DELHI PUBLIC SCHOOL

CLASS- XII
CHEMISTRY – SURFACE CHEMISTRY

CONCEPT MAP
Module -1
Topic Over View
• Adsorption
• Distinction between adsorption and absorption
• Mechanism of Adsorption
• Types of adsorption
• Characteristics of adsorption
• Effect of temperature and pressure :Adsorption isotherms
• Adsorption from solution phase
• Applications of adsorption

• Video Links

Surface Chemistry
https://www.youtube.com/watch?v=tvmV_fIa52k

Surface Chemistry is the branch of chemistry that deals with the

phenomenon that occurs on surfaces or interfaces, such phenomena
include corrosion. catalysis, electrode processes etc.
Adsorption
The phenomenon of attracting and retaining the molecules of a
substance by a solid (or a liquid) on its surface resulting into a higher
concentration of the molecules on the surface is known as adsorption.
Examples

(i)If a gas like O2 , H2 , CO, Cl2 , NH3 or SO2 is taken in a closed vessel
containing powdered charcoal, it is observed that the pressure of the gas
in the enclosed vessel decreases.

(ii) In a solution of an organic dye, say methylene blue, when animal

charcoal is added and the solution is well shaken, it is observed that the
colour of the dye fades.

(iii) Aqueous solution of raw sugar, when passed over beds of animal
charcoal, becomes colourless as the colouring substances are adsorbed
by the charcoal.
(iv) The air becomes dry in the presence of silica gel because the water
molecules get adsorbed on the surface of the gel.

Adsorbent, and Adsorbate

• The substances which attracts and retains molecules on its surface ,
is called absorbent.
• The molecular species that accumulate on the surface of adsorbent
is called adsorbate.

• Difference between adsorption and adsorption

Adsorption
It is the phenomenon of higher
concentration of particles of
gas or liquid on the surface of
the solid.
It is a surface phenomenon.
E.g. silica gel adsorbs water
vapor.
Absorption
It is the phenomenon in which the
particles of gas or liquid get uniformly
distributed throughout the bulk of the
solid.
It , is a bulk phenomenon.
E.g., anhydrous calcium chloride
absorbs moisture.

Sorption : In some cases, both adsorption and absorption occur

together and are not distinguishable. In such cases, the substance get
uniformity distributed into the bulk of the solid, but at the same time
its concentration is higher at the surface then the bulk. This is called
sorption.
E.g. – (i)Dye gets adsorbed as well as absorbed in cotton fibers i.e.
sorption takes place.

(ii)When a chalk stick is dipped in ink, the surface retains the colour
of the ink due to adsorption of coloured molecules while the solvent
of the ink goes deeper into the stick due to absorption. On breaking
the chalk stick, it is found to be white from inside.
Desorption :The process of removing an adsorbed substance from a
surface on which it is adsorbed is called desorption.

Mechanism of adsorption

https://www.youtube.com/watch?v=hcQNcTo5F0A

When we consider a solid, or a liquid it is observed that a molecules

present in the bulk of the solid is uniformly attracted from all sides by
the neighboring molecules. As a result, there is no net pull on this
molecule.
But a molecule which is near the surface is being attracted only by
molecule below it and these molecules exert a resultant downward
force. As a result, the surface of solid and liquid, tends to satisfy their
residual forces by attracting and retaining the molecules of other species
on the surface.
Adsorption is exothermic

In adsorption there is always a decrease in residual forces of the surface,

i.e., there is decrease in surface energy which appears as heat.
Adsorption, therefore, is invariably an exothermic process. In other
words, ∆H of adsorption is always negative.

Thermodynamic aspects of adsorption

• When a gas is adsorbed, the freedom of movement of its molecules

become restricted. This amounts to decrease in the entropy of the
gas after adsorption, i.e., ∆S is negative.
• For a process to be spontaneous, , ∆G = ∆H – T∆S must be
negative,
• ∆G can be negative if ∆H has sufficiently high negative value.
• As the adsorption proceeds, ∆H becomes less and less negative
ultimately ∆H becomes equal to T∆S and ∆G becomes zero. At this
state equilibrium is attained.
Types of Adsorption
https://www.youtube.com/watch?v=8QH853ffG2U&t=6s
Physical Adsorption
(Physisorption)
Weak Wanderwaals force
exist between adsorbent and
adsorbate.
The heats of adsorption are
low, viz., about 20 – 40kJ mol-1 about 80-240 kJ mol-1
.
The process is reversible.
It is not specific in naure.
If forms multimolecular layer. If forms unimolecular layer.
Adsorption is exothermic in
nature ,therefore according to
LeChatelier’s Principle
,physisorption decreases with
increase in temperature
Chemical Adsorption
(Chemisorption)
Chemical bond exists between
adsorbent and adsorbate.
The heats of adsorption are high, viz.,
The process is irreversible.
It is specific in nature
For chemisorption the adsorption
initially increases with rise in
temperature and
then decreases..
This is because as
the temperature
increase the
molecules of the
adsorbate gain energy and become
equal to or greater than activation
energy. Further increase will increase
the energy of the molecules adsorbed
and will increase the rate of desorption
and the extent of adsorption decrease.
Effect of pressure on adsorption (Adsorption of gas on solid)
The groph showing variation in the amount of gas adsorbed by the
adsorbent with pressure at constant temperature is termed as
adsorption isotherm

Freundlich Adsorption Isotherm

:The adsorption of a gas on a solid surface increases with increase in
pressure. The variation of adsorption with pressure at constant
temperature can be represented by the equation
1
x
= kp n ,(n>1)
m

where x is the mass of the gas adsorbed, and m is the mass of the solid
adsorbent at pressure p. k and n are constants which depend on the
nature of adsorbent and the gas.
The plot of x/m vs P at various temperature are shown in the fig.

The extend of adsorption increase with increase in pressure and

becomes maximum at Ps called the equilibrium pressure or saturation
pressure. Any further increase in pressure does not affect the extend of
adsorption.
1
• have values between 0 and 1.
n
 • 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

The above equation can be written as

x 1
log = log k +   log p
m n

Thus a plot of log   vs. log p will be a straight line with a slope of
x 1
m n
and Y intercept log K.

Frendlich Adsorption isotherm is applicable for a range of pressure

and it fails at high pressure of gas.

Summarizing the above facts it is seen that the extent of adsorption of a

gas on a solid depends upon the following factors:

(i) Nature of the adsorbate - Easily liquefiable gase can be

physisorbed easily. Greater the critical temperature of the gas,
more easily it will be liquefied, and more readily it will be
adsorbed.
(ii) Nature and specific area of the adsorbent.-Specific area is the
surface area available per gram of the adsorbent. Greater specific
area, more will be the adsorption.

(iii) Effect of pressure

(iv) Effect of temperature

ADSORPTION FROM SOLUTIONS

Solids can adsorb solutes from solutions.
e.g. When a solution of acetic acid is shaken with charcoal, some acetic
acid will be adsorbed by charcoal and the conc of acetic acid in the
solution decreases.
The extend of adsorption from solution phase
(a) decrease with increase in temperature.
(b) increase with increase in surface area.
(c) depends on conc. of solute in solution.
(d) depends on nature of adsorbent and adsorbate.
Freundlich adsorption isotherm is also applicable in the adsorptions
from solutions. In such cases instead of equilibrium pressures, we use
equilibrium concentrations. For adsorption from solutions
1
x
= kc n
m (n > 1)

Applications of Adsorption

https://www.youtube.com/watch?v=FRX_UABBDKU

(i)Production of high vacuum: The remaining traces of air can be

adsorbed by charcoal from a vessel evacuated by a vacuum pump to
give a very high vacuum.
(ii) Gas masks: Gas mask (a device which consists of activated charcoal
or mixture of adsorbents) is usually used for breathing in coal mines to
adsorb poisonous gases.

(iii) Control of humidity: Silica and aluminium gels are used as

adsorbents for removing moisture and controlling humidity.

(iv) Removal of colouring matter from solutions: Animal charcoal

removes colours of solutions by adsorbing- coloured impurities.

(v) 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
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 on coconut charcoal at different temperatures.

(vii) In curing diseases: A number of drugs are used to kill germs by

getting adsorbed on them.

(viii) Froth floatation process: A low grade sulphide ore is concentrated

by separating it from silica and other earthy matter by this method using
pine oil and frothing agent.

(ix) 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 point.

(x) Chromatographic analysis: Chromatographic analysis based on the

phenomenon of adsorption finds a number of applications in analytical
and industrial fields.

Solved questions

Q.What is meant by activation of adsorbent?

Ans: It means increasing the adsorbing capacity of adsorbent. It can be
achieved by powdering, heating the adsorbent in steam etc.
Q.Which will be adsorbed more readily on the surface of charcoal and
why ?NH3 or CO2.
Ans: Ammonia, as its critical temperature is high.
Q. . Give reasons:
(a) When animal charcoal is added to solutions of organic dye or
to aqueous solution of raw sugar it turns colourless.
Ans: Charcoal adsorbs coloured dye.
(b) Air becomes dry in presence of silica gel.
Ans:Silica gel adsorbs moisture.

Q. Why is adsorption exothermic?

Ans: During adsorption there is a decrease in residual force on surface
or there is a decrease in surface energy which appears as heat
making H negative.

Q. During adsorption entropy of the system decreases ,still it is a

spontaneous process. Explain.
Ans: During adsorption S = -ve (as the randomness decreases).
We know that G = H – T S
G will be negative if H has sufficiently high negative values and
the process will be spontaneous. But as adsorption proceeds, H
becomes less and less negative and become equal to TS and G
becomes zero. At this stage equilibrium is attained.

Assignments
I. MCQ
1.. At the equilibrium position in the process of adsorption ___________.
(i) ΔH > 0 (ii) ΔH = TΔS
(iii) ΔH > TΔS (iv) ΔH < TΔS
2.. The term ‘sorption’ stands for ____________.
(i) absorption (ii) adsorption
(iii) both absorption and adsorption (iv) desorption
3.Extent of physisorption of a gas increases with ___________.
(i) increase in temperature. (ii) decrease in temperature.
(iii) decrease in surface area of adsorbent. (iv) decrease in strength of
van der Waals forces.
4.. Extent of adsorption of adsorbate from solution phase increases with
________.
(i) increase in amount of adsorbate in solution.
(ii) decrease in surface area of adsorbent.
(iii) increase in temperature of solution.
(iv) decrease in amount of adsorbate in solution.
5. Which one of the following is not applicable to the phenomenon of
adsorption?
(i) ΔH > 0 (ii) ΔG < 0
(iii) ΔS < 0 (iv) ΔH < 0
6.. Physical adsorption of a gaseous species may change to chemical
adsorption
with ______________.
(i) decrease in temperature (ii) increase in temperature
(iii) increase in surface area of adsorbent (iv) decrease in surface area of
adsorbent
7.. In physisorption adsorbent does not show specificity for any
particular gas because
(i) involved van der Waals forces are universal.
(ii) gases involved behave like ideal gases.
(iii) enthalpy of adsorption is low.
(iv) it is a reversible process.
8.. Which of the following is an example of absorption?
(i) Water on silica gel (ii) Water on calcium chloride
(iii) Hydrogen on finely divided nickel (iv) Oxygen on metal surface
II. NCERT intext questions
5.1Write any two characteristics of Chemisorption.
5.2 Why does physisorption decrease with the increase of temperature?
5.3 Why are powdered substances more effective adsorbents than their
crystalline forms?
III.NCERT Exercises
5.1 Distinguish between the meaning of the terms adsorption and
absorption. Give one example of each.
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