ESD 406 ENVIRONMNETAL NANOTECHNOLOGY

LECTURE 8: Brunauer-Emmett-
Teller (BET) surface area
analysis
 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.
Adsorption Mechanism

Capillary
Monolayer Multilayer condensation

a monolayer formation of adsorbate gas molecules on the surface of the adsorbent is

assumed at low pressure and moderately high temperatures. This assumption,
however, is not valid at high pressures and low temperatures.

When the gas pressure is high, greater number of adsorbate molecules strike unit surface
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area of the adsorbent in unit time. And when the temperatures are low, the thermal
energies of the gas molecules are low, insufficient to overcome the Van der waals forces of
attraction between the adsorbed molecules and the surrounding unadsorbed molecules. As
a result of these two effects, the solid adsorbent holds on many layers of gas molecules on
to its surface, resulting into what is called as a multilayer adsorption.
 CAPILLARY CONDESNATION

❖ Capillary condensation is the "process by which multilayer

adsorption from the vapor into a porous medium proceeds
to the point at which pore spaces become filled with
condensed liquid from the vapor.
❖ The unique aspect of capillary condensation is that vapor
condensation occurs below the saturation vapor pressure,
Psat, of the pure liquid.
❖ This result is due to an increased number of van der Waals
interactions between vapor phase molecules inside the
confined space of a capillary. Once condensation has
occurred, a meniscus immediately forms at the liquid-vapor
interface which allows for equilibrium below the saturation
vapor pressure.
 SORPTION ISOTHERM

A plot of the amount of gas adsorbed at a certain temperature

against the relative pressure is called a sorption isotherm. It is
usually presented as the volume of adsorbed gas versus the
relative pressure, p/p0
 Sample preparation

❖Weigh solid sample (200 ≈ 300 mg)

❖The sample is purified by degassing

➢ Temperature
➢ Time
➢ Vacuum conditions

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BET Equipment
Instrument schematic

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 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.
 So, How Does It Work?

• Basic Construction
– Removable sample cell
– Dosing manifold
– Pressure transducers
– Vacuum system
– Analysis gas
– Valves to move gas in and out of manifold and
sample cell
– Sample thermostat (dewar, furnace, cryostat)

*** Before performing gas sorption expts, solid surfaces must be freed from
contaminants like water and oils
BET
ANALYSER
 Basic Construction

Pressure transducer(s)

Analysis gas to vacuum

Manifold

Sample cell
 What is a Gas Sorption Analyzer?

• Does it actually measure surface area and pore size?

• NO!! It simply records various pressures of gas in the

sample cell due to adsorption and desorption. The
instrument then calculates the amount (as STP volume) of gas
adsorbed/desorbed. Surface area, pore size are calculated by PC software
• Pressure measurements are critical!
 What Is The Result?
Amount adsorbed It’s called an “isotherm”

Relative pressure
 What Is The Result?
The values on the y-axis are calculated
from pressure measurements (and
temperature values)
Amount adsorbed

Relative pressure
 What Is The Result?
Desorption curve may overlay on, or
appear to left of, the adsorption curve
Amount adsorbed

Relative pressure
 What To Analyze?

If a micropore size distribution is needed:

Amount adsorbed

Relative pressure
 What To Analyze?

If just a total (BET) surface area is needed:

Amount adsorbed

Relative pressure
 What To Analyze?

If total (BET) and micropore areas are both needed:

Amount adsorbed

Relative pressure
 What To Analyze?

If a meso/macropore size distribution needed:

Amount adsorbed

Relative pressure
Very Low Pressure Behavior (micropore
filling)
Amount Adsorbed

Relative Pressure (P/Po)

Low Pressure Behavior (monolayer)
Amount Adsorbed

The “knee”

Relative Pressure (P/Po)

Medium Pressure Behavior (multilayer)
Amount Adsorbed

Relative Pressure (P/Po)

 High Pressure Behavior (capillary
condensation)

The capillary condensation in a set of pores of certain size at adsorption does not occur exactly
at the same relative pressure as capillary evaporation from the same pores at desorption, the
combined adsorption-desorption isotherms may, and usually do, show a hysteresis.
Illustration of gas molecule
adsorption-desorption
 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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 Adsorption Isotherms

□An Adsorption Isotherm is obtained by measuring the

amount of gas adsorbed across a wide range of
relative pressures at a constant temperature (typically
liquid N2, 77K).
Conversely desorption Isotherms are achieved by
measuring gas removed as pressure is reduced
 Iostherm types

described by Brunauer, Deming, Deming and Teller.

Type I

Pores are typically microporuswith the exposed surface residing

almost exclusively inside the microspores, which once filled with
adsorbate, leave little or no external surface for further
adsorption.

Concave to P/Po axis, Microporous solids

 Type II

Most frequently found when adsorption occurs on nonporouspowdersor

powderswith diameters exceeding micropores.
Inflection point occurs near the completion of the first adsorbed monolayer
Unrestricted mono-multilayer adsorption
B indicates complete monolayer coverage
Non-porous or macroporous
Amount adsorbed (n)

Relative Pressure (P/Po)

Type III

Characterised by heats of adsorption less than the adsorbate heat of

liquification, adsorption proceeds asthe adsorbate interaction with an
adsorbed layer is greater than the interaction with the adsorbent surface

➢ Convex to P/Po axis

➢ Not common
➢ Adsorbate-adsorbate interactions
Type IV

Occur on porous adsorbents with pores in the range of 1.5 – 100nm. At

higher pressures the slope shows increased uptake of adsorbate as
pores become filled, inflection point typically occursnear completion of
the first monolayer
➢ Hysteresis loop
➢ Capillary condensation that occurs in a mesopores
➢ Limit uptake of high P/Po
➢ Initial loop = mono-multilayer adsorption, 2nd loop= desorption
Type V

Are observed where there issmall adsorbate- absorbent interaction

potentials (similar to type III), and are also associated with pores in the
1.5 – 100nm range

➢ Not common
➢ Weak adsorbate-adsorbate interactions
➢ Porous adsorbents
 ISOTHERM
Type VI
➢ Sharpness of peaks depends on
Amount adsorbed (n)

the system and T

➢ Stepwise multilayer adsorption on
a uniform non-porous surface

Relative Pressure (P/Po)

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 Application
PluS nanoparticles PluS nanoparticles linked Porphyrin
80
1200

Quantity adsorbed (cm3\ g STP)

75
Quantity adsorbed (cm3/g STP)

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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Adsorption
● When a gas or vapour phase isbrought into contact with a solid, part
of it is taken up and remains on the outside attached to the surface.

● In physisorption (physical adsorption), there is a weak Van der Waals

attraction between the adsorbate and the solid surface.

● Useful to characterise porous materials allowing for the determination

of specific surface area, pore size distribution and pore volume.
 Adsorption/Desorption
• Adsorption is the sticking of gas molecules onto the surface of a solid… all available surfaces
including that surface inside open pores.

• Increasing the pressure of gas over a solid causes increasing adsorption.

• Temperature dependent

• Desorption is the removal of gas molecules from the surface of a solid… all available surfaces
including that surface inside open pores.

• Decreasing the pressure of gas over a solid causes increasing desorption.

• Done at same temperature as adsorption.
 The Nature of Gas Sorption at a Surface
• When the interaction between a surface and an adsorbate is
relatively weak only physisorption takes place.
• However, surface atoms often possess electrons or electron pairs
which are available for chemical bond formation.
• This irreversible adsorption, or chemisorption, is characterized by
large interaction potentials which lead to high heats of
adsorption. As is true for most chemical reactions,
chemisorption is usually associated with an activation energy,
which means that adsorbate molecules attracted to a surface
must go through an energy barrier before they become strongly
bonded to the surface.
Characteristics of Physical Adsorption
● 1. Low heats of adsorption, no violent or disruptive structural
changes.

● 2. Can involve multiple layers of adsorbate, thus allowing for pore

measurements.

● 3. High temperatures tend to inhibit physical adsorption.

● 4. Adsorption equilibrium isachieved quickly sincenoactivation

energy is generally required.

● 5. Physical adsorption is fully reversible, allowing adsorbate to fully

adsorb and desorb.
 Physisorption vs Chemisorption
Property Physisorption Chemisorption

Forces van der Waals Chemical bonding

Hads
(kJ mol-1) < 40 50-200
Ea
(kJ mol-1) Rare 60–100

Isothermal
Complete Slow or none
Reversibility

Extent Multilayers Monolayer

Physisorption: Surface area and porosity are physical properties that impact the
quality and character of solid phase materials, Pore size distribution, Pore Volume
etc.
Chemisorption - measures the number of surface active sites which are used to
promote a specified catalytic reaction. Critical parameters for chemisorption
measurement are: the area of the active element, metal dispersion, surface acidity,
exposed proportion of the active element.
Adsorbate
□ The most common adsorbate used is Nitrogen, however, other
adsorbates are used in some circumstances.
BET
□ Brunauer, Emmett and Teller (BET), most common method used
to describe specific surface area:
The BET equation –

W= weight of gas adsorbed

P/P0 =relative pressure
Wm = weight of adsorbate as monolayer
C = BET constant
BET equation requires a linear plot of
1/[W(P/P0)-1] against P/P0

□ Slope (s) Intercept (i)

□ Wm (weight of monolayer)
□ Total Surface area (St) can then be derived

N = Avogadro's number (6.023x1023)

M = Molecular weight of Adsorbate
Acs= Adsorbate cross sectional area (16.2Å2 for Nitrogen)

□ Specific Surface Area (S) is then determined by total

Surface area by sample weight
□ Single point BET:
Involves determining specific surface area
using a single point on the isotherm

□ Multipoint BET:
Minimum of three data points.
Multipoint BETPlot
Relative Volume @ 1/[W((Po/P)-1]
Pressur STP cc/g
e P/Po
1.10536e-01 7.5355 1.3195e+1
1.53021e-01 8.1192 1.7804e+1
1.99422e-01 8.7403 2.2803e+1
2.48028e-01 9.4102 2.8045e+1
2.97227e-01 10.1099 3.3472e+1
Summary
Slope = 108.451
Intercept = 1.195e+00
Correlation coefficient, r = 0.99999
C constant= 91.759
Surface Area = 31.762 m²/g
C Constant
□ Relative error between Single/Multi point Comparison
single and multipoint
Constant Relative error
BET, (typically measured 1 0.70
at P/P0 of 0.3) 10 0.19
50 0.04
100 0.02
1000 0.0002
Infinity 0
Porosity - pore volume

Total pore volumeisderived from the amount of vapour

adsorbed at a relative temperature close to unity
(assuming pores are filled with liquid adsorbate).

Vads = volume of gas adsorbed

Vliq = volume of liquid N2 in pores
Vm= molar vol. of liquid adsorbate (N2=34.7cm3/mol)
Pa= ambient pressure
T = ambient temperature
IUPAC classification on pores

- Macroporous >50nm

- Mesoporus 2-50nm

- Microporus <2nm
Porosity - pore radius

Average pore size is estimated from the pore volume.

Assuming cylindrical pore geometry (type A hysteresis)
average pore radius (rp) can be expressed as:

Other pore geometry models may require further

information on the isotherm hysteresis before applying
appropriate model.
Adsorption/Desorption Isotherm
Sample porosity data
● Pore Volume Data
Total pore volume for pores with Radius
lessthan 15.93 Å at P/Po = 0.395090 5.787e-01 cc/g
BJH method cumulative adsorption pore volume 2.103e+00 cc/g
BJH method cumulative desorption pore volume 2.192e+00 cc/g
DH method cumulative adsorption pore volume 2.054e+00 cc/g
DH method cumulative desorption pore volume 2.146e+00 cc/g
HK method cumulative pore volume 4.257e-01 cc/g
SF method cumulative pore volume 4.358e-01 cc/g
NLDFT method cumulative pore volume 1.904e+00 cc/g

● Pore Size Data

Average pore Radius 3.505e+01 Å
BJH method adsorption pore Radius(Mode Dv(r)) 1.698e+01 Å
BJH method desorption pore Radius(Mode Dv(r)) 1.710e+01 Å
DH method adsorption pore Radius(Mode Dv(r)) 1.698e+01 Å
DH method desorption pore Radius(Mode Dv(r)) 1.710e+01 Å
HK method pore Radius(Mode) 1.838e+00 Å
SF method pore Radius(Mode) 2.261e+00 Å
NLDFT pore Radius(Mode) 2.376e+01 Å
Other Methods
● Barrett-Joyner-Halenda Method (BJH)
● Dollimore Heal Method (DH)
● Alpha S Method (αs)
● MP Method (MP)
● Dubinn-Radushkevic Method (DR)
● Dubinin-Astakhov Method (DA)
● Horvath-Kawazoe Method (HK)
● Saito-Foley Method (SF)
● Density Functional Theory Method (DFT)
● Frenkel-Halsey-Hill Method (FHH)
● Neimark-Kiselev Method (NK)