9.

Adsorption

Prof. Mukesh Doble

DEPARTMENT of BIOTECHNOLOGY
IIT MADRAS
Adsorption
accumulation of large number of molecular species at the
surface of liquid or solid phase in comparison to the bulk.
 Adsorption process involves two components Adsorbent
and Adsorbate.

Adsorbate

Adsorbent
Adsorption is an exothermic process

Forces of attraction exist between adsorbate and adsorbent

and due to these forces of attraction, heat energy is
released.
 Types of Adsorption

Forces of attraction can be

(1) Vander waal forces which are weak forces or

(2) chemical bond which are strong forces of attraction.

can be classified into two types:

Physical Adsorption or Chemical Adsorption.

Comparison between Physisorption and Chemisorption

Comparison between Physisorption and Chemisorption

Physisorption Chemisorption
Forces of attraction are Forces of attraction are
vander Waals’ forces chemical bond forces
Low enthalpy of adsorption High enthapy of adsorption
(20 - 40 k.J/mole) (200 - 400 k.J/mole)
observed under conditions of takes place at high
low temperature temperatures

not specific highly specific

Multi-molecular layers may Generally, monomolecular
be formed layer is formed
reversible irreversible
Applications of Adsorption

1. Charcoal is used as a decoloriser as it adsorbs the

coloring matter from the coloured solution of sugar.

2. Silica gel adsorbs moisture from the desiccators.

3. Silica and alumina gels are used as adsorbents for

removing moisture and for controlling humidity of rooms.

4. Activated charcoal is used in gas masks for toxic gases

and vapours and purifies the air for breathing.

5. Adsorption processes are useful in carrying out

heterogeneous catalysis.
Factors governing Adsorption

Temperature

Is exothermic in nature. According to Le Chatleir principle, low

temperature conditions would favour the forward reaction.

A+S AS

Pressure

increase in pressure, till saturation level

is achieved.

Pr
Factors governing Adsorption

Surface Area

increases with increase in surface area.

Activation of Adsorbent

•breaking solid crystal into small pieces

•Heating at high temperature,
•Acid wash
Different adsorption isotherms

•Linear,

•Freundlich,

•Langmuir

and BET theory.

 qo x
q
Ke  x
Various adsorption isotherms (a) Linear (b) Freundlich (c)
Langmuir

q = Kx
q = amount of solute adsorbed
per amount of adsorbent
c

K = equilibrium constant.
a
q = Kxn
n = constant (if the adsorption is
b favourable, then n<1; if it is
unfavourable, then n>1)
x = solute concentration in solution
Batch adsorption qF, W

mass balance for the solute - xF , F x,F

q, W
xF F + qF W = x F + qW

x and xF = concentration of the solute in the final and feed

q and qF = final and feed concentrations of the solute in the

adsorbent,

F =amount of feed solution,

W = weight of adsorbent added.

If the adsorbent is fresh then qF may be = 0
This equilibrium is rearranged to obtain

If the adsorbent is fresh then qF = 0

Mass balance is rearranged to obtain

Operating line

The equilibrium relationship

gives another relationship
between q and x

x = solute concentration in solution

 q

Linear isotherm

Freundlich isotherm Langmuir isotherm

q q

x
x
 adsorbent
qF, W

xF , F x,F

Bulk/solute

q, W

How much adsorbent is needed???

xF = 0.1 mg/ltr and we want to adsorb 90% of the solute
using fresh adsorbent, F= 1.2 ltrs, W = ?. It follows a
linear adsorption isotherm q=Kx, with K= 1.0 10-5

Units of q = mg/gm of adsorbent

So units of K will be gm/ltr
x = 0.1 * 0.1 mg/ltr =0.01

xF * F + qF * W = x * F + q *W

0.1 * 1.2 + 0 = 0.01 * 1.2 + q *W

q = K*x

q = 1.0 10-5 * 0.01

0.1 * 1.2 = 0.01 * 1.2 + 1.0 10-5 * 0.01 *W

0.12 – 0.012 = 1.0 10-3 * W

W = 108 mg
A feed of 1.2 ltrs contains 3.9 10-4 mol/ltr of a protein. 80 cc of
an adsorbent will adsorb a maximum of 7.8 * 10-6 mol of
protein per cc of the adsorbent . The process follows Langmuir
isotherm. The constant in the isotherm (K) = 1.9 *10-5. What
will be exit concentration
q = qmax * x
-----------
K+x

W q = F (xF –x)

q = x 7.8 * 10-6
x + 1.9 *10-5

1.2 * ( 3.9 *10-4 – x) = 80 * q

x = 3.9 10-5 mol/ltr

 Linear adsorption isotherm , K = 30

qF=0, W=25 cc qF=0, W=25 cc

x1= ? x2= ?
xF = 0.1 gm/cc
F=1 ltr

q1= ? q2= ?

1000 (0.1-x1) = 25 q1 and q1=30*x1

x1= 0.0571 gm/cc, so % recovery = (0.1-.0571)*100/.1= 42.8%

1000*(0.0571-x2) = 25 q2 and q2 = 30 x2

x2 = 0.0326 , so overall % recovery = 67.4 %

 Linear adsorption isotherm , K = 30

qF=q2, W=25 cc qF=0, W=25 cc

x2= ?
xF = 0.1 gm/cc
F=1 ltr
x1= ?

q1= ? q2= ?

1000 (0.1-x1) = 25 (q1 – q2) and q1=30*x1

1000*(x1-x2) = 25 q2 and q2 = 30 x2

1000 (0.1- x1) = 25 *30 (x1-x2)

1000 (x1-x2) =25*30*x2

x1=0.0756 and x2=0.043

Overall % recovery = 56.7%
 dx
V  F ( x F  x)  (1   )Vrads
dt

Continuous stirred tank adsorber

x, F
xF, F

Feed +solute
Feed +solute
Solid adsorbent

Stirred tank V
 dx
V  F ( x F  x)  (1   )Vrads
dt

Continuous stirred tank adsorber

mass balance for the solute

V = volume of the tank, x and xF = solute concentrations in

the outlet and the feed
F = feed flow rate,
rads = rate of adsorption per volume of tank,
q = adsorbed solute concentration
ε = voidage
diffusion in the solution controls the adsorption, then the rate

rads = kL a (x-x*)

kL = mass transfer coefficient,

a =surface area of adsorbent per tank volume,
x* = concentration in the solution which would be in
equilibrium with the adsorbent.
(adsorption can follow one of the equilibrium relations )

adsorption isotherm is linear

q = Kx*
 q  1e 1t  2 e  2t
 1 
KxF ( 1   2 ) ( 1   2 )
 q

(xF - x)

time
Tubular adsorber
adsorbent

Fluid + solute Fluid

time time

ε = void fraction in the bed, v (=F/A) = superficial

velocity, A= cross sectional area of the pipe,
Dd = dispersion coefficient
 Tubular adsorber

Accumulation Due to flow Axial Dispersion/Diffusion

Transferred to the solid phase

Approximate analysis for fixed bed (packed bed ) ---- break
through curve.

xF
xE

Break through
concentration

xB
tB tE
Time
Break through time Bed exhaustion time
equilibrium zone where the bed is saturated is,
from z =0 to z = l(1-∆t/ tB),
∆t = (tE- tB).

The adsorption zone is l ∆t/ tB long

l = bed length.

equilibrium zone adsorption zone

tB tE
The equilibrium zone contains loaded adsorbent,

q (equilibrium) = q (xF)

The adsorption zone contains half that much (an approx)

q (adsorption) = ½ q (xF)

The fraction of the bed which is loaded

Q = 1- ∆t/ 2tB

∆t

tB tE
 Tubular adsorber
l= 1.3 m
ε = 0.3
solute = 1.3 mg/ltr Fluid

Linear adsorption isotherm , K = 38

Break through time=6.4 hrs and exhaustion time=10 hrs
Length of adsorption zone at break through?
Length of equilibrium zone at break through?
Fraction of bed used

equilibrium zone adsorption zone

tB tE
 Tubular adsorber
l= 1.3 m
ε = 0.3
solute = 1.3 mg/ltr Fluid

Linear adsorption isotherm , K = 38

Break through time=6.4 hrs and exhaustion time=10 hrs
Length of adsorption zone at break through?
Length of equilibrium zone at break through?
Fraction of bed used

Adsorption zone = 1.3*(10-6.4)/6.4=0.73

Equilibrium zone =1.3-0.73=0.57 m
Fraction of bed used = 1- ∆t/ 2tB = 0.72
feed of 1.2 ltrs contains 0.1 gm/cc solute that needs to be
adsorbed with 20 cc of fresh adsorbent. Freudlich Isotherm
q= 32 x1/3

1200 (0.1-x) = 20*32* x1/3

equilibrium

operating line

x
 Pressure drop in packed beds

-Bed of solids during filtration

- packed tubular bed adsorber
- packed bed distillation column
- biofilters

Pressure drop is proportional to bed length

square of velocity
inversely proportional to tube diameter
 Bed length =20 cm, diameter=2.5 cm, bed volume = 70 cc, Pressure drop = 2 bar

Bed length =?, diameter=25 cm, bed volume = 70,000 cc, Pressure drop = ? bar

Bed volume = (3.1.41*dia^2/4) length

Volume increased 1000 times and dia increased 10 times -

length to be increased 10 times
So over all pressure drop will increase 10 times , ie=20 bar
Staged process

Two streams enter and two streams leave after equilibration

Solute is transferred from one stream to another based on

Partition coefficient --- extraction

Vapour pressure -- distillation
Adsorption coefficient --adsorber
Solubility - Gas liquid absorption

Streams leaving are in equilibrium