1.

Introduction, K inetics, Therm odynam ics

Reactor Technology Fundamentals

Chemical Engineering, R Rawatlal

1. Introduction
The reactor is the heart of any chemical process; the conversion of raw materials to higher
value species is central to Chemical Engineering. The design of a reactor chiefly concerns
management of the reaction rate and the products that result (which might not all be
desirable products). The chemical engineer must maintain a reaction rate in the most cost-
effective way at a scale typically on the order of tens or even hundreds of tons per day.

Chemical reactors vary in scale; the majority are on the order of tens of cubic meters in
volume. However, micro-reactors do exist in the fine chemicals sector. Most reactors are
catalytic, meaning that catalysts in various forms are present to increase the rate of the
reaction.

Temperature control is a key is issue in a reaction; the reaction rate is a strong function of
temperature, with many reactions increasing by a factor of 2 for every 10 degree rise in
temperature. Many chemical reactors operate in the 400-800K range.

Temperature control is such an important factor that most reactors look and even operate as
if they are heat exchangers. The reaction plays a significant role in changing the temperature
in the reactor, and a significant part of the course concerns modelling and designing around
this. The hydrodynamics/flow pattern is also influences this, together with the concentration
profile.

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Another responsibility of reactor design is the development of the control system to maintain
the reaction rate. In addition to the temperature, the control system may also maintain the
levels and amounts of the various phases in the reactor, and the concentration of the species.

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Reactor with level and temperature control (reaction may be exothermic)

Catalytic reactor – catalyst packed in tubes

Scope is chemical reaction – not nuclear – change of molecules; not atomic change

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1.1 The (R eactor) R eaction R ate
The reaction rate is the rate at which the reactant feed is converted to the product feed.
There is a tendency to use the concept of “speed” and “rate” interchangeably; this leads to
errors. Abstractly, the reaction rate informs the quantity of a given species that reacts on a
basis of both time passed and reaction space occupied.

The default reactor reaction rate is defined on a basis of reactor volume:

𝑟𝑖 [=] 𝑚𝑜𝑙. 𝑠 −1 . 𝑚−3

We define 𝑟𝑖 as rate of formation of component 𝑖. We read the definition above as “The rate
of formation of component-𝑖 is 𝑟𝑖 moles per second per cubic meter of reactor volume.”. We
must carefully maintain the meaning of the reaction rate; this is a topic we return to
repeatedly.

The (value of the) reaction rate depends on:

- Kinetics – the tendency for chemical species to react. Is a strong function of

temperature (Arrenhius dependence)
- The concentration of the reacting species

The latter is influenced by

- Mass transfer – how fast can molecules move to get into contact for reaction to occur
- Hydrodynamics – how does convective flow distribute the molecules in the reactor
- The reaction itself – which either consumes or produces the component

In this course, the focus will largely be on the determination of the reaction rate under the
various possibilities and combinations of kinetics, mass transfer and heat transfer, and
hydrodynamics.

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1.2 Ideal reactor types
Generally speaking, we may solve the Navier-Stokes equations on any reactor type to predict
the reaction rate in three dimensions.

Temperature and concentration may vary across the space

This is always possible, but is somewhat brute-force. As chemical engineers, we can be much
cleverer, and be able to make very good approximations that we can solve (sometimes with
pencil and paper) without having to resort to writing code.

When developing material and energy balances as part of the reactor design, we consider
three idealisations.

We’ll talk about these ideal types in more detail later. A real reactor can be thought of as a
network of these three types of flow, and we also have clever theory that helps us determine
this network.

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2. Introduction to r eaction kinetics
It is useful at this stage to revise the kinetic theory of gases to develop a deeper
understanding of reaction kinetics.

We may also review the concept of temperature as the average kinetic energy of the
molecules. Clearly, a higher temperature is a good indication that the molecules are moving
faster, and its then obvious that there will be more collisions among molecules and hence a
stronger chance of reaction happening between any two molecules. For this simple reason, we
readily accept that higher temperatures cause all reaction rates to increase. This would also
include unwanted reactions.

2.1 R eaction stoichiom etry

Based on our understanding of the steps involved in a reaction of one group of molecules to
form another group of molecules, we may propose some reaction mechanism; a very simple
example:

2A → B
𝑟𝐴 𝑟𝐵
=
𝜈𝐴 𝜈𝐵
𝑟𝐴 𝑟𝐵
=
−2 1

We wish to determine the rate at which this happens. To define the rate, we introduce the
symbol ri, which has the default units of mol.s-1.m-3. We read ri as the rate of formation of
component i. In fact, to make our calculations more explicit, it is useful to cite the value of
the reaction rate as mol-i.s-1.m-3. This emphasises which component’s rate is being
considered.

For the example above, in the rate which A is consumed is exactly twice the rate at which B
is formed. Note that since the default for r is rate of formation, for consumption reactions,
we write –rA.

For this example, clearly, -rA = 2.rB.

More generally we can state

𝑟𝑖 𝑟𝑗
=
𝜈𝑖 𝜈𝑗

..where 𝜈𝑖 is the stoichiometric coefficient (Greek symbol 𝜈 is pronounced “new”). This

relationship holds for any two species participating in the same one reaction (even if one is a
reactant and the other is a product). For example, try out all combinations of

3𝐴 + 2𝐵 → 2𝐶

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Note that the mass is preserved in a reaction, so there is a constraint on the molecular
masses among these three species. Generally, we may write

∑ 𝑀𝑀𝑖 . 𝜈𝑖 = 0
𝑖

2.2 R eaction rates vs reaction speeds

To really understand a reaction rate, it is useful to separate the term “rate” into a “speed of
an event” and the “frequency of events”. In the example, let’s say the reaction is initiated
when two molecules of A collide. Various bonds will break and form thereafter until the two
molecules have formed B, and this will take a fixed amount of time, e.g. 5 microsceconds.
We can therefore say the speed at which the reaction happens is proportional to 1/(5s).

On the other hand, the total amount of B formed will depend on the total number of
collisions between A molecules. This depends on two main factors: how many A molecules
are present, and how fast are they moving. The more of A present, the better the chance of a
collision. The faster the molecules are moving and vibration, again, the better the chance of
a collision (more trajectories per second).

We summarise all these concepts as a reaction rate. The reaction rate must therefore be a
function that depends on the nature of the components reacting (for the speed of the
reaction event) as well as the concentration of reactants, as well as the temperature of the
reaction.

A reaction rate therefore has the ffg form:

ri  f (T , c)

The exact form of this function depends on the sequence of steps involved in the reaction (on
the mechanism). The typical representation is as follows

rA  k .c Aa

k is known as the kinetic rate constant, relates to the speed of the reaction even, and is a
strong function of temperature. The power a is the order of reaction.

The kinetic rate constant follows the Arrenhius expression (see derivation from Kinetic
Theory of Gases, Collision Theory):

 E 
k  A.exp   a 
 R.T 

where A is referred to as the pre-exponential factor and Ea is the activation energy. The
value of Ea is also interpreted as the energy required for the steps involved in the reaction
(breaking and forming of bonds) to complete.

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The reaction stoichiometry must always be known since it is required to complete the mass
balance on the species involved, and because it may even factor in determining the rate
expression.

Exam ple

2 SO2 + O2 → 2 SO3

i.e. 2 A + B → 2 C

The stoichiometric coefficients are A = - 2, B = - 1, C = 2.

𝑟𝐴 𝑟 𝑟𝐶
Clearly, −2
𝐵
= −1 = 2
=: 𝑟

For any given reaction, we may write

ri rj
  r where i and j are any species involved in the reaction.
i j

If this reaction is elementary, then clearly

2
−𝑟𝑆𝑂2 = 𝑘. 𝑐𝑆𝑂 .𝑐
2 𝑂2

We note here that a consumption rate is usually written as −𝑟𝑆𝑂2 since as mentioned
previously, we define 𝑟𝑖 to be the rate of form ation of component 𝑖.

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2.3 Elem entary R eactions
Elementary reactions are those where the species react directly to form products in a single
reaction step. An apparently elementary reaction may in fact be a stepwise reaction, i.e. a
sequence of chemical reactions, involving reaction intermediates.

For such reactions, the Collision Theory allows for prediction of the reaction rate expression.
Consider a reaction involving species i and stoichiometric coefficients i. In this case, the rate
expression is simply

ri  ki . c j j


For the example above, we have simply rSO2  k.cSO2 .cO2

2

The order of reaction can be obtained as the sum of the powers of the factors in the rate
expression; for the example shown, the order of reaction is 2 + 1 = 3.

It is often the case that an “overall” reaction equation is actually composed of a series of
reaction sub-steps. The sub-steps may be elementary, and we can develop the overall rate
expression in terms of the sub-steps; in fact, this is an important topic that will be fully
developed later in the course. This usually results in a more complex mathematical
expression. In engineering, this complexity is sometimes avoided by proposing an empirical
expression which looks like a rate expression but which is not based on the sub-steps. In this
case, the expression is no-longer empirical, and as much as we may pretend otherwise, it is
simply an equation without physical meaning. It is still useful to us as engineers, since as
long as the expression returns reasonably accurate values of the rate, it may be suitable for
the purpose. Generally speaking, we term this a non-elementary reaction, which, if you like,
is a man-made construct. [It doesn’t occur in nature but is useful for our purpose.]

The m olecularity is the number of molecules involved in the reaction. Consider:

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2.4 R eversibility
We term a reaction reversible if it is possible for the products to recombine to give us back
the reactants. Strictly speaking, this is always possible, and it is only the rate at which the
reverse reaction occurs that causes us to term the reaction reversible or not.

Reversible reactions are represented as follows

2.5 R eaction equilibrium

The equilibrium constant is defined as the ratio of the forward to the reverse reaction rate
constant; in the example above,

k1
K1 
k1

At equilibrium, the rate of the forward reaction is equal to the rate of the reverse, causing
the net reaction rate to be zero:

rA  0 => k1 cAe cBe  k1 cCe

2

Note the use of the subscript e to specify that these are the equilibrium concentrations.
Using this equation with the definition of the equilibrium constant above, obtain:

k1 c2
K1   C
k1 c AcB

2.6 C onversion

We define the conversion of a component 𝑖 as the relative difference between its initial
amount and the current amount. For example

𝑁𝐴0 − 𝑁𝐴 (𝑡)
𝑋𝐴 (𝑡) =
𝑁𝐴0

If the volume is the same initially and at the current time, we may write

𝑁𝐴0 /𝑉 − 𝑁𝐴 /𝑉 𝑐𝐴0 − 𝑐𝐴
𝑋𝐴 = =
𝑁𝐴0 /𝑉 𝑐𝐴0

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Let’s assume that we feed a reactor with stoichiometric amounts (equal amounts, in this
case) of reactants and that no product is fed. If the fractional consumption of A is XA,
clearly then

cA  cA,0 .(1  X A )
cB  cA,0 .(1  X A )
cC  2.cA,0 . X A

..and so the equilibrium becomes

 2.cA0 . X Ae 
2
c2 4. X Ae 2
K1  Ce  
cAe cBe cA0 . 1  X Ae  .cA0 . 1  X Ae  1  X Ae 2

For a given temperature, k1+ and k1- and hence K1 will take specific values. From the
relationship above, then, we can say that for a given temperature, there is a given
equilibrium conversion; at this value the net reaction rate is zero. If the net rate is zero, the
system cannot by itself change in conversion – there is no net driving force for concentration
to change. This value can then be understood as a limiting value given a temperature.

Of course, as chemical engineers, we will find ways around this; this is after all only the
equilibrium value, and we most often are not operating close to equilibrium. This is an
important topic for later in the course. At this stage, it is simply useful to know that this
value exists and that this is the method by which it can be determined. It could be said that
we now have a way to determine an operating region of the reactor which should be avoided.
More about that later.

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3. Therm odynam ics
We should also note that the equilibrium constant can also be determined using the ffg.
thermodynamic relationship:

G 0
ln K  
RT
Even more useful is the vant’ Hoff equation:

d ln K H R

dT RT 2
Therefore, even when the rate constants of the individual steps are unknown, the equilibrium
constant temperature dependence (and hence the equilibrium conversion) can be determined
as a function of temperature.

C hem ical driving force

It should be noted that the driving force for reaction should, strictly speaking, be written in
terms of activity. However, under most conditions in reaction engineering, the concentration
is close enough approximation that we will be using it almost exclusively in the further
developments. We will also occasionally use partial pressures in lieu of concentration since
the relationship between the two is, for gases, obvious.

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Sum m ary
This section only introduces the basic elements of reaction kinetics. A deep study of kinetic
studies is the beginning of a fundamental understanding of any chemical process and forms
the basis of performing effective reactor design. Many nuances emerge as we tour reaction
engineering; what is presented in these two pages serves more as an introduction to the basic
elements rather than a comprehensive coverage of this fascinating science.

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