Homework 7: CSTR & PFR Comparison

CHE 3184

1. The following liquid phase reaction is either first or second order in A. The reaction rate
was measured at low conversion as 0.2 mol.m-3.min-1 using CA0 = 2 mol.m-3.
A→B
a) Calculate the reaction rate constant for 1st and 2nd order kinetics
At low conversions:
𝐶𝐴 = 𝐶𝐴0
Thus the rate is given by:
2
𝑟 = 𝑘𝐶𝐴0 𝑜𝑟 𝑟 = 𝑘𝐶𝐴0
For the first order reaction and second order reaction respectively. Solving for the rate
constants gives the following:
𝑚𝑜𝑙 𝑚𝑜𝑙
𝑟 0.2 3 1 𝑟 0.2 3 𝑚3
𝑚 ∗𝑚𝑖𝑛 𝑚 ∗𝑚𝑖𝑛
𝑘= = 𝑚𝑜𝑙 = 0.1 𝑘= 2 = 𝑚𝑜𝑙 2
= 0.05
𝐶𝐴0 2 3 𝑚𝑖𝑛 𝐶𝐴0 (2 3 ) 𝑚𝑜𝑙∗𝑚𝑖𝑛
𝑚 𝑚
 b) Use the reaction rate constants from part a) to compare the effect of inlet flowrate on
exit conversion in PFR and CSTR reactors (plot conversion vs. V/FA0)
In order to plot these, we start with the design equations which, for a PFR and a CSTR
respectively, are:
𝑥 𝑥
𝑑𝑋 𝑉 𝑑𝑋 𝐹𝐴0 𝑋 𝑉 𝑋
𝑉 = 𝐹𝐴0 ∫ → =∫ 𝑉= → =
0 −𝑟𝑎 𝐹𝐴0 0 −𝑟𝑎 −𝑟𝐴 𝐹𝐴0 −𝑟𝑎

Plugging in the rate equations from part a:

𝑥
𝑉 𝑑𝑋
=∫
𝐹𝐴0 0 𝑘𝐶𝐴
𝑥
𝑉 𝑑𝑋
=∫ 2
𝐹𝐴0 0 𝑘𝐶𝐴

𝑉 𝑋
=
𝐹𝐴0 𝑘𝐶𝐴
𝑉 𝑋
=
𝐹𝐴0 𝑘𝐶𝐴2

Note the order is PFR first order, PFR second order, CSTR first order, CSTR second order.
Additionally at low conversion ~0, the PFR equations will be the same as CSTR (recall that
the reactors will be similar at very low conversion). In other words,
𝑉 𝑥 𝑑𝑋 𝑋
= ∫0 = since 𝐶𝐴0 is almost constant (conversion ~0)
𝐹𝐴0 𝑘𝐶𝐴 𝑘𝐶𝐴0

𝑉 𝑥 𝑑𝑋 𝑋
Similarly for 2nd order, = ∫0 =
𝐹𝐴0 𝑘𝐶𝐴2 2
𝑘𝐶𝐴0

For high conversion (PFR 1st order, PFR 2nd order, CSTR 1st order, CSTR 2nd order)
𝑥
𝑉 𝑑𝑋
=∫
𝐹𝐴0 0 𝑘𝐶𝐴0 (1 − 𝑋)
𝑥
𝑉 𝑑𝑋
=∫ 2 2
𝐹𝐴0 0 𝑘𝐶𝐴0 (1 − 𝑋)

𝑉 𝑋
=
𝐹𝐴0 𝑘𝐶𝐴0 (1 − 𝑋)
𝑉 𝑋
= 2 (1
𝐹𝐴0 𝑘𝐶𝐴0 − 𝑋)2
 2
And we need to perform the integration for the PFR (where 𝑟 = 𝑘𝐶𝐴0 𝑎𝑛𝑑 𝑟 = 𝑘𝐶𝐴0 for 1st
order and 2nd order, respectively)
𝑥 𝑥
𝑉 𝑑𝑋 1 𝑑𝑋 1 1
=∫ = ∫ = ln ( )
𝐹𝐴0 0 𝑟(1 − 𝑋)
𝑚𝑜𝑙 0 (1 − 𝑋)
𝑚𝑜𝑙 1−𝑋
0.2 0.2
𝑚3 ∗ 𝑚𝑖𝑛 𝑚3 ∗ 𝑚𝑖𝑛
𝑥 𝑥
𝑉 𝑑𝑋 1 𝑑𝑋 1 𝑋
=∫ = ∫ =
𝐹𝐴0 0 𝑟(1 − 𝑋)
2 𝑚𝑜𝑙 0 (1 − 𝑋)
2 𝑚𝑜𝑙 1 − 𝑋
0.2 3 0.2 3
𝑚 ∗ 𝑚𝑖𝑛 𝑚 ∗ 𝑚𝑖𝑛
𝑉 𝑋 1 𝑋
= =
𝐹𝐴0 𝑟(1 − 𝑋) 0.2 𝑚𝑜𝑙 1 − 𝑋
𝑚3 ∗ 𝑚𝑖𝑛
𝑉 𝑋 1 𝑋
= =
𝐹𝐴0 𝑟(1 − 𝑋)2 0.2 𝑚𝑜𝑙 (1 − 𝑋)2
3
𝑚 ∗ 𝑚𝑖𝑛
The integrals were taken from table A.1 in Fogler, Essentials of Chemical Reaction
Engineering
Notice the similarity between the second order PFR and the first order CSTR, this is also
something you should be able to explain.
Plotting all of these (note that the 2nd order PFR is directly behind the first order CSTR). Note
that the y-axis is on a log-scale to highlight the differences between the different reactors and
reaction orders. For example, for 2nd order kinetics at 80% conversion, the CSTR would need
to have a much larger volume (5 times) than a PFR! The difference becomes larger as the
conversion increases.
 c) Which reactor would be better for differentiating between the two mechanisms if you
are limited to measurements at conversion below 40%?
The conditions below can be used for both reactors in part c:
Reactor volume = 2 m3
CA0 = 2 mol.m-3
Highest possible FA0 = 25 mol.min-1
Isothermal operation with negligible pressure drop
Here we are asked which reactor would be best for determining the order. We can see from
the chart in part b that the two CSTR curves are more different than the two PFR curves. So
that is the better reactor.
We can see this better if we plug in the specific numbers and compare these curves:

Specifically, we can see the biggest difference will be when we choose a very low molar flow
rate of A and allow for a high conversion. In other words, at low conversion all the reactors
will have similar conversions regardless of reaction order. In order to differentiate between
reaction orders, we need to go to higher conversion (lower FA0). Specifically, to achieve
40% conversion (the limit from the problem statement, we need FA0 (mol.min-1) of 0.78 (1st
order PFR), 0.6 (2nd order PFR/1st order CSTR), and 0.36 (2nd order CSTR). If we use a PFR,
the difference in FA0 between 1st and 2nd order is smaller than if we use a CSTR. Therefore, a
CSTR would be best to differentiate between orders, especially given that there will be
experimental errors!
 2. Consider the following autocatalytic reaction (liquid phase)

A+B → 2B
The reaction is first order in both A and B. The reaction may be assumed to be
essentially irreversible. The pressure drop along the reactor is negligible.
CA0 = 24 mol.m-3
CB0 = 0.2 mol.m-3
FA0 = 0.0083 mol.min-1
k = 2.08x10-5 m3.mol-1.s-1
a) Plot FA0/-rA vs. conversion (note the unusual shape of the curve!)

First we want

𝐹𝐴0
= 𝑓(𝑋)
−𝑟𝐴

𝐹𝐴0 𝐹𝐴0
=
−𝑟𝐴 𝑘𝐶𝐴 𝐶𝐵

Now we need the concentrations in terms of conversion. This is a little more complicated
than normal.

Since A is obviously the limiting reagent, by definition, we still have

𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋)

For B however, if we define X=0 to be the initial conditions specified, then

𝐶𝐵 = 𝐶𝐵0 + 𝐶𝐴0 𝑋 = 𝐶𝐴0 (𝜃𝐵 + 𝑋)

Plugging these in

𝐹𝐴0 𝐹𝐴0
= 2
−𝑟𝐴 𝑘𝐶𝐴0 (1 − 𝑋)(𝜃𝐵 + 𝑋)

And plotting,
The curve has a very large value for F_A0/-r_A at high and low conversions. While for
intermediate conversions, the value is very low.
 b) Would you choose a PFR or a CSTR reactor to achieve a conversion of 50%? How
about 95% conversion? Explain and justify your answer

For 50% conversion, a CSTR would be much preferred. This can be seen from the chart,
doing the math (numerically), the CSTR would need to be about 0.02 m3 while the PFR
would need to be about 0.07 m3.

For 95% conversion, a PFR would be preferred. The CSTR would need to be 0.23 m3 but the
PFR would only need to be 0.10 m3