NIRAV J BHAVSAR

CHEMICAL ENGINEERING DEPARTMENT

DDU, NADIAD

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 Introduction to adsorption.
 Difference between adsorption and absorption
 Mechanism of adsorption
 Types of adsorbents
 Adsorption equilibrium and isotherm models
 Adsorption processes

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 Process in which certain
components of a Fluid phase,
having adsorptive nature, are
selectively transferred from the fluid
phase to the surface of insoluble
and rigid particles suspended in
vessel or packed in a coloum
 Adsorption
 Ion exchange
 Chromatography

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 Def: when a solid surface is exposed to a fluid phase,
the molecules from bulk of the fluid phase have
tendency to accumulate or concentrate at the surface of
the solid. The phenomenon of the enrichment
(concentration ) of chemical substances at the surfaces
of a solid is called as adsorption.
 In simple way, it is the binding of molecules or particles
to a surface and filling the pores in a solid.
 Involves the transfer of mass from either a gas or liquid
phase to the surface of a solid.

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 adsorb.avi

The removal of dissolved substances from solution using

adsorbents such as activated carbon
 ADSORPTION
Adsorption is the process in which matter is
extracted from one phase and concentrated at
the surface of a second phase. (Interface
accumulation). This is a surface phenomenon
as opposed to absorption where matter changes
solution phase, e.g. gas transfer.

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When adsorption?

If we have to remove soluble material from the solution phase,

but the material is neither volatile nor biodegradable, we often
employ adsorption processes. Also adsorption has application
elsewhere, as we will discuss later.

adsorbate: material being adsorbed

adsorbent: material doing the adsorption. (examples are

activated carbon or ion exchange resin).

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 Adsorption vs. Absorption
◦ Adsorption is accumulation of molecules
on a surface (a surface layer of
molecules) in contact with an air or
water phase
◦ Absorption is dissolution of molecules
within a phase, e.g., within an organic
phase in contact with an air or water
phase

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 Adsorption

PHASE I

‘PHASE’ 2

Absorption
(“partitioning”)

PHASE I
Pgas  K H caq
Henry’s Law
PHASE 2

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d

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 Micropore

Macropore

Mesopore Knudsen Diffusion Fickian Diffusion

Zone Zone

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 Separation of gases from gases (gaseous separation):
◦ Removal of toxic gases.
◦ Removal of odour from waste gases and air.
 Separation of vapors from gases (gaseous separation):
◦ Dehumidification of air and other gases
◦ Recovery of valuable solvent vapors from solvent laden air.
 Separation of solutes from solutions (Liquid separations):
◦ Removal of moisture in dissolved gasoline
◦ Decolonization of sugar solution, vegetable oils, petrolium products.
◦ Removal of organic components from aqueous wastes for water pollution
control.
 Removal of ions from solution.
◦ Demineralization of water by ion exchange.

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 The terms involved in adsorption are,
(i) Adsorbent : the substance on which adsorption takes place
(solid).
(ii) Adsorbate (substrate) : Substance which is adsorbed (liquid
or gas).
(iii) Transport pore: A pore that allows the traansfer of solute
from the bulk phase to the interior of the adsorbent.
(iv) Macro pore: Pore having width > 50 nm
(v) Meso pore : Pore having width 50 nm< w < 2 nm
(vi) Micro pore: Pore having width w < 2 nm

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Increasing magnification

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Pore size distribution:
micropores: <2nm dia
mesopores: 2nm to 50 nm dia
macropores: > 50 nm

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Pore size % pore % surface
volume area
Micro 30 - 60 >95

Meso < 10 <5

Macro 25 - 30 negligible

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 Adsorbents are made from natural or synthetic materials.
 They have an amorphous or microcrystalline structure.
 They are granular and generally extremely porous, with large
internal surface areas.
 Both the chemical and physical properties of the adsorbent must
be considered.
 Chemical properties that influence adsorbent design are
◦ Degree of ionization of the surface,
◦ Functional groups present on the surface, and
◦ Degree to which these chemical properties vary with process parameters and
by contact with the solution.
 Physical properties that influence design include surface area,
surface structure, size, and pore distribution.

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 Activated carbons, shown left,
are the oldest and most widely
used adsorbent. They are
natural, broad-based
adsorbents with a wide range
of applications. The pictures
below show close-up views of
the pores within activated
carbon from coal, coconut
shell, and wood respectively.

Coal Coconut Wood

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 Activated Carbon:
◦ Used as decolorizing agent for removal of color from sugar, drugs,
chemicals etc.
◦ Used as gas adsorbent carbon to recover solvent vapors from gas mixtures.
 Silica gel :
◦ for dehydration of air and other gases.
 Molecular sieve:
◦ for dehydration of air and other gases and liquids
 Bone char :
◦ for refining of sugar
 Activated clays:
◦ for decolorizing petroleum products.
 Fuller’s earth:
◦ for decolorizing lubricating oils, kerosene, gasoline, vegetables oil.

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 In granular form with size ranging from 12 mm to 50μm.
 Possess a large surface area per unit mass.
 Sufficient specificity and adsorptive ability.
 Highly porous material.
 Free flowing material for ease in handling.
 Offer low pressure drop for a flow of fluid when used in

fixed bed.
 Adequate strength and hardness.

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 Adsorbents have a wide variety of uses.
 Some activated carbons are used in the military for defense against gas
warfare.
 Activated carbon cartridges are placed in gas masks and adsorb harmful gases.
 The activated carbon used has 1,000,000 square meters of surface area per
kilogram of adsorbent.
 Other examples of adsorbents include Fuller's Earth and Bauxite.
 Fuller's Earth is used in petroleum refineries, and is also used to purify
vegetable and animal oils
 It is also used in face pack powder or face wash.
 Bauxite is an adsorbent used to dehydrate gas streams.


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Factors which affect the extent of adsorption : The
following are the factors which affect the adsorption,
(1) Nature of the adsorbate (gas) and adsorbent (solid)
(i) In general, easily liquefiable gases e.g., CO 2, NH3, Cl2 and
SO2 etc. are adsorbed to a greater extent than the elemental
gases e.g. H2, O2, N2, He etc. (while chemisorption is specific
in nature.)
(ii) Porous and finely powdered solid e.g. charcoal, fullers
earth, adsorb more as compared to the hard non-porous
materials. Due to this property powdered charcoal is used in
gas masks.

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(2) Effect of pressure on the adsorbate gas
(i) An increase in the pressure of the adsorbate gas increases
the extent of adsorption.
(ii) At low temperature, the extent of adsorption increases
rapidly with pressure.
(iii) Small range of pressure, the extent of adsorption is found
to be directly proportional to the pressure.
(iv) At high pressure (closer to the saturation vapour pressure
of the gas), the adsorption tends to achieve a limiting value.

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(3) Effect of temperature
(i) As adsorption is accompanied by evolution of heat, so according to the
Le-Chatelier’s principle, the magnitude of adsorption should decrease with
rise in temperature.
(ii)The relationship between the extent of adsorption and temperature at
any constant pressure is called adsorption isobar.
(iii) A physical adsorption isobar shows a decrease in x/m (where ‘m’ is
the mass of the adsorbent and ‘x’ that of adsorbate) as the temperature
rises.
(iv) The isobar of chemisorption show an increase in the beginning and
then decrease as the temperature rises.

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 The adsorption is essentially an attraction of adsorbate
molecule to an adsorbent surface due to some sort of
forces.
 Adsorption occurs when repulsive and attractive forces

are balanced.
 Depending upon the forces adsorbent and adsorbate,

Adsorption can be classified as :

◦ Physical adsorption or Van der Waals adsorption
◦ Chemisorption or Activated adsorption

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 Physical process occur at < 2000 C.
 The forces operating in these are weak - vander Waal’s forces.
 The material is adsorbed due to intermolecular forces of attraction
between the molecules of adsorbent and adsorbate.
 Intermolecular forces between molecules of solid and the gas are
greater than between the molecules of the gas molecules.
 The heat of adsorption are low i.e. about 20 – 40 kJ mol -1
 No compound formation takes place in these cases.
 The process is reversible i.e. desorption of the gas occurs by
increasing the temperature or decreasing the pressure.
 It does not require any activation energy.
 This type of adsorption decreases with increase of temperature.
 It is not specific in nature i.e. all gases are adsorbed on all solids to
some extent.
 It forms multi molecular layer.

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 Chemical process occurs at > 2000C.
 The forces operating in these cases are similar to those of a chemical bond
 Involve the formation of chemical bonds between adsorbate and adsorbent followed
by formation of chemical compound.
 During bond formation initially, monolayer is formed.
 Bond formation results in release of heat which is much larger than heat of
condensation.
 The heat of adsorption are high i.e. about 40 – 400 kJ mol -1
 The process is irreversible. Efforts to free the adsorbed gas give some definite
compound.
 It requires any activation energy.
 This type of adsorption first increases with increase of temperature. The effect is
called activated adsorption. Then decreases.
 It is specific in nature and occurs only when there is some possibility of compound
formation between the gas being adsorbed and the solid adsorbent.
 Catalysis is based on the chemisorption.

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ADSORPTION EQUILIBRIA
The relation between the amount adsorbed on
the solid(adsorbate) and the concentration of the
adsorbate in fluid (partial pressure) is called an
isotherm.

If the adsorbent and adsorbate are contacted

long enough an equilibrium will be established
between the amount of adsorbate adsorbed and
the amount of adsorbate in solution. The
equilibrium relationship is described by
isotherms. NIRAV J BHAVSAR 04/05/24 33
• Different gases and vapors
are adsorbed to different
extent under comparable
conditions.
•Benzene is more readily
adsorbed than acetone at
same equilibrium partial
pressure.
• Higher molecular weight
and low critical temperature
vapors and gases are
adsorbed more readily.
• Equilibrium adsorption
curves for same components
would be different for
different adsorbent.

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Effect of temperature:
Since adsorption is an
exothermic process, the
concentration of adsorbed
gas decreases with
increasing temperature at a
given equilibrium partial
pressure as shown for
acetone in figure

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The concentration of adsorbate on the surface of the
solid is expressed as the amount of the substance
per unit mass of the adsorbent.

The concentration of adsorbate in fluid is expressed

as partial pressure or mole percent (In case of
gases).

The concentration of adsorbate is expressed as the

amount of the substance per unit volume of the
solution.(In case of solution).

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Define the following:
qe = (x/m)= mass of material adsorbed(x)
(at equilibrium) per mass of adsorbent(m).

Ce = equilibrium concentration in solution

when amount adsorbed equals qe.

qe/Ce relationships depend on the type of

adsorption that occurs, multi-layer,
chemical, physical adsorption, etc.

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Types of Isotherm curves…

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Type I:
◦ Limited to the completion of a single monolayer of adsorbate
over adsorbent surface.
◦ Adsorption of gases over micro porous solids whose pore sizes
are not much larger than the molecular diameter of the
adsorbate.
◦ Complete filling of these narrow pores corresponds to
monolayer formation only.
◦ Example: Adsorption of oxygen on carbon black at -1830 C
Type II:
◦ Do not exhibit a saturation limit as in Type I.
◦ Multilayer formation is observed after completion of
Monolayer.
◦ Example: Adsorption of water vapor on carbon black at 300 C

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Type III:
◦ It is observed when amount of gas adsorbed increase without any
limit till its relative pressure approaches unity.
◦ It is not favorable condition for adsorption.
◦ Example: Bromine is adsorbed over silica gel at 20 0 C
Type IV:
◦ It is almost same as the Type II with little deviation in middle .
◦ Finite multilayer formation is observed corresponding to complete
filling of capillaries.
◦ The adsorption terminates near to a relative pressure of unity.
◦ Example: Water vapor is adsorbed over activated carbon at 30 0 C
Type V:
◦ It is almost same as the Type III with little deviation in middle .
◦ Example: Water vapor is adsorbed over activated carbon at 100 0 C

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Isotherm models:

The figures below show that there are

four common models for isotherms.

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 Freundlich Isotherm:
The first mathematical fit to an isotherm was published by
Freundlich and Kuster (1894) and is a purely empirical
formula for gaseous adsorbates.

For the special case of heterogeneous surface energies

(particularly good for mixed wastes) in which the energy
term, “KF”, varies as a function of surface coverage we use
the Freundlich model.
1
q e  K FCe n

n and KF are system specific constants.

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Langmuir Isotherm:
Irving Langmuir was the first to derive a scientifically based adsorption
isotherm in 1918.

The model applies to gases adsorbed on solid surfaces.

It is a semi-empirical isotherm with a kinetic basis and was derived based on

statistical thermodynamics.

It is the most common isotherm equation to use due to its simplicity and its
ability to fit a variety of adsorption data. It is based on four assumptions:
1.All of the adsorption sites are equivalent and each site can only accommodate
one molecule.
2.The surface is energetically homogeneous and adsorbed molecules do not
interact.
3.There are no phase transitions.
4.At the maximum adsorption, only a monolayer is formed. Adsorption only
occurs on localized sites on the surface, not with other adsorbates.

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Langmuir Isotherm:
This model assumes monolayer coverage and
constant binding energy between surface and
adsorbate. The model is:

0
K  Q a  Ce
qe 
1  K  Ce

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Q0a represents the maximum adsorption
capacity (monolayer coverage)
(g solute/g adsorbent).

Ce has units of mg/L.

K has units of L/mg

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BET (Brunauer, Emmett and Teller)
isotherm:
This is a more general, multi-layer model. It
assumes that a Langmuir isotherm applies to
each layer and that no transmigration occurs
between layers. It also assumes that there is
equal energy of adsorption for each layer
except for the first layer.

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 K B  Ce  Q 0
qe  a

(C S  C e ){1  (K B  1)(C e / C S )}

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CS =saturation (solubility limit) concentration of
the solute. (mg/liter)

KB = a parameter related to the binding intensity

for all layers.

Note: when Ce << CS and KB >> 1 and K = KB/Cs

BET isotherm approaches Langmuir isotherm.

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Determination of appropriate model:
To determine which model to use to describe the
adsorption for a particular adsorbent/adsorbate
isotherms experiments are usually run. Data
from these isotherm experiments are then
analyzed using the following methods that are
based on linearization of the models.

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For the Langmuir model linearization gives:

Ce 1 Ce
  0
qe K  Qa Qa
0

A plot of Ce/qe versus Ce should give a straight line

with intercept :
1
K  Qa
0

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 and slope: 1
0
Qa

Or: 1 1 1 1
 0  
q e Qa K  Qa Ce
0

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Here a plot of 1/qe versus 1/Ce should give a
straight line with intercept 1/Qao and slope
1
K  Q 0a
For the Freundlich isotherm use the log-log
version :
1
log q e  log K F  log C
n
A log-log plot should yield an intercept of log KF
and a slope of 1/n.
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For the BET isotherm we can arrange the isotherm
equation to get:

Ce K B  1 Ce 1
  
(C S  C e )  q e K B  Q a C S K B  Q 0a
0

Intercept =
1
K B  Q 0a

KB 1
Slope = 0
K B  Qa  Cs

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 Adsorption systems can be classified as,
◦ Column contact absorbers
◦ Slurry contact absorbers
◦ Pressure swing adsorbers
◦ Temperature swing absorbers

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 Column contact absorbers use a bed of adsorbent to purify solutions.
 Column contact absorbers can operate as a fixed bed, or as a moving or pulsed bed.
 The packed bed columns shown below are used in a natural gas dehydration plant.

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 Fixed bed operation is the oldest form of column contact adsorption.
 A bed of adsorbent is placed inside the column, and the solution to
be treated flows over, through, and around it.
 The bed must be taken off line to replace or regenerate the spent
adsorbent.
 In a moving or pulsed bed adsorber, untreated solution enters the
adsorber from the bottom and flows up the column.
 At the same time, fresh adsorbent enters the adsorber from the top
of the column and exits out the bottom.
 Exhausted adsorbent is continually removed, while fresh adsorbent
is continually added, allowing for more efficient operation.


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In series fixed bed column contact
mode, the effluent from the first
bed passes to a second bed.

If necessary, additional beds may

be added in series.

The lead bed is removed for

reactivation when the adsorbent
becomes saturated with adsorbate.

The next bed in sequence then

becomes the first bed, and a fresh
bed is added in the final position.

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In parallel fixed bed operations, the
effluent of all columns is blended
prior to discharge.

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Pulsed bed operations are restricted
to the up flow mode of operation.

Additional equipment is required to

recycle the adsorbent, which allows
for a more efficient operation.

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 Column contact adsorbers are used in
various industries, such as sugar
refining and petroleum processing.
 Parallel fixed bed operations are used in
areas in which high accuracy is
essential, such as in the production of
pharmaceuticals or processing of
wastewater.
 An adsorption column used to purify
gas streams in laboratory settings is
shown in figure.

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 Slurry contact adsorbers use a powdered adsorbent slurry to
adsorb desired operation.
 In slurry contact adsorption, the adsorbent powder is mixed with
the solution that is to be treated.
 Agitation evenly distributes the adsorbent throughout the
solution.
 The adsorbent is then removed from the purified solution by
filtration.
 Slurry contact adsorption can be carried out in a number of
modes, such as single stage batch, multiple stage batch, multiple
stage countercurrent, and continuous.

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In single stage batch treatment,
fresh adsorbent comes in contact
with the fluid in a completely
mixed vessel.

After the required contact time, the

adsorbent is separated from the
fluid by filtration.

The desired quality of the purified

fluid is obtained, and the spent
adsorbate is disposed of or
regenerated.
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In multiple stage batch
treatment, the solution passes
through several single batch
stages.

The effluent from one stage

enters the second stage, where it
is treated again.

Each stage achieves part of the

overall separation in this type of
treatment, also known as split
or divided treatment.
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Multiple stage countercurrent
adsorption separation is a two-step
system.

It involves contacting the untreated

solution with once-used adsorbent,
which is discarded or regenerated after
the second use usually.

The partially treated fluid is then

contacted with fresh adsorbent.

After separation, this adsorbent

becomes the once-used adsorbent to
treat a new batch of untreated feed
solution.
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In continuous slurry contact
adsorbers, a series of stirred tanks
are used to approach plug flow
pattern.

The adsorption takes place as the

adsorbent and solution travel
through the series of tanks.

When the desired purification has

been achieved, the adsorbent is
filtered from the purified solution.

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 Some common applications of
slurry contact adsorption include
water purification, pharmaceutical
applications, and decoloring.

 An activated carbon VOC recovery

system is pictured here.

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 In pressure swing adsorption (PSA), adsorbents are used
under varying pressures to separate gas mixtures. The
process is known as vacuum swing adsorption (VSA) if
these pressures fall below atmospheric.
 Special adsorptive materials (e.g., zeolites) are used as a
molecular sieve, preferentially to adsorb the target gas
species at high pressure.
 The process then swings to low pressure that desorbs the
adsorbent material.


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 In pressure swing adsorption, one or more components in a gas stream
are adsorbed on a solid adsorbent.
 PSA capitalizes on the dependence of adsorption on pressure.
 More gas can be adsorbed at higher pressures. By adsorbing at one
pressure and then "swinging" to a lower pressure for desorbing, a
majority of an adsorbed gas can be removed from a high pressure feed.
 VSA is used for low pressure feeds, while high pressure feeds usually
require PSA.
 Oxygen is usually used in low pressure applications, and can be
produced by VSA units.

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 PSA can be accomplished using one, two, or multiple-bed designs.
However, two-bed designs are the most common.


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Air Air

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• Contains two fixed beds which are operated in four
steps in cyclic manner
• Each bed operates alternately in two half cycles of equal
duration.
1. Pressurization followed by adsorption
2. Desorption by depressurization followed by a purge.
• Under high pressure, Gases tend to be attracted over the
solid surface or adsorbed.
• When pressure is reduced , the gas is released or
desorbed.

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 Air is introduced under pressure in a bed containing adsorbent
zeolite.

 When pressure is raised (under pressurization step), N2 is

adsorbed more compare to O2 over bed. Leaving gas is
enriched with O2.
 When the bed reaches the end of its capacity to adsorb
nitrogen, it can be regenerated by reducing the pressure.

 As pressure is reduced the affinity towards the adsorbent

decreases and O2 is released or desorbed from the bed.

 It is then ready for another cycle of producing oxygen

enriched air.
NIRAV J BHAVSAR 04/05/24 73
 One of the primary applications of PSA is in the removal of
carbon dioxide (CO2) as the final step in the large-scale
commercial synthesis of hydrogen (H2) for use in oil refineries
and in the production of ammonia (NH3).

 Refineries often use PSA technology in the removal of

hydrogen sulfide (H2S) from hydrogen feed and recycle
streams of hydro treating and hydrocracking units.

 Another application of PSA is the separation of carbon

dioxide from biogas to increase the methane (CH4) content.

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 Regeneration of adsorbent in a TSA process is achieved by an
increase in temperature.

 For given partial pressure of the adsorbate in the gas phase (or
concentration in the liquid phase), an increase in temperature
leads to a decrease in the quantity adsorbed.

 If the partial pressure remains constant at p 1, increasing the

temperature from T1 to T2 will decrease the equilibrium
loading from q1 to q2.

 A very important characteristic of TSA processes is that they

are used virtually exclusively for treating feeds with low
concentrations of adsorbates.

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