Fundamentals of Adsorption Process

S. Sarkar

ADSORPTION
Gas molecules

DEFINITION OF ADSORPTION
Adsorption is a surface phenomenon in which a
substance, originally present in one phase(adsorbate),
is removed from that phase by accumulation at the
interface between that phase and a separate
(adsorbent) phase.
In principle adsorption can occur at any solid-fluid
interface. Examples include:
Gas-solid interface (as in the adsorption of a VOC on
activated carbon);
Liquid-solid interface (as in the adsorption of an
organic pollutant on activated carbon).

ADSORPTION vs. ABSORPTION

Absorption is the process through which a substance,
originally present in one phase, is removed from that phase
by dissolution in another (typically a liquid), as opposed to the
accumulation at the interface as in the case of adsorption.

Adsorption

Absorption

MODELLING THE ADSORPTION PROCESS

COMMON ADSORBENTS
Activated carbon - A char-like material with high surface area.
Silica gel - Hard, granular, porous material made by
precipitation from sodium silicate solutions treated with an acid.
Activated alumina - Aluminum oxide activated at high
temperature and used primarily for moisture adsorption.

Aluminosilicates (molecular sieves) Porous synthetic

zeolites used primarily in separation processes.
Metal Oxides Iron oxide, aluminium oxide, magnesium
oxide, copper oxide.

ACTIVATED CARBON
Activated carbon is a carbon which has been activated to increase its
surface area and pore volume.

1g Anthracite = 10 m2 of surface area

1g Activated carbon = 750-1500 m2 of surface area
Macropore

Micropore

Macroporous
Mesoporous
Microprous

> 1000 A
100 A - 1000 A
< 100 A

FACTORS AFFECTING ADSORPTION

Solute tends to migrate to the adsorbing surface because of four factors :

Hydrophobic nature of solvent

London Van derWal forces

Electrostatic forces
Occasional chemisorption

Physical adsorption
( H < 2 kcal/ mol )

Electrostatic
chemisorption
( H 2-100 kcal/mol )

FACTORS AFFECTING ADSORPTION AFFINITY

PROPERTIES OF
ADSORBENT

PROPERTIES OF
ADSORBATE

PROPERTIES OF
SOLUTION

SURFACE AREA

SOLUBILTY

pH

PORE- SIZE
DISTRIBUTION

MOLECULAR
WEIGHT

TEMPERATURE

SURFACE
CHEMISTRY

FUNCTIONAL
GROUPS

IONIC
STRENGTH

ADSORPTION ISOTHERM

Adsorption isotherm provide equilibrium partitioning

between liquid phase adsorbate (Ce ) concentration
and solid phase adsorbate (qe) concentration at a
given temperature.
Qualitatively, adsorption isotherm provide the same
information as the equilibrium constant in homogenous
chemical reaction.

ADSORPTION ISOTHERM
m1

m2

m3

m4

Volume = V mL
Initial concentration = Co mg/L
Mass of adsorbent = m grams
Adsorption capacity= qe mg/g
Equilibrium concentration = Ce mg/L

qe, mg/g

5
4

Adsorption
isotherm

3
2
1
0

Ce , mg/L

10

12

14

m5

DETERMINATION OF ADSORPTION ISOTHERM

Volume of sample = V L
Mass of adsorbent used = m grams
Initial solute concentration = Co mg/L
Final solute concentration = Ce mg/L

Solute lost from solution = V (C0 Ce )

mg

Solute gained by the adsorbent = m qe where qe = mg solute

gm of adsorbent
By mass balance :
m qe = V (C0 Ce )
Therefore :
C Ce
qe V 0

LANGMUIR ISOTHERM
The model has following assumptions :
1. Adsorption is in monolayer.
2. Sites have uniform energy.

f ( 1- )
Where = fractional coverage of adsorbent at any time

fC
This implies,

f
b

At equilibrium

= Kf (1- ) C

= Kb

Kf (1- ) C = Kb
=

KfC
K f C Kb

----( Adsorption)

----- ( Desorption)

LANGMUIR ISOTHERM
Now , =

qe
Qmax

This implies qe
Qmax

where qe = No. of sites occupied at equilibrium

Qmax = Total no. of sites available

where K f = b
Kb

bCe
1 bCe

It gives the equation

qe = Qmax bCe
1 bCe

If value of Ce is high
then, bCe >> 1
It gives qe = Qmax
If value of Ce is low
then, bCe << 1
It gives qe = Qmax bCe

qe, mg/g

Ce high

4
3
2

Ce low

1
0
0

Ce , mg/L

10

12

14

LANGMUIR ISOTHERM
Linearization of the above equation gives :
1
1
1
1

qe Qmax bQmax Ce

Intercept =

Slope =

1
Qmax

1
1

Qmax b

1/qe, qe in mg/g

0.25
0.23

1
1

Slope =
Qmax b

0.21
0.19
0.17

1
Qmax

0.15
0

0.05

0.1

0.15
0.2
0.25
1/Ce, Ce in mg/L

0.3

0.35

FREUNDLICH ISOTHERM
The Freundlich equation can be mathematically represented by:

qe = Kf Ce 1/n
where:
Kf = constant (function of energy of adsorption and temperature)
n = constant
Linearization :

Intercept = log K f
Slope =

1
n

Log qe, qe in mg/g

1
log qe log K f log Ce
n

0.25

0.23
0.21
0.19
0.17

Slope =

1
n

log K f

0.15
0

0.05

0.1

0.15
0.2
0.25
logCe, Ce in mg/L

0.3

0.35

FREUNDLICH ISOTHERM

qe = Kf Ce 1/n
Unfavorable
(1/n)<1

If

1 < 1 (Favourable)
n
n = 1 (Linear)

Linear

(1/n)>1

1
n > 1 (Unfavourable)

Favorable

PROBLEMS
Ques 1. There is a 500 mL container contaminated with pesticide of
concentration 20 mg/L as shown in the figure below :

0.7 g Activated
Carbon

Pesticide = 20 mg/L

V= 500 mL

What is the equilibrium concentration of pesticide if

qe = 15 Ce

qe in mg/g and Ce in mg/L

SOLUTION
Ans 1. By mass balance :
C Ce
qe V 0

15 Ce =

0.5
(20 Ce )
0.7

10.5 Ce = 10 0.5 Ce
Ce = 0.91 mg/L
qe = 15 x 0.91
qe = 13.63 mg/g

PROBLEMS
Ques 2. The adsorbent in Q 1 is now taken out of the solution after
equilibrium is arrived and is kept in a container with same volume of
distilled water (there is no contamination of pesticide). What is the final
concentration ?

SOLUTION
Ans 2. Mass balance : Pesticide in the system (water +adsorbent) should be
constant before and after the new equilibrium.
BEFORE

AFTER

13.63mg/g*0.7g + 0 mg/L*0.5L =qe*0.5 L + Ce*0.5L

13.63*0.7 mg = 15Ce * 0.7 + 0.5 Ce
11Ce = 13.63*0.7
Ce= 0.867mg/L

APPLICATION OF ADSORPTION IN WATER AND

WASTEWATER TREATMENT
Removal of various organic and inorganic species from surface water,
groundwater and wastewater.
Adsorption techniques are used as high quality treatment processes for the
removal of dissolved organic pollutants such as dyes, from industries such as
textile finishing, food coloring, cosmetics, paper and carpet industries.
To remove organic pollutants (especially halogenated but also nonhalogenated), and to a lesser extent, inorganic contaminants, from the
wastewater.
In tertiary wastewater treatment as a polishing step before final discharge.
In the treatment of industrial wastewaters containing organic compounds
not easily biodegraded during secondary (biological) treatment or toxic.

ADSORPTION COLUMN

Three zones :
1. Adsorption zone
2. Unused zone
3. Saturated zone

Unused
zone

Saturated
zone

Idealized breakthrough curve for fixedbed adsorbent.

FLUORIDE
Fluoride in drinking water is an invisible killer. It
acts like slow poison which accumulates in our bones
and teeth over the years.
The permissible limit of fluoride in drinking water
as per WHO is 1.5 mg/L.
Presently 21 States/UT and 204 districts in India
have fluoride levels greater than permissible value.
The adverse effects of high concentration of
fluoride in water range from mild dental fluorosis to
crippling skeletal fluorosis as the level and period of
exposure increases.
Out of various defluoridation technologies,
adsorption is the best technology for fluoride removal
from contaminated drinking water.

SYNTHESIS OF HYBRID ADSORBENT

Synthesis of modified TAN 1
[ R3 N ]Cl

[ R3 N ]HPO4

2% solution of
TAN 1

( NH 4 )2 HPO4

[ R3 N ]Cl

NH 4 Cl

10% CaCl2
+ 3M NaCl
pH=10-11

Modified TAN 1 after loading

with ( NH 4 )2 HPO4 and CaCl2
+ NaCl solution.

Ca5 ( PO4 )3 OH ()
Na

CHARACTERIZATION OF HYBRID ADSORBENT

Hydroxyapatite precipitates

SEM Image

EDX Image

FTIR spectra of
modified TAN 1

PROBLEMS
Ques 3. A synthetic adsorbent for removal of fluoride was prepared in lab. Adsorption
isotherm study with 200 mL solutions at Co= 14.2 mg/L yielded the following results :

Mass(mg)
200
300
400
500
650
800
900
1000

Ce (mg/L)
10.1
8.4
6.9
5.7
3.8
1.8
1.1
0.8

We want to use it to remove fluoride from 1000 L water containing fluoride 5 mg/L. The
WHO regulation of fluoride is 1.5 mg/L. What is the amount of resin required?

SOLUTION
Step 1- Adsorption isotherm

200
300
400
500
650
800
900
1000

Ce

10.1
8.4
6.9
5.7
3.8
1.8
1.1
0.8

qe

4.34
4
3.75
3.48
3.3
3.15
2.89
2.72

qe, mg/g

Mass

5
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ce, mg/L

SOLUTION
Step 2 Finding out of value of qe

For permissible value of 1.5mg/L , qe needs to be calculated by

Freundlich isotherm .
qe = Kf Ce 1/n

1.6

Plotting the experimental values

On linearized plot,

qe = 2.8 (1.5) 1/6.28

qe = 2.98 mg/g

ln qe, qe in mg/g

Kf = 2.8
n= 6.28

1.4
y = 0.1595x + 1.0308
R = 0.9316

1.2
1
0.8
0.6
0.4
0.2
0
0

1
2
ln Ce, Ce in mg/L

SOLUTION
Step 3 Calculation of mass of adsorbent

By mass balance:

C Ce
qe V 0

m
5 1.5
2.98 1000
m

m = 1174.5 g