2.

Ideal R eactors
Reactor Technology Fundamentals

Chemical Engineering, R Rawatlal

A real reactor may exhibit complex internal and overall shapes, and irregular flow patterns. This influences the temperature
and concentration within the reactor, and complicates our effort to estimate the reaction rate and hence write the design
equations. However, by classifying ideal flow patterns, we begin to make progress in developing our designs.

2.1 G eneralised R eactor M ass B alance

Although there are many and various reactor types, and newer still types are being
developed, it is possible to link their analysis to a common framework. It is possible to
develop a generalised framework through the material, energy and momentum balances.

For the sake of reaction engineering, when writing a material balance on a molar basis over a
an arbitrarily shaped volume V,

… we recognise that the reaction rate varies from one point to the next inside the reactor. It
may also vary from one instant in time to another. From the total volume 𝑉, we may
consider a one of the sub-volumes Δ𝑉 which is small enough that the concentration and
temperature don’t really change within this small volume.

Defining 𝑁𝑖 as the moles of 𝑖 in the reactor and 𝐹𝑖 and as molar flowrate into or out of the
space, we have

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The general material may then be stated as

𝑑𝑁𝑖
= 𝐹𝑖,𝑖𝑛 − 𝐹𝑖,𝑜𝑢𝑡 + ∫ 𝑟𝑖 𝑑𝑉
𝑑𝑡 𝑉

That is, the rate of change of the number of moles of component-i, which is Ni, in reaction
space V equals the molar flowrate of component-i into minus the molar flowrate out of (Fi,in
and Fi,out respectively) the reaction space plus the total (integrated) rate of formation of
component-i across the entire reaction space (of volume V).

Note the units: Ni [=] mol, t [=] s, Fi [=] mol.s-1, ri [=] mol.s-1.m-3, dV [=] m3.

At this stage, we don’t know how to solve this equation because the don’t generally know
the function

𝑟𝑖 = 𝑟𝑖 (𝑡, 𝑥, 𝑦, 𝑧)

and so we can’t estimate

∫ 𝑟𝑖 𝑑𝑉
𝑉

Right now, this is just a framework. Now let’s make some assumptions and see if we can
simplify the expression to the point where we can solve the equation.

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 2.2 B atch R eactors

In developing the batch reactor balance, each term of the general balance will
be considered in turn.

𝑑𝑁𝑖
= 𝐹𝑖,𝑖𝑛 − 𝐹𝑖,𝑜𝑢𝑡 + ∫ 𝑟𝑖 𝑑𝑉
𝑑𝑡 𝑉

1. we do expect the number of moles to change with time, and so will retain the
𝑑𝑁𝑖
accumulation term 𝑑𝑡
2. Second, there is no flow into or out of the reactor, so 𝐹𝑖, 𝑖𝑛 = 0
𝑜𝑢𝑡

3. Last, due to mixing by impeller action, we expect that the concentration and
temperature will be the same at all points in the reactor:

(although these values will change in time), hence the rate is constant in space (but
not in time), i.e.
𝑟𝑖 (𝑡, 𝑉) = 𝑟𝑖 (𝑡, 𝑥, 𝑦, 𝑧) ≅ 𝑟𝑖 (𝑡)
If 𝑟𝑖 is a constant wrt 𝑉, we can write

∫ 𝑟𝑖 𝑑𝑉 = 𝑟𝑖 . 𝑉
𝑉

We have then

𝑑𝑁𝑖
= 𝑟𝑖 . 𝑉
𝑑𝑡
Noting that the concentration 𝑐𝑖 = 𝑁𝑖 /𝑉, we may further divide both sides of the equation by
𝑉 to obtain

𝑑𝑐𝑖
= 𝑟𝑖
𝑑𝑡
If we include initial conditions 𝑐𝑖 (𝑡 = 0) = 𝑐𝑖,0 we have a closed equation which we can
integrate to obtain the concentration of any component-i in the batch reactor as a function
of time 𝑐𝑖 (𝑡).

Exercise 1: Develop the batch reactor balance in the context of the reaction 2 SO2 + O2 →
2 SO3. Assuming isothermal operation, the reaction is elementary and that the 5m3 reactor is
initially charged with 10 mol SO2 and 10 mol O2. The rate constant is 5 × 10-2 mol-SO2.s-
1.m-3/(mol3.m-9).

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 2.3 C ontinuous Stirred Tank R eactor (C STR )
The acronym CSTR emphasise two factors: first, there is continuous flow across the reactor,
making it possible for a steady concentration to be achieved. Second, the
reactor is stirred with an expectation that it would then be perfectly
mixed. We can then apply the same simplification as for the batch reactor,
that is ∫𝑉 𝑟𝑖 𝑑𝑉 = 𝑟𝑖 . 𝑉. The overall balance then becomes

𝑑𝑁𝑖
= 𝐹𝑖,𝑖𝑛 − 𝐹𝑖,𝑜𝑢𝑡 + 𝑟𝑖 . 𝑉
𝑑𝑡
Since 𝑟𝑖 is a function of the concentration, we can move toward closing the equations if the
other state variables 𝑁𝑖 and 𝐹𝑖 can be expressed in terms of the concentration.

If we divide both sides by 𝑉, clearly 𝑁𝑖 /𝑉 is 𝑐𝑖 , where 𝑐𝑖 inside the reactor. It is important

to note again that, under this assumption of perfect mixing in the CSTR, the concentration
is the same everywhere at all points in the reactor: 𝑐𝑖 (𝑥, 𝑦, 𝑧) = 𝑐𝑖 .

For the CSTR, we also have to consider the flow terms 𝐹𝑖 , which have different
concentration at the inlet compared with the outlet. Generally, we may also have different
volumetric flowrates in each case. However, we can re-write each molar flow term as the
products:

𝐹𝑖,𝑖𝑛 = 𝑐𝑖,𝑖𝑛 . 𝑄𝑖𝑛

𝐹𝑖,𝑜𝑢𝑡 = 𝑐𝑖,𝑜𝑢𝑡 . 𝑄𝑜𝑢𝑡

We note further that the concentration in the exit stream must be identical to the
concentration just on the inside of the reactor near the exit point. Therefore

𝑐𝑖,𝑜𝑢𝑡 = 𝑐𝑖

We can now write

𝑑𝑐𝑖 . 𝑉
= 𝑐𝑖,𝑖𝑛 . 𝑄𝑖𝑛 − 𝑐𝑖 . 𝑄𝑜𝑢𝑡 + 𝑟𝑖 . 𝑉
𝑑𝑡
Even in the present form, this is a much more specific form which can be solved as a first
order ODE. We do need an expression for 𝑟𝑖 in term of 𝑐𝑖 , and this is usually given to us (see
example).

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Now let’s consider some further simplifications.

1. I N LET A N D EX IT FLOW R A TES AR E TH E SA M E

If 𝑄𝑖𝑛 = 𝑄𝑜𝑢𝑡 = 𝑄, then clearly the volume 𝑉 is constant. If we further define 𝜏 = 𝑉/𝑄, then
simply

𝑑𝑐𝑖 . 𝑉
= (𝑐𝑖,𝑖𝑛 − 𝑐𝑖 ). 𝑄 + 𝑟𝑖 . 𝑉
𝑑𝑡
(Note that 𝜏 has an important meaning which we will return to later.) We have now

𝑑𝑐𝑖 . 𝑉
= (𝑐𝑖,𝑖𝑛 − 𝑐𝑖 ). 𝑄 + 𝑟𝑖 . 𝑉
𝑑𝑡
Or

𝑑𝑐𝑖 𝑐𝑖,𝑖𝑛 − 𝑐𝑖
= + 𝑟𝑖
𝑑𝑡 𝜏(𝑡)

Note: Even if the flowrates are equal, they are not necessarily constant, i.e. it may be that
𝑄 = 𝑄(𝑡). In this case, event though 𝑉 is a time constant, 𝜏 is not. Also, 𝑐𝑖𝑛 may be a time
function – this is something we may choose to do. This balance is still valid that case.

2. T H E FLOW R A TES A R E EQU A L A N D C ON STA N T , A N D TH E IN LET C ON C E N TR A TION IS

C ON STA N T

Under these conditions, 𝜏 and 𝑐𝑖𝑛 become time-constants. Additionally, we realise that the
system can reach steady state. In other words, the system will eventually reach a point
where the rate at which 𝑖 is supplied (via the inlet flow) will equal the rate at which it is
𝑑𝑐𝑖
consumed and is removed (via exit flow). When this steady state is reached, we have = 0:
𝑑𝑡

𝑐𝑖 − 𝑐𝑖,𝑖𝑛
= 𝑟𝑖
𝜏
Compare this result with that of the batch reactor. We can see that 𝜏 plays something of a
time role. To understand this, let’s compare the velocity and the volumetric flowrate
concepts:
𝑧
𝑢=
𝑡
𝑉
𝑄=
𝜏
In the case of velocity, 𝑡 is the time taken for some object at velocity 𝑢 to travel distance 𝑧.

In the case of 𝜏, by analogy, this is the time taken for some fluid travelling at volumetric
flowrate 𝑄 to traverse a volume 𝑉. We note also 𝑄[=]𝑚3 . 𝑠 −1, 𝑉[=]𝑚3 , so then 𝜏[=]𝑠.

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Exercise 4: Develop the CSTR balance in the context of the reaction 2 SO2 + O2 → 2 SO3.
Assume the reaction is elementary and that the 5m3 reactor is initially charged with 10 mol
SO2 and 10 mol O2. The rate constant is 5 × 10-2 mol-SO2.s-1.m-3/(mol3.m-9). The inlet
flowrates of SO2 and O2 are 15 mol.s-1 and 20 mol.s-1 respectively at a total volumetric

Exercise 5: Use the steady state version of the CSTR balance to predict the final
conversions developed in exercise 4. Show that the final values are the same.

N ote on volum e expansion :

If the system is gaseous and the reaction non-equimolar, we have to account for volume
expansion.

Going back to the form below

dci ci ,in .Qin  ci .Qout

  ri
dt V
we must use

Qout  Qin 1   . y A,0 . X A  .

T .P0
T0 .P

And for the species concentrations show that

 i 
 i  X A 
A
ci  cA0   . T0 .P
1   . yA,0 .X A  T .P0

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 2.4 P lug Flow R eactor
The plug flow reactor is a conceptual model, or the hypothetical
case, where a fluid flows in discrete groups (“plugs”) where the
molecules in one group do not transfer or mix with the other groups.

Less abstractly, if we imagine a cylindrical tube containing a fluid in plug flow, then there
are two assumptions we would apply: 1. There is no axial movement of molecules. The
molecules will remain in the same group of molecules with which they first entered the tube.
Any reactions that occur will occur amongst this group molecules. 2. Each group of
molecules is perfectly mixed (e.g. radially).

There are therefore some contradictions in this type of flow; on the one hand, there is zero
mixing in the axial direction; on the other hand, there is perfect mixing in all directions
within the plug.

As unlikely a situation as we can imagine this to be, the plug flow reactor is nevertheless an
important reactor type that allows significant progress to be made in developing the theory
of reaction engineering. It may be thought of as an exact opposite pattern to the pattern of
perfect mixing.

We further anticipate that by having development for two exact opposite mixing patterns,
we would be able to develop a description of so-called real-world mixing patterns, which live
somewhere between these two points.

Since plugs are flowing through the reactor, and since each will do so at a fixed speed, the
distance down the tube indicates the amount of time spent by the plug reacting in the tube.
The closer to the entrance, the less the time spent in the tube, and hence the lower will be
the conversion.

Since prefect mixing is not possible, let’s take a smaller control volume; at an axial position
from 𝑧 to 𝑧 + Δ𝑧:

Although we’ve so far applied the general balance on entire

reactors, there is nothing to prevent us applying it on a very small
scale, i.e. between 𝑧 and 𝑧 + Δ𝑧.

We therefore apply the general balance on this differential element, and regard convective
flow in to 𝑧 and out of 𝑧 + Δ𝑧. For the differential volume, we also accept that the
concentration and temperature are the same at all points (only in the element).

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Therefore

𝑑𝑁𝑖
| = 𝐹𝑖,𝑧 − 𝐹𝑖,𝑧+Δ𝑧 + 𝑟𝑖,𝑧→𝑧+Δ𝑧 . 𝑉
𝑑𝑡 𝑧→𝑧+Δ𝑧

Define the cross-sectional area to be 𝐴𝑐 .

The volume of the control space between 𝑧 and 𝑧 + Δ𝑧 is then 𝐴𝑐 . Δ𝑧. The number of moles
within the control space is therefore the concentration at that point times this volume.

Furthermore, to model the flow, we can define the linear velocity as 𝑢 = 𝑄/𝐴𝐶 . We can then
re-write the balance above as follows

𝑑𝑐𝑖
. 𝐴 Δ𝑧 = 𝐴𝑐 . 𝑢. 𝑐𝑖,𝑧 − 𝐴𝑐 . 𝑢. 𝑐𝑖,𝑧+Δ𝑧 + 𝑟𝑖,𝑧 . 𝐴𝑐 Δ𝑧
𝑑𝑡 𝑐
Note we have made an approximation 𝑟𝑖,𝑧→𝑧+Δ𝑧 . 𝑉 ≅ 𝑟𝑖,𝑧 . 𝑉 which improves as Δ𝑧 → 0.
Dividing both sides by 𝐴𝑐 Δ𝑧 and re-grouping:

𝑑𝑐𝑖 𝑐𝑖,𝑧 − 𝑐𝑖,𝑧+Δ𝑧

= 𝑢. + 𝑟𝑖,𝑧
𝑑𝑡 Δ𝑧
Taking the limit Δ𝑧 → 0, we obtain

𝑑𝑐𝑖 𝜕𝑐𝑖
= −𝑢. + 𝑟𝑖,𝑧
𝑑𝑡 𝜕𝑧
We laid on prescription on the 𝑧-value in the writing of this balance; it therefore applies at
all interior points of the reactor. This is a PDE in two variables 𝑡 and 𝑧, and we require
initial and boundary conditions like

𝑐𝑖 (𝑡, 𝑧 = 0) = 𝑐𝑖,𝑖𝑛 (𝑡)

𝑐𝑖 (𝑡 = 0, 𝑧) = 𝑐𝑖,0 (𝑧)

to solve this equation to arrive at a solution showing 𝑐𝑖 (𝑡, 𝑧).

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P FR S TEA D Y STA TE
It is possible for this system to reach a steady state where the rates of supply (inlet flow)
and rates of disappearance (reaction consumption and exit flow) become equal. At this stage,
𝑑𝑐𝑖
𝑑𝑡
= 0 and so

𝜕𝑐𝑖
𝑢. = 𝑟𝑖,𝑧
𝜕𝑧
𝑐𝑖 (𝑧 = 0) = 𝑐𝑖,𝑖𝑛

This equation is written in terms of 𝑢 and 𝑧; we’d prefer to write in terms of volumes and
flowrates. We know that the linear velocity is 𝑢 = 𝑄/𝐴𝑐 and 𝑉 = 𝑧. 𝐴𝑐 . We note here that 𝑉
is not the total reactor volume; we are viewing it as the volume of the reactor up to the
point 𝑧. We can write the latter as 𝑑𝑉 = 𝐴𝑐 𝑑𝑧. We can therefore re-write the balance as

𝑄 𝜕𝑐𝑖 𝜕𝑐𝑖 𝜕𝑐𝑖

𝐴𝑐 . = = = 𝑟𝑖
𝐴𝑐 𝜕𝑉 𝜕𝑉/𝑄 𝜕𝜏

(Note again that 𝜏 is a variable down the axis.) We have then

𝜕𝑐𝑖
= 𝑟𝑖
𝜕𝜏
𝑐𝑖 (𝑧 = 0) = 𝑐𝑖,𝑖𝑛

Compare with the balances on the Batch and CSTR reactors.

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Exercise 6: Develop the process of exercise 5 in the context of the plug flow reactor.
Compare the final results with those of the batch reactor. Show equivalence through the use
of the space time and real time as equivalent.

N ote on volum e expansion :

If the system is gaseous and the reaction non-equimolar, we have to account for volume
expansion.

The same developments as for the CSTR apply.

2.7 C onversion
During the introduction, we had introduced the notion of conversion 𝑋, which showed the
relative difference between the concentration “after reaction” and the concentration “before”.
For the batch reactor, this would clearly be

𝑐𝑖 (𝑡 = 0) − 𝑐𝑖 (𝑡) 𝑐𝑖,0 − 𝑐𝑖 𝑐𝑖
𝑋𝑖 = = =1−
𝑐𝑖 (𝑡 = 0) 𝑐𝑖,0 𝑐𝑖,0

For the steady state CSTR, the concept of time has disappeared; it is more appropriate then
to compare the inlet and exit values:
𝑐𝑖,𝑖𝑛 − 𝑐𝑖 𝑐𝑖
𝑋𝑖 = =1−
𝑐𝑖,𝑖𝑛 𝑐𝑖,𝑖𝑛

For the steady state PFR, the difference is across space (𝑧):

𝑐𝑖 (𝑧 = 0) − 𝑐𝑖 (𝑧 = 𝐿) 𝑐𝑖,𝑖𝑛 − 𝑐𝑖 𝑐𝑖
𝑋𝑖 = = =1−
𝑐𝑖 (𝑧 = 0) 𝑐𝑖,𝑖𝑛 𝑐𝑖,𝑖𝑛

We may also write these in the differential form, e.g.

𝑑𝑐𝑖 𝑑𝑐𝑖
𝑑𝑋 = − 𝑐 or 𝑑𝑋 = − 𝑐
𝑖,0 𝑖,𝑖𝑛

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2.7 Sum m ary
We may summarise the design equations for the three reactor types as follows

B atch C ontinuous stirred P lug Flow

𝑑𝑐𝑖 𝑐𝑖 − 𝑐𝑖,𝑖𝑛 𝜕𝑐𝑖
= 𝑟𝑖 = 𝑟𝑖 = 𝑟𝑖
𝑑𝑡 𝜏 𝜕𝜏
𝑑𝑋𝑖 𝑟𝑖 𝑋𝑖 𝑟𝑖 𝑑𝑋𝑖 𝑟𝑖
=− =− =−
𝑑𝑡 𝑐𝑖,0 𝜏 𝑐𝑖,𝑖𝑛 𝑑𝜏 𝑐𝑖,𝑖𝑛
When comparing the equation forms for the three types of reactor, a clear pattern emerges.
In fact, the batch reactor and plug flow equations are the same, with only different variable
names being given for time and the entry/initial concentration. This is a consequence of
there being only a simple translation between time and space (through velocity).

The CSTR exhibits a ratio rather than a derivative relationship; this is the result of the
entire reaction space behaving as one entity, rather than differential quantities of the space
progressing in the overall conversion of reactants to products.

The observation of similarity is understood better as we further analyse these types.

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