CHEMICAL REACTION ENGINEERING-II (3170501)

Date: / /.
EXPERIMENT NO: .

Effect Of Surface Area On Adsorption

Aim: Study the effect of surface area on adsorption.

 When a solid surface is brought in contact with a gas or liquid, molecules from the
gas or liquid starts to collect at the surface of the solid. This phenomenon of a
collection of gas or liquid molecules on the surface of the solid is known as
adsorption. A substance which accumulates on the solid surface is known as adsorbate
and the solid surface on which it occurs is known as an adsorbent.

 Factors affecting the extent of adsorption

o The extent to which adsorption will happen on a solid surface depends on the
following factors:

 Nature of adsorbent
The adsorption of the gas depends on the nature of the adsorbent. A
gas can be adsorbed on different absorbent surfaces in different amounts.
For example, Hydrogen is weakly adsorbed on the alumina surface
whereas it is strongly adsorbed on the nickel surface under certain
conditions.

 Surface area
When we increase the surface area of the adsorbent there is an
increase in the adsorption of gases. This is because when we increase the
surface area there is more number of adsorbing sites. So finely divided
solids and some porous substances are good adsorbents.

 Nature of the gas

In general, if a gas is more liquefiable it will be more easily
absorbed. For example, gases like NH3, HCl, Cl2, CO2, which can be
liquefied easily are more readily adsorbed on the solids surface rather than
permanent gases like O2, H2, etc.

 Exothermic nature
The heat of adsorption can be defined as the energy liberated when
1 g mol of a gas is adsorbed on a solid surface. When the temperature is
increased the kinetic energy of the gas molecules also increases which
results in more number of collisions between the molecules and the
surface.

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 Pressure
On the solid surface, there is a fixed number of adsorption sites
where gas molecules can be adsorbed. Initially when the pressure has
increased the rate of adsorption increases due to an increase in the gas
molecules striking on the surface. Thus, an increase in the pressure
increases the rate of adsorption linearly. But after sometime, it will reach a
point when the pressure has no effect on the rate of adsorption as the
number of adsorption sites is fixed and no more adsorption can happen in
those sites. Hence, at that point, the extent of adsorption will be
independent of the pressure.
 Surface of solids plays a crucial role in many physical and chemical phenomena.
There are two main reasons for this special role. Firstly, the surface of a substance
interacts first with its surroundings. Secondly, the surface molecules are in a different
state as compared to the molecules in the interior of the solid. The surface molecules
interact more readily with other substances which come close by and are responsible
for many special properties. In this lesson we shall study about two such properties –
adsorption and catalysis.
 Nature and Surface Area of the Adsorbent:
o Different solids would adsorb different amounts of the same gas even under
similar conditions. Substances like charcoal and silica gel are excellent
adsorbents. The substances that are porous in nature and have rough surfaces
are better adsorbents. The extent of adsorption also depends upon the surface
area of the solid. Greater the surface area, more is the surface available for
adsorption and greater is the adsorption. The surface area depends upon the
particle size of the substance.
 The phenomenon of attracting and retaining the molecules of a gas or of a dissolved
substance on the surface of a solid is called adsorption. The substance which gets
adsorbed is called the adsorbate and the solid substance which adsorbs is called the
adsorbent. The substances that are porous in nature and have rough surfaces are better
adsorbent. Easily liquifiable gases are more readily adsorbed.
 Extent of adsorption decreases with rise in temperature and increases with the
increase in pressure of the gas. Physical adsorption is due to van der Waal forces and
chemisorption is due to forces similar to chemical bonds. Pressure dependence of
adsorption of a gas at a constant temperature is given by Freundich Adsorption
Isotherm catalyst is the substance which changes the rate of a reaction, but itself
remains chemically unchanged during the reaction. The catalysts which increase the
rate of a reaction are called the positive catalysts while those which decrease the rate
are called the negative catalysts. Auto catalysed reactions are those in which one of
the products acts as the catalyst

 Effect of surface area:

o The rate of a chemical reaction can be raised by increasing the surface area of
a solid reactant. This is done by cutting the substance into small pieces, or by
grinding it into a powder.

large pieces = small surface area

small pieces (powder) = large surface area

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 If the surface area of a reactant is increased:

o More particles are exposed to the other reactant
o There is a greater chance of particles colliding, which leads to more successful
collisions per second
o The rate of reaction increases

 Increasing the surface area of a reactant increases the frequency of collisions and
increases the reaction rate. Several smaller particles have more surface area than one
large particle. The more surface area that is available for particles to collide, the faster
the reaction will occur.
 Both of the concepts are related to each other which is mean the actives sites on the
surface of the catalyst. The catalyst has more porosity will be more active than that
has lower porosity because it has more surface area to form the actives sites and this
usually leads to greater activities.
 A catalyst is more effective in finely divided from because finely divided from has
more surface area. Therefore there is an increase in active centres on the surface
 Crushing or decreasing the size of the particles of the reactants will increase the
surface area and speed the rate of the reaction

 Methodology:
Adsorption isotherms have been of immense importance to research dealing with
environmental protection and adsorption techniques. The two primary methods used for
predicting the adsorption capacity of a given material are known as the Freundlich and
Langmuir isotherms.

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 Langmuir Adsorption Isotherms

The Freundlich adsorption isotherm is followed by another two isotherms,
Langmuir adsorption isotherms and BET theory. The Langmuir adsorption
isotherms predict linear adsorption at low adsorption densities and a maximum surface
coverage at higher solute metal concentrations.
The Langmuir adsorption isotherm has the form:

Where,

 θ is the fraction of the surface covered by the adsorbed molecule.

 K is an equilibrium constant known as the adsorption coefficient.
 { K= ka/kd = rate constant for adsorption/ rate constant for desorption}
 p is the pressure.
The Langmuir adsorption is applicable for monolayer adsorption onto a homogeneous
surface when no interaction occurs between adsorbed species.
 Adsorption from Solutions:

o Adsorption occurs from solutions also. The solute gets adsorbed on the surface
of a solid adsorbent. Charcoal, a good adsorbent, is often used to adsorb acetic
acid, oxalic acid and organic dyestuffs from their aqueous solutions. The
extent of adsorption, x m depends upon the concentration c of the solute.
Freundlich isotherm is applicable to adsorption from solutions when
concentration is used in place of pressure as shown below. x m = 1 n k c and
in the logarithmic form as log x m = log k + 1 n log c
o The plot of log x m against c is also a straight line, provided very low and very
high concentrations are avoided.

 BET Adsorption Isotherm:

The theory of multilayer adsorption proposed by Brunauer, Emmett and Teller
in 1938 (BET Theory) assumes that physisorption results in the formation of multilayer
adsorption. The theory also assumes that the solid surface has uniform sites of adsorption
and that adsorption at one site does not affect adsorption at neighbouring sites.
After the formation of the monolayer, the adsorption process can continue with
the formation of the multilayer involving the second layer, third layer and so on.

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Kinetic modeling:

Pseudo first order model (PFO):

Also known as Lagergren model, PFO describes the adsorption of solute onto adsorbent
following the first order mechanism;

dqtdt=k1qe−qt………………..(E1)

where qt is adsorbate adsorbed onto adsorbent at time t (mg/g), qe is equilibrium

adsorption capacity (mg/g), and k1 is rate constant per min. The integral of Eq. (1)from
t=0tot=t and qt=0andqt=qt yields a linear expression of PFO, Eq. (2).

lnqe−qt=lnqe−k1t……………………E2

The value of k1 is determined by plotting lnqe−qt vs. t. Albeit some studies have found
k1 to increase with initial solute
concentration C0 or independent of C0, the rate constant is always inversely proportional to
the initial concentration of the solute. This is because a longer time is required for a large
initial solute concentration. The controlling mechanism is affected by experimental
conditions, thus the validity of the model. PFO is varied under Henry regime adsorption, and
under high sorbent dosage [4]. To account for experimental differences during the sorption
of dyes on activated carbon, PFO is modified as follows [5];

dqtdt=k1qeqtqe−qt………………………………E3

and the linear form

qtqe+lnqe−qt=lnqe−k1t………………………….E4

The plot of qtqe+lnqe−qt against t gives a better fit of dye adsorption compared to
Lagergren PFO. Different models for adsorption of various solutes have been developed,
but the applicability and consistence of their linear and non-linear form need to be tested.

 Applications of Adsorption :
o The phenomenon of adsorption finds many applications, some of which are
given below:

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 CHEMICAL REACTION ENGINEERING-II (3170501)

1. Activated charcoal is used in gas masks in which toxic gases are adsorbed
and air passes through it.
2. Silica gel packed in small cloth bags is used for adsorbing moisture in
bottles of medicine and in small electronic instruments.
3. Animal charcoal is used for decolourizing many compounds during their
manufacture.

 Conclusion
 When we increase the surface area of the adsorbent there is an increase in the
adsorption of gases. This is because when we increase the surface area there is
more number of adsorbing sites. So finely divided solids and some porous
substances are good adsorbents.

 Reference:
o https://nios.ac.in/media/documents/SrSec313NEW/313_Chemistry_Eng/313_
Chemistry_Eng_Lesson15.pdf
o https://www.bbc.co.uk/bitesize/guides/zjs9dxs/revision/3#:~:text=If%20the%2
0surface%20area%20of,the%20rate%20of%20reaction%20increases
o https://byjus.com/chemistry/factors-affecting-the-extent-of-
adsorption/#:~:text=When%20we%20increase%20the%20surface,porous%20
substances%20are%20good%20adsorbents.

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