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BET theory

where p and p0 are the equilibrium and the saturation

v is the adsorbed gas quantity (for example, in volume
BrunauerEmmettTeller (BET) theory aims to explain the physical adsorption of gas molecules on a solid units), and vm is the monolayer adsorbed gas quantity. c
is the BET constant,
surface and serves as the basis for an important analysis technique for the measurement of the specic surface area of a material. In 1938, Stephen Brunauer, Paul
(
)
Hugh Emmett, and Edward Teller published the rst ar- c = exp E1 EL ,
(2)
RT
ticle about the BET theory in the Journal of the American Chemical Society.[1] The BET theory refers to multi
layer adsorption, and usually adopts non-corrosive gases where E1 is the heat of adsorption for the rst layer, and
(like nitrogen, argon, carbon dioxide, etc.) as adsorbates EL is that for the second and higher layers and is equal to
to determine the surface area data. It usually uses static the heat of liquefaction.
volumetric principle (like V-Sorb 2800TP), also has gas
owing technology can determine surface area data.

Concept

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 BET plot

theory, which is a theory for monolayer molecular adsorption, to multilayer adsorption with the following hyEquation (1) is an adsorption isotherm and can be plotted
potheses:
as a straight line with 1/v[(p0 /p) 1] on the y-axis and
= p/p0 on the x-axis according to experimental re1. gas molecules physically adsorb on a solid in layers sults. This plot is called a BET plot. The linear relationinnitely;
ship of this equation is maintained only in the range of
0.05 < p/p0 < 0.35 . The value of the slope A and the
2. there is no interaction between each adsorption y-intercept I of the line are used to calculate the monolayer; and
layer adsorbed gas quantity vm and the BET constant c .
The following equations can be used:
3. the Langmuir theory can be applied to each layer.
The resulting BET equation is
vm =
c1
1
=
v [(p0 /p) 1]
vm c

p
p0

)
+

1
vm c

(1)

1
A+I

c=1+
1

A
.
I

(3)

(4)

3 APPLICATIONS

The BET method is widely used in surface science for the a layer i) is proportional to both its fractional surface i
calculation of surface areas of solids by physical adsorp- and to the pressure P, and that the desorption rate R ,i
tion of gas molecules. The total surface area Stotal and the on a layer i is also proportional to its fractional surface i:
specic surface area SBET are given by

Stotal =

(vm N s)
,
V

(5)

Stotal
,
(6)
a
where vm is in units of volume which are also the units of
species, V the molar volume of the adsorbate gas, and a
the mass of the solid sample or adsorbent.
SBET =

Rdes,i = ki i ,
where ki and k-i are the kinetic constants (depending on
the temperature) for the adsorption on the layer (i1) 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

ki = exp(Ei /RT ),

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 ve assumptions:[2]

where Ei is the heat of adsorption, equal to E 1 at the sample surface and to EL otherwise.

3 Applications
3.1 Cement paste

1. Adsorptions occur only on well-dened sites of the

By application of the BET theory it is possible to detersample surface (one per molecule)
mine the inner surface of hardened cement paste. If the
2. The only molecular interaction considered is the fol- quantity of adsorbed water vapor is measured at dierent
lowing one: a molecule can act as a single adsorption levels of relative humidity a BET plot is obtained. From
the slope A and y-intersection I on the plot it is possible
site for a molecule of the upper layer.
to calculate vm and the BET constant c . In case of ce3. The uppermost molecule layer is in equilibrium with ment paste hardened in water (T = 97 C), the slope of
the gas phase, i.e. similar molecule adsorption and the line is A = 24.20 and the y-intersection I = 0.33 ;
desorption rates.
from this follows
4. The desorption is a kinetically-limited process, i.e.
a heat of adsorption must be provided:
vm =

1
= 0.0408,
A+I

these phenomenon are homogeneous, i.e.

same heat of adsorption for a given molecule
A
layer.
c = 1 + = 73.6.
I
it is E1 for the rst layer, i.e. the heat of ad- From this the specic BET surface area S
BET can be calsorption at the solid sample surface
culated by use of the above-mentioned equation (one wa the other layers are assumed similar and can be ter molecule covers s = 0.114nm2 ). It follows thus
represented as condensed species, i.e. liquid SBET = 156m2 /g which means that hardened cement
state. Hence, the heat of adsorption is EL is paste has an inner surface of 156 square meters per g of
equal to the heat of liquefaction.
cement. However, the article on Portland cement states
that Typical values are 320380 m2 kg1 for general
5. At the saturation pressure, the molecule layer numpurpose cements, and 450650 m2 kg1 for rapid hardber tends to innity (i.e. equivalent to the sample
ening cements.
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 ,i for molecules on a layer (i1) (i.e. formation of

3.2 Activated Carbon

For example, activated carbon strongly adsorbs many
gases and has an adsorption cross section s of 0.162 nm2
for nitrogen adsorption at liquid nitrogen temperature (77

3
K). BET theory can be applied to estimate the specic
surface area of activated carbon from experimental data,
demonstrating a large specic surface area, even around
3000 m g1 .[3] However, this surface area is largely overestimated due to enhanced adsorption in micropores,[4]
and more realistic methods should be used for its estimation, such as SPE method.[5]

3.3

Catalysis

In the eld of solid catalysis, the surface area of catalysts

is an important factor in catalytic activity. Porous inorganic materials such as mesoporous silica and layered clay
minerals have high surface areas of several hundred m
g1 calculated by the BET method, indicating the possibility of application for ecient catalytic materials.

Capillary condensation
Surface tension

References

[1] 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.
[2] Kenneth S.W Sing, Adsorption methods for the characterization of porous materials, Advances in Colloid
and Interface Science, Volumes 7677, 1 July 1998,
Pages 3-11, ISSN 0001-8686, http://dx.doi.org/10.1016/
S0001-8686(98)00038-4 .
Mesopores; Micropores; Physisorption; Surface area
[3] 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.
[4] 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. 4956. ISBN
9780444520227.
[5] Kaneko, K.; Ishii, C.; Ruike, M.; Kuwabara, H. (1992).
Origin of superhigh surface area and microcrystalline
graphitic structures of activated carbons. Carbon 30 (7):
10751088. doi:10.1016/0008-6223(92)90139-N. ISSN
0008-6223. Retrieved 2015-06-26.

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Images

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