Adsorption

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Adsorption

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.
Examples of Adsorption
Adsorption of a dye by a charcoal, Adsorption of a gas by
charcoal etc.
Adsorption versus Absorption
While adsorption involves deposition at the surface only, absorption
implies penetration into the body of the solid.
For example: When a chalk crayon is dipped in ink, it adsorbs the ink
and on breaking it is white from inside. While, water is absorbed by a
sponge and is distributed throughout it uniformly.
Both adsorption and absorption take place side by side and is difficult
to distinguish experimentally.
Types of Adsorption
Physical Adsorption
This is due to the gas molecules being held to the solid surface by
vander waal’s attractive forces. Also called Vanderwaal’s Adsorption.
For ex- adsorption of hydrogen or oxygen on charcoal
Chemical Adsorption
Here, the gas molecules or atoms are held to the solid surface by
chemical bonds. These bonds may be covalent or ionic in nature.
For ex- hydrogen is chemisorbed on nickel.
Adsorption Isotherms
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
= k P1/n
𝑚
where, w = mass of the gas adsorbed
m = mass of adsorbent
P = pressure
k and n = 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.

Fig 1: Freundlich isotherm; a plot of mass of Fig 2: Plot of log w/m against log P shows slight
adsorbed gas per unit mass of adsorbent curvature at higher pressures
Freundlich isotherm is not applicable at high pressures.

Taking log on both sides of equation 1, we have


𝑤 1
Log = log k + log P
𝑚 𝑛
This equation is in the form y=mx+c. Thus, if we plot log (w/m)
against log P, straight line having slope 1/n and intercept log k is
obtained.
However, it is found that plots are straight lines at low pressure and
slightly curved at higher pressure especially at low temperature.
This shows that Freundlich equation is approximate and doesnot
apply to adsorption of gases by solids at higher pressures.
Langmuir Adsorption Isotherm
Langmuir (1916) derived a simple adsorption isotherm based on
theoretical considerations which is known as Langmuir Adsorption
Isotherm.
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
Langmuir considered that the gas molecules strike a solid surface
and are thus adsorbed. Some of them evaporate or desorbed
fairly rapidly. A dynamic equilibrium is established between
adsorption and desorption.
If θ is the fraction of the total surface covered by the adsorbed
molecules, the fraction of empty area is (1-θ). The rate of
desorption (Rd) is proportional to the covered surface θ.
Therefore,
Rd = Kd θ
Where, Kd= rate constant for the desorption process
The rate of adsorption (Ra) is proportional to the available
naked surface (1-θ) and the pressure P of the gas.
Ra = Ka (1- θ) P
where, Ka = rate constant for the adsorption process.
At equilibrium,
Rd = Ra
Kd θ = Ka (1- θ) P
𝐾𝑎
𝑃
𝐾𝑑
θ= 𝐾𝑎
1 + 𝐾𝑑 𝑃
𝐾𝑃
θ=
1+𝐾𝑃
where, K = equilibrium constant known as adsorption coefficient
The amount of gas adsorbed per gram of the
adsorbent, x is proportional to θ.
𝐾𝑃
Hence, x α
1+𝐾𝑃
𝐾𝑃
x = K’ …………………….1
1+𝐾𝑃
Where, K’ = 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.
This equation can be rearranged as
𝑃 1 𝑃
= +
𝑥 𝐾′ 𝐾′′
Where, K’’ is a constant = K’/K
If we plot P/x against P,
we get straight line
with slope 1/K’’ and
the intercept 1/K’.

Fig 3: Verification of Langmuir isotherm for adsorption of


N2 on mica at 90 K
In most cases, the curves are straight lines. Thus, Langmuir isotherm
was verified. It holds true at low pressure but fails at high pressure.
Cases
❖If pressure is very low, the factor P/K’’ can be ignored thus isotherm
becomes x = K’ P
❖If pressure is very high, the factor 1/K’ can be ignored and
isotherm becomes x = K’’
Hence, at low pressure, the amount of gas adsorbed(x) is directly
proportional to pressure and at high pressure, it reaches a constant
value K’’ when adsorbent surface is covered completely with a layer
of gas. At latter stage, adsorption is independent of pressure.
Application of Adsorption
1. Production of high vacua: Used in high vacuum equipments as
Dewar flask for storage of liquid air or liquid hydrogen.
2. Gas mask: All gas masks contain activated charcoal as an
adsorbent which removes poisonous gases by adsorption and
thus purify the air for breathing.
3. Heterogeneous catalysis: In this process, the molecules of
reactants are adsorbed at the catalyst surface forming adsorption
complex that decomposes to form product molecules which then
take off from the surface.
4. Removal of colouring matter from solutions: Animal charcoal
removes colour of solutions by adsorbing coloured impurities.
Thus, in manufacturing cane sugar, the coloured solution is
clarified using animal charcoal.
5. Froth Floatation process: The low grade sulphide ores (PbS, ZnS,
Cu2S) are freed from silica and other earthy matter by froth
floatation process. The ore is mixed with pine oil and agitated
with water containing a detergent. When air is bubbled, air
bubbles are stabilized by the detergent which adsorb mineral
particles wetted with oil and rise to the surface. The earthy
matter wetted by water settles at the bottom.
6. Chromatographic analysis: Chromatography involves the
principles of selective adsorption. Here, the mixture is dissolved
in suitable solvent like hexane and poured through a tube
containing adsorbent (alumina). The most readily adsorbed
component is removed in the upper part of the tube and next is
removed next and so on. Thus, material are separated as bands
in different parts of tube.

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