Lecture 3

CHO 203

Chemical Reaction Engineering

(CRE-II)
 Adsorption
• Adsorption is the first step of a heterogeneous chemical reaction process

• Chemical reactions catalysed by heterogeneous catalysts can be viewed as a

sequence of three elementary steps: adsorption, desorption and surface reaction

Reaction
2

3
Adsorption Desorption
Surface of Catalyst
Adsorption-Desorption Models
Langmuir Model

Langmuir Hinshelwood Model

Eley Rideal Model

 Langmuir Model
Assumptions

 The solid surface needs definite no. of sites for the adsorption of gases

 Each site can adsorb only one molecule

 All sites are energetically equivalents

 The adsorption is independent on the neighboring adsorbed specie

 At equilibrium, the rate of adsorption is equal to rate of desorption

 At equilibrium and for constant temperature and pressure, there are nA

moles adsorbed molecules on the surface

 The adsorption rate of a molecule A depends on the partial pressure pA

and of the number of free sites at a constant temperature and the
desorption rate on the number of occupied sites
Langmuir Model (Unimolecular Reaction)

rads = kapA ( 1-θA)

A

rdes = kdθA

At equilibrium, rads = rdes

𝒌𝒂𝒑𝑨
θA=
𝒌𝒅+𝒌𝒂𝒑𝑨

Two Cases:
𝑲𝑨𝒑𝑨
θA= (i) If 𝑲𝑨𝒑𝑨≈ 0
𝟏+𝑲𝑨𝒑𝑨
(ii)If 𝑲𝑨𝒑𝑨>> 0
 Symmetric Dissociative Adsorption
Consider the dissociation and adsorption of a molecule A2 on two sites *

A2 (g) + 2*(s) ↔ 2A* (ads)

Adsorption rate
rads = ka pA (1-θA)2

Desorption rate
rdes = kd θ2A

Langmuir equation of adsorption for dissociative molecules

 Adsorption of n-molecules
When the adsorption and desorption of different molecules occur
simultaneously, either reactants or products
Agas 1-θA-θB-θR
θA θB θR

𝐾𝑖 𝑝𝑖
𝜃𝑖 =
1 + 𝐾𝑖 𝑝𝑖

If A is dissociative:
𝐾𝐴 𝑝𝐴
𝜃𝐴 =
1 + 𝐾𝐴 𝑝𝐴 + 𝐾𝐵 𝑝𝐵 + 𝐾𝑅 𝑝𝑅
Langmuir Hinshelwood Model (Bimolecular Reaction)
A (g)  A (ads)
B (g)  B (ads)
A (ads)  B (ads) 
rds
AB (ads) 
fast
AB (g)
pA B
pB AB Rate = k q A q B
A
QB
QA

kKA p A K B p B
Rate 
1  K A p A  K B pB 2
Langmuir Hinshelwood Model (Bimolecular Reaction)

kKA p A K B p B
Rate 
1  K A p A  K B pB 2

Two cases:

(i) When both starting materials are weakly adsorbed

reff = k’ pA pB and k’ = k K A K B

→ Reaction is first order in both reactants and second overall

(ii) When A is weakly and B is strongly adsorbed, then rate equation

reduces to
reff = k’’pA/pB and k’’ = k KA/K B
→ Reaction order is one with respect to A and minus with respect to B
Langmuir Hinshelwood Model (Bimolecular Reaction)

rate
Rate limited by
surface concentration of A Rate limited by
surface concentration
of B

PA
Q B >> Q A
Q B << Q A
 Examples of L-H Mechanism

(i) Oxidation of CO on Pt catalysts

2CO + O2 → 2CO2
CO (g) → CO (ads)
O2 (g) → 2O (ads)
CO (ads) + O (ads) → CO 2 (ads) → CO2(g)

(ii) Methanol synthesis on ZnO catalysts

CO + 2H2 → CH3OH

(iii) Hydrogenation of ethylene on Cu catalysts

C2H4 + H2 → C2H6
 Eley-Rideal

Bimolecular Surface Reactions

A
AB
B

fast

An adsorbed molecule may react directly with an impinging

gas molecule by a collision mechanism
 Bimolecular Gas Phase Reaction

Examples:

(i) Reduction of CO2 with H2

CO2,G +H2*→ H2O + CO

(ii) Oxidation of ammonia on Pt catalysts

2NH3+3/2 O2* → N2 + 3H2O
 BET Model (Brunauer, Emmet and Teller)
Assumptions:

• Heat of adsorption of first monolayer is constant

• The lateral interaction of adsorbed molecules is negligible
• The adsorbed molecules can act as new adsorption surface and the
process can repeat itself
• The heat of adsorption of all monolayers but the first is equal to
the heat of condensation
𝑷𝑨 𝟏 𝑪 − 𝟏 𝑷𝑨
= +
𝑽 𝑷𝟎 − 𝑷𝑨 𝑪𝑽𝒎 𝑪𝑽𝒎 𝑷𝟎
Thank You