JEE Advanced Revision Notes

Chemistry
Surface chemistry

Surface is an outermost or uppermost layer of a physical object or space.

Absorption:
● The phenomenon by which the molecules of a substance are attracted and
uniformly distributed into the bulk of another solid or liquid substance is
called absorption.
Example: Ink gets absorbed into the bulk of a piece of chalk. Water
molecules are absorbed into anhydrous calcium chloride.
● The molecules present on the surface of a substance are of greater energy
than the molecules present in the bulk of the substance.

Adsorption:
● The phenomenon of attracting and subsequently accumulating the
molecules of a substance by a liquid or solid on its surface is called
Adsorption.
● The surface molecules show a greater tendency to attract the molecules of
other substances, allowing them to settle on their surface and overcome
unbalanced forces.
● The substance getting adsorbed on the surface of other substances is called
adsorbate.
● Adsorbate can be solid or liquid, or gas.
● The substance providing its surface for the adsorption phenomenon is
called adsorbent.
● Adsorbent can be solid or liquid but not gas.
Example: Important absorbents are activated charcoal, silica gel, alumina
gel, clay, and colloidal particles.
● During adsorption, there is a decrease in the forces on the surface. As a
result, heat is liberated.
● H is negative, and S is negative for the adsorption process.

Free energy change, Entropy change, and Enthalpy change during

Adsorption:

Class XII Chemistry www.vedantu.com 1

 ● As adsorption is a spontaneous process, change in free energy  ΔG  for
the process is negative.
S is -ve because adhering gas molecules to the surface lowers the randomness.
Further, G  H  T S
As S is -ve,  G  can be -ve only if H is -ve. Hence, adsorption is always
exothermic.
● Adsorption is accompanied by a decrease in the system's free energy. When
G becomes zero, adsorption equilibrium is established, i.e., Rate of
adsorption = Rate of desorption.

Positive and Negative Adsorption:

● When the concentration of the adsorbate is more on the surface of the
absorbent than in bulk, it is called positive adsorption.
● If the adsorbate concentration is less on surface relative to its concentration
in bulk, it is called Negative adsorption.

Difference between physisorption and chemisorption:

S.No. Property Physisorption Chemisorption

1 Nature of adsorption Adsorption is weak Adsorption is strong

Easy since weak Vander Not easy since
2 Ease of desorption Waals forces are chemical forces are
involved involved
Reversibility of Reversible and occurs Irreversible and
3
process. rapidly occurs slowly
Insignificant and very Significant and
4 Energy of activation
low. relatively high
Highly specific since
Not specific since it
Specificity of it takes a place on a
5 takes place on the
adsorption. specified surface with
surface of any solid
only
The extent of adsorption
Effects of temperature The Extent of
6 decreases with an
on adsorption. adsorption increases
increase in temperature

Class XII Chemistry www.vedantu.com 2

 with increase in
temperature
Increases with a the
increase in pressure of Pressure of adsorbate
Effect of pressure on
7. adsorbate gas and gas has a negligible
absorption
finally attain a limiting effect
value
Several adsorbate
8. Usually, multi-layered Only uni-layered
layers formed
Depending on the
Depends on the nature
Dependence on the nature of absorbate as
of adsorbate gas only,
9. nature of the adsorbate well as adsorbent. No
Easily liquefiable gases
and the adsorbent correlation can be
are readily adsorbed
given
Increases with increases Increases with
Surface area of
10 in surface area of increases in surface
absorbent
adsorbent area of adsorbent

Catalyst:
● A catalyst is a substance that increases the rate of a chemical reaction to
which it is added without itself being consumed in the reaction.
● The substance which destroys or reduces the activity of the catalyst is
known as catalytic poison. The phenomenon is called catalytic poisoning.
● AS2O3 acts as a poison for platinum in the Contact process of manufacture
of H2SO4 . H2S acts as a poison for Fe catalyst in Haber's process. CO
poisons platinum in the oxidation reaction of H 2 to H 2O
● A substance that promotes the activity of the catalyst, to which it is added
in small amounts is called a promoter or activator. The process is known
as activation.
● Molybdenum (MO) is a promoter to the catalyst iron in the Haber process.
● The presence of a foreign substance which retards the rate of a reaction is
called a negative catalyst or inhibitor. The phenomenon is negative
catalysis.
● In homogeneous catalysis, the catalyst and the reactants are in the same
phase. It is not possible in solid-state.

Class XII Chemistry www.vedantu.com 3

 ● In heterogeneous catalysis, the catalyst is in a different phase from the
reactants.
● The action of a catalyst is explained by two different theories: Intermediate
compound formation theory and the adsorption theory.
● A positive catalyst lowers the activation energy of the reaction by
providing a new pathway.
● When one of the intermediates formed in a reaction itself acts as a catalyst
for the reaction, the catalysis is called autocatalysis.
● Mn2 in the oxidation of oxalic acid by acidified KMnO4 and As in the
decomposition of arsenic are examples.
● The nature of a catalyst to speed up a reaction is called activity. The nature
of a catalyst to lead the reaction towards a specific product is called
selectivity.
Enzymes:
● Enzymes are biological catalysts produced by living plants and animals
which catalyze the biochemical reaction in living organisms. The activity
of enzymes can be increased in the presence of co-enzymes and activators.
● Enzyme catalyzed reaction proceeds in two steps:
E + S →ES and ES →E+P

Aggregation methods:
● These involve the joining together of a large number of smaller particles to
form colloidal particles. This is done by the following methods
● By double decomposition:
As2O3 aq   3H 2 S( aq )  As2 S3  3H 2O
● By reduction:
2 AuCl3( aq )  3SnCl2( aq )  2 Au  3SnCl4
● By oxidation:
Br2 aq   H 2 S aq   S  2 HBr
● By hydrolysis:
FeCl3  3H 2O  Fe(OH )3  3HCl
● Ultrasonic dispersion: In this method, ultrasonic vibrations having a
frequency more than audible range can change the suspension or liquids
like oil, mercury, etc., colloidal range.

Class XII Chemistry www.vedantu.com 4

 ● If a colloidal sol contains all colloidal particles of nearly the same size, it
is called a monodisperse colloid. However, if it contains colloidal particles
of different sizes, it is called polydisperse colloid.
● The presence of trace amounts of the electrolyte is essential for the stability
of the colloidal sol, whereas the presence of large amounts results in
coagulation.

The dialysis process finds application in the purification of blood by the artificial
kidney. This method introduces impure blood into the artificial kidney apparatus
when the waste materials (electrolytes) diffuse through the dialyzing membrane.
At the same time, colloidal blood particles are retained, and blood is purified.

Tyndall effect:
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. There is a large difference in the refraction index of the dispersed phase
and the dispersion medium.

Coagulation:
● The stability of lyophobic sols is due to the presence of charge on colloidal
particles.
● If the charge is removed, the particles will come near each other to form
aggregates and settle down under the force of gravity.
● The process of settling colloidal particles is called coagulation.
● This is also called Flocculation or precipitation of the sol.

The minimum amount of the electrolyte in millimoles must be added to one litre
of the colloidal sol to bring about complete coagulation or precipitation.
● The smaller the flocculation value of an electrolyte, the greater its
coagulating or precipitating power.
● As coagulating power is Inversely proportional to coagulation or
flocculation value, to compare the relative coagulating powers of two
electrolytes for the same colloidal sol we have the relation
Coagulating power of electrolyte 1 Coagulating value of electrolyte 2

Coagulating power of electrolyte 2 Coagulating value of electrolyte 1

Class XII Chemistry www.vedantu.com 5

Coagulating value of electrolyte I Coagulation can also be caused by
electrophoresis, mutual precipitation (mixing colloidal sols of opposite charge),
and prolonged dialysis or by heating or cooling the sol.

The isoelectric point of a colloid:

● In the case of certain lyophilic sols, particularly proteins, the charge sign
depends upon the pH. The particles are negatively charged, while they have
a positive charge below this pH.
● At one particular pH, the particles are uncharged and, therefore, do not
migrate under the influence of an electric field. This pH is called the
isoelectric point of the. For example, for gelatine, the pH is 4.7; for casein,
it is 4.1 — 4.7, and for haemoglobin, it is 4.3 — 5.3.

Sedimentation potential and Dorn effect:

● The reverse of electrophoresis. The sedimentation potential is set up when
a particle is forced to move in a resting liquid.
● The phenomenon discovered by Dorn is also known as the drone effect.

Hardy-Schulze laws:
The ion with a charge opposite to the charge of the colloidal particle is very
effective. The greater the charge of the ion greater the ability for coagulation.
● Positive colloids are coagulated by negative ions and decreasing order of
4
effectiveness is:  Fe  CN 6   PO43  SO42  Cl 
● Positive colloids are coagulated by positive ions and decreasing order of
effectiveness is: Al 3  Ba 2  K  .

Emulsion:
● An emulsion is a colloidal system in which both the dispersed phase and
the dispersion medium are liquids.
● Emulsion is classified into two classes:
i. Oil in water (O/W) emulsion.
ii. Water in oil (W/O) emulsion.
● The emulsifying agent is usually a soap or a sulfate detergent (or) a
hydrophilic colloid (like gelatine, egg albumin, carbon powder, or graphite
powder).

Class XII Chemistry www.vedantu.com 6

 ● Soap emulsifies kerosene in water emulsion. Egg albumin emulsifies an
olive oil in water emulsion. Solid mercuric iodide emulsifies water in
benzene emulsion. Casein emulsifies oil in water (milk) emulsion.
● Emulsions are used in the washing process of clothes and crockery, in the
digestion of in intestines, in metallurgy, like lotions, creams, and ointments
in pharmaceuticals and cosmetics, as drugs of oily type in the form of
emulsions to facilitate their easy absorption.
● Emulsion can be broken into constituent liquid by heating, freezing, etc.
This is called demulsification.
Example: The churning of curd
● Emulsions are used to convert cream into butter by churning. This is the
breaking of an emulsion of fats in water. In natural oil wells, oils and water
form emulsions that require oil separation from water.

Solved questions:
Q 1. One gram of charcoal adsorbs 100 mL of 0.5M CH3COOH to form a
monolayer. Thereby the molarity of acidic acid is reduced to 0.49M.
Calculate the charcoal surface area adsorbed by each acetic acid molecule.
(Surface area of charcoal is (3.01×102 m 2 / g) .
Ans: Number of moles of acetic acid before the adsorption=
Molarity  Volumeof solution 100
= 0.5   0.05
1000 1000
100
Number of moles of acetic acid after the adsorption= 0.49   0.049.
1000
Number of molecules of acetic acid adsorbed= 0.001 6.023  1023  6.023  1020
Surface area of the charcoal occupied by each acetic acid molecule=
3.01 102
 5  1019 m2 .
6.023  10 20

Q 2. Is it possible to know the size and shape of colloidal particles by using

ultramicroscope
Ans: With the ultramicroscope, we can see only the light scattered by the
colloidal particles, but not an actual colloidal particle.
Thus, an ultramicroscope does not provide any information about the size and
shape of the colloidal particle.

Class XII Chemistry www.vedantu.com 7