28/5/2014 BET theory - Wikipedia, the free encyclopedia

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BET theory
From Wikipedia, the free encyclopedia
BrunauerEmmettTeller (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 a material. 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.
[1]
Contents
1 Concept
2 Derivation
3 Example
3.1 Cement paste
3.2 Activated Carbon
4 See also
5 References
Concept
The concept of the theory is an extension of the Langmuir theory, which is a theory for monolayer molecular
adsorption, to multilayer adsorption with the following hypotheses: (a) gas molecules physically adsorb on a
solid in layers infinitely; (b) there is no interaction between each adsorption layer; and (c) the Langmuir theory
can be applied to each layer. The resulting BET equation is
where and are the equilibrium and the saturation pressure of adsorbates at the temperature of adsorption,
is the adsorbed gas quantity (for example, in volume units), and is the monolayer adsorbed gas quantity.
is the BET constant,
where is the heat of adsorption for the first layer, and is that for the second and higher layers and is
equal to the heat of liquefaction.
Equation (1) is an adsorption isotherm and can be plotted as a straight line with on the y-
axis and on the x-axis according to experimental results. This plot is called a BET plot. The linear
relationship of this equation is maintained only in the range of . The value of the slope
and the y-intercept of the line are used to calculate the monolayer adsorbed gas quantity and the BET
constant . The following equations can be used:
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BET plot
The BET method is widely used in surface science for
the calculation of surface areas of solids by physical
adsorption of gas molecules. The total surface area
and the specific surface area are given by
where is in units of volume which are also the units
of the molar volume of the adsorbate gas, is
Avogadro's number, the adsorption cross section of
the adsorbing species, the molar volume of the
adsorbate gas, and the mass of the solid sample or
adsorbent.
Derivation
The BET theory can be derived similar 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 phenomenon are homogeneous, i.e. same heat of adsorption for a given molecule layer.
it is E
1
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 E
L
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)
Let us consider a given amount of solid sample in a controlled atmosphere. Let
i
be the fractional coverage of
the sample surface covered by a number i of successive molecule layers. Let us assume that the adsorption rate
R
ads,i-1
for molecules on a layer (i-1) (i.e. formation of a layer i) is proportional to both its fractional surface
i-1
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and to the pressure P, and that the desorption rate R
des,i
on a layer i is also proportional to its fractional surface

i
:
where k
i
and k
-i
are the kinetic constants (depending on the temperature) for the adsorption on the layer (i-1)
and desorption 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
where E
i
is the heat of adsorption, equal to E
1
at the sample surface and to E
L
otherwise.
Example
Cement paste
By application of the BET theory it is possible to determine the inner surface of hardened cement paste. If the
quantity of adsorbed water vapor is measured at different levels of relative humidity a BET plot is obtained.
From the slope and y-intersection on the plot it is possible to calculate and the BET constant . In
case of cement paste hardened in water (T = 97C), the slope of the line is and the y-intersection
; from this follows
From this the specific BET surface area can be calculated by use of the above mentioned equation (one
water molecule covers ). It follows thus which means that hardened
cement paste has an inner surface of 156 square meters per g of cement. However, the article on Portland
cement states that "Typical values are 320380 m
2
kg
1
for general purpose cements, and 450650 m
2
kg
1
for "rapid hardening" cements."
Activated Carbon
For example, activated carbon, which is a strong adsorbate and usually has an adsorption cross section of
0.16 nm
2
for nitrogen adsorption at liquid nitrogen temperature, is revealed from experimental data to have a
large surface area around 3000 m g
-1
. Moreover, in the field of solid catalysis, the surface area of catalysts is
an important factor in catalytic activity. Porous inorganic materials such as mesoporous silica and layer clay
minerals have high surface areas of several hundred m g
-1
calculated by the BET method, indicating the
possibility of application for efficient catalytic materials.
See also
Adsorption
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Capillary condensation
Surface tension
Sorption isotherm
References
1. ^ S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309. doi:10.1021/ja01269a023
(http://dx.doi.org/10.1021%2Fja01269a023)
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