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