NED University of Engineering and Technology.
Course No.: CY-501 Unit Operations
Instructor: Mr. Ghazanfar Hussain.
Topic: BET Theory
Assignment # 01
By, Mudassir Mubin Baig
Roll No.: CY-01/2024
BET Theory:
The purpose of BET theory is to explain the physical adsorption of gas molecules
on a solid surface. It also forms the foundation of a significant analytical method
for determining a material's specific surface area.
The terms "physical adsorption" or "physisorption" are frequently used to descri
be the observations.
The idea was first stated by Edward Teller, Paul Hugh Emmett, and Stephen Brun
auer in the Journal of the American Chemical Society in 1938.
BET theory is applicable to multilayer adsorption systems, which typically use a p
robing gas (referred to as the adsorbate) to quantify specific surface area withou
t the gas's chemical reaction with the adsorptive (the substance to which the gas
attaches).The most often used gaseous adsorbate for probing surface(s) is nitrog
en.
Because of this, normal BET analysis is often carried out at N2's boiling temperat
ure (77 K).
Although they are used less frequently, other probing adsorbates are also used t
o measure surface area at various temperatures and scales of measurement.
These consist of water, carbon dioxide, and argon.
Since there is no one correct value for specific surface area, it is a scale-
dependent feature. As a result, the amount of specific surface area found using
BET theory may vary depending on the adsorbate molecule used and its adsorpti
on cross section.
Concept:
The theory's notion is an extension of the monolayer molecular adsorption Lang
muir theory to multilayer adsorption, using 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.
4. the enthalpy of adsorption for the first layer is constant and greater than the
second (and higher).
5. the enthalpy of adsorption for the second (and higher) layers is the same as
the enthalpy of liquefaction.
cp
θ=
p
(1− )( pₒ+ p ( c−1 ))
pₒ
The resulting BET equation is θ=cp/(1−p/po)(po+p(c−1)), where po is the
adsorptive bulk liquid phase's vapor pressure, which would be at the adsorbate'
s temperature, and δ is the surface coverage, which is defined as:
θ=nads /nm
θ=nads/nmHere, nm is referred to as the monolayer equivalent, and nads is the
amount of adsorbate.
The nm is the total quantity of adsorbate that would cover the surface in exactl
y one layer if it were present as a monolayer, which is theoretically impossible f
or physical adsorption.
For convenience of analysis, the aforementioned equation is typically rearrange
d to produce the following equation:
p / pₒ
=
c−1 p
( )+
1
,(1)
v [1− ( )p
pₒ
]
v m c pₒ v m c 2
Where p and pₒ are the equilibrium and the saturation pressure of adsorbates at
the temperature of adsorption, respectively; v is the adsorbed gas quantity (for
example, in volume units) while vm is the monolayer adsorbed gas quantity. vm
is the BET constant,
c=exp ( E RT−E ) ,(2)
1 L
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 heat of liquefaction or heat of vaporization.
BET plot
Equation (1) is an adsorption isotherm and can be plotted as a straight line with
1 ❑ 1/v ¿ on the y-axis and φ= p/ pₒφ 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 0.05< p / pₒ<0.350.05000 . The value 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:
1
v m= (3)
A +I
A
c=1+ (4 )
I
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 area Stotal and the specific surface area S BET are given by
( vm N S )
Stotal = ,(5 )
V
S total
S BET = , ( 6)
a
where vm is in units of volume which are also the units of the monolayer volume
of the adsorbate gas, N is the Avogadro number, s the adsorption cross section of
the adsorbate, V the molar volume of the adsorbate gas, and a the mass of the
solid sample or adsorbent.
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)
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 Rdes,i on a layer i is
also proportional to its fractional surface θi:
Rads ,i−1=k i Pθi−1
Rdes , i=k i θi
Where ki 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 constants are assumed similar whatever the surface. Assuming
an Arrhenius law for desorption, the related constants can be expressed as
k i=exp (−Ei / RT ) ,
where Ei is the heat of adsorption, equal to E1 at the sample surface and
to EL otherwise.
Consider some substance A. The adsorption of A onto an available surface
site (*) produces a new site (*)1 on the first layer. In summary,
A ( g ) +(¿)0 ⇌ (¿)1
Extending this to higher order layers one obtains
A ( g ) +(¿)1 ⇌ (¿)2
And similarly
A ( g ) +(¿)n−1 ⇌(¿)n
Denoting the activity of the number of available sites of the nth layer with θn and
the partial pressure of A with P, the last equilibrium can be written
θn
K n=
P θn−1
It follows that the coverage of the first layer can be written
θ1=K 1 Pθ0
and that the coverage of the second layer can be written
θ2=K 2 Pθ1=K 2 P K 1 Pθ0
Realizing that the adsorption of A onto the second layer is equivalent to
adsorption of A onto its own liquid phase, the rate constant for n>1 should be the
same, which results in the recursion
θn =¿ ¿
In order to simplify some infinite summations, let x=K t P and let y=K t P Then
the nth layer coverage can written
n
θn =c θ 0 x , n>0
If c=¿y/x. The coverage of any layer is defined as the relative number of available
sites. An alternative definition, which leads to a set of coverage's that are
numerically to those resulting from the original way of defining surface coverage,
is that θn denotes the relative number of sites covered by
only n adsorbents. Doing so it is easy to see that the total volume of adsorbed
molecules can be written as the sum
∞ ∞
V ads =V m ∑ nθ n=¿ V m cθ 0 x ∑ n x n−1 ¿
n=1 n=1
where V m is the molecular volume. Employing the fact that this sum is the first
derivative of a geometric sum, the volume becomes
x
V ads =V m cθ 0
¿¿
Since the total coverage of a mono-layer must be unity, the full mono-layer
coverage must be
∞
1=∑ θ n
n=1
In order to properly make the substitution for θn , the restriction n>1 forces us to
take the zeroth contribution outside the summation, resulting in
∞ ∞
x
∑ θ n=¿ θ0 + cθ0 x ∑ x n=θ 0+ cθ0 1−x ,|x|<1 ¿
n =1 n=1
Lastly, defining the excess coverage as V excess =V ads/V mono, the excess volume relative
to the volume of an adsorbed mono-layer becomes
∞ ∞
∑ nθ n ∑ nθn cx
V exces= n=1 = n =1∞ =
1 (1−x )(1+ ( c−1 ) x)
∑ θn
n=1
where the last equality was obtained by making use of the series expansions
presented above. The constant c must be interpreted as the relative binding
affinity the substance A has towards a surface, relative to its own liquid.
If c>1 then the initial part of the isotherm will be reminiscent of the Langmuir
isotherm which reaches a plateau at full mono-layer coverage,
whereas c<1 means the mono-layer will have a slow build-up. Another thing to
note is that in order for the geometric substitutions to hold, x<1. The isotherm
above exhibits a singularity at x ¿=1. Since
x=K t P one can write x ¿= K t P∗¿ , implying that
1
Kt=
P∗¿ ¿
. This means X=P/p* that must be true, ultimately resulting in x ϵ (0,1).
BET Isotherms:
1. Type I Isotherm (Langmuir Isotherm)
Shape: Rapid increase in adsorption at low pressures, followed by a plateau at higher pressures.
Interpretation: This isotherm is typical of microporous materials (pore size < 2 nm), such as
activated carbon or zeolites.
The initial rise suggests a high affinity between the adsorbent and adsorbate, and the plateau
indicates the formation of a monolayer of adsorbate molecules.
It follows Langmuir's assumption of limited adsorption sites, after which no more adsorption
occurs.
Material examples: Activated carbons, zeolites, microporous materials.
2. Type II Isotherm
Shape: Initial steep increase at low pressure, followed by a smooth curve and leveling off at
high pressure.
Interpretation: This isotherm indicates non-porous or macroporous materials where
monolayer adsorption is followed by multilayer adsorption.
The knee at the lower pressure indicates the completion of the monolayer, and the gradual
slope suggests multilayer formation as pressure increases.
It is the most common type for surface area determination using the BET method.
Material examples: Non-porous adsorbents like silica or metal oxides.
3. Type III Isotherm
Shape: Gradual increase in adsorption with no distinct knee, forming a convex curve.
Interpretation:
This isotherm indicates weak interactions between the adsorbate and adsorbent. The absence
of a plateau suggests there is no clear saturation point, meaning multilayer adsorption occurs
without strong adsorption in the first layer.
This is characteristic of adsorbents with weak adsorbate interactions, leading to higher
multilayer adsorption at relatively low pressure.
Material examples: Adsorbents with low affinity for the adsorbate, such as poorly activated
materials.
4. Type IV Isotherm
Shape: Similar to Type II but with a noticeable hysteresis loop in the higher pressure region.
Interpretation: Indicates the presence of mesopores (2–50 nm in size).
The initial portion (similar to Type II) corresponds to monolayer and multilayer adsorption, but
the hysteresis loop is due to capillary condensation in mesopores.
The sharp uptake at a certain relative pressure corresponds to filling of the mesopores by
condensation, with hysteresis due to differences in adsorption and desorption mechanisms.
Material examples: Mesoporous materials like silica gels, MCM-41, SBA-15.
5. Type V Isotherm
Shape: Similar to Type III, with a hysteresis loop.
Interpretation: Indicates weak interactions between the adsorbate and adsorbent, but with
capillary condensation in mesopores at higher pressures.
This isotherm is less common and can be seen in some materials with weak adsorbent-
adsorbate interactions in combination with mesopores.
Material examples: Some porous polymers or inorganic materials.
6. Type VI Isotherm (Stepwise Isotherm)
Shape: Step-like curve with sharp increases in adsorption at specific pressures.
Interpretation: This isotherm represents layer-by-layer adsorption on a highly uniform surface.
Each step corresponds to the completion of one layer of adsorption, followed by the start of a
new layer.
Rarely seen, but may occur on highly structured surfaces.
Material examples: Graphite or crystalline surfaces.
Questions
Q#1. Which assumption is taken in bet surface analysis theory?
Q#2. How to interpretate the adsorption isotherm based on BET theory?
