Exercises and Questions (without Answer)

Reactors and Kinetics (CH3681a)

Made by Pouyan E. Boukany and Freek Kapteijn

This document offers a series of exercises and questions related to essential

and important concepts of this course.
Please read lecture notes and book to prepare for answering them.
Use these exercises to follow progress through the course material and test
yourself. These exercises are provided without solution to increase the level
of learning.
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Topic: Quasi Steady State Approximation (QSSA)

(Reading: Chapter 5 (Rawlings Book))

Q1: Consider the decomposition of dinitrogen pentoxide (N2O5) to give NO2

and O2.
The overall reaction is represented by
2N2O5 → 4NO2 +O2
The following reaction mechanism has been proposed for the decomposition
of dinitrogen pentoxide (N2O5):
k
N2O5 ←
"""1

k "
→ NO2 + NO3
−1

NO3 + NO2 !k!

2
→ NO + NO2 + O2

NO3 + NO !k!
3
→ 2NO2

(a) Explain the Quasi-Steady state Assumption (QSSA).

(b) Which are the reactive radicals generated and consumed in the above
reaction?
(c) Assume these reactive radicals are QSSA species. Derive expressions
for the steady state concentrations of these radicals
Derive an expression rate r of oxygen (O2) based on QSSA. The expression
rate of oxygen should be only dependent on the concentration of N2O5.

Q2: The classic example of a chain reaction is the gas phase decomposition
of acetaldehyde (CH3CHO) to methane (CH4) and carbon monoxide (CO).
The overall reaction is given by
   𝐶𝐻! 𝐶𝐻𝑂 → 𝐶𝐻! + 𝐶𝑂

The following reaction mechanism has been proposed for this acetaldehyde
decomposition, including the formation of side products hydrogen and ethane.
     !!      
                               𝐶𝐻! 𝐶𝐻𝑂        𝐶𝐻! + 𝐶𝐻𝑂
     !!      
             𝐶𝐻𝑂          𝐶𝑂 + 𝐻
    !!      
 𝐻 + 𝐶𝐻! 𝐶𝐻𝑂          𝐶𝐻! 𝐶𝑂 +  𝐻!
   !!        
𝐶𝐻! + 𝐶𝐻! 𝐶𝐻𝑂      𝐶𝐻! + 𝐶𝐻! 𝐶𝑂
     !!      
         𝐶𝐻! 𝐶𝑂    𝐶𝐻! +𝐶𝑂
     !!      
     2𝐶𝐻!            𝐶! 𝐻!

a) Which are the free radicals that play a role in these reactions?

b) Assume these reactive radicals are QSSA species. What are the
steady state concentrations of these radicals, expressed in terms of
cCH CHO ?
3
c) Derive an expression for the rate of methane formation based on
QSSA in terms of only k1, k4, k6 and acetaldehyde concentration.

Q3: Chain reaction usually involves free radicals. Example of chain reaction is
the formation of HBr from hydrogen and bromine. (The temperature must be
high enough that bromine is a gas and not a liquid.)
H 2 + Br2 !!
→ 2HBr
The proposed model of elementary steps for this reaction is:
Br2 !k!
1
→ 2Br Initiation
Br + H2 !k!
2
→ HBr + H Propagation
H + Br2 !k!
3
→ HBr + Br Propagation
H + HBr !k!
4
→ H2 + Br Termination
Br + Br !k!
5
→ Br2 Termination

d) Assume reactive radicals are ‘QSSA species’. Give expressions for the
steady state concentrations of the reactive radicals in terms of the stable
gaseous species.

Derive an expression for the production rate of HBr based on QSSA.

Show that the reaction is first order in hydrogen.

Topic: Questions for reactor types

1. Give three reactor types that can be used for kinetic data
acquisition.
2. Give also various reactors that are in use and give a brief
description, the type they belong to and pros and cons of each.
Topic: Transition State Theory
(Reading: Lecture notes, Dumesic Book)

In derivation of microkinetic relations values of the pre-exponential rate

constant of an elementary step are often estimated based on transition state
theory (TST). Partition functions are considered for changes in translation,
rotation and vibration degrees of freedom. Crude loss estimates per degree of
freedom are 5×108 cm-1, 10 and 1, respectively. Site densities of surfaces are
~1015 cm-2.
a. What are the assumptions in this TST approach?

b. Estimate the value of the pre-exponential and dimension for the

following elementary steps (explain your approach):
1. Adsorption from the gas phase of a nonlinear molecule to a
mobile TS on a surface
2. Desorption of an immobile adsorbed non-linear molecule via an
immobile TS

c. This approach for estimating the pre-exponential of a rate constant can

also be applied to estimate that of an equilibrium constant of a process.
Estimate values of K0 and dimension for the following processes:
1. A linear gaseous molecule adsorbs to a two-dimensional gas at
a surface
2. Two nonlinear gas molecules dimerize to a single gas molecule

d. What is the difference between the first case of b. and that of c.?

Topic: Reactor performance and kinetics, Brønsted-Evans-Polanyi (BEP)

(Reading: Lecture notes, 3, 4)

Q1: In the microkinetic description of rate processes sometimes semi-

empirical relations are used. One of these is the Brønsted-Evans-Polanyi
(BEP) relation. For families of reactions (e.g. C-C skeletal isomerization, C-H
bond rupture) it is observed that for an elementary step the activation energy
barrier is related to the enthalpy change over that step by a proportionality a.

a) Give the expression for the BEP relation for an exothermal process, and
sketch the energy profile for two different cases in one drawing.

b) Assume an irreversible two step monomolecular catalytic reaction:

adsorption (quasi equilibrium, K) and surface reaction (rate determining,
k).
Show (derive) that the rate expression can be given as:
 k0 K 1−α p
r~
1 + Kp

c) What is the implication of this relation if K is varied over a broad range of

values? Describe the physical interpretation of this phenomenon. How is it
called in catalysis?

Topic: Reactor types type for kinetic studies.

Q1: Give three reactor types that can be used for kinetic data acquisition.
Give also various reactors that are in use and give a brief description, the type
they belong to and pros and cons of each

Q2: Which aspects should be considered to make sure you get the instrinsic
kinetics formation from experiments done in the lab with a gas-liquid reaction
catalyzed by a porous solid catalyst.

Topic- Temperature programming techniques (TPD)

(Reading: Lecture notes)

Q1: Temperature programming techniques are often applied to determine rate

parameters of elementary steps, like in temperature programmed desorption
(TPD), as taught in class.
This approach has been applied especially in surface science with single
crystal metal surfaces under UHV conditions.

a) Describe the advantages of this operation in surface science.

b) Why do you think this TPD method has not found widespread application
in the quantitative study of desorption rate parameters in porous supported
metal catalysts? Argument both on the reactor as on the particle scale.
Describe how you would carry out such an experiment and what you
should keep in mind.

c) TPD is nevertheless applied with porous catalysts, e.g. in the desorption of

ammonia or CO or CO2. What type of information do you think is obtained?
Can it be quantitative? If so, in what respect?

d) Do you know a technique that uses desorption from porous particles to

determine a kinetic parameter? Which and what parameter(s) can be
determined?

Q2: Temperature Programmed Desorption (TPD) is used to determine

desorption rate parameters of molecules from a surface. This is often done
using single crystal surfaces in an ultra-high-vacuum cell, where desorbing
molecules are continuously pumped off. In an experiment molecules are
adsorbed at low temperatures to a certain initial occupancy of the surface.
Then, the temperature of the surface is raised at a constant heating rate β and
the flow of desorbing molecules is monitored in time by a mass spectrometer.

a. Set up a molar balance for the TPD process and derive an expression for
dθ
the occupancy change with temperature ( ) for a first order desorption
dT
rate in terms of linear heating rate β, preexponential k0 and activation
energy Ed for desorption. Preexponential is independent of occupancy.
(don’t try to solve)

b. The desorption rate is measured by the mass spectrometer. Should the

signal be processed before it can be used to determine the unknown
parameters k0 and Ed (and if so how)? Is the initial amount of molecules
adsorbed important? Explain.

c. What can you say about the profiles for different heating rates? Show by
derivation that for this case the expression relating the heating rate, the
temperature of the desorption maximum, and the desorption activation
energy reads:
2
⎛ Ed ⎞ ⎛ k0RTmax ⎞
⎜ ⎟ = ln ⎜ ⎟
⎝ RTmax ⎠ ⎝ β Ed ⎠

d. How would you determine the activation energy for desorption in this case?
Give an outline and support your procedure.

e. Compare zeroth, first and second order desorption. How does the location
of the maximum desorption rate depend on the initial fractional coverage?
Sketch the profiles for different initial loadings.

The above relation was derived by Kissinger, but assumes that the
parameters are all constant. Activation energies may vary with loading,
however, resulting in wrong estimates. Friedman proposed an elegant
solution to address this and determine the activation energy for desorption
as a function of occupancy.

f. Outline clearly how this can be done. (Hint: start with a. )

Q3: TPD is carried out in high vacuum equipment using single crystal
surfaces and in packed bed reactors, using real porous solid catalyst. What
are the aspects should be taken into consideration for each approach (pros
and cons).
Q4
a. How can we determine the heat of adsorption through TPD if this heat of
adsorption is not constant but varies with loading?
b. Model a desorption curve assuming a linear profile of heat of adsorption
with loading (do you expect a decreasing or increasing trend?).
c. Vary the heating rate, determine the rate and temperature at equal loading
and plot these in an Arrhenius plot.

Topic: Mass transport-Effectiveness factor

(Reading: Lecture Notes, Chapter 7 (Rawlings))

Q1: What is the definition of the Catalyst effectiveness factor?

Q2: Which parameter determines the isothermal internal effectiveness factor?

What is its physical interpretation (explain it in terms of relevant phenomena,
important parameters and dimensions)?

Q3: Different regimes can be observed on the measurement of activation

energy during operation of catalyst particles. For instance, Bernardo and
Trimm studied the steam gasification of activated carbon catalyzed by Ni:
!"
   𝐶 + 𝐻! 𝑂 𝐶𝑂 + 𝐻!

The following figure is a plot of the observed reaction rates [mg s-1] as a
function of reciprocal temperature (1000/T [K-1] ).

a. Explain the observed three regimes and the parameters in the plot.
b. In what temperature range can you determine De (effective diffusivity),
how and what is needed?
c. At what temperature would you run experiments to measure the
intrinsic rate constant and the true activation energy?
d. If you find your experiments are externally mass transfer limited, can
you still determine the kinetics of the reaction? And what if the
experiments were internal diffusion limited (motivate answer)?
Q4: You have collected a set of rate data for a reaction catalyzed by a porous
solid catalyst in a small packed bed reactor. You suspect that transport of
mass (external or internal) may have disguised your data. Now you will set up
some tests to verify experimentally if this is the case. You may assume that
the 1st order internal catalyst effectiveness is approximated by
tanhφ
ηi =
φ
a. What does the parameter φ represent (give an expression and a physical
meaning in terms of characteristic times of relevant phenomena, and
explain all parameters in the expression, including dimensions)? How is
the internal effectiveness defined?

b. How would you define the external catalyst effectiveness ηe ? Cast it in an

expression with the rate constant and mass transfer coefficient kf. Indicate
all parameters used and their dimensions

c. Now explain what the observed activation energy and reaction order for
this system will be if the reaction is:
1. Kinetically controlled
2. Internal diffusion controlled
3. External mass transfer controlled
Support your answers by showing the related expressions. What can
you say more about dependencies on experimental conditions in these
three cases?

d. Based on your answers under c. propose two experimental tests to check

if the original data were contaminated by mass transport phenomena.

e. The slab-type catalyst under consideration is being homogeneously

poisoned by a strongly adsorbing species. This can be described by a
small Thiele modulus of the poison.
1. Derive an expression for the observed catalyst deactivation F as a
function of the fraction α of sites that are poisoned. Here F is
defined as the observed rate after deactivation relative to the
unpoisoned observed rate:
observed
rpoisoned
F = observed
runpoisoned
2. Consider two limiting cases, a small and a large Thiele modulus for
the reaction and simplify the expression for F for these cases.
Sketch also the profile of F as a function of α
Topic: Catalyst deactivation
(Reading: Lecture notes)

(a) What causes of catalyst deactivation can you give, and include in what
way they affect the catalyst performance.

1.0

Fraction of initial activity

0.8

0.6

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0

Fraction poisoned α
(b) The graph indicates three relations between the observed fraction of initial
catalyst activity F during deactivation as a function of the fraction of active
sites poisoned α.
r observed
F = deactivated
observed
rinitial
Give four situations to which they apply and explain the trends
qualitatively.

(c) Catalyst deactivation caused by poisons can be described in an analogous

way as catalysed reactions by a diffusion-reaction model and introducing a
Thiele modulus. To reduce the effect of the poison and to maximize
catalyst life the active phase distribution in a particle may be optimized. In
the graph below four quadrants are indicated for combinations of the
Thiele moduli of the main reaction and of the poisoning reaction, together
with four active phase
Egg shell Egg white Egg yolk Uniform
distributions.
Place the distributions in the
proper quadrant (see figure)
and clearly motivate your
answer 10

Poison

φ poison 1

0.1
0.1 1 10 40

Main
φmain reaction
Topic: Mixing/RTD in Ideal and Non-ideal reactors
(Reading: Lecture notes, Chapter 8, Mixing (Rawlings))

Q1: What is the Residence Time Distribution (RTD)? How can we measure it?

Q2: How does mixing occur in ideal reactors? How does stimulus response
look like for these ideal reactors? How does pulse input in an ideal PFR and
CSTR look like?

Q3: Derive the equation of a first-order reaction using the segregation model
when the RTD is equivalent to (a) an ideal PFT, (b) an ideal CSRT, and (c) a
laminar flow reactor. Compare these conversions with those obtained from the
design equation.

Q4: What is difference between dispersed plug flow and tanks-in-series

model?

Q5: What is the dispersion model? Compare plug flow model with Dispersed
plug flow model (show all derivation, steps and assumption). What are the
boundary conditions for dispersed plug flow reactors?

Q6: What is expression for the Peclet number? What does it represent?

Q7: Derive an expression that can describe the performance of a dispersed

plug flow reactor with reaction (design equation).