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Chapter 3

Adsorption from Gaseous Phase I

Introduction
The term adsorption was introduced for the first time Heinrich
Kayser in 1881 (A German Physicist).

Lenard-Jones model for physisorption and chemisorption of molecules Born: March 16, 1853,
Died: October 14, 1940

• some properties of adsorption (physisorpion):

exothermic, non-specific, adsorption energy low,
not activated, multilayer, no dissociation/electron
transfer

Partial and Total Oxidation of Methane in Monolithic

Catalysts at Short Contact Times

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Factors affecting adsorption from Gas phase

Nature of gas - easily liquefiable gases easily gets adsorbed

Nature of adsorbent- More the surface area per unit mass of the adsorbent, more will be

the adsorption.

Temperature- adsorption increases as temperature decreases.

Pressure- magnitude of adsorption increases with increase in pressure.

Adsorption equilibria
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 gas or solution

Adsorption isotherms
The variation in the amount of gas adsorbed by the adsorbent with pressure at
constant temperature can be expressed by means of acurve termed asadsorption
isotherm.

Adsorption isobars
The variation in the amount of gas adsorbed by the adsorbent with
temperature at constant pressure.

Adsorption Isosteres
The constant amount adsorbed of an adsorbent
t different relative pressure and temperature

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• In adsorption, adsorbate gets adsorbed on adsorbent.

• The direction of equilibrium would shift in that direction where the tension
can be relieved.

• In excess of pressure to the equilibrium system, the

equilibrium will shift in the direction where the
number of molecules decreases.
• Number of molecules decreases in forward direction. Therefore, forward
direction of equilibrium will be favored.

Basic Adsorption isotherm

Limited numbers of vacancies on the surface of the adsorbent.

After saturation pressure Ps, adsorption does not occur anymore.

At high pressure, a stage is reached when all the sites are occupied and
further increase in pressure does not cause any difference in adsorption
process.

At high pressure, Adsorption is independent of pressure.

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Stages of Adsorption isotherms

Sample preparation
• A small amount with homogenized particle size is weighed
• Transferred to the clean adsorption tube and weighed again.
• Tube is fixed in the BET system

Degassing
Degassing involves heating the sample and vacuum application
(P/Po = 10-4 : 10-3)

This is to free the surface from and adsorbed gas or vapor molecules

Stages of Adsorption isotherms

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Adsorption isotherm stages

1. Very low pressure
• Fast adsorption
• Micropore filling

2. Low pressure (monolayer)

• Monolayer is formed, Vmono
• Sharp knee is detected

3. Medium pressure (multilayer)

Multilayer formation
Slow adsorption of gas molecules
Only physisorption takes place

4. High pressure (capillary condensation)

Amount of gas adsorbed increases suddenly 5. Decrease pressure back to low pressure
Condensation takes place in pores and capillaries Desorption takes place
Pores are filled

IUPAC Classification of adsorption Isotherms

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Type I isotherm

Type I isotherm
• Typical of adsorbents with a predominantly microporous structure
• Corresponds to unimolecular adsorption (monolayer formation)
• Maximum limit in the amount adsorbed knee
• Molecules are large for the small pores
• Chemical adsorption (Chemisorption) follows Type I isotherm.
• Described by Langmuir Equation.
• Example: nitrogen on carbon at 77K and ammonia on charcoal at 273K

Type II isotherm
• Physical adsorption of gases by non-porous or
macroporous solids (pore diameter > 50 nm).
• Corresponds to multimolecular adsorption (monolayer
coverage
• followed by multilayering at high relative pressures).
• The heat of adsorption for the first adsorbed layer is greater
than that for the succeeding layers.
• Described by BET equation.

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Type III isotherm

• Type III isotherm
• Convex and undesirable (extent of adsorption is low
except at high P).
• Characteristic of weaker adsorbate-adsorbent interactions than
adsorbate-adsorbate interactions.
• Corresponds to multimolecular adsorption
• The heat of adsorption of the first adsorbed layer is less than that of
succeeding layers
• Example: adsorption of iodine vapor on silica gel, adsorption of water
vapour on activated carbons.

Type IV Isotherm
• The maximum extent of adsorption occurs before the
saturation pressure is reached knee

• A hysteresis loop, which is commonly associated

with the presence of mesoporosity
• Capillary condensation gives rise to a hysteresis loop.
• Example: adsorption of nitrogen on mesoporous carbons at 77 K.
• Similar to Type II but with condensation in pores.

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Type V isotherm
• Convex to the relative pressure axis
• Characteristic of weaker adsorbate-adsorbent
interactions than adsorbate-adsorbate interactions
• Microporous or mesoporous solids
• Hysteresis in multimolecular adsorption regions
• Capillary condensation version of Type III.
• Example: adsorption of water vapour on mesoporous activated
carbon

Type IV isotherm
• Complete formation of monomolecular layers
before progression to a subsequent layer
(Stepwise multilayer adsorption)
• Adsorption on extremely homogeneous, non-porous surfaces where
the monolayer capacity corresponds to the step height
• Examples: adsorption of krypton on carbon black at 90 K.
adsorption of butanol on aluminosilicate
adsorption of spherical non-polar molecules on graphite.

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Hysteresis loop
• Occurs due to capillary condensation (gas adsorption in the pores at a
low density → after a sufficient amount of gas has been supplied, it
spontaneously condenses into a liquid-like state inside the pores).
• Change of geometry during adsorption and desorption process

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H1
channels with uniform sizes and shapes with pores open from both
sides
Evaporation on desorption takes place fast.

H2
channels with a pore mouth smaller than pore body (ink-
bottle-shaped pores)

H3
slit shaped pores in non-rigid aggregates and flake like particles
solids here have a very wide distribution of pore size

H4
limited amounts of mesopores
dominated by micropores

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