Department of Chemical and Biomolecular Engineering

CN2105 Reaction Engineering

Assignment 3

Prof Ning Yan, 2023/2024 Sem 2

 2

Indirect method (integral analysis )

Analyze whether the cA – t/𝜏 data satisfy the

guessed rate law rA = f(cA)

0h 1h 2h 3h 4h
t or 𝜏
Batch, PFR or CSTR

Constant density
𝑟 = 𝑠𝑙𝑜𝑝𝑒 𝑐 −𝑐
−𝑟 =
𝜏 Direct method
(differential analysis )

Analyze the mathematical

relationship of cA-rA

0h 1h 2h 3h 4h 0h 1h 2h 3h 4h
Batch or PFR t or 𝜏 CSTR t or 𝜏
 3

Categories of Questions

For this entire unit, questions are mostly about:

1) How to conduct experiments to collect kinetic data in different reactors;
2) How to derive rate equations from kinetic data achieved in different reactors;
3) How to use rate law or other kinetic information to conduct reactor design
 4

Question 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?

Solutions:
𝑑
For batch reactor, the data is collected as a series of cA-time measurements where −rA was calculated as − 𝑟 =− .
𝑑𝑡

For a CSTR, the data is collected in a series of cA-𝜏 measurements where −rA could be calculated directly:
𝑐 −𝑐
−𝑟 =
𝜏
𝑑
For PFR, the data is collected in a series of cA-𝜏 measurements where − 𝑟 =− .
𝑑𝜏
 5

Question 1 (continued)
(b) Use differential analyses (direct analysis) to identify whether the reaction kinetics follows a simple power law?

Solutions:
Guess power law: 𝑟 =− 𝑘𝑐 ln (− 𝑟 ) = 𝛼ln 𝑐 + ln 𝑘

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
𝒍𝒏 (− 𝒓𝑨 ) -4.0 -3.4 -2.9 -2.5 -2.4 -2.3
𝐥𝐧 𝒄𝐀 -2.3 -1.6 -0.91 -0.22 0.18 0.69

Plot : ln (− 𝑟 ) 𝑣𝑠. ln 𝑐

The curve is not liner.

The rate equation can not be described by a
simple power law.
 6

Question 1 (continued)
(c) It is suspected that the following rate law may be applicable to the reaction in question:
𝑘 𝑐
𝑟=
(1 + 𝑘 𝑐 )
Suggest a graphical method which can extract the parameters k1 and k2.
Solutions:
𝑘 𝑐 𝑟 𝑘 𝑐 1 𝑘
The rate equation can be rearranged into 𝑟= = = + 𝑐
1+𝑘 𝑐 𝑐 1+𝑘 𝑐 𝑟 𝑘 𝑘

1
Plotting against 𝑐 would result in a straight line with slope and intercept of :
𝑟

1
Regression of the data yields = 2.2427 and = 1.1124
⇒ k1 = 0.2 s−1 and k2 = 0.5 mol−1 L
 7

Question 2
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/min 0 2 4 6 8 10 12 14 ∞
pA/mmHg 760 600 475 390 320 275 240 215 150

Suggest a rate equation for the decomposition reaction. Use integral analysis (indirect analysis).

Solutions:
Since 𝑝 ≠ 0 at 𝑡 → ∞, this is indeed a reversible reaction: A ⇌ R

Assume the forward reaction is 1st order.

Because of the thermodynamic consistency of rate laws, reverse reaction is also 1st order:
𝑟 =− 𝑘 𝑐 + 𝑘 𝑐

𝑐 −𝑐 , 1
From lecture notes: − ln = 𝑘 (1 + )𝑡
𝑐 −𝑐 , 𝐾

𝑝 𝑐 −𝑐 , 𝑝 −𝑝 ,
Since 𝑐 = =
𝑅 𝑇 𝑐 −𝑐 , 𝑝 −𝑝 ,
 8

Question 2 (continued)
− ,
Plot of − ln vs t gives a straight line with gradient = 0.160 min−1,
− ,
hence the data satisfy the assumptions of first order kinetics for the
forward reaction.

The values of k1 and k2 can be determined by first finding K from the data
corresponding to equilibrium:
𝑝 , +𝑝 , =𝑝 +𝑝 = 760

𝑝 , = 150 ⇒ 𝑝 , = 610
𝑝 , 610
𝐾= = = 4.07
𝑝 , 150
1
Therefore: 0.160 = 𝑘 1+ ⇒ 𝑘 = 0.128 min
4.07

𝑘 0.128
𝑘 = = = 0.031 min
𝐾 4.07
 9

Question 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.
Solutions:
Apply half-life analysis to the experimental data:
Time to reduce concentration from 2.45 to 1.23 ppm = 20 min
Time to reduce concentration from 1.74 to 0.88 ppm = 20 min
Time to reduce concentration from 1.23 to 0.62 ppm = 20 min
Time to reduce concentration from 0.88 to 0.44 ppm = 20 min
As the half-life of 20 min is independent concentration ⇒ n = 1

ln(2) ln(2)
𝑘= = = 0.035 min
𝑡 / 20
 10

Question 3 (continued)
(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. (Hint: What type of reactor is the pool?
Is there chlorine leaving the pool?) Will the amount be lower if chlorine is delivered hourly on an intermittent basis (the
concentration of Cl2 has to be kept at least 1 ppm)?
Solutions:
Model the pool as a mixed reactor with no outflow for chlorine (chlorinated pool water is internally circulated):
1 mg 60 min
𝐹 − 𝐹 = (−𝑟 )𝑉 = 𝑘𝑐 𝑉 = 0.035 min × × 25000 L ×
L 1h
= 52.5 g/hr
For continuously supply (Mode 1), the Cl2 level is always kept at 1 ppm.

For intermittent supply (Mode 2), new supply has to be added once Cl 2 level drops to 1 ppm. The time-averaged
concentration of Cl2 is higher than 1 ppm.
For 1st order reaction, reaction rate is proportional to concentration.
Since the time-averaged concentration of Cl2 is higher in Mode 2, the consumption rate of Cl2 is higher, thus more Cl2
has to be added.
 11

Question 4
The aqueous decomposition of A was studied in an experimental cA (mol/L) Space time
CSTR. The table below shows the steady state measurements. In feed In exit stream (s)
2.00 0.65 300
Determine the space time of a PFR for 75% conversion of A with
2.00 0.92 240
a feed of cA0 = 0.8 mol/L. 2.00 1.00 250
Analysis: 1.00 0.56 110
1.00 0.37 360
Rate law is a function of T and 𝑐 , but not of the type of reactor ⇒
0.48 0.42 24
Can use CSTR data to derive rate law, then use it for PFR design.
0.48 0.28 200
0.48 0.20 560
Solutions:
𝟏
The reaction rate in CSTR is described by: cA0 cA τCSTR −rA lncA ln(−rA)
− 𝒓𝐀
𝑐 −𝑐 2.00 0.65 300 0.0045 222 -0.431 -5.40
−𝑟 =
𝜏 2.00 0.92 240 0.0045 222 -0.083 -5.40
2.00 1.00 250 0.0040 250 0.000 -5.52
The rate (−rA) can be calculated for each data point. 1.00 0.56 110 0.0040 250 -0.580 -5.52
1 1.00 0.37 360 0.0018 571 -0.994 -6.35
− , ln𝑐 and ln(−𝑟 ) values are also generated for further analysis. 0.48 0.42 24 0.0025 400 -0.868 -5.99
0.48 0.28 200 0.0010 1000 -1.273 -6.91
0.48 0.20 560 0.0005 2000 -1.609 -7.60
 12

Question 4 (continued)
ln 𝑐
Guess power law: 𝑟 =− 𝑘𝑐
-4
ln (− 𝑟 ) = 𝛼ln 𝑐 + ln 𝑘 -1.8 -1.3 -0.8 -0.3 -4.5 0.2

Plot ln (− 𝑟 ) against ln 𝑐 . ln(-r_A) = 0.0168ln(c_A) - 5.458 -5

-5.5
There is no single rate law! 𝑐 = 0.56 mol/L
-6 ln (− 𝑟
When 𝑐 > 0.56 mol/L, the reaction is close to zeroth order: -6.5
-7
𝑟 =− 0.00426 mol L min
ln(-r_A) = 2.0516ln(c_A) - 4.2894 -7.5
When 𝑐 < 0.56 mol/L, the reaction is second order: -8

𝑟 =− 0.0137𝑐
 13

Question 4 (continued)
V1 V2

cA0 = 0.8 mol/L cA = 0.56 mol/L cA = 0.2 mol/L

xA0 = 0 xA = 0.3 xA = 0.75

Along the reactor, the concentration of A crossed the critical value of 0.56 mol/L: Both rate laws have to be used!
0.3 0.75
𝑑𝑥 𝑑𝑥
𝑉=𝑉 +𝑉 =𝐹 +𝐹
0 −𝑟 0.3 −𝑟
0.3 0.75
𝑑𝑥 𝑑𝑥
𝜏=𝑐 +𝑐
0 0.00426 0.3 0.0137𝑐 1−
𝑐 = 𝑐 = (1 − 𝑥 )𝑐
0.75 1+
0.3 − 0 𝑑𝑥
= 0.8 × + 0.8
0.00426 0.3 0.0137𝑐 (1 − 𝑥 )
1 1 1
= 56 + 0.8 × −
0.0137 × 0.8 1 − 0.75 1 − 0.3
= 56 +235
= 290 s
 14

Question 4 (continued)
Alternative Solutions:
1
For PFR, we have: −𝑟A
𝑑𝐹 𝑑𝑣 𝑐 𝑣 𝑑𝑐 𝑑𝑐 𝑑𝑐
𝑟 = = = = =
𝑑𝑉 𝑑𝑉 𝑑𝑉 𝑑𝑉/𝑣 𝑑𝜏

𝑑𝑐
𝑑𝜏 =
𝑟
𝑑𝑐 𝑑𝑐 cA
Integrate: 𝜏= =
𝑟 −𝑟

1 1
Plot vs cA then integrate from cA = 0.2 mol/L to cA = and cA are both obtained in CSTR. We plot them
− −
0.8 mol/L: based on an equation derived from PFR. Is it correct?

𝜏PFR ≈ 300 s
 15

Question 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?

Analysis:
1
Based on question statement: 𝑐 = constant × 𝑐 𝑣 = constant
𝑣
Need to analyse design equation to check what is needed to make 𝑐 𝑣 a constant.

Solutions:

For CSTR measurements at constant density (diluted liquid phase):

𝐹 −𝐹 𝑣 (𝑐 − 𝑐 )
𝑉= = 𝑉𝑟 = 𝑣 𝑐 − 𝑣 𝑐 𝑣 𝑐 = 𝑉𝑟 + 𝑣 𝑐
−𝑟 −𝑟

Therefore: 𝑐 𝑣 = constant 𝑉𝑟 + 𝑣 𝑐 = constant 𝑟 = constant

It is a zeroth order reaction (𝑟 is independent of cA)!

 16

Question 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?

Solutions:
𝑣 = 𝑣 (1 + 𝜀 𝑥 ) so 𝑣 = 𝑣 is only possible with 𝜀 = 𝛿 =0

If 𝛿 ≠ 0, for ≈ 0 to hold, inert can be used to dilute the feed.

Advantages: Both differential and integral analyses are simpler using a constant density system, e.g. − 𝑟 =− .
𝑑𝜏

Disadvantages: The rate law determined as such is only valid for low cA (since ≈ 0).

If such approximation is not applicable, use the full form of the reactor design equation:

E.g. for differential analysis with a PFR, use − 𝑟 = 𝑐 .

𝑑𝜏
 17

Question 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
Solutions:
(a) Derive the design equation for a catalytic packed bed reactor, assuming plug flow behaviour for the reacting gas.

A→ →A+R

The PFR design equation is modified to utilise reaction rates xA

normalised by the weight of the catalyst:
𝑑𝑥 𝑑𝑥
𝑉=𝐹 𝑊=𝐹
0 −𝑟 0 −𝑟

𝑑𝑥 𝑑𝑥
or 𝑑𝑊 = 𝐹 ⇒ −𝑟 =
−𝑟 𝑊
𝑑( )
𝐹
𝑊
Plot xA against using the given data and FA0 = 10 kmol/h. 𝑊/𝐹
 18

Question 7 (continued)
(b) Find the reaction rate at 40% conversion.
Exact value may vary depending on
Reaction rate (at xA = 0.4) = slope (at xA = 0.4) = 0.42 kmol∙kg(catalyst)-1∙h-1.
the method used to find slope.

(c) How much catalyst is needed for treating 400 kmol/h of feed to 40% conversion?

Since cA0 remained the same as that used in the experimental reactor (same feed), W ∝ FA0 for the same xA:
400
𝑊= × 5.9 ≈ 240 kg Exact value may vary depending on
10
curve fitting.

(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?

For cA0 which is twice the value of the feed used in the laboratory measurements, the design of a PFR requires the rates
for concentrations above the laboratory feed concentration to be known. Since these data are not available, the PFR
design cannot be performed.

Note: It would also be a poor suggestion to use a more concentrated feed if the product specification (cAf and cRf) cannot
be changed. Halving the volumetric flow rate can only keep either cAf or cRf the same, but not both, in the “new design”.
 19

Question 8
Tests were run on a small experimental CSTR for decomposing 𝑥 (%)
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?

Solutions:
𝐹 𝑥 𝑥
For CSTR: 𝑉= −𝑟 =
−𝑟 𝑉
𝐹
𝑉
The plot of 𝑥 vs is a straight line ⇒ −𝑟 is constant

This implies zeroth order reaction.

Zeroth order reactions cannot be elementary reactions.
 20

Question 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

Solutions:
Reaction stoichiometry: A(g) + B(g) → C(g)
𝑐 (1 − 𝑥 ) 𝑐 −𝑐 𝑥
𝑐 = 𝑐 =
1+𝜀 𝑥 1+𝜀 𝑥

When v0 = ∞, concentrations at reactor exit are equal to the inlet values:

𝑐 = 1 mol/L and 𝑐 = 1.5 mol/L

𝐹 −1 − 1 + 1 1
𝜀 =𝛿 = × =− 0.4
𝐹 1 1 + 1.5
𝑐 −𝑐 1−𝑐
Therefore: 𝑥 = =
𝑐 +𝜀 𝑐 1 − 0.4𝑐
 21

Question 9 (continued)
For CSTR measurements:
𝐹 𝑥 𝑐 𝑣 𝑥 𝑣 1−𝑐
−𝑟 = = =
𝑉 𝑉 10 1 − 0.4𝑐

.
Multiple regression of –rA on cA and cB in Polymath (or other suitable software) gives 𝑟 =− 𝑘𝑐 𝑐 .
 22

Question 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.

Solutions: These values were obtained by manually draw

Differential analysis requires concentration-rate data. For PFR, rates tangent in 𝑥 − τ curve and then obtain the
corresponding to the given concentrations can be calculated as −𝑟 = slope. Using this method, everyone will get
slightly different -rA values.
𝑐 .
𝑑𝜏

xA is calculated from the concentration as follows:

A → 2B
𝐹 −1 + 2
𝜀 =𝛿 = ×1=1
𝐹 1
𝑐 (1 − 𝑥 ) 𝑐 −𝑐 𝑐 −𝑐
𝑐 = ⇒𝑥 = =
1+𝜀 𝑥 𝑐 +𝜀 𝑐 𝑐 +𝑐

Regression of –rA on cA gives rA = −1.2cA.

 23

Question 11
The liquid phase reaction A → R is to be carried out in a batch reactor. The rates of cA −rA (mol L−1
reaction measured as a function of concentrations of A are tabulated below. What is (mol/L) min−1)
the reaction time to drop the concentration of A from 1.3 mol/L to 0.3 mol/L in a 0.1 0.1
batch operation? 0.2 0.3
Analysis: 0.3 0.5
A plot of
1
vs cA showed that the data cannot be fitted to a simple power law. 0.4 0.6
− 0.5 0.5
Hence the data has to be used directly for finding the reaction time. This is 0.6 0.25
permissible if the experimental data covers the concentrations involved in the 0.7 0.10
0.8 0.06
actual operation, which is indeed the case in this example.
1.0 0.05
Solutions: 1.3 0.045
1 𝑑𝑁 2.0 0.042
The batch reactor design equation is: 𝑟 =
𝑉 𝑑𝑡
𝑑𝑐
For the constant density system for aqueous phase reactions, the equation simplifies to: 𝑟 =
𝑑𝑡
𝑑𝑐 𝑑𝑐
The integrated form of the design equation is: 𝑡 = =
𝑟 −𝑟

1
The reaction time can be obtained by integrating vs cA graphically (or numerically) over the interval [cA, cA0]. The
−
answer is 12.75 min.
 24

Question 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.
Solutions:
For a first order reversible reaction, the integrated conversion equation in a batch reactor (constant volume for liquid)
is given by:
𝑐 −𝑐 , 1
− ln =𝑘 1+ 𝑡
𝑐 −𝑐 , 𝐾

Using cA0 = 0.5 mol/L, t = 8 min, cA = 0.333 mol/L, 𝑐 , = 0.167 mol/L and K = 2, we find: 𝑘 = 0.0578 min
𝑘 𝑘 0.0578
𝐾= 𝑘 = = = 0.0289 min
𝑘 𝐾 2

Thus, the rate expression for A is 𝑟 =− 0.0578𝑐 + 0.0289𝑐

 25

Question 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.

Analysis:
Data are very limited, so accurate data regression (required by differential analysis) is not possible. We guess a power
law rate equation and calculate its reaction order.
Solutions:
We try nth order kinetics. Taking ratios gives:
𝑐
𝑐 −1
(𝑛 − 1)𝑘𝑡 𝑐
=
(𝑛 − 1)𝑘𝑡 𝑐
𝑐 −1
𝑐
0−1 1
Substituting values gives: 2 = 1
⇒𝑛=
−1 2
4
1 1
1
Substituting back into numerator of both sides gives: − 1 𝑘(2) = 1(0 − 1) ⇒ 𝑘 = 1 mol2 L 2 h
2
1 1 1
Therefore: 𝑟 =− 𝑘𝑐 where 𝑘 = 1 mol L
2 2 2 h
 26

Question 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.
Solutions:
Since we are told that the reaction is elementary, the stoichiometric equation shows that the reaction is 2nd order. So, for
a relatively small concentration change (1%), we can write:
∆𝑐
− = 𝑘𝑐
∆𝑡
∆𝑐 1 20 × 0.01 1
𝑘 =− =− × = 6.6 × 10 mol Lh
∆𝑡 𝑐 7.67 (20 × 0.995)

Therefore: 𝑟 =− 𝑘𝑐 where 𝑘 = 6.6 × 10 mol Lh