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ADSORPTION

What is Adsorption?
Adsorption is a process
that occurs when a gas or
liquid solute accumulates
on the surface of a solid or
a liquid (adsorbent),
forming a molecular or
atomic film (adsorbate)

ADSORBENT ADSORBATE SOLUTION


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Adsorption & Absoption

Adsorption vs Absorption
• Adsorption is accumulation / adhesion of
molecules at the surface of a solid material
(usually activated carbon) 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
Absorption vs. Adsorption

Bulk (Volume) Surface


Phenomenon
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Phenomenon
Adsorption
PHASE I

‘PHASE’ 2

Absorption (“partitioning”)

PHASE I

PHASE 2
: fase teradsorbsi (adsorbat)
: fase pengadsorpsi (adsorben)

ADSORPSI ABSORPSI
Adsorption & Absoption

• absorpsi ( materi mengubah fase


larutan, e.g. transfer gas).
• adsorpsi ≠absorpsi
absorpsi : proses difusi materi/zat ke
dalam zat cair atau padat
untuk membentuk “larutan”.
d
• Adsorbat
• Adsorben
Why does Adsorption occur ?

• Consequence of surface energy


• Atoms on the surface experience a bond
deficiency, because they are not wholly
surrounded by other atoms

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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 Phenomenon
The surface of a solid shows a strong affinity for molecules that
come into contact with it.
Certain solid materials concentrate specific substances from a
solution onto their surfaces.
Physical adsorption (physisorption):
Physical attractive forces
(van der Waals forces)
e.g. Carbon ads, Activated alumina
Adsorption
Phenomenon Chemical adsorption (chemisorption):
the adsorbed molecules are held to the
surface by covalent forces.
Adsorpsi Fisik [Physisorption ]
 adsorbat melekat pada permukaan hanya melalui interaksi
Van der Waals (interaksi intermolekuler yang lemah).

 Karakteristik :
 Suhu lingkungan rendah, selalu di bawah suhu kritik adsorbat;
 Entalpi (kalor adsorpsi) rendah : ΔH < 20 kJ/mol;
 Energi pengaktifan (activation energy) rendah.
 Gaya tarik tidak pada tempat spesifik, adsorbat relatif bebas
bergerak pada permukaan  adsorpsi berlangsung dalam
multilayer

 Keadaan energi adsorbat tidak berubah.


 Keseimbangan adsorpsi reversibel.
Adsorpsi Kimia [Chemisorption ]
• molekul melekat pada permukaan melalui pembentukan
ikatan kimia yang kuat; dapat berupa ikatan kovalen antara
adsorbat dan permukaan (adsorben)
• Karakteristik :
 Suhu tinggi
 Entalpi tinggi :50 kJ/mol <ΔH< 800 kJ/mol.
 Kalor adsorpsi  kalor reaksi kimia  ikatan kimia
pembentukan senyawa permukaan
 Derajat spesifisitas tinggi  adsorpsi monolayer
 Molekul adsorbat tidak bebas bergerak pada permukaan
 Terdapat kenaikan densitas elektron pada antar permukaan
adsorben-adsorbat.
 Jarang reversibel ; hanya terjadi pada suhu tinggi
Adsorption isotherm
• The relationship at a given temperature between the
equilibrium amount of gas adsorbed and the pressure
of the gas
• Plot of the amount of adsorbate on the adsorbent
as a function of its pressure (if gas) or concentration
(if liquid) at constant temperature
Adsorption Isotherms

• Langmuir isotherm (adsorbed layer one molecule


thick)
• Freundlich isotherm (Heterogeneous adsorbent
surface with different adsorption sites)
• Brunauer, Emmett and Teller (BET) isotherm
(molecules can be adsorbed more than one layer
thick)
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Adsorption Isotherms

 Jika adsorben dan adsorbat kontak cukup lama  akan


tercapai kesetimbangan antara :
- jumlah adsorbat yang teradsorbsi dan
- jumlah adsorbat (“yang tertinggal”) dalam larutan/gas
 Hubungan kesetimbangan  isoterm adsorpsi
yaitu hubungan antara jumlah adsorbat yang
teradsorpsi pada adsorben dengan tekanan (untuk
gas) atau konsentrasi (untuk zat cair) pada suhu
konstan.
Langmuir Isotherm
 Irving Langmuir (1916)
 Assumptions:
Uniformity of sites Non interaction
Common Mechanism Monolayer only
 Semi-Empirical Formula:

Q- Mass of adsorbate / mass of


adsorbent
Qmax- Maximum Q to form a
mono-layer
c- equilibrium con. of adsorbate
in solution
K - constant
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Freundlich Isotherm
 Freundlich and Küster (1909)
 Empirical formula:

 Limitation: Fails at high pressures


Q- Mass of adsorbate /
mass of adsorbent
p- equilibrium pressure of
adsorbate
c- equilibrium con. Of
adsorbate in solution
K,n- constants
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BET Isotherm
 Stephen Brunauer, Paul Hugh Emmett
and Edward Teller (1938)
 Assumptions:
Multilayer No Transmigration
Equal Energy Langmuir to each layer

CS - saturation (solubility limit)


concentration of the solute(mg/liter)
KB - a parameter related to the binding
intensity for all layers.
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Adsorbents

• Adsorbents are used usually in the form of


spherical pellets, rods, moldings, or monoliths with
hydrodynamic diameters between 0.5 and 10 mm.
• They must have high abrasion resistance, high
thermal stability and small pore diameters, which
results in higher exposed surface area and hence
high surface capacity for adsorption.
Type Of Adsorbents

Most industrial adsorbents fall into one of three classes:


• Oxygen-containing compounds – Are typically
hydrophilic and polar, including materials such as silica gel
and zeolites.
• Carbon-based compounds – Are typically hydrophobic
and non-polar, including materials such as activated
carbon and graphite.
• Polymer-based compounds - Are polar or non-polar
functional groups in a porous polymer matrix.
Silica gel

• Silica gel is a chemically inert, nontoxic, polar and


dimensionally stable (< 400 °C or 750 °F). It is prepared
by the reaction between sodium silicate and acetic acid,
which is followed by a series of after-treatment processes
such as aging, pickling, etc. These after treatment methods
results in various pore size distributions.
• Silica is used for drying of process air (e.g. oxygen, natural
gas) and adsorption of heavy (polar) hydrocarbons from
natural gas.
Zeolites

• Zeolites are natural or synthetic crystalline


aluminosilicates which have a repeating pore network
and release water at high temperature. Zeolites are
polar in nature.
Activated carbon

• Activated carbon is used for adsorption of organic


substances and non-polar adsorbates and it is also
usually used for waste gas (and waste water)
treatment. It is the most widely used adsorbent. Its
usefulness derives mainly from its large micropore
and mesopore volumes and the resulting high surface
area.
Applications
• Activated Carbon
Hydrophobic Surface area-500m2/g
 Waste water treatment
 Decontaminant in pharmacy

• Silica Gel and Zeolites


Hydrophilic Polar
 Drying of process air
 CO2 and Hydrocarbon removal from natural gas
 Vapor Adsorption Refrigeration

• Protein Adsorption on biomaterials(cells)


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Applications
• 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 effecting Carbon Adsorption

• Physical and chemical characteristics of carbon


(surface area, pore size)
• Physical and chemical characteristics of adsorbate
(molecular size, molecular polarity, chemical
composition)
Higher molecular weight more easily adsorbed
Molecular weight  Size
Factors effecting Carbon Adsorption

• Concentration of adsorbate in the liquid phase


(solution)
• Characteristics of the liquid phase ? (pH, temperature)
• Contact time
• Increasing solubility of the solute in the liquid carrier
decreases adsorbability
• Branched chains are usually more adsorbable than
straight chains
Factors effecting Carbon Adsorption

• Substituent groups (hydroxyl, amino, carbonyl


groups, double bonds)
• Molecules with low polarity are more sorbable than
highly polar ones.