Ideal Reactors

We typically consider three ’ideal’ reactors.

Batch Reactor: The composition (and temperature) is typically uniform throughout the

reactor, there is no flow into the reactor, or flow out of it. This is the ’fill it shut it’ model. We

drop the reactants in at the beginning and dont mess with things later. As the reaction(s)

proceed(s), the composition changes, so time variation in reactant and product compositions

(and temperature) has to be considered.

Industrial uses: Small-scale operation, manufacture of expensive products, testing stud-

ies.

Continuously Stirred Tank Reactor (CSTR): Also referred to as a jet-stirred reactor or

mixed flow or batchmix reactor. The reactor contents are uniformly mixed, so there is no

spatial variation in composition or temperature. There is inflow and outflow in this case,

with a difference in compositions between components flowing in and those found inside

the reactor. However, properties are same within the reactor and at the exit. Typically we

consider the CSTR at steady-state (no time variations)

Industrial uses: When intense agitation and/or maintainance of good temperature con-

trol are needed.

Plug Flow Reactor (PFR): This can be envisaged as flow in a tube. In fact the PFR is

also referred to as tubular flow reactors. There is no variation of properties in the radial

direction of the tube. Reactants are continuously consumed as they flow down the length of

the reactor. All components move at the same speed, so there is no overtaking. The PFR also

is typically considered in a steady-state mode.

Industrial uses: Homogeneous gas-phase flow reactors.

General Mole Balance

We have learnt in earlier courses that writing down mass, energy and momentum bal-

ances is crucial for solving problems in chemical engineering. In this course we concentrate

heavily on mass balance, just like in fluid mechanics you would have concentrated on mo-

mentum balance. At some point, we will look at energy balance as well, as applicable to

reactors. But first, let us examine a very general means of writing a mole (or mass) balance

1
on a reactor.
Rate of inflow + Rate of generation - Rate of outflow = Rate of accumulation



 

+  - =  


Here,  represents the number of moles of species j in the reactor at any time t, and



are the flow rates of species j.  , the generation term is where our previous work in

the course comes in handy, in this case the generation is from chemical reaction so this is

related to chemical reaction rate.





 or  depending on whether the rate varies with position in the reactor

or not. V is system volume.

This general mole balance, which is the basis for most of the further calculations we per-

form in this course, can be simplified under the assumptions applicable to different ideal

reactors.

Mole Balance for a Batch Reactor



By definition, there is no inflow or outflow from a batch reactor. So the terms drop out.

If we can assume that the reaction rate is uniform within the reactor (no spatial variations),

then we can write

 


 
If this assumption about the spatial uniformity cannot be made, we get,
 
  
 
  where the integral is over the reactor volume.

Note the these balances are for the species, therefore the reaction rate here is the rate

of the species, and appropriate scaling to reflect the stoichiometric coefficient has to be done.

Mole Balance for a CSTR

Since typical operation of a CSTR is at steady-state, the accumulation term in the general

mole balance drops out and a general balance for CSTR can be written as:

"!#
%$&
'(*)

since there are no spatial variations in a CSTR. This is a simple algebraic equation,

oftentimes, we will use it as a ’design equation.’ This means we can figure out the volume

of the reactor required given the flow rates and rate. It is further important to note that in

2
the ideal CSTR, the outlet stream is assumed to be at the same conditions as the reactor

itself, so the molar flow rate can be written in terms of the volumetric flow rate and species

concentration as






where is the concentration of species j in the reactor and v is the volumetric

flow rate.

In case of unsteady-state operation, the accumulation term is to be included in the bal-

ance above.’

Mole Balance for a PFR

The only difference in this case from CSTR is that the rate is not spatially uniform, in fact

it varies continuously along the length of the reactor

 !#
$ 
(*)

This can be equivalently expressed in the differential form as

 

*

 

if we can assume that the cross-sectional area of the tubular reactor is a constant, we

can express the mole balance as a function of the axial distance as

 

 



These mole balances are useful in two very different ways:

1. In kinetic studies: if we have data from experiments performed in such well-characterised

ideal reactors, using these equations we should be able to derive the rate expression and rate

parameters.

2. In reactor design: if we know the rate expression well, we can use these equations for

practical design of a reactor, finding appropriate reactor volume or length or length of time

we have to perform the reaction, etc.

Example Problems

1. Example 1.3 from Fogler

3
 First order reaction being carried out in a tubular reactor. volumetric flow rate is con-

stant. Determine the reactor volume necessary to reduce the exiting concentratoin to 10% of
)


the concentration entering the reactor. Volumetric flow rate is and specific reaction
) 
 
rate (another name for reaction rate constant) is . The reaction is .

Draw a picture of the reactor. Its a tube with inlet and outlet. If inlet concentration (of

  ) 

 
reactant A) is , then the outlet concentration is supposed to be . Since volumetric

flow rate is given to be constant, and we know the molar flow rate
 
 
where v is the volumetric flow rate, we can write the general mole balance as

 "!
  $    (*)

By the same arguments as above, we can convert it to the following differential equation:
! #"$     !('

&% We have additional made use of the fact that the reaction is first order

in A. The negative sign reflects that A is consumed by the reaction. We can integrate this

)  ) 
 

differential equation, as concentration of A goes from to , the volume of the reactor
) 
will go from (nothing happens) to (the volume we require). Thus,

!  *
,+  "$.-  

 * %
 
' "$/-
 

 )
2 1 ) 
 
0 1 )   0
4365.7 ) )

' ) 

2. Fogler P1-19 Calculate the volume of the reactor required above if a CSTR is to be

used.

 "! )
   !8':9; ) 9
    )
(<

The PFR in fact produces the highest conversion per unit volume among all flow reactors.

3. Consider a spatially uniform constant volume batch reactor where a gaseous reac-

tant A is being converted to products. Derive an expression for the variation of the molar

concentration of A wrt time if the reaction can be assumed to be first order in A.

4
 Since volume is constant, we can write the mole balance for the reactor as
&" $ (!('

  (concentration is number of moles divided by volume)

Rearranging and integrating the equation, we get

 03  
  5
  !(' 3 

so the concentration of species A exponentially decreases with time, asymptotically ap-

 
proaching 0 at infinite time. is the initial concentration in the reactor.

4. Now assume that the batch reactor is not of constant volume. In fact assume that the

pressure of the system is held constant. What changes in expression for concentration as a

function of time?
 
 
 where all three quantities are at any arbitrary time t. So the balance equation

becomes

  

  
  $ (!('

/3  3
.  . 3

or


 
0 
$ 

 (!' 


 3
.  3
.

Clearly the term representing the volume change with time is extra in this case, and

therefore we can expect the variation of concentration wrt time to be different.

Conversion

We have seen how we dealt in the problems above with percentage concentration at the

reactor outlet. In both examples, the absolute value of the reactant concentration was not

used, instead, the concentration at the outlet was given to be a fraction of at the inlet. A

related concept is conversion. Conversion is defined as


  
      



  
Typically, conversion is defined on the basis of one of the reactants. Using the stoi-

chiometric coefficients of the reaction, the conversion of other reaction participants can be

represented using the conversion defined as above, with A as basis. It is more handy to

5
write the mole balance equations for the different reactors in terms of conversions instead of

concentrations and number of moles.

    !    
Batch Reactor:    . In other words, the number of moles of A at any

time t is the number of moles of A initially minus the number of moles of A reacted. So the

mole balance equation for constant volume reactor becomes

  


   $ (!   
bear in mind that reaction rate in this case is a negative quantity.

CSTR: In this case, we represent the molar flow rate (or molar concentrations, remember

that molar concentration multiplied by volumetric flow rate is the molar flow rate) in terms

of conversion:
     !   

Thus the molar flow rate at which the fluid leaves the CSTR is given by the molar flow

rate at the feed minus the molar rate at which reactant is consumed in the system. The

CSTR mole balance is

  !#  $&   *)     $    *)
and can be re-written as .

PFR: Similar derivations in terms of the molar flow rate should give us


   $  !" 
&%

In design of reactors (or for that matter in determination of rate from experimental data),

these mole balances defined in terms of converison turn out to be very handy. The reac-

tion rate in this case, which we have so far learned is a function of concentration, can be

expressed in terms of conversion as well. We have to just bear in mind that

 
 "!
   

or, the concentration of a reactant A at any time (or at any point in the reactor) is given

by the initial concentration minus the moles per volume of A that have reacted.

Another important thing to do is expressing the number of moles or concentrations of

other species involed in the reaction, in terms of the conversion defined wrt A. Consider
  
 $ # 
$  
For every mole of A reacted, b/a moles of B have reacted, c/a moles of C have been

formed and so on. So, starting with 


and  

moles of B and C respectively at a point of

time when the converison is

  
we will have

6
    "!    
  
 
 "!
 $/- $


 "

 "
 $  $.- $




   $
  $.- $


Finally, the total number of mole initial and at time t are given as


    $  $ "  $ 
   
  $        $  !
!
   where   
In case of flow systems the molar flow rate can similarly be expressed in terms of the

conversion of one of the reactants and the stoichiometric coefficients in the reaction. Note

that concentration is defined in two different ways, in case of batch reactor,

    
 where V is the volume. For flow systems (CSTR and PFR), the concentration

is

    
where v is the volumetric flow rate. A quick examination of units should

convince you of the validity of these expressions. The above equations for number of moles

(or molar flow rate) at any given time (or any point in the reactor) can be used to get the

concentrations as a function of conversion very simply, as long as the volume (or volumetric

flow rate) are constant.