Department of Chemical and Biomolecular Engineering

CN2105 Reaction Engineering

Assignment 5

Prof Ning Yan, 2023/2024 Sem 2

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Question 1
The stoichiometry of a liquid phase decomposition reaction is known to be:
A → R (desired)
A → S (unwanted)
The following data were collected using a CSTR from a series of steady-state flow experiments with a feed
of cA0 = 100 a.u. and cR0 = cS0 = 0.
cA (a.u.) 90 80 70 60 50 40 30 20 10 0
cR (a.u.) 7 13 18 22 25 27 28 28 27 25

(a) Explain how these measurements were made.

(b) Further experiments indicated that concentrations cR and cS have no effect on the reaction kinetics. From
the shape of the instantaneous selectivity curve φR/A, recommend the reactor to use and calculate the
maximum yield of R for a feed with cA0 = 80 a.u.
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Question 1
Solutions: cA cR cA0 − cA 𝜑 /
90 7 10 0.7
(a) The experimental data were generated from CSTR measurements 80 13 20 0.65
by varying the reactor flow rates. 70 18 30 0.6
60 22 40 0.55
(b) For CSTR: 50 25 50 0.5
40 27 60 0.45
/ / 30 28 70 0.4
20 28 80 0.35
The values of φR/A are calculated from the data and plotted: 10 27 90 0.3
/ /
0 25 100 0.25

The shape of the plot suggests that a PFR should be used to increase
the yield of R. For cA0 = 80 a.u., the maximum yield occurs at cA = 0:
/
/
80 80
0 / 0
/
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Question 2
Equimolar quantities of diluted solutions of A, B and D are fed continuously to a CSTR where they react
according to two elementary reactions:
A+ D → R k1
B+D→S k2

where = 0.2.

(a) If 50% of incoming A is consumed, determine what fraction of the products (R + S) formed is R.
(b) If 50% of incoming D is consumed, determine what fraction of the products (R + S) formed is R.

Analysis:

Need to find cB.

cB is determined by the relative reaction rates of the first and second reactions.
Apply mole balance equations for A and B.
Reaction volume and molar flow rate are the same and will cancel out.
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Question 2
Solutions:
Overall mole balances of A and B: (b) Based on the stoichiometric table:

Substituting cD = 0.5cD0, cA0 = cB0 = cD0:

(a) Substituting c A0 = c B0 , c A = 0.5c A0 and = 0.2 Combining (1) and (2), and substituting cA0 = cB0
into (1): and = 0.2:
5
cB = cA0 cA = 0.612cA0 and cB = 0.888cA0
6

5
Substituting cB = cA0, cA = 0.5cA0 and = 0.2:
6
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Question 3
Chemical A reacts to form R, S and T according to the following reaction scheme. In this scheme, all
reactions are first order:
1 k k
A→ R →2 S
k3

→
T

where k1 = 6 h−1, k2 = 3 h−1 and k3 = 1 h−1.

If the feed is a solution containing A without any R, S and T:
(a) What reactor (type and size) should be used to maximise the yield of R? What is the product
composition ( , , and ) from this reactor?

(b) What reactor (type and size) should be used to achieve 90% of the maximum yield of S?
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Question 3
Solutions:
k1 k'
The reaction can be taken to be equivalent to A → R →2 S or T where k1 = 6 h−1 and k2’ = k2 + k3 = 4 h−1.
(a) A PFR or batch reactor would maximise the yield of R from A.

The following equations apply:

4
− 4−6

× .

Since and cS = 3cT, = 0.195 and = 0.065

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Question 3
(b) As S is an end product, it will be formed in any reactor with a sufficiently long space time. Since all
reactions are of positive orders, a PFR should be used to minimise the reactor size.
3
Since cS = 3cT, cS = 90% × 4
= 0.675cA0 and cT = 0.225cA0:

Slides 20-21 unit 5

https://www.calculatorsoup.com/calculators/algebra/cubicequation.php
Need to solve a cubic equation
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Question 4
The concentrations of reactant A as well as products R and S were monitored continuously in a batch
reactor. The following two figures show the concentration-time curves and the instantaneous selectivity
curves (φR and φS).
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Question 4
(a) Which of the following reaction systems is consistent with the experimental data?
(i) A → R + S rA = −kAcAm (m > 0)
(ii) A → R → S rA = −kAcAm and rS = kScRn (m, n > 0)
(iii)A → R and A → S rR = kRcAm and rS = kScAn (m, n > 0)
𝑑 𝑑
For (i) A → R + S, 𝑑𝑡 𝑑𝑡
. This is not the case
with the data shown.
𝑑
For (ii) At time = 0, both cR and cS = 0 but 𝑑𝑡 .
This rules out the series reaction A → R → S.
Therefore, only (iii) is possible.
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Question 4
(b) Describe how the instantaneous selectivity curves are obtained from the raw data shown in the
concentration-time curves and, if applicable, what is the relative magnitude of the reaction orders suggested
by the given data?

𝑑
As −𝑑
, the instantaneous selectivity curves
were obtained by measuring the slopes of the
concentration-time curves at fixed time intervals.

Since decreases as cA increases, m < n.

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Question 4
(c) If R is the desired product, recommend with reasons the most suitable type of reactor for the reactions.

Instantaneous selectivity of R is largest at cA = 0. A CSTR should be used.

However, since rA = 0 at cA = 0, the CSTR will have infinite volume. In practice, a balance should be
struck between achieving the theoretical maximum overall selectivity and minimising the reactor size.
This can probably be done by operating at a low (but not zero) cA to attain a relatively high overall
selectivity with a reasonable reactor size.
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Question 4
(d) It is found that the instantaneous selectivity of R, φR increases with temperature. What can you deduce
from this information on the reaction rate constants?

𝑇
𝑇 𝑇
𝑇

This implies that the activation energy for the formation of R is higher.
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Question 4

lnk 𝑇
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Question 5
In the following elementary reactions, P* is a reactive radical which reacts with M to form a valuable
product Q. However, P* can also be easily annihilated by reaction (2):
P* + M → Q (1)
P* + P* → T (2)
What will happen if the following equilibrium reaction is added to the reaction system?
[D]
P* + Z D [ ∗ ][Z]

Solutions:
Adding the equilibrium reaction with a very large K could significantly reduce the concentration of P*,
thereby suppressing both reactions (1) and (2). The inhibition of reaction (2) would be greater because its
bimolecular kinetics is more sensitive to the decrease in concentration of P*. Therefore, the selectivity
towards Q is improved by adding the equilibrium reaction to the reaction system.
There will be no P* or D remaining at the end of reaction since the irreversible reactions (1) and (2)
consume P* and the position of the equilibrium reaction continuously shifts to the left.
At the end of reactions, Q, T, Z and any excess M are present.
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Question 6
Consider the following reactions which can be run between 900 and 1200 K, where S is the compound of
interest:

The following Arrhenius relations are known.

k1 = k2 = 2 × 1013 exp(−19124/T) [h−1]
k3 = 8.15 × 1017 exp(−25138/T) [h−1]
k4 = 2.1 × 105 exp(−10055/T) [h−1]
(a) Write down the mole balance equations for all species in a batch reactor.
(b) Suggest the operating temperature that will maximise the yield of S.
(c) What can you say about the concentration of R at any time?
(d) Present an isothermal reactor design (size and type) that maximises the yield of S.
(e) What is the value of the corresponding overall selectivity?
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Question 6
Solutions:
(a)

(b) Based on the values of the activation energies, the reactions should be operating at the highest possible
temperature, i.e. 1200 K.
(c) Since k3 >> k1, cR ≈ 0
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Question 6
𝑑
(d) Since k3 >> k1, 𝑑𝑡
≈ 0:

k1 + k2 k4
Therefore, the reaction may be viewed as A → S → T
A PFR should be used:

× ×
×
(e)
48.2
−( + ) × 48.2−4.8×

Since there is very little A left in the system, the overall selectivity of S is:
/
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Question 7
A decomposes to R and S in an aqueous phase reaction with the following kinetics:
A → R (wanted) R1 = k1cA2
A → 2S (unwanted) R2 = k2cA
(a) Derive the instantaneous selectivity function φR/A.
(b) Currently, a feed with cA0 = 1.0 mol/L without any R and S enters a CSTR with τ = 2.5 min and leaves
with the composition cA = 0.4 mol/L, cR = 0.2 mol/L and cS = 0.8 mol/L. What is the effect of adding
another CSTR of the same size in series? Will the overall selectivity of R be improved? If not, suggest a
means to improve the situation.

Solutions:
(a)
/
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Question 7
(b) Mole balances on R and S over the original CSTR:

Substituting known values, k1 = 0.5 mol−1 L min−1 and k2 = 0.4 min−1

With a second CSTR connected in series, mole balances on A and R over the second CSTR:

Substituting known values, cA2 = 0.18 mol/L and cR2 = 0.241 mol/L
Overall selectivities:

/ ,

/ ,

Therefore, adding a CSTR has not improved the overall selectivity. Possible solution: Use a PFR (this is
evident from the shape of the φR/A curve.
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Question 8
Consider the following first order liquid phase decompositions with rate constants (in the same units) as
shown:
40 0.1 0.02 10
A→ R → S A→R→S
10 0.2 0.01 20

→
T→U T→U

If c S = 0.2cA0 in the exit stream of a PFR, for each of the above schemes, what can be said about the
concentrations of the other reactor components, A, R, T and U, in the exit stream?

Solutions:
In the general reaction scheme:
k11 k21
A→ R → S
k12 k22
→

T→U

where only A is present initially.

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Question 8
Solution process
For the first parallel reaction:
𝑑𝑐
= 𝑑𝑡
− (𝑘 + 𝑘 )𝑐 𝑑𝑐 𝑑𝑐
=
𝑑𝑐 𝑘 − (𝑘 + 𝑘 )
= 𝑑𝑡
𝑘 𝑐

𝑑𝑐 𝑑𝑐
=
0 𝑘 − (𝑘 + 𝑘 )
For the second parallel reaction:

10
In the case k11 = 40, k12 = 10, k21 = 0.1 and k22 = 0.2, cA ≈ 0 and cT = 10+40cA0 = 0.2cA0
0.2
Given cS = 0.2cA0, cU = × cS = 0.4cA0 and cR = cA0 − cA − cS − cT − cU = 0.2cA0
0.1
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Question 8
In the case k11 = 0.02, k12 = 0.01, k21 = 10 and k22 = 20, cR ≈ 0.
20
Given cS = 0.2cA0, cU = × cS = 0.4cA0
10
In addition:

Solving simultaneously gives cA = 0.1cA0 and cT = 0.3cA0

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Question 9
Consider the parallel decomposition of A of different orders:
A→ R rR = k R
A → S (desired) r S = k Sc A
A→T rT = kTcA2
where kR = 1 mol L−1 min−1, kS = 2 min−1 and kT = 1 mol−1 L min−1.
Given that cA0 = 4 mol/L, determine the concentration of the desired product (S) when the maximum yield
is obtained in:
(a) a PFR.
(b) a CSTR.

Solutions:
/
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Question 9
(a) For PFR, operate at cA = 0 for maximum area:

+ +

4 2
0 1+2 +

4 1 1
0 1+ (1+ )

1
1+

1
1+4
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Question 9
(b) For CSTR:

Differentiate with respect to cA and equate the derivative to zero to obtain maximum cS:
 27

Question 10
When aqueous A and B are brought together, they react in two possible ways:
A+ B →R rR = kRcA
A+ B →S r S = k Sc B
where kR = 50 h−1 and kS = 100 h−1.
Find the space time of the CSTR needed and the R/S ratio produced for 90% conversion of an equimolar
feed of cA0 = cB0 = 0.03 mol/L.

Solutions:
×
/
× ×
×
/
× ×

× ×
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Question 11
Consider the following series-parallel reactions:
A+ B →R R1 = k1cAcB
R+B→S R2 = k2cRcB
The concentration of the desired product R may be maximised by using a semi-batch reactor, where A is
initially present in the reactor while B is fed through the inlet. Write down the ODEs describing the
variations of concentrations of A, B, R and S as well as their initial conditions. For two different values of
the inlet flow rate, solve the set of simultaneous ODEs numerically using MATLAB to obtain the
concentration profiles. In each case, determine the value of when the concentration of R is maximum.
The values of the parameters are provided below:
k1 = 1 mol−1 dm3 s−1; k2 = 1 mol−1 dm3 s−1; V0 = 10 dm3;
v0 = 0.1 dm3 s−1 (Case 1), 0.5 dm3 s−1 (Case 2);
cA0 (initial concentration of A) = 1 mol dm−3; cB0 (inlet concentration of B) = 1 mol dm−3
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Question 11
Solutions:
ODEs:

Initial conditions: When t = 0, cA = cA0, cB = cR = cS = 0.

 30

Question 11

Concentration (mol dm -3 )
Concentration (mol dm -3 )

Case 1 (left):
Maximum cR occurs at t = 63.6 s, where cR = 0.208 mol dm−3, cS = 0.085 mol dm−3 and = 2.44
Case 2 (right):
Maximum cR occurs at t = 14.1 s, where cR = 0.199 mol dm−3, cS = 0.081 mol dm−3 and = 2.47