Adsorption

December 2014

1
 Nanosized objects have a large
surface area

Dividing the size of an object by 2...

doubles the accessible surface

2
 Adsorption Absorption

Absorption is a phenomenon Adsorption is a phenomenon

that occurs in a volume that occurs on a surface

The word sorption encompasses both types of phenomena

3
 Adsorption of methylene blue from bentonite

https://www.youtube.com/watch?v=3xDjTEv9D1o

4
 Applications of adsorption

5
 Making charcoal at the
Jack Daniel Distillery, ca. 1920-1935

6
 Carbon blacks

7 Estimate an order of magnitude of the specific surface area of carbon blacks

 Orders of magnitude

Figure : 1kg of active carbon has a surface

of about 106 m, i.e. 1026 A;

One generally assumes that a molecule of nitrogen occupies a surface of

about 16 A;

The total number of molecules needed to cover the surface of 1 kg of

carbon black is therefore roughly 10 mol;

This is 220 l of gas STP

i.e. the volume of 22 buckets of gas

8
 Adsorption isotherm (liquid phase)

Amount adsorbed vs concentration

Chemical potential

Dye adsorption in peat

9
 Langmuir isotherm

N molecules adsorb on a surface with a

total of A adsorption sites.
The binding energy per molecule is u. Irving Langmuir
(1881-1957)
What is the chemical potential of an
adsorbed molecule?

10
 The Langmuir model

11
 Chemical potential of adsorbed
species

12
 Langmuir Isotherm
Fraction of surface coverage

K=20
K=10

K=5

P or C
13
 Gas-phase Adsorption Measurement
(volumetric device)

pressure gauges
gas inlet P
(adsorption)
valve valve
P

To vacuum
(desorption) thermostat
(liquid nitrogen)
calibrated
piston

14 sample
 Building up the isotherm

Pressure The pressure decrease following

each piston injection results from
the adsorption of a measurable
quantity of gas

Time

Piston injections
Quantity adsorbed
The adsorption isotherm is
(e.g. mmol/g material)
obtained by plotting the
cumulated quantity adsorbed
against the equilibrium Pressure
pressure (e.g. mmHg)

15
 A rule of thumb

The lowest surface you can accurately measure with nitrogen

adsorption on a volumetric device is 20 m.

That figure can be reduced to, say 1 m if an adsorbate with lower

condensation pressure is used (e.g. 2 mm Hg for Kr at 77K).

In the case of silica spheres, the

surface to volume
S 6 10 9
=
[ ]
m 2 10 6 g / m3 d [nm ]

Measurable For a sample of about 1g, the

materials
largest measurable particle is about
100 nm across.
16
 Gas-phase
adsorption

17
 Adsorption-desorption isotherm

Pore-filling
phenomena

Surface
phenomena

Chemical potential
18
 Adsorption Lexicon

l Adsorbent: The solid itself (e.g. carbon black, silica,

etc.);
l Adsorbate: The adsorbed gas (e.g. nitrogen, krypton,
argon, etc.);
l Mesopore: A pore having a size from 2 nm to 50 nm;
l Micropore: A pore smaller than 2 nm;
l Macropore: A pore larger than 50 nm.

19
 IUPAC Recommendations

20
 The 6 types of isotherms
according to the IUPAC classification

I: microporous solids

II & III: multilayer adsorption

in non-porous solids

IV & V: capillary condensation

in mesoporous solids

VI: stepped asdorption

21
 Type II & III isotherms:
multilayer adsorption on non-porous solids

300
Progressive adsorption
Nitrogen on closed
250 with no hysteresis
MWCNTs
V ads (cm STP/g)

200

150

100

50

0
0 0.2 0.4 0.6 0.8 1
P/P0

22
 Multilayer adsorption
the BET equation (1938)

Stephen Brunauer

Edward Teller

Paul Emmett

From I. Hargittai,
The Martians of Science
23 Oxford University Press
The BET equation

The assumptions of the BET equation are:

1) Adsorption occurs layer by layer;
2) Molecules in the first layer interact with the solid & molecules in the
following layers behave as in bulk liquid;
3) Lateral interactions between adsorbed molecules are neglected.

C P / P0
W = W0
(1 P / P0 )(1 + (C 1)P / P0 )
where W is the amount adsorbed at pressure P, W0 is the amount needed
to cover the total surface with a monomolecular layer (or monolayer),
and C is a parameter related to the energy of interaction between the
adsorbent and adsorbate.
 BET adsorption isotherms

C=3
C=10
C=50
C=0.3
C=1

25
Practical use of the BET equation

The equation is rearranged as

P / P0 1 C 1
= + P / P0
W (1 P / P0 ) CW0 CW0

When the left-hand-side is plotted against P/P0, a straight line is expected,

which enables to determine W0 and C.

The volume of the monolayer is converted to a specific surface area S by

assuming that each molecule in the monolayer occupies a given surface
(16.2 A for nitrogen).
 Examples of BET plots

0.02

A real non-porous solid

A mesoporous solid
0.015
3

BET function
0.01
2.5 0.01
A microporous solid
2
BET function

0.005

BET function
1.5

0.005
1
0
0 0.2 0.4 0.6 0.8
0.5 P/P0

0
0 0.2 0.4 0.6 0.8
0
P/P0 0 0.2 0.4 0.6 0.8
P/P0