Problems

1. The kinetics of benzene hydrogenation to cyclohexane over a Ni=SiO2 catalyst were studied
using a small fixed-bed reactor. The bed had 0.87 g of 0.22-mm catalyst particles diluted with
19.2 g of glass beads. Data for a bed temperature of 67.68C are given in Table 2.1. Investigate
how the competitive adsorption model for benzene and hydrogen compare with the data given
below. Assumption: The reaction of two hydrogen atoms with adsorbed benzene is rate limiting.

Table 1: Experimental data

PH2 PB FB XB 103 r mol/hr, g

1050 70 0.1034 3.2 3.81

2105 70 0.0498 7.47 4.27
2988 70 0.0337 11.6 4.50
2110 185 0.1038 4.53 5.40
2110 286 0.0156 3.41 6.12
2. The synthesis of methanol from carbon monoxide and hydrogen is an important industrial
reaction, as methanol is the feedstock for many other processes. The synthesis reaction may be
represented by the following overall reaction:

This reaction has been widely studied, and there is still a certain amount of controversy regarding
the mechanism. However, it is necessary to have an appropriate rate model to design reactors.
One proposed mechanism following LHHW principles is based on the molecular adsorption of
carbon monoxide and hydrogen, followed by a surface reaction among two adsorbed hydrogen
molecules and an adsorbed carbon monoxide molecule. Derive the LHHW-type rate equation for
this proposed mechanism, assuming that the surface reaction is the rate-determining step and that
the adsorption steps are in equilibrium.
3. The oxidation of SO2 on platinum is believed to occur according to the following steps;

When surface reaction is rate-controlling show that the kinetics can be expressed as below: [15]

c) What will be the effect of increasing oxygen partial pressure infinity? [5]

4. a) Langmuir-Hinshelwood kinetics is used to come up with reaction rates for adsorbing

species on solid surfaces. With the aid of a schematic diagram explain an isomerization or
decomposition reaction that requires dual sites. [4]
b) Furusaki (1973) studied the kinetics of the following Deacon process for the production of
chlorine

The rate of disappearance could be correlated to the following expression:

 * ( ) +

[ ]
c) Postulate a series of elementary steps and show that they yield this rate expression. [15]

b) With the aid of a diagram illustrate, what will be the effect of increasing hydrochloric acid
concentration infinity? [6]

6 a) Propose a rate law based on the Langmuir-Hinshelwood model for synthesis of methanol
over a Cu-ZnO-CrzOa catalyst, the rate-controlling process appears to be a termolecular reaction
in the adsorbed phase:

Consider a case were the product is weakly absorbed. [10 marks]