Porosity and surface area by gas

physisorption techniques

Luca Lucarelli
2
The concept of free surface energy
Solid phase:
atoms or molecules
are in equilibrium
Gaseous phase
Degassing
Gaseous phase: adsorbate
Solid phase: adsorbent
3
Physisorption measures surface areas
Pore size is determined by gas
condensation pressure into the
pores
Very low temperature
(77 K), vacuum, injection of
known doses of inert gas
Surface area is measured by
counting the number of
molecules deposed in a
monolayer
4
Montecarlo simulation of multilayer
adsorption
First layer
Second layer
Third layer
Solid surface
5
Adsorbed molecules in equilibrium with
pressure
The dispersion forces between
the adsorptive molecules and the
surface atoms or ions of the
adsorbing solid are described by
the Lennard-Jones potential [1]:
c(r)
r
12 6
+ = Br Cr r c
Gas molecules remain in contact with the surface for a certain
time before returning to the gaseous phase. This delay is
responsible for the phenomenon of adsorption
6
Physisorption and Chemisorption
Physisorption main
application fields

Catalysts
Active carbons
Charcoals
Pharmaceuticals
Building materials
Silica and alumina
Metal powders
Oxides and salts
Adsorbents
Ceramics
Zeolites
Pigments
Glass
7
Information provided physisorption
Commonly used gases
Nitrogen/Argon
Krypton
Carbon dioxide

Results on porous media
Total specific surface area
Meso-micropore size distributions
Meso-micropore total volumes
8
Types of adsorption isotherms
II
B
I III
V
VI
IV
B
Adsorption isotherms can be classified in six types according to IUPAC
[3,4]. The Type I is typical for microporous solids and chemisorption
isotherms. Type II is shown by finely divided nonporous solids. Type III and
Type V are typical of vapors, i.e. water on hydrophobic solids. Type IV and
Type V feature an hysteresis loop generated by the capillary condensation
in mesopores. The rare Type VI, the steps-like isotherm, is shown e.g. with
nitrogen on special carbons.
9
Mechanism of adsorption on non-porous
surfaces
p/p
0
n
1 0
p/p
0
n
1 0
0.548
1
t
s
/nm
o
n
0
t
s
/nm
o
n
0.548
1
0
p/p
0
n
1 0
t
s
/nm
o
n
0.548
1
0
10
Adsorption on mesoporous samples:
capillary condensation
p/p
0
n
1 0
p/p
0
n
1 0
p/p
0
n
1 0
p/p
0
n
1 0
p/p
0
n
1 0
p/p
0
n
1 0
11
Why nitrogen condenses before the
saturation
At low relative pressures the surface of the pores walls adsorbs a
multilayer of adsorbate. If the pressure is raised, droplets of
adsorbate occur on optimal energetic points of the pore surface
with curvatures according to the Kelvin equation. If the droplets
touch each other, the pores will be filled with condensed
adsorbate. This will evaporate during the desorption from pores
showing core openings larger than the Kelvin radius. The
adsorption branch is pore-dimension dependant, the desorption
branch is related to the pore openings.
12
Pore size evaluation in mesoporous samples
r
2
r
1
y
y+dy
x
x+dx
dz
u
u
r
m
r
k
The Kelvin equation gives directly the core radius, considering
that the wetting angle is equal to zero. Then, the pore radius is
calculated taking into account the adsorbed film thickness on
the pore walls and a cylindrical pore geometry [5].
The Young-Laplace equation [1]
describes the pressures at the interface
of a liquid droplet and the gas phase
above, using the surface tension:
p p
r r r
m
o |


= +
|
\

|
.
=
1 1 2
1 2
Considerations on the surface energy
lead to the Kelvin equation, that put in
relation the relative pressure and the
curvature radius of the liquid meniscus:
ln
p
p
V
RT r
liq
m
0
2
1
=
13
Adsorption in micropores
p/p
0
n
0.25 0
p/p
0
n
0.25 0
p/p
0
n
0.25 0
p/p
0
n
1 0
p/p
0
n
1 0
14
Mechanism of adsorption in micropores is complex
In micropores the potentials of both sides of the pore walls ovelap,
thus enhancing the adsorption potential [7]. The smaller the pore
width the deeper the resulting potential becomes. This results in
an enhanced adsorption energy and adsorption takes place at
very low pressures (see the right box figure). Micropores with the
smaller width fill firstly but adsorption on the surface of larger
micropores occurs at the same time (secondary micropore filling).
-1
-2
0 +1 -1
-1
-2
0 +1 -1
z/r
0
-1
-2
0 +1 -1
9:3
10:4
Enhancement of Potential in Micropores
15
Points of remark
Physisorption is non-specific
Adsorption energy is very small, similar to the heat of
condensation
Physisorption is completely reversible
Physisorption is a spontaneous phenomenon occuring
at any temperature and pressure
Detectable amount of adsorbed species is achievable
by analytical instruments only at very low temperature
Adsobates often must be chosen according to the
sample nature
16
Common adsorbates
Gas Temp.
K
Area per molecule
(angstron
2
)
Notes
Nitrogen 77 16.2 Most of materials can be
analyzed in these conditions
except very low surfaces and
some micropores
Argon 87, 77 14.2 Specially used for some
microporous zeolites that
cannot be measured by
nitrogen
Krypton 77 21
(other values are also
reported)
Used for extremely low
surfaces. Difficult analysis
due to saturation and
expensive
17
Common models for adsorption interpretation Specific Surface Area
Model Assumptions
Langmuir Gases can form only one molecular layer on surfaces. Mainly used in chemisorption
analysis or physisorption showing isotherms type 1 with almost 90 knee
Brunauer, Emmet
and Teller (BET 2
parameters)
Gases form an unlimited number of layers over surfaces. It is a generalized Langmuir.
Forces active in condensation of gases are responsible of multilayers formation.
Applicable to isotherms type II, IV, VI.
BET 3 parameters
(full equation)
Needs non-linear regression function to fit the experimental points. In addition to
monolayer volume and C value of standard BET, it gives also the number of layers N.
Applicable to all types of physisorption isotherms
t-plot and alpha
plot
Introduces the concept of a standard isotherm. Adsorption data are plotted versus the
average thickness of the adsorbed layer or referred to the amount adsorbed at a reference
pressure. Reference data must be collected on a non-porous material of the same nature
of sample under test
Dubinin
Raduskevitch plot
Applicable only when pores are of molecular dimension size (microporous materials,
isotherms type 1). Based on the differential molar work of adsorption (Polanyi).
18
Common models for pore size calculation
Model Assumptions
Kelvin
Relates the equilibrium pressure (mainly desorption) to the core radius of evaporated
gas inside mesopores. It is applicable whenever capillary condensation takes place
(isotherms type IV, V and relevant sub-groups).
Barret, Joiner,
Halenda (BJH),
and other similar
methods
These models are based on the Kelvin equation correcting the Kelvin radius with the
thickness of the still adsorbed gas. They differ for the way of calculating the thickness
(Pr = Kr + t). Applicable to isotherms type IV, V and relevant sub-groups.
Horvath and
Kavazoe (HK)
and related
models (Saito-
Foley, etc.)
It is based on the Lennard-Jones interaction between gas and solid. Potential function
of both are required. HK was developed for slit-shaped pores in microporus carbons.
SF is an extension to cylindrical pores. The adsorbed phase is considered to behave
as a two-dimensional ideal gas. HK is applicable to isotherms type I on active carbons,
SF to microporous zeolites or silica.
Other methods
A huge number of other methods are available for surface area and pore size
calculation. New models or variations are born every year due to the difficulty of
interpretating the mechanisms of adsorption/desorption.
19
Examples of Type I Isotherms: Activated Carbon
1.0
p/p
0
0.0 0.2 0.4 0.6 0.8 1.0
500
V
a
d
s

/

c
m
3
g
-
1
0
100
200
300
400
500
1
p/p
0
0.000001 1 0.00001 1 0.0001 1 0.001 1 0.01 1 0.1 1
500
V
a
d
s

/

c
m
3
g
-
1
0
100
200
300
400
500
Example of an activated
microporus carbon tested
using nitrogen at 77 K
Linear plot
Logarithmic plot
Features:
Gas is adsorbed at very
low relative pressures
Hysteresis is almost
absent
Calculation examples:
BET 3, DR, HK
20
Activated Carbon Surface Area by BET 3
21
Activated Carbon Surface Area by DR
22
Activated Carbon Pore size by HK
23
Examples of Type I Isotherms: Zeolite
1.0
p/p
0
0.0 0.2 0.4 0.6 0.8 1.0
500
V
a
d
s

/

c
m
3
g
-
1
0
100
200
300
400
500
1
p/p
0
0.000001 1 0.00001 1 0.0001 1 0.001 1 0.01 1 0.1 1
500
V
a
d
s

/

c
m
3
g
-
1
0
100
200
300
400
500
Example of a
microporus zeolite tested
using nitrogen at 77 K
Linear plot
Logarithmic plot
Features:
Gas is adsorbed at very
low relative pressures
Hysteresis is almost
absent
Calculation examples:
BET 3, SF
24
Zeolite Nitrogen Surface Area: BET 3
25
Zeolite Nitrogen Pore Size: Saito-Foley
26
Examples of Type I Isotherms: Zeolite
Example of a
microporus zeolite
tested using argon at 87
K
Linear plot
Logarithmic plot
Features:
Gas is adsorbed at very
low relative pressures
Hysteresis is almost
absent
Calculations:
SF
1.0
p/p
0
0.0 0.2 0.4 0.6 0.8 1.0
300
V
a
d
s

/

c
m
3
g
-
1
0
100
200
300
1
p/p
0
0.0000001 1 0.000001 1 0.00001 1 0.0001 1 0.001 1 0.01 1 0.1 1
300
V
a
d
s

/

c
m
3
g
-
1
0
100
200
300
27
Zeolite Argon Pore Size: Saito-Foley
28
Comparison: two zeolites pore size (Argon)
1
p/p
0
0.0000001 1 0.000001 1 0.00001 1 0.0001 1 0.001 1 0.01 1 0.1 1
500
V
a
d
s

/

c
m
3
g
-
1
0
100
200
300
400
500
10
/ nm
0.1 10 1 10
0.25
V
P
o
r
e

/

c
m
3
g
-
1
0.00
0.05
0.10
0.15
0.20
0.25
3
d
V
/
d

/

c
m
3
n
m
-
1
g
-
1
0
1
2
3
Isotherms Overlay: log plot
Pore Size Overlay:
Saito-Foley
29
Examples of Type IV Isotherms: mesoporous alumina
1.0
p/p
0
0.0 0.2 0.4 0.6 0.8 1.0
250
V
a
d
s

/

c
m
3
g
-
1
0
50
100
150
200
250
Mesoporous alumina measured by nitrogen at 77 K
-Presence of hysteresis depending on pore size
-BET 2 parameters applicable
30
Surface area on mesoporous samples: BET
31
Surface area on mesoporus samples: BET 3
32
Mesopore pore size: BJH
33
Examples of Type IV Isotherms: large mesopores
1.0
p/p
0
0.0 0.2 0.4 0.6 0.8 1.0
140
V
a
d
s

/

c
m
3
g
-
1
0
20
40
60
80
100
120
140
Capillary condensation and saturation pressure occurring almost
contemporary. Maximum limit of pore size by the gas adsorption technique
34
The upper pore size limit
35
Examples of Type II Isotherms: non-porous sample
1.0
p/p
0
0.0 0.2 0.4 0.6 0.8 1.0
4
V
a
d
s

/

c
m
3
g
-
1
0
1
2
3
4
Very small amount of gas adsorbed. No capillary condensation (macropores),
No hysteresis. The only available result is the BET surface area.
For pore size it is necessary another technique (mercury porosimetry)
36
BET surface area on non-porous sample
37
Example of very low surfaces: Kr adsorption
1.0
p/p
0
0.0 0.2 0.4 0.6 0.8 1.0
0.20
V
a
d
s

/

c
m
3
g
-
1
0.00
0.05
0.10
0.15
0.20
Kr is used when surface area is extremely small therefore adsorbed nitrogen
is not detectable. Kr saturation at 77 K is about 2 torr (it is not a real saturation).
38
Example of isotherms overlay
1.0
p/p
0
0.0 0.2 0.4 0.6 0.8 1.0
1200
V
a
d
s

/

c
m
3
g
-
1
0
200
400
600
800
1000
1200
39
Example of t-plot overlay of different surfaces
2.0
t / nm
0.0 0.5 1.0 1.5 2.0
1200
V
a
d
s

/

c
m
3
g
-
1
0
200
400
600
800
1000
1200
40
Two most common methods for gas adsorption
The static volumetric
technique
The dynamic flow
technique
Sorptomatic 1990 Qsurf analyzers
41
The static-volumetric technique
P
P
Doser
piston
Sample
holder
Gas inlet
42
Measuring adsorption equilibrium pressure
P
time
Peq 1
Peq n
P sat
43
Features of static volumetric method
High vacuum required
Very accurate results
Proper and relatively fast degassing under vacuum
Dead volumes calibration required
Pressure transducers calibration required
Analysis time is relatively long
Can measure all type of samples (in the physisorption
method range)
Can measure pore size distribution in micropores and
mesopores
44
The dynamic flow technique
Helium
Nitrogen
45
Detection of adsorbed gas: single point BET
Time
T
C
D

s
i
g
n
a
l

1
2
3
4
5
1- Loop calibration
Peak
2- Immersion in liquid
Nitrogen
3- Adsorption peak
4- Exiting from liquid
Nitrogen
5- Desorption peak
46
Detection of adsorbed gas: multi point BET
1
2
3
1 25% of Nitrogen in Helium
2 15% of Nitrogen in Helium
3 5 % Nitrogen in Helium
47
Features of dynamic method
Extremely fast and easy operations
No need of dead volume calibration
Extremely high reproducibility of results
Single point test results are less accurate but show higher
reproducibility
Multi point test results are more accurate but show a lower
reproducibility
Anyway reproducibility is comparable and often better that
static methods
Analytical method must be carefully chosen for very low or
very high surface areas
Provide surface area and total pore volume (pore size is less
reliable than static methods)
Degassing in flow requires more time than in vacuum
48
Recommended literature
Literature
1 S.J. Gregg, K.S.W. Sing, Adsorption, Surface Area and Porosity, Academic Press, London, 2nd Ed. (1982)
2 S. Brunauer, P.H. Emmet and E. Teller, J. Amer. Chem. Soc., , 309 (1938)
3 S. Brunauer, L.S. Deming, W.S. Deming and E. Teller, J. Amer. Chem. Soc., , 1723 (1940)
4 IUPAC Reporting physisorption data for gas/solid systems, Pure Appl. Chem., , 603 (1985)
5 E.P. Barrett, L.G. Joyner and P.P. Halenda, J. Amer. Chem. Soc. , 373 (1951)
6 M.M. Dubinin, Quart. Rev. Chem. Soc. , 101 (1955)
7 D.H. Everett and J.C. Powl, J. Chem. Soc., Faraday Trans. I, , 619 (1976)
8 G. Horvath and K. Kawazoe, J. Chem. Eng. Jap. , 6, 470 (1983)
B.C. Lippens and J.H. de Boer, J. Catalysis , 319 (1965)
a K.S.W. Sing, Chem. & Ind. 1968, 1520
60
62
57
73
9
72
16
4 t
s