REACTION ENGINEERING II (CHE505)

TUTORIAL 1 (PART 2)

QUESTION 1

With the aid of sketch, briefly describe the steps involved in heterogeneous catalytic reaction.

(10 marks)

QUESTION 2

In Langmuir-Hinshelwood kinetics mechanism approach, the rate determining step, RDS is usually either
an adsorption step, a surface reaction step or a desorption step. As an engineer, briefly describe on how
you can eliminate the diffusion step in heterogeneous catalytic reaction, to narrow down the possibilities
of the RDS.

QUESTION 3 (DEC 2014)

A low-boiling solvent, methyl ethyl ketone (MEK) is used for nitrocellulose, acrylic, vinyl surface
coatings and also for polymerisation processing of polystyrene, acrylonitrile butadiene styrene (ABS) and
styrene-butadiene rubber (SBR).

Industrially, it can be produced from the dehydration of 2-Butanol (Bu) over a zinc oxide catalyst. The
reaction is carried out at 500°C in a differential reactor. The rate equation is Bu → MEK + H2 where the
reaction is dual site surface reaction and irreversible.

i) If desorption of H2 is dissociative, write the mechanism of reaction and the respective rates for each
steps. (8 marks)

ii) If surface reaction is the rate-controlling step and H2 is weakly adsorbed, prove that the overall rate is:
(8 marks)

𝑘𝑃𝐵𝑢
−𝑟𝐴′ =
[1 + 𝐾𝐵𝑢 𝑃𝐵𝑢 + 𝐾𝑀𝐸𝐾 𝑃𝑀𝐸𝐾 ]2
 REACTION ENGINEERING II (CHE505)

QUESTION 4 (JUNE 2015)

a) Explain with the aid of a sketch the definition of Eley-Rideal mechanisms for surface catalytic
reactions. (4 marks)

b) The formation of propanol from oxidation of propylene on a catalytic surface is believed to proceed
by the following mechanism:
O2(g) + 2S ↔ 2O·S

C3H6 (g) + O·S → C3H5OH·S

C3H5OH·S ↔ C3H5OH (g) + S

Identify these elementary steps and their respective rate laws. By assuming surface reaction is
limiting, develop the overall rate law for the reaction by applying pseudo-steady-state approximation
(PSSA). (12 marks)

QUESTION 5 (DEC 2015)

a) Dual site mechanism is a common surface reaction model in Langmuir-Hinshelwood kinetics.

Explain with the aid of sketches, the dual site surface reaction mechanism between an adsorbed
 REACTION ENGINEERING II (CHE505)

species and a vacant site. Write the corresponding surface reaction rate law. (6 marks)

b) Methanol can be made from a wide array of feedstocks, making it one of the most flexible
chemical commodities and energy sources available today. One of the most important industrial
reactions in the synthesis of methanol is through the reaction of carbon monoxide and hydrogen,
which can be represented by the following overall reaction:

CO + 2H2 ↔ CH3OH

The reaction follows Langmuir-Hinshelwood kinetics.

i) Propose an adsorption-surface reaction-desorption mechanism for the reaction. The

mechanism should indicate that carbon monoxide and hydrogen adsorb non-dissociatively,
followed by a reversible surface reaction among two adsorbed hydrogen molecules and an
adsorbed carbon monoxide molecule. (4 marks)
ii) By assuming that surface reaction is the rate controlling step and that the adsorption steps are
in equilibrium, derive the overall rate law for the reaction by applying PSSA. (10 marks)

QUESTION 6 (JUNE 2016)

Hydrogenation of propionaldehyde to propanol, [CH3CH2CHO (l) + H2 (g) → CH3CH2CH2OH (l)] often

takes place on a supported nickel catalyst. The reaction is said to be limited by the reversible
chemisorptions of propionaldehyde. It is also known that dihydrogen adsorbs dissociatively on the
nickel surface.

a) Propose a reasonable Langmuir-Hinshelwood kinetic mechanism that may well represent the
overall reaction. The mechanism should indicate that the surface reaction happens through two
steps, with the dissociatively adsorbed hydrogen atom reacts in each step. (5 marks)

b) Derive a rate expression for the overall reaction. (15 marks)

 REACTION ENGINEERING II (CHE505)

QUESTION 7 (TEST 1 SEPT 2016)

The synthesis of water from hydrogen and oxygen gasses (H2 + 0.5O2  H2O) is catalyzed by nickel
catalyst and happens on the surface of the metal catalyst. Both reactants respectively adsorbed
reversibly on the surface of the catalyst dissociatively. The surface reaction consists of two steps. The first
surface reaction step is the rate limiting step for the overall reaction, and is written as follows:

HS + OS  HOS + S

The second surface reaction step is a reversible dual site surface reaction mechanism. The product
produced (water) adsorbed very weakly on the surface active site once it is produced, that the
desorption required to remove it from the surface active site is negligible.

a) Propose the most reasonable Langmuir-Hinshelwood kinetic mechanism that may well represent
the overall reaction. (4 marks)
b) Derive a rate expression for the overall reaction. (12 marks)