CN2116 Chemical Kinetics & Reactor Design

2021-22 Semester 2 – Assignment 1

Homework
𝑟B
1. Describe qualitatively how the ratio may change from t = 0 to t = τ (where τ > 0)
−𝑟A
(increasing, decreasing or invariant) for the following reactions in a batch reactor where
only A is present initially.
(a) A → B + C
(b) A → B → C

2. Fluid catalytic cracker (FCC) reactors are among the largest processing units used in the
petroleum industry. The following figure shows an example of such units. A typical unit
is 4-10 m ID and 10-20 m high and contains 50 metric tons of 𝜌 = 800 kg/m3 porous
catalyst. It is fed about 38000 barrels of crude oil per day (6000 m3/day at a density of
900 kg/m3), and it cracks these long chain hydrocarbons into shorter molecules.

To get an idea of the rate of reaction in these giant units, let us simplify and suppose that
the feed consists of just C20 hydrocarbon, i.e.

If 60% of the vapourised feed is cracked in the unit, what is the rate of the reaction,
expressed as −r’ (molreacted kg−1cat s−1) and as −r” (molreacted m−3cat s−1)?
Ans: 133 mol/s, 0.0027 mol kg−1cat s−1, 2.13 mol m−3cat s−1

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3. What are the orders of reaction for the forward, the reverse and the overall reactions of:
(a) A ⇌ 2B
(b) The same reactions as above but with the added information that both forward and
reverse reactions are elementary.

4. A reaction with the stoichiometry of 0.5A + B → R + 0.5S has the rate law 𝑅 = 𝑘𝑐A0.5 𝑐B .
Is the reaction elementary? What will become of the rate law if the stoichiometry of the
reaction is rewritten as A + 2B → 2R + S?

5. A certain reaction has a rate given by 𝑟A = −0.005𝑐A2 mol cm−3 min−1. If the concentration
is to be expressed in mol/L and time in h, what will be the value and units of the rate
constant?
Ans: 3 × 10−4 mol−1 L h−1

6. The high temperature water-gas shift reaction CO + H2O ⇌ CO2 + H2 is industrially

important for hydrogen production. It has the following rate law under the given operating
conditions:
[CO2 ][H2 ]
𝑘([CO][H2 O] − )
𝑅= 𝐾
1 + 𝐾CO [CO] + 𝐾H2 O [H2 O] + 𝐾CO2 [CO2 ] + 𝐾H2 [H2 ]
(a) Is the rate law thermodynamically consistent?
(b) Are the forward and reverse reactions bimolecular?
(c) Can the forward and reverse reactions be bimolecular?
(d) What is the reaction order with respect to CO at the start of the reaction in the presence
of a large excess of steam?

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Extra Practice
7. Determine the values of constants a, b and c in the relation 𝑎𝑟A + 𝑏𝑟R + 𝑐𝑟S = 0 for the
reactions A → 2R → S.

8. The following three reactions involving A, B and C are studied in a batch reactor:
A→B (1)
A→C (2)
B + C → 2A (3)
Express the reaction rates of species A, B and C (𝑟A , 𝑟B and 𝑟C ) in terms of the rates of the
three reactions (𝑅1 , 𝑅2 and 𝑅3 ). If only A is present in the reactor initially, what do you
expect to find in the reactor after some lapse of time?

9. The hydrogenation of cyclohexene on supported Pd catalysts was carried out at 308 K,

atmospheric pressure of hydrogen and 0.24 M cyclohexene in a CSTR.
C6H10 + H2 → C6H12
The reaction rates measured under these conditions were 7.66 × 10−4 mol g−1cat s−1 for a
4.88 wt% Pd catalyst supported on Al2O3 and 1.26×10−3 mol g−1cat s−1 for a 3.75 wt% Pd
catalyst on SiO2. The fractions of Pd atoms on the surface of the supported Pd particles
were 0.21 for Pd/Al2O3 and 0.55 for Pd/SiO2. Are the two supported Pd catalysts different
in a significant way to indicate an effect due to the support?
Notes: In supported catalysts, the catalytic metal is present as metal particles on the support
and catalysis occurs only on the metal sites. The catalyst support is there to disperse
(“distribute”) the metal to increase the utilisation of the catalytic metal. Since catalysis is
a surface phenomenon, only those metal atoms on the metal particle surface can contribute
to catalysis. A fair comparator of catalytic activity should therefore be based on the
turnover frequency (TOF), which is the number of reactant molecules reacted (“turned
over”) per unit time per catalytically active site.
Ans: Pd/Al2O3: 9.63 × 10−5 mol, 7.95 s−1; Pd/SiO2: 1.943 × 10−4 mol, 6.50 s−1

10. Express the overall reaction rates of species (𝑟A , 𝑟B , 𝑟C ,…) in terms of the rates of the steps
for the following reaction network:

11. Can the kinetics of the second order gas phase reaction A → B in a batch reactor be written
𝑑𝑝A
as = −𝑘p 𝑝A2 ? Is 𝑘p a specific rate constant?
𝑑𝑡

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12. The measurements of a gas phase reaction at 400 K in a constant volume batch reactor
resulted in the following equation:
𝑑𝑝A
= −3.66𝑝A2 atm/h
𝑑𝑡
𝑑𝑝
(a) Is A = −3.66𝑝A2 a rate law?
𝑑𝑡
(b) What is the unit of the constant 3.66 in the above equation?
(c) Show how the above equation may be transformed into the following standard form of
rate law. If so, what is the value of the rate constant k? Assume ideal gas behaviour.
1 𝑑𝑁A
𝑟A = = −𝑘𝑐A2 mol m−3 s−1
𝑉 𝑑𝑡
Ans: (c) 3.34 × 10−5 mol−1 m3 s−1

13. The decomposition of reactant A at 400 °C for pressures between 1 and 10 atm follows a
first-order rate law.
(a) Show that a mechanism similar to azomethane decomposition is consistent with the
observed kinetics.
A + A ⇌ A* + A
A* → R + S (slow step)
(b) Different mechanisms can be proposed to explain first-order kinetics. To claim that this
mechanism is correct in the face of the other alternatives requires additional evidence.
For this purpose, what further experiments would you suggest we run and what results
would you expect to find?

14. The kinetics of the vapour-phase addition of methanol (M) to isobutene (I) to yield methyl
tert-butyl ether (E) on the ion-exchange resin Amberlyst 15 was studied and the following
forward rate law was proposed. Suggest a thermodynamically consistent rate law.
(CH3 )2 CCH2 (𝐈) + CH3 OH (𝐌) ⇌ CH3 OC(CH3 )3 (𝐄)
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(1 + 𝐾M 𝑝M )2 + 8(𝐾I 𝑝I + 𝐾E 𝑝E )1/2 − (1 + 𝐾M 𝑝M )
𝑟f = 𝑘𝐾I 𝐾M (𝑝I2 𝑝M
2
)[ ]
8(𝐾I 𝑝I + 𝐾E 𝑝E )

1/2
𝑘1 𝑐A
15. If the forward reaction of the reversible reaction A ⇌ 2B has rate law of 𝑅f = , which
1+𝑘2 𝑐A
of the following is the rate law for the reverse reaction?
(a) 𝑅r = 𝑘−1 𝑐B2
(b) 𝑅r = 𝑘−1 𝑐B
1/2
𝑘−1 𝑐A
(c) 𝑅r =
1+𝑘2 𝑐A
(d) None of the above

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16. The rates of a chemical reaction are found to satisfy the following hyperbolic rate law:
𝑘1 𝑐
𝑅=
1 + 𝑘2 𝑐
If the reaction rates are all measured at the same concentration but different temperatures,
what will a plot of ln𝑅 vs reciprocal absolute temperature look like? Is this an Arrhenius
plot? What happens when 𝑘2 has a higher activation energy than 𝑘1 ?

17. In the following plots, the reaction rates were measured in terms of product R using the
same concentration of A at different temperatures. Explain the observed trends.

18. Using suitable plots of the Maxwell-Boltzmann distribution, explain how an increase in
temperature may lead to higher reaction rates.

19. The pyrolysis of ethane proceeds with an activation energy of about 300 kJ/mol. How much
faster is the decomposition at 650 °C than at 500 °C?
Ans: 1971 times

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20. [HSF P3-5] Corrosion of high nickel stainless steel plates was found to occur in a
distillation column used to separate HCN and water. Sulfuric acid is added at the top of the
column to prevent the polymerisation of HCN. Water is collected at the column bottom and
HCN at the column top. The amount of corrosion on each tray as a function of plate location
in the column is shown below.

Can you determine whether there was an operation problem and, if so, what was the cause
of the problem and how could the problem be resolved in the most expeditious way?