Brunauer-Emmett-Teller (BET) surface

area analysis

Refilwe Matshitse
 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

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 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
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 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

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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

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 Basic Principle Cont.
Pore classification

Pore size

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 Basic Principle Cont.
Adsorption Mechanism

Capillary
Monolayer Multilayer condensation

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 Sample preparation

Weigh solid sample (200 ≈ 300 mg)

The sample is purified by degassing

 Temperature
 Time
 Vacuum conditions

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BET Equipment Experimental
Gas lines

Data
Degassing collector
Port

Heating
mantle

Sample holder Dewar (liquid nitrogen) 6

 Instrument schematic
BET Equipment
Graphene oxide

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 Results
Presentation of data

Surface Pore
Sample area size
(m2/g) (nm)
SiO2 25.7 100
Q Ads

SiO2/Al2O3 215.5 11
P/Po

Graphically Tabulated

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 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
 Application
PluS nanoparticles PluS nanoparticles linked Porphyrin
80
1200

Quantity adsorbed (cm3\ g STP)

Quantity adsorbed (cm3/g STP)

75
1000 70

800 65

60
600
55
400
50
200 45

0 40
0 0.5 1 1.5 0 0.5 1 1.5
Relative Pressure (P/Po) Relative Pressure P/Po

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 Application

Sample Surface area Pore size

(m2/g) (nm)
PluS NPs 330.0 18.9

PluS NPs-Porphyrins 192.5 2.4

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 Acknowledgements
Prof T. Nyonkong
Dr J. Briton
Muthumuni
Rhodes University
NRF
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