CHEMICAL ENGINEERING TRIPOS

Part I
Tuesday 30 May 2000 9 to 12

PAPER 3

Answer two questions from Section A, two questions from Section B and one question
from Section C.
Data from the following may be used in any question:
The Chemical Engineering Data Book
Thermodynamic and Transport Properties of Fluids

This paper should be accompanied by the following supplementary materials:

Enthalpy of caustic soda solutions
Dühring lines for aqueous solutions of sodium hydroxide.

Write on one side of the paper only.

SECTION A
1 A continuous reactor produces acetylene from a methane stream by the reaction:

2 CH4(g) → C2H2(g) + 3 H2(g) (1)

Undesired decomposition of acetylene also occurs in the reactor:

C2H2(g) → 2 C(s) + H2(g) (2)

Pure methane at 1500 °C is fed to the reactor at a rate of 10 mol/s. When heat is
transferred to the reactor at a rate of 975 kW, the product temperature is found to be 1500 °C
and the fractional conversion of methane is 0.6. All the solid carbon formed leaves the
reactor as soot.
(a) Calculate the enthalpies of reactions 1 and 2 at 1500 °C.
(b) Determine the extents of reactions 1 and 2. Hence calculate the product flowrates.
(c) Calculate what the temperature of the products would have been for the same
methane conversion if there had been negligible acetylene decomposition by reaction 2.
Data:
Enthalpies of formation at 25 °C:
CH4(g) –74.85 kJ/mol ; C2H2(g) +226.75 kJ/mol
Heat capacities CP (assumed to be independent of temperature):
CH4(g) 0.079 kJ/mol.K ; C2H2(g) 0.052 kJ/mol.K
H2(g) 0.031 kJ/mol.K ; C(s) 0.022 kJ/mol.K

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 2

2 (a) What forces cause the deviation of real gases from ideal gas behaviour? Sketch the
expected shape of a plot of how compressibility factor Z varies with pressure for a gas at
three different temperatures.
(b) What is meant by the critical temperature Tc and critical pressure Pc of a substance?
Explain why the reduced temperature, Tr = T/Tc, and the reduced pressure, Pr = P/Pc, are
often used in equations of state.
(c) A 3 litre tank contains 2 moles of N2 which obeys the virial equation of state
PV B
=1+
RT V

where

( B0 + ωB1 )
RTc
B=
Pc
0.422
B0 = 0.083 −
Tr1.6
0.172
B1 = 0.139 −
Tr4.2

(i) Calculate the tank pressure at 275 °C.

(ii) Calculate the tank pressure at –155 °C.
(iii) Compare your answers to those expected for an ideal gas.
(iv) Explain the physical origins of the parameter ω.
Data:
For N2: Tc = 126.2 K; Pc = 33.5 atm; ω = 0.04
 3

3 (a) What factors influence the choice of operating pressure in an evaporator?

(b) It is desired to concentrate a solution of 10 wt% NaOH at 40 °C to 40 wt% NaOH
in a continuous evaporator. Calculate the heat required per kg of feed if the evaporator is:
(i) maintained at a pressure such that the temperature of the product solution is
120 °C,
(ii) instead operated at an evaporation pressure of 0.1 bara.
[Charts of enthalpy of caustic soda solutions and Dühring lines for aqueous solutions of
sodium hydroxide are provided.]

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 4
SECTION B
4 (a) (i) Sketch the expected shape of a graph of molar volume against composition for
a binary mixture that has attractive interactions between the two components present.
(ii) The molar volume of a binary mixture may sometimes be represented by the
equation

V = b1 x1 + b2 x2 + ax1 x2

where b1, b2 and a are constants. Derive an expression for the partial molar volume of
species 1 in this case.
(b) The molar excess Gibbs free energy, G ex , of liquid argon-methane mixtures at a
fixed pressure obeys
G ex
RT
[ ]
= x Ar (1 − x Ar ) A − B(1 − 2 x Ar )

where xAr is the mole fraction of argon, and values of the parameters A and B are given
below.
(i) Prove that the enthalpy of mixing, ∆ H mix , is
∂  G ex 
∆ H mix = − T 2  
∂T  T  P, ni

(ii) Estimate the molar isothermal enthalpy change on producing an argon-methane

mixture with xAr = 0.5 from its pure components at 112.0 K.
Data:
T /K A B
109.0 0.3036 –0.0169
112.0 0.2944 0.0118
115.7 0.2804 0.0546
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5 (a) What is meant by the activity coefficient of a species in a mixture? Prove for a
binary mixture that

1  ∂G ex 
ln γ 1 =
RT  ∂n1  P,T , n
2

where γ1 is the activity coefficient of species 1 and Gex is the excess Gibbs free energy of the
mixture.
(b) Hence use the Gibbs-Duhem equation to obtain a relationship between γ1 and γ2 at
constant temperature and pressure.
(c) Comment on the number of fitting parameters that are truly independent in the
following proposed Margules equations:
(i) ln γ 1 = Ax22 ln γ 2 = Bx12
(ii) ln γ 1 = Ax2n ln γ 2 = Ax1n
(iii) ln γ 1 = Ax2n ln γ 2 = Bx1n

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 6

6 (a) Show that in a gas the number of molecules passing through an area of 1 m2 in 1 s is
nc / 4 , where n is the number of molecules per unit volume of gas, and c is the mean speed
of the molecules in the gas.
(b) Evaluate the frequency of collisions of O2 (in air at 1 bara and 50 °C) with 1 m2 of a
flat surface. Hence calculate the maximum possible rate of production of SO2 from 1 m2 of a
flat surface of sulphur in air at 1 bara and 50 °C.
(c) The rate law for the reaction S(s) + O2(g) → SO2(g) may be written in the form:

rate of SO2 formation = k [O2]

where [O2] is the concentration of O2, and k is the rate constant based on unit area of solid.
(i) Evaluate the maximum possible value of the rate constant k at 50 °C.
(ii) An apparent activation energy, Eapp, may be defined by the following
relationship (which is equivalent to the Arrhenius equation):
d ln k
Eapp = RT 2
dT
Calculate the apparent activation energy for the reaction at 50 °C based on the
assumption that reaction occurs at every collision between reagents. Comment on the
magnitude of your answer.
Data:
The ratio between mean speed squared and mean square speed of molecules in a gas is:

( c )2 8
=
c2 3π
 7
SECTION C
7 (a) Discuss the concept of inherent safety as applied to the manufacture of hazardous
chemicals.
(b) Caro’s acid (H2SO5) is a strong oxidising agent made by reacting concentrated
sulphuric acid with hydrogen peroxide. It is highly unstable and must be kept below 0 °C at
all times, otherwise it decomposes violently. It also reacts highly exothermically, even at low
temperatures, in the presence of most transition metals.
It is proposed to use Caro’s acid to treat a particularly intractable organic waste stream.
The mass ratio of Caro’s acid to effluent would be of the order of 1 to 50, and tonnage
quantities of acid would be required. The only manufacturing facility of Caro’s acid in the
country is some distance away, and this makes it in a 30 litre stirred batch reactor with
refrigerant cooling. The chemical reaction is almost instantaneous, but it requires 30 minutes
to process each batch of material.
Outline the problems associated with the current method of manufacture, and suggest
ways in which the Caro’s acid treatment could be performed in a safe manner. Comment on
the risks involved in your proposed solution.

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 8

8 One of two chemical plants, A or B, may be built. The following data are available:
A B
Capital required (£) 1,000,000 1,500,000
Production rate (te/yr) 10,000 20,000
Manufacturing cost (£/te) 150 160
Predicted sales price (£/te) 180 180
(a) The company policy is that all projects must show an annual rate of return on
investment of at least 25%. Recommend which plant, if any, should be chosen on this basis,
and explain your reasoning.
(b) Project evaluation is then requested using a Net Present Value calculation with a
discount rate of 11% per annum. Each plant can be built in year 0, and should operate at full
capacity for 8 years. At the end of the 8th year, the plant may be sold for half of its initial
capital value. Recommend which plant, if any, should be chosen on this basis and explain
your reasoning.
(c) It is feared that competition from a rival company may force down the product sales
price to £170/te after four years of operation. Calculate the corresponding Net Present Values
of the two projects using a discount rate of 11% per annum.
(d) What action would you recommend? Explain your reasoning, and indicate what
other factors may need to be considered before making a final decision.

END OF PAPER