CLL 222/CHL221, CRE II: L7

cll222_2015-16@googlegroups.com.

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in

Langmuir Adsorption Isotherm

Simple approach to
quantitatively describe
an adsorption process
at the gas/solid interface

N =N +N numberof vacantsites
V
S
Assumptions:
Solids surface is homogeneous and contain a
number of equivalent sites,each of which is
occupied by a single adsorbate molecule.
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Chemisorption rates:
Adsorption data is reported in the form of
isotherms
Chemisorption may be considered as a
reaction between a reactant molecule and
an active site resulting in an adsorbed
molecule
A + A (or) A + S AS
Turnover Frequency (N): defined as the
number of molecules reacting per active
site per second at the conditions of the
experiment a measure for the activity of
the catalyst
3

Isotherms
Type I Langmuir Adsorption Isotherm
I

ad

Kp
nad nm nm
1 K p
p /p

Assumptions:
homogeneous surface
(all adsorption sites energetically identical)
monolayer adsorption (so no multilayer
adsorption)
no interaction between adsorbed molecules

Langmuir Isotherm - Assumptions:

Surface is uniformly active
All sites are identical
Amounts of adsorbed molecules will not
interfere with further adsorption
Uniform layer of adsorption
Site balance:
No. of vacant sites v
v Fraction of vacant sites

total sites
t
No. of occupied sites A
A Fraction of sites occupied by A

total sites
t
v A 1

Alternately:
Ct Molar conc. of active sites
Cv Molar conc. of vacant sites
C AS Molar conc. of sites by A

No. of active sites / unit mass

Avogadro ' s number
No. of vacant sites / unit mass
Avogadro ' s number
No. of sites by A / unit mass
Avogadro ' s number

Cv C AS Ct
Though other isotherms account for non-uniform
surfaces, they have primarily been developed for
single adsorbing components. Thus, the extensions to
interactions in multi-component systems is not yet
possible, as with the Langmuir isotherm.
Langmuir isotherms are only used for developing
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kinetic rate expressions.

Effect of increasing reactant concentration:

n-2
g io
Re

rate

Re
gio
n-1

Increasing the reactant concentration

increases both the driving force and adsorption
inhibition terms.

CA

Volcano shape results from a competition between

kinetic driving force and adsorption inhibition terms.
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Remarks:
For a given mechanism, the driving force is
unique, irrespective of RDS.
The product of equilibrium constant of all steps in
the mechanism yield the overall eq. constant
In the kinetic term, the rate constant of RDS will
appear.
If adsorption of A is not RDS, then KApA will
appear in the adsorption term.
If desorption of B is not rate limiting, then pB/KD
will appear in the adsorption term.
If SR is RDS, then the adsorption term will be
raised to the power equal to the number of sites
involved in the SR step.
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Exercise:

Al2O3

n-pentane

i-Pentane

Suggested Mechanism:
N + N
N + I +
I I +
Rate laws for each of the steps:
Net rate of Adsorption k A p NV k A N
Net rate of Surface reaction k S N v k S I v

Net rate of Desorption k D I k D pI V

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pI
k A ( pN
)
K eq
rN
pI
pI
1

KS KD KD

rN

rN

p
kS K A ( pN I )
K eq
(1 K A p N pI / K D ) 2
pI
kD K A K S ( pN
)
K eq

1 K A pN K A K S pN

Case-1

r0 k A pN

Case-2

kS K A pN
r0
(1 K A pN ) 2

kD K A K S pN

0
Case-3
1 K A pN K A K S pN

n-pentane (N)

i-Pentane (I)

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Development of Rate Equation:

For a given mechanism, the driving force is
unique, irrespective of RDS.
The product of equilibrium constant of all steps in
the mechanism yield the overall eq. constant
In the kinetic term, the rate constant of RDS will
appear.
If adsorption of A is not RDS, then KApA will
appear in the adsorption term.
If desorption of B is not rate limiting, then pB/KD
will appear in the adsorption term.
If SR is RDS, then the adsorption term will be
raised to the power equal to the number of sites
involved in the SR step.
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