Capillary Condensation: Ali Ahmadpour Chemical Eng. Dept. Ferdowsi University of Mashhad

Capillary Condensation
Ali Ahmadpour
Chemical Eng. Dept.
Ferdowsi University of Mashhad
Contents
 Adsorption in mesoporous solids
 Kelvin equation
 Generalized Kelvin equation
 Desorption from a pore
 Filling of a pore during the adsorption cycle
 Pore Size Distribution
 Surface area determination
2
Pore volume and pore size
distribution
 The range of validity of BET equation is between 0.05 and
0.35 relative pressure.
 Adsorption beyond this range will result in filling of
mesopore with adsorbate liquid through the action of
capillary condensation.
 Capillary condensation and its variation with the pore size
will be discussed, and how to get useful information about
the mesopore size distribution from the data of volume
adsorbed versus pressure.
 The range of validity for the capillary condensation is
between 0.35 and 0.99 relative pressure.
3
Adsorption in mesoporous solids
 A typical adsorption-desorption isotherm of a practical porous solid
usually exhibits a hysteresis over the pressure range where the capillary
condensation phenomenon is operating.
 The onset of the hysteresis loop indicates the start of the capillary
condensation mechanism.
4
Kelvin equation for Capillary
Condensation
 Due to the capillary force in small pores, the vapor pressure
of a liquid inside such pores is less than that of a flat
surface.
 The pressure at which the liquid will condense in a pore of
radius r is:
σ : surface tension
Po: vapor pressure of the bulk phase
 : contact angle
vM : liquid molar volume.
5
Cont.
 When the pore is very large, i.e.:
the pressure at which the species condenses or

evaporates is equal to the vapor pressure of the
liquid, i.e. P/Po = 1.
 On the other hand, for pores of radius r, the liquid
will form at pressure P/Po < 1.
6
Basis of the capillary condensation
theory
 For gas having a pressure lower than the condensation
pressure Pk, there is no capillary condensation except a
submonolayer adsorption, while for gas having pressure
equal to or greater than the condensation pressure Pk, the
capillary of size D will be filled completely with liquid.
7
Cont.
Evaporation of liquid from a pore of radius r (rm is the radius of curvature)
Capillary pressure as a function of radius for nitrogen at 77 K
8
Generalized Kelvin equation
 In the region of hysteresis, there are two values of the
pressure that give rise to the same amount uptake (i.e. two
values of the pore size).
 To properly account for this, one must investigate the way
liquid is condensed or evaporated during the adsorption and
desorption cycles.
 We can apply the capillary condensation to adsorption and
desorption cycles.
Generalized form
of Kelvin equation
rm is the mean radius of curvature 9

Desorption from a pore
 During evaporation (desorption) the pore is filled and the
sorbate starts to evaporate from the liquid meniscus, taking
the form of hemispherical shape having a contact angle of .
 The radius of curvature of this hemispherical, rm, is related
to the pore radius as follows:
Classical Kelvin equation

10
Filling of a pore during the
adsorption cycle
For adsorption, the radius of curvature is:
Cohan equation
11
Adsorption and desorption
where r’ is the radius of

curvature of the meniscus
(r’ = r/cos, where  is the
contact angle).
For zero contact angle, the

radius of curvature is the
same as the capillary radius.
12
Cont.
 The reduced pressure required to empty a capillary
is equal to the square of that necessary to fill it.
 For example, a pore of radius r which fills with
liquid adsorbate at a reduced pressure P/Po of 0.7
would have its filled liquid evaporated at a
reduced pressure of about 0.5.
 The status of filling and emptying at two different
relative pressures is the basis of hysteresis in
mesoporous solids.
13
Pore Size Distribution
 For each pore of radius r, there exists a threshold pressure for condensation
and a threshold pressure for evaporation.
 This can be used to determine the pore size and its distribution.
 During the adsorption cycle the filling of pore with adsorbate is in a radial
fashion, and hence the rise in the amount adsorbed versus pressure is
gradual.
 After the pore is filled, and when the pressure is reduced the liquid in the
pore will remain until the pressure in the gas phase reaches the evaporation
pressure at which the liquid will instantaneously evaporate, leaving only the
adsorbed layer behind.
 As the pressure is reduced further the amount adsorbed will decrease and the
relationship between the amount adsorbed and the pressure is dictated by the
equilibrium between the two phases (e.g. BET equation).
14
Cont.
 Knowing this condensation pressure from the desorption branch
of point A, the pore radius then can be calculated from the
Kelvin equation:
 Unfortunately, this ideal situation never occurs in practice as all

practical porous solids have a distribution of pore size, so there
will be a gradual change in the desorption branch rather than an
abrupt change as in the case of ideal solids.
15
Solids with no adsorbed layer (pure
Condensation and Evaporation)
 Consider a porous solid having a PVD of f(r), then f(r) dr is the pore
volume of pores having radii ranging between r and r + dr.
 For a gas phase of pressure P, the threshold radius (rK) is calculated
from either equations for condensation or evaporation mechanisms.
 The amount adsorbed at a pressure P is simply the fraction of pores
having radii less than rK, that is:
For simplicity,
the lower limit
where is zero.
16
Cont.
 If Maxwellian pore volume distribution
 where Vs is the total pore volume and r0 is the characteristic pore radius.
 Figure shows a typical plot for Vs =0.4 cc/g, and r0 = 3 nm
17
Cont.
 Then, the adsorbed volume by capillary condensation as a
function of pressure is:
18
Double Gamma PVD
19
Solids with adsorbed layer prior
to condensation
 If we let "t" to represent the statistical thickness of the adsorbed layer (which
is a function of pressure), then the effective pore radius available for
condensation is related to the true pore radius as follows:
 σ is the thickness of one layer, or obtain the film thickness measured for a
nonporous reference material.
 The statistical adsorbed film thickness as a function of pressure for nitrogen

adsorption at 77 K.
where 0.354 nm is the thickness of one nitrogen molecule. 20

Cont.
 The threshold radius corresponding to a gas phase of pressure P is:
 The amount adsorbed at a given pressure P is then:
 The pores are assumed cylindrical in shape, and the film thickness is
independent of the pore radius. The factor (2/r) is the surface area per unit
void volume. The parameter rmax is taken as the upper limit of the mesopore
21
range, that is 25 nm.
Surface area determination
 Knowing the pore volume distribution f(r), the surface area is
determined from:
22
Cont.
Typical surface area, pore volume and mean pore radius of some solids
23

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Capillary Condensation

the pressure at which the species condenses or

Evaporation of liquid from a pore of radius r (rm is the radius of curvature)

Capillary pressure as a function of radius for nitrogen at 77 K

rm is the mean radius of curvature 9

Classical Kelvin equation

where r’ is the radius of

For zero contact angle, the

 Unfortunately, this ideal situation never occurs in practice as all

 The statistical adsorbed film thickness as a function of pressure for nitrogen

where 0.354 nm is the thickness of one nitrogen molecule. 20

 The amount adsorbed at a given pressure P is then:

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