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Adsorption Isotherm

Subtitle
Adsorption Processes
› Classified as Physical and Chemical Ads.
1) Physical adsorption
› The gas molecules adhere to the surface of the solid adsorbent as a
result of intermolecular attractive forces (van der Waals forces)
between them
› The process is exothermic: the heat liberated is in the order of the
the enthalpy of condensation of vapor (2-20 kJ/gmole)
› The process is reversible (recovery of adsorbent material or
adsorbed gas is possible) by increasing the temperature or
lowering the adsorbate conc.
› Physical adsorption usually directly proportional to the amount of
solid surface area
› Adsorbate can be adsorbed on a monolayer or a number of layers
› The adsorption rate is generally quite rapid
2) Chemical adsorption
› Results from a chemical interaction between the
adsorbate and adsorbent. Therefore formed bond is
much stronger than that for physical adsorption
› Heat liberated during chemisorption is in the range of 20-
400 kj/g mole
› It is frequently irreversible. On desorption the chemical
nature of the original adsorbate will have undergone a
change.
› Only a monomolecular layer of adsorbate appears on the
adsorbing medium
Mechanism
Absorption vs adsorption
Terminology
› 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 adsorbing. (examples are


activated carbon or ion exchange resin).
Adsorbent Material
– Silica gel Dehyrdating
purposes
– Activated alumina
– Activated carbon
– Synthetic zeolite
• Molecular sieve
Properties of Activated Carbon
Bulk Density 22-34 lb/ft3
Heat Capacity 0.27-0.36 BTU/lboF
Pore Volume 0.56-1.20 cm3/g
Surface Area 600-1600 m2/g
Average Pore Diameter 15-25 Å
Regeneration Temperature 100-140 oC
(Steaming)
Maximum Allowable 150 oC
Temperature

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Adsorbent Material
Properties of Silica Gel
Bulk Density 44-56 Properties of Activated Alumina
lb/ft3 Bulk Density
Heat Capacity 0.22-0.26
Granules 38-42 lb/ft3
BTU/lboF
Pore Volume 0.37 Pellets 54-58 lb/ft3
cm3/g Specific Heat 0.21-0.25
Surface Area 750 m2/g BTU/lboF
Average Pore Diameter 22 Å Pore Volume 0.29-0.37
cm3/g
Regeneration 120-250 Surface Area 210-360 m2/g
Temperature oC

Maximum Allowable 400 oC Average Pore Diameter 18-48 Å


Temperature Regeneration Temperature 200-250 oC
(Steaming)
Maximum Allowable 500 oC
Temperature

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Adsorbent Materials
Properties of Molecular Sieves
Anhydrous Anhydrous Anhydrous
Sodium Calcium Aluminosilicat
Aluminosilicate Aluminosilicate e
Type 4A 5A 13X
Density in bulk (lb/ft3) 44 44 38
Specific Heat (BTU/lboF) 0.19 0.19 -
Effective diameter of pores (Å) 4 5 13
Regeneration Temperature (oC) 200-300 200-300 200-300
Maximum Allowable Temperature 600 600 600
(oC)

• Crystalline zeolite
• Uniform pores to selectively separate compounds by size & shape

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Adsorption Equilibria
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.
Some general isotherms
Isotherm models
Langmuir Isotherm:
This model assumes monolayer coverage and
constant binding energy between surface and
adsorbate. The model is:

a 'plot of p/V versus p should give a straight line of slope l/Vm and
an intercept of l/aVm on the p/V axis. At low pressures the Langmuir
isotherm equation reduces to V = Vmap - i.e. the volume of gas adsorbed
varies linearly with pressure. At high pressures a limiting monolayer
coverage, V- Vm, is reached
Freundlich Isotherm:

For the special case of heterogeneous surface energies


(particularly good for mixed wastes). The variation of adsorption
with pressure can often be represented (especially at
moderately low pressures) we use Freundlich model.

where k and n are constants, n usually being greater than unity. A plot
of log V versus log p should give a straight line
Freundlich equation of an adsorption from solution
where x –quantity of the adsorbed substance, m-adsorbent’s mass, p
and c-equilibrium pressure and concentration. The linear form of the
equation: ln Г = ln k + 1/n ln с
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.
K B  Ce  Q 0
qe  a

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

› In general, an adsorption isotherm relates the volume


or mass adsorbed to the partial pressure or
concentration of the adsorbate in the main gas
stream at a given temperature
› The equilibrium concentration adsorbed is very
sensitive to T
› There are many equations proposed to fit analyticaly
the various experimental istoherms

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Adsorption from a solution
› Adsorption from solution is important in many practical
situations, such as those in which modification of the solid
surface is of primary concern (e.g. the use of lyophilic material
to stabilise dispersions) and those which involve the removal
of unwanted material from the solution (e.g. the clarification of
sugar solutions with activated charcoal).
› The adsorption of ions from electrolyte solutions and a special
case of ion adsorption, that of ion exchange. Adsorption
processes are, of course, most important in chromatography
Factors affecting adsorption extent (and therefore
affect isotherm)
Adsorbate:
Solubility
In general, as solubility of solute increases the extent of
adsorption decreases. This is known as the “Lundelius’
Rule”. Solute-solid surface binding competes with solute-
solvent attraction as discussed earlier. Factors which affect
solubility include molecular size (high MW- low solubility),
ionization (solubility is minimum when compounds are
uncharged), polarity (as polarity increases get higher
solubility because water is a polar solvent).
Factors affecting adsorption extent (and therefore
affect isotherm
pH
pH often affects the surface charge on the adsorbent as well as
the charge on the solute. Generally, for organic material as pH
goes down adsorption goes up.

Temperature
Adsorption reactions are typically exothermic i.e., D H rxn is
generally negative. Here heat is given off by the reaction
therefore as T increases extent of adsorption decreases.
Factors affecting adsorption extent (and therefore
affect isotherm

Presence of other solutes


In general, get competition for a limited
number of sites therefore get reduced extent
of adsorption or a specific material
Adsorbent: Activated Carbon (AC)
AC prepared from many sources:
• Wood
• Lignite
• Coal
• Nutshells
• Bone
Spent AC can be regenerated at high temperatures
(roughly a maximum of fifteen times).
Carbon Regeneration
Since activated carbon is relatively expensive, adsorption would
not be feasible unless the carbon can be regenerated after
exhaustion. Spent carbon is usually regenerated at 500 oC under
low oxygen conditions in the presence of steam. Activated
carbon loss is about 5-15% for each regeneration. Adsorbed
organics are volatilized and oxidized during the regeneration
process.
Summary of the lecture
Chemistry efects
Composition influences the adsorption potential - for
example the alkaline zeolites adsorbed nitrogen at very low
pressure.

Structure
Adsorption potential also follows pore size - for example a
5A pore adsorbs nitrogen at lower pressures than an 8A
pore.
Surface Area
Surface area increases as pore size decreases