Porosity and surface area by gas

physisorption techniques

Luca Lucarelli
 The concept of free surface energy

Gaseous phase: adsorbate

Degassing Gaseous phase

Solid phase:
atoms or molecules
are in equilibrium

Solid phase: adsorbent

2
 Physisorption measures surface areas

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

Pore size is determined by gas

condensation pressure into the
pores

3
 Montecarlo simulation of multilayer
adsorption

Third layer

Second layer

First layer

Solid surface

4
 Adsorbed molecules in equilibrium with
pressure
T h e d is p e r s io n f o r c e s b e t w e e n
t h e a d s o r p t iv e m o le c u le s a n d t h e
s u r fa c e a to m s o r io n s o f th e
a d s o r b in g s o lid a r e d e s c r ib e d b y  (r )
th e L e n n a r d - J o n e s p o te n tia l [1 ]: r

6 12
 r  C r  B r

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

5
 Physisorption and Chemisorption

• Physisorption main
application fields
– Metal powders
– Oxides and salts
– Catalysts
– Adsorbents
– Active carbons
– Ceramics
– Charcoals
– Zeolites
– Pharmaceuticals
– Pigments
– Building materials
– Glass
– Silica and alumina

6
 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

7
 Types of adsorption isotherms

I II III

IV V VI

A d s o r p tio n is o th e r m s c a n b e c la s s ifie d in s ix ty p e s a c c o r d in g to IU P A C
[ 3 ,4 ] . T h e T y p e I is t y p ic a l f o r m ic r o p o r o u s s o lid s a n d c h e m is o r p t io n
is o t h e r m s . T y p e I I is s h o w n b y f in e ly d iv id e d n o n p o r o u s s o lid s . T y p e I I I a n d
T y p e V a r e t y p ic a l o f v a p o r s , i. e . w a t e r o n h y d r o p h o b ic s o lid s . T y p e I V a n d
T y p e V f e a t u r e a n h y s t e r e s is lo o p g e n e r a t e d b y t h e c a p illa r y c o n d e n s a t io n
in m e s o p o r e s . T h e r a r e T y p e V I, th e s te p s - lik e is o th e r m , is s h o w n e . g . w ith
n itr o g e n o n s p e c ia l c a r b o n s .

8
 Mechanism of adsorption on non-porous
surfaces

n n n

0 p /p
0

1 0 p /p
0

1 0 p /p
0

n n n

0 t/n m 0 .5 4 8 0 t/n m 0 .5 4 8 0 t/n m 0 .5 4 8

s 1 s 1 s 1

9
 Adsorption on mesoporous samples:
capillary condensation

n n n

0 p /p
0

1 0 p /p
0

1 0 p /p
0
1

n n n

0 p /p
0

1 0 p /p
0

1 0 p /p
0

10
 Why nitrogen condenses before the
saturation

A t lo w r e la t iv e p r e s s u r e s t h e s u r f a c e o f th e p o r e s w a lls a d s o r b s a
m u lt ila y e r o f a d s o r b a t e . I f t h e p r e s s u r e is r a is e d , d r o p le t s o f
a d s o r b a te o c c u r o n o p tim a l e n e r g e tic p o in ts o f th e p o r e s u r fa c e
w it h c u r v a t u r e s a c c o r d in g t o t h e K e lv in e q u a t io n . I f t h e d r o p le t s
t o u c h e a c h o t h e r, t h e p o r e s w ill b e fille d w ith c o n d e n s e d
a d s o r b a t e . T h is w ill e v a p o r a t e d u r in g t h e d e s o r p t io n f r o m p o r e s
s h o w in g c o r e o p e n in g s la r g e r t h a n t h e K e lv in r a d iu s . T h e
a d s o r p t io n b r a n c h is p o r e - d im e n s io n d e p e n d a n t , t h e d e s o r p t io n
b r a n c h is r e la t e d t o t h e p o r e o p e n in g s .

11
 Pore size evaluation in mesoporous samples

The Young-Laplace equation [1] x+dx

describes the pressures at the interface r
1
x dz

of a liquid droplet and the gas phase

above, using the surface tension: r2
y y+dy

 
 1 1  2
p  p    
 r1 r2  rm r
k


Considerations on the surface energy
lead to the Kelvin equation, that put in r
m

relation the relative pressure and the

curvature radius of the liquid meniscus: 
p 2 V liq 1
ln 0 
p RT r m

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].

12
 Adsorption in micropores

n n n

0 p /p
0

0 .2 5 0 p /p
0

0 .2 5 0 p /p
0

n n

0 p /p
0

1 0 p /p
0

0 .2 5

13
 Mechanism of adsorption in micropores is complex

I n m ic r o p o r e s th e p o t e n tia ls o f b o t h s id e s o f t h e p o r e w a lls o v e la p ,
t h u s e n h a n c in g t h e a d s o r p t io n p o t e n t ia l [ 7 ] . T h e s m a lle r t h e p o r e
w id t h t h e d e e p e r th e r e s u ltin g p o te n t ia l b e c o m e s . T h is r e s u lt s in
a n e n h a n c e d a d s o r p t io n e n e r g y a n d a d s o r p tio n ta k e s p la c e a t
v e r y lo w p r e s s u r e s ( s e e th e r ig h t b o x f ig u r e ) . M ic r o p o r e s w it h t h e
s m a lle r w id th fill f ir s t ly b u t a d s o r p tio n o n t h e s u r f a c e o f la r g e r
m ic r o p o r e s o c c u r s a t th e s a m e t im e ( s e c o n d a r y m ic r o p o r e fillin g ) .

z /r 0

-1 0 +1 -1 0 +1 -1 0 +1

9 :3 1 0 :4

-1 -1 -1

-2 -2 -2

E n h a n c e m e n t o f P o t e n t ia l in M ic r o p o r e s

14
 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

15
 Common adsorbates

Gas Temp. Area per molecule Notes

K (angstron2)

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 Used for extremely low

(other values are also surfaces. Difficult analysis
reported) due to saturation and
expensive

16
 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 Gases form an unlimited number of layers over surfaces. It is a generalized Langmuir.
and Teller (BET 2 Forces active in condensation of gases are responsible of multilayers formation.
parameters) Applicable to isotherms type II, IV, VI.

BET 3 parameters Needs non-linear regression function to fit the experimental points. In addition to
(full equation) 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 Introduces the concept of a standard isotherm. Adsorption data are plotted versus the
plot 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 Applicable only when pores are of molecular dimension size (microporous materials,
Raduskevitch plot isotherms type 1). Based on the differential molar work of adsorption (Polanyi).

17
 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, These models are based on the Kelvin equation correcting the Kelvin radius with the
Halenda (BJH), 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.
and other similar
methods

Horvath and It is based on the Lennard-Jones interaction between gas and solid. Potential function
Kavazoe (HK) 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
and related
as a two-dimensional ideal gas. HK is applicable to isotherms type I on active
models (Saito- carbons, SF to microporous zeolites or silica.
Foley, etc.)

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.

18
 Examples of Type I Isotherms: Activated Carbon

Example of an activated 500

microporus carbon tested 400

Vads / cm3g-1
using nitrogen at 77 K 300

•Linear plot 200

•Logarithmic plot
100

Features: 0.0 0.2 0.4

p/p0
0.6 0.8 1.0

Gas is adsorbed at very 500

low relative pressures 400

Hysteresis is almost Vads / cm3g-1 300

absent 200

Calculation examples: 100

BET 3, DR, HK 0
0.000001 0.00001 0.0001 0.001 0.01 0.1 1
p/p0

19
 Activated Carbon Surface Area by BET 3

20
 Activated Carbon Surface Area by DR

21
 Activated Carbon Pore size by HK

22
 Examples of Type I Isotherms: Zeolite

500

Example of a 400

Vads / cm3g-1
microporus zeolite 300

tested using nitrogen at 200

77 K 100

•Linear plot 0
0.0 0.2 0.4 0.6 0.8 1.0

•Logarithmic plot p/p0

Features: 500

Gas is adsorbed at very Vads / cm3g-1 400

low relative pressures 300

Hysteresis is almost 200

absent 100

Calculation examples:
0
0.000001 0.00001 0.0001 0.001 0.01 0.1 1
p/p0
BET 3, SF
23
 Zeolite Nitrogen Surface Area: BET 3

24
 Zeolite Nitrogen Pore Size: Saito-Foley

25
 Examples of Type I Isotherms: Zeolite

300

Example of a
microporus zeolite

Vads / cm3g-1
200

tested using argon at 87 100

K
•Linear plot 0

•Logarithmic plot 0.0 0.2 0.4

p/p0
0.6 0.8 1.0

300
Features:
Gas is adsorbed at very Vads / cm3g-1 200

low relative pressures

Hysteresis is almost 100

absent
Calculations: 0
0.0000001 0.000001 0.00001 0.0001 0.001 0.01 0.1 1
p/p0
SF

26
 Zeolite Argon Pore Size: Saito-Foley

27
 Comparison: two zeolites pore size (Argon)

500

400
Vads / cm3g-1

300 Isotherms Overlay: log plot

200

100

0
0.0000001 0.000001 0.00001 0.0001 0.001 0.01 0.1 1
p/p0
0.25

3
0.20

dV/dØ / cm3nm-1g-1
VPore / cm3g-1

0.15
2
Pore Size Overlay:
Saito-Foley 0.10

1
0.05

0.00 0
0.1 1 10
Ø / nm

28
 Examples of Type IV Isotherms: mesoporous alumina

250

200
Vads / cm3g-1

150

100

50

0
0.0 0.2 0.4 0.6 0.8 1.0
p/p0

Mesoporous alumina measured by nitrogen at 77 K

-Presence of hysteresis depending on pore size
-BET 2 parameters applicable

29
 Surface area on mesoporous samples: BET

30
 Surface area on mesoporus samples: BET 3

31
 Mesopore pore size: BJH

32
 Examples of Type IV Isotherms: large mesopores

140

120

100
Vads / cm3g-1

80

60

40

20

0
0.0 0.2 0.4 0.6 0.8 1.0
p/p0

Capillary condensation and saturation pressure occurring almost

contemporary. Maximum limit of pore size by the gas adsorption technique

33
 The upper pore size limit

34
 Examples of Type II Isotherms: non-porous sample

3
Vads / cm3g-1

0
0.0 0.2 0.4 0.6 0.8 1.0
p/p0

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)

35
 BET surface area on non-porous sample

36
 Example of very low surfaces: Kr adsorption

0.20

0.15
Vads / cm3g-1

0.10

0.05

0.00
0.0 0.2 0.4 0.6 0.8 1.0
p/p0

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).

37
 Example of isotherms overlay

1200

1000
Vads / cm3g-1

800

600

400

200

0
0.0 0.2 0.4 0.6 0.8 1.0
p/p0

38
 Example of t-plot overlay of different surfaces

1200

1000
Vads / cm3g-1

800

600

400

200

0
0.0 0.5 1.0 1.5 2.0
t / nm

39
 Two most common methods for gas adsorption

The static volumetric The dynamic flow

technique technique

Sorptomatic 1990 Qsurf analyzers

40
 The static-volumetric technique

P P
Gas inlet

Doser Sample
piston holder

41
 Measuring adsorption equilibrium pressure

P sat

Peq n

Peq 1

time

42
 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

43
 The dynamic flow technique

Nitrogen

Helium

44
 Detection of adsorbed gas: single point BET

1- Loop calibration
5 Peak
2- Immersion in liquid
1
Nitrogen
TCD signal

2 3- Adsorption peak
4 4- Exiting from liquid
Nitrogen
5- Desorption peak

Time

45
 Detection of adsorbed gas: multi point BET

1 2

1 – 25% of Nitrogen in Helium

3 2 – 15% of Nitrogen in Helium
3 – 5 % Nitrogen in Helium

46
 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

47
 Recommended literature

L ite r a tu r e
1 S .J . G r e g g , K .S .W . S in g , A d s o r p tio n , S u rfa c e A r e a a n d P o ro s ity , A c a d e m ic P re s s , L o n d o n , 2 n d E d . ( 1 9 8 2 )
2 S . B r u n a u e r, P .H . E m m e t a n d E . T e lle r, J . A m e r. C h e m . S o c ., 6 0 , 3 0 9 (1 9 3 8 )
3 S . B r u n a u e r, L .S . D e m in g , W .S . D e m in g a n d E . T e lle r, J . A m e r. C h e m . S o c ., 6 2 , 1 7 2 3 ( 1 9 4 0 )
4 IU P A C R e p o rtin g p h y s is o rp tio n d a ta fo r g a s /s o lid s y s te m s , P u re A p p l. C h e m ., 5 7 , 6 0 3 (1 9 8 5 )
5 E .P . B a rre tt, L .G . J o y n e r a n d P .P . H a le n d a , J . A m e r. C h e m . S o c . 7 3 , 3 7 3 (1 9 5 1 )
6 M .M . D u b in in , Q u a rt. R e v . C h e m . S o c . 9 , 1 0 1 (1 9 5 5 )
7 D .H . E v e re tt a n d J .C . P o w l, J . C h e m . S o c ., F a ra d a y T r a n s . I, 7 2 , 6 1 9 ( 1 9 7 6 )
8 G . H o rv a th a n d K . K a w a z o e , J . C h e m . E n g . J a p . 1 6 , 6 , 4 7 0 (1 9 8 3 )
t B .C . L ip p e n s a n d J .H . d e B o e r, J . C a ta ly s is 4 , 3 1 9 (1 9 6 5 )
as K .S .W . S in g , C h e m . & In d . 1 9 6 8 , 1 5 2 0

48