BET and related Isotherms

Langmuir type, roughly Corresponds to a multilayer

characterized by a formation (physical
monotonic approach to a adsorption). Formerly it was Relatively rare: e.g., Considered to reflect
limiting adsorption that a common practice to take adsorption of nitrogen on capillary condensation
presumably corresponds the point B , at the knee of ice, and seems to be phenomena in that they level
to a complete monolayer. the curve, as the point of characterized by a heat of off before the saturation
Here the flat region has completion of a monolayer, adsorption heat of pressure is reached and may
never been observed up to and surface area obtained so liquefaction of the show hysteresis effects.
pressure approaching po. are fairly consistent with adsorbates.
This is typically observed in those found using
chemisorption, at adsorbates that give type I • Type IV and V specially refers to porous solids.
pressures far below Po. isotherms.
• Type II and III approach the Po line asymptotically, experimentally such behavior is observed for adsorption
on powdered samples, and the approach towards infinite film thickness is actually due to particle
condensation.
• Although such behavior is expected even for adsorption on a flat surface if bulk liquid adsorbate wets the
adsorbent.

• These are two simple types possible

for adsorption on a flat surface for
the case where bulk liquid
adsorbate rests on the adsorbent
with a finite contact angle.
4. BET (Brunauer–Emmett–Teller) Isotherm

Brunauer, Emmett and Teller's model of multilayer adsorption is

a random distribution of molecules on the material surface.
o If the initial adsorbed layer can act as a substrate for further (for example, physical) adsorption, then, instead of the isotherm
levelling off to some saturated value at high pressures, it can be expected to rise indefinitely. The most widely used isotherm
dealing with multilayer adsorption was derived by Stephen Brunauer, Paul Emmett, and Edward Teller, and is called the BET
isotherm, which is an actually the extended Langmuir’s approach to multilayer adsorption.
o This 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.
o An alternate term of adsorbate, which is more popular in Europe than US, is adsorptive. The distinction may be made that
adsorbate refers to the species actually adsorbed, while adsorptive refers to a gas-phase species that is capable of being
adsorbed.
o The derivation follows the traditional approach of detailed balancing of forward and reverse rates. The basic assumptions
are:
1. The Langmuir equation applies to each layer. Hence rate of adsorption of each layer corresponds to fraction of lowest layer
still vacant and rate of desorption proportional to amount present in that layer.
2. Heat of adsorption of first layer formed (and hence and of first layer) may have some special value, whereas for all
succeeding layers, it is equal to the heat of condensation to the liquid adsorbate.
3. Evaporation and condensation can occur only from or on exposed surface.
o Let the no. of surface sites exposed on surface, corresponds to zero, monolayer bilayer, …, coverage be S 0, S1, S2, …, Si,.
o The condition of equilibrium is taken to be that the amount of each type of surface reaches a steady-state value with respect
to the next deeper one. Hence:
Rate of adsorption of first layer = and rate of desorption for this is =
Therefore, at equilibrium: So,
=(
This gives number of sites exposed from first layer, Similarly for second layer:
=(
Using value of : =((
=((
Similarly for third layer:
=(((( =((((
In general for ith layer:
=
Let = x and = C.x, (As, Chemisorption forms stronger bonds than physical adsorption, This implies C > 1)
Then above equation becomes:
= C.x (x) or = C (x) ………….(A)
Since >>
Now the total volume (Vtotal) of the adsorbate at a given pressure is proportional to the total number of molecules adsorbed,
that is:
11 22 33 ….
=
Volume of adsorbate required for complete monolayer coverage is proportional to:

1 2 3 ….
Each layer will contribute single molecule to the monolayer.
Dividing Vtotal by Vmono, we get:

From equation A using value of in above equation, we get:

Or
On putting = and using regression series, which is and
Therefore, or
Or or or
Giving its value, we can write
Now, considering the equilibrium between the gas and the solid surface and applying the Langmuir adsorption isotherm, we
will have:

/X
Since p is the equilibrium pressure and is equal to the bulk vapor pressure p o above a layer of substrate (adsorbate) that is
more than one molecule thick and which resembles a pure bulk liquid. Therefore we can write:
/X
Using this value of x in above equation, we get:
𝑉 𝑡𝑜𝑡𝑎𝑙 ¿
=C (𝑝/𝑝 𝑜¿
𝑉 𝑚𝑜𝑛𝑜 ( 1−𝑝/𝑝𝑜 )(1+ \{C−1\}𝑝/𝑝𝑜 )
This equation is known as BET equation.
is vapor pressure of gas and is equilibrium vapor pressure.
o From BET equation it follows that is independent of pressure, while is a function of pressure and its value is determined by
C/, which is usually greater than 1.
o When , approaches to infinity,
or approaches infinity, there is abrupt rise in the slope of the plot.
Actually at high pressure, there is no limit to the amount of material adsorbed,
which may condense during multilayer adsorption.
 

 
BET gives important information on the physical structure of solids as the area of a material’s surface affects how that solid
will interact with its environment.
Many properties such as dissolution rates, catalytic activity, moisture retention, and shelf life are often correlated to a
material’s surface area.
Critical to the design and manufacture of solids, surface area analysis is one of the most widely used methods in material
characterization.
Using the BET theory, the true or specific surface area, including surface irregularities and pore walls, of a particle is
determined at an atomic level by adsorption of an un-reactive gas.
Because most gases and solids interact weakly, the solid material must be cooled, typically using a cryogenic liquid.
The temperature of the solid sample is kept constant (under isothermal conditions) while the pressure or concentration of
the adsorbing gas is increased.
o The plot of against gives BET adsorption isotherm
and accounts for multilayer adsorption.
o BET equation seems to cover three of the five
isotherm types (discussed earlier).
o Thus for large values of C (> 1) (That is heat of
adsorption on first and succeeding layers are greater
than heat of vaporization), the isotherm reduces to
Langmuir isotherm.
o For small C values, type third isotherm results, where
heat of adsorption heat of liquefaction of the
adsorbates.
o The adsorption of relatively inert gases, such as N and
Ar on polar surfaces generally gives C values around
100, which corresponds to type II isotherm. For such
systems BET isotherm reduces to: