Lecture 1

Introduction & Overview to Chemical Reaction Engineering II

Introduction & Overview

Chemical reaction engineering

� Central topic in chemical engineering

– synthesis of materials
– remediation of polluted air, water, soil
– energy generation
� Two main areas
– chemical reaction kinetics
– reactor design

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.

What is a 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

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

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).

Other examples
 The energy required to vaporize 1 mole of liquid water at 100 oC, 1 atm is 40.7 kJ; there is
thus an increase in the mass of H2O of 0.45 ng upon vaporization.
 If 1 mole of liquid water is cooled from 100 oC to 0oC, the mass of the water decreases by
0.084 ng.
 Don’t try the E = mc2 exercise weight loss plan; you need to burn 9.8 quadrillion calories
to lose 1 lbm!

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.

Definitions of and Notation for Reaction Rates:

Reaction rate, r
The series of collisions must occur over a short time period. If not, we’d expect to see additional
chemical species that are reaction intermediates. If the collisions occur quickly, the intermediate
species are transient – only present for a short duration of time and never present in significant
concentrations.

We will discuss reaction mechanisms in more detail later; for now, we can consider this to be a
single “reaction event”.

Reaction rate: 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

In these expressions, -a, -b, c, and d are the stoichiometric coefficients of the chemical species A,
B, C, and D, respectively. C , C , C , and C are the concentrations (number of molecules or
A B C D
moles per unit volume) of the chemical species.

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.

As presented here, 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. 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.
th th
With the above form, we refer to the ν ij as the order of the i reaction with respect to the j
species.

In your Chemical Reaction Engineering-I course, you learned all of this. Be sure you know how
to take a reaction mechanism and write the kinetic equations (which are first-order ordinary
differential equations) for the concentrations of the species in a constant temperature, constant
volume system.

Solving Simple Kinetics Problems Analytically

As an undergraduate, you also learned how to analytically integrate the rate equations for 1 st
order, 2nd order, and probably nth order reactions. 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

On a test, you would be expected to be able to write this down from memory (that is, in less than
10 seconds).

You will find some other simple integrated rate equations in the text by Octave Levenspiel and H
S Fogler. There are many more in other kinetics texts, but of course you can always integrate the
rate equations by hand or using Mathematica or Matlab. Be sure that you are proficient in this as
well.

Example:
Suppose we have the two reactions
-1 -1
A + B → C, with r1 = k1CACB and k1 = 10 liter mol s
-1 -1
C + D → E, with r2 = k2CCCD and k2 = 5 liter mol s

and the initial concentrations of the species are

CAo = 1 mol/liter
CBo = 2 mol/liter
CCo = 1 mol/liter
C = 0.5 mol/liter
Do
C = 0 mol/liter.
Eo
We can write the rate equations for these reactions in terms of the concentrations as

Since there are only two reactions, we know that at most two of these equations are independent.
That is, we can solve for two concentrations or two extents of reaction, and the other
concentrations can then be determined from the reaction stoichiometry. There are several
possible approaches to this. 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

We can write

Substituting these into the rate equations for A and D, we get

We could now integrate these equations. Alternatively, we can write equations in terms of two
fractional conversions. The definition of these is somewhat arbitrary, but one choice is

These are dimensionless terms, but we could equally well choose extensive rates of reaction
(with units of moles or units of concentration). 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

or

the first of these equations is a separable equation that we can integrate directly as

integrating this equation (using Matlab, Mathematica, integral tables or whatever method is most
convenient) gives

which we can solve for x1 to get

substituting this into the equation for x2 gives

this ODE does not have an explicit analytical solution for x2 (or at least I couldn't readily solve
it). However, it can be integrated numerically for particular values of the rate constants and
initial concentrations. 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, , as a counter used to keep track of the number of reaction events. 
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 (of words shown in italics):

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

Note that this reaction contains species that are not part of the overall reaction (the highly
reactive radicals OH and CH3). Species such as these are referred to as reactive intermediates.

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.

A necessary, but not sufficient, condition for a reaction to be elementary is that its rate follows
the law of mass action. This simply means that the reaction order with respect to each reactant is
the absolute value of its stoichiometric coefficient. Note that some reactions that are not
elementary may coincidentally obey the law of mass action – especially over limited regimes of
species concentrations, temperature and pressure. Most observed reactions are not elementary,
but are the sum of many elementary reaction steps. Most reactions do not obey the law of mass
action over wide ranges of species concentrations.

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

Noting that the net rate is zero at equilibrium shows that the above relationship between the rate
constants and equilibrium constants is true. This requires that the form of the rate expression
does not change for concentrations away from equilibrium. This is true for elementary reactions,
which obey the law of mass action at all concentrations.

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. You should know how to make
an Arrhenius plot from a set of data and extract the activation energy and pre-exponential factor
from it.

Reaction mechanism
Consider a single reaction:
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.

The reaction mechanism is the set of elementary reactions that lead to the overall reaction that is
observed. Generally, it consists of a large number of reactions, and it is not possible to
analytically integrate the reaction rates to find the species concentrations as an explicit function
of time. 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)

(Disclaimer: this is highly simplified for pedagogical purposes and should not be interpreted as a complete reaction mechanism
for dichlorosilane decomposition).

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.

The complete set of rate equations for this mechanism is

This is a set of coupled, nonlinear ODE’s that cannot readily be integrated analytically.
Numerical means of integrating such systems may be employed. You should also note that not
all of the equations given above are independent – three of them could be eliminated by taking
linear combinations of the others (try this for yourself). For now, however, we will consider
some classical approximation techniques that have often been applied in simplifying reaction
mechanisms. With the advent of modern computers it is no longer necessary to apply these to get
a solution, since we could always integrate the full equations numerically. However, their
application can still be very useful in developing physical understanding the reaction mechanism.

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 above, 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.

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. 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.

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.