution of solid
particles such as carbon, arsenic compounds, dust, etc., in air. The smoke, before
it comes out from the chimney, is lead through a chamber containing plates
having a charge opposite to that carried by smoke particles. The particles on
coming in contract with these plates lose their charge and get precipitated. The
particles thus settle down on the floor of the chamber. The precipitator is called
Cottrell precipitartor. Colloidal dispersions of certain substance, like TiO 2 (as
dispersed phase) in air (as the dispersion medium) are used a smoke screens in
warfare for the purpose of concealment. The dispersed phase particles (i.e. TiO 2)
being very heavy rapidly drops down in the form of a curtain of drizzling
whiteness.
11. Artificial rain: Tiny water droplets in clouds are electrically charged. In any cloud
all such water particles carry the same charge. Artificial rain can be caused by
spraying oppositely charged dust or fine sand or precipitates like Agl (which has a
crystal structure similar to ice and as such particles of Agl can act as nuclei for
precipitation) on to a cloud. Even certain salts in t he form of fine particles can be
sprayed. The neutralization of charge results in coagulation of water droplets or
rain. Cloudbrusta natural disaster resulting in a very heavy down pour over a
very short time is believed to occur due to the mutual discharge of oppositely
charged clouds.
12. Cleaning Action of Soaps and Detergents: Dust and dirt particles on clothes
are colloidal in nature. Soaps being sodium salts of higher fatty acids coagulate
them which become suspension particles called micelle and roll out due to greater
volume and greater mass.
13. Rubber Industry: Latex is a colloidal solution of rubber particles which are
negatively charged. Rubber is obtained by coagulation of Latex. Rubber is
electroplated on metals when they act as anode.

IIT JEE Assignment


3
Q.1 The coagulation of 100 cm of gold solution so completely prevented by addition of
0.25g of starch to it before adding 10 ml of 10% NaCl solution. The gold number of
starch is
(a) 0.025 (b) 0.25 (c) 2.5 (d) 25
Q.2 For adsorption of a gas on a solid, the plot of log x/m vs log P is linear with slope
equal to: (n being a whole number)
(a) k (b) log k (c) n (d) 1/n
Q.3 For the coagulation of 100 mL of As 2S3 sol, 5 mL of 1 M NaCl is required. The
flocculation value of NaCl is
(a) 50 (b) 5 (c) 47.6 (d) None of these
Q.4 Which of the following colloid can be prepared by electrical dispersion as well as
reduction method?
(a) Sulphur (b) Ferric hydroxide (c) Arsenioussulphide (d) Gold
Q.5 Silver iodide is used for producing artificial rains because silver iodide
(a) is easy to spray at high altitude (b) is insoluble in water
(c) has crystal structure similar to ice (d) is easy to synthesize

Answers
1. d 2. d 3. a 4. d 5. c

IIT JEE Assignment


Q.1 The particles of a particular colloidal solution of arsenic trisulphide (As 2S3) are
negatively charged. Which 0.0005M solution of the following salts would be most
effective in coagulating this colloidal solution, KCl, MgCl 2, AlCl3 or Na3PO4? Explain.
Q.2 A sample of charcoal weighing 6g was brought into contact with a gas contained in
a vessel of one litre capacity at 27 oC. The pressure of the gas was found to fall
from 700 to 400 mm of Hg. Calculate the volume of the gas (reduced to STP) that
is adsorbed per gram of the adsorbent under the condition of the experiment
(density of charcoal sample is 1.5 g cm3).
Q.3 1 gm of active charcoal is taken and its surface area is 3.01 10 2 m2/gm. It
adsorbs 100 ml of 0.5 M CH 3COOH in a single layer. After adsorption, its molarity
becomes 0.49M. Find the surface area of the charcoal covered by one molecule of
acetic acid.
Q.4 A solution of palmitic acid (M = 256 g mol 1) in benzene contains 4.24g of acid per
dm3. When this solution is dropped on a water surface the benzene evaporates and
the palmitic acid forms a monomolecular film of the solid type. If we wish to cover
an area of 500 cm2 with a monolayer, what volume of solution should be used? The
area covered by one palmitic acid molecule may be taken to be 0.21 nm 2.
Q.5 A one-litre vessel contained a gas at 27oC. 6g of charcoal was introduced into it.
The pressure of the gas fell down from 700 mm Hg of 400 mm Hg. Calculate the
volume of the gas (at S.T.P.) adsorbed per gram of charcoal. Density of charcoal
sample used was 1.5g cm3.
Q.6 In an adsorption experiment, a graph between log (x/m) versus log p was found to
be linear with a slope of 45o. The intercept on the log (x/m) axis was found to be
0.3010. Calculate the amount of the gas adsorbed per gram of charcoal under a
pressure of 0.5 atmosphere.
Q.7 The volume of nitrogen gas vm(measured at S.T.P.) required to cover a sample of
silica gel with a mono-molecular layer is 129 cm 3 g1 of gel. Calculate the surface
area per gram of the gel if each nitrogen molecule occupies 16.2 10 20 m2.
Q.8 1 g of charcoal adsorbs 100 ml of 0.5M CH 3COOH to form a monolayer, and
thereby the molarity of CH3COOH reduces to 0.49. Calculate the surface area of
the charcoal adsorbed by each molecule of acetic acid. Surface area of charcoal =
3.01 102 m2/g.
Q.9 20% of surface sites are occupied by N 2 molecules. The density of surface sites is
6.023 1014 cm2 and total surface area is 1000 cm 2. The catalyst is heated to 300
K while N2 is completely desorbed into a pressure of 0.001 atm and volume 2.46
cm3. Find the active sites occupied by each N 2 molecule.
Q.10 A particle of radius 1 cm is broken to form colloidal particles of radius 1000.
Calculate the no. of colloidal particles produced and their total surface area.
Q.11 When 5.19 105 g of palmitic acid (C15H31COOH) in the form of a dilute solution in
benzene was spread on the surface of water, it could be compressed to an area of
265 cm2 before the resisting force increased sharply. Calculate the area occupied
by a single molecule in the closely packed layer.
Q.12 Compare the coagulating power of AlCl 3 with that of NaCl. Given that their
coagulation values are 0.093 and 52 respectively.
Q.13 One gram of activated charcoal has a surface area of 1000 m 2. If complete
coverage is assumed, how much ammonia (in cm 3 at STP) could be adsorbed on
the surface of 25g of the charcoal? Given: diameter of NH 3 molecule = 0.3 nm.
Q.14 50 mL of standard gold sold needs 0.05 mg of gelatin for its protection from
coagulation. Calculate the gold number of gelatine.

Answer

1. AlCl3 2. 60.19 ml g1 3. 5 1019 m2


4. 0.024 ml 5. 60.168 cm3 6. 1.0
7. 562 m2 8. 5 1019 m2 9. 2
10. 12.57 105 cm2 11. 2.17213 1015 cm2 12. 559
13. 13151 cm3 14. 0.01

Objective Assignment
Q.1 Which of the following metal sols cannot be prepared by Bredigs arc method?
(a) copper (b) potassium (c) gold (d) platinum
Q.2 Gelatin protects
(a) gold sol (b) As2S3 sol (c) Fe(OH)3 sol (d) all of these
Q.3 Flocculation value is expressed in terms of
(a) milli mole/L (b) mole/L (c) grams/L (d) mole/ mL
Q.4 The gold numbers of four protective colloids O, P, Q and R are 0.005, 0.01, 0.1 and
0.5 respectively. The decreasing order of their protective power is
(a) R, Q, P, O (b) O, P, Q, R (c) P, Q, R, O (d) Q, R, O, P
Q.5 A sol has positively charged colloidal particles. Which of the following solutions is
required in lowest concentration for coagulation?
(a) NaCl (b) K4[Fe(CN)6] (c) ZnCl2 (d) Na2SO4
Q.6 The protective power of lyophilic sol is
(a) dependent on the size of colloidal particles
(b) expressed in terms of gold number (c) expressed by x/m
(d) directly proportional to the magnitude of charge on it
Q.7 Which plot is the adsorption isobar for chemisorptions?
Q.8 The stability of the dispersed phase in a lyophobic colloid is due to
(a) high viscosity of the medium (b) the formation of electrical layer between two
phases
(c) high surface tension of solution (d) none of the answer is correct
Q.9 Tyndall effect is due to
(a) reflection of light (b) scattering of light (c) absorption of light (d)
adsorption of light
Q.10 The ability of ion to bring about coagulation of a given colloidal solution depends
upon
(a) the size of its ion (b) the magnitude of charge
(c) the sign of charge (d) both magnitude and sign of
charge
Q.11 Purple of cassius is
(a) colloidal solution of gold (b) colloidal solution of silver
(c) colloidal solution of platinum (d) oxyacids of gold

Q.12 Which of the following is not a colloid?


(a) chlorophyll (b) smoke (c) Paint (d) milk

Q.13 Gold number is minimum in case of


(a) gelatin (b) egg albumin (c) gum arabic (d) starch
Q.14 Lyophilic sols are more stable than lyophobic sols because
(a) the colloidal particles have positive charge (b) the colloidal particles have
negative charge
(c) the colloidal particles are solvated
(d) there are strong electrostatic repulsions between the negatively charged
colloidal particles
Q.15 On adding few drops of dil. HCl to freshly precipitated ferric hydroxide, a red
coloured colloidal solution is obtained. This phenomenon is known as
(a) peptisation (b) dialysis (c) protective action (d)
dissolution
Q.16 Asenioussulphide solution caries a negative charge. The maximum precipitating
power of this sol is possessed by
(a) K2SO4 (b) CaCl2 (c) Na3PO4 (d) AlCl3
Q.17 In colloidal state, particles size ranges from
(a) 1 to 10 (b) 20 to 50 (c) 10 to 1000 (d) 1 to 280
Q.18 Which one of the following substance gives a positively charged sol?
(a) gold (b) A metal sulphide (c) Ferric hydroxide (d)
an acidic dye
Q.19 Peptisation denotes
(a) digestion of food (b) hydrolysis of proteins
(c) breaking and dispersion into colloidal state(d) precipitation of a solid from
colloidal state
Q.20 A colloidal solution is subjected to an electrical field. The particles move towards
anode. The coagulation of same sol is studied using NaCl, BaCl 2 and AlCl3 solutions.
Their coagulating power should be
(a) NaCl> BaCl2> AlCl3 (b) BaCl2> AlCl3>NaCl
(c) AlCl3> BaCl2>NaCl (d) BaCl2>NaCl> AlCl3
Q.21 Which of the following is les than zero during adsorption?
(a) G (b) S (c) H (d) all of the above
Q.22 Cellulose dispersed in ethanol is called
(a) emulsion (b) micelle (c) colloidion (d) hydrophilic solution
Q.23 Which of the following is most suitable for the coagulation of ferric hydroxide sol.
(a) KCl (b) KNO3 (c) K2SO4 (d) K3[Fe(CN)6]
Q.24 Which of the following is not a characteristic of chemisorptions?
(a) adsorption is irreversible (b) H is of the order of 900 kJ
(c) adsorption is specific (d) adsorption increases with increase of surface
area
Q.25 Alums purify muddy water by:
(a) dialysis (b) adsorption (c) coagulation (d) forming a true
solution

IITJEESingle Choice Correct

Q.26 According to Freundlich adsorption isotherm, which of the following is correct?


(a) x/m p1 (b) x/m p1/n (c) x/m po
(d) all the above are correct for different ranges of pressures

Q.27 The critical micellization concentration (CMC) is:


(a) the concentration at which micellization begins
(b) the concentration at which true solution is formed
(c) the concentration at which one molar electrolyte is present per 1000gm of
solution
(d) the concentration at which solute and solution form equilibrium
Q.28 Which one of the following is correctly matched?
(a) emulsion curd (b) foam mist (c) aerosol smoke (d) solid sol cake
Q.29 Adsorption is accompanied by:
(a) decrease in entropy of the system (b) decrease in the enthalpy of the
system
(c) decreases in Gibbs free energy (d) all of these
Q.30 Which reaction gives colloidal solution:
(a) Cu + HgCl2 CuCl2 + Hg (b) 2 HNO3 + 3H2S 3S + 4H2O +
2NO
(c) 2Mg + CO2 2MgO + C (d) Cu + CuCl2 Cu2Cl2
Q.31 A freshly prepared Fe(OH)3 precipitate is peptized by adding FeCl 3 solution. The
charge on the colloidal particle is due to the preferential adsorption of:
(a) Cl (b) Fe3+ ions (c) OH ions (d) none of these
Q.32 Which statement is incorrect?
(a) higher the gold number of lyophilic substance better is its protective action
(b) lower the gold number of a lyophilic substance better is its protective action
(c) theBredigs arc method is usually suitable for preparing sols of metals
(d) the osmotic pressure method gives the average molar mass of a polymer
Q.33 50 mL of 1M oxalic acid (hydrated) is shaken with 0.5g wood charcoal. The final
concentration of the solution after adsorption is 0.5 M. What is the amount of oxalic
acid adsorbed per gm of carbon?
(a) 3.15 g (b) 3.45 g (c) 6.30 g (d) none of these
Q.34 Colloidol solution of arseniussulphide can be prepared by:
(a) electro dispersion method (b) peptization
(c) double decomposition (d) hydrolysis
Q.35 Ferric chloride is applied to stop bleeding due to a cut because:
(a) Fe3+ ion coagulates blood which is a negatively charged sol
(b) Fe3+ ion coagulated blood which is a positively charged sol
(c) Cl ion coagulates blood which is a positively charged sol
(d) Cl ion coagulated blood which is a negatively charged sol
Q.36 Minimum concentration of an electrolyte which is able to cause coagulation of a sol
is termed as its:
(a) emulsification value (b) saponification value
(c) flocculation value (d) gold number
Q.37 Which of the following forms cationic micelles above certain concentration?
(a) sodium dodecyl sulphate (b) sodium acetate
(c) urea (d) cetyltrimethyl ammonium
bromide

Q.38 Critical micelle concentration (CMC) of soap solutions lies in the range:
(a) 106 105 M (b) 105 104 M (c) 104 103 M (d) 103 102 M

Q.39 Which equation represents Freundulich adsorption isotherm (physical adsorption is


basis of this theory)
x
K ( P)1/ n
m
(a) where x is amount of gas adsorbed on mass m at pressure P
x 1 x x
log log K log P K.P. K
m n m m
(b) (c) at low pressure and at high pressure
(d) all of these
Q.40 The Brownian motion is due to:
(a) temperature fluctuations with in the liquids phase
(b) attraction and repulsion between charges on the colloidal particles
(c) impact of the molecules of dispersion medium on the colloidal particles
(d) convective currents
Q.41 The cotterells precipitator is used to:
(a) neutralize charge on carbon particles in air is smoke
(b) coagulate carbon atoms of smoke
(c) bring in cataphoresis in carbon particles (d) all of these
Q.42 An example of intrinsic colloid is:
(a) As2S3 sol (b) Fe(OH)3 sol (c) egg albumin (d) Au sol
Q.43 Freundlich adsorption isotherm gives straight line on plotting
x x x x 1
vs. P log vs. P log vs. log P vs.
m m m m P
(a) (b) (c) (d)
Q.44 In homogeneous catalytic reactions, there are three
alternative paths A, B and C (shown in the figure). Which
one of the following indicates the relative ease with which
the reaction can take place?
(a) A > B > C
(b) C > B > A
(c) B > C > A
(d) A = B= C
Q.45 For the reaction (A B + C); the energy profile diagram
is given in the figure. The decrease in energy of
activation in presence of catalyst is
(a) z
(b) z p
(c) y z
(d) z x
Q.46 The colloidal system consisting of a liquid adsorbate in a solid adsorbent is termed
as
(a) aerosol (b) foam (c) emulsion (d) gel
Q.47 Which is false for a catalyst?
(a) a catalyst can initiate a reaction
(b) it does not alter the position of equilibrium in a reversible reaction
(c) a catalyst remains unchanged in quality and composition at the end of reaction
(d) catalysts are very specific in reaction
Q.48 Which of the following statements is incorrect?
(a) adsorption always leads to a decrease in enthalpy and entropy of the system
(b) adsorption arises due to unsaturation of valence forces of atoms or molecules
on surface
(c) adsorption increases with rise in temperature
(d) adsorption decreases the surface energy
Q.49 Which of the following gas molecules have maximum value of enthalpy of physio
sorption?
(a) C2H6 (b) Ne (c) H2O (d) H2
Q.50 Which of the following gases is adsorbed most by activated charcoal?
(a) CO2 (b) N2 (c) CH4 (d) Ar

More than One Choice Correct


Q.51 Which of the following statements are correct?
(a) physical adsorption is multilayer, nondirectional and non specific
(b) chemical adsorption first increases and than decreases with increase in
temperature
(c) insame cases, solvent may be adsorbed in preference to the solute on the
surface of the adsorbent
(d) as a result of adsorption, there is increase of surface energy

Q.52 Which of the following are aerosols?


(a) smoke (b) fog (c) milk (d) butter
Q.53 Which of the following are correctly matched?
(a) milk emulsion (b) butter gel (c) fog aerosol (d) dust solid sol

Q.54 Which of the following increases the activation of a solid adsorbent?


(a) polishing the surface of the solid adsorbent
(b) subdividing the solid adsorbent
(c) blowingsuper heated steam through the porous adsorbent
(d) carrying out the adsorption at very high temperature

Q.55 Which of the following is incorrect about chemisorptions:


(a) multilayer adsorption (b) reversible in nature
(c) strong adsorption by free valences (d) Exothermic in nature

Q.56 Adsorption is accompanied by:


(a) decrease in enthalpy (b) increase in free energy of system
(c) decrease in entropy of system (d) the value of TS is negative
Q.57 Which of the following will give linear plots?

x x 1 m 1 p
log v / s log c log v/s v/s v/s p
m m p x p ( x / m)
(a) (b) (c) (d)
Q.58 Zeolites are:
(a) hydratedaluminosilicates which can be used for shape selective catalysis
(b) have general formula Mx/n [(AlO2)x (SiO2)y]. mH2O where, n is charge on metal
Cation Mn+.
(c) have pore sizes between 260 pm to 740 pm
(d) ZSM5 which is used in petroleum industry as a catalyst, converts hydrocarbons
into alcohols
. Q.59 Lyophilic sols are characterized by:
(a) colloidal particles are solvated (b) reversible in nature
(c) colloidal particles always have charge (either positive or negative)
(d) smallquanity of electrolyte is required for precipitation

Q.60 Colloidal solutions prepared by chemical processes contains impurities in the form
of electrolyte or the soluble substance. Which of the following methods are
commonly used to purify a colloidal solution.
(a) peptization (b) eletrodialysis
(c) Bredigs arc method (d) ultra centrifugation
Q.61 If x/m is the mass of adsorbate adsorbed per unit mass of adsorbent, P is the
pressure of the adsorbate gas, a & b are constants, which of the following represent
Langmuir adsorption isotherm?
x a 1 x aP
log log P
m b a m 1 bP
(a) log (b)
x a x
a.P
m b m
(c) (when the pressure is high) (d) (when the pressure is low)
Q.62 Which one of the following graphs correctly represents effect of temperature on the
process of adsorption?

Q.63 The extent of adsorption of a gas on solid depends on:


(a) nature of the gas (adsorbate) (b) pressure of the gas
(c) temperature of the gas (d) nature of adsorbent

Q.64 The coagulation of sol particles may be brought in by:


(a) adding oppositely charge sol (b) adding electrolyte
(c) heating (d) persistent dialysis

Q.65 With the help of electrophoresis


(a) formation of colloidal sol occurs
(b) coagulation of colloidal solution occurs if carried out for prolonged times
(c) charge on colloidal particles can be predicted
(d) it is possible to separate different proteins, carbohydrates & nucleic acids
Match the following
Q.66 Note: Each statement in column I has one or more than one match in column II.

Column I Column II
I. Tyndall effect (A) Au, Ag, Pt sol
II. Sluphur sol (B) Oxidation
III. Electrical disintegration (C) Scattering of light
IV. Lyophobic sol (D) Colloidal solution
Q.67
Column I Column II
I. Physical adsorption (A) stable
II. Chemical adsorption (B) less stable
III. Gelatin (C) Irreversible
IV. Gold sol (D) reversible
Note:Each statement in column I has only one match in column II.
Q.68
Column I Column II
I. Purple of cassius (A) congorubin dye
II. Langmiur isotherm (high p) (B) x/m = a/b
III. freundlich isotherm (C) colloidal sol
(intermediate p)
IV. Rubin number (D) x/m = k.p1/n
(E)
Assertion & Reason Type
Direction: Read the following questions and choose
(A) If both Assertion and Reason are true and Reason is the correct
explanation of the Assertion.
(B) If both Assertion and Reason are true but Reason is not correct
explanation of the Assertion.
(C) If Assertion is true but Reason is false(D)If Assertion is false but Reason
is true
Q.69 Assertion: A sol of As2S3 prepared by the action of the H 2S on As2O3 is negatively
charged.
Reason: It is due to the adsorption of H + ions on the surface of colloidal particles
and S2 ion get diffused in todispersion medium.
Q.70 Assertion: For As2S3, sol, BaCl2 has higher coagulation value than NaCl
Reason: Higher the valency of the oppositely charged ion of the electrolyte added,
higher is the coagulation value of the electrolyte.
Q.71 Assertion: Aqueous gold colloidal solution is red in colour.
Reason: The colour arises due to scattering of light by colloidal gold particles.
Q.72 Assertion: Physical adsorption of molecules on the surface required activation
energy.
Reason: The physical adsorption is due to weak Vander Waal force of attraction
between adsorbent and adsorbate.
Q.73 Assertion: Habers synthesis of NH3 is carried out in the presence of catalyst.
Reason: The catalyst shifts the position of the equilibrium of the reaction.
(a) (A) (b) (B) (c) (C) (d)
(D)
Passage Based Problems
A colloid is a heterogeneous system in which one substance is dispersed (dispersed
phase) as a very fine particles in another substance called dispersion medium.
Depending upon whether the dispersed phase and the dispersion medium are solids,
liquids or gases, eight type of colloidal systems are possible. They are prepared in the
industry or in the laboratory by a number of methods and then purified. Hardy and &
Schulze made a substantial contribution in studying the coagulation of colloids. The
protective power of lyophilic sol was studied by Zsigmondy and he introduced the term
Gold number.

Q.74 For the coagulation of 100 mL of arseniussulphide sol 5 mL of 1 M NaCl is required.


The coagulating value of NaCl is
(a) 46.7 (b) 47.6 (c) 49.9 (d) 42.0

Q.75 In an experiment on electroosmosis, in which of the following the level of the


dispersion medium will fall on the cathode side?
(a) gold sol (b) starch sol (c) Fe(OH)3 sol (d) As2S3 sol

Q.76 If dispersed phase is a liquid and the dispersion medium is solid, the colloid is know
as
(a) a sol (b) a gel (c) an emulsion (d) a foam
Q.77 Which of the following anions will have minimum flocculation value for ferric
hydroxide so?
SO 24
(a) (b) Cl (c) Br (d) [Fe(CN)6]3

Answers
1 b 11 a 21 d 31 b 41 d
2 d 12 a 22 c 32 a 42 c
3 a 13 a 23 d 33 c 43 c
4 b 14 c 24 b 34 c 44 b
5 b 15 a 25 c 35 a 45 b
6 b 16 d 26 d 36 c 46 d
7 c 17 c 27 a 37 d 47 a
8 b 18 c 28 c 38 c 48 c
9 b 19 c 29 d 39 d 49 c
10 d 20 c 30 b 40 c 50 a
Answers More than One Option
51 a,b, c, 52 a,b 53 a,b, c 54 b,c 55
a,b
56 a, c,b 57 a, c,d 58 a,b, c 59 a, b 60 b, d
61 b,c, d 62 a, c 63 a,b,c, d 14 a, b,c,d
65 b,c, d
Match the following
66 Ia, c, d ;IIb,c,d ;IIIa,c,d ;IVa,b,c,d
67 Ib,d ;IIa,c ;IIIa,d ;IVb,c
68 Ic ;IIb ;IIId ;IVa
Assertion & Reason
69 c 70 d 71 a 72 d 73 c
74 b 75 c 76 b 77 d