Problems 1.

1. The oxidation of SO2 on platinum is believed to occur according to the following steps;

O2 +2 S ↔ 2 O. S

S O2+ O. S → SO3 . S

SO 3 . S ↔ S O3 +S

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

0.5 0.5
k K A (O) (S O 2)
r= 0.5 O .5
k=k s C T
1+ K A (O) + K C (S O3 )

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:
CO+ 2 H 2 ↔CH 3 OH

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. Consider the methanation of synthesis gas, represented by the overall reaction:

3 H 2 +CO ↔ CH 4 + H 2 O
A proposed LHHW-type mechanism is shown below.
CO+ 2 S ↔ C . S +O . S
 H 2+2 S ↔ 2 H . S
C . S+3 H . S ↔ CH 3 . S +¿3S
CH 3 . S+ H· S ↔ CH 4 +2 S
2 H . S+O . S ↔ H 2 O+3 S
Derive a rate expression for the disappearance of CO if step (3) is the rate-determining step.

Source: Introduction to Chemical Reactor Analysis, Second Edition

4. The rate law for the hydrogenation (H) of ethylene (E) to form ethane over cobalt-
molybdenum catalys is given by;
k PE P H
−r ' E=
1+ K E P E
a) Suggest a mechanism and the rate-limiting step consistent with the rate law

7. To remove oxides of nitrogen (assumed to be NO) from automobile exhaust, a scheme has
been proposed that uses not completely burn carbon, carbon monoxide, according to the reaction
CO+ NO → Products ( N 2 ,CO 2 )
Experimental data for a particular solid catalyst indicate that the reaction rate can be represented
by;
' k P N PC
−r N = 2
(1+ K 1 PN + K 2 PC )
Where PN = gas-phase partial pressure of NO
PC = gas-phase partial pressure CO
k,K1, K2 = Coefficients depending only on temperature
(a)Proposed an adsorption-surface reaction-desorption mechanism that will explain the
experimentally observed kinetics
(b) A certain engineer thinks that it would be desirable to operate with very large stoichiometric
excess of CO to minimize reactor volume. Do you agree or disagree? Explain
Assignment 1

1. Furusaki (1973) studied the kinetics of the following Deacon process for the production of
chlorine

1 1 1
HCI + O2 ↔ C I 2+ H 2 O
4 2 2

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

r=
[
k C HCI CO 0.25−
2 ( K1 ) C CI 2
0.5
CH
❑
2O
0.5
]
[ 1+ K 1 C HCI + K 2 C CI ] 2

Postulate a series of elementary steps that will yield this rate expression. [20]
Problems 1.2

1. The double bond isomerization of 1-hexene to form 2-hexene was studied in a laboratory
reactor containing rhodium particles supported on alumina at 150°C and atmospheric pressure:

The reaction was found to be first order in I-hexene with a rate constant of 0.14 s-1. Find the
largest pellet size that can be used in an industrial reactor to achieve 70 percent of the maximum
rate. The pore radius of the alumina is 10 nm, and DAB is 0.050 cm2 s-1.

2. In the absence of pore diffusion resistance a particular first-order gas phase reaction proceeds
as reported below.

''' −6 3
r =10 mol /cm cat . s

at: CA = 10-6 mol/cm3, at 1 atm and 400°C

What size of spherical catalyst pellets (De = 10-3cm3/cm cat as) would ensure that pore resistance
effects do not intrude to slow the rate of reaction?

3. The reaction A →B + C was studied in a differential reactor using 1/4" spherical catalyst
pellets. At 150°C and 1.2 atm, the reaction rate was 7.6 ×10-3 mol/hr.g with 10% A and 90% N2
and 14 × 10-3mol/hr.g with 20% A and 80% N2 in the feed. The estimated diffusivity of A is
De=0:0085 cm2/sec, and the pellet density is 1.4 g/cm3. Did pore diffusion influence the rate?

4. A reaction A + R is to take place on a porous catalyst pellet (d, = 6 mm, De = 10-6m3/m cat. s).
How much is the rate slowed by pore diffusional resistance if the concentration of reactant
bathing the particle is 100 mol/m3 and the diffusion-free kinetics are given by
 2 mol
−r A =0.1 C A 3 Selective catalytic reduction (SCR) of NOx is an important, effective
m cat . s
process for reducing NO, emissions from electric power plants. Wong and Nobe (1984) have
reported first-order reaction kinetics, i.e. rp= k C NO for a 5% V205/Ti02 catalyst. Nackos et al.
(2004) have observed a first-order rate constant of 0.566 cm3/gcat-s at 226°C (499 K) and an
activation energy of 109 kJ/mole for a commercially representative 1 % V205/9% W03/Ti02
catalyst.

Calculate the effectiveness factor and reaction rate at the inlet to a commercial SCR unit
containing an extruded cellular monolith consisting of 1% V 205/9% WO3/TiO2 with a channel
wall thickness of 1.35 mm and open frontal area of 64% under typical commercial operating inlet
conditions of 400 ppm NO, 35OoC, and 1 atm. Assume catalyst in the square monolith walls can
be treated as a flat plate. Additional
data: ρp= I .48; De = 0.070 cm2/s, Vp/Sp= T/2 t-thickness. Also, assume film mass transfer
resistance is negligible.
The rate of isomerization of n-butane with a silica-alumina catalyst is measured at 5 atm and
50°C in a laboratory reactor with high turbulence in the gas phase surrounding the catalyst
pellets. Turbulence ensures that external-diffusion resistances are negligible, and so Cs = Cb
Kinetic studies indicate that the rate is first order and reversible. At 50°C the equilibrium
conversion is 85%. The effective diffusivity is 0.08 cm 2 /sec at reaction conditions, and the
density of the catalyst pellets is 1.0 g/cm3 regardless of size. The measured, global rates when
pure n-butane surrounds the pellets are as follows:

The first-order, irreversihle reaction (A → B) takes place in a 0.3 cm radius spherical catalyst
pellet at T = 450 K. At 0.7 atm partial pressure of A, the pellet's production rate is -2.5 x 1 0 -5
mol/(g s). Determine the production rate at the same temperature in a 0.15 cm radius spherical
pellet. The pellet density is ρp = 0.85 g/cm3. The effective diffusivity of A in the pellet is D A =
0.007 cm2/s.

A catalytic reaction that is first order in the concentration of A

A→B
is carried out in a spherical pellet with a 0.20-cm radius. The effective diffusivity of A in the
pellet is 0.015cm2/s. The rate of reaction at 398 K is 2.63 X 10 -5 mol/cm3·s when the
concentration of A is 3.25 X 10-5 mo1/cm3. The intrinsic activation energy is 20 kcal/mol.
(a) Assuming DA is independent of temperature, what is the rate at 448 K for the same
concentration of A?

4. The first-order reaction

was carried out over two different-sized pellets. The pellets were contained in a spinning basket
reactor that was operated at sufficiently high rotation speeds that external mass transfer
resistance was negligible. The results of two experimental runs made under identical conditions
are as given in Table below.
(a) Estimate the Thiele modulus and effectiveness factor for each pellet.
(b) How small should the pellets be made to virtually eliminate all internal diffusion resistance?

The rate constant for the first-order cracking of cumene on a silica-alumina catalyst was
measured to be 0.80 cm3/(s.gcat) in a laboratory reactor:

a) Is the observed rate constant the true rate constant or is there influence of pore diffusion?
b) Determine particle size which will eliminate influence of pore diffusion resistance
Additional data:
Rp = 0.25 cm
ρp =1.2gcat/cm3
DeTA = 1.0 X 10-3 cm2 S-1

Solution
Problems 1.3

1. A first-order isothermal reaction occurs in a bed of 3 mm diameter spherical catalyst pellets.

The first-order rate constant is 0.3 s−1. The effective diffusivity in the catalyst pellets is 3 × 10 −7
m2/s. The reactor length is 2 m. It is desired to replace the 3 mm diameter particles with 6 mm
diameter particles. Calculate the length of the reactor required to maintain the same conversion
as before. Assume that the bulk densities of the two beds are the same.
2. The following kinetic data on the reaction A → R are obtained in an experimental packed bed
reactor using various amounts of catalyst and a fixed feed rate FA = 10 kmol/hr.

W,kg cat 1 2 3 4 5 6 7
XA 0.12 0.20 0.27 0.33 0.37 0.41 0.44

(a) Find the reaction rate at 40% conversion.

(b) In designing a large packed bed reactor with feed rate FA = 400 kmol/hr how much catalyst
would be needed for 40% conversion.

3. We want to build a packed bed reactor filled with 1.2-cm porous catalyst particles (ρs =
2000kg/m3, De = 2 x 10-6m3/m cat. s) to treat 1 m3/s of feed gas (1/3 A, 1/3 B, 1/3 inert) at 336°C
and 1 atm to 80% conversion of A. Experiments with fine catalyst particles which are free from
diffusional resistance show that
6
' 0.01m
A+ B → R+ S n=2 , k =
mol . kg . s

How much catalyst must we use?

Problems 1.4

1) A batch of solids of uniform size is treated by gas in a uniform environment. Solid is

converted to give a nonflaking product according to the shrinking-core model. Conversion is
about 7/8 for a reaction time of 1 h, conversion is complete in two hours. What mechanism is
rate controlling?

2) Two small samples of solid are introduced into a constant environment oven and kept there for
one hour. Under these conditions the 4mm particles are 58% converted, the 2 mmm particles are
87.5 % converted.

a) Find the rate controlling mechanism for the conversion of solid.

b) Find the time needed for complete conversion of 1 mm particles in this oven.