ChE 553 Lecture 6

Equilibrium Adsorption
1
Objective
Introduce Adsorption Isotherms
How much gas adsorbs at equilibrium as a
function of pressure
Qualitative features of isotherms
Types 1-5
More complex phase behavior
2
Topics
Introduction to Adsorption Isotherms
Five types
Langmuir Adsorption Isotherm
Simple Adsorption Isotherm
Finite number of surface spaces to hold
gas
More complex behavior: surface phase
transitions due to adsorbate/adsorbate
interactions
3
Introduction To Adsorption
Isotherms
Adsorption Isotherm
amount adsorbed
as a function of
pressure
4
S-shaped curve
typical at T>300K
Typical Behavior At Low
Temperature

5
Figure 4.2 Isotherms for adsorption of
krypton, argon at 77 K, argon at 91.3 K,
and ammonia on graphitized carbon black.
(Data of Putnam and Fart [1975], Ross and
Winkler [1955], Basset, Boucher, and
Zettlemoyer [1968], and Bomchil et al.
[1979], respectively.)
S-Shaped Curve At Low
Pressure

6
Figure 4.3 A blowup of the low-pressure part of the krypton data in Figure 4.2.
General Adsorption Isotherms
7
Figure 4.4 The five types of adsorption isotherms described by Brunauer [1945].
Next Langmuirs Model Of
Adsorption:

8
Figure 4.5 Langmuirs model of the structure of the adsorbed layer. The black dots
represent possible adsorption sites, while the white and mauve ovals represent adsorbed
molecules.
Key Features Of Langmuirs
Model
Finite sites to adsorb gas
Ideal behavior in surface phase (no
interactions between adsorbed molecules?
At low pressures coverages proportional to
pressure (or p
1/2
)
Eventually surface fills up
Adsorption limited by availability of sites
If multiple species competition for sites
Maximum coverage 1ML

9
Kinetic Derivation Of
Langmuirs Model
Assume equilibrium
10

(4.1)


(4.2)



(4.3)

ad
A S +
g
A
| | S P k r
A ad ad
=
| |
ad d d
A k r =
At equilibrium r
d
=r
ad
.
Solving



(4.4)

| |
| |
A
equ
d
ad
A
ad
K
k
k
S P
A
= =
Isotherm Arises From A Site
Balance
] [A [S] S
ad 0
+ =
(4.7)

equation (4.4) are 4.7 are two equations
in two unknowns ([S], [A
ad
]). Solving
yields

A
A
equ
A
A
equ
A
P K
P K
+
= u
1

(4.10)
11
Qualitative Features of
Langmuirs Model

12
0 10 20 30 40 50
Pressure
0
0.2
0.4
0.6
0.8
1
1.2
C
o
v
e
r
a
g
e
0.01 0.1 1 10 100
Pressure
0
0.2
0.4
0.6
0.8
1
1.2
C
o
v
e
r
a
g
e
Derivation Of Langmuir Isotherm For
Competitive Adsorption
13
| |
| |
| |
| |
B
equ
B
ad
A
equ
A
ad
K
S P
B
K
S P
A
= =
(4.22)

| | | | | | | |
ad ad
B A S S =
o

(4.23)
Solving Equations
Simultaneously

B
B
equ A
A
equ
A
A
equ
A
P K P K
P K
+ +
=
1
u

(4.24)

B
B
equ A
A
equ
B
B
equ
B
P K P K
P K
+ +
= u
1

(4.25)
14
Qualitative Picture

15
0 10 20 30 40 50
Pressure
0
0.2
0.4
0.6
0.8
1
1.2
C
o
v
e
r
a
g
e
0
0.1
1
5
10
0.01 0.1 1 10 100
Pressure
0
0.2
0.4
0.6
0.8
1
1.2
C
o
v
e
r
a
g
e
0
0.1
1
5
10
Derivation Of Langmuir Adsorption For
Dissociative Adsorption
1/2D
2
+ S

D
ad



| |
| |
D
equ
/
D
ad
K
S P
D
=
2 1
2

(4.26)

2 1
2
2 1
2
1
/
D
D
equ
/ D
equ
D
P K
P K
+
= u

(4.27)

16
Qualitatively the same
as non-dissociative
Comparison To Data

Figure 4.1 A plot of a series of adsorption isotherms for hydrogen adsorption on
Pt(111). Dotted lines are symbols: data. Solid Lines: fits to the Langmuir
adsorption isotherm. (Data of Ertl, Neuman, and Steit [1977].)
17
(4.27)

Rearranging



2 / 1
2
2 / 1
2
1
D
D
equ
D
equ
D
P K
P K
+
= u
1
1
1 1
2 / 1
2
+ =
P K
D
equ
D
u
Real Situation: Interactions
Between Molecules
Attractive interactions lead to islands
18
Repulsive Interactions Order
Overlayer Continued
19
Phase Diagrams For
Adsorption

Figure 4.13 A phase diagram for oxygen on W(110). (Adapted from one
presented by Lagally et al. [1980].)
20
Qualitative Behavior



Figure 4.21 A replot of the data from Figure 4.20 as a function of dimensionless
pressure.
21
Strength of
Attraction
1/RT
Universal Curve: Monolayer Adsorption: Only
Nearest Neighbor Interactions

Figure 4.23 A series of adsorption isotherms calculated via the lattice gas
method for adsorption on a square lattice with first nearest neighbor interactions.
Curves are shown for h = -0.50, -0.25, 0, , 2.0. 22
Equilibrium
constant at half
coverage
Complication: Multilayer
Adsorption
23
The BET Equation
Assume
Random distribution of sites with
1, 2, 3 adsorbed molecules
No lateral interactions between molecules





Does not work that well in practice
24
| |
( ) ( ) | |
B B B
B B
x c x
x c
S
A
1 1 1 + =
=
o


(4.189)
A Comparison Of The Krypton Data In Figure 4.12
To The Best Fit With The BET Equation
25
Comparison Continued










Figure 4.45 A blowup of the portion of the date in Figure 4.44 below 4 torr.
Used anyway
26
Why 5 Types Of Adsorption
Isotherms?
27
Type I
Type I arises when only
one type of site:
Initially surface fills
randomly
Eventually saturates when
surface filled (or pores filled
with a porous material)
28
Type III
Type III arises when there
are strong attractive
interactions leading to
condensation
Initially, no adsorption
Pressure increases lead to
nucleation and growth of
islands
Eventually liquids
condense on the surface
29
Type II
Type II arises when the is
more than one adsorption site
Initial rapid adsorption
Saturates when first site filled
Second rise when second site
fills
Second site could be a
second monolayer, a second
site on the surface. In porous
materials, it can also be a
second type of pore.
30
Type V
Type V is another case for
attractive interactions
Initially no adsorption
Next nucleation and growth
of islands or liquid drops
Coverage saturates when
no more space to hold
adsorbates
31
Type IV
Type V occurs when there
are multiple phase
transitions due to a
mixture of attractive and
repulsive interactions
Can also arise in
multilayer adsorption
where adsorption on
second layer starts before
first layer saturates
32
Summary
Introduction to Adsorption Isotherms
Five types
Langmuir Adsorption Isotherm
Simple Adsorption Isotherm
Finite number of surface spaces to hold gas
More complex behavior: surface phase transitions
due to adsorbate/adsorbate interactions
Attractive Interactions: Classical two phase regions i.e.
solids and gases
Repulsive interactions - adsorbate ordering
Leads to universality (general phase diagrams that do not
depend on gas and solid)
33