Catalysis & Catalysts

Adsorption On Solid Surface

Adsorption

Adsorption is a process in which molecules from gas (or liquid) phase land
on, interact with and attach to solid surfaces.

The reverse process of adsorption, i.e. the process in which adsorbed

molecules escape from solid surfaces, is called Desorption.

Molecules can attach to surfaces in two different ways because of the

different forces involved. These are Physisorption (Physical adsorption) &
Chemisorption (Chemical adsorption)
Physisorption

Chemisorption

force

van de Waal

chemcal bond

number of adsorbed layers

multi

only one layer

adsorption heat

low (10-40 kJ/mol)

high ( > 40 kJ/mol)

selectivity

low

high

temperature to occur

low

high

Catalysis & Catalysts

Solid Catalysts
Catalyst composition
Active phase

Textual promoter (e.g. Al - Fe for NH3 production)

Electric or Structural modifier

Poison resistant promoters

Support / carrier

ph
as

Promoter

te r
mo
Pro

Where the reaction occurs (mostly metal/metal oxide)

e

tiv
e

Ac

Catalyst
Support

Increase mechanical strength

Increase surface area (98% surface area is supplied within the porous structure)
may or may not be catalytically active

Catalysis & Catalysts

Solid Catalysts
Some

common solid support / carrier materials

Alumina

Inexpensive
Surface area: 1 ~ 700 m2/g
Acidic

Silica
Inexpensive
Surface area: 100 ~ 800 m2/g
Acidic

Other supports

Active carbon (S.A. up to 1000 m2/g)

Titania (S.A. 10 ~ 50 m2/g)
Zirconia (S.A. 10 ~ 100 m2/g)
Magnesia (S.A. 10 m2/g)
Lanthana (S.A. 10 m2/g)
Active site

Zeolite
mixture of alumina and silica,
often exchanged metal ion present
shape selective
acidic

porous
solid

pore

Pores of Porous Solids

Pore

sizes

micro pores dp <20-50 nm

meso-pores 20nm <dp<200nm

macro pores dp >200 nm

Pores can be uniform (e.g. polymers) or non-uniform (most metal oxides)

Pore

size distribution

Typical curves to characterise pore size:

Cumulative curve

Frequency curve

Uniform size distribution (a) &

non-uniform size distribution (b)

dw
dd

wt
wt
a

b
d

b
d

Cumulative curve

Frequency curve

Catalysis & Catalysts

Adsorption On Solid Surface

Adsorption

process

Adsorbent and adsorbate

Adsorbent (also called substrate) - The solid that provides surface for adsorption
high surface area with proper pore structure and size distribution is essential
good mechanical strength and thermal stability are necessary

Adsorbate - The gas or liquid substances which are to be adsorbed on solid

Surface coverage,
The solid surface may be completely or partially covered by adsorbed molecules

define

number of adsorption sites occupied

= number of adsorption sites available

= 0~1

Adsorption heat

Adsorption is usually exothermic (in special cases dissociated adsorption can be

endothermic)

The heat of chemisorption is in the same order of magnitude of reaction heat;

the heat of physisorption is in the same order of magnitude of condensation heat.

Catalysis & Catalysts

Adsorption On Solid Surface

Applications

of adsorption process

Adsorption is a very important step in solid catalysed reaction processes

Adsorption in itself is a common process used in industry for various purposes

Purification (removing impurities from a gas / liquid stream)

De-pollution, de-colour, de-odour

Solvent recovery, trace compound enrichment

etc

Usually adsorption is only applied for a process dealing with small capacity

The operation is usually batch type and required regeneration of saturated adsorbent

Common adsorbents: molecular sieve, active carbon, silica gel, activated alumina.

Physisorption is an useful technique for determining the surface area, the pore
shape, pore sizes and size distribution of porous solid materials (BET surface area)

Adsorption On Solid Surface

Characterisation of adsorption system

Adsorption isotherm - most commonly used, especially to catalytic reaction system, T=const.
The amount of adsorption as a function of pressure at set temperature

Adsorption isobar - (usage related to industrial applications)

The amount of adsorption as a function of temperature at set pressure

Adsorption Isostere - (usage related to industrial applications)

Adsorption pressure as a function of temperature at set volume
V3>V2
V2>V1

T2 >T1
T3 >T2
T4 >T3

P3>P2
P2>P1
P1

V4>V3
V1

Pressure

T1

Vol. adsorbed

P4>P3

Vol. adsorbed

T5 >T4

Pressure
Adsorption Isotherm

Temperature
Adsorption Isobar

Temperature
Adsorption Isostere

Adsorption On Solid Surface

The

Langmuir adsorption isotherm

Basic assumptions

surface uniform (Hads does not vary with coverage)

monolayer adsorption, and

no interaction between adsorbed molecules and adsorbed molecules immobile

Case I - single molecule adsorption

when adsorption is in a dynamic equilibrium

A(g) + M(surface site) AM
the rate of adsorptionrads = kads (1-) P

case I

the rate of desorptionrdes = kdes

at equilibrium rads = rdes kads (1-) P = kdes
rearrange it for
let

(k ads / k des ) P
1 (k ads / k des ) B0 P

k ads
Cs
B0 P
B

0
B0 is adsorption
coefficient
k
C 1 B P
des

Adsorption On Solid Surface

The

Langmuir adsorption isotherm (contd)

Case II - single molecule adsorbed dissociatively on one site

A-B(g) + M(surface site) A-M-B

the rate of A-B adsorption rads=kads (1))PAB=kads (1)2PAB

==
the rate of A-B desorption rdes=kdes=kdes2
at equilibrium
rearrange it for
Let.

A
A

case II

rads = rdes kads (1)2PAB= kdes2

(kads / kdes ) PAB

1 (kads / kdes ) PAB

k
B0 ads
k des

Cs
( B0 PAB )1/2

C 1 ( B0 PAB )1/2

Adsorption On Solid Surface

The

Langmuir adsorption isotherm (contd)

Case III - two molecules adsorbed on two sites

A(g) + B(g) + 2M(surface site) A-M + B-M

the rate of A adsorption

rads,A = kads,A (1) PA

the rate of B adsorption

rads,B = kads,B (1) PB

the rate of A desorption

rdes,A = kdes,A

the rate of B desorption

rdes,B = kdes,B

at equilibrium

rads ,A = rdes ,A

A B

case III

and rads ,B = rdes ,B

kads,A(1)PA=kdes,A and kads,B(1)PB=kdes,B

C
B0 ,A PA
C
B0 ,B PB
A s ,A
B s ,B
rearrange it for
C 1 B0 ,A PA B0 ,B PB
C 1 B0 ,A PA B0 ,B PB
k
k
B0 ,A ads ,A and B0 ,B ads ,B
where
k des ,A
k des ,B are adsorption coefficients of A & B.

Adsorption On Solid Surface

The

Langmuir adsorption isotherm (contd)

A

case I

C
BP
s 0
C 1 B0 P
B0

k ads
k des

Cs
( B0 PAB )1/2

C 1 ( B0 PAB )1/2
k ads
k des

Adsorption

Adsorption
Strong

kads>> kdes

Weak

kads<< kdes
B0<<1

A, B both strong

kads>> kdes
Cs
1
C

B0>>1

B0>>1

kads<< kdes

case III
B0 ,A PA

1 B0 ,A PA B0 ,B PB
B0 ,B PB

1 B0 ,A PA B0 ,B PB

Cs ,A
C
C
B s ,B
C
k
k
B0 ,A ads ,A and B0 ,B ads ,B
k des ,A
k des ,B

case II

B0

A B

Cs
1
C

Cs
C
B0 P
s ( B0 P)1/2
C
C
B0<<1

A strong, B weak
A weak, B weak

C s ,A
B0 ,A PA

C
B0 ,A PA B0 ,B PB
C
B0 ,B PB
B s ,B
C
B0 ,A PA B0 ,B PB

A C s , A / C 1
B Cs ,B / C ( B0 ,B / B0 ,A )
A Cs ,A / C B0 ,A PA
B Cs ,B / C B0 ,B PB

PB
PA

Adsorption On Solid Surface

adsorption isotherm
Cs
BP
0
C 1 B0 P

case I

case II

Cs
( B0 PAB )1/2

C 1 ( B0 PAB )1/2
C
B0 ,A PA
A s ,A
C 1 B0 ,A PA B0 ,B PB
C
B0 ,B PB
B s ,B
C 1 B0 ,A PA B0 ,B PB

Case III

Strong adsorption

kads>> kdes

Weak adsorption

kads<< kdes

Amount adsorbed

Langmuir

Cs
1
C
C
s B0 P
C

mono-layer
large B0 (strong adsorp.)
moderate B0
small B0 (weak adsorp.)
Pressure

Langmuir
It

adsorption isotherm established a logic picture of adsorption process

fits many adsorption systems but not at all

The

assumptions made by Langmuir do not hold in all situation, that causing error

Solid surface is heterogeneous thus the heat of adsorption is not a constant at different
Physisorption of gas molecules on a solid surface can be more than one layer

Adsorption On Solid Surface

Five types of physisorption isotherms are found over all solids

I

amount adsorbed

II

III

IV

1.0
relative pres. P/P0

Type I

is found for porous materials with small pores e.g. charcoal.

It is clearly Langmuir monolayer type, but the other 4 are not

Type II for non-porous materials

Type III porous materials with cohesive force between adsorbate

molecules greater than the adhesive force between adsorbate
molecules and adsorbent

Type IV staged adsorption (first monolayer then build up of additional

layers)

Type V porous materials with cohesive force between adsorbate

molecules and adsorbent being greater than that between adsorbate
molecules

Adsorption On Solid Surface

Other adsorption isotherms

Many other isotherms are proposed in order to explain the observations

The Temkin (or Slygin-Frumkin) isotherm

Assuming the adsorption enthalpy H decreases linearly with surface coverage

From ads-des equilibrium, ads. rate des. rate

rads=kads(1-)P rdes=kdes
B0 P
b1eQs / RT P

s
1 B0 P
1 b1eQs / RT P

H of ads

Langmuir
Temkin

where Qs is the heat of adsorption. When Qs is a linear function of i. Qs=Q0-iS (Q0 is a

constant, i is the number and S represents the surface site),
Q / RT
1
1 [b e s

P
RT
1 b1 P
1

dS

dS

ln
0 s 0 (1 b1eQs / RT P
the overall coverage
i 1 b1 P exp RTi

When b1P >>1 and b1Pexp(-i/RT) <<1, we have =c1ln(c2P), where c1 & c2 are constants

Valid for some adsorption systems.

Adsorption On Solid Surface

The Freundlich isotherm

assuming logarithmic change of adsorption enthalpy H with surface coverage

From ads-des equilibrium, ads. rate des. rate
rads=kads(1-)P rdes=kdes
B0 P
b1eQi / RT P

i
1 B0 P
1 b1eQi / RT P

H of ads

Langmuir
Freundlich

where Qi is the heat of adsorption which is a function of i. If there are Ni types of surface sites,
each can be expressed as Ni=aexp(-Q/Q0) (a and Q0 are constants), corresponding to a
fractional coverage i,
i i Ni 0 [b1eQ / RT P / (1 b1eQ / RT P)] aeQ/Q0 dQ

the overall coverage

Q/Q
N
i
ae 0 dQ
i

the solution for this integration expression at small is:

ln=(RT/Q0)lnP+constant, or
as is the Freundlich equation normally written,

c1 p1 / C2 where c1=constant, 1/c2=RT/Q0

Freundlich isotherm fits, not all, but many adsorption systems.

Adsorption On Solid Surface

BET (Brunauer-Emmett-Teller) isotherm

Many physical adsorption isotherms were found, such as the types II and III, that the
adsorption does not complete the first layer (monolayer) before it continues to stack
on the subsequent layer (thus the S-shape of types II and III isotherms)

Basic assumptions
the same assumptions as that of Langmuir but allow multi-layer adsorption
the heat of ads. of additional layer equals to the latent heat of condensation
based on the rate of adsorption=the rate of desorption for each layer of ads.
the following BET equation was derived

P / P0
1 c 1

( P / P0 )
V ( 1 P / P0 ) cVm cVm
Where

P - equilibrium pressure
P0 saturate vapour pressure of the adsorbed gas at the temperature
P/P0 is called relative pressure
Vvolume of adsorbed gas per kg adsorbent
Vm volume of monolayer adsorbed gas per kg adsorbent
cconstant associated with adsorption heat and condensation heat
Note: for many adsorption systems c=exp[(H1-HL)/RT], where H1 is adsorption heat of 1st layer &
HL is liquefaction heat, so that the adsorption heat can be determined from constant c.

Adsorption On Solid Surface

Comment on the BET isotherm

BET equation fits reasonably well all known adsorption isotherms observed so far
(types I to V) for various types of solid, although there is fundamental defect in the
theory because of the assumptions made (no interaction between adsorbed
molecules, surface homogeneity and liquefaction heat for all subsequent layers being
equal).

BET isotherm, as well as all other isotherms, gives accurate account of adsorption
isotherm only within restricted pressure range. At very low (P/P 0<0.05) and high
relative pressure (P/P0>0.35) it becomes less applicable.

The most significant contribution of BET isotherm to the surface science is that the
theory provided the first applicable means of accurate determination of the surface
area of a solid (since in 1945).

Many new development in relation to the theory of adsorption isotherm, most of them
are accurate for a specific system under specific conditions.

Adsorption On Solid Surface

Use of BET isotherm to determine the surface area of a solid

At low relative pressure P/P0 = 0.05~0.35 it is found that

P / P0
1 c 1

( P / P0 ) ( P / P0 )
V ( 1 P / P0 ) cVm cVm

=
The

a +

P / P0
V (1 P / P0 )

P/P0

principle of surface area determination by BET method:

A plot of

P / P0
V (1 Pagainst
/ P0 )

P/P0 will yield a straight line with slope of equal to (c-1)/(cVm) and

intersect 1/(cVm).
For a given adsorption system, c and Vm are constant values, the surface area of a solid
material can be determined by measuring the amount of a particular gas adsorbed on the
surface with known molecular cross-section area Am,

V
As Am N m Am m 6.022 1023
VT , P

Vm - volume of monolayer adsorbed gas molecules calculated from the plot, L

VT,P - molar volume of the adsorbed gas, L/mol
Am - cross-section area of a single gas molecule, m 2

* In practice, measurement of BET surface area of a solid is carried out by N 2 physisorption

at liquid N2 temperature; for N 2, Am = 16.2 x 10-20 m2

Adsorption On Solid Surface

Summary of adsorption isotherms

Name

Isotherm equation
Cs
BP
0
C 1 B0 P

Application

Note

Chemisorption and
physisorption

Useful in analysis of
reaction mechanism

Langmuir

Temkin

=c1ln(c2P)

Chemisorption

Chemisorption

Freundlich

c1 p1 / C2

Chemisorption and
physisorption

Easy to fit adsorption

data

BET

P / P0
1 c 1

( P / P0 )
V ( 1 P / P0 ) cVm cVm

Multilayer physisorption

Useful in surface area

determination

The BET isotherm

Theoretical development based on several

assumptions:

OT fig1.3

multimolecular adsorption
1st layer with fixed heat of adsorption H 1
following layers with heat of adsorption
constant (= latent heat of condensation)
constant surface (i.e. no capillary
condensation) gives

p
1
C 1 p

va p0 p v m C vm C p0
or
p
p
I s
va p0 p
p0

The BET isotherm, cont.

Plot of left side vs. p/p0 should give

straight line with slope s and intercept I

p
p
I s
va p0 p
p0

OT fig1.5

Reorganizing gives

vm

1
Is
and C
sI
I

Knowledge of S0 (specific area for a

volume of gas then allows the
calculation of the specific surface area
Sg:
v S

Sg

mp

where mp is the mass of the sample

BET contd

BET method useful, but has limitations

microporous materials: mono - multilayer adsorption cannot occur, (although BET surface
areas are reported routinely)
assumption about constant packing of N2 molecules not always correct?

theoretical development dubious (recent molecular simulation studies, statistical

mechanics) - value of C is indication o f the shape of the isotherm, but not necessarily
related to heat of adsorption

Simplified method

1-point method

simplefied BET assuming value of C 100 (usually the case), gives

p
1
C 1 p
p

'
va p0 p v m C v m C p0 v m p0
v 'm

va p0 p
p0

usually choose p/p0 0,15

method underestimates the surface area by approx. 5%.

Adsorbates

An adsorbate molecule covers an area , calculated assuming dense packing of the

molecules in the multilayer. The corresponding area per volume gas is S 0:

Gas

Temp.
[K]

[2/molecule]

S0
[m2/cm3 gas (STP)]

N2
Kr
Ar
H2O
C2H6
CO2

77,5
77,5
77,5
298
90
195

16,2
19,5
14,6
10,8
22,5
19,5

4,36
5,24
3,92
2,90
6,05
5,24

Porosity and pore size

The pore structure (porosity, pore diameter, pore shape) is important for the catalytic
properties
pore diffusion may influence rates
pores may be too small for large molecules to diffuse into

Measurement techniques:
Hg penetration
interpretation of the adsorption - desorption isotherms
electron microscopy techniques

Hg penetration

Based on measuring the volume of a non-wetting liquid forced into the pores by
pressure (typically mercury)
Surface tension will hinder the filling of the pores, at a given pressure an equilibrium
between the force due to pressure and the surface tension is established:

P r 2 2 r cos
where P = pressure of Hg, is surface tension and is the angle of wetting
Common values used:
= 480 dyn/cm and = 140 give average pore radius

75000

P[kp / cm 2 ]

valid in the range 50 - 50000

Pore size distribution

If the Hg-volume is recorded as a function of

pressure and this curve is differentiated we can find
the pore size distribution function
V(r)=dV/dr

OT fig 2.3.

The Kelvin equation

If adsorbent is mesoporous we get Type

IV isotherm
Deviation upwards is due to filling of
mesopores by capillary condensation curved liquid meniscus in narrow
_ pores
with radius rk:
2 V

rk

RT ln
p0

V is molar volume of the liquid, minus

sign introduced since in the actual range
of measurement 0 < p/p0 <1

The Kelvin equation

Since capillary condensation is preceeded by multilayer adsorption on the wall the value
is corrected with t, the thickness of this layer:
Cylindrical pores: rp = rk + t
Parallell sided slits: dp = rk + 2t

Value of t determined from measurements without capillary condensation

Practical experience, typical values give for circular pores:
rk

9,547
[ ]
p

ln
p0

Values for t have been found to be a function of rk, e.g. for rk > 20:

t 0,429 ln rk

2 , 61

Adsorption-desorption hysteresis
Hysteresis is classified by IUPAC (see fig.)
Traditionally desorption branch used for
calculation
H1: narrow distribution of mesopores
H2: complex pore structure, network
effects, analysis of desorption loop
misleading

Handbook
fig 2 s 431

H2: typical for activated carbons

H3 & 4: no plateau, hence no well-defined

mesopore structure, analysis difficult

H3: typical for clays