ADSORPTION

• 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
 Causes of Adsorption
• Dislike of Water Phase – ‘Hydrophobicity’
• Attraction to the Sorbent Surface
– van der Waals forces: physical attraction
– electrostatic forces (surface charge interaction)
– chemical forces (e.g., - and hydrogen bonding)
ADSORPTION: separation of component(s)
from liquid or gaseous mixtures by attachment
to a solid phase – the adsorbent

The most simple case: component A is separated

from a mixture with (inert) component B by solid
adsorbent C
feed raffinate
adsorbent adsorbate

A +B + C C+A + B+A
 Adsorbent, in
Cu2+ suspension at
Cu2+ concentration
Cu2+ Cu2+ csolid

Cu2+ Dissolved
Cu2+ Cu2+ adsorbate, at
concentration cCu(aq)
Cu2+
Cu 2+
Cu2+
Cu2+
Adsorbed species,
Cu2+ with adsorption
density q mg Cu per
g solid or per m2

Surface area per

Adsorbed species present gram of solid is the
at an overall concentration specific surface area
of cCu(ads)

 mg adsorbed   mg adsorbed   g solid per 

ci ,ads    qi   csolid  
 per L of solution   per g adsorbent   L of solution 
ADSORPTION IS AN EQUILIBRIUM PROCESS
 Adsorption Equilibria

An adsorption isotherm is a curve relating the

equilibrium concentration of a solute on the surface of an
adsorbent, qe, to the concentration of the solute in the
liquid, Ce, with which it is in contact.

The adsorption isotherm is also an equation relating the

amount of solute adsorbed onto the solid and the
equilibrium concentration of the solute in solution at a
given temperature.
q, = amount of solute adsorbed per unit weight of solid at
equilibrium. Unit is either g/g or mg/mg
Ce equilibrium concentration of solute remaining in
= solution when amount adsorbed equals q;

q8/C8 relationships depend on the type of adsorption that

occurs, multi-layer, chemical, physical adsorption, etc.
 Adsorbents in Natural & Engineered
Systems
• Natural Systems
– Sediments
– Soils
• Engineered Systems
– Activated carbon
– Metal oxides (iron and aluminum as coagulants)
– Ion exchange resins
– Biosolids
Engineered Systems - Removal Objectives
• Activated carbon (chemical functional groups)
– Adsorption of organics (esp. hydrophobic)
– Chemical reduction of oxidants
• Metal oxides (surface charge depends on pH)
– Adsorption of natural organic matter (NOM)
– Adsorption of inorganics (both cations & anions)
• Ion exchange resins
– Cations and anions
– Hardness removal (Ca2+, Mg2+)
– Arsenic (various negatively charged species), NO3-, Ba2+
removal
APPLICATIONS:
• removal of impurities from liquids
• purification of gases
• decolourizations
• separations of components of multicomponent
mixtures – chromatography
• separation and/or purification of biological
products
• environmental protection
• ….

SEPARATED COMPONENT(S) IN THE FEED IS (ARE)

TYPICALLY PRESENT IN LOW CONCENTRATIONS AS
CAPACITY OF THE ADSORBENT IS LIMITED
ADSORBENTS - examples
• activated carbon (charcoal …)
• silica gel
• aluminium oxide/alumina
• anorganic adsorbent …)
• (zeolites
• synthetic materials-polymers
• functionalized polymers
• nanostructured materials
spent biomass
ADSORBENTS
• particulate solids (spheres, cylinders, tablets,
irregular particles, fibers, flat sheets ….
• high internal porosity – open/connected
• pores
high surface density (m2/m3 = m-1)
• mechanical strength, stability
• density/buoyancy ( separation from liquid)
Activated carbon
 SILICA GEL
Basic component: SiO2
Basic applications:
- moisture adsorption from gases
- chromatographies
 ALUMINA
Basic component: Al2O3
Basic applications:
- chromatographies
- catalysts support
molecular sieve
 ZEOLITES
Zeolites are microporous crystalline solids
with well-defined structures. Generally
they contain silicon, aluminium and oxygen
in their framework and cations, water
and/or other molecules wthin their pores.
Many occur naturally as minerals, and are
extensively mined in many parts of the
world. Others are synthetic, and are made
commercially for specific uses, or produced
molecular sieves
by research scientists trying to understand
more about their chemistry.
 SYNTHETIC ADSORBENTS - resins
Example: Classification Chemical Auxiliary Agent
CAS No. 9003-05-8
Other Names super absorbent polymer
MF (C3H5NO)n

Number of synthetic
adsorbents is huge; can be
adjusted to specific tasks
 NANOSTRUCTURED ADSORBENTS

The most new adsorbents

 results of research in nanotechnology and
nanomaterials
 can be precisely tailored to specific tasks
 expensive
 premature state?
 SPENT BIOMASS

Spent microbial cells or fytomass are used

mainly in environmental applications –
water treatment
Cell walls frequently exhibit specific interactions
with dissolved components
 ADSORPTION
• PHYSICAL vs. CHEMICAL adsorption
• PHYSICAL adsorption is based on der
van Waals interactions between A
and C; reversible (A can be released
from C)
• CHEMICAL adsorption is based on formation
of chemical bonds between A and C;
irreversible (A can be only hardly released
from C)
 DESORPTION
= release of adsorbed component A from adsorbent C
– in case of physical adsorption

1) by heating, i.e., by increased temperature

(steaming)
2) by decreasing pressure of the gas phase
3) by elution with a proper eluent (a solution
of
different pH value, ionic strength, composition….,
sweeping gas)
 ADSORPTION IS A MULTISTEP PROCESS

1) CONVECTIVE TRANSPORT OF A COMPONENT IN BULK PHASE

(FAST)

2) EXTERNAL DIFFUSION IN STAGNANT FILM AROUND

PARTICLE (SLOW)

3) INTRAPARTICLE DIFFUSION WITHIN PORES (SLOW)

4) SURFACE DIFFUSION AND/OR DIFFUSION IN SOLID PHASE
5) ADSORPTION TO ACTIVE SITE OF THE ADSORBENT
(a) Linear (b) Langmuir

(c) BET (d) Freundlich

Summary of Lecture 1 and 2
Isotherm models

There are several models for predicting the

equilibrium distribution.
However, the following four models are most
commonly observed.
Characteristic of adsorbent make it suitable and effective for
separation of a mixture:

(i) Selectivity
(ii) Adsorption capacity
(iii) Reversibility of adsorption
(iv) Particle size and its distribution
(v) Porosity and pore-size distribution
(vi) Specific surface area
(vii) Structural strength and stability
 ADSORPTION EQUILIBRIUM

• ADSORBING COMPONENTS bind to ACTIVE

SITES of the adsorbents
• Number of active sites is limited  of
amount
adsorbed component(s) is limited/saturation

C
As Al/g XA
K eq  c
A

K eq depends on T, p, cA and XA
63
 ADSORPTION EQUILIBRIUM

• adsorbate typically forms monomolecular

layer
• multimolecular layers are (sometime)
• possible
• theoretical models
for liquid phase of adsorption
adsorption exist
the equilibrium is
measured

64
Lecture #1

ADSORPTION EQUILIBRIUM

• is described by ADSORPTION ISOTHERMS

• dependence of Xi on ci at T = const.

Xi

65
 Adsorption Equilibria

i. Linear
ii. Langmuir
iii. Freundlich
iv. Brunauer, and Teller (BET)
Emmet,
The most commonly used isotherms for the application
of activated carbon in water and wastewater treatment
are the Freundlich and Langmuir isotherms.
Freundlich isotherm is an empirical equation.
Langmuir isotherm has a rational basis.
Commonly Reported Adsorption Isotherms
K Lc
Linear: q  klin c Langmuir: q  qmax 1  K c
L

n
Freundlich: q  k f c
 Langmuir Isotherm

Assumptions used for the Langmuir isotherm

1. Gaseous molecules behave ideally
2. Only one monolayer forms
3. All sites on the surface are equivalent
4. No adsorbate - adsorbate interactions
5. An adsorbed molecule is immobile
Freundlich Isotherm

log q= log K’ + 1/n log P

BET isotherm (adsorption from gases)
(1938: Stephen Brunauer , Paul Hugh Emmett and Edward Teller)
Assumptions
1. Gas molecules physically adsorb on a solid in layers infinitely
2. There is no interaction between each adsorption layer
3. Langmuir theory can be applied to each layer.
4. Uppermost layer is in equilibrium with vapor phase
5. First layer: Heat of adsorption; Higher layers; Heat of condensation
 1 (C  1) P 1
 
Vads ( Ps / P)  1 VmC Ps VmC
 MOST FREQUENTLY USED ADSORPTION
ISOTHERMS
Freundlich isotherm
(adsorption from liquids, empirical)
q
XA  b c A
Tëmkin isotherm (adsorption from liquids)

XA  a  b
ln(cA)
The Type I isotherm is typical of microporous solids and chemisorption isotherms.
Type II is shown by finely divided non-porous solids.
Type III and type V are typical of vapor adsorption (i.e. water vapor on hydrophobic
materials).
Type VI and V feature a hysteresis loop generated by the capillary condensation of
the adsorbate in the mesopores of the solid.
Finally, the rare type VI step-like isotherm is shown by nitrogen adsorbed on special
carbon.
 ADSORBERS

• stirred adsorbers (one or two stages)

• fluidized-bed adsorber

• multistage counter-current adsorbers

• fixed-bed adsorbers
Single-stage stirred adsorber
mc q 0

, - equilibrium stage
- mass balance of A
- equilibrium

Vf (cAF  cAe )  mC (XAe  XA0 )

Vf , CAF
XAe  feq ( cAe ) ads. isotherm

two equations for two unknowns

70
Contacting Separation
Carbon

B qo

V
V C1
Co
B
q1 Treated
Spent Wastewater
Carbon
The previous diagram can be seen as a stage
operation, i.e.:
B
qo

V C1
Co
V

q1
B
At a given time t when the carbon is separated the
following mass balance can be written:

V Co  C   Bq qo 

where: V = wastewater volume ( constant)

B = mass of activated carbon
q = qo at t=0
Co = initial concentration of pollutant in wastewater
At the generic time t it is:
B
C  Co  q qo
 V
This equation represents an operating line (from a mass
balance) for the system.
If the time elapsed is long enough for equilibrium to be
established then this equation becomes:
B
Ceq  Co  V qeq 
q 
A mass balance for a pollutant in an differential time interval,
dt, during a batch adsorption operation is:
V dC   K Ap C  C *dt
where: V = volume of wastewater (m 3)
K = mass transfer coefficient between carbon particle and
wastewater (m/s)
Ap = cumulative surface area of carbon particles (m2)
C = pollutant concentration (g/L)
C* = pollutantconcentration in
equilibrium with concentration q in the particle at time
t (g/L)
The previous equation can be integrated to give:

t 1 C dC'

K ap  C C' C'*
o

where: a = surface area of particles/liquid volume

This equation can be integrated if the equilibrium
isotherm is known and by knowing that the mass
balance at a generic time, t, is given by:

V Co  C   B q  qo 
During the initial stages of the process it is:
C  C *
Then:
C
1 dC' 1 C
t 
  ln
K ap  C C' 
o

This equation can

be used o
approximately
to
K ap C
estimate
concentrationthe time required
in the wastewater the drop pollutant
to to a
for
desired level.
If the adsorption follows a known adsorption model (e.g.,
Freundlich isotherm) then:

1n

q eq  KF Ceq

combined with: Ceq  Co  eq

 o

gives: B
V q q 
Ceq  Co 
V

B K F C eq1 n
 o

q 
which can be solved to find Ceq for the case in which enough
time is allowed for equilibrium to be reached.
Multistage Crosscurrent Adsorption
. .
B1 B 2
qo qo

. . .
V V V
Stage Stage
Co 1 C1 2 C2
. .
B1 q1 B2 q2
Multistage Crosscurrent Adsorption
Co Operating Line

(g/L) . .

- B. 1/V
C

C1
. Isotherm
- B2/V
C2 q2 q1
qo
q (g solute/g carbon)
Multistage Crosscurrent Adsorption
In this case fresh carbon is added to each stage of the
adsorption process.
If equilibrium is assumed to be achieved in each stage
then one can write:
Multistage Crosscurrent Adsorption
Multistage Crosscurrent Adsorption
The total amount of carbon used per volume of liquid
treated is:

Note that the amount of carbon needed for a given

process is a function of the initial, intermediate and
final concentration in the wastewater (Co, C1, and C2,
respectively), the equilibrium constant KF, and the level
of pollutant already present in the carbon (if the
carbon is fresh qo = 0)
Multistage Countercurrent Adsorption
 Multistage Countercurrent Adsorption
 The streams leaving each stage are assumed to be
in equilibrium with each other
 The numbers attached to the streams leaving any
stage are the same as the number of the stage the
streams are leaving
 The rates of wastewater and activated carbon
moving from stage to stage are constant
 In wastewater applications typically no more than
two (2) stages are used

PIERO M. ARMENANTE NJIT

Multistage Countercurrent Adsorption
 ION EXCHANGE

Ion exchange is an adsorption phenomenon where

the mechanism of adsorption is electrostatic.

Electrostatic forces hold ions to charged functional

groups on the surface of the ion exchange resin.

Ion exchange is a rate-controlled process,
usually governed by diffusion in the bead or
the surrounding stagnant liquid film.

80
CATION EXCHANGERS: contain fixed anionic groups and movable
cations
R-SO3 H 
R-COO H
strong acid weak acid

ANION EXCHANGERS: contain fixed cationic groups and

movable anions

 
R-CH2 -N(CH3 )3 Cl

strong base weak base

 Cation exchange resin schematic showing
negatively charged matrix and exchangeable
positive ions

82
 Since ion exchange occurs between a solution
and the internal surface of a solid it can be
viewed as a special type of sorption process.
 There are many similarities between
adsorption and ion exchange. The two
processes are often analyzed using similar
models.
 Unlike adsorption ion exchange requires
an interchange of materials, i.e., the ions
(as opposed to a unidirectional transfer)
since the electroneutrality of the solution
must be maintained.
 Classification of resins
• According to the chemical nature
• 1. Strong cation exchange resin 2. Weak cation exchange resin
• 3. Strong anion exchange resin 4. Weak anion exchange resin
• According to the source
• Natural: cation Zeolytes, clay etc
• anion  Dolomite
• Synthetic: inorganic & organic resins
• Organic resins are the most widely used
• Org ion exchange resins are polymeric resin matrix containing exchange sites.
• The resin is composed of polystyrene & Divinyl benzene, polystyrene contains
sites for exchangeable functional groups
• Divinyl benzene acts as a cross linking agent & offers adequate strength i.e,
mechanical stability
 Physical properties or resins
• 1. Particle size: 50-200 mesh fine powder,
• should allow free flow of mobile phase, should
contain more exchangeable functional groups
• 2. Cross linking & swelling:
• When more cross linking agent is present, they
are more rigid, but swells less
• When swelling is less, separation of ions of diff
sizes is difficult as they can’t pass through the
pores present.
 Physical properties or resins
• When less cross linking agent is present, they
are less rigid, but swell more
• Separation will not be efficient as exchange of
functional groups does not take place due to
wide pore
• Hence an optimum quantity of cross linking
agent should be added to the polymeric ion
exchange resin for the separation to be
effective.
Factors affecting ion exchange separations
• B) Size of ions: for similar charged ions, exchange increases with
decrease in the size of hydrated ion.
• Li < H+ < Na+ < NH4+ < K+ < Rb+ < Cs+
• C) Polarizability: exchange is preferred for greater polarizable ion
• Eg: I- < Br- < Cl- < F-
• D) conc of solution: in dilute solutions, polyvalent anions are generally
adsorbed preferentially
• E) conc and charge of ions: if resin has higher +ve charge and solution
has lower +ve charge , exchange is favoured at higher conc.
• If the resin has lower +ve charge and solution has high +ve charge ,
then exchange is favoured at low conc.
 applications
• Softening of water
• Demineralisation or deionisation of water
• Purification of some solutions to be free from
ionic impurities
• Separation of inorganic ions
• Organic separations: mixture of pharmaceutical
compounds can be separated
• Biochemical separations like isolation of drugs or
metabolites from blood, urine etc
• Conc of ionic solutions
separation factor (definition)

yA x B
AB 
y B xA

86
ION EXCHANGERS
 Stirred vessels with ion exchanger perticles in
suspension or spouted bed systems.
 Fixed-bed (column) exchangers.

87
 ION EXCHANGE
CHROMATOGRAPHY
 Chromatography
 The process or technique of separating molecules or
components in a mixture solution (gas or liquid) according
to the differential absorption and elution
 Invented in 1906 by the Russian botanist Mikhail Tsvet
 Chromatography is the physical separation of a mixture
into its individual components.
 Used in qualitative and quantitative analysis of biological
and chemical substances
 This technique employs two immiscible
substances- mobile phage and stationary phage

 Mobile phage
-solution of gas or liquid components, works
as transporter, moves in a definite direction

 Stationary phage

-liquid or solid, absorbs or impedes different

components of the solution to different degrees
Principle……

Different affinity of the different

components to stationary phase causes the
separation
Types of Chromatography

Adsorption Chromatography
Partition Chromatography
Ion Exchange Chromatography
Molecular Exclusion Chromatography
Affinity Chromatography
 Ion Exchange Chromatography
Ion exchange chromatography -- is a separation based on
charge
Used for almost any kind of charged molecules --- large
proteins, small nucleotides and amino acids
Ion-exchange chromatography preserves analyte
molecules on the column based on ionic interactions
Mobile phage – buffer, pH and salt concentration---
opposite charged solute ions attracted to the stationary
phase by electrostatic force
Stationary phase– resin is used to covalently attach anions
or cations onto it
 Principle……….

Ion Exchange Chromatography

relies on charge-charge interactions
between the proteins
 Types of IEC….

anion exchangers
cation exchangers
Cation exchange chromatography
---positively charged molecules are attracted to a
negatively charged solid support. Commonly used
cation exchange resins are S-resin, sulfate
derivatives; and CM resins, carboxylate derived
ions
Anion exchange chromatography
---negatively charged molecules is attracted to a
positively charged solid support. Commonly used
anion exchange resins are Q-resin, a Quaternary
amine; and DEAE resin, DiEthylAminoEthane