University of Al-Qadisiyah

Engineer of college
`
Chemical engineering

Separation process
Adsorption and ions exchange

By

ALI F. HASAN
Supervisor by

Prof. Dr. SALIH A. SALIH

* Adsorption: is the accumulation of a substance at a surface
or interface
* Absorption: is the accumulation and distribution of a
substance throughout a phase.

Adsorption differs from absorption in which complete permeation

occurs of the solute in the solvent e.g. sugar in water.

• Drugs are adsorbed by a membrane; enzyme or cell wall when they

are attached to its surface.

• Drugs are absorbed by a tissue, organ or blood when they permeate

its entire bulk or volume.
The process creates a film of the Adsorbate on the surface of the
adsorbent.
 Solid substrate is called Adsorbent.
 The substance being adsorbed called Adsorbate.
 Sorption: general term if the uptake is thought to consist of both
adsorption and absorption processes.
 Desorption is the reverse of adsorption, both adsorption and
desorption are named sorption

* Adsorption of gases on solid surfaces: removal of toxic gases,

adsorption of objectionable odors from rooms and foods
* Adsorption from liquid on solid surfaces: decolonization of liquids,
removal of toxins by oral administration of charcoal e.g: strychnine
* The amount of the substance adsorbed at equilibrium depends on:
a) temperature, b) gas vapor pressure, c) specific surface area of the
adsorbent.
*The basic feature of a good adsorbent is a large specific surface area. The
larger the surface area, the more molecules are trapped on its surface.
* The nature of a solid or gas also plays a significant role.
* The nature of the adsorbent has a profound effect on the adsorption
process.
*a good adsorbent is very porous. The specific area of an adsorbent is
the surface area available for adsorption per gram of the adsorbent.
 Micropores dpore < 2 nm
 Mesopores dpore = 2-50 nm
 Macropores dpore > 50 nm

Adsorption processes are characterized by the following:

1. Adsorption is more complete from dilute solutions than from
concentrated ones.
2. More complex structures are more easily adsorbed than simple ones.
3.In contrast to chemical reactions, adsorption processes proceed more
rapidly at lower temperatures.
4. A change of pH may affect the process of adsorption e.g. adsorption
of methylene blue.
5. Adsorption is a surface phenomenon, thus increasing the surface
area of the adsorbent (by size reduction) increases the adsorption.
 Classification of Adsorption

Physical adsorption Chemical adsorption

(Physisorption )
Reversible
Weak van der Waals forces
Common at low temp
Doesn’t acquire activation
energy
Fast adsorption rate, since it is
a non-activated process
Ex) adsorption of gases on
charcoal
(Chemisorption )
Irreversible
Strong chemical bond
Occurs at high temp
acquire activation energy
Slow adsorption rate
Ex) e.g. adoption of oxygen on
tungsten

Equilibrium of Adsorption:
 Between the adsorbate and adsorbent dynamic equilibrium is established
which results from equalization of the number of adsorbed molecules with that
of molecules undergoing desorption:Aads↔Ades
 This follows as in the same time unit the same number of adsorbate
molecules is undergoing adsorption and desorption.
 The adsorbed substance is expressed in grams, moles or cm3 per the adsorbent
mass unit. In adsorption equilibrium these quantities depend on the gas,
temperature and pressure.
• The general relationship between the amount of gas (volume, V) or the
concentration of solute in solution (C) adsorbed by a solid at a constant
temperature (T) and as a function of the gas pressure (P) is defined as its
adsorption 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 adsorption isotherms.

6.2.2 Equilibria
In adsorption, a dynamic equilibrium is established between the molecules in
the fluid phase and molecules adsorbed on the solid surface as shown in
Figure 6.9.

When the rate of adsorption and desorption are in balance, a dynamic

equilibrium is established.
This equilibrium is commonly expressed in the form of an isotherm, a
diagram showing the equilibrium adsorbed-phase concentration or loading as
a function of the fluid-phase concentration, CA, or partial pressure, pA, at a
fixed temperature.

For pure gases, experimental physical adsorption isotherms are represented in

amount of molecules adsorbed qA versus partial pressure pA or concentration
cA.
According to their shapes, Brunauer classified adsorption isotherms into five
types as shown in Figure 6.10.
The simplest and the most commonly encountered isotherm is the Langmuir
type I isotherm:

Figure 6.9: Schematic of the dynamic adsorption/desorption equilibrium

fraction occupied θA = 6=14; fraction not occupied 1 − θA = 8=14.

where θA is the fraction of

sites occupied (see Figure 6.9); qA is the amount adsorbed per unit volume or
unit weight adsorbent; qmax,A is the monolayer capacity, referring to maximum
occupancy or θA = 1; bA is the Langmuir adsorption constant in reciprocal
pressure unit; and b’A is the Langmuir adsorption constant in reciprocal
concentration unit.
Both types I and II are desirable isotherms as they exhibit strong adsorption at
lower partial pressures or concentrations.
This facilitates operation of an adsorption process at low pressures while
enabling large loading.
Figure 6.10 demonstrates the two limiting cases of a type I isotherm: linear
behavior at low (relative) pressures (bApA ≪ 1) and maximum occupancy at
higher concentrations (bApA ≫ 1).
For bApA ≪ 1, the Langmuir isotherm reduces to a linear form and the
following functional form of Henry’s law,1 called a linear isotherm, is
obeyed:
 Figure 6.10: The Brunauer classification of adsorption isotherms.

The Langmuir isotherm can be derived based on four assumptions:

1. The adsorbed molecule or atom is held at definite, localized sites.
2. Each site can accommodate only one molecule or atom.
3. The energy of adsorption is constant over all sites.
4. There is no interaction between neighboring adsorbates.
At equilibrium, the rates of adsorption and desorption are equal. at
equilibrium, the difference between the adsorption and desorption rates
vanishes:

Rearrangement of eq.(6.6) and introducing eq.(6.7)

 results in eq.(6.4), the Langmuir equation for adsorption from
the gas phase.
However, in practice adsorption isotherms are often reported in dimensional
form as given in eq.(6.9a):

The adsorption constant bA is temperature dependent in a way that is related

to the activation energy of adsorption, ΔEads, through an Arrhenius-type
equation:

For an exothermic process, ΔEads is negative, and the adsorption constant

decreases with increasing temperature.
The Langmuir model can faithfully represent a type I isotherm, since at low
pressure it approaches Henry’s law while at high pressure it tends
asymptotically to the saturation limit.
For adsorption from a liquid phase, it is convenient to replace the (partial)
pressure by concentration

where b′ is the Langmuir adsorption constant in reciprocal

concentration units.
In many cases, however, the equation is still applicable; both parameters can
be treated as empirical constants, qmax and bA, obtained by fitting the nonlinear
equation directly to experimental data or by employing a linearized form of
eq.(6.9a):
The Langmuir model can be extended to multicomponent systems, reflecting
the competition between species for the adsorption sites:

The equilibrium selectivity of the adsorbent, α′AB (see eq.(1.10)), now simply
corresponds to the ratio of the equilibrium constants from the multicomponent
Langmuir model:

Because this selectivity is independent of composition, the ideal Langmuir

model is often referred to as the constant separation factor model.
As the pore size decreases, this effect becomes more pronounced and it is
represented in Kelvin equation as follows

where Psat(d) and Psat are the vapor pressure of liquid in pore of
diameter d and the vapor pressure of liquid in bulk.
Moreover, υL, σ, θ, R, T denote the interfacial energy of liquid in pore, molar
volume of liquid, the contact angle liquid–pore material, gas constant and
temperature in Kelvin, respectively.
# Kinetics
In general, the rate of physical adsorption is controlled by mass transfer
limitations rather than by the actual rate of equilibrium adsorption/desorption
inside the adsorbent pores.
As illustrated schematically in Figure 6.11, the adsorption of a solute onto the
porous adsorbent surface requires the following steps:
1. External mass transfer of the solute from the bulk fluid through a thin film
or boundary layer to the outer solid surface of the adsorbent.
2. Internal mass transfer of the solute by pore diffusion from the outer adsorbent
surface to the inner surface of the internal pore structure.
3. Surface diffusion along the porous surface.
4. Adsorption of the solute onto the porous surface

During the adsorbent regeneration, these four steps follow in reverse order,
that is, step 4 to step 1.
From this perspective, adsorbents may be divided into two broad classes:
homogeneous and composite.
Figure 6.12 illustrates that in homogeneous adsorbents (activated alumina and
silica gel) the pore structure persists throughout the particle, while the
composite adsorbent particles (zeolites and carbon molecular sieves) are
formed by aggregation of small microporous microparticles.
Transport in a macropore can occur by bulk molecular diffusion, Knudsen
diffusion, surface diffusion and laminar convection/ Poiseuille flow.

Figure 6.12: Homogeneous (a) and composite (b) microporous adsorbent

particle (adapted from).

In micropores, the diffusing molecule never escapes from the influence of the
pore wall, and the Knudsen mechanism no longer applies.
Diffusion occurs by jumps from site to site, just as in surface diffusion, and
the diffusivity becomes strongly dependent on both temperature and
concentration.
The selectivity in a kinetically controlled adsorption process is dictated by
both kinetic and equilibrium effects.
This kinetic selectivity can be approximated when two species (A and B)
diffuse independently and their isotherms are also independent.
Under these conditions, selectivity or the ratio of their uptakes at any time will
be given by the Langmuir isotherm constants bA,bB and diffusion constants
DA, DB of species A and B:
Fixed-bed adsorption
6.3.1 Bed profiles and breakthrough curves
A fixed bed is considered ideal under the following conditions: (i) external
and internal mass transfer resistances are very small; (ii) plug flow is achieved
instantaneously inside the bed, and the axial dispersion, that is, deviation from
plug flow is negligible; (iii) the adsorbent is initially free of adsorbate.

03
After a period of time called the stoichiometric time, the stoichiometric wave
front reaches the end of the bed and the concentration of the solute in the fluid
rises abruptly to the inlet value.
Because no further adsorption is possible, this point is referred to as the
breakthrough point.
In a real fixed-bed adsorber, internal and external transport resistances are
finite and axial dispersion can be significant.
The S-shaped curve in Figure 6.15 is called the breakthrough curve,
representing the outlet-to-inlet solute concentration in the fluid as a function
of time from the start of the flow.
The region between tbp and tsat is the MTZ, where adsorption takes place.
For a flow rate Q, the useful capacity of the bed, Quc, and its total capacity
Qtot are, respectively:
Langmuir Adsorption Isotherm

This isotherm characterizes chemical adsorption where only a monolayer

formation occurs.
It is based on 4 assumptions:
1. The surface of the adsorbent is uniform, that is, all the adsorption sites are
equivalent.
2. Adsorbed molecules do not interact.
3. All adsorption occurs through the same mechanism.
4.At the maximum adsorption, only a mono-layer is formed i.e. molecules of
adsorbate do not deposit on others, already adsorbed.
Langmuir considered the adsorption as a dynamic process
Adsorption and desorption are continuous processes till equilibrium occurs.
Ion chromatography (or ion-exchange chromatography) is a chromatography
process that separates ions and polar molecules based on their affinity to the ion
exchanger. It works on almost any kind of charged molecule including large
proteins, small nucleotides, and amino acids.
PRINCIPLE: Adsorption process (Surface phenomenon)
Ion Exchange chromatography is used in the separation of charged
biomolecules. The crude sample containing charged molecules is used as the
liquid phase. When it passes through the chromatographic column, molecules
bind to oppositely charged sites in the stationary phase
CLASSIFICATION OF RESINS: According to the chemical nature they
classified as:-
1. Strong cation exchange resin – Sulphonic acid
2. Weak cation exchange resin – Carboxy methy compound
3. Strong anion exchange resin – Quaternary ammonium compound
4. Weak anion exchange resin - Diethyl aminoethyl compound
According to the Source they are classified as:
Natural : Cation - Zeolytes, Clay Anion - Dolomite
Synthetic : Inorganic & Organic resins
Organic resins are polymeric resin matrix
The resin composed of – Polystyrene (sites for exchangeable functional
groups), Divinyl benzene (Cross linking agent)- it offers stability
 APPLICATIONS
 Softening of water
 Demineralization of water
 Purification of solutions free from ionic impurities
 Separation of inorganic ions
 Separation of sugars, amino acids
 To separate creatine kinase (CK) isoenzymes from human serum and
tissue sourced in autopsy material (mostly CK rich tissues were used such as
cardiac muscle and brain)
 Ion Exchange Chromatography is used in different aspects of product
development and quality control testing. For example, IC is used to improve
stabilities and solubility properties of pharmaceutical active drugs molecules
as well as used to detect systems that have higher tolerance for organic
solvents.