Department of Chemical and Biomolecular Engineering

CN2105 Reaction Engineering

Assignment 1

Prof Ning Yan, 2023/2024 Sem 2

 2

Warm up exercise: car crash

Three cars crash into trash. If we regard this as a chemical
reaction, is this reaction elementary?
3C → T
Propose a reaction rate law for car crash on high way.
nC → T (n ≥ 2)
For part 1: Most
likely no!

Step 1: Step 2: Overall reaction:

car 2 collides with car 1 car 3 collides with car 2 3 cars → trash
For part 2: most car crash accidents starts with collision of two cars. It is a second order reaction!
�����ℎ = ��2���
 3

N + box = N adsorbed on surface

��’ =− �’�α�

N + N = N2

β
��’’ =− �’’��
 4

Categories of Questions

I. Definitions of reaction rates; extent of reaction

II. Rate laws, reaction orders; reaction rate constants; reaction mechanisms and elementary vs
non-elementary reactions
III. Relationship between thermodynamics and chemical kinetics; thermodynamic consistency of
rate laws for reversible reactions
IV. Activation energy; temperature effect on reaction rates
V. Applications
 5

Question 1 (I)
�B
Describe qualitatively how the ratio may change from t = 0 to t = τ (where τ > 0) (increasing,
−�A
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
Solutions:
�A �B �C �D
Recall: aA + bB → cC + dD − =− = = =�
� � � �
�A �B �C �B �
For (a), only one reaction: − = = =� = =1
1 1 1 −�A �
�A1 �B1 �B2 �C2
For (b), two reactions: = = �1 = = �2
−1 1 −1 1
�A = �A1 =− �1 �B = �B1 + �B2 = �1 − �2

�B �1 − �2 �2 At t = 0, R1 > 0 and R2 = 0 ⇒
��
=1−
�2
=1
= =1− −�� �1
−�A �1 �1
�� �2
At t = τ (τ > 0), R1 > 0 and R2 > 0 ⇒ =1− <1
−�� �1
 6

Question 2 (I)
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 � = 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 C 2 0
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)?
 7

Question 2 (I) (continued)

Solutions:
1 ��C20H42 1 ��C20H42
By definitions: �′C20H42 = �′′
C20 H42 =
�cat �� �cat ��

Substituting all known values:

�cat = 50000 kg
�cat 50000 kg
�cat = = 3 = 62.5 m3
�cat 800 kg/m
��C20H42 = 20 12 + 42 1 = 0.282 kg/mol

6000 m3 900 kg
∆�C20H42 day m3 1 day
= �. � = 133 mol/s
∆� 0.282 kg 24 3600 s
mol
1 ��C20H42 1 ∆�C20H42 1 Note: These are not real
′ −1 −1
−�C20H42 =− ≈ = 133 = 0.0027 mol kgcat s reaction rates in the chemical
�cat �� �cat ∆� 50000
kinetics sense. They are figures
′′ 1 ��C20 H42 1 ∆�C20 H42 1 −3 −1
of merits to indicate what the
−�C20 H42 =− ≈ = 133 = 2.13 mol mcat s
�cat �� �cat ∆� 62.5 reactors can do on the average.
 8

Question 3 (II)
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.

Solutions:
(a) Since only the reaction stoichiometry is known and the rate laws are unknown, there is no reaction
order of any kind to speak of (the rate laws may not even be power laws).

(b) 1st order (unimolecular) for the forward reaction (�f = �f �A ) and 2nd order (bimolecular) for the reverse
reaction (�r = �r �2B ).

R = �f − �r = �f �A − �r �2B
No overall order since the rate law of the overall reaction is not a power law.
 9

Question 4 (II)
A reaction with the stoichiometry of 0.5A + B → R + 0.5S has the rate law � = ��0.5 A �B . Is the reaction
elementary? What will become of the rate law if the stoichiometry of the reaction is rewritten as A + 2B →
2R + S?

Solutions:
Part 1: No. Elementary reaction will not have half order.

Part 2: Rate laws written in terms of species do not change with reaction stoichiometry. (Rate laws written
in terms of steps may change depending on how 1 mole of reaction is being defined.)

�1 =− �A /0.5

�2 =− �A

�A is a physical quantity that would not change with the definition of one mole of reaction.

Therefore: �2 = 0.5�1 = 0.5��0.5

A �B
 10

Question 5 (II)
A certain reaction has a rate given by �A =− 0.005�2A 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?

Consider: what is the unit for k?

It depends on the reaction order!

For 0th order, �A =− ��0A =− � units of � = ����−1 �−1

For 1st order, �A =− ��1A units of � = �−1

……
Method 1
�A =− ��2A
mol cm−3 min−1 = units of � mol2 cm−6
units of � = mol−1 ��3 ���−1

� = 0.005mol−1 ��3 ���−1 = 0.005 × 10−3 × 60 mol−1 � ℎ−1 = 3 × 10−4 mol−1 � ℎ−1
 11

Question 5 (II) (continued)

Method 2

Originally: �A =− 0.005�2A ; �A = mol cm−3 min−1 ; �A = mol/cm3 (1)

New form: �′A =− � �′A 2 ; �′A = mol L−1 h−1 ; �′A = mol/L (2)

Note:
3 3
60 min 1000 cm 1000 cm
�′A = �A × × ; �′A = �A ×
1h 1L 1L
�′A �′A
�A = �A =
60 × 1000 1000

Substituting into (1):

2
�′A �′A
=− 0.005 �′A =− 3 × 10−4 �′A 2
k = 3 × 10−4 mol−1 L h−1
60 × 1000 1000
 12

Question 6 (III)
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
� CO H2 O −
�= �
1 + �CO CO + �H2O H2 O + �CO2 CO2 + �H2 H2
Solutions:
(a) Is the rate law thermodynamically consistent? General procedure:
At equilibrium, we have R = 0 Assume equilibrium: R = 0 or rf = rr

CO2 H2 Substitute rate law into the equilibrium condition

� CO H2 O −
�= � =0
1 + �CO CO + �H2O H2 O + �CO2 CO2 + �H2 H2 Simplify the formula

CO2 H2 CO2 H2 Check whether the remaining term equals to

� CO H2 O − =0 �= thermodynamic constant (Yes → consistent / No
� CO H2 O
→ inconsistent)
The expression of K is exactly the expected equilibrium
constant. The rate law is thermodynamically consistent.
 13

Question 6 (III) (continued)

(b) Are the forward and reverse reactions bimolecular?
No. We cannot assume that the forward and reverse reactions are elementary.

(c) Can the forward and reverse reactions be bimolecular?

No. The rate expressions are not of the power law form and hence there is no possibility that the forward
and reverse reactions are bimolecular.
(d) What is the reaction order with respect to CO at t = 0 in the presence of a large excess of steam?
There is no reverse reaction at the start of the reaction ( CO2 , H2 = 0).
CO2 H2
� CO H2 O − � CO H2 O
�= � �=
1 + �CO CO + �H2O H2 O + �CO2 CO2 + �H2 H2 1 + �CO CO + �H2O H2 O

� CO H2 O �
�≈ = CO
�H2O H2 O �H2O
The reaction order with respect to CO is one.
 14

Question 7 (I)
Determine the values of constants a, b and c in the relation ��A + ��R + ��S = 0 for the reactions A → 2R → S.

Solutions:

(1) A → 2R
(2) 2R → S

�A1 �R1 �R2 �S2

= ; =
−1 2 −2 1

�R = �R1 + �R2 = −2�A1 − 2�S2 �A = �A1 �S = �S2

2�A + �R + 2�S = 0

a = 2, b = 1, c = 2
 15

Question 8 (I)
The following three reactions involving A, B and C are studied in a batch reactor:
A → B, A → C, B + C → 2A
Express the reaction rates of species A, B and C (�A , �B and �C ) in terms of the rates of the three reactions (�1 , �2 and
�3 ). If only A is present in the reactor initially, what do you expect to find in the reactor after some lapse of time?
Solutions:
�A1 �B1 �A2 �C2 �B3 �C3 �A3
= = �1 ; = = �2 ; = = = �3
−1 1 −1 1 −1 −1 2
Therefore:
�A = �A1 + �A2 + �A3 =− �1 − �2 + 2�3
�B = �B1 + �B2 + �B3 = �1 − �3
�C = �C1 + �C2 + �C3 = �2 − �3
Analysis by extents of reaction:
∆�A = ∆�A1 + ∆�A2 + ∆�A3 = �A1 �1 + �A2 �2 + �A3 �3 =− �1 − �2 + 2�3
∆�B = ∆�B1 + ∆�B2 + ∆�B3 = �B1 �1 + �B2 �2 + �B3 �3 = �1 − �3
∆�C = ∆�C1 + ∆�C2 + ∆�C3 = �C1 �1 + �C2 �2 + �C3 �3 = �2 − �3
Since all extents are generally different, there will be A, B and C in the reactor at any time.
 16

Question 9 (I)
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?
Solutions:
Number of surface metal atoms (in moles) per gram of the supported catalyst (MWPd = 106.42 g/mol):
For Pd/Al2O3: 0.0488 × 0.21/106.42 = 9.63×10−5 mol
For Pd/SiO2: 0.0375 × 0.55/106.42 = 1.94×10−4 mol

Number of cyclohexene molecules reacted per unit time per surface metal atom (TOF):
For Pd/Al2O3: TOF = 7.66×10−4/(9.63 × 10−5) = 7.95 s−1
For Pd/SiO2: TOF = 1.26×10−3/(1.94 × 10−4) = 6.50 s−1

The TOFs are not significantly different to indicate strong support effects in the two supported Pd catalysts.
 17

Question 10 (I)
Express the overall reaction rates of species (�A , �B , �C ,…) in terms of the rates of the steps for the following reaction
network:

Solutions:
�A = �A1 = −�1
�B = �B1 + �B2 + �B3 = �1 − �2 − �3
�C = �C2 + �C4 + �C5 = �2 − �4 + �5
�D = �D3 + �D5 = �3 − �5
�E = �E4 = �4
 18

Question 11 (II)
��A
Can the kinetics of the second order gas phase reaction A → B in a batch reactor be written as =− �p �2A ? Is �p a
��
specific rate constant?

Solutions:
1 ��A �A �
For a 2nd order reaction in a batch reactor: �A = = −��2A � 2
� ��
Therefore: 1 �g � �A
�A � �A �A =− �
For an ideal gas: �A = , �A = = � �� �g �
�g � � �g �

For batch reactor, V is a constant. If T is also a constant:

� �
� A 2
1 �g � 1 ��A �A
This equation is simplified to = =− �
� �� �g � �� �g �
��A � 2
=− �A = −�p �2A
�� �g �
�
�p =
�g �
k is a true rate constant and will satisfy the Arrhenius equation.
Unless at constant T, �p will not satisfy the Arrhenius equation and is not a true rate constant.
 19

Question 12 (II)
The measurements of a gas phase reaction at 400 K in a constant volume batch reactor resulted in the following
equation:
��A
=− 3.66�2A atm/h
��
Solutions:
��A
(a) Is =− 3.66�2A a rate law?
��

��A ��A
is not a reaction rate and �A is not concentration, the relation =− 3.66�2A is not a rate law.
�� ��

(b) What is the unit of the constant 3.66 in the above equation?

atm 1
= atm 2 ; =
h atm h
 20

Question 12 (II) (continued)

(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 ��A
�A = =− ��2A mol m−3 s−1
� ��

Since the reaction is carried out at constant volume:

1 ��A 1 � �A × � ��A
�A = = = = −��2A
� �� � �� ��
��A
We already know: =− 3.66�2A atm/h
��
Need to establish linkage between k and kp
�
From last question, we know: �p =
�g �

3.66 −5
� = �p �g � = 5 × 8.314 × 400 = 3.34 × 10 mol−1 m3 s−1
3600 × 1.013 × 10
 21

Question 13 (II)
The decomposition of reactant A at 400 °C for pressures between 1 and 10 atm follows a first-order rate law.

Solutions:
(a) Show that a mechanism similar to azomethane decomposition is consistent with the observed kinetics.
A + A ⇌ A* + A
A* → R + S (slow step)
1 3
Consider the mechanism: 2A ⇌ A* + A A* → R + S
2
2
For reactant A: �A =− �1 A + �2 A∗ A (1)
2
For intermediate A*: �A∗ = �1 A − �2 A∗ A − �3 A∗ = 0

∗ �1 A 2
For which: A = (2)
�2 A +�3

�1 �3 A 2
Replacing (2) in (1) to eliminate the unmeasurable A* gives: �A =− (3)
�2 A +�3
�1 �3 A
Reaction 3 is slow, we can assume k2[A] >> k3: �A =−
�2
 22

Question 13 (II) (continued)

(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 to run and what results would you expect to find?

Now at low enough [A], we may reach conditions where k2[A] << k3. In such a situation, equation (3) on the previous
slide will reduce to:
2
�A =− �1 A or second order kinetics
Hence [A] is decreased continuously. This mechanism predicts that a point will be reached where the reaction order will
start rising from one, and will approach and eventually become two.
 23

Question 14 (III)
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 � + CH3 OH � ⇌ CH3 OC CH3 3 �
2 3
1 + �M �M + 8 �I �I + �E �E 1/2 − 1 + �M �M
�f = ��I �M �2I �2M
4 �I �I + �E �E

Solutions:
�r = �f
2 3
1 + �M �M + 8 �I �I + �E �E 1/2 − 1 + �M �M
= ��I �M �2I �2M
�E 4 �I �I + �E �E
Note: �=
�I �M eq

Keep the two parts in circles and replace pIpM by pE and K:

3
�2E 1 + �M �M 2
+ 8 �I �I + �E �E 1/2 − 1 + �M �M where � =
�E
is the equilibrium constant
�r = ��I �M �I �M eq
�2 4 �I �I + �E �E
 24

Question 15 (III)
1/2
�1 �A
If the forward reaction of the reversible reaction A ⇌ 2B has rate law of �f = , which of the following is the rate
1+�2 �A
law for the reverse reaction?

(a) �r = �−1 �2B

(b) �r = �−1 �B
1/2
�−1 �A
(c) �r =
1+�2 �A

(d) None of the above

Solutions:
From thermodynamic consistency considerations when Rf = Rr (at equilibrium), simplification of terms must lead to the
�2B �−1 �B
conclusion �eq = . This is only possible if the reverse rate law is of the form . Hence the only correct answer
�A 1+�2 �A
is (d).
 25

Question 16 (IV)
The rates of a chemical reaction are found to satisfy the following hyperbolic rate law:
�1 �
�=
1 + �2 �

If the reaction rates are all measured at the same concentration but different temperatures, what will a plot of ln� vs
reciprocal absolute temperature look like? Is this an Arrhenius plot? What happens when �2 has a higher activation
energy than �1 ?
Solutions: �
− a1
�g �
�
− a2
� 1 = �1 � �g �
� 2 = �2 �
If c is kept constant, R can only vary with temperature changes. The plot of lnR vs 1/T picks up the temperature
dependence of reaction rates through the Arrhenius effect. It is not an Arrhenius plot per se but can be used to pick up
important information such as the activation energy.
For an arbitrary c, the plot of lnR vs 1/T will be curvilinear since k1 and k2, with different pre-exponential factors and
activation energies, will vary with T according to the Arrhenius equation independently of each other.
If c is very low, � = k1c, the plot of lnR vs 1/T is Arrhenius-like with an “apparent” activation energy equal to the
activation energy of k1 (Ea1).
k
If c is very high, � = 1 , the plot of lnR vs 1/T is Arrhenius-like with an “apparent” activation energy equal to the
k2
activation energy difference (Ea1 – Ea2).
If E a2 > E a1, increase in temperature causes the reaction rate to decrease - one gets to see an anomalous apparent
“negative” activation energy effect.
 26

Question 17 (IV)
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.
Solutions: �
− a �a
� = �� �g � ln � =−
�g �
A → R (1); A → R (2)
�R = �1 + �2
For reactions in parallel, rR is dominated by the larger one of the two terms (faster of the two
reactions).
For Ea1 > Ea2, Arrhenius equation infers that Reaction 1 is faster at high temperature and Reaction
2 is faster at low temperatures.
Hence at low temperature one sees the characteristics of Reaction 2 (an Arrhenius plot with the
shallower slope of Ea2/R) and at high temperature one sees the characteristics of Reaction 1 (the
slope increases to Ea1/R).
For Ea2 > Ea1, the plot still looks the same except that the slope in the low temperature region is
now the characteristics of reaction 1 (and the slope in the high temperature region is now the
characteristics of reaction 2).
 27

Question 17 (IV) (continued)

A→X→R
For reactions in series, rR is the rate of the reaction outcome and is determined by the slower of the
two reactions.
For Ea1 > Ea2, Arrhenius equation infers that Reaction 1 is faster at high temperature (Reaction 2 is
rate limiting) and Reaction 2 is faster at low temperature (Reaction 1 is rate limiting).
Hence at low temperatures one sees the characteristics of Reaction 1 (an Arrhenius plot with a
steeper slope of Ea1/R) and at high temperature one sees the characteristics of Reaction 2 (the slope
eases to Ea2/R).
Ea1 < Ea2 generates a similar looking plot.

Note: If the reaction rate instead refers to (−rA), only the first step of the reaction is implicated. The
Arrhenius plot is then a straight line with slope Ea1 and is independent of the relative magnitudes of
Ea1 and Ea2.

Corollaries:
1. Changes in the slope of an Arrhenius plot indicate the presence of at least two rate constants in the reaction system.
2. In the case where the two rate constants come from the two parallel reactions, there will be a transition from a shallower
slope at low temperature to a steeper slope at high temperatures. The transition from a shallower slope at low temperature
to a steeper slope at high temperature suggests a parallel reaction scheme.
3. The transition from a steeper slope at low temperature to a shallower slope at high temperature suggests a series reaction
scheme.
 28

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

Solutions:

As temperature increases (from T1 to T2), the peak of the Maxwell-Boltzmann distribution shifts to a higher velocity.
Since only molecules with velocities above a minimum value (Umin) have sufficient kinetic energy to overcome the
activation barrier, the fraction of molecules that can undergo reaction is higher at a higher temperature. The frequency
of effective collisions is hence higher, resulting in higher reaction rates.
 29

Question 19 (IV)
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?
Solutions:

We can write:
�650 � 1 1 300,000 1 1
− − − −
=� � � 650 � 500 = � 8.314 923 773 = 1971
�500
 30

Question 20 (V)
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?

Solutions:
Corrosion rate is low at tower bottom because of low H2SO4 concentration there.
Corrosion rate is low at tower top because of low temperature there.
Mid-way through the tower moderate values of H2SO4 concentration and temperature combined to result in the highest
corrosion rate.
No operation problem is identified.
The most expeditious solution is to use corrosion inhibitors.