Lecture on

CL-302: Chemical Reaction Engineering II

Instructor

Prof. Bishnupada Mandal

Room No. 102, Block - K
Department of Chemical Engineering
Indian Institute of Technology Guwahati

Copyright ©: All contents in this lecture, no matter the form it takes (whether digital, print, or
media) is protected under copyright law. The contents are only for the purpose of academic use.
 Course Objectives
The general objectives of Chemical Reaction Engineering-II are:
Provide an overview of chemical kinetics and reactor design at basic to an
intermediate level.
Applies the concepts of reaction rate, stoichiometry and equilibrium to the analysis
of chemical reacting systems
For example derivation of rate expressions from reaction mechanisms
equilibrium or steady state assumptions
Design of chemical reactors via synthesis of chemical kinetics, and mass and
energy balances.

The goal is to provide students with the theoretical/analytical background

to understand chemical kinetics and reactor design and to tackle the
sort of complex heterogeneous reaction problems.
 Syllabus
Introduction to heterogeneous reactions
Fluid-solid catalytic reactions: mechanism and rate-limiting step, external and
internal diffusion effects
Design of packed bed reactor: Staged adiabatic reactors, single and two packed
bed systems
Catalyst deactivation: Types and mechanisms, rate and performance equations
with various flow arrangements, pore diffusion effects, design principles
Multi-phase reaction kinetics: Performance equations with various flow regimes
Fluid-fluid non-catalytic reaction kinetics and reactor design: Mass transfer with
and without reaction, instantaneous reaction and fast reaction
Fluid-solid non-catalytic reaction kinetics and reactor design: Performance
equations
Progressive conversion model and Shrinking-core model
Time of operation under various controlling regimes
 Books and Resources

Textbooks
H. S. Fogler, Elements of Chemical Reaction Engineering, 4th Edition, Prentice
Hall, 2013.
O. Levenspiel, Chemical Reaction Engineering, 3rd Edition, Wiley Eastern, 2006.

Reference Book
J. M. Smith, Chemical Engineering Kinetics, 3rd Edition, McGraw-Hill Education
India Pvt. Ltd - New Delhi, 2014.
 Course Plan
No. of Lectures
S. No. Lecture Topic excluding Tutorial

1. Introduction to heterogeneous reactions 2

2. Fluid-solid catalytic reactions 9
3. Packed bed and suspended solid reactors 4
(bubbling fluidized bed, and circulating fluidized
bed)
4. Catalyst deactivation 3
5. Gas-liquid reactions on solid catalysis: trickle bed, 4
slurry, and three-phase fluidized bed reactors
6. Fluid-fluid reaction kinetics and reactor design 4
7. Fluid-particle (solid) reaction kinetics and reactor 4
design
Introduction to Chemical Reaction Engineering II

Central topic in chemical engineering

– Synthesis of materials
– Remediation of polluted air, water, soil
– Energy generation

Two main areas

– Chemical reaction kinetics
– Reactor design
Introduction to Chemical Reaction Engineering II

Motivation for understanding chemical kinetics and reactor

design:
 This is what makes us chemical engineers – the reactor is the
central feature of most chemical processes. Even if separation
costs dominate, the reactor often determines the separation
costs.
Chemical reactions are ubiquitous in nature and industry
 In this course, we will construct mathematical descriptions of
chemical reactions and chemical reactors. These allow us to
predict and understand the behavior of these reactions and
reactors.
 Chemical reactions
What is chemical reaction?
 A chemical reaction is a process in which at least one species is
transformed into a chemically different species.
 Although the number and/or type of molecules may change,
there is no change in the elemental constituents = the atomic
building blocks of the molecules.
 Three general types of reactions:
1. decomposition: A → P
2. combination: A + B → P
3. isomerization: cis-A → trans-A
 Chemical Reactor
What a reactor able to do?
 To find what a reactor is able to do we need to know the kinetics,
the contacting pattern and the performance equation.
 Performance Equation
Why is the performance equation important?
 Because with this expression we can compare different designs
and conditions, find which is best, and then scale up to larger
units.
What involves in reactor design?

Mass
Transfer
Heat Fluid
Transfer Mechanics

REACTANT(S) PRODUCT(S)
REACTOR

Thermodynamics
Reaction Economics
Kinetics
 Mass and Energy of a System
Albert E
 Einstein taught us that the mass and energy of a system are
proportional; if a system loses energy its mass decreases; if it
gains energy its mass increases.
 The relationship between mass and energy is:
E = mc2
 Mass and energy are equivalent; they are simply different forms of
the same entity.
 Let’s consider the combustion of methane, a highly exothermic
chemical reaction:
CH4 + 2O2 → CO2 + 2H2O
 Mass and Energy of a System
 Let’s consider the combustion of methane, a highly exothermic
chemical reaction:
CH4 + 2O2 → CO2 + 2H2O
 Suppose 1 mole CH4 is completely burned with 2 mole O2 (16 g + 64 g
= 80 g total):

 This reaction releases Q = 802 kJ of energy, and so there is a

corresponding decrease in mass of ~9 ng (9 × 10-9 g).
 Decoupling the Mass and Energy Balances
 Mass changes in chemical reactions (and all other chemical
processes) are extremely small, usually much too small to even
detect.
 We can therefore “decouple” mass and energy and make two
separate assumptions:
mass is conserved in all chemical processes
energy is conserved in all chemical processes
 For nuclear processes, this is not valid – the energy changes are
huge and so the mass changes are significant.
 Reaction Rate, r

 In a perfectly mixed, closed, constant volume system (or in some

region of space over which conditions are uniform) with the generic
reaction:
aA + bB ↔ cC + dD
 The reaction rate is defined as
 -a, -b, c, and d are the stoichiometric coefficients of the chemical
species A, B, C, and D, respectively. CA, CB, CC, and CD are the
concentrations of the chemical species.
 Reaction Rate, r
 For a homogeneous reaction (in the gas, liquid, or solid phase) the
rate has units of concentration per time or moles per volume per
time.
 For a heterogeneous reaction (at a surface) the rate has units of
moles per area per time or surface concentration per time.
 The rate is an intensive quantity, which means that it is independent
of the size of the system. Sometimes, one also refers to the
extensive rate, which is simply the intensive rate multiplied by the
total system volume.
 In general, the reaction rate is a function of temperature, pressure,
and composition.
 Reaction Rate, r
 At fixed temperature and pressure, the reaction rate is usually
expressed as a function of the species concentrations. That is

 The most commonly used functional dependence of the rate on the

concentrations is to set the rate proportional to a product of algebraic
powers of the species concentrations:

 The constant of proportionality (ki) is often referred to as the rate

constant. Perhaps a better term is rate coefficient – since it is only
constant with respect to the species concentrations. It can still
depend on temperature, total pressure, etc.
 With the above form, we refer to the νij as the order of the ith reaction
with respect to the jth species.
 Solving Simple Kinetics Problems Analytically
 You should memorize the simplest of these – especially the 1st order
result:
dC A
A  B, with rA  kC A , so   rA  kC A , and C A  C A0 exp(kt )
dt

 Suppose we have the two reactions:

A + B → C, with r1 = k1CACB and k1 = 10 liter mol-1 s-1

C + D → E, with r2 = k2CCCD and k2 = 5 liter mol-1 s-1

 and the initial concentrations of the species are

CAo = 1 mol/liter
CBo = 2 mol/liter
CCo = 1 mol/liter
CDo = 0.5 mol/liter
CEo = 0 mol/liter.
 Solving Simple Kinetics Problems Analytically
A + B → C, with r1 = k1CACB

C + D → E, with r2 = k2CCCD

 We can write the rate equations for these

reactions in terms of the concentrations as:
 One way to do this is to write the concentrations
in terms of CA and CD. Either directly from the
reaction stoichiometry, or by observing that
 Solving Simple Kinetics Problems Analytically
 Alternatively, we can write equations in terms of two fractional
conversions. The definition of these is somewhat arbitrary, but one
choice is

 With these definitions, the concentrations can be written in terms of the

fractional conversions as
 Substituting the above expressions into the
rate equations for CA and CD gives
 Solving Simple Kinetics Problems Analytically
 the first of these equations is a separable equation that we can integrate
directly as

 Integrating this equation gives

 which we can solve for x1 to get

 Solving Simple Kinetics Problems Analytically

 Substituting this into the equation for x2 gives

 This ODE does not have an explicit analytical solution for x2. However,
it can be integrated numerically for particular values of the rate
constants and initial concentrations.
 Solving Simple Kinetics Problems Analytically
 For the values given at the beginning of this example, the fractional
conversions vs. time are as plotted here:

 What's the point?

This example illustrates two main points:
(1) We can write kinetic equations and solve kinetics problems in terms of either
concentrations or fractional conversions.
(2) Even a simple-looking problem like two consecutive second-order reactions may not
have a simple analytical solution.
 Reaction extent, ε
 An alternate but related concept to the fractional conversion is the
extent or degree of advancement of the reaction.
 Think of the reaction extent, ε, as a counter used to keep track of the
number of reaction events. ε is incremented by +1 every time the
forward reaction occurs, and decremented by –1 every time the reverse
reaction occurs.

 If  is the number of reactions events that occur during time interval

t, then the reaction rate is:
 Some Additional Important Definitions
 Another important concept in chemical kinetics is the difference
between an elementary reaction and the overall or stoichiometric
reaction. The overall reaction is what is observed macroscopically, for
example in a methane flame, the overall reaction is
CH4 + 2 O2 → CO2 + 2 H2O
 However, this occurs in many steps. At the molecular level, two oxygen
molecules do not come together with a methane molecule and
rearrange to give two water molecules and carbon dioxide.
 An elementary reaction is one that occurs as a single, irreducible event.
That is, the molecules react as written. An elementary step that occurs
during methane combustion is
CH4 + OH → CH3 + H2O
 Some Additional Important Definitions
 Elementary reactions are often classified by their molecularity. This is
simply the number of molecules participating in the reaction.
A → B and A → B+C
are unimolecular reactions – they each have one reactant. The first
reaction is an isomerization and the second reaction is a unimolecular
decomposition reaction.
A+B → C+D
is a bimolecular reaction.
A+B → C
is also bimolecular, and is often referred to as a recombination reaction.
 Unimolecular reactions and recombination reactions often have
pressure dependent rate parameters. Termolecular reactions (which
have three reactants) are very rare. No elementary reactions of
molecularity higher than 3 are known.
 Law of Microscopic Reversibility
 All reactions are, in principle, reversible. We generally only consider a
reaction reversible when, under some conditions of interest, it does not
go to completion. That is, it attains equilibrium, with detectable amounts
of all reactants and products present.
 For elementary reactions, the law of microscopic reversibility states
that the forward and reverse rate coefficients are related by the
equilibrium constant.

 For example, the reversible reaction

A+B↔C+D
 has net reaction rate
 Arrhenius Equation
 The temperature dependence of the rate coefficient is generally
expressed by the Arrhenius equation or a generalized form of it. This is

 Ea is known as the activation energy, and A is called the pre-exponential

factor. This functional form was established on empirical grounds, but
there are theoretical reasons why a form like this should work.
 A more general form that is often used when rate coefficients must be
parameterized over a large temperature range is

 Note the strong temperature dependence of the rate coefficient on

temperature, and note that small uncertainties in the activation energy
can lead to large uncertainties in reaction rate.
 An Arrhenius plot is a plot of ln(k) vs. (1/T), which gives a straight line with a slope of -
Ea/R if the temperature dependence of k obeys the Arrhenius equation.
 Reaction Mechanism
 The temperature dependence of the rate coefficient is generally
expressed by the Arrhenius equation or a generalized form of it. This is

 How does this reaction actually take place on the molecular level? What
is the reaction mechanism?

 It is extremely unlikely that this reaction occurs as written, with six

molecules colliding simultaneously, and then disassociating into the
seven product molecules. Instead, this reaction takes place in a series
of steps, probably a series of bimolecular collisions.
 Reaction Mechanism
 A simple reaction mechanism describing the thermal decomposition of
dichlorosilane is:
SiH2Cl2 ↔ SiHCl + HCl (1)
SiHCl + SiH2Cl2 ↔ HCl2SiSiH2Cl (2)
HCl2SiSiH2Cl ↔ HCl2SiSiCl + H2 (3)
HCl2SiSiCl ↔ HClSiSiCl2 (4)
HClSiSiCl2 ↔ SiHCl + SiCl2 (5)

 The overall process described by this mechanism is

SiH2Cl2 → SiCl2 + H2
 The other species (SiHCl, HCl2SiSiH2Cl, HCl2SiSiCl, and HClSiSiCl2) are
produced in relatively small amounts and can be considered reactive
intermediates.
 Reaction Mechanism
 The complete set of rate equations for this mechanism is
 Classical Approximation Methods
 The first approximation that we will consider is the partial equilibrium
approximation.
 Here we assume that a particular reaction (or set of reactions) is so fast
(in both the forward and reverse direction) that it reaches equilibrium on
a time scale much shorter than the time scale for the overall process.
 In the reaction mechanism discussed, reaction (4) is very fast relative to
the others, and it may be a good approximation to assume that it is in
equilibrium. If so,

 Thus, we can eliminate one concentration variable from the system of

equations by making this approximation.
 Classical Approximation Methods
 A more widely applicable approximation is the pseudo-steady-state
approximation. This is also called the steady state approximation or the
Bodenstein steady state approximation.
 Here, we assume that the reactive intermediates are produced and
consumed at rates much faster than the stable species.
 Their concentrations therefore adjust very rapidly to the concentrations
of the stable species, and they behave as if they are in steady state on
the time scale of the concentration changes of the stable species.
 We therefore assume that the rates of change of the concentrations of
the reactive intermediates are zero. Mathematically, this allows us to
replace ordinary differential equations with algebraic equations.
 Classical Approximation Methods
 If we apply the pseudo-steady-state approximation to the reactive
species in the mechanism above (without applying any partial
equilibrium approximations) we obtain

 In principle, this allows us to eliminate all of the reactive intermediates’ concentrations

from the system of equations. In practice, this still may not be easy.
 Classical Approximation Methods
 For the above system, it allows us to write

 This illustrates that the overall reaction is in fact

SiH2Cl2 ↔ SiCl2 + H2
 and that HCl inhibits the overall reaction, even though it is neither a
reactant nor a product in the overall reaction. However, it is still not
simple to obtain an analytical expression for the rate of change of
SiH2Cl2 concentration with time.