CN2116 Chemical Kinetics & Reactor Design

2021-22 Semester 2 – Assignment 2

Homework
1. A stream of aqueous monomer A (1 mol/L, 4 L/min) enters a 2 L CSTR, is radiated therein
and polymerises as follows:
+A +A +A
⏞ R→
A→ ⏞ S→
⏞ T…
In the exit stream, 𝑐A = 0.01 mol/L and, for a particular reaction product W (a polymer),
𝑐W = 0.0002 mol/L. Find the rate of reaction of A and the rate of reaction of W. Assume
volume change is insignificant.
Ans: −1.98 mol L−1 min−1, 0.0004 mol L−1 min−1

2. 10 mol% of A in nitrogen (inert) at 100 °C and 2 atm enters an isothermal open tubular
reactor operating at 300 °C, where the following gas phase reaction occurs:
A → 2B
The reactor was designed to convert at least 50% of A entering the reactor. A technician
sampling the reactor exit gas reported ~10 mol% of B in the leaving gas mixture. There is
a 10% pressure drop across the reactor. Does the reactor operate as per the design
specification?

3. Consider the following reactions in diluted aqueous phase in a batch reactor:

A+B→R
R+B→S
The feed contains only A and B. Prove the following concentration relations after a finite
time into the reactions.
𝑐S 𝑐A 𝑐R
=1− −
𝑐A0 𝑐A0 𝑐A0
𝑐R 2(𝑐A0 − 𝑐A ) 𝑐B − 𝑐B0
= +
𝑐A0 𝑐A0 𝑐A0
Are these relations still valid if the reactions are gas phase reactions in a batch reactor?
Hint: Since more than one reaction is involved, when constructing the stoichiometric table,
use the molar extent of each reaction instead of the conversion of a single species.

4. The gas phase reaction A + B → R + 2S is run in a PFR with a feed where B is present in
excess of the stoichiometric requirement (cA0 = 1 mol/L and cB0 = 2 mol/L). What is the
maximum concentration of R possible at the reactor outlet?
Ans: 0.75 mol/L

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5. A gas phase reaction A → 2B with k = 0.5 h−1 is carried out in a (batch) piston reactor at
constant temperature and pressure. 1 mole of A and 9 moles of inert are introduced to the
reactor at the start of the reaction. What is the composition of the gas in the reactor after
1 hour?
Ans: 0.607 mol A, 0.787 mol B, 9 mol inert

6. At 650 °C, phosphine vapour decomposes as follows:

4PH3 → P4(g) + 6H2(g) rPH3 = −kcPH3
where k = 10 h−1. What size of PFR operating at 649 °C and 11.4 atm is needed for 75%
conversion of 10 mol/h of phosphine in a feed with phosphine-inert ratio of 2:1?
Ans: 17 L

Extra Practice
7. Consider the following variation to PFR where the feed to the reactor is distributed
uniformly along the reactor length (at α mol h−1 m3reactor). Derive the design equation from
the general mole balance equation.

Hint: Apply the mole balance equation to ΔV, a differential element of the reactor.
Integration of the differential form of the mole balance equation yields the design equation.

1.5𝑐A
8. An irreversible aqueous phase reaction A → products with the rate law 𝑟A = − 2
1+0.6𝑐A
(with −rA in mol L−1 min−1 and cA in mol/L) is run in a PFR. A is delivered to the reactor
at a concentration of 1.2 mol/L and a volumetric flow rate of 0.7 L/min. Plot the
concentration profile along the length of reactor and, from which, determine the volume
required for at least 95% conversion of the feed.
Ans: ~1.6 L

9. For a liquid phase reaction between A and B in a semi-batch reactor (where A is initially
present in the reactor while B is fed through the inlet), the design equations describing the
variations of concentrations of A and B have been derived during the lectures. Derive the
corresponding design equation governing the concentration of product C. Write down the
appropriate initial conditions.

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10. Steam reforming of methane (SRM) is a high temperature (700-1000 °C) catalytic reaction
for producing hydrogen by splitting water. The product is a mixture of CO and H2 generally
known as the synthesis gas:
CH4 + H2O → CO + 3H2
The water-gas shift (WGS) reaction also occurs under the steam reforming conditions:
CO + H2O → CO2 + H2
With the help of a stoichiometric table, discuss the effect of WGS on hydrogen production
for the following two cases:
(a) Methane as the limiting reactant while water is in large excess in the SRM reaction
(b) Water as the limiting reactant in the SRM reaction
With the help of a stoichiometric table, show how the concentrations of all reaction species
may be calculated from the process variables (temperature, pressure and feed composition)
in terms of the conversions of methane and water.
Hint: If methane is the limiting reactant, we can assume it is fully consumed and therefore
we do not find methane in the outlet.

11. Identify the correct statement below after carrying out a stoichiometric table analysis of
the following methane coupling reactions in a flow reactor:
1
2CH4 + O2 ⇌ C2H6 + H2O (1)
2
CH4 + 2O2 → CO2 + 2H2O (2)
(a) This is always an expanding reaction system.
(b) This is always a contracting reaction system.
(c) This is an expanding reaction system if the molar extent of reaction (1) is greater than
the molar extent of reaction (2).
(d) This is a contracting reaction system if the molar extent of reaction (2) is greater than
the molar extent of reaction (1).

12. [OL 5.17] A 20% ozone-80% air mixture at 1.5 atm and 93 °C is delivered to a PFR at
1 L/s. Under these conditions, ozone decomposes by the homogeneous reaction:
2O3 → 3O2
𝑅 = 𝑘𝑐O3 where k = 0.025 L mol−1 s−1
2

What reactor size is needed for 50% decomposition of ozone?

Hint: Use the design equation. Express the reaction rate as a function of conversion (tricky
step). Finally, use MATLAB or other software to evaluate the integral.
Ans: 2125 L

13. The gas phase reaction A → B + C is run at constant temperature and pressure in a PFR.
The feed is pure A at cA0 = 1 mol/L and the concentration of B in the reactor exit gas is cB
= 0.45 mol/L. What is the composition of the reactor exit gas?
Ans: cA = 0.1 mol/L, cC = 0.45 mol/L

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14. [OL 4.4] Consider an isothermal single-phase reactor operating at steady state and constant
pressure. Given the reaction A + 2B ⇌ R and a gaseous feed of cA0 = cB0 = 100, cB = 20.
Find xA and xB.
Ans: 0.444, 0.888

15. [OL 5.1] Consider a gas-phase reaction 2A → R + 2S with unknown kinetics. If a space
velocity of l min−1 (based on the inlet flow rate at process conditions) is needed for 90%
conversion of A in a PFR, find the corresponding space time and mean residence time of
fluid in the PFR. What if this is a liquid-phase reaction?

16. The data in the following table have been obtained on the decomposition of gaseous
reactant A in a constant volume batch reactor at 100 °C. The stoichiometry of the reaction
is 2A → R + S. What size of CSTR (in L) operating at 100 °C and 1 atm can treat
100 mol/h of A in a feed consisting of 20% inerts to obtain 95% conversion of A? (This
question requires some knowledge in reaction kinetic analysis. Attempt it after learning
Unit 3.)

Ans: 2.13 m3