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Lec 9

This document discusses the BET adsorption isotherm model for determining the surface area of porous catalysts and materials. It describes how the BET isotherm is derived and linearized to calculate the monolayer capacity and surface area from adsorption data. It also notes some limitations of the BET model and methods like the single point analysis for surface area calculation. The document emphasizes the importance of characterizing catalysts to understand their properties and performance.

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0% found this document useful (0 votes)
51 views14 pages

Lec 9

This document discusses the BET adsorption isotherm model for determining the surface area of porous catalysts and materials. It describes how the BET isotherm is derived and linearized to calculate the monolayer capacity and surface area from adsorption data. It also notes some limitations of the BET model and methods like the single point analysis for surface area calculation. The document emphasizes the importance of characterizing catalysts to understand their properties and performance.

Uploaded by

ankitsharma67280
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Lecture # 9

Principles of Heterogeneous Catalysis


CHE633A, IIT Kanpur
 Introduction and History
 Important properties of heterogeneous catalysts
 Practical applications of catalysts
 Supports and Supported Catalyst
 Steps in a heterogeneously catalyzed reaction
 Adsorption and Potential Energy Diagrams
 Adsorption Isotherms
 LangmuirAdsorption isotherm
 Non-Langmuirian Adsorption isotherms
 BET Adsorption Isotherms
The BET isotherm can be derived
 The surface of the layer adsorption is divided into different sites as
shown below (dynamic)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

o if the number of sites possessing i molecules = ni


o then the total number of sites available =

o and the total no. of molecules adsorbed =


o Considering equilibrium, where the rate of formation = rate of destruction
o For ith layer:
The generalized equation relating and is the used to
develop the BET isotherm
 , where is , which is less than 1 and is

 Total number of sites available =


 Total no. of molecules adsorbed =
 , since

 Thus, and
Finally the BET isotherm is obtained
 The total no. of surface sites, , is proportional to the monomer
volume, , and the total no. of molecules/atoms adsorbed, , is
proportional to the adsorbed volume,

 Thus,

 This is a relationship between volume adsorbed, , and

- The BET isotherm


The BET isotherm possesses 2 constants, and
 The BET isotherm is given by:

 For layers ( is finite):

 The constant was introduced as:

o Where and are given by:

( )
( )
 Thus, ( )
( )
Monolayer volume, , gives information about the
amount of surface of the catalysts
 Main use of the BET model is to calculate the surface area, , of
porous catalysts/materials from Catalyst
Monolayer
 is determined from , and to determine is necessary to
linearize the BET isotherm (

 plotting of should give a straight line

o From the slope and intercept the values of can be


determined
BET Method for Determining Catalyst Surface Areas
 Adsorption of N2 onto catalyst surface at 77K 𝑥 𝑣
0.05 0.105
0.09 0.251
0.08

𝑥 0.06
 𝑣 1−𝑥 Slope =
0.04

𝑥
0.1 0.2 0.3 0.4 0.5

 Need to know mass of catalyst sample


Bulk metal / sulfides < 0.1 m2/g

Bulk metal oxides 0.1 – 50 m2/g

Typical oxide supports 10-350 m2/g

Zeolites ~1000 m2/g


From the value the surface area can be calculated

 The surface area will be product of the number of molecules/atom


adsorbed and cross-sectional area of a single molecule/atom
 Thus,
o where, is the surface area of material
- volume of gas required to occupy a monolayer at STP
22400 cc - volume occupied by 1 mol of gas at STP
- Avogadro’s number
- cross-sectional area of gas molecule being adsorbed
(for N N, the molecular cross-sectional area = 0.162 nm2)
The constant is related to the difference in the heat of
adsorption of the first layer and other layers
( )
( )
( )
( )

 Since physisorption does not require activation energy the rate


constant for desorption from the first and other layers are given by

( )
( )
 ( )
( )

o where is the heat for liquefaction,


The value of c can be used to calculate the heat of
adsorption of the 1st layer

 The authors of BET theory assumed that the combined pre-


exponential terms is approximately equal to one
o With this assumption, the heat of adsorption can be determined
from the constant and knowledge of the heat of liquefaction
o Assumption not always true and order of the heat of adsorption
of the first layer can be determined
Single point method for calculation of
 The linearized form of the BET isotherm is given by:

 For large values of , the above reduces to:


 Thus, if only one data point (value of and ) is available, then the
monolayer volume, , can be determined
o Fortunately, large values of are common while studying
adsorption of N2 on various materials and the single point
method can be used
 Using single point N2 adsorption method for a the error
involved is 5% of the value obtained from the entire plot
Applicability of the BET isotherm
 Applicability of BET eqn is usually limited to ‘x’ values of 0.3 (usual
range 0.05 to 0.3). The BET eqn given by

 can be put in the form of

 where the 1st term is the value of obtained by the single point
method and the 2nd term gives the error involved
Drawbacks of the BET isotherm
 Even though the BET isotherm is widely used it does not always give
reliable data
o The reliability is governed by the “knee-bend”, which ideally should be
well defined
o The knee bend or Point B method is governed by the heat of
adsorption and, hence, c. Higher value of , higher is the value
of c, and more reliable is the data
 Other drawback
o homogeneous surface
o lateral interaction
o heat adsorption of 2nd layer onwards (= heat of liquefaction) is not
usually true → developments taken along this line of taking the 3rd and
subsequent layers to be liquid like
It is essential to characterize the catalyst
 Determine those physical and chemical properties of the catalyst
that may be related to its sustained catalytic action
 Characterization provides some information and understanding
about the catalysts and how they function
o Quality control
o Foundation to improve process
o Superior product

 Catalysts used in the Industry are extremely complex


o Multicomponent and in different phases and in different combinations
and different oxidation states
 Wherever possible the results should be confirmed by more than
one characterization technique

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