Department of Chemical and Biomolecular Engineering

CN2105 Reaction Engineering

Assignment 4

Prof Ning Yan, 2023/2024 Sem 2

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Question 1
A pharmaceutical company is considering a process change from batch manufacturing to continuous
manufacturing using mostly existing resources (i.e., no new reactor will be purchased). As the lead process
engineer, you are required to carry out a feasibility study and advise the management for a go/no-go
decision. These are the salient process details: The production process is based on a first order liquid phase
reaction which is carried out to 95% completion. Presently, this is done in a large 100 L batch reactor. The
time to achieve 95% conversion in this reactor is 20 h. 4 h of turnaround is however needed in between the
batches. Feed from the supplier is available at a concentration of 1 mol/L.
Analysis:
1) We know the reaction is first order, and we know it takes 20 h to reach 95%
conversion in the batch reactor. We can obtain the reaction rate constant. V
Batch
2) From the size of the batch reactor, we can calculate how many moles of
reagent it can process per day.

3) Apply design equation of CSTR (with known x and V), we can find the V
productivity of CSTR. Compare it with batch reactor performance. CSTR
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Question 1
Solutions:

Substitute and t = 20 h:

There is one batch in 24 h and the amount of feed that can be processed in this time period is:
× ×

When using a CSTR:

× × × ×

Amount of feed processed in 24 h = 0.790 × 24 = 19.0 mol

This is about 20% of batch operation. Therefore, it is not advisable to switch to continuous manufacturing.
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Question 2
An aqueous stream containing 4 mol/L of reactant A passes through a CSTR followed by a PFR. The
reaction is second order with respect to A and the volume of the PFR is three times that of the CSTR. Find
the concentration at the exit of the PFR if the concentration of A in the CSTR is 1 mol/L.

Solutions:
For the CSTR: 3V
V
𝑐 = 4 mol/L 𝑐 = 1 mol/L 𝑐 = ? mol/L

For the PFR:

1

×
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Question 3
The following network of reactors is used to process a first order
reaction A → R to 90% completion. In this network, R1 is a 4 L
CSTR while R2, R3, R4 and R5 are 1 L PFRs. How would you
balance the flows (v01 and v02) through the two arms of the network
to support the same concentration exiting R1, R4 and R5?

Analysis: In lecture notes:

This relation always applies to PFRs in series, and also applies for PFRs in parallel as long as the
conversion is the same for all reactors. The reactor network simplifies to a 4 L CSTR and a 4 L PFR in
parallel:

𝑐 ,𝑥 = 0, ν01 4VL 𝑐 = 0.1𝑐 , 𝑥 = 0.9

𝑐 ,𝑥 = 0, ν02 𝑐 = 0.1𝑐 , 𝑥 = 0.9

4L
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Question 3
Method 1 (equation method):
×
× ×

Method 2 (graphical method):

Using N = 1 and 1 − xA = 0.1,

A PFR is equivalent to a CSTR that is 3.9 times of its size.

At the same size (4 L), PFR can process 3.9 times of A compared to CSTR.
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Question 4
The first order reaction A → B is carried out in a CSTR to produce a marketable product containing
90 mol% B with balance A. In anticipation of an increase in the demand for this product to 4 times of its
current production capability at the same purity, the management decided to acquire more CSTR(s) with the
same specifications as the one in use. Engineer 1 proposed to buy three more CSTRs while Engineer 2
proposed to buy just one.

The conversion will be kept the same as there is no incentive to produce a purer product.

(a) Is this a prudent decision, i.e. can you instead make do with the current reactor to meet the new market
demand?

Yes, this is a prudent decision as it is not possible to increase the product throughput without additional
resources (i.e. a new reactor).
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Question 4 (continued)
(b) If you are the manager, whose recommendation will you follow?
F0,1CSTR 0.1F0,1CSTR
If CSTRs are connected in parallel, 3 more CSTRs are needed.
x0 = 0 V x = 0.9
If CSTRs are connected in series, use design equation of CSTR:
𝐹 , 𝑥 𝐹 , 𝑥 𝐹 , 0.9 𝐹 , 0.9 ……
When N = 1, 𝑉= = = =
−𝑟 −𝑟 𝑘𝑐 0.1𝑘𝑐
F0,1CSTR 0.1F0,1CSTR
𝐹 , 𝑥 𝐹 , 𝑥
When N = 2, 𝑉 = = x0 = 0 x = 0.9
−𝑟 𝑘𝑐 V

𝐹 , (𝑥 − 𝑥 ) 𝐹 , 𝑥 𝐹 , 𝑥
𝑉 = = −
−𝑟 𝑘𝑐 𝑘𝑐
𝑐 −𝑐
𝑉 =𝑉 𝑥 = 𝑐 = 𝑐 𝑐 =𝑐 0.1
𝑐
F0,2CSTR ? 0.1F0,2CSTR
𝑐
𝑥 =1− = 1 − 0.1 xA0 = 0 xA’ = ? xA = 0.9
𝑐 V V

𝑉 1 ,
= Two CSTRs in series can already increase productivity to > 4 times!
𝑉 +𝑉 2 ,
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Question 4 (continued)
Method 2 (use equation for equal size CSTRs in series):
F0,1CSTR 0.1F0,1CSTR
If CSTRs are connected in series, from lecture notes Unit 4: x0 = 0 x = 0.9
V
1
𝑁 ……

F0,1CSTR 0.1F0,1CSTR

When N = 1, x0 = 0 V x = 0.9

/
When N = 2,
𝑉 𝑉
Note:
F0,2CSTR ? 0.1F0,2CSTR
,
x0 = 0 V x=? V x = 0.9
,

Two CSTRs in series increase productivity to > 4 times!

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Question 4 (continued)
Method 3 (graphical method):
If the 2 CSTRs are connected in series:
Method 3.1:
Using N = 1 and 1 − xA = 0.1, kτ1CSTR ≈ 9
Using N = 2 and 1 − xA = 0.1, kτ2CSTR ≈ 4.5
𝑘𝑉 2𝑘𝑉
Since 𝑘𝜏 = and 𝑘𝜏 = ,

𝐹 , 𝑣 2𝑉/𝜏 9
= = =2× =4
𝐹 , 𝑣 𝑉/𝜏 4.5

Method 3.2:
Using N = 1 and 1 − xA = 0.1, ≈ 3.9

Using N = 2 and 1 − xA = 0.1, ≈ 1.9

𝑘𝑉 2𝑘𝑉
Since 𝑘𝜏 = and 𝑘𝜏 = ,

𝐹 , 𝑣 2𝑉/𝜏 3.9
= = =2× = 4.1
𝐹 , 𝑣 𝑉/𝜏 1.9
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Question 5
Three equal-size CSTRs connected in series are used for the liquid phase reaction A + B → R where the
rate law is R = kcAcB. The conversion of A is 95% using a feed of cA0 = 1 mol/L and cB0 = 10 mol/L. If the
three reactors are now run with a feed of a different composition (cA0 = 1 mol/L, cB0 = 1 mol/L) while
keeping everything else unchanged, what is the conversion of A? Use a graphical method to solve the
problem.
Solutions:
In the original case, c B0 >> c A0 , the reaction is
pseudo first order with respect to A. R ≈ k’cA where
k’ = kcB0.

The left figure on Unit 4 Slide 22 may be used to

determine k’τ:

Using N = 3 and 1 − xA = 0.05:

𝜏 5
k’τ = 5 and 10
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Question 5
Under the new conditions, where cA0 = cB0, the
reaction stoichiometry dictates that cA = cB and
so R = kcA2.
The right figure on Unit 4 Slide 22 may be used
to determine k’τ:

Using N = 3 and kcA0τ = 0.5:

1 − xA ≈ 0.7 and xA = 0.3
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Question 6
Describe how you will design N equal-size CSTRs in series for a constant density first order reaction
without the use of a design chart. Given the number of reactors (N), the feed composition (c0) and the
conversion leaving the last reactor (xN), write down clearly the equations used to obtain the ratio, the
𝑘
space time for each CSTR ( and the intermediate conversions (x1, x2, ..., xN−1).
𝑁

Solutions:
The following equations from the notes may be used:
1
𝑁 1
𝑁

1
𝑁 1
𝑁
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Question 7
Pure A at a volumetric flow rate of 1 m3/h and a concentration of 5 × 10−3 mol/m3 is fed to a 1.2 m3 CSTR.
What is the conversion of A that is achievable with this reactor? The figure below shows the reciprocal rate
as a function of the conversion of pure A under the prevailing reaction conditions.

Solutions:
From the CSTR design equation, cA0v0xA = (−rA)V
1
Substituting known values, × × ×
xA must satisfy this equation and the reciprocal rate curve graphical solution/trial-and-error gives xA =
0.6
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Question 8
With the help of the figure for first order reactions on Unit 4 Slide 22 or otherwise, perform the following
calculations:

Solutions:

(a) At a conversion of 90%, calculate the volume of PFR required if the corresponding volume of CSTR
required is 1 L.
1
Using N = 1 and 1 − xA = 0.1, 3.9

(b) If the CSTR in (a) is replaced by two equal-size CSTRs in series while keeping the overall conversion
unchanged, what will be the volume of each reactor? If there any advantage in doing so?
1.9×0.256
Using N = 2 and 1 − xA = 0.1, 2

The combined volume of two CSTRs is smaller than the volume of a single CSTR required, lowering both
capital and operational costs.
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Question 8
(c) Find the intermediate conversion in the CSTR cascade in (b).
4
kτ2CSTR ≈ 4 Using N = 1 and 2
, 1 − xA = 0.34 and xA = 0.66

(d) How does the arrangement in (b) perform relative to equal-size CSTRs in parallel?

Two CSTRs in parallel are functionally equivalent to a single CSTR with volume equal to their combined
volume. If two equal-size CSTRs in parallel are used, their respective volume is 0.5 L, which is more than
double that for equal-size CSTRs in series.

(e) If the PFR in (a) is replaced by two equal-size PFRs, what will be their respective volume and the
intermediate conversion?
0.256
2
Using N = ∞ and 1 − xA = 0.1, kτ2PFR = 2.4
2.4
For the first PFR: Using N = ∞ and 2
, 1 − xA = 0.34 and xA = 0.66
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Question 9
Four 2 L PFRs operating at constant temperature and pressure are connected according to the network
shown below. If reactor R4 is shut down for maintenance, how should you adjust the space times of the
remaining reactors (i.e. increase or decrease, and by what percentages) so that the product quality is not
compromised?

Solutions:
Initially, the network of reactors is functionally equivalent to a 8 L PFR.
After R4 is shut down, the network of reactors is equivalent to a 6 L PFR.
The overall volumetric flow rate must be adjusted downwards from v0 to 0.75v0 (decrease by 25%) to
maintain the same product quality.
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Question 9
Initially:

After the shut down of R4:

The space time of R1 is increased by 33% while the space times of R2 and R3 are decreased by 11%.
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Question 10
The reciprocal rate curve for a reaction of interest under the actual
operating conditions is given below. Design a single reactor system with
the smallest reactor volume for the conversion of A from xA = 0.1 to 0.9.
Solutions:
Since this reaction shows both positive and negative order behaviours,
the single reactor which handles it well is a recycle PFR with an optimal
R value.
The recycle reactor design equation for a partially converted feed can be
derived by the same method in the notes:
Visual inspection suggests that the
+𝑅 optimal value of x Ai is around 0.24
𝑅+1
(next page):
The same rule for optimal R still applies:
×

+𝑅 1
where 𝑅+1
and − is evaluated at xAi.
The value of V can then be computed
through graphical integration.
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1 𝑑𝑥
(𝑥 −𝑥 )=
−𝑟 −𝑟
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Question 11
The second order gas phase reaction A → 2R is to be carried out in a batch reactor to 95% conversion of a
feed of pure A. As a process engineer, would you recommend constant pressure or constant volume
operation and what reactor characteristic time (kcA0t) would it be?

Solutions:
For n > 1 reactions, the figure on Unit 4 Slide 4 indicates that a constant density (volume) operation will
result in a shorter processing time:
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Question 12
The overall second order (first order with respect to each reactant) liquid phase reaction A + B → R + S
takes place in a PFR using equal molar quantities of A and B. Conversion is 96% with cA0 = cB0 = 1 mol/L.
If a CSTR 10 times as large as the PFR is hooked up in series with the existing unit, which unit should
come first and in what way is the present production being improved by the addition?

Solutions:
As the reaction is second order, the CSTR should be placed after the PFR.
Generally, it is prudent to run the combined reactor system not for higher conversion (since the current
conversion of 96% is already high) but for an increase in production rate.
Under the new scheme, the leading PFR will convert a fresh feed of increased flow rate to xA1 and the
CSTR will convert from xA1 to 96% completion.
For the leading PFR: VCSTR = 10VPFR and xA2 = 0.96 solve
simultaneously to get xA1 = 0.861.
0 𝑘
For the following CSTR: Use value of xA1 to evaluate
6.19

𝑘 𝑘
Since 1
−1 24
(1−0.96)
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Question 13
Using either the design chart for first order reactions on Unit 4 Slide 22 or otherwise, determine the
approximate percentage increase in conversion when a third CSTR is added to two CSTRs connected in
series currently running a first order reaction to 80% completion.

Solutions:
Using N = 2 and 1 − xA = 0.2:
kτ2CSTR = 2.5 (calculated value = 2.47)

3
Using N = 3 and ×2 :
1 − xA = 0.09 (calculated value = 0.09)

The increase in xA from 0.8 to 0.91 is approximately 13.8%.

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Question 14
The kinetics of the aqueous phase decomposition of A is investigated in two CSTRs in series, with the
second reactor having twice the volume of the first reactor. With a feed concentration of 1 mol/L and space
time of 96 s in the first reactor, the concentrations of A in the first and second reactors are 0.5 mol/L and
0.25 mol/L, respectively. Find the kinetic equation for the decomposition.

Solutions:
Assume the form of power law for the kinetic equation: rA = −kcAn
For a CSTR:

For the first CSTR:

× × ×
For the second CSTR:
× × × ×
Solving simultaneously gives n = 2 and k = 0.0208 mol−1 L s−1
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Question 15
The elementary irreversible aqueous phase reaction A + B → R + S is carried out by introducing two liquid
streams of equal volumetric flow rates into a 4 L CSTR. One stream contains 0.02 mol/L of A while the
other contains 1.4 mol/L of B. The outlet of the CSTR is then passed through a 16 L PFR. If the
concentration of R formed in the CSTR is 0.002 mol/L, find the concentration of R at the exit of the PFR
and the fraction of initial A that has been converted in the system.

Solutions:
Since cB0 >> cA0, the reaction is pseudo first order with respect to A.
Note that the inlet concentration of A is effectively 0.01 mol/L after the two inlet streams of equal flow
rates are mixed.
For the CSTR: For the PFR:

× ×