ADSORPSI

Fenomena

d
DEFINISI

Fenomena yang berkaitan erat dengan

permukaan yang melibatkan interaksi antara
molekul yang bergerak (cairan atau gas) dengan
molekul yang relatif diam pada permukaan atau
antar permukaan
atau
akumulasi berkumpulnya partikel adsorbat pada
permukaan adsorben (substrat)
 DEFINISI

Adsorbate:
the material being
adsorbed. gas Adsorbed
molecules
Adsorbent:
the material doing the
adsorbing.

solid

Adsorption of gas molecules

Why is Adsorption Useful?

Used in many industrial processes:

 dehumidification
 odour/colour/taste removal
 gas pollutant removal (H2S)
 water softening and deionisation
 hydrocarbon fractionation
 pharmaceutical purification
Thermodinamika Adsorpsi

G  H  TS
Adsorption is spontaneous, G  0
Entropy decreases during adsorption S  0
Therefore: H  0
adsorption is a exothermic process
 Thermodinamika Adsorpsi
 Fenomena bahan hidrofob dalam air
air memilih mengumpulkan bahan hidrofob pada permukaan, karena
energi ikatan dan afinitas diantara mereka sangat lemah sehingga
air menempatkannya di permukaan agar lebih sedikit energinya.
 tegangan permukaan pelarut menurun

 Fenomena bahan hidrofil dalam air

air akan bergabung dengan bahan hidrofil, karena energi ikatan
dan afinitas keduanya sangat kuat sehingga air melarutkannya.
Kondisi ini akan meningkatkan kekuatan air di permukaan.
 tegangan permukaan pelarut meningkat
 Surface excess
Massa partikel yang berkumpul di permukaan memberikan pengaruh
(excess) pada antar permukaan, sejauhmana pengaruhnya ditentukan
dengan persamaan surface excess ( G ):

(C initial  C afteradsorption)" Volume "

G
" surface area"
Cinitial = konsentrasi awal adsorbat
Cafter adsorption = konsentrasi adsorbat setelah adsorpsi
Volume = volume larutan adorbat
Surface area = luas area adsorbat
 Hubungan G dan γ
Didefinikan pada persamaan Gibb’s :
d   Gi dm i
i
d  Gd(m 0  RT ln C)
dC d
d  GRT 0
C dC
results in increases in G
d R TG d
 0
dC C dC results in decrease in G
mi = the molar free energy of solute i.
Ci = the bulk concentration of this solute
 Jenis adsorpsi
 Dibedakan berdasarkan fase :
 Interaksi antara solven dan solute (hidrofobisitas – surfaktan)  emulsion

 Interaksi antara solida dan solute  suspension

 Dibedakan berdasarkan energi ikatan :

o Physical Adsorption / Physisorption (van der Waals adsorption):

weak bonding of gas molecules to the solid;

exothermic (~ 0.1 Kcal/mole);
reversible;
o Chemisorption:

chemical bonding by reaction;

exothermic (>10 Kcal/mole);
irreversible;
o Dissociative adsorption:
Physical vs Chemical Adsorption
 Physical vs Chemical Adsorption
Physisorption :
no activation barrier, fast, reversible, surface
symmetry insensitive, multilayer formation
possible, Tsurface < Tcondensation
Chemisorption :
activation barrier possible (b), variable uptake
kinetics, covalent / ionic / metallic bonding,
often irreversible, surface symmetry specific,
limited to monolayer, wide range of Tsurface
 Physical vs Chemical Adsorption

sorption physisorption chemisorption

interaction Van der Waals force, hydrogen Chemical bond
bond
Thermal effect Condensation heat < 40 kJ mol-1 Chemical reaction heat >
80 kJ mol-1
temperature Around b.p. Relative higher
Adsorbed layer multilayer monolayer

reversibility Reversible. equilibrium Less reversible

established rapidly.
selectivity poor good
 Transition from physisorption to chemisorption

Transition
state

The potential curve of adsorption Physical Chemical

adsorption adsorption
 Adsoption Condition

The amount of adsorption (a) of a certain kind of solid for

certain gases is a function of T and P.

a  a (T , P )

constant pressure : isobar a ~T

constant temperature : isotherm a~P
constant adsorption : isochore T~P
 Adsoption Condition
isobar

As temperature increases,
adsorption decrease.

Adsorption heat can be determined

from isochore on the base of Clausius-
Clappeyron equation equation.

  ln P   ads H m
  
 T  a RT 2 isochore
 Adsoption Condition
isotherm

Adsorption increases with

increase of pressure under
low pressure. While at high
pressure, adsorption attains
maximum value.

adsorption isotherm:
an expression that gives the fraction  of a surface that is
covered by adsorbed molecules in equilibrium at constant
temperature as a function of pressure or concentration.
Adsorption Isotherm
Brunauer found that the isotherms of substances can be
subdivided into five types.
Adsorption Isotherm

 Langmuir isotherm
 Henry isotherm
 Freundlich isotherm
 BET isotherm
 Polanyi’s Potential Theory
 Gibbs adsorption isotherm
Adsorption Isotherm

surface coverage Θ depends adsorption enthalpy changes

linearly on pressure p logarithmically
 Kp   K p α = 1/n
Valid if n > 1
x = bobot bahan teradsorpsi (gr) log x/m = n log c + log K
oleh m gram adsorben
c = konsentrasi dalam larutan mol atau gr/L
K = konstanta
n = konstanta yang besarnya
berkisar antara 0,1 - 0,5
Adsorption Isotherm
Polanyi’s Potential Theory

ε = Polanyi’s Potensial
Rg = Konstanta gas
T = suhu
p = tekanan uap adsorbat
ps = tekanan uap jenuh adsorbat

Gibbs adsorption isotherm

A = luas area permukaan adsorben

π = spreading pressure
n = jumlah mol
p = tekanan uap adsorbat
Adsorption Mechanism
 Sorbent Materials

 Activated Carbon  Silica Gel

 Activated Alumina  Molecular Sieves (zeolite)
Polar and Non-polar adsorbents
http://www.activatedcarbonindia.com/activated_carbon.htm
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
 Sorbent Materials
Properties of Silica Gel
Bulk Density 44-56 lb/ft3
Heat Capacity 0.22-0.26
BTU/lboF
Pore Volume 0.37 cm3/g
Surface Area 750 m2/g
Average Pore Diameter 22 Å
Q: What if it is heated over
Regeneration Temperature 120-250 oC
250 oC?
Maximum Allowable Temperature 400 oC

H2 H2
O O
H2O
OH OH OH OH O

heating

hydrophilic hydrophobic
 Properties of Activated Alumina
Bulk Density
Granules
Pellets
Specific Heat
38-42 lb/ft3
54-58 lb/ft3
0.21-0.25 BTU/lboF
Sorbent
Pore Volume
Surface Area
Average Pore Diameter
0.29-0.37 cm3/g
210-360 m2/g
18-48 Å
Materials
Regeneration Temperature (Steaming) 200-250 oC
Maximum Allowable Temperature 500 oC

Properties of Molecular Sieves

Anhydrous Sodium Anhydrous Calcium Anhydrous
Aluminosilicate Aluminosilicate Aluminosilicate
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 (oC) 600 600 600
Air Pollution Engineering Manual., 1992
• Crystalline zeolite
• Uniform pores to selectively separate compounds by size & shape