CN2105 Reaction Engineering

2022-23 Semester 2 – Assignment 3

Homework
1. The following are the data from a new liquid phase chemical reaction (A → products)
slated for process development.
cA (mol/L) 0.1 0.2 0.4 0.8 1.2 2
−rA (mol L−1 s−1) 0.018 0.033 0.055 0.082 0.094 0.100
(a) How to obtain these data from batch reactor, CSTR and PFR, respectively?
(b) Use differential analyses (direct analysis) to identify whether the reaction kinetics
follows a simple power law.
(c) It is suspected that the following rate law may be applicable to the reaction in question:
𝑘1 𝑐A
𝑅=
(1 + 𝑘2 𝑐A )2
Suggest a graphical method which can extract the parameters k1 and k2.
Hint: for b) you may guess reaction rate follows power law; for c) rearrange the equation
so one would be able to make a liner plot based on experimental data.
Ans: (c) k1 = 0.2 s−1, k2 = 0.5 mol−1 L

2. [OL 3.25 Modified] The gas phase reversible reaction A ⇌ R was investigated in a
constant volume batch reactor at 0 °C. The following data were obtained using a feed of
pure A in the gas phase. The reaction started with pure A.
Time 0 2 4 6 8 10 12 14 ∞
pA 760 600 475 390 320 275 240 215 150
Suggest a rate equation for the decomposition reaction. Use integral analysis (indirect
analysis).
Hint: for integral analysis we have to make a guess of the rate law. If there is no other
clue, starting from guessing 1st order (for both forward and backward in this case) is a
common practice.

3. Chlorine is an effective disinfectant for swimming pools. However, it loses its efficacy by
undergoing photochemical decay under bright sunlight. The following is the data collected
from a laboratory study.
Time (min) 10 20 30 40 50 60
Concentration of Cl2 (ppm) 2.45 1.74 1.23 0.88 0.62 0.44
(a) Does the reaction satisfy a power law? If so, show how you would apply the method
of half-life to measure the order of reaction and the rate constant.
(b) Assuming ideal exposure conditions, calculate the hourly injection rate (continuous
injection mode) of chlorine to maintain a sterilising Cl2 level of 1 ppm by mass in a
pool 25,000 L in volume. Will the amount be lower if chlorine is delivered hourly on
an intermittent basis?
Hint: for b, if Cl2 concentration is kept at 1 ppm, the swimming pool may be regarded as
a CSTR where FCl2out = 0. Apply CSTR design equation to obtain the injection rate.
Ans: (a) 0.035 min−1 (b) 52.5 g/h

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4. [OL 5.25] The aqueous decomposition of A was studied in an experimental CSTR. The
table below shows the steady state measurements.
cA (mol/L)
Space time (s)
In feed In exit stream
2.00 0.65 300
2.00 0.92 240
2.00 1.00 250
1.00 0.56 110
1.00 0.37 360
0.48 0.42 24
0.48 0.28 200
0.48 0.20 560
Determine the space time of a PFR for 75% conversion of A with a feed of cA0 = 0.8 mol/L.
Hint: 1) Rate law is a function of T and 𝒄𝐀 , but not of the type of reactor ⇒ Can use CSTR
data to find rate law, then use PFR design equation and the identified rate law to find t.
2) you are suggested to use differential analyses to find rate law;
3) a reaction may not follow the same order in the entire concentration range (recall
enzyme kinetics where substrate has 1st order at low concentration and 0th order at high
concentration);
Ans: 300 s or 269 s (depending on the method used)

Extra Practice
5. In a series of CSTR measurements of a diluted liquid phase reaction A ? 2B, it was found
that the concentration of A at the reactor exit varied linearly with reciprocal volumetric
flow rate. What is a likely rate law for the reaction within the measurement range?

6. How do you render the gas phase reaction A → mR (m ≠ 1) approximately constant

density in a PFR? What are the advantages and disadvantages of using a constant density
system for the analysis of rate law? What will you do if you cannot apply this
approximation?

7. The following data on the gas-phase reaction A → R were measured from an experimental
packed bed reactor using a fixed feed rate of FA0 = 10 kmol/h and different amounts of the
catalyst. The concentration of A in the feed was cA0.
W (kgcat) 1 2 3 4 5 6 7
xA (-) 0.12 0.2 0.27 0.33 0.37 0.41 0.44
(a) Derive the design equation for a catalytic packed bed reactor, assuming plug flow
behaviour for the reacting gas.
(b) Find the reaction rate at 40% conversion.
(c) How much catalyst is needed for treating 400 kmol/h of feed to 40% conversion?
(d) If a feed with twice the cA0 concentration is available, how much catalyst is needed for
treating 200 kmol/h of the more concentrated feed to the same cAf as in (c) above?
Ans: (b) 0.4375 kmol/kgcat (c) 238 kg

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8. [HSF P5-12] Tests were run on a small experimental CSTR for decomposing nitrogen
oxides in an automotive exhaust stream. In one series of tests, a nitrogen stream containing
various concentrations of NO2 was fed to a reactor, and the fractional decomposition of
NO2 fed to the reactor is shown in the figure below. Propose a rate law that fits the
experimental data. Is the reaction elementary?

9. The kinetics of the gas phase reaction A + B → C was investigated in a 10 L CSTR at

constant temperature and pressure. The following data was collected at the reactor outlet.
Suggest a power law that could fit the experimental data.
v0 (L/min) 1 2 5 10 20 ∞
cA at reactor exit (mol/L) 0.099 0.181 0.36 0.54 0.71 1
cB at reactor exit (mol/L) 0.9 0.954 1.07 1.19 1.30 1.5

10. The kinetics of the gas phase reaction A → 2B was studied in a 1 L PFR. The volumetric
feed rate to the reactor was varied to give the concentrations of A at the reactor exit.
v0 (L/min) 4.76 1.92 0.97 0.5 0.32
cA (mol/L) 0.67 0.43 0.25 0.11 0.053
All experimental runs were carried out isothermally and isobarically with a feed of pure A
at cA0 = 1 mol/L. Apply the differential analysis to obtain a power law that fits the data.

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11. [OL 5.21] The liquid phase reaction A → R is to be carried out in a batch reactor. The
rates of reaction measured as a function of concentrations of A are tabulated below. What
is the reaction time to drop the concentration of A from 1.3 mol/L to 0.3 mol/L in a batch
operation?
cA (mol/L) −rA (mol L−1 min−1)
0.1 0.1
0.2 0.3
0.3 0.5
0.4 0.6
0.5 0.5
0.6 0.25
0.7 0.10
0.8 0.06
1.0 0.05
1.3 0.045
2.0 0.042
Ans: 12.75 min

12. The first-order reversible liquid reaction takes place in a batch reactor with cA0 = 0.5 mol/L
and cR0 = 0:
A⇌R
After 8 minutes, the conversion of A is 33.3% while the equilibrium conversion is 66.7%.
Find the rate equation for this reaction.

13. For the decomposition A → R with cA0 = 1 mol/L in a batch reactor, the conversion is 75%
after 1 hour and the reaction is just complete (close to 100% conversion) after 2 hours.
Find a rate equation to represent these kinetics.

14. When a concentrated urea solution is stored, it slowly condenses to biuret by the following
elementary reaction:
2NH2CONH2 → NH2CONHCONH2 + NH3
To study the rate of condensation, a sample of urea (c0 = 20 mol/L) is stored at 100 °C and,
after 7 h 40 min, we find that 1 mol% has turned into biuret. Find the rate equation for this
condensation reaction.