QUIZ CE203

Catalytic Reactions
Lucas Montogue and Thierry Deschamps

A PROBLEMS
[ Problem 1 (Levenspiel, 1999, w/ permission)
Kinetic experiments on the solid catalyzed reaction 𝐴𝐴 → 3𝑅𝑅 are conducted
at 8 atm and 700oC in a basket type mixed reactor 960 cm³ in volume and
containing 1 g of catalyst of diameter 𝑑𝑑𝑝𝑝 = 3 mm. Feed consisting of pure A is
introduced at various rates into the reactor and the partial pressure of A in the exit
stream is measured for each rate. The results are summarized below. Find a rate
equation to represent the rate of reaction on catalyst of this size.

Feed rate (L/hr) 100 22 4 1 0.6

𝒑𝒑𝑨𝑨,𝐨𝐨𝐨𝐨𝐨𝐨⁄𝒑𝒑𝑨𝑨,𝐢𝐢𝐢𝐢 0.8 0.5 0.2 0.1 0.05

g Problem 2.1 (Levenspiel, 1999, w/ permission)

The following kinetic data on the reaction 𝐴𝐴 → 𝑅𝑅 are obtained in an
experimental packed bed reactor using various amounts of catalyst and a fixed feed
rate 𝐹𝐹𝐴𝐴,0 = 10 kmol/hr. Find the reaction rate at 40% conversion.

𝑾𝑾 (kg catalyst) 1 2 3 4 5 6 7
𝑿𝑿𝑨𝑨 0.12 0.20 0.27 0.33 0.37 0.41 0.44
A) −𝑟𝑟𝐴𝐴 = 0.11 kmol converted/kg cat∙hr
B) −𝑟𝑟𝐴𝐴 = 0.23 kmol converted/kg cat∙hr
C) −𝑟𝑟𝐴𝐴 = 0.36 kmol converted/kg cat∙hr
D) −𝑟𝑟𝐴𝐴 = 0.45 kmol converted/kg cat∙hr

g Problem 2.2
In designing a large packed bed reactor with a feed rate 𝐹𝐹𝐴𝐴,0 = 400 kmol/hr,
how much catalyst would be needed for 40% conversion?
A) 𝑊𝑊 = 103 kg catalyst
B) 𝑊𝑊 = 226 kg catalyst
C) 𝑊𝑊 = 310 kg catalyst
D) 𝑊𝑊 = 444 kg catalyst
g Problem 2.3
How much catalyst would be needed in the previous part if the reactor
employed a very large recycle of product stream?
A) 𝑊𝑊 = 103 kg catalyst
B) 𝑊𝑊 = 226 kg catalyst
C) 𝑊𝑊 = 310 kg catalyst
D) 𝑊𝑊 = 444 kg catalyst

g Problem 3.1 (Levenspiel, 1999, w/ permission)

Determine how much catalyst is needed in a packed bed reactor for 80%
conversion at 1000 m³/hr of pure gaseous A (𝐶𝐶𝐴𝐴,0 = 100 mol/m³) if the
stoichiometry and rate are given by

50C A mol
A → R ; − rA′ =
1 + 0.02C A kg ⋅ hr

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A) 𝑊𝑊 = 64.2 kg catalyst
B) 𝑊𝑊 = 93.1 kg catalyst
C) 𝑊𝑊 = 122 kg catalyst
D) 𝑊𝑊 = 151 kg catalyst

g Problem 3.2
How much catalyst is needed in a packed bed reactor for 80% conversion of
1000 m³/hr of pure gaseous A (𝐶𝐶𝐴𝐴,0 = 100 mol/m³) if the stoichiometry and rate are
given by

mol
A → R ; − rA′ =
8C A2
kg ⋅ hr
A) 𝑊𝑊 = 5.0 kg catalyst
B) 𝑊𝑊 = 8.61 kg catalyst
C) 𝑊𝑊 = 12.4 kg catalyst
D) 𝑊𝑊 = 16.6 kg catalyst

[ Problem 4 (Hill & Root, 2014, w/ permission)

The cumene (isopropyl benzene, MW = 120) cracking reaction is often used
as a model reaction for determining the relative activities of cracking catalysts.

This reaction takes place on silica-alumina catalysts in the temperature

range 300 to 600oC. There is negligible production of by-products in the reaction.
Suppose we wish to calculate the effective diffusivity of cumene in a mixture of
benzene and cumene at 1 atm total pressure and 500oC within the pores of a
typical TCC (Thermofor catalytic cracking) catalyst bead. The following properties
are associated with the TCC beads.

Surface Area (𝑆𝑆𝑔𝑔 ) 336 m²/g

Porosity (𝑛𝑛𝑝𝑝 ) 0.45
Equivalent Particle Diameter (𝑑𝑑𝑝𝑝 ) 0.39 cm
Density of an individual particle (𝜌𝜌𝑝𝑝 ) 1.18 g/cm³

A narrow pore size distribution and a tortuosity factor of 3 may be

assumed. The ordinary molecular diffusivity may be taken as 𝐷𝐷𝐴𝐴𝐴𝐴 ≈ 0.11 cm²/s.
What is the effective diffusivity for this situation?
A) 𝐷𝐷eff = 2.31×10-4 cm²/s
B) 𝐷𝐷eff = 7.98×10-4 cm²/s
C) 𝐷𝐷eff = 3.11×10-3 cm²/s
D) 𝐷𝐷eff = 7.71×10-3 cm²/s

[ Problem 5
For a first-order reaction in a porous spherical catalyst pellet, diffusional
effects are most likely to lower the observed rate of reaction for
A) a slow reaction and small catalyst pellets.
B) a slow reaction and large catalyst pellets.
C) a fast reaction and small catalyst pellets.
D) a fast reaction and large catalyst pellets.

[ Problem 6 (Nptel)
Two experiments involving a first-order reaction 𝐴𝐴 → 𝐵𝐵 were carried out
and the following data were obtained. With the exception of measured rate and
catalyst particle radius, all conditions were equal in both experiments. Assuming
negligible external mass transfer resistance, estimate the effectiveness factor for
each pellet.

Measured rate (mol/g∙cat∙s) × 105 Pellet radius (m)

Run 1 4.0 0.02
Run 2 16.0 0.002

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A) 𝜂𝜂1 = 0.229 and 𝜂𝜂2 = 0.636
B) 𝜂𝜂1 = 0.229 and 𝜂𝜂2 = 0.916
C) 𝜂𝜂1 = 0.444 and 𝜂𝜂2 = 0.636
D) 𝜂𝜂1 = 0.444 and 𝜂𝜂2 = 0.916

[ Problem 7 (Schmal, 2014, w/ permission)

The reaction

( CH3 ) C=CH 2 + H 2O → ( CH3 )3 COH

with excess of water is done in a fixed-bed reactor, using a spherical catalyst with
radius 0.24 cm and density of 1.82 g/cm³. The reaction is carried out at 100oC and
1 atm, it is reversible and the final conversion is 80% of equilibrium conversion. The
equilibrium constant at 100oC corresponds to 16.6. The reaction takes place
isothermally, the reaction rate is 1.12×10-5 mol/s∙g cat, and the external
concentration of the limiting reactant is equal to 1.54×10-5 mol/cm³. The mean
effective diffusivity is 2.1×10-2 cm²/s. Determine the effectiveness factor.
A) 𝜂𝜂 = 0.117
B) 𝜂𝜂 = 0.351
C) 𝜂𝜂 = 0.675
D) 𝜂𝜂 = 0.844

[ Problem 8 (Schmal, 2014, w/ permission)

A commercial cumene (MW = 120) cracking catalyst is in the form of pellets
with a diameter of 0.35 cm which have a surface area 𝐴𝐴𝑚𝑚 of 420 m²/g and a void
volume 𝑉𝑉𝑚𝑚 of 0.42 cm³/g. The pellet density is 1.14 g/cm³. The measured 1st-order
rate constant for this reaction at 685 K was 1.49 cm³s-1g-1. Assume that Knudsen
diffusion dominates and the path length is determined by the pore diameter 𝑑𝑑𝑃𝑃 . An
average pore radius can be estimated from the relationship 𝑟𝑟̅𝑝𝑝 = 2𝑉𝑉𝑚𝑚 /𝐴𝐴𝑚𝑚 . If the
pores are modeled as noninterconnected cylinders, determine the effectiveness
factor 𝜂𝜂 under these conditions.
A) 𝜂𝜂 = 0.181
B) 𝜂𝜂 = 0.497
C) 𝜂𝜂 = 0.736
D) 𝜂𝜂 = 0.911
g Problem 9.1 (Nptel)
A first-order heterogeneous irreversible reaction is taking place within a
spherical catalyst pellet plated with platinum. The reactant concentration halfway
between the external surface and the center of the pellet (i.e., at 𝑟𝑟 = 𝑅𝑅/2) is equal to
one-tenth the concentration of the pellet’s external surface. The concentration at
the external surface is 0.001 g∙mol/dm³, the diameter (2𝑅𝑅𝑝𝑝 ) is 2×10-3 cm, and the
diffusion coefficient is 0.1 cm²/s. Find the concentration of reactant at a distance of
3.5×10-4 cm from the external pellet surface.
A) 𝐶𝐶𝐴𝐴 = 1.88×10-5 mol/dm³
B) 𝐶𝐶𝐴𝐴 = 6.14×10-5 mol/dm³
C) 𝐶𝐶𝐴𝐴 = 1.88×10-4 mol/dm³
D) 𝐶𝐶𝐴𝐴 = 6.14×10-4 mol/dm³
g Problem 9.2
To what diameter should the pellet be reduced if the effectiveness factor is
to be 0.75?
A) 𝑑𝑑𝑝𝑝 = 8.0×10-5 cm
B) 𝑑𝑑𝑝𝑝 = 3.2×10-4 cm
C) 𝑑𝑑𝑝𝑝 = 8.0×10-4 cm
D) 𝑑𝑑𝑝𝑝 = 1.4×10-3 cm

[ Problem 10 (Vannice, 2005, w/ permission)

A 1.0% Pd/SiO2 catalyst for SO2 oxidation is being studied using a
stoichiometric O2/SO2 feed ratio at a total pressure of 2 atm. At a temperature of
673 K, a rate of 2.0 mole SO2 s-1 L cat-1 occurs. The average velocity for SO2
molecules is 3×104 cm/s, and the average pore diameter in the alumina is 120 Å.
Assume the Pd is uniformly distributed throughout the catalyst particles. What is
the largest particle diameter one can use in the reactor and still be assured that
there are no significant diffusional effects?

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A) 𝑑𝑑𝑝𝑝 = 4.19×10-3 cm
B) 𝑑𝑑𝑝𝑝 = 7.45×10-3 cm
C) 𝑑𝑑𝑝𝑝 = 1.32×10-2 cm
D) 𝑑𝑑𝑝𝑝 = 6.71×10-2 cm

[ Problem 11 (Nptel)
The reaction

C + CO 2 → 2CO

was conducted in a catalytic reactor containing particles of radius 𝑅𝑅𝑝𝑝 = 0.7 cm. The
bulk concentration was 𝐶𝐶𝐴𝐴,𝑆𝑆 = 1.22×10-5 mol/cm³ and the observed reaction rate
was −𝑟𝑟obs 𝜌𝜌𝑐𝑐 = 4.67×10-9 mol/cm³∙sec. After the reaction was conducted, the
particles were cut open and the reacted carbon profiles were measured. These
profiles suggested strong diffusional effects to be present. Verify this observation.

The rate law in concentration units is

kC A
−rA =
1 + K 2 C D + K 3C A

where 𝑘𝑘 is the rate constant, 𝐾𝐾2 = 4.15×109 cm³/mol, 𝐾𝐾3 = 3.38×105 cm³/mol, 𝐶𝐶𝐴𝐴
is the concentration of CO2 (species A), and 𝐶𝐶𝐷𝐷 is the concentration of CO at the
surface. The mass diffusivity of species A on the catalyst is 0.1 cm²/sec.

[ Problem 12 (Vannice, 2005, w/ permission)

Vapor phase benzene (Bz) hydrogenation over carbon-supported Pd
catalysts has been studied. A 2.1% Pd/C catalyst prepared with a carbon black
cleaned in H2 at 1223 K had a surface-weighted Pd crystallite size of 21 nm, giving
a Pd dispersion of 5% based on transmission electron microscopy (TEM). The carbon
itself had an average mesopore diameter of 25 mm, while the average micropore
diameter was 0.9 nm; thus the majority of the Pd resided in the mesopores. The
highest activity of this catalyst at 413 K and 50 Torr Bz (total P = 1 atm; balance
H2) was 1.99 μmole Bz s-1g-1. The density of the catalyst was 0.60 g/cm³. The
catalyst particle radius ranged from 10 to 500 microns. Assuming all the Pd is in
the mesopores, are any mass transfer limitations expected based on the Weisz-
Prater criterion? If, instead, this catalyst had all the Pd in the micropores and it gave
this performance, would mass transfer limitations exist?
All Pd in mesopores All Pd in micropores
Pore diffusion limitations Pore diffusion limitations
A)
are negligible. are negligible.
Pore diffusion limitations Pore diffusion limitations
B)
are not negligible. are negligible.
Pore diffusion limitations Pore diffusion limitations
C)
are negligible. are not negligible.
Pore diffusion limitations Pore diffusion limitations
D)
are not negligible. are not negligible.

[ Problem 13 (Vannice, 2005, w/ permission)

Utilizing the data given in the previous problem, assume the benzene
hydrogenation reaction is zero order in benzene and first order in H2, and then
calculate the Thiele modulus for the largest and smallest catalyst particles
assuming all the Pd is in the mesopores. Also, compute the Thiele modulus for the
largest (500 μm) particles if all the Pd were dispersed in only the micropores. Should
there be any concern about the pore diffusion limitations for any of the three
possibilities? If need be, use 𝜎𝜎 = 2.4×10-8 cm as the molecular diameter of
hydrogen.
Case 1 Smallest particle, all Pd in mesopores
Case 2 Largest particle, all Pd in mesopores
Case 3 Largest particle, all Pd in micropores

A) Pore diffusion limitations are not a concern in any of the three cases.
B) Pore diffusion limitations are of concern in one of the three cases.
C) Pore diffusion limitations are of concern in two of the three cases.
D) Pore diffusion limitations are of concern in all three cases.

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A SOLUTIONS
P.1 c Solution
The initial concentration of A is determined first,

pA 8
C= = = 0.1 mol/L
RT 0.0821× ( 700 + 273)
A,0

The volume expansion factor is 𝜀𝜀𝐴𝐴 = (3 – 1)/1 = 2. Accordingly, the ratio

𝐶𝐶𝐴𝐴 /𝐶𝐶𝐴𝐴,0 can be written as

CA 1− X A 1− X A
= =
C A,0 1 + ε A X A 1 + 2 X A

Solving for conversion, we obtain

CA 1− X A 1 − C A C A,0
= →X
= A (I)
C A,0 1 + 2 X A 1 + 2 C A C A,0

The performance equation to use is

W X
= A
FA,0 −rA′

which, solving for 𝑟𝑟𝐴𝐴′ , becomes

X F
−rA′ = A A,0 (II)
W
This latter expression can be used in conjunction with other results to
determine the rate. Thus, the following table is prepared.
𝐶𝐶𝐴𝐴 𝑃𝑃
𝐶𝐶𝐴𝐴 𝐶𝐶𝐴𝐴,0
= 𝑃𝑃 𝐴𝐴 𝑋𝑋𝐴𝐴 (Eq. I) 𝐹𝐹𝐴𝐴,0 = 𝑣𝑣𝐶𝐶𝐴𝐴,0 −𝑟𝑟𝐴𝐴′ (Eq. II)
𝐴𝐴,0
0.08/0.1 = 0.2/2.6 = 100×0.1 = 0.0769×10/1.0 =
0.08
0.8 0.0769 10 0.769
0.05 0.5 0.25 2.2 0.55
0.02 0.2 0.571 0.4 0.228
0.01 0.1 0.75 0.1 0.075
0.005 0.05 0.864 0.05 0.0482

We attempt to fit the data to a first-order reaction, which is the simplest of

rate forms. To do so, we plot −𝑟𝑟𝐴𝐴′ , the red column, versus 𝐶𝐶𝐴𝐴 , the blue column, as
follows.

Clearly, we there is a good straight-line fit for the data. The slope of the line
is 9.91 ≈ 10. Thus, the rate equation is found to be

=−rA′ 10C A mol/hr ⋅ g cat

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P.2 c Solution
Part 1: The data are plotted below.

Since

W dX
=∫ A
FA,0 −rA

we have, in differential form,

dW dX A dX A
= →−
= rA
FA,0 −rA  
d W 
 FA,0 

which is the slope of the curve. It follows that, at 40% conversion,

0.482 − 0.23 kmol converted

=−rA = 0.36
0.8 − 0.1 kg cat ⋅ hr

♦ The correct answer is C.

Part 2: Mapping a conversion 𝑋𝑋𝐴𝐴 = 0.4 onto the graph, we read 𝑊𝑊/𝐹𝐹𝐴𝐴,0 =
0.566. Thus, the mass of catalyst required is

W
= 0.566 → W= 0.566 FA,0
FA,0

∴W= 0.566 × 400

= 226 kg cat

♦ The correct answer is B.

Part 3: For completely mixed flow, we can write

W XA 0.4
= =
FA,0 − rA,40% 0.36
0.4
∴W= × 400= 444 kg
0.36
♦ The correct answer is D.
P.3 c Solution
Part 1: For plug flow, we have

W X A ,F dX C A ,0 dC A 1 100 1 + 0.02C A
= C A,0 ∫ = ∫= k ∫20
A
dC A
v 0 −rA −r
CA
A 50C A

Carrying out the integration, we obtain

v   C A,0  
W
= ln   + k2 ( C A,0 − C A ) 
k ′   CA  
where, in the case at hand, 𝑘𝑘′ = 50 m³/kg∙s and 𝑘𝑘2 = 0.02 m³/mol. Accordingly,

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© 2020 Montogue Quiz
 1000 m3 hr   100  m3 
=W 3  ln   + 0.02 = (100 − 20 ) 64.2 kg cat
50 m kg ⋅ s   20  mol 

♦ The correct answer is A.

Part 2: Since 𝐶𝐶𝐴𝐴 = 𝐶𝐶𝐴𝐴,0 (1 – 𝑋𝑋𝐴𝐴 ), we can write

−rA′= 8C A2= 8C A2 ,0 (1 − X A )
2

Appealing to the performance equation for plug flow, it follows that

W X A , f dX X A, f dX A
=
FA,0 ∫0 −rAA
= ∫ 0
8C 2
(1 − X A )
2
A,0

The initial molar flow of reactant is 𝐹𝐹𝐴𝐴,0 = 𝑣𝑣𝐶𝐶𝐴𝐴,0 = 1000×100 = 100,000

mol/hr. Substituting in the equation above, we get

0.8 dX A  0.8 dX 
100, 000 × ∫
W= 1.25
=  ∫ A

8 ×1002 × (1 − X A )  0 (1 − X A ) 
0 2 2

The integral in brackets can be evaluated to give 4.0. The mass of catalyst
required then becomes

W = 1.25 × 4.0 = 5.0 kg

♦ The correct answer is A.

P.4 c Solution
The average pore radius 𝑅𝑅�𝑝𝑝 is given by

2Vg
Rp =
Sg

where 𝑉𝑉𝑔𝑔 is the void volume per gram and 𝑆𝑆𝑔𝑔 is the surface area per gram. The
former is evaluated as

n p 0.45
V
=g = = 0.381 cm3 g
ρ p 1.18

so that

2 × 0.381
Rp
= = 4
2.27 ×10−7 cm
336 × 10
or, equivalently, 𝑅𝑅�𝑝𝑝 = 2.27 nm. The Knudsen diffusivity is given by

2 8 RT
DKn = Rp
3 πM
When simplified and written in terms of CGS units, this equation becomes

T
= 9.7 ×103 R p
DKn
M
Noting that the molar mass of cumene is 𝑀𝑀 ≈ 120 g/mol and substituting
the pertinent variables, we obtain

773
DKn = 9.7 ×103 × ( 2.27 ×10−7 ) × = 5.59 ×10−3 cm 2 s
120
Equipped with this quantity and the binary diffusivity 𝐷𝐷𝐴𝐴𝐴𝐴 = 0.11 cm²/s, we
can determine the combined diffusivity 𝐷𝐷𝑐𝑐 ,

1 1 1 1 1
= + = −3
+
Dc DKn DAB 5.59 ×10 0.11

∴ Dc = 5.32 ×10−3 cm 2 /s
Observe that, from the magnitudes of the diffusion coefficients, it is clear
that under the conditions cited the majority of the mass transport will occur by

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Knudsen diffusion. Finally, using the porosity 𝑛𝑛𝑝𝑝 = 0.45 and the tortuosity 𝜏𝜏′ = 3,
the effective diffusivity is calculated as

D
=
Dc n p
=
( 5.32 ×10 ) × 0.45
=
−3

7.98 ×10−4 cm 2 s
eff
τ′ 3
♦ The correct answer is B.
P.5 c Solution
Pore diffusion mass transfer limitations are particularly relevant for a fast
reaction with large catalyst pellets.
♦ The correct answer is D.
P.6 c Solution
The Thiele modulus for spherical catalyst particles is of course

rA,obs R p2 ρc
− = 3 (φ1 coth φ1 − 1)
ηφ12 =
Deff C A, S

Let 𝜙𝜙11 and 𝜙𝜙12 denote the Thiele moduli at run 1 and run 2, respectively; in
addition, let −𝑟𝑟𝐴𝐴,1 and −𝑟𝑟𝐴𝐴,2 denote the observed reaction rates and 𝑅𝑅1 and 𝑅𝑅2 the
corresponding radii. Substituting the pertinent variables in the equation above and
dividing the two ensuing expressions, we get

−rA,2 R22 φ12 coth φ12 − 1

= (I)
−r R A,1 1
2
φ11 coth φ11 − 1

The ratio of Thiele moduli is

−rA, S ρc
R1
φ11 Deff C A, S R1 R 0.002
= = → φ12 = 2 φ11 = = 0.1φ11 (II)
φ12 −rA, S ρc R2 R1 0.02
R2
Deff C A, S

Substituting in equation (I) gives

16.0 × 0.0022 0.1φ11 × coth ( 0.1φ11 ) − 1

=
4.0 × 0.022 φ11 coth (φ11 ) − 1

The equation above can be solved with Mathematica’s FindRoot command,

using an initial guess of, say, 1.0,

16.∗ 0.0022 0.1 ∗ 𝜙𝜙 ∗ Coth[0.1 ∗ 𝜙𝜙] − 1

FindRoot � − , {𝜙𝜙, 1}�
4.∗ 0.022 𝜙𝜙 ∗ Coth[𝜙𝜙] − 1.

This returns 𝜙𝜙11 = 12.02. The corresponding effectiveness factor is then

3 3
η= φ11 coth (φ11 ) − 1=
 × 12.0 × coth (12.0 ) − 1=
 0.229
12.02 
1
φ 2
11

From equation (II), we have 𝜙𝜙12 = 0.1×12.0 = 1.2. Lastly, effectiveness

factor 𝜂𝜂2 is

3 3
η2= φ11 coth (φ11 ) − 1=
 × 1.2 × coth (1.2 ) − 1= 0.916
φ 2
12 1.22 

♦ The correct answer is B.

P.7 c Solution
We assume a reversible first-order forward and reverse reaction,
represented as


A R
The rate is

 1 
r ′′ =kC A − k ′CR =k  C A − CR 
 K 

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 At equilibrium, the resulting rate is zero and

CR ,e X A, e
K= = =16.6 → X A,e = 0.943
C A, e 1 − X A, e

Since the final conversion is 80% of equilibrium conversion, we write 𝑋𝑋𝐴𝐴 =

0.8×0.943 = 0.754. The observed rate is given by

K
= ′′ k ′′C A,0
robs
K +1
( X A,e − X=
A )η k * C A,0 ( X A,e − X A )η

Appealing to the definition of Thiele modulus, we write

R p k *1 2 ρ s1 2 ′′ ρ s
robs
=φ = Rp
12
Deff C A,0 ( X A,e − X A ) Deffη

∴φ= 0.24 ×
(1.12 ×10 ) ×1.82
−5

(1.54 ×10 −5
) × ( 0.943 − 0.754 ) × ( 2.1×10 ) ×η −2

333
∴φ =0.24
η
4.38
∴φ = (I)
η
However, we know that the effectiveness factor and 𝜙𝜙 are related by the
equation

3 1 1
=η  −  (II)
φ  tanh φ φ 
Equations (I) and (II) constitute a system of nonlinear equations with two
unknowns. We can solve these equations simultaneously with Mathematica’s
FindRoot command,
3
FindRoot ��𝜙𝜙 == 4.38⁄�𝜂𝜂 , 𝜂𝜂 == (Coth[𝜙𝜙] − 1⁄𝜙𝜙 )� , �{𝜙𝜙, 1. }, {𝜂𝜂, 1. }��
𝜙𝜙

This returns 𝜙𝜙 = 7.39 and 𝜂𝜂 = 0.351.

♦ The correct answer is B.

P.8 c Solution
The effectiveness factor 𝜂𝜂 is given by

ℜ kmeas 3  1 1
η
= = =  − 
ℜo ko φ  tanh φ φ 
The Thiele modulus is given by

R p ko1 2
φ= 12
Deff
so that

kmeas φ 2 Deff
φ
=ko =
3 1 1 R p2
−
 tanh φ φ 
 
 1 1  kmeasℜ2
∴φ  − = (I)
 tanh φ φ  3 D eff

The mean pore radius is given by

2Vm 2 × 0.42 cm/g

R=
p r=
p = = 2.0 ×10−7 cm
420 m /g × (100 cm/m )
2
Sm 2

The average velocity for the cumene catalyst molecules is given by

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© 2020 Montogue Quiz
  8 × (1.38 ×10−16 erg/K ) × 685 K 
12
12
 8k T 
v  B =
=   
= 3.48 ×104 cm/s
 πm   π ×120 amu × (1.66 ×10 g/amu ) 
−24

The cumene has a typical pore diameter much lower than its mean free
path. Accordingly, pore diffusion will be dominated by Knudsen diffusion and the
effective diffusivity can be estimated as

1 1
Deff ≈ DKn =d p v =× ( 4.0 ×10−7 ) × ( 3.48 ×104 ) =4.64 ×10−3 cm 2 /s
3 3
Substituting the pertinent variables in the right-hand side of equation (I),
we obtain

=
 1
φ
1
− 
(1.49=
cm /s ⋅ g ) × (1.14 g/cm ) × ( 0.35cm/2 )
3 3 2

3.77
 tanh φ φ  3 × ( 4.6 ×10 cm /s )
−3 2

To determine the value of 𝜙𝜙, we apply Mathematica’s FindRoot function

with an initial guess of, say, 𝜙𝜙 = 3.0. The pertaining code is

FindRoot[𝜙𝜙(Coth[𝜙𝜙] − 1⁄𝜙𝜙 ) − 3.77, {𝜙𝜙, 3}]

The command returns 𝜙𝜙 = 4.77. The final step is to compute the efficiency
factor 𝜂𝜂,

3  1 
η= ×  coth 4.77 −  =0.497
4.77  4.77 

♦ The correct answer is B.

P.9 c Solution
Part 1: We have 𝐶𝐶𝐴𝐴 /𝐶𝐶𝐴𝐴,𝑆𝑆 = 0.1 and 𝜆𝜆 = 0.5, so that

CA 1  sinh (φ1λ )  1  sinh ( 0.5φ1 ) 

ψ= =   → 0.1=  
C A, S λ  sinh φ  0.5  sinh φ1 

We can solve for the Thiele modulus with Mathematica’s FindRoot

command,

FindRoot[0.1 − 1⁄0.5 ∗ (Sinh[0.5 ∗ 𝜙𝜙]⁄Sinh[𝜙𝜙]), {𝜙𝜙, 0.5}]

This returns 𝜙𝜙 = 5.9864 ≈ 6.0. The dimensionless length 𝜆𝜆 for a distance of

3.5×10-4 cm from the pellet surface is

1×10−3 − 3.5 ×10−4

=λ = 0.65
1×10−3
so that

CA 1  sinh (φ1λ )  CA 1  sinh ( 6.0 × 0.65 ) 

ψ= =  → = × 
C A, S λ  sinh φ1  0.001 0.65  sinh 6.0 

∴ C A = 1.88 ×10−4 mol/dm3

♦ The correct answer is C.

Part 2: From the definition of Thiele modulus, we can determine rate
constant 𝑘𝑘1𝑟𝑟 ,

k1r k
φ=Rp 1×10−3 × 1r
→ 6.0 =
DAB 0.1

∴ k1r = 3.6 ×106 sec −1

For the effectiveness factor to be 0.75, the Thiele modulus must be such
that

3
η 0.75
= = φ coth (φ1 ) − 1
φ12  1
As before, we can apply the FindRoot command,

FindRoot[0.75 − 3⁄𝜙𝜙 2 ∗ (𝜙𝜙 ∗ Coth[𝜙𝜙] − 1), {𝜙𝜙, 2}]

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© 2020 Montogue Quiz
 This returns 𝜙𝜙 = 2.399 ≈ 2.4. From the definition of Thiele modulus, we can
establish the catalyst particle radius,

3.6 ×106
φ =2.4 =R p → R p =4 ×10−4 cm
0.1

8 10−4 cm
∴ d p =×

♦ The correct answer is C.

P.10 c Solution
The pertaining reaction is

2SO 2 + O 2 → 2SO3
Per the Weisz-Prater criterion, diffusional effects are not significant if

ℜR p2
NW − P
= ≤ 0.3
Cs Deff

Here, 𝐶𝐶𝑠𝑠 is the reactant concentration, which can be estimated from the
ideal gas law,

P 2 3 × 2 atm
Cs
= = = 2.42 ×10−5 mol/cm3
RT 82.06 atm ⋅ cm³
× 673 K
mol ⋅ K
The mass diffusivity is determined next,

1 1
Deff =vd p =× ( 3.0 ×104 cm/s ) × (120 ×10−8 cm ) =
1.20 ×10−2 cm 2 /s
3 3
In addition, we have the global reaction rate ℜ = 2 mole SO2/s∙ L × 1
L/1000 cm³ = 0.002 mole SO2/s∙cm³. Substituting in the definition of 𝑁𝑁𝑊𝑊−𝑃𝑃 brings
to

0.002 × R p2
=NW − P ≤ 0.3
( 2.42 ×10 ) × (1.20 ×10 )
−5 −2

0.3 × ( 2.42 ×10−5 ) × (1.20 ×10−2 )

∴ Rp ≤ = 6.6 ×10−3 cm
0.002
Thus, in order for no relevant diffusional effects to take place, the particle
diameter should be no greater than 2×6.6×10-3 = 1.32×10-2 cm.

♦ The correct answer is C.

P.11 c Solution
In the situation at hand, the Weisz-Prater parameter is

NW − P =
−rA,obs ρc RP2
=
( 4.67 ×10 ) × 0.7
−9 2

= 1.88 ×10−3 < 0.3

DABC A, S 0.1× (1.22 ×10 ) −5

Accordingly, the Weisz-Prater criterion does not predict internal diffusion

limitations, even though experimental observations suggest otherwise. The main
reason why this disparity occurs is the fact that the Thiele modulus used in the WP
criterion pertains to a first-order reaction, and the rate law we were given clearly
indicates that the reaction in question is not first order. We can still predict
diffusional limitation effects with the generalized Thiele modulus. Assuming
equimolar counter-diffusion, 𝐷𝐷eff,𝐴𝐴 = 𝐷𝐷eff,𝐷𝐷 , and that the concentration of CO at the
surface 𝐶𝐶𝐷𝐷,𝑆𝑆 ≈ 0, the rate expression can be rewritten as

kC A
−rA′ =
(1 + 2 K 2C A,s ) + ( K3 − 2 K 2 ) C A
Assuming the pellet was infinitely long with 𝐶𝐶𝐴𝐴,𝑒𝑒𝑒𝑒 = 0, we have the modified
parameter

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© 2020 Montogue Quiz
 −rA,obs R p2 ρc ( −rA, s )
Φ ηφ=
= 2
C A ,s
2∫ Deff,A ( −rA′ ) dC A
0

−1
r R 2 ρ 1 + K 3C A, s  1 + 2 K 2 C A, s  1 + K 3C A, s   
=∴Φ A,obs p c  1 − ln    

2 Deff,A  K 3 − 2 K 2
  C A, s ( K 3 − 2 K 2 )  1 + 2 K 2C A, s   
−1
 1 + ( 3.38 ×105 ) × (1.22 ×10−5 ) 
 × 
(=
4.67 ×10 ) × 0.7 
−9 2  ( 3.38 × 10 5
) (
− 2 × 4.15 × 10 9
) 

∴Φ   2.08
2 × 0.1   1 + 2 × ( 4.15 × 10 9
) × (1.22 × 10 −5
)  1 + ( 3.38 × 10 5
) × (1.22 × 10 −5
)   
 1 − ln   
  (1.22 ×10 ) × ( 3.38 ×10 ) − 2 × ( 4.15 ×10 )   1 + 2 × ( 4.15 ×10 ) × (1.22 ×10 )   
−5 5 9  9 −5


This result is substantially greater than the threshold of the WP criterion

and indicates that diffusion limitations are in fact appreciable.

P.12 c Solution
To begin, we compute the global reaction rate ℜ,

μmole Bz g cat
=ℜ 1.99 × 0.60
= 3
1.19μmole Bz/s ⋅ cm3
s ⋅ g cat cm
The reagent concentration follows from the ideal gas law,

P 50 Torr Bz ×1atm/760 Torr

Cs
= = = 1.94 ×10−6 mol/cm3
RT atm ⋅ cm3
82.06 × 413K
g ⋅ mol ⋅ K
Assuming the mean free path in the gas phase is much greater than the
average pore diameter of the catalyst, mass transport is dominated by Knudsen
diffusion and we can write 𝐷𝐷eff ≈ 𝐷𝐷Kn . The average velocity of benzene molecules is
given by

 8 × (1.38 ×10−16 erg/K ) × 413 K 

12
12
 8k T 
v  B =
=   = 3.35 ×104 cm/s
 πm   π × 78amu × (1.66 × 10 −24
g/amu ) 
so that

1 1
′ =vd p =× ( 3.35 ×104 ) × ( 0.9 ×10−7 ) =
DKn 1.0 ×10−3 cm 2 s
3 3
where we have used the mesopore diameter 𝑑𝑑𝑝𝑝 = 25 nm. Now, the worst case
occurs if the catalyst particle radius 𝑅𝑅𝑝𝑝 = 500 μm, in which case the Weisz-Prater
criterion yields

(1.19 ×10 mol Bz/s ⋅ cm ) × ( 500 ×10 =

cm )
−6 3 −4 2
ℜR p2
NW − P =
= 0.0550
Cs DKn (1.94 ×10 mol/cm ) × ( 2.79 ×10 cm /s )
−6 3 −2 2

In the best case, the catalyst particles have a radius of 10 μm and the W-P
criterion becomes

(1.19 ×10 mol Bz/s ⋅ cm3 ) × (10 ×10−4 cm )

−6 2
ℜR p2
NW= = = 2.20 ×10−5
−P
Cs DKn (1.94 ×10 −6
mol/cm ) × ( 2.79 ×10 cm /s )
3 −2 2

Since 𝑁𝑁𝑊𝑊−𝑃𝑃 < 0.3 in both cases, we surmise that diffusional limitations are
negligible when all the Pd is in the mesopores. Suppose next that all Pd is contained
in the micropores. The Knudsen diffusivity now becomes

1 1
′ =vd p =× ( 3.35 ×104 ) × ( 0.9 ×10−7 ) =
DKn 1.0 ×10−3 cm 2 s
3 3
As before, in the worst case the catalyst particle radius 𝑅𝑅𝑝𝑝 = 500 μm. The
W-P criterion gives

(1.19 ×10 mol Bz/s ⋅ cm ) × ( 500 ×10 =

cm )
−6 3 −4 2
ℜR p2
NW − P =
= 1.53
′
Cs DKn (1.94 ×10 mol/cm ) × (1.0 ×10 cm /s )
−6 3 −3 2

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© 2020 Montogue Quiz
 which of course is greater than 0.3. Now, in the best case the catalyst particles have
a diameter of 10 μm, so that

(1.19 ×10 mol Bz/s ⋅ cm ) × (10 ×10 cm=)

−6 3 −4 2
ℜR p2
NW= = 6.13 ×10−4
−P
′
Cs DKn (1.94 ×10 mol/cm ) × (1.0 ×10 cm /s )
−6 3 −3 2

We conclude that, if all the Pd is in the mesopores, pore diffusion

limitations are negligible. If, however, all the Pd is in the micropores, we cannot
conclude that diffusion limitations are negligible.

♦ The correct answer is C.

P.13 c Solution
The hydrogen concentration is

P 710 760 atm

C=
H2 = = 2.76 ×10−5 mol/cm3
RT cm3 ⋅ atm
82.06 × 413 K
g mole ⋅ K

Since the reaction is zero order in benzene and first order in H2, we can
write

ℜ
ℜ k ′=
= PH 2 kCH 2 →
= k
CH 2

1.19 ×10−6 mol/s ⋅ cm3

=∴k = −5 3
0.0431 s −1
2.76 ×10 mol/cm

where we have used ℜ obtained in the beginning of the previous problem. Now, the
mean velocity of hydrogen molecules is given by

 8 × (1.38 ×10−16 erg/K ) × 413 K 

12
12
 8k T 
vH 2  B =
=   
= 2.09 ×105 cm/s
 πm   π × 2 amu × (1.66 ×10 g/amu ) 
−24

The mean free path is, in turn,

cm3 ⋅ atm 1 mol

82.06 × 413 K ×
RT g ⋅ mol ⋅ K 6.02 ×1023 molec
λ
= = = 2.20 ×10−5 cm
2π × ( 2.4 ×10 cm ) ×1 atm total P
2
2πσ 2 PH 2 −8

where, in addition to other familiar variables, we have the molecular diameter of

hydrogen 𝜎𝜎 = 2.4×10-8 cm. Since 𝜆𝜆 ≫ 𝑑𝑑𝑝𝑝 , Knudsen diffusion predominates and
𝐷𝐷eff ≈ 𝐷𝐷Kn , where

1
DKn = vd p
3
Now, in case 1 we consider the Thiele modulus for the smallest particle with
all Pd in the mesopores. The diffusion coefficient is calculated as

1
DKn =× ( 2.09 ×105 cm/s ) × ( 25 ×10−9 m ) ×102 cm/m  =
0.174 cm 2 /s
3
so that

R p k 1 2Cs( −1) 2 (10 ×10 m ) ×10 cm/m  × ( 0.0431 s ) × ( 2.76 ×10 mol/cm )
−6 2 −1 −5 3 0.5 0
n

=φ =
( 0.174 cm/s )
12 12
Deff

∴φ= 4.98 ×10−4

The corresponding efficiency factor is

3 1 3  1 
η  coth φ −= coth ( 4.98 ×10 ) − 4.98 ×10−4  ≈ 1.0
−4
= 
φ φ  4.98 ×10−4
In case 2, we consider the Thiele modulus for the largest particle with all Pd
in the mesopores. The diffusion coefficient remains 𝐷𝐷Kn = 0.174 cm²/s, with the
result that

13
© 2020 Montogue Quiz
 R p k 1 2Cs( n 1) 2 ( 500 ×10 m ) ×10 cm/m  × ( 0.0431 s ) × ( 2.76 ×10 mol/cm )
−6 2 −1 −5 0.53 0
−

=φ =
( 0.174 cm/s )
12 12
Deff

∴φ =0.0249
The corresponding efficiency factor is

3  1 
=η  coth 0.0249 −  ≈ 1.0
0.0249  0.0249 
In case 3, we consider the Thiele modulus for the largest particle with all Pd
in the micropores. The Knudsen diffusivity is updated as

1
DKn =× ( 2.09 ×105 cm/s ) × ( 0.9 ×10−9 m ) ×102 cm/m  =
6.27 ×10−3 cm 2 /s
3
so that

( 500 ×10−6 m ) ×102 cm/m  × ( 0.0431 s −1 ) × ( 2.76 ×10−5 mol/cm3 )

0.5 0
R p k 1 2Cs( n − )
1 2

=φ =  
( 6.27 ×10−3 cm/s )
12 12
Deff

∴φ =0.131
The corresponding efficiency factor is

3  1 
=η  coth 0.131 −=  0.999
0.131  0.131 
The values of 𝜂𝜂 for all three cases are very close to unity. Thus, pore
diffusion limitations are not a concern in any of the three cases.

♦ The correct answer is A.

A ANSWER SUMMARY
Problem 1 Open-ended pb.
2.1 C
Problem 2 2.2 B
2.3 D
3.1 A
Problem 3
3.2 A
Problem 4 B
Problem 5 D
Problem 6 B
Problem 7 B
Problem 8 B
9.1 C
Problem 9
9.2 C
Problem 10 C
Problem 11 Open-ended pb.
Problem 12 C
Problem 13 A

A REFERENCES
• HILL, C. and ROOT, T. (2014). Introduction to Chemical Engineering
Kinetics and Reactor Design. 2nd edition. Hoboken: John Wiley and
Sons.
• LEVENSPIEL, O. (1999). Chemical Reaction Engineering. 3rd edition.
Hoboken: John Wiley and Sons.
• SCHMAL, M. (2014). Chemical Reaction Engineering. Boca Raton: CRC
Press.
• VANNICE, M. (2005). Kinetics of Catalytic Reactions. Heidelberg:
Springer.

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