BET Analysis fundamentals

Surface Area What is it?

Surface Area is the means through which a solid
interacts with its surroundings, especially liquids
and gases.
Surface area is created by division of particles (size
reduction) and the generation of porosity.
Surface area is destroyed by sintering (exceeding
Tg), melting and Ostwald ripening.

How to Create Area ?

Size Reduction
Grinding,
milling,
nanoscale

preparation

Make pores
Partial

decomposition

Leach
Gel

then lyophilize

How to Destroy Area ?

Surface area is destroyed by

melting

sintering

(exceeding Tg), and

Ostwald ripening

Adsorption Absorption

Absorption is a phenomenon
that occurs in a volume

Adsorption is a phenomenon
that occurs on a surface

The word sorption encompasses both types of phenomena

Adsorption processes
Adsorption
Physical (physisorption)
- van der Waals interactions
(result in attractive forces between
adsorbent and adsorbate molecules)

- Adsorbed molecules maintain their

identity
- Multilayers
- No activation energy
- Always reversible

Chemical (chemisorption)

- Chemical bonds between adsorbate

and adsorbent formed
- Adsorbed molecules loose their
identity
- Monolayers
- Often activation energy required
- Can be irreversible

The gas sorption process

Langmuir[1] described the kinetic behavior of the

adsorption process. He postulated that at
equilibrium, the rate of arrival of adsorptive
(adsorption) and the rate of evaporation of
adsorbate (desorption) were equal
Furthermore, the heat of adsorption was taken to
be constant and unchanging with the degree of
coverage, .
[1] I. Langmuir, J. Amer. Chem. Soc., 40, 1368 (1918)

Irving Langmuir (1881-1957)

Graduated as a metallurgical engineer from
the School of Mines at Columbia University in
1903
1903-1906 M.A. and Ph.D. in 1906 from
Gttingen.
1935-1937 With Katherine Blodgett studied thin
films.
1948-1953 With Vincent Schaefer discovered
that the introduction of dry ice and iodide into a
sufficiently moist cloud of low temperature could
induce precipitation.

1932 The Nobel Prize in Chemistry "for his

discoveries and investigations in surface
chemistry

Langmuirian behavior
Confining adsorption to a monolayer, the Langmuir equation can be
written

V
KP

Vm 1 KP
where V is the volume of gas adsorbed at pressure P, Vm is the
monolayer capacity (i.e. =1) expressed as the volume of gas at STP
and K is a constant for any given gas-solid pair. Rearranging in the
form of a straight line (y=ab+x) gives

P
1
P

V KVm Vm

Suitable Methods of Determination

Gas adsorption allows probing of entire surface
including irregularities and pore interiors.
The amount adsorbed is a function of temperature,
pressure and the strength of attraction or interaction
potential.
Physisorption is generally weak and reversible. The
solid must be cooled and a method used to estimate the
monolayer coverage from which surface area can be
calculated.

Adsorption Process

Adsorbate

Adsorptive

Adsorbent

The Isotherm
The amount of gas adsorbed is a function of

The strength of interaction between gas and solid

(intrinsic)

Temperature (fixed)

Pressure (controlled variable) expressed as

relative pressure P/Po

Physisorption Process

4)
2

Very Low Pressure Behavior

Amount Adsorbed

(micropore filling)

Relative Pressure, P/Po

Low Pressure Behavior

Amount Adsorbed

(monolayer)
The knee

Relative Pressure, P/Po

Medium Pressure Behavior

Amount Adsorbed

(multilayer)

Relative Pressure, P/Po

High Pressure Behavior

Amount Adsorbed

(capillary condensation)

Relative Pressure, P/Po

Gas Sorption: Isotherm

Desorption isotherm

Va

Adsorption isotherm

p
po

p
V a f po

where
p
pressure of adsorbate
o
p saturated pressure of adsorptive

Isotherm is a measure of
the volume of gas
adsorbed at a constant
temperature as a function
of gas pressure.
Isotherms can be
grouped into six classes.

Types of isotherms
according to the IUPAC classification

I: microporous solids
II & III: multilayer adsorption
in non-porous solids
IV & V: capillary condensation
in mesoporous solids
VI: stepped asdorption

Volume adsorbed

Types of Isotherms

Limiting value (plateau) due to filled

pores and essentially zero external
area.
Type I or
pseudo-Langmuir

Steep initial region due to

very strong adsorption, for
example in micropores.

Relative Pressure (P/Po)

Types of Isotherms

Volume adsorbed

Absence of hysteresis indicates

adsorption on and desorption from a
non-porous surface..
Type II

Low slope region in middle of

isotherm indicates first few
multilayers

Rounded knee
indicates approximate
location of monolayer
formation.
Relative Pressure (P/Po)

Gas Sorption: Isotherm

Va

Concave to the P/Po axis

Type I
or
Langmuir

Va

P/Po

Type II
B

Exhibited by microporous solids ( < 2nm )

Exhibited by nonporous or macroporous

solids ( > 50nm )
Unrestricted monolayer-multilayer
adsorption
Point B indicates the relative pressure at
which monolayer coverage is complete
S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
Chapman & Hall, New York, 1991

Types of Isotherms

Volume adsorbed

Example: krypton on polymethylmethacrylate

Type III

Lack of knee represents extremely

weak adsorbate-adsorbent
interaction
BET is not applicable
Relative Pressure (P/Po)

Types of Isotherms

Volume adsorbed

Type IV

Hysteresis indicates capillary

condensation in meso and
macropores.

Closure at P/Po~0.4 indicates

presence of small mesopores
(hysteresis would stay open
longer but for the tensilestrength-failure of the nitrogen
meniscus.
Rounded knee
indicates approximate
location of monolayer
formation.

Low slope region in middle of

isotherm indicates first few
multilayers

Relative Pressure (P/Po)

Va

Gas Sorption: Isotherm

Convex to the P/Po axis

Type III

Exhibited by nonporous solids

Exhibited by mesoporous solids

Type IV
Va

Initial part of the type IV follows

the same path as the type II

P/Po

S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
Chapman & Hall, New York, 1991

Types of Isotherms

Volume adsorbed

Example: water on carbon black

Type V

Lack of knee represents extremely

weak adsorbate-adsorbent interaction

BET is not applicable

Relative Pressure (P/Po)

Gas Sorption: Hysteresis

Va

Hysteresis

P/Po

Hysteresis indicates the presence of mesopores.

Hysteresis gives information regarding pore shapes .
Types I, II and III isotherms are generally reversible but type I can
have a hysteresis. Types IV and V exhibit hysteresis.
S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
Chapman & Hall, New York, 1991

Gas Sorption: Isotherm

Type V
Va

Highly uncommon
Exhibited by mesoporous solids

P/Po

Exhibited by nonporous solids with

an almost completely uniform surface

Va

Type VI

P/Po

S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
Chapman & Hall, New York, 1991

Choice of Gas and Temperature

Temperatures

Gases
Nitrogen
Argon
Krypton
Carbon
Others

dioxide

Liquid Nitrogen
Liquid Argon
Dry ice/acetone
Water/ice
Others

Choice of Gas and Temperature

Temperatures

Gases
Nitrogen
Argon
Krypton
Carbon
Others

dioxide

Liquid Nitrogen
Liquid Argon
Dry ice/acetone
Water/ice
Others

Measurement Method
Manometric
(Classical vacuum, volumetric.)
Requires that adsorbate be adsorbed by the
sample, at some reduced temperature, as a
function of pressure of pure adsorptive.

Manometric

P/Po values are achieved by creating conditions

of partial vacuum

High precision and accurate pressure

transducers monitor pressure changes due to
the adsorption process

Working Equation

PV = nRT
nads = ndosed - nvoid
nads = (PV/RT)man. - (PV/RT)cell

Working Equation

nads = (PV/RT)man. - (PV/RT)cell

That is, the amount adsorbed is calculated as the difference between
a) the amount of gas dosed from the manifold to the cell and b) the
amount of gas which remains not adsorbed at the end of the
equilibration time.

Principles of BET Surface Area Measurement

and Calculation
Determine the monolayer capacity Vm from which
the surface area of the solid can be computed.
Adsorbate most commonly used is nitrogen
Readily available in high purity
Appropriate coolant, liquid nitrogen.

Gas-solid interaction relatively strong.

Widely accepted cross sectional area.

Multilayer adsorption
the BET equation (1938)
Stephen Brunauer
Edward Teller

Paul Emmett

Brunauer, Emmett & Teller

Model of adsorption extended to multilayers.

S. Brunauer, P.H. Emmett and E. Teller, J. Amer. Chem. Soc., 60, 309 (1938)

V
C ( P P0 )

Vm (1 P P0 )(1 P P0 C ( P P0 )

Brunauer, Emmett & Teller

Or, in its familiar linearized form

1
1
C 1 P

V [( P0 P) 1] VmC VmC P0

BET C constant varies from solid to solid.

Low values represent weak gas adsorption
typical of low surface area solids, organics
and metals in particular.

Measurement
Obtain at least three data points in the relative pressure
range
0.025 to 0.30
Plot 1/[VSTP(Po/P)-1] versus P/Po. It should yield a
straight line if the BET model holds true.

On all surfaces the BET model fails to accurately predict

the multilayer adsorption behavior above P/Po = 0.5 (the
onset of capillary condensation which fills pores with
liquid adsorbate)

X[(Po/P)-1]

Calculation of Surface Area by

the BET method

negative intercepts are unacceptable

0

relative pressure, P/Po

Calculation
Fit best straight line through BET data
set using least squares regression to
find:

C 1
slope s
Vm C
intercept

1
i
Vm C

Calculation
Solving for Vm

1
Vm
si

Total surface area, St, is calculated thus

Vm Lav Am
St
Mv
Adsorbate cross sectional area
(0.162 nm2 for Nitrogen

Lav = 6.022 x 1023

Am = 0.162 nm2
Mv = 22 414 mL
nm2 to m2, x 10-18

Multi-Point BET Plot (Interpretation)

Never use data points too low in relative pressure (P/Po).

Never use data points too high in (P/Po).

Multi-Point BET Plot (Interpretation)

Discard under-equilibrated points (at low P/Po)

Never use less than three, preferably five data points.

Porosity
Pore Volume
Total pore volume is derived 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

Concept of Porosity: Open vs.

Closed Pores
Inter-connected
(open)

Closed

Open pores are accessible

whereas closed pores are
inaccessible pores.

Open pores can be interconnected, passing or dead

end.
Passing
(open)

Dead end
(open)

F. Rouquerol, J. Rouquerol, K. S. W. Sing, Adsorption by Powders and Porous Solids, Academic Press, 1-25, 1999

Size of Pores (IUPAC Standard)

Mesopores

Micropores

Zeolite,
Activated
carbon,
Metal organic
framework

Macropores

Mesoporous silica,
Activated carbon

2 nm

Sintered metals
and ceramics

50 nm

Porous material are classified according to the size of pores: material

with pores less than 2 nm are called micropores, materials with pores
between 2 and 50 nm are called mesopores, and material with pores
greater than 50 nm are macrospores
Sing, K. S. W. et al. Reporting Physisorption Data for Gas/Solid Systems. Pure & Appl. Chem. 57, 603-619 (1985).

Shapes of Pores
Cylindrical

Slits

Pore
Shapes

Conical

Spherical or
Ink Bottle

Interstices

F. Rouquerol, J. Rouquerol, K. S. W. Sing, Adsorption by Powders and Porous Solids, Academic Press, 1-25, 1999

Techniques for Porosity Analysis

Techniques for Porosity Analysis

Techniques for Porosity Analysis

Techniques for Porosity Analysis

Techniques for Porosity Analysis

Techniques for Porosity Analysis

Techniques for Porosity Analysis

Gas Sorption: Hysteresis

Type B

Type C

Type D

Type E

Va

Type A

P/Po

Cylindrical

P/Po

Slits

P/Po

Conical

P/Po

P/Po

Bottle neck

Pore Radius
The average pore size can be 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.