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Physisorption and pore size

analysis
Gerhard Pirngruber
Direction Catalyse et Séparation
[email protected]
© IFP
Characterization of porous solids - Characterization of Catalysts and Surfaces - G Pirngruber 25 october 2016
CV Gerhard Pirngruber
 1995 – 1999 PhD in heterogeneous catalysis

 Universiteit Twente (NL)
 2000 – 2005 Oberassistent
 ETH Zurich, Inst of Chemical and Bioengineering
 Research activity
 zeolites
 mesoporous silica
 2005 – now R&D Scientist, project leader
 IFP Energies nouvelles, Catalysis and Separation Division
 Research activity
 2005 – 2012 : CO2 capture, separation of hydrocarbons
 2012 – now: hydrotreating and hydrocracking catalysts
© IFP
Porous solids in catalysis
 Supported catalysts
 e.g. noble metals, transition metal sulfides
 Porous support
 provides surface for dispersing the catalyst
 provides mechanical stability
 has an influence on diffusion of reactants and products
 has an influence on adsorption of reactants and products
 determines reactor volume
 Porous catalysts
 Zeolites Optimising porosity is often the
 Oxydes key to improving catalytic
performance.
© IFP
Types of porosity
 Porous cristalline structures

 Zeolites,
 Metal Organic Frameworks
 Ordered or disordered stacking of small particles

generates an interparticles porosity
 oxides (silica, alumina, etc.)
 activated carbon
© IFP
Characterisation of porosity
 Physisorption (N2, Ar, Kr)

 surface area
 pore volume
 pore size distribution
 Hg intrusion
 pore volume
 pore size distribution
 surface area
 Imaging methods
 Transmission Electron Microscopy
 Secondary Electron Microscopy
© IFP
Terminology
 Adsorption is a surface phenomenon.
 Adsorbent = solid that provides a surface for
adsorption.
 Adsorbate = molecule adsorbed on the surface.
 Adsorptive = molecule susceptible of being adsorbed.
 Physisorption: no formation of chemical bonds, no

transfer of electron density
 Chemisorption: formation of a chemical bond
(exchange of electrons)
© IFP
Terminology
 IUPAC distinguishes 3 catagories of pore sizes

 Micropores < 2 nm
 Mesopores 2 – 50 nm
 Macropores > 50 nm
© IFP
Forces involved in physisorption
 van der Waals forces
 amplified by multiple interactions with atoms or pore wall (i)
5000
   ij 12   ij 6 
4000 U LJ  4        
 r   r  
3000  
Energy
2000
adsorbate
1000 i j
0
-1000
0 2 4 6 8 pore wall
Distance
 maximal when size of adsobate (j) close to pore size
pore wall
adsorbate
© IFP
Forces involved in physisorption
 Electrostatic forces
 Any non-symmetric charge distribution in the adsorbent
generates an electric field
 adsorbates with an electric moment (dipole, quadrupole)
interact with the electric field
 undesirable in analysis of porosity/pores size because
surface chemistry/chemical composition enter into the game
 N2 has a small quadrupole moment → use of Ar, Kr is
preferable for precise micropore size analysis
© IFP
Adsorption in micropores
 Gradual filling of pore volume starting
from surfcae
Saturation zone
Adsorbed amount
Transition zone
additional adsorbate-
adsorbate interactions
Initial slope depends on adsorbent-

adsorbate interactions
Pressure
© IFP
Adsorption in mesopores
monolayer multilayer onset of pore filled by

adsorption adsorption capillary capillary
condensation condensation
© IFP
Adsorption in macropores
 Opposite pore wall is too far away to influence

adsorption and provoke capillary condensation
 First monolayer, then multilayer adsorption
© IFP
How to measure an adsorption isotherm?
 Volumetric method
Réservoir étalon : Vres Réservoir étalon : Vres
Etat initial : PriHe, TriHe Etat initial : PriN2, TriN2

Hélium Azote
Etat final : PrfHe, TrfHe Etat final : PrfN2, TrfN2
Bilans Matières : He et N2
 PrHe
i f
PrHe V
nHe   i  f  res

 TrHe TrHe  R
Température nHe  
V
 Pc f  Pci cel
RTm
ambiante
Cellule mesure : Vcel

 PrNi 2 PrNf 2  Vres
nN 2   i  f 
Température  TrN 2 TrN 2  R
 
N2 liquide V
77 K nN 2  Pc f  Pci cel  nNads2
RTm
Etat initial : PciHe, TciHe Etat initial : PciN2, TciN2

Etat final : PcfHe, TcfHe Etat final : PcfN2, TcfN2
Masse d'adsorbant : Msol

Réservoir d'azote
© IFP
liquide à 77 K Quantité adsorbée : Qads=nN2ads/Msol
Material balance
 Reservoir : 1 Sample cell : 2

 without adsorption (He), sample cell initially under
vacuum
pinitV1 p finalV1 p finalV2 V2 V1 pinit  p final
   
RT1 RT1 RT2 T2 T1 p final
 with adsorption (N2) determined with He
pV1 pV2
quantity initially ntot    nads
present in the RT1 RT2
reservoir
© IFP
Experimental difficulties
 Precise measurement of pressure required

 difficult at low pressure
 difficult to measure a micropore distribution
 Isotherm !!
 T2 in principle 77 K (temperature of liquid N 2 )
 part of the cell is not plunged into liquid N2, but is at ambient
temperature
 temperature gradient must be the same as during the initial
calibration of the volume with He
 pay attention to the level of liquid N 2
© IFP
Example zeolite NaX
220
powder
200
Adsorbed volume ( cm3/g)
180
160 after shaping with a

N2 at 77 K NaX (ADS 57701, Powder)
binder
140 N2 at 77 K NaX (ADS 48100) SPX 3003
N2 at 77 K NaX (ADS44956) SPX 3001

120
100
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
P/P0
 Micropores are entirely filled at very low pressure.

 Isotherm is totally flat once micropores are filled.
© IFP
 saturation zone
Examples - ZnO
180
Quantité adsorbée (cm3 STP/g) 160 capillary condensation
140 in the mesopores
120
100
80
multilayer adsorption on the ZnO
surface of the particles

60
40
20
0
0 0.2 0.4 0.6 0.8 1
p/p0
 no micropores
 mesopores generated by stacking of inidividual
particles
© IFP
Comparison of two ZnO samples
180
160
Quantité adsorbée (cm3 STP/g)
140
120
100 65811
80 70299
60
40
20
0
0 0.2 0.4 0.6 0.8 1
p/p0
 Surface : 65811 > 70299

 Pore size : 70299 > 65811
© IFP
Example – Al2O3
300
capillary condensation
250
in mesopores
200
150
100
multilayer adsorption
50
on surface of particles
0
0 0.2 0.4 0.6 0.8 1
p/p0
 no micropores
 high surface area, broad pore size distribution
© IFP
Comparison Al2O3
500
450
400
350
300 79999
250 61399
200 47148
150
100
50
0
0 0.2 0.4 0.6 0.8 1
p/p0
 Surface : 79999 > 61399 > 47148

 Pore size : 47148 > 61399 > 79999
© IFP
Quantitative treatment of N2 isotherms
 Pore volume: Vmicro, Vmeso, Vtotal

 t-plot
 Dubinin-Radushkevitch
 Surface area
 BET (Brunauer-Emerett-Teller)
 Langmuir
 Pore size distribution
 Micropores
 Horwath-Kawazoe, Saito-Foley
 Mesopores
 BJH (Brunauer-Joyner-Halenda)
 DFT (Density Functional Theory)
© IFP
Determination of the surface area
 BET (Brunauer Emmet Teller): multilayer adsorption

 first layer: adsorption on the surface
 all the other layers are considered like a condensed liquid
Kcondensation
Ksurface
nm = number of surface adsorption sites (monolayer)

nads = total number of adsorbed molecules
© IFP
BET equation
P 1 C 1  P 
   
 BET equation Vads P0  P  VMC V M C  P0 
K surface
C
K condensation Recommended
range of p/p0 :
 VM = monolayer volume 0,05 - 0,35 max.
 Vads = adsorbed volume
Plot p/Vads(p0-p) vs. p/p0
1/[V.(P/P0-1)]

 Calculation of surface area:
NAv : Avogadro number
PNT. = (C-1)/(VM.C)

 a : area of N2 molecule (16,2 Ǻ2)
O.O. = 1/(VM.C)
0,1 0,2 0,3 0,4 P/P0

p0VM
S BET  a. .N A S BET (m2 / g )  4.355 Vm (cm3 STP / g )
R  273K
© IFP
Exemple ZnO
Isothermes BET plot
4.355 slope
180
S BET  CBET  1
160 0.05
slope  int ercept int ercept
0.045
140
0.04 y = 0.1196x + 0.0005
120
0.035
prel / Vads(1-prel)
100 65811 0.03
80 70299 65811
0.025
70299
60
0.02
40 0.015
20 0.01 y = 0.0594x + 0.0003
0 0.005
0 0.2 0.4 0.6 0.8 1 0
p/p0 0 0.1 0.2 0.3 0.4 0.5
prel = p/p0
SBET (m2/g) CBET

65811 74 136
70299 36 237
© IFP
Example NaX
 The multilayer adsorption 0.0007
model does not apply well to 0.0006 y = 0.0064x - 3E-05
microporous solids when the 0.0005
prel / Vads(1-prel)
pores are filled. 0.0004
 Choose a lower pressure 0.0003
range for microporous solids. 0.0002
 p/p0 = 0.05 – 0.10 0.0001
C constant may be negative.

0
 0.0000 0.0200 0.0400 0.0600 0.0800 0.1000 0.1200
Does not make physical sense prel = p/p0
 lower the pressure range

4.355
further S BET   685m 2 / g
0.0064  0.00003
© IFP
Langmuir Surface Area
 Langmuir theory
 is a model of monolayer adsorption
 this hypothesis is never fulfilled
 Do not use Langmuir surface areas !!
 SLangmuir is always > SBET because multilayer
adsorption is treated like monolayer adsorption.
© IFP
Determination of the pore volume
300
250
Volume adsorbé (cm3 STP/g)
200
Vads = 240
150
cm3 STP/g
100 → Vtotal
Vads = 178
cm3 STP/g 50
Vmeso = Vtotal - Vmicro
→ Vmicro
0
0 0.2 0.4 0.6 0.8 1
p/p0
 In some cases possible without using any model.

© IFP
Conversion gas volume – pore volume
 Volume of adsorbed gas correponds to a certain

number of moles
Vads p
 STP = Standard Temperature Pressure nads 
 T = 273 K, p = 1 bar = 100 kPa RT
 The adsorbed phase is considered like a liquid phase
 Density of liquid N2 at 77 K : 0.807 g/ml
mN 2 nads  M N 2
Vp  
 N 2,liq  N 2,liq
Vp (ml / g )  1.5468 103 Vads (cm3 STP / g )

© IFP
t-plot
 Transform adsorbed amount in an average thickness

(t) of the adsorbed layer
 For multilayer adsorption on a flat surface Vads
t
S
© IFP
Universal curve t vs. p/p0
 The isotherms (Vads/SBET) of
many low surface area oxides
(SiO2, Al2O3, ZrO2, TiO2, MgO)
form a universal curve
t = f(p/p0). Vads
t
 Numerical description of that S BET
curve
 valid for t = 3.5 – 10 Å
 and p/p0 = 0.1 – 0.8
13.99
Harkins t ( )1/ 2
p
Jura  log  0.034
p0
1/ 3
 
 5 
Halsey t  3,54 
 ln  P0  
  P  
© IFP
Isotherm expressed as Vads = f(t)
180 180
160 160
140 limit of validity 140 Vads
S
Vads (cm3 STP/g)
Vads cm3 STP/g

120 120
100 100
t
65811
80 80
60 60
40 40
20 20
0 0
0 0.2 0.4 0.6 0.8 1 0 0.5 1 1.5 2
p/p0 t (nm)
t = thickness that the

13.99
t ( )1/ 2 adsorbed phase
p
 log  0.034 would have on a non-
p0 porous material
© IFP
Interpretation of t-plots
 Adsorption on a non-porous solid
Vads
Vads
S
p/p0 t
 Adsorption on a microporous solid t

 micropores rapidly filled
 then adsorption on external surface Vads
Vads
S
t
Vmicro
p/p0
© IFP
t
Example zeolite NaX
Isotherm t-plot
300 300
limit of validity
250 250
Volume adsorbé (cm3 STP/g)
Vads (cm3 STP/g)

200 200
150 150
100 100
50
Vmicro
50
0 0
0 0.2 0.4 0.6 0.8 1
0.00 0.50 1.00 1.50 2.00
p/p0
t (nm)
 Vmicro = 175 cm3 STP/g = 0.271 ml/g

© IFP
Surface BET vs. Surface t-plot
70 St  plot (m2 g 1 )  1.5468  PNT (cm3 g 1nm1 )
60
50
Vads cm3 STP/g
40 y = 45.11x + 0.965
30
20
y = 21.83x + 0.685
10
0
0 0.2 0.4 0.6 0.8 1 1.2
t (nm)
SBET (m2/g) St-plot

65811 74 70
70299 36 34
© IFP
Micro- and mesoporous solids
Solide non poreux : Adsorption sur Surface Externe - Courbe t = t(P/P0)
------------------ Pressions relatives P/P0 croissantes ------------------
µP mP
Solide poreux : Adsorption sur Surfaces Interne & Externe

Vol. Ads.
Solide Non Poreux Solide µ et m-Poreux

Vol. Ads.
Adsorption sur
Surface Externe
Adsorption sur Surface Externe VµP+VmP
VµP Adsorption sur

Surface Interne
(mésopores) => SB.E.T.
© IFP
Epaisseur t Epaisseur t
t-plot may be ambiguous
 Zeolite beta with supermicropores

 no clear linear region in the t-plot
 micropore volume depends on the interval chosen for
extrapolation
200
220 H-MCBeta
H-MCBeta steamed and leached
Vads cm /g STP
N2 ads cm /g STP
180
200
160
3
3
180
140
160
120
140 100
0.0 0.2 0.4 0.6 0.8 1.0 0 2 4 6 8 10 12
p/p0 Thickness - Halsey [A]

© IFP
Méthode de Dubinin-Radushkevitch
 Théorie de remplissage de micropores

Vads
Vmicro

 exp   A / E 
2
 A   RT ln
p
pvap, sat
 A = potentiel d'adsorption
 E = energie caracteristique de l'adsorbant
 pvap,sat = pression vapeur saturante
 pvap,sat = p0 (1 atm) pour N2 à 77K
 Equation linéarisée
2
 p
log Vads  log Vmicro  D log 
 p0 
© IFP
Example NaX
-0.51
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
-0.52
Pression élevée
-0.53 Potentiel faible
Adsorption dans mesopores
log10(Vol. liquide)
-0.54
-0.55 Pression faible

Potentiel élevée
-0.56
Début remplissage
micropores
-0.57
-0.58
log10(P/Po)^2
Vmicro = 10^(-0.548) = 0.283 ml/g

© IFP
Average pore size
 From geometrical rules

 Cylindrical Pore:
V = pore volume V  r h
2
 S 2 4V
  d
 S = surface S  2rh V r S
 Spherical pore :  4 3
V  r S 3 6V
 3  d
S  4r 2 V r S

 Slit pore :
V  lhr S 1 2V
  d
S  lh V r S
© IFP
Micropore size distribution
 Based on the relation between adsorption strength
and the ratio between adsorbate size and pore size
 condition: adsorption controled by van der Waals interactions
only
 Mathematical models
 Horvath-Kawazoe
 Saito-Foley Saito, Foley, AICHE Journal 1991, 37, 429.
 Input parameters
 pore geometry: slit-shaped, cylinder, sphere
 parameters of the Lennard-Jones potential well: ε and σij
 not always well known for atypical solids
 Input data
high precision isotherm at very low pressure !
© IFP

Mesopore size distribution
 via the theory of capillary condensation

A B C->D
D
Vads
E
D->E E->F F->A

F
C
A
B
P/P0
© IFP
Kelvin equation
 Capillary forces in the pore lower the vapor pressure of the
condensed liquid
 Pressure at the concave side of an interface is higher than at the
convex side.
overpressure counteracts the surface tension, which tries to collapse the

interface area
 Application to interface between gas and pressure
adsorbed liquid film in a pore difference Δp
 Pressure in liquid is lower than gas pressure.
 Means that chemical potential in liquid surface
is lower, in other words tension
that the equilibrium vapor pressure
is lower.
 Capillary condensation occurs at a
lower pressure than condensation.
© IFP
Kelvin equation
 Mathematic formalism
 Work against interfacial tension = change in free enthalpy
dA    dncapliq  capliq  dnliq  liq

dVcapliq
dncapliq  dnliq 
Vm
dVcapliq dVcapliq
dA      capliq   liq
Vm Vm
dA Vm    dVcapliq (  capliq  liq ) pcap
capliq  0  RT ln
dA p0
( capliq  liq )   Vm   psat
dVcap, g liq  0  RT ln
p0
pcap dA
RT ln  Vm
© IFP
psat dVcap, g
Generalized Kelvin equation
pcap V  dA dV/dA = change in volume per change in

ln  m  interface area
psat RT dV Vm = molar volume
 dV/dA depends on the pore geometry

 Sphere: dV/dA = r/2
 Cylinder dV/dA = r
 Slit dV/dA = d distance between slits
 Relation to curvature of the pore
pcap 2 Vm
ln 
psat r RT
© IFP
Capillary condensation
p p
2rp
vl
pc  p0  exp( )
RT  (rp  t )
2(rp – t)
 Multilayer adsorption on the surface: layer thickness t 
 At a certain effective pore radius r p-t, capillary condensation
occurs
© IFP
 Pore is filled. There is a step in the adsorption isotherm.

Example isotherm with hysteresis
Type H1
1200
capillary
1000
evaporation
Volads (cm3/g)
800
600
400
capillary condensation
200
0
0.0 0.2 0.4 0.6 0.8 1.0
p/p0
© IFP
Application of the Kelvin equation
1200
1000
Harkins-Jura t-plot equation
Volads (cm3/g)
800
p 13.99
600 log  0.034  2
p0 t
p  4.14
400 log 
p0 rm
200 Kelvin equation
0
0.0 0.2 0.4 0.6 0.8 1.0 Cylinder !!
p/p0
pc/p0 t(pc) rm rc rp= rc+t

Ads 0.671 8.2 23.9 11.9 20.2
Des 0.565 7.0 16.7 16.7 23.7
© IFP
Origin of the hysteresis
Adsorption: Desorption:
cylindrical meniscus hemisperical meniscus
rm = 2reff rm = reff
 The lower rm, the lower is the pressure of capillary

condensation/evaporation
 rm,ads = 2 rm,des
 Capillary evaporation at a lower pressure than capillary
condensation
 Hysteresis loop in isotherm
© IFP
L.H. Cohan, JACS 60 (1938)

Origin of the hysteresis
 Truth seems to be complicated than in Cohan’s
theory.
 Cohan’s theory, based on the shape of mensiscus,
theory suggests that different vapor liquid equilibria
exist in a spherical or cylindrical meniscus, which
leads to hysteresis => is an equilibrium picture.
 Molecular simulations (DFT) suggest that adsorption
branch is not in thermodynamic equilibrium, but is a
metastable state.
© IFP
Hysteresis and metastability
 Adsorption branch comprises metastable states.

 grand free energy of filled pore is lower than
that of the empty pore in the hysteresis
 Desorption branch is in thermodynamic
equilibrium.
 Reason for metastability in adsorption branch
 barrier of nucleation by formation of a liquid
bridge across the pore
 condensation occurs when limit of
metastability is reached
limit of metastability
gas phase
liquid phase
© IFP
Monson, MMM, 2012.

Peterson, JCS Farad 2, 1986.
Pore size distribution – BJH model
p0 – all pores filled
p1 – capillary evaporation in
largest pore
reduction of layer thickness
p2 – capillary evaporation in
2nd largest pore
reduction of layer thickness in
both pores
© IFP
Mathematic description - BJH
rp rp
(rk  t ) 2
V  2
V p
rk rk + t rp
 In each desorption step pn-1  pn, capillary

evaporation occurs from a pore of size r pn
 The volume desorbed in that step (Vn) can be related
to the pore volume by the geometrical relation given
above.
 Complication: Reduction in layer thickness in the
pores, which were already emptied, also contributes to
© IFP
Vn. of porous solids - Characterization of Catalysts and Surfaces - G Pirngruber 25 october 2016
Characterization
The BJH-equation E.P. Barret, L.G. Joyner, P.P. Halenda, JACS 73 (1951) 373.
rpj  t j
2 2 n 1
rpn rpn 2V p
V pn   Vn   tn   Apj Ap 
(rkn  tn ) 2
(rkn  tn ) 2
j 1 rpj rp
capillary evaporation correction term

 For each desorption step the average diameter of the pore, which
undergoes capillary evaporation is calculated from the Kelvin
equation and the t-plot equation: rp = rk + t
p 13.99
log  0.034  2
p0 t
p  4.14
log 
p0 rk
 t is the change in layer thickness in each desorption step
 Vn is the volume desorbed in each step
 A plot of pore volume vs. pore radius is obtained.
© IFP
Limits of the BJH-model
 BJH underestimates the pore size below 7.5 nm –

WHY?
 Model separates the adsorbed film and the capillary
condensate – not a realistic picture
 Fluid-wall interactions are neglected
 Kelvin equation may not be valid in very narrow pores
 Surface tension might increase with curvature
 One should speak about a BJH-value rather than pore

diameter.
© IFP
Adsorption vs. desorption isotherm
 Adsorption isotherm – Pros and cons

 Condensation can be delayed – not in thermodynamic
equilibrium
 Cylindrical meniscus not stable – not advisable to use
adsorption branch for cylindrical pores
 Desorption branch – Pros and cons
 Evaporation not delayed, in thermodynamic equilibrium –
generally preferred
 Ink-bottle type pores: smallest openening determines the
desorption
 In a network of interconnected pores: percolation (transport)
effects determine the desorption
Conclusion: look at both and compare them
© IFP

Ink-bottle pores
rdes
rdes
 In desorption smallest pore openening is determining.

 When pressure of capillary evaporation is reached for
the smallest pore opening, whole pore is suddenly
emptied.
 Sudden drop in the desorption isotherm – type H2
© IFP
Pore network effects
N2 can only desorb from

pore A and C if pore B has
already been emptied.
Seaton, CES, 1991.
 Desorption branch of isotherm not in thermodynamic

equilibrium any more, due to pore blocking.
 Desorption is controlled by a percolation process.
 probability that the pore is connected to the outer surface.
© IFP
Ink-bottle type hysteresis loop
Type H2
Adsorbent:
xerogel and
alcogel
• If pore size distribution is calculated from desorption branch, an

artificially narrow pore size distribution is obtained
• The adsorption branch has to be used to calculate the pore size
distribution.
© IFP
Ink-bottle type hysteresis loop
Isotherm Pore size distribution
1000
900 6
800 Desorption
Vol ads (cm /g)
700
3
dV/dD
600
500 Adsorption
400 0
300
0 2 4 6 8
200
Pore size (nm)
100
0.0 0.2 0.4 0.6 0.8 1.0
p/p0
 Narrow peak in the pore size distribution of the adsorption branch

is an artefact caused by the forced closure of the isotherm at p/p 0
= 0.43
© IFP
Isotherm without hysteresis loop
700
600
Vol ads (cm /g)
500
3
400
300
200
100
0.0 0.2 0.4 0.6 0.8 1.0
p/p0
© IFP
Closure point of the isotherm
 Critical temperature inside a pore lower than in bulk:

Tc,pore < Tc, bulk
 Tc,pore decreases with decreasing pore diameter1
 Above Tc no condensate-vapour meniscus
 For narrow pores Tc < 77 K
 No hysteresis for filling and emptying of these pores
 Tc,pore < 77 K for pores, which show capillary
condensation at p/p0 = 0.4  closure point of isotherm
 Tc(Ar) > Tc(N2)  Ar isotherms show hysteresis when
N2 isotherms don‘t2
© IFP
[1] R. Evans, J. Phys. Condensed Matter 2 (1990) 8989.

[2] M. Thommes, R. Köhn, M. Fröba, J.Phys.Chem. B 104 (2000) 7932.
Summary – Pore size analysis
 BJH relies on Kelvin equation and the universal t-
curve for determining pore size distribution
 both concepts have weaknesses
 Alternative methods exist
 Density Functional Theory
 Broekhoff de Boer – improvement of BJH
 Derjaguin – concept of disjoining pressure
 surface tension concept that takes interaction with solid into
account
 Every model assumes a certain pore geometry
(cylindrical, spherical, slit-shaped) – influences the
results!!
 The adsorption and the desorption branch contain
© IFP
different
Characterization information
of porous solids – look
- Characterization of Catalysts at both.
and Surfaces - G Pirngruber 25 october 2016
Literature
 Textbooks on adsorption
 D.A. Ruthven, Principles of Adsorption and Adsorption
Processes, Wiley
 D.D. Do, Adsorption Analysis: Equilibria and Kinetics,
Imperial College Press
 Review articles discussing a more moderne view of
hysteresis effects and pore size analysis
 P.A. Monson, Understanding adsorption/desorption
hysteresis for fluids in mesoporous materials using simple
molecular models and classical density functional theory,
Microporous Mesoporous Materials 160 (2012) 47.
 B. Coasne et al., Adsorption, intrusion and freezing in porous
silica: the view from the nanoscale, Chem. Soc. Rev. 42
(2013) 4141.
© IFP
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Alternative explanations of the

Kelvin equation
© IFP
Physical principles of capillary
condensation
 Vapour pressure of a liquid under external pressure

External pressure  Equlibrium gas-liquid g = l
H2O vapour pressure pg,0
H2O H2O
g  Equilibrium disturbed by external
H2O pressure
dg = dl  vl dpl = vg dpg
H2O l vl dpl = RT/pg * dpg
vlpl = RT ln (pg/pg0)
pg = new vapour pressure of H2O
pg0 = orignial vapour pressure of H2O vl
pl = external pressure on liquid (H2O), pg  pg ,0  exp( pl )
which induces the change in vapour RT
pressure
© IFP
vl = molar volume of liquid (H2O)

Vapour pressure of a drop of liquid
2
pin  pout 
r pout pin - pout
 = surface tension overpressure

r = radius of curvature inside the drop
holds against
2 pin
pl  pout 
r
surface tension
2 tries to contract
pl  p  the drop
r
© IFP
Vapour pressure of a liquid void
2 pout pin - pout

pin  pout 
r overpressure
in gas bubble
holds against
2
pin  pl  pin
r
2 surface tension
pl  p  tries to collapse
r the void
2vl
pg  pg ,0  exp( ) Kelvin equation: vapour pressure
RT  r inside a void is lowered
© IFP
Kelvin equation
 Capillary forces in the pore lower the vapor pressure
of the condensed liquid
pcap Evaporate n moles from capillary
p
cap  0  RT ln liq  0  RT ln sat and condense on a flat surface.
p0 p0
You have to work against the
surface tension γ.
n
The work done to overcome the surface

tension is equal to change in chemical
Δl θ potential.
V psat
n    RT ln
Vm pcap
Explains why vapor pressure of the
unconfined liquid is higher than in the
© IFP
capillary unconfined liquid

capillary.

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Physisorption and pore size

 1995 – 1999 PhD in heterogeneous catalysis

 Porous cristalline structures

 Ordered or disordered stacking of small particles

 Physisorption (N2, Ar, Kr)

 Physisorption: no formation of chemical bonds, no

 IUPAC distinguishes 3 catagories of pore sizes

 maximal when size of adsobate (j) close to pore size

Initial slope depends on adsorbent-

monolayer multilayer onset of pore filled by

 Opposite pore wall is too far away to influence

Etat initial : PriHe, TriHe Etat initial : PriN2, TriN2

Cellule mesure : Vcel

Etat initial : PciHe, TciHe Etat initial : PciN2, TciN2

Masse d'adsorbant : Msol

liquide à 77 K Quantité adsorbée : Qads=nN2ads/Msol

 Reservoir : 1 Sample cell : 2

 with adsorption (N2) determined with He

 Precise measurement of pressure required

160 after shaping with a

N2 at 77 K NaX (ADS44956) SPX 3001

 Micropores are entirely filled at very low pressure.

surface of the particles

 Surface : 65811 > 70299

 Surface : 79999 > 61399 > 47148

 Pore volume: Vmicro, Vmeso, Vtotal

 BET (Brunauer Emmet Teller): multilayer adsorption

nm = number of surface adsorption sites (monolayer)

0,1 0,2 0,3 0,4 P/P0

SBET (m2/g) CBET

 The multilayer adsorption 0.0007

model does not apply well to 0.0006 y = 0.0064x - 3E-05

microporous solids when the 0.0005

 Choose a lower pressure 0.0003

range for microporous solids. 0.0002

 p/p0 = 0.05 – 0.10 0.0001

C constant may be negative.

Does not make physical sense prel = p/p0

 lower the pressure range

 In some cases possible without using any model.

 Volume of adsorbed gas correponds to a certain

Vp (ml / g )  1.5468 103 Vads (cm3 STP / g )

 Transform adsorbed amount in an average thickness

Vads cm3 STP/g

t = thickness that the

 Adsorption on a non-porous solid

 Adsorption on a microporous solid t

Vads (cm3 STP/g)

 Vmicro = 175 cm3 STP/g = 0.271 ml/g

SBET (m2/g) St-plot

------------------ Pressions relatives P/P0 croissantes ------------------

Solide poreux : Adsorption sur Surfaces Interne & Externe

Solide Non Poreux Solide µ et m-Poreux

VµP Adsorption sur

 Zeolite beta with supermicropores

p/p0 Thickness - Halsey [A]

 Théorie de remplissage de micropores

-0.55 Pression faible