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+
u
=
u
m m
p
K
1 p
u
+
u
=
u
m
c
1 c
slope
u
=
c
1
intercept
m
u
=
( ) p p
p
o
u
o
p
p
Surface Area Determination
Solve these slope/intercept equations for
the monolayer adsorption volume (u
m
):
b m
1
m
+
= u
m
c
1 c
m slope
u
=
c
1
b intercept
m
u
=
Surface Area Determination
If o is the total surface area covered by
one adsorbed molecule, the total surface
per gram of solid (S
g
) can be found as,
where N
o
is Avogadros number and V is
the volume of gas at conditions of u
m
.
o
(
u
=
V
N
S
o m
g
Surface Area Determination
Emmett and Brunauer proposed that o is
simply the projected area of a molecule
on the surface when the molecules are
arranged in close 2D packing.
3
2
o
N
M
09 . 1
(
= o
Surface Area Determination
Example calculations based on Figure 8-1
of Smith, Chemical Engineering Kinetics.
Void Volume and Solid Density
The void (pore) volume of a catalyst
particle can be estimated by filling the
pores with a liquid of known density,
followed by weighing of the particle.
The weight difference (before/after filling)
is due to liquid contained in the pores.
Standard system is helium-mercury.
Void Volume and Solid Density
Finding the void fraction:
( )
p g
s g
s g
s p g p
g p
p
V
1 V
V
1 m V m
V m
particle of volume total
particle of volume pore
=
+
=
+
=
= c
particle porous of density
phase solid of sity den
particles gram per volume void V
particle of mass m
orosity p
p
s
g
p
p
c
sample catalyst
displaced He displaced Hg
g
m
V V
V
=
displaced He
sample catalyst
s
V
m
=
Pore-Volume Distribution
Mercury-penetration method
Hg porosimetry is based on the intrusion of mercury into a
porous structure under stringently controlled pressures.
From pressure versus intrusion data, volume and size
distributions may be generated.
Hg does not wet most substances and will not
spontaneously penetrate pores by capillary action, it must
be forced into the pores by the application of external
pressure. The required pressure is inversely proportional to
the size of the pores, only slight pressure being required to
intrude Hg into large macropores, whereas much greater
pressures are required to force Hg into micropores.
Pore-Volume Distribution
Micromeritics
AutoPore IV 9500
Able to measure pore
diameters from 0.003 to 360 m
Can achieve pressures to
33,000 psi or 60,000 psi
Pore-Volume Distribution
Equate force of surface tension with the
force of the applied pressure
( )
( )
2
5
2
p
in lb p
10 75 . 8
a
p
cos 2
a
cos a 2 p a
F F
=
u o
=
u o t = t
=
o
Hg
u ~ 140
Pore-Volume Distribution
Use the data of Table 8-3 (Smith,
Chemical Engineering Kinetics) to
calculate the pore-volume distribution
shown in Figure 8-5.