Lecture 3.

Adsorption (Part II)

3-4. Adsorption Isotherm

* Isotherm ns = f(P) at constant T

[Langmuir Isotherm]
- Ideal adsorption ~ Ideal gas law (PV = nRT)
- Chemisorption on perfectly smooth surface: one kind of adsorption site
- No interaction between adsorbates
- Heat of adsorption (ΔHads): constant

A. Unimolecular adsorption

M(g)

M(ads)

ⅹ ⅹ ⅹ ⅹ ⅹ

active site of adsorption, θ + θv = 1

At equilibrium. ra = rd

ka[M]Nθv = kdNθ (where N = total number of surface sites)

 k
= [M ] = K[M ]
a

1− k d

K[M ]
 =
1 + K[M ]

1
Equilibrium constant

k  exp(− E / RT ) E −E H
K= =
a a
= C exp( ) = C exp(
a
) d a ads

k  exp(− E / RT )
d d
RT d
RT

for unimolecular adsorption.

[M]

B. Dissociative adsorption

M2(g)

M(ads) M(ads)

ⅹ ⅹ ⅹ ⅹ

active site of adsorption. 1= θ + θv

M2 (g) + 2*  2M* ka, kd : rate constants for adsorption/desorption

At equilibrium
k [ M ] = k 
a 2 v
2

d
2

k [ M ](1 −  ) = k 
a 2
2

d
2

k  2
1 1 1

=   [M ] = K [M ] a 2 2 2

1−  k 
2 2

1 1

K [M ]
2 2

= 1
2
1

1 + K [M ]
2
2
2

2
 C. Competitive adsorption

1 =  + +
v A B

for A, k [ A](1 −  −  ) = k 
a
A

A B d
A

for B, k [ B ](1 −  −  ) = k 
a
B

A B d
B

A
K [ A] k
 = A
K = a

1 + K [ A] + K [ B]
A A A

A B
k d

B
K [ B] k
 = B
K = a

1 + K [ A] + K [ B]
B B B

A B
k d

3
4
5
3-5. Dependence of surface coverage () on temperature and pressure

Θ = K’P/(1+K’P) where K’ = K’(T)

At constant temperature,

 = K’P at low pressures

=1 at high pressures

The value of K’ is increased by

i) reduction in the system temperature

ii) increase in the strength of adsorption (heat of adsorption)

6
Determination of Enthalpies of Adsorption (Heat of Adsorption)

Step 1:
Obtain a number of
adsorption isotherms
corresponding to
given temperatures

Step 2:
A number of pairs of
values of pressure and
temperature which
yield the same surface
coverage

Step 3:
Clausius-Clapeyron
equation

7
3-6. Nonideal Isotherm

- Multilayer adsorption.

- Inhomogeneity of surface sites.

- Heat of adsorption = f(  )

K[M ] K ( )[ M ]
= =
1 + K [ M ] 1 + K ( )[ M ]
k E −E   H 
K= = C exp 
a
 = C exp  
d a ads

k d  RT   RT 

- Empirical models.

[Temkin isotherm]

H ( ) = H (1 −  )
ads 0

 = C ln P + C
1 2

C , C ;constants
1 2

[Freundlich Isotherm]

H =  ln  + 
ads
 ,  ;constants
 =CP 3
n
C , n ;constants
3

- Isosteric

d ln P H
P = f (T ) ⎯⎯⎯→ at cons tan t 
=− ads
2
dT RT