Introduction
BET
Gas adsorption or Nitrogen adsorption
Stephen Brunauer, Paul Hugh Emmett, and Edward
Teller
Directly measures surface area & pore size
distribution
BET theory deviates from ideal to actual analysis
2
Basic Principle
Ideal PV = nRT Actual
No gas molecules
Never start from no gas molecules
Q Ads
P/Po
Nitrogen gas molecules
Monolayer: Gas molecules clump
Q Ads
together
P/Po
Saturated Nitrogen gas molecules Multilayer: Gas molecules clump
together
Q Ads
P/Po Some pores are not filled 3
Basic Principle Cont.
BET is an extension of Langmuir model
Kinetic behavior of the adsorption process
Rate of arrival of adsorption is equal to the rate of
desorption
Heat of adsorption was taken to be constant and
unchanging with the degree of coverage, θ
4
Basic Principle Cont.
Assumptions
Gas molecules behave ideally
Only 1 monolayer forms
All sites on the surface are equal
No adsorbate-adsorbate interaction
Adsorbate molecule is immobile
5
BET Theory Basic Principle Cont.
Homogeneous surface
No lateral interactions between molecules
Uppermost layer is in equilibrium with vapour phase
First and Higher layer: Heat adsorption
All surface sites have same adsorption energy for
adsorbate
Adsorption on the adsorbent occurs in infinite layers
The theory can be applied to each layer
5
Basic Principle Cont.
Pore classification
Pore size
5
Basic Principle Cont.
Adsorption Mechanism
Capillary
Monolayer Multilayer condensation
5
Results-Cont
6 types of adsorption isotherm
Type I
Concave to P/Po axis
na approaches limiting value as
Amount adsorbed (n)
P/ Po → 1
Microporous solids
Type II
Unrestricted mono-multilayer
adsorption
B indicates complete monolayer
coverage
Non-porous or macroporous
Relative Pressure (P/Po) 10
Preliminary Results-Cont
Graphene oxide Type III
Convex to P/Po axis
Not common
Amount adsorbed (n)
Adsorbate-adsorbate interactions
Type IV
Hysterisis loop
Capillary condensation that occurs
in a mesopores
Limit uptake of high P/Po
Initial loop = mono-multilayer
adsorption
Relative Pressure (P/Po) 2nd loop= desorption 11
Preliminary Results
Type V
Not common
Amount adsorbed (n)
Weak adsorbate-adsorbate
interactions
Porous adsorbents
Type VI
Sharpness of peaks depends on
the system and T
Stepwise multilayer adsorption on
a uniform non-porous surface
Relative Pressure (P/Po) 12
Inert Gas Adsorption
– What can be measured using this technique?
• Specific Surface Area
• Pore Size Distribution
• Heats of Adsorption
– Who would be interested in such results?
– Everyone who needs to understand how pore structure
affects material performance.
• Surface Area
– affects dissolution rates.
– affects electron/ion current density at electrode interface with electrolyte.
– affects adsorption capacity.
– represents surface free energy available for bonding in tabletting and
sintering.
• Pore Size Distribution
-affects diffusion rates.
-affects molecular sieving properties.
- affects surface area per unit volume.
