Porosity and sorption

behavior
2
Out line
Whats of the adsorption???.
Porosity.
Classification of pores.
Pore size distribution.
Adsorption isotherms.



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3
Whats of the adsorption???
adsorbate
adsorbent
Unimolecular
adsorption
Multimolecular
adsorption 14/02/1435
4
Physical Adsorption (van der Waals
adsorption):
weak bonding of gas molecules to the solid;
usually not exceeding 80 KJ/mol.
Its the reversible process.
Chemisorption:
Chemical bonding by reaction;
bond energy ~600KJ/mol for C-N bond and
800KJ/mol for Chemical band.
Its the irreversible process.
Types of adsorption
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5
impuretans
Out gasing of the
surface
Flow of the gas
inert
N
2
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The mechanism of adsorption
Contaminant molecules
Step (1):
Diffusion to adsorbent
surface
Step (2):
Migration in to pores of
adsorbent
Step (3):
Mono layer build up
of adsorbent
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7
Porosity

The word pore comes from the Greek word
which means passage.


This indicates the role of a pore acting as a
passage between the external and the internal
surfaces of a solid, allowing material, such as
gases and vapours, to pass into, through or out
of the solid.
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Transport pores
Close pores
Open pore
Blind pores
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Open
pore
Closed
pore
Dense
strut
Transport
pores
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11
supermicroporosity
(size 1.4-2.0 nm)
Microporosity
(diameter ~0.5 1.4 nm )
Ultramicroporosity
(dirameter <0.5 nm)


Ultramicroporosity
(d
r
<0.5 nm)
Microporosity
(d
r
~0.5 1.4 nm )
supermicroporosity
(size 1.4-2.0 nm)
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Total pore volume
The total pore volume is essentially the sum
of two fractions:

Vt = Vo + Vc
Where:
Vt: is the total pore volume
Vo: is the pore volume due to the open porosity in the
solid including transport and blind pores
Vc : is the closed pore volume

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Adsorption Isotherms
III
n
a
d

p / p
0
VI
n
a
d

p / p
0
V
n
a
d

p / p
0
I
n
a
d

p / p
0
p / p
II
n
a
d

0
B
IV
n
a
d

p / p
0
B
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Langmuir Adsorption Isotherm
(Type I)
Assumptions:
homogeneous surface
(all adsorption sites energetically identical)
monolayer adsorption (so no multilayer adsorption)
no interaction between adsorbed molecules
p K
p K
n n n
m m ad
+
= u =
1
I
n
a
d

p / p
0
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Type III and V Isotherms
III
n
a
d

p / p
0
V
n
a
d

p / p
0
Strong cohesion force between
adsorbed molecules, e.g. when
water adsorbs on hydrophobic
activated carbon
Similar to III at low p
Pore condensation at high p
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Type II and IV Isotherms
Multilayer adsorption (starting at B)
Common for pore-free materials
Similar to II at low p
Pore condensation at high p
p / p
II
n
a
d

0
B
IV
n
a
d

p / p
0
B
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Surface Area & Monolayer Capacity
S = n
m
A
m
N
monolayer
capacity (mol/g)
specific surface area
(m
2
/g)
area occupied by one
molecule
(m
2
/molecule)
Avogadros number
(molecules/mol)
BET model: S
BET

t model: S
t

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BET (Brunauer, Emmett, Teller) Method
Modification of Langmuir isotherm
Both monolayer and multilayer adsorption
Layers of adsorbed molecules divided in:
First layer with heat of adsorption AH
ad,1

Second and subsequent layers with H
ad,2
= AH
cond


BET isotherm:


BET equation does not fit entire adsorption isotherm
different mechanisms play a role at low and at high p

( )
0
m m
0
ad
1 1
p
p
C n
C
C n p p n
p

+ =

|
.
|

\
| A A
=
RT
H H
C
cond ad
exp
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Kelvin Equation for Nitrogen
micro meso macro
V
L
= 34.6810
-6

m
3
/mol
= 8.88 mN/m
d
m
(nm)
R
e
l
a
t
i
v
e

p
r
e
s
s
u
r
e

p
/
p
0

0
0.2
0.4
0.6
0.8
1
0.1 1 10 100 1000 10000
d
m
= -2 cos .V
l
/ RT . 1/ln P/P
0
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20
t-method
BET
only valid in small pressure interval
interpretation not very easy
thickness (t ) of adsorbed layer can be calculated



plot of t versus p for non-porous materials is the same
(has been checked experimentally)
t-plot helps in interpretation
0.354 nm
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21
p/p
0

A
d
s
o
r
b
e
d
-
l
a
y
e
r

t
h
i
c
k
n
e
s
s

t

(
n
m
)

0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0 0.2 0.4 0.6 0.8 1
t-curves
a
b
Halsey
Harkins-Jura-de Boer
( )
333 . 0
0
/ ln
00 . 5
354 . 0
(

=
p p
t
( )
5 . 0
0
/ log 034 . 0
99 . 13
1 . 0
(

=
p p
t
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22
t-plot of -alumina
0
2
4
6
8
10
0.0 0.2 0.4 0.6 0.8 1.0 1.2
t ( nm)
n
a
d

(
m
m
o
l
/
g
)
S
t,micro
= 0 m
2
/g
V
t,micro
= 0 ml/g
mesopores
macropores
S
t,micro
= 0 m
2
/g
V
t,micro
= 0 ml/g
S
t
= 200 m
2
/g
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23
Shape of t-plots
nm 354 . 0
m
ad
=
n
n
t
t
n
ad

t
n
ad

t
n
ad

Non-porous Microporous
Micro- and
mesoporous
S
t

S
mesopores

p
n
ad

Adsorption isotherm
t = f(p)
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Pore-Size Distribution of -Alumina
0.0
0.1
0.2
0.3
0.4
0.5
1 10 100 1000
d
p
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)

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125
Mercury Porosimetry
Usaed to measure large pores (macropores , d >>500

A) as
in the silica-support catalysts.
This technique based on forcing mercury to intrusion into
the pores of the sample. (Hg does not wet surfaces).
From a force balance:
d
p
= -2 cos /P
Where:
= the surface tension of mercury.
= the contact angle,( is larger than 90).
(d in nm, p in bar)
d
p
= 14860/ P

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126
Discrepancy S
Hg
and S
BET

for Microporous Materials
Hg cannot penetrate small (micro)pores, N
2
can.
Uncertainty of contact angle and surface tension values
Cracking or deforming of samples
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127
N
2
Adsorption Isotherms & Pore Volume
Distributions
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)


1



wide-pore silica
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128
0.00
0.02
0.04
0.06
0.08
0.10
1 10 100 1000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)

wide-pore silica
14/02/1435
129
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)

1
-alumina
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130
0.0
0.1
0.2
0.3
0.4
0.5
1 10 100 1000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
-alumina
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131
Hg Intrusion Curves & Pore Volume
Distributions
wide-pore silica
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.1 1 10 100 1000
p (MPa)
V

(
m
l
/
g
)
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132
0
0.02
0.04
0.06
0.08
1 10 100 1000 10000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
wide-pore silica
14/02/1435
133
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.1 1 10 100 1000
p (MPa)
V

(
m
l
/
g
)
-alumina
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134
0.0
0.1
0.2
0.3
0.4
0.5
1 10 100 1000 10000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
-alumina
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135
BET- & t-plots
wide-pore silica -alumina
0.0
0.1
0.2
0.3
0.4
0.5
0.00 0.05 0.10 0.15 0.20 0.25 0.30
p/p
0
p
/
[
n
a
d
(
p
0
-
p
)
]


(
g
/
m
m
o
l
)
S
BET
= 78 m
2
/g
C = 146
0.0
0.1
0.2
0.3
0.4
0.5
0.00 0.05 0.10 0.15 0.20 0.25 0.30
p/p
0
p
/
[
n
a
d
(
p
0
-
p
)
]


(
g
/
m
m
o
l
)
S
BET
= 196 m
2
/g
C = 97
0.0
0.5
1.0
1.5
2.0
2.5
0.0 0.2 0.4 0.6 0.8 1.0 1.2
t ( nm)
n
a
d

(
m
m
o
l
/
g
)
S
t,micro
=28 m
2
/g
V
t,micro
= 0.013 ml/g
0
2
4
6
8
10
0.0 0.2 0.4 0.6 0.8 1.0 1.2
t ( nm)
n
a
d

(
m
m
o
l
/
g
)
S
t,micro
= 0 m
2
/g
V
t,micro
= 0 ml/g
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