t Method

t-Method
Macropores
p
solids
The volume adsorbed for unit of surface with
relation to the ppressure follows an unique
q curve,,
independent of the surface structure.

Multilayer adsorption
Thickness (t) depends of the pressure in the
equilibrium,
equilibrium
p
t = f 0
p
CatalysisandCatalysts PhysicalAdsorption

t Method
t-Method
Reference Isotherm for N2 (77
(77K)
K)
n
[nm]
t = 0.354
nm

Thickness (t) of adsorbed layer can be calculated.

Plot of t vs. p for non-porous materials is the
same (has been checked experimentally)
Interpretation in t-Method is more easy that BET
Method (BET is only valid in small pressure
interval)
CatalysisandCatalysts PhysicalAdsorption

t Method
t-Method
For the Reference Isotherm
Isotherm,
n = bt t

nAD

ProportionaltoSt

Note:
nAD isanexperimentalresult.
t iscalculatedasfunctionofp.
is calculated as function of p

nm
bt =

St = n m A m N
St = 3.37 10 4 b t

CatalysisandCatalysts PhysicalAdsorption

BJH (Barret, Joiyner, Halendaer) Method

D
Determination
i i off volume
l
andd diameter
di
off pore
by adsorption of gas.
Gas condenses to liquid in narrow pores, to low
pressures that saturation pressure of adsorbate. This
is related by Kelvin Equation,
p 2 V cos 2 V
ln 0 =
=
, [ = /2]
R T rk
R T rk
p

CatalysisandCatalysts PhysicalAdsorption

BJH (Barret, Joiyner, Halendaer) Method

Based on N2 adsorption (
(=88.8510
8510-5Ncm-1 and
V=34.6 cm3mol-1), the total volume and the
distribution of the size of the pore is calculated
as follows,
2 Thickness of the
2.
adsorbed layer 1/ 3

1 Radio of Kelvin
1.
Kel in

9.53
rk =
ln (p/p 0 )

t = 4.3
0
ln (p/p )

3. Radio of pore

rp = rk + t
CatalysisandCatalysts PhysicalAdsorption

BJH (Barret, Joiyner, Halendaer) Method

4 Decrease of volume
4.

V = Vi Vi 1

5 Decrease of thickness
5.

t = t i t i 1

6. Decrease of volume of gas,

which film adsorbed decrease

7. Volume by desorption
where pores

Vf = 0.064 t S

Vk = V Vf

8 V
8.
Volume
l
d
decrease
ratio
ti

rp
Vp = Vk
rk

CatalysisandCatalysts PhysicalAdsorption

BJH (Barret, Joiyner, Halendaer) Method

9. Superficial specific area

S = 31.26

Vp
rp

12 Volume percentage
12.
n

10. Superficial total area

V = Vi Vi 1

% Vi =

11. Volume that fill the pores

Vpl = Vp 1.558 10 3
CatalysisandCatalysts PhysicalAdsorption

V
i
n

pl i

V
i =1

pl i

BJH (Barret, Joiyner, Halendaer) Method

Distribution of pore size
0,30

Vpl/
rp, [cm3/gA]]

0,25
0,20
0,15
0,10
0,05
0,00
0

10

15

20

25

rp, [A]

CatalysisandCatalysts PhysicalAdsorption

30

35

40

BJH (Barret, Joiyner, Halendaer) Method

A
Accumulative
l ti distribution
di t ib ti
off pore volume
l
90
80

% Volume

70
60
50
40
30
20
10
0
0

10

15

20

25

rp, [A]

CatalysisandCatalysts PhysicalAdsorption

30

35

40