BASIC REACTORS

Homogeneous Reactions

As a student of chemical engineering, you will have been exposed to chemical reactions during
your chemistry studies e.g. when hydrochloric acid reacts with sodium hydroxide an irreversible
reaction occurs which results in two products, water and salt:

HCl + NaOH  H2O + NaCl

This reaction may be represented as:

A+BC+D

Here A and B are called the reactants and C and D are called the products.

Let us now examine the example of a reversible chemical reaction:

2SO2 + O2  2SO3

This reaction may be represented as follows:

2A + B  2C

Here A and B are the reactants and C is the product.

Chemical engineers especially interested in the rate at which the reaction occurs under given
physical conditions. Armed with this information we are able to design industrial reactors.

Reaction Mechanism

Assume that a gas phase reaction occurs in a sealed container as follows:

A + B  2C

A
B

Molecules of A and B will travel around the inside of this container and when they happen to
collide with one another the reaction may occur and C may form. Clearly the concentration of
reactant molecules in the container will dictate how often molecules collide and hence the
rate at which the reaction occurs.

When the number of reactant molecules in a confined space is low, then the number of collisions
that will occur per unit time will be low and hence the number of molecules that will convert to
product, with time, will be low. The rate of reaction therefore will be slow. In addition, if the
number of reactant molecules in a confined space is high, then the number of collisions that will
occur per unit time will be high and hence the number of molecules that will convert to product,
with time, will be high. The rate of reaction will therefore be high.

Equilibrium is the point at which A and B will have reduced to a minimum concentration and C,
the product, will have reached its maximum concentration.

When we deal with a reaction that is particularly slow i.e. equilibrium is attained after some hours.
A long residence time will be necessary to achieve the required conversion and we would
therefore have to use a correspondingly large reactor.

Defining a rate of reaction

How do we define the rate of reaction in a meaningful and useful way?

The example we have above was one of A combining with B to give C. The system parameters
were, a container of fixed dimensions, a starting concentration of A and a starting concentration
of B. We could easily relate the reaction rate to any one of the following:

1. The rate at which A disappears

[A] At any point on this graph, the rate would be -d[A]/dt

time
2. The rate at which B disappears

[B] At any point on this graph, the rate would be -d[B]/dt

time

2. The rate at which C appears

[C] At any point on this graph, the rate would be

d[C]/dt

time

In all three cases above there is a steep gradient initially and the gradient eventually decreases to
zero. This corresponds to a high initial rate of reaction and as time passes, the system approaches
equilibrium and the rate of reaction is zero.

All the cases above the graphs shows exponential relationships, therefore they linearizable with
natural log function
Reaction Rate Directly Proportional to Reactant Concentration
(Elementary Reaction Mechanism)

Our theory that reaction rate depends on concentration holds. We observe this in the previous
example, where the concentrations of the reactants are high; the rate of reaction is high. As the
concentration of reactants decreases the rate of reaction decreases, until equilibrium is achieved.

If the rate of reaction is proportional to the concentration of the reactants then the following must
be true:
1 dN A dC
   A  CA
V dt dt

V is the volume of the container (dm3)

NA is the number of moles of A present in the container (mol)
t is time (s)
CA is the concentration of A in the container (mol.dm-3)

When we introduce proportionality constant an equation results:

dC A
  kC A
dt

The unit of the proportionality constant is s-1. Notice the negative sign on the left. This is
expected as A’s concentration reduces as the reaction proceeds and the rate of change of
concentration (dCA/dt) is negative. We have here a rate equation for an elementary reaction. In
an elementary reaction, a elementary reaction mechanism is present and the rate equation may be
deduced from the stoichiometry of the chemical reaction. The rate equation above is for a “FIRST
ORDER REACTION”, as the rate of the reaction is directly proportional to the concentration
of species A.

A Non-elementary Reaction Mechanism

Acetylene gas is thermally decomposed in the absence of oxygen:

C2H2  H2 + C2*  C(s)

Here the mechanism of the reaction occurs in two stages:

First stage: Heat causes the acetylene to break down into hydrogen and free carbon
radicals (C2*)

Second stage: The free carbon radicals combine to form long chains of amorphous carbon
without an ordered crystal structure.

How would the rate of the chemical reaction that results in the formation of C2* and C(s), with
C2H2 as the reactant be expressed? As there is an intermediary (C2*) that forms and then
disappears, the concentration of C2* will play a role in the rate at which C2H2 converts to C(s).
Although, the concentration of C2*will probably be too small to be measured it will now not be
reasonable to expect the rate of disappearance of A to be directly proportional to the concentration
of A. This is makes the above a non-elementary reaction.

Although it is possible to determine the rate of reaction if the exact mechanism of reaction
is known we will not examine this matter further as it is considered to be beyond the scope
of this course. It is discussed at length in the BTech. For further study consult “Chemical
Reaction Engineering” Chapter 2 by Octave Levenspiel.

Reaction Rate with a Non-elementary Reaction Mechanism

When a chemical reaction is not at equilibrium, it moves towards a state of equilibrium. The
changes in concentrations of the reactants and products on this journey are referred to as kinetic
behaviour. Another source of data often used is that of kinetic decay curve. This is. the way in
which the concentrations decays to the equilibrium concentration. The study of these curves or
“kinetic data” we refer to as reaction kinetics. The modelling of these curves is an area of chemical
engineering research.

[A] [Z]

Reactants Products
If the reaction mechanism is complex, it is sufficient for the purposes of this course to say that:
dC A
  kC An
dt

where CA is the concentration of the reactant (mol.dm-3)

k is the rate constant (s-1.(mol.dm-3)1-n)
t is time (s)
n is the order of reaction

n is called the order of the reaction and although many systems are not perfectly modelled with
a single value of n, a single value of n can be found which may closely fit the data. Note that for
a first order reaction we have the same equation where n is equal to 1.

Conversion (X)

Assume that X is a value between 0 and 1 and represents the extent of conversion of a reactant.
Assume also that we have the following reversible reaction that may, or may, not be elementary.

AB

In a batch test, at time equal to 0 (t = 0) we confirm that our container will hold 100% A and no
B. As time progresses A will decrease as B increases. Eventually equilibrium will be reached.
When only A is present, there has been no conversion and therefore X is equal to 0 and then as A
converts to B, X increases. If the reaction were to go to completion meaning all of A is consumed,
we then say that X becomes 1. From a mathematical perspective:

CA,t=0 is the concentration of A at the beginning of the reaction

CA,t=t is the concentration of A at any time during the reaction
X is the degree of conversion (0 = no conversion)
(1 = total conversion)
C A ,t  0  C A ,t  t
X
C A ,t  0
We should also note that A does not disappear completely at equilibrium, which may occur if the
reaction was irreversible. Given this X may fall short of 1 at equilibrium where the concentration
of A will be CA,t = . The equilibrium value of X will be:

C A ,t 0  C A ,t  
X 0 X 1
C A ,t  0

The integration of kinetic models

Let us now put theory into practice. Let’s assume that we are given kinetic data for a reaction
that is part of a chemical process and that we are tasked with modelling the reaction for the
purposes of designing a reactor. The following is the systematic approach to this task:

1. Postulate a kinetic model that represents the reaction. (First order if we think the reaction
is elementary)
2. Fit the model to laboratory generated kinetic data.
3. If a good fit is obtained in 2, we state that our kinetic model assumption given in 1 is
probably correct, if not then we re-postulate a kinetic model and re-attempt a fit
There are a number of ways in which we may fit a particular kinetic model (rate equation) to raw
concentration data. However, for the purposes of this introductory course we will simply use the
technique of model linearisation. If the data gives the appearance of a straight line this would tend
to indicate that the model applies to the system. Remember that a reasonable model fit does not
guarantee the location of the correct reaction mechanism but does mean that a dynamic model
has been located that effectively imitates the system under the given conditions.

Let’s examine the fitting of a first order kinetic model to data in the following example.

Prove that the first order kinetic equation (  dC A

 kC1A )describes the disappearance of A in the
dt

following non-reversible reaction where A completely converts to B:

AB
The kinetic data is as follows:

Time (s) [A] (mol.dm-3) (X) (1-X)

0 0.01 0 1
1 0.0099 0.01 0.99
3 0.0097 0.03 0.97
9 0.0091 0.09 0.91
27 0.0076 0.24 0.76
81 0.0044 0.56 0.44
 0.0000 1.00 0.00

To determine if the first order model equation correctly represents the kinetic data, manipulate
dC A
  kC A
dt
1
dC A   kdt
CA
C A ,t  t t t
1

C A ,t  0
C A
dC A   k  dt
t 0

ln C A,t  t  ln C A,t 0   k ( t  0)
the first order equation into something more useful:
Simplify
We also know the following:

C A ,t  0  C A ,t  t C A,t 0 C A ,t  t C A ,t  t
X    1
C A ,t  0 C A,t 0 C A ,t 0 C A ,t  0
C A ,t  t
or 1  X 
C A ,t  0

C A ,t  t
ln   kt
C A ,t  0
C A ,t  t
 e kt
C A ,t  0
C A ,t  t
When we combine equations we find the following: 1  X   e kt
C A ,t  0

When we now plot 1- X against time we will find the following curve:
 1.2
1
0.8

(1-X)
0.6
0.4
0.2
0
0 50 100

time (s)
An exponential decay curve, showing how A slowly disappears, results. We have a number of
options to which we may resort to get the model in the form of a linear equation. Linear forms of

C 
 ln  A,t t   kt  0
 C A ,t  0 
 ln( 1  X )  kt  0
the first order model are the following:

Observe the linear relationship between the left of each equation and time (t) on the right-hand
side? If the data is truly from an elementary reaction then a plot of –ln(1-X) against time (t) should
give a straight line passing through the origin with k being the slope.

1
0.8 y = 0.01x + 0
-ln(1-X)

0.6 R2 = 1
0.4
0.2
0
0 50 100

time (s)

We see that when we plot -ln(1-X ) against time we do indeed achieve a straight line. If we plotted
–ln(CA,t=t/CA,t=0) against time we would achieve the same. Notice that the slope of the curve is
0.01 and hence we can report that the RATE CONSTANT (k) is equal to (0.01 s-1). We also
notice that the intercept is equal to zero.

An R2 of 0 means that there is no correlation to a straight line and an R2 of 1 means it is a perfect

correlation.

To determine the intercept for a particular set of data use the following equation:
(Y )( X 2 )  (X )( XY )
 intercept
NX 2  (X ) 2

To determine the slope of the curve use the following equation:

N (XY )  (X )( Y )
 slope
NX 2  (X ) 2

To determine the R2, use the following equation:

2
 
 N (XY )  (X )( Y )   R2

 N  X 2

  X  N  Y 2   Y 
2 2
 


In summary, when given kinetic data we postulate a elementary kinetic model. We linearise the
model and plot the raw data on a graph in a linearised form. When the data is linear, we conclude
that the kinetic model is representative of the data. We also conclude that it is an elementary
reaction and that no intermediary radicals exist.

Searching for the correct model

A number of kinetic models may be postulated and R2 may be used to establish which represents
the best fit to the given data.

Example

The following gaseous, irreversible, reaction has been studied in the laboratory. The reaction
takes place in a confined space and there is no net change in pressure or temperature. Observe
from the equation the number of moles of gas present, before and after conversion is the same.

A  B

Establish whether the data represents first or second order kinetics.

dC A
First order model:   kC1A
dt
dC A
Second order model:   kCA2
dt

Reaction data:

Time [A]
0 0.1
4 0.099602
16 0.098425
64 0.093985
256 0.079618
1024 0.049407

The integration of the first order model has already been covered in the previous section and the
C 
 ln  A,t t   kt  0
 C A ,t  0 
 ln( 1  X )  kt  0
linearised forms of the model that we will use is
Now let us find the linearised form of the second order equation:
dC A
  kC A2
dt
C A ,t  t t t

 C A dC A  k  dt
2

C A ,t  0 t 0

1 1
C C
A ,t  t A ,t  0
   kt
1 1
1 1
   k ( t  0)
C A ,t  t C A ,t  0
1 1
   kt
C A ,t  0 C A ,t  t
1 1
  kt
C A ,t  t C A ,t  0

Now plot the data in the from of the two integrated models and see which one gives us a straight
line and which does not.

time [A] 1/CA,t=t- -

1/CA,t=0 Ln(CA,t=t/CA,t
=0)
0 0.1 0 0
4 0.0996 0.04 0.0040
16 0.0984 0.16 0.0159
64 0.0940 0.64 0.0620
256 0.0796 2.56 0.2279
1024 0.0494 10.24 0.7051
 12
Second order function
First order function y = 0.01x
first order and second order

10 R² = 1

y = 0.0007x
4 R² = 0.9926

0
0 200 400 600 800 1000 1200

time (s)

First order plot gives us R2 = 0.9926

Second order plot gives us R2 = 1.0

The reaction is a second order reaction.

This means that the kinetic data given indicates that the reaction is not an elementary reaction.
Tutorial 1 (MODULE 5 – Basic Reactors)

1. Is the following data part of a kinetic decay curve of a first or second order reaction? The
reaction is irreversible A  B

Time [A]
0 0.5
2 0.45
4 0.42
8 0.36
16 0.28
32 0.19

2. The following data is part of kinetic decay curve and the reaction is irreversible and is
deemed to be non-elementary. The order of reaction is unknown but is through to be
between 1 and 2. What is the order of reaction? A  B

Time [A]
0 0.8
1 0.73
3 0.62
9 0.41
27 0.16
81 0.037