19CHE301 CHEMICAL REACTION ENGINEERING I

1. On doubling the concentration of reactant, the rate of reaction triples. Find the reaction
order.
2. The pyrolysis of ethane proceeds with an activation energy of about 75000 cal. How
much faster is the decomposition at 650oC than at 500oC?
3. A reaction 2HI(g)  H2(g) + I2(g) is studied over a range of temperatures. The results
obtained are tabulated below:

Temperature, K 633 666 697 715 781

-5 -4 -4 -3
Rate constant k, 1.7 X 10 1.07 X 10 5.01 X 10 1.05 X 10 1.51 X 10-3
l/(mol.s)
(i) Find the value of activation energy graphically.
(ii) Determine by what factor the rate increases when the temperature rises from
300K to 310K.
4. The reaction:
2D2E  2DE + D2
rD2 = K’[D2E]2/ ([DE] + K”[D2E])
Explain a mechanism that will satisfactorily explain the given rate equation and derive
the rate equation.
5. Show that the decomposition of N2O5 at 67oC is a first-order reaction. Calculate the value
of the rate constant.

Time, min 0 1 2 3 4
CN2O5, mol/l 0.16 0.113 0.08 0.056 0.040
6. In a gaseous reaction, the time for a half change (t 1/2) for various initial partial pressures
(p) of the reactant was given as follows:

pAO (torr) 200 300 400

t 1/2 (min) 150 99.8 75.3
Find the order of the reaction.
7. Decomposition of a gas is of second order when the initial concentration of gas is 5 X 10-
4
mol/l, it is 40% decomposed in 50 min. Calculate the value of the rate constant.
8. The partial pressure of azomethane, CH3N2CH3, was observed as a function of time at
600K with results given below. Confirm that the decomposition is first order in
CH3N2CH3 and find the rate constant at this temperature.
CH3N2CH3  CH3CH3 + N2

Time, s 0 1000 2000 300 4000

0
Partial pressure, torr (mm Hg) 82 572 399 278 194
0
9. In the case of first-order reaction, show that the time required for 75% conversion is
double the time required for 50% conversion.

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10. For the reaction A  Products the following data were obtained at 25oC, in which the
concentration of A is given at different intervals of time:

t, min 0 10 20 30 40
CA, mol/l 0.860 0.740 0.635 0.546 0.405
Find the order of reaction, and calculate the rate constant and the half-life period.
11. A polymerization reaction occurs at constant temperature in a homogeneous phase. For
initial monomer concentration of 0.3, 0.5 and 0.9 mol/l, 30% of the monomer reacts in 40
minutes. Find the reaction rate.
12. The time for half change (t 1/2) of a gaseous substance undergoing the thermal
decomposition was determined for various initial pressure (P) with the following results:

P mm Hg 250 300 350 400 450

t 1/2, min 136 112.5 97 85 75.5
Find the order of the reaction.
13. An aqueous solution of ethyl acetate is to be saponified with sodium hydroxide. The
initial concentration of ethyl acetate is 5 g/l and that of caustic is 0.1 normal. The values
of second order rate constant at 0oC and 20oC are k = 0.235 and 0.924 (l/mol) (min)-1
respectively. The reaction is irreversible. Calculate the time required to saponify 95% of
ester at 40oC.
14. A 10 minutes experimental run shows that 75% of liquid reactant ‘A’ is converted to
product by a ½ order rate. What would be the amount of A converted in 30 minutes run?
15. In a homogeneous isothermal liquid polymerization, 20% of the monomer gets
disappeared in 34 minutes for initial monomer concentration of 0.04 and also for 0.8
mol/l. What is the rate expression for the disappearance of the monomer?
16. After 8 minutes in a batch reactor, reactant is 80% converted and after 18 minutes the
conversion is 90%. Find the rate expression to represent this reaction if CAO = 1 mol/l.
17. The liquid phase reaction A  R + S proceeds as follows.

Time, min 0 36 65 100 160 ∞

CA, mol/l 0.182 0.1453 0.121 0.1025 0.079 0.0494
3 6 5
With CAO = 0.1823 mol/l, CRO = 0 and CSO = 55 mol/l, find the rate expression for this
reaction.
18. The following kinetic data are obtained in a constant volume batch reactor at 273 K using
pure gaseous A.

Time, min 0 2 4 6 8 10 12 14 ∞
Partial pressure of A (mm 760 60 475 390 320 275 24 215 150
Hg) 0 0
The stochiometry of decomposition is A  2.5R. Find a rate equation which will
satisfactorily fit the data.

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19. The gaseous reaction 2A  R + 2S is second order with respect to A. If pure A is
introduced at 1 atm into a constant volume batch reactor, the pressure rises by 40% in 3
minutes. In case of a constant pressure batch reactor, find (i) the time required for the
same conversion (ii) the fractional increase in volume at that time.
20. Thermal decomposition of dimethyl ether is carried out in a constant volume batch
reactor. The reactor is initially filled with pure ether and the reactor pressure is 312 mm
Hg. From the following data find the rate equation that satisfactorily represents this
decomposition.

Time, s 39 777 1195 3355

0
Rise in pressure, mm Hg 96 176 250 476
21. Consider a gas phase reaction 2A  R + 2S with unknown kinetics. If for 90%
conversion of A in a plug flow reactor the space velocity of 1/min is needed, find the
corresponding space time and mean residence time or holding time of fluid in the reactor.
22. In an isothermal batch reactor 70% of a reactant A is converted in 13 minutes. Find the
space time and space velocity needed to effect this conversion in a plug flow reactor and
in a mixed flow reactor.
23. Assuming a stochiometry A  R for a first order gas phase reaction, the size (volume) of
a plug flow reactor for 99% conversion of pure A is calculated to be 32 litres. In fact,
however, the reaction stochiometry is A  3R. With this corrected stochiometry, what is
the required volume of a reactor?
24. A high molecular weight hydrocarbon stream A is continuously fed to a heated high
temperature mixed flow reactor where it thermally cracks into lower molecular materials,
collectively called R, as per the reaction A  5R. It is a homogeneous gas phase
reaction. The different extents of cracking obtained by varying the feed rate to the reactor
are as follows:

FAO, millimol/h 30 1000 3000 5000

0
CA,out, millimol/l 16 30 50 60
The reactor volume is V = 0.1 litre and feed concentration at the temperature of reactor is
CAO = 100 millimol/l. Find a rate equation which satisfactorily represents the cracking
reaction.
25. Find a rate equation for the gas phase decomposition A  R + S occurring isothermally
in a mixed flow reactor from the following data:

Run number 1 2 3 4 5
τ, seconds 0.423 5.1 13.5 44 192
0
XA 0.22 0.6 0.75 0.88 0.96
3
XA values are given for CAO =0.002 mol/l

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26. A homogeneous gas phase reaction A 3R satisfactorily follows second order kinetics.
For a feed rate of 4 m3/h of pure A at 350oC and 5 atm, an experimental reactor (25 mm
ID pipe X 2 m length) gives 60% conversion of feed. A commercial plant is to handle
320 m3/h of feed containing 50 mole% A and 50 mole % inerts at 350oC and 25 atm for
obtaining 80% conversion of A.
(i) How many 2 m lengths of 25 mm ID pipe are required
(ii) Should they be installed in parallel or in series?
(Assume plug flow in pipe and ideal gas behavior)
27. The data on decomposition of gaseous reactant A in constant volume batch reactor at
100oC is given below. The stochiometry of decomposition is 2A  R + S. Determine size
of plug flow reactor operating at 100oC and 1 atm that can process 100 molA/h in a feed
containing 20 mole% inerts to obtain 95% conversion of A.

t, s 0 20 40 60 80 100 140 200 260 330 420

pA, atm 1.0 0.8 0.68 0.5 0.45 0.3 0.25 0.1 0.08 0.0 0.02
0 6 7 4 4
28. A first order homogeneous gas phase reaction, A  3R, is first studied in a constant
pressure batch reactor. At a pressure of 2 atm and starting with pure A, the volume
increases by 75% in 15 min. If the same reaction is carried out in constant volume reactor
and the initial pressure is 2 atm, how long is required for the pressure to reach 3 atm?
29. The liquid phase reaction A + B <-- P + Q
k1 = 7 l/(mol.min), k2 = 3 l/(mol.min) is to take place in a 120 litre steady state mixed
reactor. The two feed streams, one containing 1.4 mol A/l and the other containing 0.8
mol B/l, are to be introduced in equal volumes into the reactor, and 75% conversion of
the limiting component is desired. What should be the flow rate of each stream assuming
constant density throughout?
30. A homogeneous gas reaction A  3R has a reported rate at 200oC.
–rA=10-1 CA, mol/(l.s)
Find the space time required for 80% conversion of a 50% A and 50% inerts feed to a
plug flow reactor operating at 200oC and 5 atm pressure. Initial concentration of A is
0.0625 mol/l.
31. The liquid phase reaction A + B  R + S
k1 = 7 l/(mol.min), k2 = 3 l/(mol.min)
is to take place in a 120 litres steady state mixed reactor. Two feed streams, one
containing 2.8 mol A per litre and the other containing 1.6 mol B per litre, are to be
introduced in a volume ratio of 1:1.5 (one volume of stream containing A to 1.5 volumes
of stream containing B) into the reactor. 75% conversion of the limiting reactant is
desired. What should be the volumetric flow rate of each stream assuming constant
density throughout?
32. The laboratory measurements of rate vs conversion for reactant A are given below.
Compare the volumes of a CSTR and plug flow reactor required to achieve 60%

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 conversion. The feed conditions are same in both cases and molar flow rate of A entering
a reactor is 10 mol/s.

XA 0 0.20 0.40 0.60 0.80

-rA, mol/(l.s) 0.182 0.143 0.10 0.0667 0.0357
33. A gas phase decomposition of A is carried in a mixed reactor. The stochiometry of
decomposition is A  R + S. Initial concentration of A is 0.003 mol/l. The following
data were obtained at various runs.

Run No. 1 2 3 4 5
τ, s 0.4 5.0 14 45 195
XA 0.2 0.60 0.76 0.9 0.97
0 0
Find the rate equation for this decomposition.
34. We plan to replace our mixed flow reactor with one having double the volume. Find the
conversion for same aqueous feed (10 mol A/l) and the same feed rate. The reaction
kinetics is represented by A  R, -rA = kCA 1.5
The conversion with original unit is 70%.
35. An aqueous feed of A and B with 400 l/min, CAO = 100mmol/l and CBO=200 mmol/l is to
be converted to product in a plug flow reactor. The kinetics of the reaction is represented
by
A + B  R, -rA = 200CACB, mol/(l.min)
Estimate the volume of reactor for 99% of A to product.
36. An aqueous feed of A and B (400 l/min) with CAO = 100 mmol/l and CBO = 200 mmol/l is
to be converted into product in a mixed flow reactor. The kinetics of this reaction is given
by
A + B  R –rA = 200 CACB, mol/(l.min)
Estimate the volume of mixed flow reactor needed to achieve 99% conversion of A to
product.
37. Substance A reacts according to second order kinetics and conversion is 95% from a
single flow reactor. We buy a second unit identical to the first. For the same degree of
conversion, by how much is the capacity increased if we operate these two units in
parallel or in series?
(i) The reactors are both plug flow
(ii) The reactors are both mixed flow
38. A liquid phase elementary reaction A + B  R + S is carried in a plug flow reactor. For
equimolar amounts of A and B (CAO = CBO=0.9 mol/l), 94% conversion is achieved. If a
CSTR, 10 times as large as the plug flow reactor, is arranged in series with the existing
unit, which unit needs to be arranged first (in series) to enhance the production rate?
39. The elementary liquid phase reaction A + B  R + S takes place in a plug flow reactor
using equimolar quantities of A and B. Conversion is 96%. CAO =CBO = 1 mol/l.

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 If a mixed reactor ten times as large as plug flow reator were hooked up series with the
existing unit, which unit should come first and by what fraction could the production
increased for that set up?
40. Liquid reactant A decomposes as follows
A  R, rR = k1CA2, k1 =0.4 m3/(mol.min)
AS rS = k2 CA, k2 = 2 min-1
A feed to aqueous A (CAO = 40 mol/m3) enters a reactor, decomposes and a mixture of A,
R and S leaves. Find CR, CS and τ for XA =0.9 in a mixed flow reactor.

1. The reaction of saponification:

NaOH + C2H5(CH3COO)  Na(CH3COO) + C2H5OH

is second-order and irreversible at low concentrations. In a batch reactor at constant
temperature, a water solution is loaded containing NaOH and ethyl acetate, both with initial
concentrations of 0.1 N. After 15 minutes, the conversion of ethyl acetate is 18%. Calculate
the reaction time needed to obtain a conversion of 25% NaOH when loading the reactor with a
solution of 0.2 N NaOH and 0.1 N ethyl acetate.

2. For the production of propionic acid, the corresponding sodium salt is dissolved in HCl
according to:

C2H5COONa + HCl  C2H5COOH + NaCl

The reaction is reversible and second global order in both directions (first order for each
reagent, in both direct and reverse direction). In the laboratory, a stirred batch reactor is tested
at 50°C, a value that remains constant. Samples of 100 mL at different times are collected. In
order to find the concentration of HCl in each sample it is necessary to neutralize HCl with
NaOH 0.979 N. The initial concentrations of acid and salt are equal. Initially there was
nothing of propionic acid or NaCl.

Data from the laboratory tests (neutralizing 100 mL of sample):

t (min) 0 8 16 23 30 39 ∞
VNaOH (mL) 52.5 32.1 23.5 18.9 16.7 14.4 10.5

6
 a) From the table of experimental results, determine the value of the conversion in the
equilibrium and kinetic constants of direct and reverse reactions.
b) How long will it take to reach a conversion of 75% with the initial concentrations and
temperature above mentioned?
c) This reaction will also be carried out on an industrial scale in a stirred tank batch
reactor, starting from those moles of reagents that would produce 453 kg of propionic
acid with a conversion of 75%, with the initial concentrations and temperature above
mentioned. Knowing that in the manufacturing process there is an additional
load/heating time of 20 min and a discharge/cooling time of 10 min, at which time the
maximum production rate (moles/min) of propionic acid will be reached? Assuming
that the process stops at that point, which will be the total production time in that
case?

3. The first-order reaction A  2.5 B is carried out in a gas-phase batch reactor at 2 atm and
constant T with 20% of inerts and the rest of A. Under these conditions, the volume
increases by 60% in 20 min. In a similar reactor operating at constant volume and the same
T:

a) Calculate the time required to reach a pressure of 8 atm if the initial pressure is 5 atm,
2 of which correspond to inerts
b) Calculate the value of the conversion degree to give the maximum production per
day if the time of loading, unloading and cleaning of the reactor is 40 min

4. Isothermal batch reactor, first-order reaction

An isomerization reaction is carried out in a batch reactor. The reaction is first-order, both
isomers are liquids with a density of 900 kg/m3 at 163 °C. The reactor is filled in 10 minutes
and emptied in 12 minutes. During the 14 minutes required to heat up the reactor, the
reaction is negligible, it can be assumed to begin only when 163 °C is reached. 900 t of
product must be synthesized in 7000 hours of operation per year. Conversion is 97%.
What is the required volume of the stirred batch reactor operated isothermally at 163 °C? The
reaction rate coefficient is 0,8 1/h.
V  0,74 m3

5. Isothermal batch reactor, second-order reaction

The reaction A+2BC+2D is carried out in an isothermal, perfectly stirred batch reactor at
80 °C. The reaction rate can be described as second-order, i.e. r = k cA cB , where k =
0,058 m3/(kmol min).
At 80 °C, 200 kg of material A (MA=90 g/mol) and 400 kg of material B (MB=90 g/mol) is
measured into the reactor. At this point, the (liquid) reaction mixture has a volume of 850
dm3. The reaction does not change the volume. What conversion can be achieved in 35

7
minutes?
X = 0,914
6. Isothermal, second-order reaction
The reaction A+BC+D is carried out at 80 °C in an isothermal, perfectly stirred tank
reactor. The reaction rate can be described as second-order, where k = 0,058 m3/(kmolmin).
At 80 °C, 240 kg of material A (MA=60 g/mol) and 400 kg of material B (MB=90 g/mol) is
measured into the stirred tank. At this point, the volume of the (liquid) reaction mixture is
900 dm3. The reaction does not change the volume. How much time is required to reach 95%
conversion?
Solution
t = 9,96 min

7. In aqueous solution, the reaction is reversible and second-order. A series of isothermal

experiments with 2.7 mol/dm3 initial concentration were performed in a laboratory-scale
batch reactor to determine the reaction rate coefficient. A sample was taken from the
reactor every 10 minutes, and the conversion of sodium propanoate was determined:
time (min) 0 10 20 30 50 ∞
Conversion (%) 0 39 55 64 72,5 80
Based on the data in the table, design an isothermal batch reactor do produce 1360 kg/h
propanoic acid. Servicing time (loading, heating, cooling and emptying) is 45 minutes per
batch. Since the equilibrium conversion of sodium propanoate is 80%, use an operating
conversion of 75%. Initial concentrations in the industrial reactor are 323 kg/m 3 sodium
propanoate and 123.4 kg/m3 hydrochloric acid (100% HCl). The density of the reaction
mixture is constant, 1200 kg/m3.
V= 11,8 m3

8. Isothermal gas phase reaction, changing number of moles

Determine the reaction rate coefficient for the gas phase decomposition of dimethyl ether,
based on the pressure change measured in a constant volume reactor! The reaction is first-
order and irreversible:
(CH3)2O →CH4 +H2 + CO
The measurement was carried out by filling the reactor with pure dimethyl ether at time t = 0
and measuring the increase in pressure at a constant temperature of 504 °C.
time (s) 390 777 1195 3155 ∞
pressure change (mmHg) 96 176 250 476 619
k = 0,0005 1/s.