Вы находитесь на странице: 1из 15

1

Chapter 5: Surface Chemistry


Adsorption: The accumulation of molecular species at the surface rather than in the bulk of a
solid or liquid is termed as adsorption. Adsorption is essentially a surface phenomenon.
Adsorbate: The substance which is being adsorbed on the surface of another substance (adsorbent).
Adsorbent: The substance on the surface of which adsorption takes place is called adsorbent.
Eg: Water vapours are adsorbed by silica gel.
Water vapour adsorbate; Silica gel Adsorbent.
Desorption: The process of removing an adsorbed substance from a surface on which it is adsorbed.
.
Sorption: The process in which both adsorption and absorption take place simultaneously.
Difference between adsorption and absorption:
Adsorption
Absorption
Adsorption is a surface phenomenon
Absorption is a bulk phenomenon
The accumulation of molecular species at the surface
It is the phenomenon in which a substance is
rather than in the bulk of a solid or liquid.
uniformly distributed throughout the bulk of the solid.
In adsorption, the concentration of adsorbate
In absorption, concentration is uniform throughout the
increases only at the surface of the adsorbent
bulk of the solid.
Eg: Water vapours are adsorbed by silica gel.
Eg: Water vapours are absorbed by anhydrous CaCl2
Enthalpy or heat of adsorption: Adsorption generally occurs with release in energy, i.e., it is exothermic in
nature. The enthalpy change for the adsorption of one mole of an adsorbate on the surface of adsorbent is
called enthalpy or heat of adsorption.
Mechanism of Adsorption
Adsorption arises due to the unbalanced or residual attractive forces on the surface of the adsorbent
which attract adsorbate particles on its surface. During adsorption, there is decrease in surface energy
which appears as heat. Therefore adsorption is an exothermic process. H of adsorption is always
negative. When a gas is adsorbed, the freedom of movement of its molecules becomes restricted, S is
negative. Adsorption is thus accompanied by decrease in enthalpy as well as decrease in entropy of the system.
For a process to be spontaneous, at constant temperature and pressure, G must be negative, i.e.,
G = H TS, G can be negative if H has sufficiently high negative value as TS is positive.
G = H TS ; S is - ve; H of adsorption is always negative [surface energy, during adsorption].
For an adsorption process to be spontaneous, G must be negative, i.e., - H > TS.
Therefore adsorption is always exothermic.
Types of adsorption:
a. Physical adsorption or physisorption
b. Chemical adsorption or chemisorption
Difference between Physical and chemical adsorption:
Physisorption
Chemisorption
1. There are weak van der Waals forces between
1. There is strong chemical bond between adsorbate
adsorbate and adsorbent.
and adsorbent..
2. It is not specific in nature.
2. It is highly specific in nature.
3. It is reversible in nature.
3. It is irreversible.
4. Enthalpy of adsorption is low (20-40 kJ mol-1 ).
4. Enthalpy of adsorption is high (80-240 kJ mol-1).
5.No appreciable activation energy is needed.
5. High activation energy is sometimes needed.
6. Low temperature is favourable for physisorption. It 6. High temperature is favouable for chemisorption. It
decreases with increase of temperature(adsorption is
increases with the increase of temperature (Activation
exothermic)
energy is required) and then decreases (adsorption is

2
exothermic).
7.It forms multimolecular layers on adsorbent surface. 7. It forms unimolecular layer.
8. It depends on the nature of gas. More easily
8. It also depends on the nature of gas. Gases which
liquefiable gases like NH3, CO2, are adsorbed readily. can react with the adsorbent show chemisorption.
9. It depends on the surface area. It increases with an
9. It also depends on the surface area. It too increases
increase of surface area.
with an increase of surface area.
Factors affecting adsorption of gases on solids:
a. Nature of adsorbate: In physical adsorption, easily liquefiable gases like NH3. HCl, CO2, etc. which have
higher critical temperatures are absorbed to greater extent due to strong intermolecular forces whereas H2,
O2, N2 etc. are adsorbed to lesser extent.
b. Nature of adsorbent:
c. Specific area of the adsorbent: The greater the surface area of adsorbent, more will be the extent of
adsorption. Solids, particularly in finely divided state, have large surface area and therefore, charcoal,
silica gel, alumina gel, clay, colloids, metals in finely divided state, etc. act as good adsorbents. That is why
porous or finely divided forms of adsorbents adsorb larger quantities of adsorbate.
d. Pressure of the gas: Physical adsorption increases with increase in pressure.
Adsorption isotherm:
The variation in the amount of gas adsorbed by the adsorbent with pressure at constant temperature
can be expressed by means of a curve is termed as adsorption isotherm.
a. Freundlich Adsorption isotherm:
The relationship between the quantity of gas adsorbed by unit mass of solid adsorbent (x/m) and
pressure of the gas at constant temperature is called adsorption isotherm and is given by:
Where x- mass of the gas adsorbed on mass m of the adsorbent at pressure P.
k and n depends upon the nature of the adsorbent and the gas at particular temperature.
x/m first increases with increase in pressure at low pressure but becomes independent of pressure at
high pressure.

Taking logarithm on both sides, we get,


If we plot a graph between log x/m and log P, we get a straight line.

3
The slope of the line is 1/n and intercept = log k.
The factor 1/n can have values between 0 and 1 (probable range 0.1 to 0.5).
When 1/n = 0, x/m = constant, the adsorption is independent of pressure.
When 1/n = 1, x/m = k P, i.e. x/m P, the adsorption varies directly with pressure.
b. Freundlich s equation for adsorption from solution: Freundlich s equation describes the behaviour of
adsorption from solution with concentration of the solution. i.e.,
Where C is the equilibrium concentration when adsorption is complete. Taking logarithm on both sides,

Applications of Adsorption
(i) Production of high vacuum: Traces of air can be adsorbed by charcoal from a vessel to give a very high
vacuum.
(ii) Gas mask, consists of activated charcoal or mixture of adsorbents adsorb poisonous gases, used for
breathing in coal mines.
(iii) Silica and aluminium gels adsorbs moisture and control humidity.
(iv) Aqueous solution of raw sugar becomes colourless as the colouring substances are adsorbed by the
charcoal.
(v) Heterogeneous catalysis: Adsorption of reactants on the solid surface of the catalysts increases the rate
of reaction. Manufacture of ammonia using iron as a catalyst, manufacture of H2SO4 by contact process and
use of finely divided nickel in the hydrogenation of oils are excellent examples of heterogeneous catalysis.
(vi) Separation of inert gases: Due to the difference in degree of adsorption of gases by charcoal, a mixture
of noble gases can be separated by adsorption.
(vii) In curing diseases: A number of drugs are used to kill germs by getting adsorbed on them.
(viii) Adsorption indicators: Surfaces of certain precipitates such as silver halides have the property of
adsorbing some dyes like eosin, fluorescein, etc. and thereby producing a characteristic colour at the end pt.
(ix) Chromatographic analysis based on the phenomenon of adsorption finds a number of applications in
analytical and industrial fields.
Catalyst:
Substances which alter the rate of a chemical reaction and themselves remain chemically and quantitatively
unchanged after the reaction are known as catalysts and the phenomenon is known as catalysis.
Promoters: Those substances which increase the activity of catalyst are called promoters
eg: Mo is promoter whereas Fe is catalyst in Haber s Process

Catalytic poisons (Inhibitors): The substances which decrease the activity of catalyst are called catalytic
poisons or inhibitors e.g., arsenic acts as catalytic poison in the manufacture of H2SO4 by contact process
Types of catalysis:
a. Homogeneous catalysis: When the catalyst and the reactants are in the same phase, the catalytic process is
known as homogeneous catalysis.

4
b. Heterogeneous catalysis: When the catalyst and the reactants are in different phases, the catalytic process
is said to be heterogeneous catalysis.
(i)
(ii) Habers process.
(iii) Ostwalds process.
(iv)
Adsorption theory of Heterogeneous catalysis: It explains the mechanism of heterogeneous catalyst.
The mechanism involves 5 steps:1. Diffusion of reactants to the surface of catalyst.
2. Adsorption of reactant molecules on the surface of catalyst.
3. Chemical reaction on the catalyst surface through formation of an intermediate.
4. Desorption of reaction product from the catalyst surface.
5. Diffusion of reaction product away from the catalyst surface.

Activity of catalyst:
The ability of a catalyst to increase the rate of a chemical reaction is called activity of a catalyst.
Selectivity of catalyst:
It is the ability of catalyst to direct a reaction to yield particular product.
For example: CO and H2 react to form different products in presence of different catalysts as follows:

Shape selective catalysis:


The catalytic reaction which depends upon the pore structure of the catalyst and molecular size and shape of
reactant and product molecules is called shape- selective catalysis. E.g. Zeolites are shape selective catalysts
due to their honey- comb structure.
They are microporous aluminosilicates with three dimensional network of silicates in which some silicon
atoms are replaced by aluminium atoms giving AlOSi framework.
Zeolites are widely used as catalysts in petrochemical industries for cracking of hydrocarbons and
isomerisation. An important zeolite catalyst used in the petroleum industry is ZSM-5. It converts alcohols
directly into gasoline (petrol) by dehydrating them to give a mixture of hydrocarbons
Enzymes: Enzymes are complex nitrogenous organic compounds which are produced by living plants and
animals. They are actually protein molecules of high molecular mass. They are biochemical catalysts.

5
Eg:- (i) Inversion of cane sugar:

(ii)
(iii) Conversion of starch into maltose:

(iv)
(v)
(vi) In stomach, the pepsin enzyme converts proteins into peptides while in intestine, the pancreatic trypsin
converts proteins into amino acids by hydrolysis.
(vii) Conversion of milk into curd by lacto bacilli enzyme present in curd.
Mechanism of enzyme catalysis:
1. There are a number of cavities of characteristic shape and possess active groups (active site} such as
-NH2, -COOH, -SH, - OH, etc. present on the surface of colloidal particles of enzymes.
3. These are the active centres on the surface of enzyme particles.
4. The molecules of the reactant (substrate), which have complementary shape, fit into these cavities just
like a key fits into a lock.
5. This specific bonding results in the formation of an activated complex which decomposes to yield the
products.
Steps of enzyme catalysis:
i) Binding of enzyme to substrate to form an activated complex.
ii) Decomposition of the activated complex to form product.

Characteristics of enzyme catalysis:


1. They are highly efficient. One molecule of an enzyme can transform 106 molecules of reactants per minute.
2. They are highly specific in nature, e.g., urease catalysis hydrolysis of urea only.
3. They are active at optimum temperature (298K - 310 K).
4. They are highly active at a specific pH called optimum pH (5-7).
5. Enzymatic activity can be increased in presence of coenzymes (non-protein vitamins) which can be called as
promoters.
6. Activators are metal ions Na+, Co2+ and Cu2+ etc. that are weakly bonded to enzyme and increase its activity.
[Amylase in presence of sodium chloride i.e., Na+ ions are catalytically very active].
7. Enzymes can also be inhibited or poisoned by the presence inhibitors or poisons. [The inhibitors interact
with the active functional groups on the enzyme surface and often reduce or completely destroy the catalytic
activity of the enzymes].Eg: Drug action.
Colloids:
A colloid is a heterogeneous system in which dispersed phase is dispersed as very fine particles in dispersion
medium called dispersed medium. Particle size is in between 1 and 1000 nm.
Dispersed phase: The substance which is dispersed as very fine particles in dispersion medium.
Dispersion medium: The substance present in larger quantity is called dispersion medium.
Distinction between true solution, colloids and Suspension:

6
True solution
It is homogeneous
Its particle size is less than 1nm
It passes through filter paper
It does not show Tyndall effect
Its particles cannot be seen by
microscope

Colloids
It appears to be homogeneous but
actually heterogeneous
Its particle size is 1 1000 nm
It passes through ordinary filter
paper but not through ultra-filters
It shows Tyndall effect
Its particles can be seen by
powerful microscope due to
scattering of light

Suspension
It is heterogeneous
Its particle size is larger than
1000nm
It does not pass through filter
paper.
It does not show Tyndall effect
Its particles can be seen even with
naked eye.

Classification of colloids on the basis of the physical state of dispersed phase and dispersion medium:
Dispersed
Dispersion
name
Examples
phase
medium
Solid
Solid
Solid sol
Some colored glasses and gem stones
Solid
Liquid
Sol
paints , cell fluids
Solid
Gas
Aerosol
Smoke, dust
Liquid
Solid
Gel
Cheese, butter, jellies
Liquid
Liquid
Emulsion
Milk , hair cream
Liquid
Gas
Aerosol
Fog, Mist, Cloud, insecticide sprays
Gas
Solid
Solid sol
Pumice Stone, Foam Rubber
Gas
Liquid
Foam
Froth, whipped cream, soap lather
Classification of colloids on the basis of nature of interaction between dispersed phase and dispersion
medium:
(a) Lyophobic colloid (b) Lyophobic colloid
Lyophilic sols
Lyophobic sols
These colloids are solvent loving.
These colloids are solvent hating.
In these colloids, the particles of dispersed phase have In these colloids the particles of dispersed phase have
great affinity for the dispersion medium.
no affinity for the dispersion medium
They can be prepared by mixing the dispersed phase
They cannot be prepared by mixing the dispersed
and the dispersion medium directly.
phase and the dispersion medium directly. They are
prepared only by special methods
They are stable, cannot be coagulated easily. They do They are not stable, hence coagulated easily. They
not need stabilizing agents for their preservation.
need stabilizing agents for their preservation.
They are reversible sols.
They are irreversible sols.
Eg: starch, gum, gelatin, rubber sols
e.g. metal (gold) sols, metal sulphide sols.
Classification of colloids on the basis of types of particles of the dispersed phase:
a. Multimolecular colloids:
b. Macromolecular colloids:
c. Associated colloids (Micelles):
On dissolution, a large number of
These are the colloids in which the Those colloids which behave as
atoms or smaller molecules of a
dispersed particles are themselves
normal, strong electrolytes at low
substance aggregate together to
large molecules (usually polymers) concentrations, but show colloidal
form species of colloidal size. Eg; of colloidal dimensions.
properties at higher concentrations
gold sol, Sulphur sol.
e.g., Naturally occurring
due to the formation of aggregated
macromolecules - starch, cellulose, particles of colloidal dimensions.
proteins and enzymes; and manSuch substances are also referred
made macromolecules - polythene, to as associated colloids. The
nylon, polystyrene, synthetic
aggregate particles are called
rubber, etc.
micelles. Eg: Soaps and synthetic
detergents.

7
Kraft Temperature (Tk): The temperature above which Micelles are formed is called Kraft temperature.
Critical Micelle Concentration (CMC): The concentration above which Micelles are formed are called
critical micelle concentration.
Soaps: Soaps are sodium or potassium salts of higher fatty acids e.g., sodium stearate CH 3(CH2)16COO-Na+,
Sodium palmitate CH3(CH2)14COO-Na+.
Cleansing action of soaps and detergents: Explain the cleansing action of soap.
The cleansing action of soap is due to emulsification and micelle formation.
Soaps are basically sodium and potassium salts of long chain fatty acids, R-COO-Na+.
A soap molecule consists of two parts polar COO- is hydrophilic and a long hydrocarbon chain (nonpolar) is hydrophobic.
When soap is added to water containing dirt, the soap molecules forms a micelle around the oil
droplet, in such a manner that their hydrophobic parts get attached to the dirt molecule and the
hydrophilic parts point away from the dirt molecule (soluble in water). This is known as micelle
formation.
Thus, the polar group (COO- ) dissolves in water while the non-polar group (hydrocarbon) dissolves
in the dirt particle.
Now, as these micelles are negatively charged, they do not come together and a stable emulsion is
formed. These ionic micelles are then washed with excess of water.

Methods of preparation of colloids:


a. Chemical methods:
1. Oxidation: SO2 +2H2 S 3S (Sol) + 2H2 O
2. Hydrolysis: FeCl3 +3H2O Fe(OH)3(sol) + 3HCl
3. Double decomposition: As2O3 + 3H2S As2S3(sol) + 3H2O
4. Reduction: 2 AuCl3 + 3 HCHO + 3H2O 2Au(sol) + 3HCOOH + 6HCl
b Electrical disintegration or Bredig s Arc method -Preparation of metal sols like gold, silver, platinum.
It involves dispersion as well as condensation. In this method, electric
arc is struck between metal electrodes immersed in the dispersion
medium. The intense heat produced vaporizes the metal which then
condenses to form particles of colloidal size.

c. Peptization: Peptization may be defined as the process of converting a precipitate into colloidal sol by
shaking it with dispersion medium in the presence of a small amount of electrolyte. The electrolyte used for
this purpose is called peptizing agent.
Purification of colloidal sols:
The process used for reducing the amount of impurities to a requisite minimum.
a. Dialysis:
It is a process of removing a dissolved substance from a colloidal solution by means of diffusion through
a suitable membrane.
Particles of true solution can pass through animal membrane but not
the colloidal particles. The

8
apparatus used for this purpose is called dialyser. A bag of suitable
membrane containing the colloidal solution is suspended in a vessel
through which fresh water is continuously flowing. The molecules and
ions diffuse through membrane into the outer water and pure colloidal
solution is left behind.

b. Electro dialysis:
It is a process of removing a dissolved substance from a colloidal solution by means of diffusion through
a suitable membrane under an electric field.
The process of dialysis is quite slow. It can be made faster by applying
an electric field if the dissolved substance in the impure colloidal
solution is only an electrolyte. The ions of the electrolyte migrate
towards the oppositely charged electrodes.

c. Ultrafiltration:
It is the process of separating the colloidal particles from the solvent and soluble solutes present in the
colloidal solution by ultra- filters, which are permeable to all substances except the colloidal particles.
Colloidion is a 4% solution of nitro- cellulose in a mixture of alcohol and ether. An ultra-filter paper may be
prepared by soaking the filter paper in a colloidion solution, hardening by formaldehyde and then finally
drying it.
Properties of colloids:
a. Colour: The colour of colloidal solution depends upon the wavelength of light scattered by the colloidal
particles which in turn depends upon the nature and size of particles. The colour also depends upon the manner
in which light is received by the observer.
b. Brownian movement: It is the zig - zag motion of colloidal particles due to the unbalanced
bombardment of the dispersed particles with the molecules of the dispersion medium.
The Brownian movement has a stirring effect which does not permit the particles to settle and thus, is
responsible for the stability of sols.
c. Colligative properties: Colloidal particles being bigger aggregates, the number of particles is small, hence,
the values of colligative properties are small as compared to values shown by true solutions at same
concentrations..
d. Tyndall effect: It is the scattering of light by colloidal particles due to which path of beam becomes
visible. The bright cone of light is called the Tyndall cone.
Tyndall effect is observed only when (a) The diameter of the dispersed particles is not much smaller than the
wave length of the light used (b) The refractive indices of the dispersed phase and the dispersion medium differ
greatly in magnitude.
e. Charge on colloidal particles: Colloidal particles always carry an electric charge either positive or
negative.
The colloidal particles develop charge due to the following reasons (a) Electron capture by sol particles during
electro dispersion of metals (b) Due to preferential adsorption of ions from solutions (c) Due to formulation of

9
electrical double layer.

When AgNO3 solution is added to KI solution, the precipitated AgI adsorbs I- ions from the dispersion
medium and negatively charged colloidal solution results, AgI/I .
When KI solution is added to AgNO3 solution, positively charged sol results due to adsorption of
Ag+ ions from dispersion medium, AgI/Ag+
If FeCl3 is added to excess of hot water, a positively charged sol of hydrated ferric oxide is formed due
to adsorption of Fe3+ ions, Fe2O3.xH2O/Fe3+ .
When FeCl3 is added to NaOH a negatively charged sol is obtained with adsorption of
OH- ions,Fe2O3.xH2O/OH

f. Helmholtz electrical double layer: When the colloidal particles acquire negative or positive charge by
selective adsorption of one of the ions, it attracts counter ions from the medium forming a second layer.
The combination of fixed and diffused layers of opposite charges around colloidal particles is called
Helmholtz electrical double layer. Eg: AgI/I- K+ & AgI/Ag+Ig. Electrokinetic potential or zeta potential: The potential difference between the fixed layer and the
diffused layer of opposite charges is called electrokinetic potential or zeta potential.
h. Electrophoresis: The movement of colloidal particles towards oppositely charged electrodes under an
applied electric potential is called electrophoresis.
Coagulation or precipitation: The process of settling of colloidal particles as precipitate is called coagulation.

The coagulation of the lyophobic sols can be carried out in the following ways:
(i) By electrophoresis: The colloidal particles move towards oppositely charged electrodes, get discharged and
precipitated.
(ii) By mutual coagulation by mixing two oppositely charged sols: Oppositely charged sols when mixed in
almost equal proportions, neutralise their charges and get partially or completely precipitated. Mixing of
hydrated ferric oxide (+ve sol) and arsenious sulphide (ve sol) bring them in the precipitated forms.
(iii) By boiling: When a sol is boiled, the adsorbed layer is disturbed due to increased collisions with the
molecules of dispersion medium. This reduces the charge on the particles and ultimately gets precipitated.
(iv) By persistent dialysis: On prolonged dialysis, traces of the electrolyte present in the sol are removed
almost completely and the colloids become unstable and ultimately coagulate.
(v) By addition of electrolytes: When excess of an electrolyte is added, the colloidal particles are precipitated.
The reason is that colloids interact with oppositely charged ions causes neutralisation and coagulation.
The ion responsible for neutralisation of charge on the particles is called the coagulating ion. A negative
ion causes the precipitation of positively charged sol and vice versa.
a. Hardy Schulze Rules: i) Opposite charged ions are effective for coagulation.
ii) Greater the valence of the flocculating/ coagulating ion , the greater is its coagulating power.
e.g.

for negatively charged colloids.


for positively charged colloids.

b. Coagulating value of an electrolyte: The minimum concentration of an electrolyte in millimoles per litre
required to cause precipitation of a sol in two hours.

10

Protection of colloids: Lyophilic sols are more stable than lyophobic sols due to extensive solvation.
Protective colloids: When a lyophilic sol is added to the lyophobic sol, the lyophilic particles form a layer
around lyophobic particles and thus protect the lyophobic particles from electrolytes. Lyophilic colloids used
for this purpose are called protective colloids.
Emulsion: colloidal system in which dispersed phase and dispersion medium are liquids. [a liquid is dispersed
in another liquid].
Types of emulsions:
a. Water dispersed in oil: When water is the dispersed phase and oil is the dispersion medium.
E.g. butter, cold cream.
b. Oil dispersed in water: When oil is the dispersed phase and water is the dispersion medium.
E.g. milk, vanishing cream.
Emulsification: The process of stabilizing an emulsion by means of an emulsifier.
Emulsifying agent: The substances which are added to stabilize the emulsions are called
emulsifying agents or emulsifiers. E.g. soaps, gum
Demulsification: The process of breaking an emulsion into its constituent liquids is called demulsification.
This can be done some process like freezing, boiling, centrifugation or by some chemical methods.
Colliods Around Us
(i) Blue colour of the sky: Dust particles along with water suspended in air scatter blue light which reaches
our eyes and the sky looks blue to us.
(ii) Fog, mist and rain: When a large mass of air containing dust particles, is cooled below its dewpoint, the
moisture from the air condenses on the surfaces of these particles forming fine droplets. These droplets being
colloidal in nature continue to float in air in the form of mist or fog. Clouds are aerosols having small droplets
of water suspended in air. On account of condensation in the upper atmosphere, the colloidal water droplets
grow bigger and bigger in size, and come down in the form of rain. Sometimes, the rainfall occurs when two
oppositely charged clouds meet.
It is possible to cause artificial rain by throwing electrified sand or spraying a sol carrying charge opposite to
the one on clouds from an aeroplane.
(iii) Food articles: Milk, butter, halwa, ice creams, fruit juices, etc., are all colloids in one form or the other.
(iv) Blood: It is a colloidal solution of an albuminoid substance. The styptic action of alum and ferric chloride
solution is due to coagulation of blood forming a clot which stops further bleeding.
(v) Soils: Fertile soils are colloidal in nature in which humus acts as a protective colloid. On account of
colloidal nature, soils adsorb moisture and nourishing materials.
(vi) Formation of delta: River water is a colloidal solution of clay. Sea water contains a number of
electrolytes. When river water meets the sea water, coagulation take place. Deposition of coagulated clay
results in delta formation.
Applications of colloids
(i) Electrical precipitation of smoke: Smoke is a colloidal solution of solid particles such as carbon, arsenic
compounds, dust, etc., in air. In Cottrell precipitator, charged smoke particles are passed through a chamber
containing plates with charge opposite to the smoke particles. Smoke particles lose their charge on the plates
and get precipitated.
(ii) Purification of drinking water: Alum is added to water to coagulate the suspended impurities and make
water fit for drinking purposes.
(iii) Medicines: Most of the medicines are colloidal in nature. Colloidal medicines are more effective
because they have large surface area and are therefore easily assimilated. For example, argyrol is a silver
sol used as an eye lotion. Colloidal antimony is used in curing kalaazar. Colloidal gold is used for

11
intramuscular injection. Milk of magnesia, an emulsion, is used for stomach disorders.
(iv) Tanning: Animal hides are colloidal in nature. When a hide, which has positively charged particles, is
soaked in tannin, which contains negatively charged colloidal particles, mutual coagulation takes place. This
results in the hardening of leather. This process is termed as tanning. Chromium salts are also used in place of
tannin.
(v) Cleansing action of soaps and detergents:
(vi) 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.
(vii) Rubber is obtained by coagulation of latex which is a negatively charged colloidal particles.
(viii) Paints, inks, synthetic plastics, rubber, graphite lubricants, cement, etc., are all colloidal solutions.
==============================================================================
Chapter 5: Surface Chemistry
1. Adsorption is always exothermic. Why?
Adsorption decreases the surface energy of the adsorbent, which appears as heat. So it is exothermic.
2. The enthalpy of adsorption of chemisorption is high. Why?
Chemisorption involves chemical bond formation.
3. What is meant by co-enzyme?
The non- protein substance present along with enzymes, which enhances the activity of enzymes
4. 1 gm of activated charcoal adsorb more SO2(g) (critical temperature 630K) than methane (critical
temperature 190K ).Why?
Easily liquefiable gases (higher critical temperature) are easily adsorbed by a solid, because near the critical
temperature the van der Waal forcess between the gas molecules and the solid adsorbents is stronger.
5. Why is FeCl3 preferred over KCl in case of a cut leading to bleeding?
FeCl3 helps in coagulation of blood more effectively than KCl. Greater the valency of coagulating ion, more
will be coagulating power.
7. What are aerosols? Give an eg.

Colloids of a solid in gas. eg :- smoke

8. Why are powdered substances more effective adsorbents than their crystalline forms?
Because powdered form provides more surface area due to which extent of adsorption increases.
9. Give 2 examples of positively charged colloids. (i) haemoglobin (blood) (2) Fe(OH)3 sol
10. Write the suitable adsorbent for the following adsorbate (a) chlorine gas (b) moisture (c) polluting
gases like NO2& SO2 (d) gases like H2,O2,CO etc
(a)Charcoal (b) silica gel (c) charcoal (d) transition metals like Ni, Co etc
11. What happens when?
(a)A beam of light is passed through As2S3 sol - Tyndall effect -The path of the light becomes visible due to
the scattering of light by colloidal particles.
(b) KCl is added to Fe(OH)3sol - Fe(OH)3 sol gets coagulated.
(c) Gelatin is added to gold sol- gold sol gets stabilized.
(d) Colloidal sol of Fe2O3 and As2S3 are mixed- Mutual coagulation i.e,The oppositely charged colloids get
neutralized and gets coagulated.
(e) Alum is added to water for purification- For coagulating suspended impurities like sand & soil particles.
(f) The sky appears blue- Due to scattering of blue light by dust particles.
(g) Freshly prepared Fe(OH)3 is shaken with little amount of dil.FeCl3 A colloidal solution of Fe(OH)3 is
obtained (peptization)

12
(h) Electrodes connected to a battery are dipped into a sol- Electrophoresis i.e, colloidal particles move
towards oppositely charged electrodes.
(i) an electrolyte added to a sol sol get coagulated.
(j) an emulsion is subjected to high speed centrifugation.- Demulsification.
(k) electric current is passed through a colloidal solution electrophoresis.
12. Explain why hydrophilic sols are relatively more stable than hydrophobic sols?
This is because hydrophilic sols are extensively hydrated and there is strong interaction between dispersed
phase and dispersion medium
13. Account for the following:
(a)Fe(OH)3 sol is positively charged- A deep red sol of Fe(OH)3 is obtained by the hydrolysis of FeCl3 . The
sol particles are positively charged because of preferential adsorption of Fe3+ ions.
(b)The extent of physical adsorption decrease with rise in temperature- Adsorption is an exothermic
process. So the rate of physisorption decreases with the rise in temperature in accordance with the Le-Chatlier
principle.
14. Name two industrial heterogeneous catalytic processes.
Haber s process for the manufacture of ammonia iron is used as catalyst
Contact process for the manufacture of sulphuric acid, V2O5is used as catalyst.
15. Explain why deltas are formed where river & sea water meet.
River water (colloidal solution of clay) gets coagulated by electrolytes in sea water so as to form deltas.
16. Cottrell smokes precipitator is fitted at the mouth of the chimney used in factories.
It removes poisonous gases by adsorption & smoke free from poisonous gases comes out. It works on the
principle of electrophoresis.
17. Which one of the following electrolytes is most effective for the coagulation of ferric hydroxide sol
(+ve) & why? (i) NaCl, Na2SO4, Na3PO4.
Na3PO4 is more effective because phosphate ion has highest negative charged ion, greater coagulating power.
18. Which one of the following electrolytes is most effective for the coagulation of As 2S3 sol (-ve) & why?
AlCl3, BaCl2, NaCl
AlCl3
19. What is collodion? What is its use?
Collodion is 4% solution of nitro-cellulose in a mixture of alcohol and ether. Filter paper is soaked in it and
hardened by formaldehyde and dried. Used for making membranes for ultrafiltration, which stops the flow of
colloidal particles.
\
20. The colloidal solution of gold prepared by different methods have different colours. Why?
Due to difference in the size of colloidal particles.
21. A sol is prepared by addition of excess AgNO3 solution to KI solution. What charge is likely to
develop on the colloidal particles?
Positive [AgI/ Ag+]
22. What are the physical states of dispersed phase and dispersion medium of froth?
Dispersed phase is gas, dispersion medium is liquid.
23. What is the cause of Brownian movement among colloidal particles?
Due to collision between colloidal particles and molecules of dispersion medium.

13
24. Arrange the solutions: True solution, colloidal solution, suspension in decreasing order of their
particles size? Suspension > colloidal > true solution.
25. Give an example of micelles system? Sodium stearate (C17 H35 COO- Na+)
26. How is adsorption of a gas related to its critical temperature?
Higher the critical temperature of the gas, greater is the ease of liquefaction. i.e. greater Vander walls forces of
attraction and hence large adsorption will occur.
27. Write down the Example of Negative Sol? Arsenic sulphide.
28. What is difference between Sol. & Gel?
Both are colloidal solutions. Sol has solid as dispersed phase & liquid as dispersion medium. While Gel has
liquid as dispersed phase and solid as dispersion medium.
29. Name the enzyme which converts milk into curd. - Lactobacilli
30. Arrange the gases CO, N2 and CH4 in increasing order of adsorption on the surface of charcoal in a
closed vessel. Give reasons also. N2 < CO < CH4 as critical temp, intermolecular force of attractions ,
Extent of adsorption.
31. A small amount of silica gel and a small amount of anhydrous calcium chloride are placed separately
in two beakers containing water vapour. Name of phenomenon that takes place in both the beakers.
Silica gel - Adsorption, Anhydrous CaCl2 - Absorption, as it forms CaCl2. 2H2O
Intext Questions
5.1 Write any two characteristics of
Chemisorption.[notes pg -1]]
5.2 Why does physisorption decrease with the
increase of temperature?
5.3 Why are powdered substances more effective
adsorbents than their crystalline forms?
5.4 Why is it necessary to remove CO when
ammonia is obtained by Habers process?
5.5 Why is the ester hydrolysis slow in the
beginning and becomes faster after sometime?
5.6 What is the role of desorption in the process of
catalysis.
5.7 What modification can you suggest in the
Hardy Schulze law?

5.8 Why is it essential to wash the precipitate with


water before estimating it quantitatively?
Reader back exercises

[notes pg -1]]
Physisorption is an exothermic process. According to
Le-chateliers principle, it decreases with an increase
in temperature. This means that physisorption occurs
more readily at a lower temperature.
Because powdered form provides more surface area
due to which extent of adsorption increases.
CO acts as catalyst poison for Haber s process
therefore it will lower the activity
CH3COOC2H5 + H2O CH3COOH + C2H5OH
The acid produced in the reaction acts as autocatalyst
and makes the reaction faster.
It makes the surface of the solid catalyst free for the
fresh adsorption of the reactants on the surface.
Hardy-Schulze law states that the greater the valence
of the coagulating ion added, greater is its coagulating
power.
This law takes into consideration only the charge
carried by an ion, not its size. The smaller the size of
an ion, the more will be its polarizing power. Thus
Hardy-Schulze law can be stated as the greater the
polarizing power of the coagulating ion added, the
greater is its coagulating power.
It is done so as to remove soluble impurities adsorbed
on the surface of the ppt.

14
5.1 Distinguish between the meaning of the
terms adsorption and absorption. Give one ex.
5.2 What is the difference between physisorption
and chemisorption?
5.3 Give reason why a finely divided substance is
more effective as an adsorbent.
5.4 What are the factors which influence the
adsorption of a gas on a solid?
5.5 What is an adsorption isotherm? Describe
Freundlich adsorption isotherm.
5.6 What do you understand by activation of
adsorbent? How is it achieved?

5.7 What role does adsorption play in


heterogeneous catalysis?
5.8 Why is adsorption always exothermic ?
5.9 How are the colloidal solutions classified on
the basis of physical states of the dispersed
phase and dispersion medium?
5.10 Discuss the effect of pressure and
temperature on the adsorption of gases on
solids.

5.11 What are lyophilic and lyophobic sols? Give


one example of each type. Why are hydrophobic
sols easily coagulated ?
5.12 What is the difference between
multimolecular and macromolecular colloids?
Give one ex. of each. How are associated colloids
different from these two types of colloids?
5.13 What are enzymes ? Write in brief the
mechanism of enzyme catalysis.
5.14 How are colloids classified on the basis of
(i) physical states of components
(ii) nature of dispersion medium [refer Q. 26]
(iii) interaction between dispersed phase and
dispersion medium?
5.15 Explain what is observed
(i) when a beam of light is passed through a
colloidal sol.
(ii) an electrolyte, NaCl is added to hydrated
ferric oxide sol.
(iii) electric current is passed through a colloid
5.16 What are emulsions? What are their
different types? Give example of each type.

Refer
Refer
Refer
(i) Nature of gas (ii). Nature of adsorbent (iii).
Temp. (iv). Pressure (v). Activation of adsorbent
(vi). Surface area of adsorbent.
Refer
Activation of adsorbent means increasing the
adsorbing power of the adsorbent which can be
achieved by making adsorbent more porous &
rough, by breaking into small pieces or powdering
it, thereby increasing surface area.
Refer
Refer
Refer
Adsorption increases with increase in pressure.
x/m = k P1/n.
Adsorption is exothermic process. Thus in
accordance with Le-Chateliers principle, the
magnitude of adsorption decreases with an increase
in temperature.
Hydrophobic sols are easily coagulated because
they are unstable due to least force of attraction
between dispersed phase and dispersioin medium.
Refer
Refer
Refer

(i)Tyndall effect
(ii)Coagulation, positive hydrated ferric oxide sol
attracts Cl- ion, neutralized and coagulated.
(iv) Electrophoresis
Refer

15
5.17 What is demulsification? Name two
demulsifiers.
5.18 Action of soap is due to emulsification and
micelle formation. Comment.
5.19 Give four ex. of heterogeneous catalysis.
5.20 What do you mean by activity and
selectivity of catalysts?
5.21 Describe some features of catalysis by
zeolites.
5.22 What is shape selective catalysis?
5.23 Explain the foll. terms:(i) Electrophoresis
(ii) Coagulation (iii) Dialysis (iv) Tyndall effect.
5.24 Give four uses of emulsions.

5.25 What are micelles? Give an example of a


micellers system.

5.26 Explain the terms with suitable examples:


(i) Alcosol (ii) Aerosol (iii) Hydrosol.

5.27 Comment on the statement that colloid is


not a substance but a state of substance.

Refer
Refer
Refer
Refer
Refer
Refer
Refer
i. Cleansing action of soaps is based on the
formation of emulsions.
ii. Antiseptics and disinfectants when added to
water form emulsions.
iii. The process of emulsification is used to make
medicines.
iv. Digestion of fats in intestine takes place by the
process of emulsification
Micelle formation is done by substances such as
detergents when dissolved in water. Soap molecules
contain a hydrophobic and hydrophilic part. When
present in water, these substances form a spherical
structures in such a manner that their hydrophobic
part are present towards the centre, while the
hydrophilic parts are pointing towards outside
(water). This is known as micelle formation.Eg:
Sodium stearate C17H35COONa
(i) Alcosol : A colloidal solution having alcohol as
the dm and a solid as the dp. Eg: colloidon
cellulose nitrate in ethanol.
(ii) Aerosol : A colloidal solution having gas as the
dm and a solid/ liquid as the dp. Eg: smoke , fog.
(iii) Hydrosol: A colloidal solution having water as
the dm and a solid / liquid as the dp. Eg: Starch sol,
gold sol.
Common salt (a typical crystalloid in an aqueous
medium) behaves as a colloid in a benzene
medium. Hence, we can say that a colloidal
substance does not represent a separate class of
substances. When the size of the solute particle lies
in between 1 nm - 1000 nm, it behaves as a colloid.
Hence, we can say that colloid is not a substance
but a state of the substance which is dependent on
the size of the particle. A colloidal state is
intermediate between a true solution and a
suspension.