CH-5010: Chemical Reactor Theory

July – Nov. 2023

Assignment – 2a
Suggested Due Date: Monday, 28th August 2023
• Please start each new problem on a fresh page
• Please submit a hard copy in class
• You may choose to submit both Assignment – 2a and 2b together on 4th September

Problem 1: Gas-Phase Decomposition Reaction

Problem 2: Ping-Pong Bi-Bi Mechanism (Davis & Davis, Problem 4.5)

CH-5010: Chemical Reactor Theory

 CH-5010: Chemical Reactor Theory
July – Nov. 2023
Assignment – 2b
Due Date: Monday, 4th September 2023

Problem 3: Mechanism of Catalytic Dehydrogenation

Part-1: Derivation of Reaction Rate (Davis and Davis, Prob. 5.3)

Part-2: Test your Understanding (Davis and Davis, Prob. 5.4)

Franckaerts and Froment (Chem. Eng. Sci., 19 (1964) 807) analyzed the same reaction over
CuO/CoO/Cr2O3 catalyst and instead obtained the following rate expression:

What is different in the reaction sequence / assumptions compared to that used in Part-3.1?

Problem 4: Reaction Mechanism (Adapted from Fogler and Davis & Davis)
Chlorination of ethylene (E) to ethyl chloride (C) takes place over a metal-oxide catalyst.
Various mechanisms may be postulated for this reaction. These include Langmuir-Hinshelwood type
as well as Elay-Rideal type mechanisms. Derive the rate expressions for the following mechanisms
proposed for this process. The reaction in bold represents the rate limiting step. Let !! represent
equilibrium constant for adsorption of ", !"# be for desorption of T and !$% be for the surface
reaction. All the steps are elementary.
Mechanism (a) Mechanism (b) Mechanism (c) Mechanism (d)
# + ∗ ⇌ #∗ E + ∗ ⇌ E∗ E + ∗ ⇌ E∗ E + ∗ ⇌ E∗
HCl + ∗ ⇌ HCl∗ HCl + ∗ ⇌ HCl∗ HCl + 2 ∗ ⇌ H∗ + Cl∗ #∗ + ,-. ⇌ -∗
E∗ + HCl∗ ⇌ C∗ +∗ #∗ + ,-.∗ ⇌ -∗ +∗ #∗ + -.∗ ⇌ #-.∗ +∗ C∗ ⇌ C + ∗
C∗ ⇌ C + ∗ C∗ ⇌ C + ∗ ECl∗ + H∗ ⇌ C∗ +∗
C∗ ⇌ C + ∗
Write down the net reaction rate expressions for each of these mechanisms.

CH-5010: Chemical Reactor Theory

 CH-5010: Chemical Reactor Theory
July – Nov. 2023
Problem 5: Dual-Site Mechanism
Let us consider a case where the chlorination of Problem 4 takes place on two different active
sites. Let us represent * as a metal-oxide site and # as a basic site. Ethylene adsorbs on * as before:
E + ∗ ⇌ E∗
However, HCl adsorbs on the # site in this mechanism:
HCl + # ⇌ HCl#
The following step is rate-limiting (Note: this step is actually a simplification for this Problem):
#∗ + ,-.# ⇌ -∗ + #
Finally, chloroethane desorbs as:
C∗ ⇌ C + ∗
Please derive the overall rate expression for this dual-site mechanism.

CH-5010: Chemical Reactor Theory