Module 4

BASIC REACTORS

Understanding Homogeneous reactions

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

HCl + NaOH → H2O + NaCl

We can present this reaction in another manner

A + B → C + D

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

Let’s look at another example. This reaction is reversible.

2SO2 + O2 ↔ 2SO3

Again we can represent this reaction in the following way

2A + B2 ↔ 2C

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

Now as chemical engineers we are not so interested in the reaction itself, the chemists tell
us that it exists in addition to giving us the fully balanced equation. What we are
interested in is the rate at which the reaction will occur, for the given circumstances.
Armed with this information we can then design industrial size reactors.
A mechanism of reaction

How do we begin to rationalise the rate at which a reaction occurs? Lets begin by
assuming we have a gaseous reaction occurring in a sealed container thus.

A + B ↔ 2C

A
B

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

If 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 will be slow.

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 be high.

How does knowing the rate of reaction help us? Well if we have a reaction that is
particularly slow. Let’s say reactant A and B are put into a container and by experience
we know that only after some hours is equilibrium attained. 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. We will then know that a large reactor with a
long residence time will be necessary to achieve the conversion we are looking for.
Defining a rate of reaction

How do we express our rate of reaction, or 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

3. The rate at which C appears

 [C] At any point on this graph, the rate would be
d[C]/dt
time
In all three above graphs the rate of reaction to begin with, is high, as there is a steep
gradient to begin with. As time moves on and the system approaches equilibrium the
gradient eventually flattens to zero and hence we say that the rate of reaction is zero.
Reaction rate directly proportional to reactant concentration
(A simple reaction mechanism)

Our theory that reaction rate is proportional to concentration, holds. We see how, in the
previous example, when the concentrations of reactants are high the rate of reaction is
high. As the concentration of reactants diminish the rate of reaction decreases, until
equilibrium is achieved.

If the rate of reaction is proportional to the concentration of reactants then the following
must be true:

1 dN A dC A
− ∝− ∝ CA
V dt dt
Where
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)

If we introduce a constant (proportionality constant) we can turn this proportionality into

an equation thus:

dC A
− = kC A
dt
What are the units of the proportionality constant? (s-1) Notice the negative sign on the
left. This we expect as A is reducing in concentration. This situation given here is what
we call a rate equation for an elementary reaction. A simple mechanism is present. We
also refer to this as a “FIRST ORDER REACTION”

A more complicated reaction mechanism

What happens in the case where the following reaction occurs:

Acetylene gas is thermally decomposed in the absence of oxygen
C2H2 → H2 + C2* → C(a)
Here we see two mechanisms occurring in one reaction

First stage The heat causes the acetylene to breakdown into hydrogen and free
carbon radicals (C2*)

Second stage The free carbon radicals combine to form long chains of
amorphous carbon (amorphous means no ordered crystal structure)

Just as before we can present this reaction in the following manner

A → B2 → D(a)
→ C2

As we essentially have a chemical reaction that results in the formation of D and C, with
A being the reactant we now ask ourselves what would be the rate of reaction here. As
there is an intermediary (B) that has to form and then disappear. The concentration of B
will play a role in the rate at which A converts to D and the concentration of B will
probably be too small to effectively detect let alone measure. 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 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 boundaries of this course. It is discussed at length in the Btech. For
further study consult “Chemical Reaction Engineering” Chapter 2 by Octave
Levenspiel.
How do we determine the rate of reaction of a more complicated reaction
mechanism?
Firstly we have to understand the term “kinetic data”. When a chemical situation is
created that is not at equilibrium, the system tries to move towards a state of equilibrium.
The concentration change of the reactants and products we refer to as kinetic behaviour.
Another term that is often used is that of kinetic decay curve i.e. the way in which the
concentrations decay to the equilibrium situation. The study of these curves we refer to as
reaction kinetics.

[A] [Z]

Reactants Products

The modelling of these curves is an exclusive area of chemical engineering research. For
the purposes of this course it is sufficient to say that the disappearance of a reactant, if the
mechanism is considered to be complicated, could be given by the following equation.
 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

The n term we refer to as the rate of reaction and although many systems are not
perfectly modelled from a single value of n, a single value of n can be found which may
closely fit the data. Notice that in a first order reaction, referred to earlier, we have the
same equation but n is equal to 1, hence first order reaction
Conversion and the X factor

For the purposes of understanding conversion lets assume that X is a value between 0 and
1 and represents the extent of conversion of a reactant. Lets assume we have the
following reaction that may, or may, not be elementary. The reaction is reversible.
A ↔ B

Now 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.
Let’s make the statement that when only A is present, there has been no conversion and
therefor X is equal to 0 and then as A converts X increases. If the reaction were to go to
completion meaning all of A is consumed, we then say that X becomes one. Lets look at
the matter from a mathematical perspective
Where
CA,t=0 is the concentration of A at the beginning
CA,t=t is the concentration of A at any time during the reaction

C A , t =0 − C A , t = t
=X
C A , t =0
X is the degree of conversion (0 = no conversion)
(1 = total conversion)

We should also make the statement that should A not disappear completely at
equilibrium, which may occur if the reaction is reversible, then X may fall short of 1 at
equilibrium. We refer to the equilibrium concentration of A by using the following term
CA,t = ∞. The equilibrium value of X will therefor be:
The integration of kinetic models

All this theory is great but how do we actually apply it in practice? Let’s assume that we
C A , t = 0 − C A ,t = ∞
=X 0< X <1
C A ,t = 0
are given kinetic data from a reaction that is part of a process and that we are tasked with
modelling the reaction for the purposes of designing a reactor for industrial application of
the process. The following is the systematic approach to this task:

1. We start by postulating a kinetic model that we say represents the reaction. (First
order if we think the reaction is elementary)

2. We then 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 can 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. As a senior student of chemical
engineering you will have had some exposure to this technique. The model is linearised
and the data is then presented on a graph in the manner of linearisation. If the data gives
the appearance of a straight line this would tend to indicate that the model is good for the
system. Let’s examine the fitting of a first order kinetic model to data in the following
example.

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.

Example

Prove that the first order kinetic equation,

dC A
− = kC 1A
dt
describes the disappearance of A in the following reaction,

A → B

where A completely converts to B in a non-reversible reaction.

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, lets
integrate our first order equation into something more useful:
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)

Continuing with the integration. We achieve the following two versions of the integrated
equation.

C A ,t = t
ln = − kt
C A ,t =0
C A ,t = t
= e −kt
C A ,t = 0
We also know the following:

C A ,t = 0 − C A , t = t C A , t = 0 C A , t = t C
X= = − = 1 − A,t = t
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

If we combine equations we come up with the following:

C A, t = t
1− X = = e − kt
C A,t = 0
If we now plot 1- X against time we will achieve the following curve:
We notice that we clearly have an exponential decay curve, showing how A slowly
disappears.
Now to get our model in the form of a linear equation we have a number of options that
we can use. Linear forms of the first order model are the following:

1.2
1
0.8
(1-X)

0.6
0.4
0.2
0
0 20 40 60 80 100
time (s)

C 
− ln A,t =t  = kt + 0
 C A ,t = 0 
− ln(1 − X ) = kt + 0
Do you see the straight-line relationship between what is on the left-hand side of each
equation and time (t) on the right? The intercept is also present but it just happens to be
zero. If the data is truly from an elementary reaction then the plotting of –ln(1-X) against
time (t) should give a straight line passing through the origin with k being the slope, lets
check.

1 y = 0.01x + 0
0.8 2
R =1
-ln(1-X)

0.6
0.4
0.2
0
0 50 100
time (s)
We see that if 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. Notice also that the R2
correlation coefficient is equal to 1. This means that the fit is perfect.

An R2 of 0 means that there is no correlation to a straight line at all and an R2 or 1 means

it is a perfect fit. On the next page are some old favourite equations that you should
already know, to be used when completing linear regression.
To determine the intercept for a particular set of data we use the following equation:
(ΣY )(ΣX 2 ) − (ΣX )(ΣXY )
= intercept
NΣX 2 − (ΣX ) 2

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

N (ΣXY ) − (ΣX )(ΣY )

= slope
NΣX 2 − (ΣX ) 2

To determine the R2 correlation i.e. to determine how well the straight line fits we use the
following equation:

2
 
 N (ΣXY ) − (ΣX )(ΣY )  = R2

 [N ∑ X 2 2
][
− (∑ X ) N ∑ Y 2 − (∑ Y )
2
] 


Now lets recap.

We are given kinetic data. We postulate a simple kinetic model. We linearise the model
and plot the raw data on a graph in a linearised form. We see the data follows a straight
line. We conclude that the kinetic model is representative of the data. We also conclude
that it is an elementary reaction that we have i.e. no intermediary radicals exist.

Searching for the correct model

This process could require the searcher to postulate a number of kinetic models and then
to see which model gives the best fit. The best fit would be the fit that has the highest R2
correlation value i.e. the one that is the closest to 1. Study the next example to see how
this is done.
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. As you can see from the equation the number of moles of gas present,
before and after conversion is the same.
A → B

The data generated is given to you and you are also told that the order of reaction may be
first or second order. That means it follows one of the two following equations. Find out
which represents the data.

A first order model

The second order model
dC A
− = kC 1A
dt

dC A
− = kC A2
dt
Reaction data is the following

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 linerised from of the model that we will use is

C 
− ln A,t =t  = kt + 0
 C A ,t = 0 
− ln(1 − X ) = kt + 0
What about a linerised form of the second order equation? The equation has to be
integrated
 dC A
− = kC A2
dt
C A ,t = t t =t
−2
∫C
C A ,t =0
A dC A = − k ∫ dt
t =0

C A−1,t =t C A−1,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
Giving us the integrated from of the equation. Now if we plot the data in the form of the
two integrated models, let’s see which one gives us a straight line and which does not.
Clearly the model that gives us the straightest line will be the correct model.

Here is the data with the applicable calculations

time [A] 1/CA,t=t-1/CA,t=0 -Ln(CA,t=t/CA,t=0)

0 0.1 0 0
4 0.099602 0.04 0.003992
16 0.098425 0.16 0.0158733
64 0.093985 0.64 0.0620354
256 0.079618 2.56 0.2279321
1024 0.049407 10.24 0.7050758
 12 y = 0.01x
first order and
second order

10 2
Second order
R =1
8 function
6 y = 0.0007x
4 First order
2
2 R = 0.9926 function
0
0 1000 2000
time (s)

When plotting the two equations against one another both are semi-straight lines but
notice the R2 correlation

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 we have been given indicates that the reaction is a
complicated reaction i.e. it 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 0.454545
4 0.416667
8 0.357143
16 0.277778
32 0.192308

2. The following data is part of kinetic decay curve and the reaction is irreversible
and is deemed to be highly complex. The order of reaction is unknown but is
though to be between 1 and 2. What is the order of reaction? A → B

time [A]
0 0.8
1 0.732975
3 0.621925
9 0.406714
27 0.164171
81 0.037441