‘ADSORPTION

When a solid surface is exposed to a gas or a liquid, molecules from the gas or the
solution phase accumulate or concentrate at the surface.

The phenomenon of concentration of molecules of a gas or liquid at a solid

surface is called adsorption.
The substance that deposits at the surface is called Adsorbate and the solid on
whose surface the deposition occurs is called the Adsorbent.

Adsorption versus absorption (illustration).

Examples of Adsorption

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(1) Adsorption of a dye by a charcoal. If finely divided charcoal is stirred into a
dilute solution of methylene blue (an organic dye), the depth of colour of the
solution decreases appreciably. The dye molecules have been adsorbed by charcoal
particles.
(2) Adsorption of a gas by charcoal. If a gas (SO2, Cl2, NH3) is treated with
powdered charcoal in a closed vessel, the gas pressure is found to decrease. The
gas molecules concentrate on charcoal surface and are said to be adsorbed.
Adsorption versus Absorption
The term ‘adsorption’ must be carefully distinguished from like-sounding term
‘absorption’. While adsorption implies deposition at the surface only,
absorption implies penetration into the body of the solid For illustration a chalk
crayon when dipped in ink adsorbs the latter and on breaking it is found to be
white from within. On the other hand, water is absorbed by a sponge and is
distributed throughout the sponge uniformly.
Both adsorption and absorption often take place side by side. It is thus difficult to
distinguish between the two processes experimentally. Mc Bain introduced the
general term Sorption which includes both the adsorption and absorption

Mechanism of Adsorption
Atoms or molecules of a solid surface behave like the surface molecules of a
liquid. These are not surrounded by atoms or molecules of their kind. Therefore,
they have unbalanced or residual attractive forces on the surface which can hold
adsorbate particles.

The adsorbed atoms or molecules can be held on the surface of a metal such as
platinum (Pt) by physical van der Waal’s force or chemical forces due to residual

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valence bonds. Thus the adsorption of hydrogen on platinum may take place in two
ways (molecularly or atomically as shown above).

TYPES OF ADSORPTION
The adsorption of a gas into a solid surface is mainly of two types :
(a) Physical Adsorption
This is due to the gas molecules being held to the solid surface by van der
Waal’s attractive forces. It is also referred to as van der Waal’s Adsorption. For
example, adsorption of hydrogen or oxygen on charcoal is Physical Adsorption.
(b) Chemical Adsorption or Chemisorption
In this kind of adsorption, the gas molecules or atoms are held to the solid
surface by chemical bonds. These bonds may be covalent or ionic in nature. For
example, hydrogen is chemisorbed on nickel. A hydrogen molecule is first
adsorbed by van der Waal’s forces and then dissociates. The hydrogen atoms are
thus chemisorbed on nickel.

ADSORPTION OF GASES BY SOLIDS

The adsorption of gases by solid adsorbents has certain characteristic feature.
Physical adsorption and chemisorption are found to differ in many respects.

(1) Adsorption and Surface area

Adsorption being a surface phenomenon, the extent of adsorption depends on the
surface area.
Increase in the surface area of the adsorbent, increases the total amount of the
gas adsorbed. Thus finely divided metals (nickel, platinum) and porous substances
(charcoal, silica gel) provide a large surface area and are best solid adsorbents.

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(2) Nature of Gas
The amount of gas adsorbed by a solid depends on the nature of the gas. In
general, more easily liquefiable a gas is (i.e., higher its critical temperature ),
the more readily will it be adsorbed. Thus
1 g of activated charcoal adsorbs 380 ml of sulphur dioxide (critical temperature
157°C), 16 ml of methane (critical temperature – 83°C) and 4.5 ml of hydrogen
(critical temperature –20°C).
Chemisorption on the other hand, is much more specific than physical adsorption.
However, it will not occur when there is some possibility of chemical action
between the gas adsorbed and the solid.

(3) Heats of Adsorption

Heat of adsorption is defined as the energy liberated when 1 gm mole of a gas
is adsorbed on the solid surface. In physical adsorption, gas molecules
concentrate on the solid surface. Thus it is similar to the condensation of a gas to
liquid. Therefore, adsorption like condensation is an exothermic process. Since
the attractions between gas molecules and solid surface are due to relatively weak
van der Waal’s forces, heats of adsorption are small (about 5 kcal mol–1).
In chemisorption the attractive forces are due to the formation of true chemical
bonds. Therefore, the heats of adsorption are large (20 to 100 kcal mol–1).

(4) Reversible character

Physical adsorption is a reversible process. The gas adsorbed onto a solid can be
removed (desorbed) under reverse conditions of temperature and pressure. Thus,
Gas Gas/Solid + Heat
Chemisorption, on the contrary, is not reversible because a surface compound is
formed.

(5) Effect of temperature

Physical adsorption occurs rapidly at low temperature and decreases with
increasing
temperature (Le Chatelier’s Principle).
Chemisorption, like most chemical changes, generally increase with
temperature. Thus a rise
of temperature can often cause physical adsorption to change to chemisorption.
Nitrogen, for example,
is physically adsorbed on iron at 190°C but chemisorbed to form a nitride at
500°C.

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(6) Effect of pressure
Since a dynamic equilibrium exists between the adsorbed gas and the gas in
contact with the solid as stated in (4), Le Chatelier’s Principle is applied. Actually
it has been found that increase of pressure leads to increase of adsorption and
decrease of pressure causes desorption.
(7) Thickness of Adsorbed layer of gas
From a study of the isotherms relating to the amount of gas adsorbed to the
equilibrium pressure,
Langmuir showed that at low pressure, the physically adsorbed gas forms only one
molecular thick layer. However, above a certain pressure, multimolecular thick
layer is formed.

COMPARISON OF PHYSICAL ADSORPTION AND CHEMISORPTION

Physical adsorption
1. Caused by intermolecular van der Waal’s forces.
2. Depends on nature of gas. Easily liquefiable gases are adsorbed readily.
3. Heat of adsorption is small (about 5 kcal mol–1).
4. Reversible.
5. Occurs rapidly at low temperature; decreases with increasing temperature.
6. Increase of pressure increases adsorption; decrease of pressure causes
desorption.
7. Forms multimolecular layers on adsorbent surface.
Chemisorption
1. Caused by chemical bond formation.
2. Much more specific than physical adsorption.
3. Heat of adsorption is large (20–100 kcal mol–1).
4. Irreversible.
5. Increases with increase of temperature.
6. Change of pressure has no such effects.
7. Forms unimolecular layer.

In chemisorption, the adsorbed layer of gas is one-molecule thick since

chemical combination can take place with the adsorbent surface only directly.

ADSORPTION ISOTHERMS
The adsorption of a gas on a solid adsorbent in a closed vessel is a reversible
process.
Free Gas Gas adsorbed on solid

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The amount of the gas adsorbed depends on equilibrium pressure (P) and
temperature.

The relationship between the equilibrium pressure of a gas and its amount
adsorbed on the solid adsorbent at any constant temperature is called an
Adsorption isotherm. It may be given in the form of an equation or graphical
curve.
Freundlich Adsorption Isotherm
Freundlich proposed an empirical relation in the form of a mathematical equation.

𝑊
=k𝑃1/2
𝑀

where w is the mass of the gas adsorbed on a mass m of adsorbent at a pressure P;

k and n are constants depending on the nature of the gas and the adsorbent and on
temperature. This relation is generally represented in the form of a curve obtained
by plotting the mass of the gas adsorbed per unit mass of adsorbent (w/m) against
equilibrium pressure.

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This is equation for a straight line. Thus a plot of log (w/m) against log P should be
a straight line with slope 1/n and intercept log k. However, it is actually found that
the plots were straight lines at low pressures, while at higher pressure they showed
a slight curvature, especially at low temperature. This indicated that Freundlich
equation is approximate and does not apply to adsorption of gases by solids at
higher pressures.

LANGMUIR ADSORPTION ISOTHERM

Langmuir (1916) derived a simple adsorption isotherm based on theoretical
considerations. It was named after him.
Assumptions
Langmuir made the following assumptions.
(1) The layer of the gas adsorbed on the solid adsorbent is one-molecule thick.
(2) The adsorbed layer is uniform all over the adsorbent.
(3) There is no interaction between the adjacent adsorbed molecules.

Derivation of Langmuir Isotherm

Langmuir considered that the gas molecules strike a solid surface and are thus
adsorbed. Some of these molecules then evaporate or are ‘desorbed’ fairly rapidly.
A dynamic equilibrium is eventually established between the two opposing
processes, adsorption and desorption.
If θis the fraction of the total surface covered by the adsorbed molecules, the
fraction of the naked area is (1 – θ). The rate of desorption (Rd) is proportional
to the covered surface θ. Therefore,

where kd is the rate constant for the desorption process.

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The rate of adsorption (Ra) is proportional to the available naked surface (1 –
θ) and the pressure (P) of the gas.

where ka is rate constant for the adsorption process.

At equilibrium the rate of desorption is equal to the rate of adsorption. That is,

where K is the equilibrium constant and is referred to as the adsorption coefficient.

The amount of the gas adsorbed per gram of the adsorbent, x, is proportional to θ
Hence,

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Or

where K' is a new constant. Equation (1) gives the relation between the amount of
gas adsorbed to the pressure of the gas at constant temperature and is known as
Langmuir Adsorption isotherm.
In order to test the Langmuir isotherm, equation (1) is rearranged so that

The equation (2) is similar to an equation for a straight line. Thus if P/x is plotted
against P, we should get a straight line with slope 1/K'' and the intercept 1/K'. It
was found in most cases that the actual curves were straight lines. Thus Langmuir
isotherm stood verified

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As stated above, Langmuir Adsorption isotherm may be written as

If the pressure (P) is very low, the factor P/K'' may be ignored and the isotherm
assumes the form

x = K' P (at low pressure)

If the pressure (P) is very high, the factor 1/K' may be ignored and the isotherm
becomes

x = K'' (at high pressure)

Hence, at low pressures, the amount of gas adsorbed (x) is directly proportional to
pressure (P).
At high pressures the mass adsorbed reaches a constant value K'' when the
adsorbent surface is completely covered with a unimolecular layer of the gas. At
this stage adsorption is independent of pressure.

ADSORPTION OF SOLUTES FROM SOLUTIONS

Porous or finely divided solid substances can also adsorb dissolved substances
from solution.
Thus activated charcoal is used to remove colored impurities from solutions.
Charcoal will also adsorb many dyestuffs. When a solution of acetic acid is shaken
with activated charcoal, part of the acid is removed by adsorption and
concentration of solution is decreased. Again, precipitates obtained in qualitative
analysis often act as absorbents. For example, magnesium hydroxide when
precipitated in the presence of the dye-stuff magneson forms a blue ‘lake’.
Adsorption from solution generally follows the same principles as laid down
for adsorption of gases by solids and is subject to the same factors. Thus,
(1) Some adsorbents specifically adsorb certain solutes more effectively than
others.
(2) An increase of temperature decreases the extent of adsorption.
(3) An increase in surface area increases the extent of adsorption.
(4) Adsorption of solutes also involves the establishment of equilibrium between
the amount adsorbed and the concentration of the solute in solution.

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The precise mechanism of adsorption from solution is not clear. However there is a
limit to the adsorption by a given mass of adsorbent and hence possibly adsorption
takes place unless a unimolecular layer is formed. Freundlich Isotherm, using
concentration instead of pressure is obeyed by adsorption from solution.
That is,

where w = mass of solute adsorbed on a mass m of adsorbent ; C = equilibrium

concentration of the solution ; and k and n are constants. Taking logs of the above
equation

This implies that a plot of log w/m against log C should be a straight line. The
validity of Freundlich isotherm has been tested by plotting the experimental values
of log w/m versus log C determined for adsorption of acetic acid on charcoal at
25°C.

APPLICATIONS OF ADSORPTION

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Adsorption finds numerous applications both in the laboratory and industry. Some
of these are listed below.
(1) Production of high vacua

If a partially evacuated vessel is connected to a container of activated charcoal

cooled with liquid air, the charcoal adsorbs all the gas molecules in the vessel. This
results in a very high vacuum.
This process is used in high vacuum equipments as Dewar flask for storage of
liquid air or liquid hydrogen. Silica gel is also useful as an adsorbent in production
of high vacua.

(2) Gas mask

All gas masks are devices containing an adsorbent (activated charcoal) or a series
of adsorbents.
These adsorbents remove poisonous gases by adsorption and thus purify the air for
breathing.

(3) Heterogeneous catalysis

In heterogeneous catalysis, the molecules of reactants are adsorbed at the catalyst
surface where they form an ‘adsorption complex’. This decomposes to form the
product molecules which then take off from the surface.

(4) Removal of colouring matter from solutions

Animal charcoal removes colours of solutions by adsorbing coloured impurities.
Thus in the manufacture of cane-sugar, the coloured solution is clarified by treating
with animal charcoal or activated charcoal.

(5) Froth Flotation process

The low grade sulphide ores (PbS, ZnS, Cu2S) are freed from silica and other
earthy matter by
Froth Flotation Process. The finely divided ore is mixed with oil (pine oil) and
agitated with water containing a detergent (foaming agent). When air is bubbled
into this mixture, the air bubbles are stabilized by the detergent. These adsorb
mineral particles wetted with oil and rise to the surface.
The earthy matter wetted by water settles down at the bottom.

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6) Chromatographic analysis
Mixtures of small quantities of organic substances can be separated with the help
of Chromatography which involves the principles of selective adsorption.
The mixture is dissolved in a suitable solvent (hexane) and poured through a tube
containing the adsorbent (alumina). The component most readily adsorbed is
removed in the upper part of the tube. The next most readily adsorbed component
is removed next, and so on. Thus the material is separated into ‘bands’ in different
parts of the tube. Now pure solvent is poured through the tube.
Each component dissolved in the solvent comes down by turn and is collected in a
separate receiver.
Mixtures of gases can be separated by selective adsorption of gases by liquids (Gas
chromatography).

ION–EXCHANGE ADSORPTION
In recent years, many synthetic resins have been made which function as ion-
exchangers. In effect, the resin has one ion adsorbed on it. The resin releases this
ion and adsorb another like ion. The process is called ion-exchange adsorption.
When cations are exchanged, the resin is known as cation exchanger. When
anions are exchanged, it is referred to as anion exchanger .

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Cationic exchange
The cationic exchangers are high polymers containing acidic groups such as
sulphonic acid group, –SO3, H. The resulting macro-anion has adsorbed H+ ions.
When solution of another cation (Na+) is allowed to flow over it, H+ ions are
exchanged for Na+ ions. This process in fact, consist of desorption of H+ ions and
adsorption of Na+ ions by the resin

Since the above cationic exchange is reversible, the sodium ‘salt’ upon treatment
with an acid regenerates the original resin.

Anionic exchange
A resin containing a basic group such as quaternary ammonium hydroxide, –N+ R3
O– H, will act as anion exchanger. It will, for example, exchange OH– ion for Cl–.

The original anion exchanger resin can be regenerated by treatment of the resin
‘chloride’ with a base (OH– ions).

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APPLICATIONS OF ION–EXCHANGE ADSORPTION
Ion-exchange adsorption has many useful applications in industry and medicine.
(1) Water softening
Hard water contains Ca2+ ions and Mg2+ ions. These form insoluble compound
with soap and the latter does not function as detergent. Hard water is softened by
passing through a column packed with sodium cation-exchanger resin, R–Na+. The
Ca2+ and Mg2+ ions in hard water are replaced by Na+ ions.

(2) Deionization of water

Water of very high purity can be obtained by removing all dissolved salts. This is
accomplished by using both a cation and anion exchanger resin. The water freed
from all ions (cations and anions) is referred to as Deionized or Demineralized
water.
The water is first passed through a column containing a cation-exchanger resin, R–
H+. Here any cations in water (say Na+) are removed by exchange for H+. The
water is then passed through a second column packed with an anion-exchanger, R+
OH–. Any anions (Cl–) are removed by exchange of OH– for Cl–.

R–H+ + Na+ ⎯⎯→ R–Na+ + H+ (First Column)

R+OH– + Cl– ⎯⎯→ R+Cl– + OH– (Second Column)

The H+ and OH– ions thus produced react to form water.

Thus the water coming out of the second column is entirely free from ions, whether
cations or anions. The water is purer than distilled water and is called
Conductivity water.
In another process, which is more common way, the tap water is passed into a
column containing both types of resin (cation and anion exchanger). Here cations
and anions are removed simultaneously.

Electrical demineralization of water

Ion-exchange resins supported on paper or fibre can be used as membranes through

which only cations or anions will pass. Such membranes are used in electrical

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demineralization of water and they act as ionic sieves .Upon application of the
electric current, cations move through the cation-exchanger membrane to the
negative electrode. The anions move in the opposite direction through the anion
exchanger membrane. Thus the water in the middle compartment is demineralized

(3) Medical uses

Excess sodium salts can be removed from the body fluids by giving the patient a
suitable ion-exchanger to eat. Weakly basic anion-exchangers are used to remove
excess acid or ‘ acidity’ in the stomach.

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