Kinetics of Catalytic Reactions: (Ch.5 Adsorption and Desorption Process)

Kinetics of Catalytic Reactions
(Ch.5 Adsorption and desorption process)
M. Albert Vannice
Springer Science & Business Media, Inc., 2005
Vu Ngoc Duy, Cao The Ha – Sep. 2014 – Oct. 2017
CONTENTS
5. Adsorption and Desorption Processes . . . . . . . . . . . . . 87

5.1 Adsorption Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.2 Desorption Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
5.3 Ads. Equilibrium on Uniform (Ideal) Surfaces-Langmuir Isotherms 91
5.3.1 Single-Site (Nondissociative) Adsorption . . . . . . . . . . . . 92
5.3.2 Dual-Site (Dissociative) Adsorption . . . . . . . . . . . . . . . . 92
5.3.3 Derivation of the Langmuir Isotherm by Other Approaches. . . . . . . . 95
5.3.4 Competitive Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . 97
5.4 Adsorption Equilibrium on Nonuniform (Nonideal) Surfaces . . 98
5.4.1 The Freundlich Isotherm. . . . . . . . . . . . . . . . . . . . . . . . . . 98
5.4.2 The Temkin Isotherm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
5.5 Activated Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
2
5.1 Adsorption rate
1/ 2
 8k T 
Kinetic theory of gases: v B 
 m 
Mean molecular velocity:
vC
Rate of collision between gas molecule and unit surface area: rcol  (5.1)
Where C is concentration of molecules: C = P/kBT 4
P
rcol 
→
2mkBT 1/ 2 (5.2)
Not all collisions result in chemisorption due to:

- Activation energy
- Steric factor
- Energy transfer efficiency
- Surface heterogeneity
- Occupied sites
→ sticking probability: s << 1
P
Adsorption rate: rcol  s (5.3)
2mkBT 1/ 2
3
5.1 Adsorption rate
Lennard – Jones expression for potential energy: Epot =-ar-6 + br-12 (5.4)
r: distance from surface
a b: constant
-ar-6: van der Waals interactions + London dispersive forces
br-12 : repulsive forces
Figure 5.1 a: nonactivated dissociation

Figure 5.1 b: activated dissociation (Ead)
4
5.1 Adsorption rate
Sticking probability (for activ. ads.):
s   f ( )e Ead / RT (5.5)
 = Steric factor
f ( ) Probability of collision with an empty site

 = Fractional surface coverage
rad   f  e  Ead / RT P / 2mkBT 

1/ 2
(5.6)
rad   f  e  Ead   / RT P / 2mkBT 

1/ 2
(5.7)
If activation energy and steric factor vary with θ
5
5.2 Desorption rate
- Desorption is always activated
- Mininum Edes = Qad =-∆Had
rdes  k des f '  e  Edes / RT (5.8)
kdes: rate constant

f’(θ): fraction of covered sites
If kdes, Edes vary with θ

rdes  k des   f '  e  Edes / RT (5.9)
For simple unimolecular desorption step:

Kdes~L ([L] = act. sites/unit of surface = m2, cm2)
 = vibrational frequency
f’(θ) = θ
rdes   L e Edes / RT (5.10)
6
5.3 Adsorption equilibrium on uniform (ideal)
surface: Langmuir isotherms
Assumptions associated with an ideal unifrom surface:
1. Adsorption on vacant sites

2. One adsorbed species per site → monolayer
3. Heat of adsorption is constant and independent of coverage, no interaction between
adsorbed species
At equilibrium, rates of adsorption and desorption are equal
From (5.6) and (5.8) :
K: depends only on temperature
Different equations for f(θ), f’(θ) → different models
7
5.3 Adsorption equilibrium on uniform (ideal) surface: Langmuir isotherms
5.3.1 Single site (nondissociative) adsorption
For both mobile and immobile adsorption: (5.14)
(5.15)
Substitution in to (5.12): (5.16)
The Langmuir isotherm relates coverage to pressure:

𝑛 𝐾𝑃 𝐾′ 𝐴
𝜃 = 𝑛 = 1+𝐾𝑃 = 1+𝐾′ 𝐴 (5.17)
𝑚
n: adsorbate up take (mole g-1) at pressure P

nm: maxium uptake
[A]: concentration of ideal gas
Surface concentration of adsorbed species:

8
[A] = CA,s = Lθ (5.18)
5.3 Adsorption equilibrium on uniform (ideal) surface: Langmuir isotherms
5.3.2 Dual-site (dissociative) adsorption

For mobile adsorption: (5.19)
(5.20)
Substitution in to (5.12): (5.21)
𝐾1/2 𝑃1/2
or 𝜃= (5.22)
1+𝐾1/2 𝑃1/2
For immobile adsorbed species: (5.23)

(dissociated molecules)
(5.24)
Z: nearest neighbor sites
(5.25)
(5.26) 9
One straightforward way to test
isotherms is to linearize them:
Single site model:
(5.27)
Dual-site model:
(5.28)
10
5.3.3 Derivation of the Langmuir Isotherm by different approaches
Nondissociative chemisorption:
, A: absorbing gas-phase molecule, *: site
(5.29), CA*, CV: surface concentration of adsorbed species and vacant sites
CA* = LθA, CV = LθV
11
5.3.3 Derivation of the Langmuir Isotherm by other approaches
Dissociative adsorption:
, A: absorbing gas-phase molecule, *: site
(5.35)
CA*, CV: surface concentration of adsorbed species and vacant sites
CA* = LθA, CV = LθV
→ (5.36)
(5.37)
K can be calculated by:
(5.38)
∆G0ad, ∆H0ad, ∆S0ad: the changes in standard Gibbs free energy, enthalpy, entropy.
12
5.3.4 Competitive Adsorption: Adsorbates A and B
Nondissociative adsorption:
Total site concentration: (5.45)

or (5.46)
(5.48)
(5.49)
→ (5.50)
(5.51)
In general for nondissociative adsorption:

(5.52)
Vacancy: (5.53)
Dissociative adsorption:
(5.54)
(5.55)
Next = Other approach (file WORD) 13
5.4. Adsorption Equilibrium on nonuniform (nonideal) surfaces
5.4.1 Freundlich Isotherm

(see textbook)
5.4.2 Temkin Isotherm

(see textbook)
Linearization to determine the best isotherms fits experimental data:
(5.71)
(5.72)
14
5.5 Activated adsorption
The rate of absorption: (5.75) Elovich equation
q: absorbed amount (mole/unit surface area); a,b: constants
For simplicity: f(θ) = (1- θ), Ead = E0 + αθ (5.76)

1/ 2
Insert in (5.6)
→ (5.77)
Neglect variation of σ, 1-θ → (5.78)
Take integration to give: t0 = RT/αkad, (5.79)

1/ 2 15
(5.6)
5.5 Activated adsorption
Ritchie’s approach: simply assume that more than 1 site is required in the adsorption process
(5.80)
kad is rate constant, n is the number of sites occupied by each adsorbate
n=1→ (5.81)
(5.82)
Nad, : the amount adsorbed at time t and infinite.
n > 1: (5.83)
n = 2: (5.84)
16

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Kinetics of Catalytic Reactions

(Ch.5 Adsorption and desorption process)

5. Adsorption and Desorption Processes . . . . . . . . . . . . . 87

Not all collisions result in chemisorption due to:

Figure 5.1 a: nonactivated dissociation

f ( ) Probability of collision with an empty site

rad   f  e  Ead / RT P / 2mkBT 

rad   f  e  Ead   / RT P / 2mkBT 

rdes  k des f '  e  Edes / RT (5.8)

kdes: rate constant

If kdes, Edes vary with θ

For simple unimolecular desorption step:

1. Adsorption on vacant sites

At equilibrium, rates of adsorption and desorption are equal

From (5.6) and (5.8) :

K: depends only on temperature

Different equations for f(θ), f’(θ) → different models

5.3.1 Single site (nondissociative) adsorption

For both mobile and immobile adsorption: (5.14)

Substitution in to (5.12): (5.16)

The Langmuir isotherm relates coverage to pressure:

n: adsorbate up take (mole g-1) at pressure P

Surface concentration of adsorbed species:

5.3.2 Dual-site (dissociative) adsorption

Substitution in to (5.12): (5.21)

For immobile adsorbed species: (5.23)

Z: nearest neighbor sites

Single site model:

, A: absorbing gas-phase molecule, *: site

, A: absorbing gas-phase molecule, *: site

K can be calculated by:

Total site concentration: (5.45)

In general for nondissociative adsorption:

5.4.1 Freundlich Isotherm

5.4.2 Temkin Isotherm

Linearization to determine the best isotherms fits experimental data:

The rate of absorption: (5.75) Elovich equation

q: absorbed amount (mole/unit surface area); a,b: constants

For simplicity: f(θ) = (1- θ), Ead = E0 + αθ (5.76)

rad   f  e  Ead / RT P / 2mkBT 

Neglect variation of σ, 1-θ → (5.78)

Take integration to give: t0 = RT/αkad, (5.79)

rad   f  e  Ead / RT P / 2mkBT 

kad is rate constant, n is the number of sites occupied by each adsorbate

Nad, : the amount adsorbed at time t and infinite.

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