INTRODUCTION OF BET THEORY :

Brunauer–Emmett–Teller (BET) theory aims to explain the

physical adsorption of gas molecules on a solid surface and serves as
the basis for an important analysis technique for the measurement of
the specific surface area of materials.

In 1938, Stephen Brunauer, Paul Hugh Emmett, and Edward

Teller published the first article about the BET theory in the Journal
of the American Chemical Society. The BET theory applies to
systems of multilayer adsorption and usually utilizes probing gases
that do not chemically react with material surfaces as adsorbates to
quantify specific surface area. 

Nitrogen is the most commonly employed gaseous adsorbate

used for surface probing by BET methods. For this reason, standard
BET analysis is most often conducted at the boiling temperature of
N2 (77 K). Further probing adsorbates are also utilized, albeit with
lower frequency, allowing the measurement of surface area at
different temperatures and measurement scales. These have included
argon, carbon dioxide, and water.

Specific surface area is a scale-dependent property, with no

single true value of specific surface area definable, and thus quantities
of specific surface area determined through BET theory may depend
on the adsorbate molecule utilized and its adsorption cross section.

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CONCEPT & EQUATIONS :

BET model of multilayer adsorption, that is, a random

distribution of sites covered by one, two, three, etc., adsorbate
molecules.

The concept of the theory is an extension of the Langmuir

theory, which is a theory for monolayermolecular adsorption, to
multilayer adsorption with the following hypotheses:

1. gas molecules physically adsorb on a solid in layers infinitely;

2. gas molecules only interact with adjacent layers; and
3. the Langmuir theory can be applied to each layer.

The resulting BET equation is

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 Where p and p0 are the equilibrium and the saturation pressure
of adsorbates at the temperature of adsorption, v is the adsorbed
gas quantity and Vm is the monolayer adsorbed gas quantity, c is
the BET constant.

Where E1 is the heat of adsorption for the first layer, and EL is

that for the second and higher layers and is equal to the heart of
liquefaction or heat of vaporization.

BET Plot

Equation (1) is an adsorption isotherm and can be plotted as a

straight line with 1/v[(p0/p)-1] on the y-axis and φ= p/ p0 on the x-axis
according to experimental results.

This plot is called a BET plot. The linear relationship of

equation is maintained only in the range of 0.05<p/p0<0.35. The value
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of the slope A and the y-intercept I of the line are used to calculate the
monolayer adsorbed gas quantity Vm and the BET constant c. The
following equations can be used :

The BET method is widely used in materials science for the

calculation of surface areas of solids by physical adsorption of gas
molecules.

The total surface are Stotal and the specific surface are SBET are given
by

Where Vm is in units of volume which are also the units of the

monolayer volume of the adsorbate gas, N is Avogadro’s number, s
the adsorption corss section of the adsorbing species, V the molar
volume of the adsorbate gas, and a the mass of the solid sample or
adsorbent.

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DERIVATION :

The BET theory can be derived similarly to the Langmuir

theory, but by considering multilayered gas molecule adsorption,
where it is not required for a layer to be completed before an upper
layer formation starts. Furthermore, the authors made five
assumptions:

1. Adsorptions occur only on well-defined sites of the sample

surface (one per molecule)
2. The only molecular interaction considered is the following one:
a molecule can act as a single adsorption site for a molecule of
the upper layer.
3. The uppermost molecule layer is in equilibrium with the gas
phase, i.e. similar molecule adsorption and desorption rates.
4. The desorption is a kinetically-limited process, i.e. a heat of
adsorption must be provided:
 these phenomena are homogeneous, i.e. same heat of adsorption
for a given molecule layer.
 it is E1 for the first layer, i.e. the heat of adsorption at the solid
sample surface
 the other layers are assumed similar and can be represented as
condensed species, i.e. liquid state. Hence, the heat of
adsorption is EL is equal to the heat of liquefaction.
5. At the saturation pressure, the molecule layer number tends to
infinity (i.e. equivalent to the sample being surrounded by a
liquid phase)

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 Let us consider a given amount of solid sample in a controlled
atmosphere. Let θi be the fractional coverage of the sample surface
covered by a number i of successive molecule layers. Let us assume
that the adsorption rate Rads,i-1 for molecules on a layer (i-1) (i.e.
formation of a layer i) is proportional to both its fractional surface θi-
1  and to the pressure P, and that the desorption rate Rads,i on a layer i is
also proportional to its fractional surface θi:

Rdes,i = k-iθi,
Where, ki and k-i are the kinetic constant (depending on the
temperature) for the adsorption on the layer (i-1) and adsorption on
layer i, respectively. For the adsorptions, these constant are assumed
similar whatever the surface. Assuming an Arrhenius law for
desorption, the related constants can be expressed as

ki = exp(-Ei/RT),
where Ei is the heat of adsorption, equal to E1 at the sample
surface and to EL otherwise.

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FINDING THE LINEAR BET RANGE
It is still not clear on how to find the linear range of the BET
plot for microporous materials in a way that reduces any subjectivity
in the assessment of the monolayer capacity. Rouquerol et
al. suggested a procedure that is based on two criteria:
C must be positive implying that any negative intercept on the
BET plot indicates that one is outside the valid range of the BET
equation.
Application of the BET equation must be limited to the range
where the term V(1-P/P0) continuously increases with P/P0.

APPLICATIONS
Cements and concretes

The rate of curing of concrete depends on the fineness of

the cement and of the components used in its manufacture, which may
include fly ash, silica fume and other materials, in addition to
the calcinated limestone which causes it to harden. Although
the Blaine air permeability method is often preferred, due to its
simplicity and low cost, the Nitrogen BET method is also used.

When hydrated cement hardens, the calcium silicate

hydrate (or C-S-H), which is responsible for the hardening reaction,
has a large specific surface area because of its highporosity.

This porosity is related to a number of important properties of

the material, including the strength and permeability, which in turn
affect the properties of the resulting concrete. Measurement of

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the specific surface area using the BET method is useful for
comparing different cements. This may be performed using
adsorption isotherms measured in different ways, including the
adsorption of water vapour at temperatures near ambient, and
adsorption of Nitrogen at 77 K (the boiling point of liquid nitrogen).
It should be noted that different methods of measuring cement paste
surface areas often give very different values, but for a single method
the results are still useful for comparing different cements.

Activated carbon

For example, activated carbon strongly adsorbs many gases and

has an adsorption cross section  of 0.162 nm2 for nitrogen adsorption
at liquid-nitrogen temperature (77 K). BET theory can be applied to
estimate the specific surface area of activated carbon from
experimental data, demonstrating a large specific surface area, even
around 3000 m2/g.

However, this surface area is largely overestimated due to

enhanced adsorption in micropores, and more realistic methods
should be used for its estimation, such as the subtracting pore effect
(SPE) method.

Catalysis

In the field of solid catalysis, the surface area of catalysts is an

important factor in catalytic activity. inorganic materials such
as mesoporous silica and layered clay minerals have high surface
areas of several hundred m2/g calculated by the BET method,

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indicating the possibility of application for efficient catalytic
materials.

Specific surface area calculation

The ISO 9277 standard for calculating the specific surface area
of solids is based on the BET method.

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REFERENCES :

 Brunauer, Stephen; Emmett, P. H.; Teller, Edward (1938).

"Adsorption of Gases in Multimolecular Layers". Journal of the
American Chemical Society. 60 (2):
309–319. doi:10.1021/ja01269a023. ISSN 0002-7863.
 Hanaor, D. A. H.; Ghadiri, M.; Chrzanowski, W.; Gan, Y.
(2014). "Scalable Surface Area Characterization by Electrokinetic
Analysis of Complex Anion Adsorption" (PDF). Langmuir. 30 (50):
15143–15152. doi:10.1021/la503581e. PMID 25495551.
 J. Rouquerol, P. Llewellyn, and F. Rouquerol, Is the BET equation
applicable to microporous adsorbents? In: Characterisation of
porous solids VII. P. Llewellyn, F. Rodriguez-Reinoso, J.
Rouquerol, and N. Seaton (Eds): Studies in Surface Science and
Catalysis, 2007, 160, 49-56.
 Nakayama, Atsuko; Suzuki, Kazuya; Enoki, Toshiaki; Koga, Kei-
ichi; Endo, Morinobu; Shindo, Norifumi (1996). "Electronic and
Magnetic Properties of Activated Carbon Fibers". Bull. Chem. Soc.
Jpn. 69 (2): 333–339. doi:10.1246/bcsj.69.333. ISSN 0009-2673.
Retrieved 2015-06-26.
 Rouquerol, J.; Llewellyn, P. L.; Rouquerol, F. (2007). "Is the BET
equation applicable to microporous adsorbents?". Characterization
of porous solids VII. Studies in surface science and catalysis.
Elsevier. pp. 49–56. ISBN 9780444520227.
 Sing, Kenneth S.W. (1998). "Adsorption methods for the
characterization of porous materials". Advances in Colloid and
Interface Science. 76–77: 3–11. doi:10.1016/S0001-8686(98)0003-4

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