BET surface area measurements

K. Gopalakrishnan
MS Engg. Student
CPMU
Adsorption vs Absorption

Adsorption is the
adhesion of atoms, ions or
molecules of gas, liquid, or
dissolved solids to a
surface.

This process creates a

film of the adsorbate on
the surface of the
adsorbent. It differs from
absorption, in which a fluid
permeates or is dissolved
by a liquid or solid.
 Langmuir equation

θ is the fractional
coverage of the
surface,
P is the gas
pressure or
concentration,
α is a constant.

1. The surface of the adsorbent is uniform, that

is, all the adsorption sites are equivalent.
2. Adsorbed molecules do not interact.
3. All adsorption occurs through the same
mechanism.
4. At the maximum adsorption, only a monolayer
is formed: molecules of adsorbate do not
deposit on other, already adsorbed, molecules
of adsorbate, only on the free surface of the
adsorbent.
 Brunauer, Emmett and Teller Theory

Often molecules do form multilayers, that

is, some are adsorbed on already
adsorbed molecules and the Langmuir
isotherm is not valid.

S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309.
Basic assumptions
1. the same assumptions as that of Langmuir but allow multi-layer
adsorption
2. the heat of ads. of additional layer equals to the latent heat of
condensation
3. based on the rate of adsorption=the rate of desorption for each
layer of ads. the following BET equation was derived

P / P0 1 c −1
= + ( P / P0 )
V ( 1 − P / P0 ) cVm cVm

Where P - equilibrium pressure

P0 -saturate vapour pressure of the adsorbed gas at the
temperature
P/P0 is called relative pressure
V - volume of adsorbed gas per kg adsorbent
Vm - volume of monolayer adsorbed gas per kg adsorbent
c - constant associated with adsorption heat and condensation
heat
Applications of BET surface area
measurements:

Its main application is in catalysis

1. Calculation of surface areaof a solid material

2. Pore Size of Porous materials

3. Pore Volume of Porous materials

 Choice of Gas and Temperature

• Gases Temperatures
– Nitrogen – Liquid Nitrogen
– Argon – Liquid Argon
– Krypton – Dry ice/acetone
– Carbon dioxide – Water/ice
– Others – Others
Sorption isotherm measurement –volumetric methods
“Dead-space”
Physical volume
that the gas occupies
in the sample cell.

Dead space
Vtube-Vsample
 Particle size Determination using
BET surface area analysis

The particle size, D is given by

D=6000/(SBET X ρ)

Where, SBET is BET surface area

ρ is the true density of the sample

e.g., ρ of titania is 4.2 g/mL

• Five types of physisorption isotherms are found over all solids
I

– Type I is found for porous materials with small pores e.g. charcoal.
It is clearly Langmuir monolayer type, but the other 4 are
II not
amount adsorbed

– Type II for non-porous materials

III

– Type III porous materials with cohesive force between adsorbate

IV
molecules greater than the adhesive force between
adsorbate molecules and adsorbent

– Type IV staged adsorption (first monolayer then build up of

V
additional layers)

1.0 – Type V porous materials with cohesive force between adsorbate

relative pres. P/P0 molecules and adsorbent being greater than that between
adsorbate molecules
Nitrogen adsorption-desorption isotherm of
SBA-15
Thank You