ADSORPTION

Adsorption involves, in general, the accumulation (or depletion) of solute molecules at an

interface (including gas-liquid interfaces, as in foam fractionation, and liquid-liquid interfaces, as
in detergency). It is the principal ways in which high-energy interfaces lower the overall energy of
a system and a complex process which is different to be described precisely by theoretical model.

In the process of adsorption, adsorbate gets absorbed on adsorbent.


Adsorption
Adsorbate + Adsorbent   Adsorption
Desorption


 AB
A + B 


According to Le-Chatelier principle, the direction of equilibrium would shift in that

direction where the stress can be relieved. In case of application of excess of pressure to the
equilibrium system, the equilibrium will shift in the direction where the number of molecules
decreases. Since number of molecules decreases in forward direction, with the increases in
pressure, forward direction of equilibrium will be favored.

Adsorption Isotherms

Adsorption isotherm is the relation between the amount of adsorbate adsorbed on a given
surface at constant temperature and the equilibrium concentration of the substrate in contact with
the adsorbent. It is the process of adsorption that is usually studied through graphs.

There are two types of typical adsorption isotherms they are the adsorption with
monolayer formation of saturation point (Figure 1.0) and multilayer adsorption in which the
several adsorbate molecules are formed on the surface of the adsorbent (Figure 2.0)

Figure 1.0 – Monolayer Adsorption

 Figure 2.0 – Multilayer Adsorption

Xm is the amount of the substrate required to make a monolayer whereas Po is the saturation
equilibrium concentration of the substrate.

1. Gibb’s Adsorption Isotherms

This isotherm can be used when adsorbents are liquids and adsorbates are soluble or
partially soluble. In the Gibbs approach to defining the surface excess concentration, the Gibbs
dividing surface (GDS) is defined as the plane in which the solvent excess concentration becomes
zero. The surface excess in component i will be then be the difference in the concentrations of the
component on either side of the plane. See Figure 3.0.

Figure 3.0 – Gibb’s Approach

In the Gibb’s free energy equation of a system containing two components, an additional
term of surface energy was introduced, and hence, the Gibb’s free energy equation modifies to

G  n11  n22   (1)

where n1 and n2 are the number of moles, 1 and  2 are the chemical potentials of the two
components respectively,  is the surface energy per unit area and  is the surface area.

When solution is very dilute, the activity a2 of solute could be replaced by its concentration.

c2  d  (2)
2    
RT  c2 T

or, in general for any solute and liquid adsorbent,

c2  d   (3)
  
RT  c T

The component potential of solute is

 2  02  RT ln a2

Or (4)

d 2  RTd ln a2

2. Freundlich Adsorption Isotherm

It is an empirical relation between the amount of an adsorbate adsorbed per unit weight
(x/m, mg g-1) of adsorbent and the adsorbate equilibrium concentration (Ce, moles L-1) in the fluid.
The relation is given below

x
 KCe n (5)
m

where K and n are Freundlich coefficients. Here x is the weight of adsorbate absorbed on m unit
weight of adsorbent and Ce as the equilibrium concentration of adsorbate. The isotherm
corresponds approximately to an exponential distribution of heats of adsorption. Although it lacks
the required linear behavior in the Henry’s law region, it can often be used to correlate data on
heterogeneous adsorbents over wide ranges of concentration.

Taking the logarithm of the equation (5) will give

x
log    log K  n log Ce (6)
m
 x
The plot of log   vs. log Ce gives a straight line.
m

Figure 4.0 – Freundlich Adsorption Isotherm

3. Langmuir Adsorption Isotherm

Irving Langmuir published a new model isotherm for gases adsorbed to solids in 1916, which
retained his name. It is a semi-empirical isotherm derived from a proposed kinetic mechanism.
This isotherm based on different assumptions one of which is that dynamic equilibrium exists
between adsorbed gaseous molecules and free gaseous molecules. His assumptions are:

a. There are fixed adsorption sites on the surface of the adsorbent. At a given temperature
and pressure, some fraction of these sites are occupied by adsorbate molecules. Let this
fraction be θ .
b. Each site on the surface of the adsorbent can hold one adsorbate molecule.
c. The heat of adsorption is the same for each site and is independent of θ .
d. There is no interaction between molecules on different sites.

According to Langmuir, the rate of adsorption depends on the following four factors

 The rate of collision of the adsorbate molecule of mass m which is at pressure p is

p
proportional to per unit surface area at the constant temperature.
2mkT
  The activation energy of adsorption, since this determines the fraction of the colliding
molecules possessing the necessary energy to be adsorbed.
 The fractional coverage of the surface f () which is the amount of surface that is
exposed/available for a single site adsorption  (1  ) , where
number of sites which have absorbed molecules
  fraction of sites covered =
total number of sites

  which is the fraction of the total number of colliding molecules which is result in
adsorption.

Based on the previous assumption and the factors, the rate of adsorption can be written as

p   E ads 
rads  f () exp   (7)
2mkT  RT 

The rate of desorption can be written as

  E des 
rdes  k1() exp   (8)
 RT 

At equilibrium

p   E ads    E des  (9)

f () exp  
 1k ( ) exp  
2mkT  RT   RT 

As given above,

()  
f ()  1  
E des  E ads  Q

Therefore the above equation can be written as

k1  Q 
p
2 mkT exp  
  RT 
(10)
1 k  Q 
Put  1 2 mkT exp  
b   RT 

Since all the terms as constant at constant equation. Hence,

 1 
p
b 1 
bp (11)

1  bp

This is the standard for Langmuir adsorption isotherm.

Figure 5.0 – Langmuir Adsorption Isotherm

4. BET Isotherm

It assumes that the surface possesses uniform, localized sites and that adsorption on one
site does not affect the adsorption on neighboring sites just as in the Langmuir theory. Also,
molecules can be adsorbed in second, third and nth layers with the surface available for layer equal
to the coverage of the next lower layer.

The rate constants for adsorption and desorption of the primary layer are ka and kd and
those of the subsequent layers are all ka' and kd'. The number of sites corresponding to zero,
monolayer, bilayer coverage at any stage are N0, N1, N2, etc. and Ni in general. The condition for
equilibrium of the initial layer is the equality of the rates of its formation and desorption,

ka pN0  kd N1 (12)

The condition for equilibrium of the next layer is

ka ' pN1  kd ' N 2 and in general ka ' pNi 1  kd ' Ni , i=2,3,...

 The classical isotherm for multilayer adsorption on a homogenous, flat surface is the BET
isotherm [Brunauer, Emmett, and Teller, J. Am. Chem. Soc., 60, 309(1938)]

nis Ki pi
ni  (13)
[1  Ki pi  ( pi / Pi s )][1  ( pi / Pi s )]

Where pi is the pressure of the adsorbable component and Pi s is its vapor pressure. It is useful
for gas-solid systems in which condensation is approached, fitting type-II behavior.

Figure 6.0 – BET Adsorption Isotherm

5. Tóth Isotherm

The Tóth isotherm is an empirical model that was developed to yield an improved fit
versus traditional Langmuir isotherm modelling. It is often useful for describing heterogeneous
systems. The Tóth isotherm model approaches the Henry region at infinite dilution.
n ap

nm 1
(14)
1  (ap) y  t

The Tóh isotherm may be rearranged to give a linear transform.

 nt  (15)
ln  t t 
 t ln p  t ln a
 nm  n 

The Tóth isotherm model has been added to MicroActive to allow users greater flexibility for
modelling their experimental isotherm data.
 Figure 7.0 - Tóth Isotherm

6. Radke-Prausnitz Isotherm

The Radke-Prausnitz model [Radke and Prausnitz, 1972], was used to fit the isotherm data.
The Radke-Prausnitz equation runs as follows:

K RPC
Q 1 N RP
(16)
1  ( K RP / FRP )C

Q is the carbon loading in kg adsorbate per kg adsorbent. C [kg.m-3] is the adsorbate concentration
in the solvent. KRP, FRP and NRP are the model parameters, which are obtained by a non-linear
statistical fit of the equation to the experimental data.

The Radke-Prausnitz equation has several important properties which make it suitable for
use in many adsorption systems. At low concentrations it reduces to a linear isotherm. At high
concentrations it becomes the Freundlich isotherm and for the special case of NRP =0 it becomes
the Langmuir isotherm. This Radke-Prausnitz model gives a good fit over a wide concentration
range and was therefore preferred above isotherm models like Langmuir, Freundlich and Jossens.
 Figure 8.0 – Radke-Prausnitz Isotherm

7. Sips Isotherm

The Sips isotherm is a combination of the Langmuir and Freundlich isotherms and is given
in the following general form:

nm (bp)t (17)
n
1  (bp)t

and may be rearranged to a linear form

 n  (18)
  t ln p  t ln b
t
ln 
 nm  n 

The Sips isotherm has the benefit of reducing to the Freundlich isotherm at low pressures
and approaches the monolayer capacity at high pressure similar to the Langmuir isotherm. A
Nelder-Mead simplex algorithm may be employed to fit the Sips isotherm model. The Sips
isotherm has been added to the advanced reporting system in MicroActive.
Figure 9.0 – Sips Isotherm