Adsorption and Ion Exchange

Course Coordinator: Dr Shina Gautam

Class and Sem: Chemical Engineering, VI sem

Shroff S R Rotary Institute of Chemical Technology,

Ankleshwar, Gujarat
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Difference between adsorption and absorption

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Adsorption process

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• Most adsorbents are highly porous materials and adsorption takes
place primarily on the walls of the pores or at specific sites inside the
particles.
• The internal surface area is orders of magnitude greater than external
area and may be as large as 2000 m2/g.
• Separation occurs due to difference in molecular weight, shape or
polarity. Some molecules have more affinity towards absorbent than
other.

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Definition of adsorption
• Adsorption is a separation process in which certain components of
a fluid phase are transferred to the surface of a solid adsorbent.
• The ability of certain solids to concentrate specific substances onto
their surface from solution.
• For example dehumidification of air and removal of odor and
impurities from industrial gases such as CO2.
• Fractionate the mixture of hydrocarbons such as methane, ethane,
ethylene, propylene and propane.
• In liquids, removal of moisture from gasoline, decolorization of
petroleum products and objectionable odor and taste from
wastewater.
• The small particles of adsorbent are held in a fixed bed and fluid
passed continuously through the bed until the solid is saturated.
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Types of adsorption
• Physical Adsorption
Physical adsorption or Van der Walls adsorption
o It is the result of intermolecular forces of attraction between
molecules of the solid and the substance adsorbed.

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Chemisorption
• Chemisorption or activated adsorption is the result of chemical
interaction between the solid and the adsorbed substance.
• The strength of the bond may vary, but the adhesive force is
much greater than the physical adsorption.
• The heat liberated during chemisorption is quite large of the
order of heat of reaction.
• The process is irreversible and on desorption the original
substance will often found to have undergone a chemical
change.

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Nature of adsorbents

• Adsorbents are usually in granular form with their size range

from 0.5 mm to 12 mm.
• It must neither offer high pressure drop nor get carried away by
flowing stream.
• They must not loose their shape and size while handling and
have high surface area and pore size.

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Assignment

• What is adsorption? What are different types of it, explain in brief?

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 Adsorption equilibria
Single gases and vapors
•At 100 ºC, pure acetone vapor at a
pressure 190 mm Hg is in equilibrium
with an adsorbate concentration of
0.2 kg adsorbed acetone/kg carbon.
•Increasing the pressure will cause
more vapors to be adsorbed until its
saturation pressure 2790 mmHg and
decreasing the pressure will cause to
desorbed from the carbon.
•At higher pressures, no acetone can
exist in the vapor state but will
condense to liquid at this
temperature.
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• Vapors and gases are more readily adsorbed, the higher their
molecular weight and the lower the critical temperature.
• The extent of unsaturation also influence the extent of adsorption.

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Adsorption Hysteresis
• The equilibrium curves represents
completely irreversible phenomena.
• This condition can be obtained either
by adsorption onto fresh carbon or by
desorption of a sample with an initially
higher adsorbate concentrations.
• Different equilibria result, over a part of
a isotherm, depending on adsorption or
desorption gives rise to a phenomena
hysteresis.
• When hysteresis is observed, the
desorption equilibrium pressure is
always lower than that obtained by
adsorption.
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 Effect of temperature
• Adsorption is an exothermic
process, the concentration of
adsorbed gases decreases with
increasing temperature at a given
equilibrium pressure.

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Heat of adsorption

• The differential heat of adsorption is defined as the heat

liberated at constant temperature when unit quantity of vapor is
adsorbed upon a large quantity of solid already containing
adsorbate.

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 Adsorption isotherm
• The adsorption isotherm is the equilibrium relationship between
the concentration in the fluid phase and the concentration in the
adsorbent particles at a given temperature.
• The concentration of adsorbate on the solid is given as mass
adsorbed per unit mass of original adsorbent.
Types of isotherms
(1) Linear isotherm: The linear isotherm goes through the origin
and the amount adsorbed is proportional to the concentration
in the fluid.

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• Isotherms that are convex upward are called favourable, because a
relatively high solid loading can be obtained at low concentration in
the fluid.
• The limiting case of a very favourable isotherm is irreversible
adsorption where the amount adsorbed is independent of
concentration down to very low values.
• An isotherm that is concave upward is called unfavorable because
relatively low solid loadings are obtained and because it leads to
quite long mass transfer zones.
• These adsorption isotherms are useful to study the desorption from
solids or regeneration of solids.

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Linear Isotherm
• At low concentrations of solute, the molecules are widely spaced on the
adsorbent surface and have no influence on one another.

• For these limiting conditions, it is reasonable to assume that the

concentration on the solid is proportional to that in the fluid phase, and the
adsorption isotherm will be linear.

• If this linear relation is applicable over a broader concentration range, the

equilibrium can be represented by an equation similar to the Henry's law.
• q is the adsorbate loading (moles, mass
q = kC or volume adsorbed per unit mass of
adsorbent)
• C is the concentration of the solute
• k is an empirical constant, which depends
on temperature. 20
• For gaseous systems, concentration in the fluid can be
represented by the partial pressure of the solute and the
isotherm can be written as

q=kp
• where p is the partial pressure of the solute in the gas

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 Freundlich Isotherm
• The Freundlich equation is an empirical equation relating
adsorbate loading and the fluid concentration under equilibrium.

k and n are temperature-dependent constants.

k & n decreases with increase in the temperature. Value of n lies in
the range of 1 to 5.

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• The experimental q - C or q - p data can be used for the
evaluation of the constants n and k, either by using a nonlinear
curve fitting technique or by converting Equation into a linear
form

• log q may be plotted against log C and the best straight line
through the data has a slope 1/n and makes an intercept log k,
from which n and k are calculated.
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 Langmuir Isotherm
• The Langmuir theory on adsorption assumes that:

1. Adsorption is limited to mono layer.

2. There is no interaction between adjacent molecules on the
surface.
3. The energy of adsorption remains constant over the entire
surface.
4. The molecules adsorb at fixed sites on the surface and do not
migrate to other locations.

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• The rate of adsorption is proportional to the empty surface
available for adsorption and the fluid concentration.
• Process of adsorption is also accompanied by the desorption of
adsorbed molecules from the surface.
• the rate of desorption is proportional to the surface occupied by
a monomolecular layer of the adsorbate.
• When the rate of adsorption and desorption are equal, a
dynamic equilibrium is established.

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• Let θ be the fraction of the surface occupied by the adsorbate.
Then the fraction of the bare surface is (1 - θ).

ka*(1 - θ)*C = kd*θ

• ka is the velocity constant for adsorption to the empty surface

and kd is that for desorption from a monolayer.
• Let K denote the adsorption equilibrium constant.

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• θ is the ratio of the concentration of the adsorbate (q) to the
concentration when the surface coverage by the monolayer is
complete (qm).

• The best straight line drawn through the points

when C/q is plotted against C has slope = 1/ qm
and intercept = 1/ qmK from which the constants K
and qm are determined.
• Equation indicates that a plot of 1/q versus 1/C
also will give values of the constants K and qm.
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 Stage contact operations
• Adsorption operations can be carried out either as stage operations or as continuous
contact operations.
• In both cases, batch, continuous and semi-continuous operations are common.
• The adsorption systems include

1. Dispersed contact units such as the agitated vessels or the contact filtration units
2. The fixed bed units such as the percolation tanks
3. The continuous countercurrent units such as the hypersorption unit
4. The fluidized bed systems.

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 In general, three steps are invariably involved in all adsorption processes.

(i) Contacting the fluid (gas or • In the following discussion, we consider the systems
liquid) with the adsorbent. Certain in which only one component of the solution is
adsorbed.
components get adsorbed on the
solid surface.
• The calculations involved in such cases are analogous
to those involved in the absorption of a component
(ii) Separation of the unadsorbed from a gas mixture using a liquid solvent.
fluid from the adsorbent carrying
the adsorbate. • Even in many cases where more than one
component is adsorbed, the solute is adsorbed much
more strongly than the other components, so that
(iii) Regeneration of the adsorbent or the adsorption of the latter can be safely ignored.
its replacement with fresh solids.

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Assignment

• What are different types of isotherms in adsorption? Explain their

conditions of application.

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Single stage adsorption

• Adsorption of liquids using the contact

filtration systems, fluidized bed
adsorption for gases or liquids are
examples of the units that can be
operated stage-wise.

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