Government Engineering College,

Bharuch(014)
Subject : Chemical Reaction Engineering-II

Topic : Adsorption Isotherms & Rate of Adsorption

Group No. : 10

Students Name Enrollment No.

Khoradiya Ravi 130140105015
Panchal Priyansh 130140105021
Patel Dhaval 130140105027
Patel Smit 130140105035
Parsana Sanket 130140105046
 Adsorption
Definition:

Adsorption can be simply defined as the concentration of a solute, which may be molecules in a gas
stream or a dissolved or suspended substance in a liquid stream, on the surface of a solid.

In an adsorption process, molecules or atoms or ions in a gas or liquid diffuse to the surface of a
solid, where they bond with the solid surface or are held there by weak intermolecular forces. The
adsorbed solute is called the adsorbate, and the solid material is the adsorbent.
 Types of Adsorption
Adsorption on solid surfaces may be divided into two categories, viz. physical and chemical
adsorption. Physical adsorption is non-specific and similar to condensation. The forces that attract
the fluid molecules to the solid surface are weak van der Waals forces. The physical adsorption is
also known as van der Waals adsorption.

Chemical adsorption or chemisorption is specific. It involves forces which are much stronger than
physical adsorption. The amount of heat evolved in chemisorption is large (e.g., 50500 kJ/mol),
which is similar to chemical reactions.

Unlike physical adsorption, chemisorption does not take place on all solids. It occurs with some
chemically reactive gases. Chemisorption usually occurs at high temperatures. The surface coverage
is limited to a monolayer. The process is often irreversible. Chemisorption is used for finding the
active centers of a catalyst.
 Adsorption Isotherm
A relationship between an amount of
adsorbate adsorbed on the surface of a given
amount of adsorbent and an equilibrium
concentration of adsorbate in contact with
the adsorbent is known as an adsorption
isotherm.
 General types of Adsorption Isotherms
Adsorption Isotherms can be broadly classified into two classes:
1) Adsorption with monolayer formation
2) Adsorption with multilayer formation

Monolayer Adsorption Multilayer Adsorption

 General types of Adsorption Isotherms

Not always but generally, Monolayer Adsorption occurs due to chemisorption whereas Multilayer
Adsorption occurs due to physisorption.
Sometimes, Multilayer adsorption occurs due to chemisorption followed by physisorption
 Different types of Adsorption
Isotherms
Henrys Law:
It is a simple adsorption isotherm which is used to describe the adsorption
at a gas-solid interface which can be represented by the following
equation,

x/m = kH p

At low temp., adsorption of gas increases very rapidly as the pressure

rises. However, when the temp. is high, the increase in adsorption is
relatively less.
Limitation:
This Isotherm is applicable to lower conc. Of adsorbate since at lower
conc.(Ca ), x/m is proportional to p(or Ca) which is shown in fig. in slide
no. 4
 Different types of Adsorption
Isotherms
Freundlichs Isotherm:
It has been found that the relationship between x/m & p is not
linear but varies according to the following equation,

x/m = kF(p)1/nF , nF > 1 Freundlich Isotherm Curve

By applying ln both sides of the equation we get,

ln(x/m) = ln kF + (1/nF) ln p

Freundlichs Isotherm can also be expressed in the terms of

conc. If p is replaced by equilibrium conc. Ca .

Log x/m versus log p

 Different types of Adsorption Isotherms
Langmuir Adsorption Isotherm:
In this Adsorption Isotherm it is considered that the adsorbent surface possess a number of active
interaction sites for adsorption.

Assumptions:
1) At a given temp. & press., from fixed no. of adsorption sites on adsorbent surface some fraction of
these sites are occupied by adsorbate, let it be .

2) Each site can hold one adsorbate molecule

3) Heat of Adsorption is same for each site & is independent of .
4) No interaction between molecule & different sites.

Different types of Adsorption Isotherm
Langmuir Adsorption Isotherm:
Considering the processes of adsorption and desorption of the molecules on the surface, the Langmuir
adsorption isotherm may be obtained as follows:
Rate of adsorption of molecules on the surface of the adsorbent = ka Ce (1-)
Rate of desorption = kd
At equilibrium,
kd = ka Ce (1-)

= = where, KL = is adsorption co efficient.

Since, =

= where x and xm are the amount of the adsorbent adsorbed at equilibrium concentration Ce and
maximum
amount of adsorbate for the formation of monolayer, respectively.

Different types of Adsorption Isotherms
Langmuir Adsorption Isotherm:
Rearranging the last previous equation,

If we plot vs. Ce , we will get a straight line. Slope of which will be and intercept as
Therefore, from values of intercept and slope of the plot values of Xm and KL could be calculated. In the
case for the adsorption of gaseous substrate, Ce, X, and Xm will be replaced by p.V, and Vm, respectively.

Limitation:

For chemisorption too, Langmuirs equation works very well but fails for the cases where multilayer
formation takes place.
 Different types of Adsorption Isotherms

Langmuir Adsorption Isotherm:

Langmuir adsorption isotherm for several non-dissociatively adsorbed species:
If two species A and B are adsorbed on the surface. Then applying Langmuir hypothesis for species A,
we have,

Equation (1)
 Different types of Adsorption Isotherms
Langmuir Adsorption Isotherm:
Similarly for species B,

Equation (2)

Now putting the value of B from Equation (2) into (1) we get,
 Different types of Adsorption Isotherms
Langmuir Adsorption Isotherm:

Similarly we can obtain,

 Different types of Adsorption Isotherms
Langmuir Adsorption Isotherm:
In general, Langmuir adsorption isotherm for species A under conditions of several non-dissociatively
adsorbed species could be derived as,

Where the sum runs over all species.

 Rate of Adsorption
The rate of adsorption, Rads, of a molecule onto a surface can be expressed in the same manner as any kinetic
process. For example, when it is expressed in terms of the partial pressure of the molecule in the gas phase above
the surface:

Rads=k' Px where: x- kinetic order

k'- rate constant
P- partial pressure

If the rate constant is then expressed in an Arrhenius form, then we obtain a kinetic equation of the form:

Rads=Aexp (
-Ea/RT).Px

where Ea is the activation energy for adsorption, and A the pre-exponential (frequency) factor.
 Rate of Adsorption
It is much more informative, however, to consider the factors controlling this process at the molecular level....
The rate of adsorption is governed by,

1.the rate of arrival of molecules at the surface

2.the proportion of incident molecules which undergo adsorption

i.e. we can express the rate of adsorption (per unit area of surface) as a product of the incident molecular flux, F ,
and the sticking probability , S .
Rads=S . F [molecules m-2s-1]

The flux of incident molecules is given by the Hertz-Knudsen equation

Where
Flux F = P / P - gas pressure [ N m-2 ]
[ molecules m s ]
-2 -1
(2mkT)1/2 m - mass of one molecule [ kg ]
T - temperature [ K ]
 Rate of Adsorption
In general,

S=f() . exp ( -Ea/RT)

where, once again, Ea is the activation energy for adsorption and f() is some, as yet undetermined, function of
the existing surface coverage of adsorbed species.
Combining the equations for S and F yields the following expression for the rate of adsorption :
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