Indian Institute of Technology Delhi

Department of Chemical Engineering

CHL727: Heterogeneous Catalysis and Catalytic Reactors

Lab Report
BET Surface Area Analysis
Supervisor: Professor K.K. Pant
Date:

Submitted by:
Hemlata Malav
Priyanka Gupta
Sanjna Mandrai
Shubam Gupta
Vinita Kumari

2011CH10084
2011CH70177
2011CH10113
2011CH70182
2011CH70188

Aim
To determine the BET surface area of the given catalyst (MCM-41) using Micromeritics
ASAP 2010.

Theory:
The BET theory is aimed to explain the physical adsorption of gas molecules on a solid
surface and is taken to be the basis for an important analysis technique used for the
measurement of the specific surface area of a material.
This theory is an extended version of the Langmuir theory, which is a theory developed
for monolayer molecular adsorption, for multilayer adsorption with the following
assumptions:
1.
2.
3.
4.
5.

Homogeneous surface.
No lateral interactions between molecules of each adsorption layer.
Uppermost layer is in equilibrium with vapor phase.
For the first layer- heat of adsorption and for higher layers- heat of condensation
At saturation pressure, the number of layers becomes infinite i.e. the gas
molecules physically adsorb on a solid in layers infinitely.

The resulting equation using these assumptions, known as BET equation is given as:

[( ) 1]

1
( )

where

V = the volume (at STP) of gas adsorbed at pressure P

PO = the saturation pressure which is the vapour pressure of liquefied gas at the
adsorbing temperature
P = the equilibrium pressure of the adsorbate at the adsorbing temperature.
VM = the volume of gas (STP) required to form an adsorbed monomolecular layer.
C = a constant related to the energy of adsorption given by-

exp(1 )

where
E1 is the heat of adsorption for the first layer and EL is the heat of
liquefaction/condensation.
The BET equation is an adsorption isotherm and can be plotted as a straight line with
1/v[(PO/P) 1] on the y-axis and P/PO on the x-axis according to the experimental results.
This plot is called a BET plot. The value of the slope s and the y-intercept l of the line are

used to calculate the monolayer adsorbed gas quantity vm and the BET constant C varies
from solid to solid- low values represent weak gas adsorption typical of low surface area
solids, organics and metals in particular. The following relations are used-

1
=
+

c=1+

The BET equation is widely used in surface science for the calculation of the surface areas
of various types of catalysts by physical adsorption of gas molecules.

Principle of operationA sample contained in an evacuated sample tube is cooled to very low (cryogenic)
temperature and then exposed to analysis gas, mixture of N2 and He gas, at a series of
precisely controlled pressures. The number of adsorbed gas molecules increases with
each incremental increase in pressure. The pressure at which the adsorption equilibrium
occurs is measured and universal gas law is applied to find the quantity of gas adsorbed.
The adsorbed film thickness increases over time due to adsorption. The micropores in
the surface are instantaneously filled, then the free surface and after it the large pores are
filled. The process may continue to the point of bulk condensation of the analysis gas.
Then the desorption process begins in which pressure is reduced systematically resulting
in release of adsorbed molecules. As with adsorption the changing quantity of the gas on
the solid surface is quantified. The two data sets represent the adsorption and the
desorption isotherms.

LimitationsSometimes, the calculated singlepoint value may not go through a maximum during the
gradual decrease in slope in the BET plot. Also that the graph may not be linear in
nature in region of lower relative pressures. If there is no truly linear region, then it can
be said that the BET equation is invalid for that particular sample.

Apparatus-

Micromeritics ASAP 2010

The ASAP 2010- (Accelerated Surface Area and Porosimetry System) has enough
felxibility in the gas selection and high vacuum for high-resolution low surface area
measurements. It is based on the theory of physisorption to obtain adsorption and
desorption isotherms and more inference about the surface area and porosity of a solid
material. It is capable of performing various measurements such as surface area analysis
plus pore size and pore volume distribution, typically using gases like: Nitrogen, Carbon
dioxide, Carbon monoxide, Oxygen, Argon and Butane, as the standard gas. It calculates
the BET and Langmuir surface areas, average and total pore volumes, BJH pore size
distribution and perform micro-pore analysis using various techniques such as HorvathKawazoe, Dubinin (both Astokhov and Radushkevich models), MP-Method, t-plot
method, and Saito-Foley method.

Techniques:
t-plot
It is used to mathematically model multi-layer formation to calculate a layer thickness,
t as a function of increasing relative pressure (P/Po). The resulting t-curve is
compared with the experimental isotherm in the form of a t-plot, i.e. experimental
volume adsorbed is plotted versus statistical thickness for each experimental P/Po
value. The linear range of this graph lies between monolayer and capillary
condensation. The slope of this t-plot (V v/s t) is equal to the external area, i.e. the

area of those pores other than micropores. Mesopores, macropores and the outside
surface is able to form a multiplayer, whereas micropores which have already been
filled cannot contribute further to the adsorption process. It is recommended to initially
select P/Po range 0.2 0.5, and subsequently adjust it to find the best linear plot.

Barrett-Joyner-Halenda (BJH) Method

It uses modified Kelvin equation. We know that Kelvin equation predicts pressure at
which adsorptive will spontaneously condense (and evaporate) in a cylindrical pore of a
given size. Condensation occurs in pores that already have some multilayers on the
walls. Therefore, the pore size is calculated from combining the modified Kelvin
equation and the selected statistical thickness (t-curve) equation.

Dollimore Heal (DH) Method

Extremely similar calculation to BJH and hence, gives very similar results. Differs only
in minor mathematical details.

OBSERVATIONS1.
2.
3.
4.
5.

Saturation pressure : 763.62518 mm Hg

Correlation coefficient : 25.9965
Weight of (tube + catalyst) = 36.3055 gm
Weight of tube = 35.7875 gm
Weight of catalyst = 0.5177 gm

Data table:
P/P0

P/ VA (PO P)

43.79810
60.48724
75.24563

Volume of adsorbed
gas
(cm3/gm
of
catalyst)
219.9858
236.3629
249.1444

0.057320403
0.079142991
0.098431427

0.000276
0.000364
0.000438

87.79890
103.22732
119.32848
134.79208
148.14983

259.5286
272.9192
289.6722
311.5749
336.6670

0.114834635
0.134981392
0.155998316
0.176159170
0.193554217

0.000500
0.000572
0.000638
0.000686
0.000713

P(mm Hg)

Graph-

P/ VA (PO P) vs P/P0
0.0008

P/ VA (PO P)

0.0007
0.0006
0.0005
0.0004
0.0003
0.0002
0.0001
0

0.05

0.1

0.15

0.2

0.25

P/P0

Calculation:
1.
2.
3.
4.
5.

Intercept l = 1/vmc = 0.000110 0.000021

Slope s = (c-1)/ vmc = 0.003274 0.000157
Volume of one molecular layer of gas, vm = 1/ (l + s) = 295.553791 cm3/ gm
Molecular cross- section area = 0.1620 nm2
BET surface area, S = 1286.6044 60.3414 m2/g

Conclusion:
1. The BET surface area of the catalyst MCM-41 was found to be 1286.6044 m2/g.
Because of the inaccuracy in measurement, according to the rule of significant
digits, the BET surface area will be 1290 m2/g.
2. In accordance with IUPAC classification, this isotherm can be classified as a Type
IV isotherm. Isotherm shows hysteresis nature because of capillary condensation
at higher partial pressures which matches with a Type IV category isotherm and
is associated with meso-porosity. Hysteresis falls into H3 category of IUPAC
classification, hence it can be concluded that the given sample contains disordered
lamellar pore structures, slit and wedge, shape pores. In this case, pore blocking,
percolation, and cavitation effects play an important role.