SCHOOL OF ENGINEERING & PHYSICAL SCIENCES

Chemical Engineering

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B49CE

MULTIPHASE THERMODYNAMICS

Semester 2 – 2014/15

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Wednesday, 20th May 2015

Duration: 2 Hours

Instructions to candidates:

Answer THREE questions from Section A and ONE question from

Section B.

(2 separate booklets – answer Section A in one book and Section B in

the other)

Candidates are expected to make reasonable assumptions where

necessary.

Marks for sections of questions are shown in round brackets.

Candidates are expected to show all calculation steps, equations

used and assumptions made (if any).
 B49CE

SECTION A
(Answer three questions)

1. (a) Table 1.1 lists the p-v-T data for n-butane at 110°C. Explain why there is
a difference between the specific and ideal volume.
(5 marks)

(b) What is the Ф (fV/p ratio) for n-butane at 110°C and 15.2 bar?
(14 marks)

(c) Use the de Priester chart to find the fL for n-butane at 110°C and 15.2 bar.
(6 marks)

Table 1.1: p-v-T data for n-butane at 110°C

Pressure Specific volume Ideal volume

[bar] [L/mol] [L/mol]
3.8 8.03 8.39
7.6 3.79 4.20
11.4 2.37 2.80
15.2 1.57 2.10

A de Priester chart can be found at the end of this paper.

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2. (a) A 50:50 mole mixture of n-butane and n-pentane is kept at 5 bar and
heated from 50°C to 100°C. Describe the phase changes that are
occurring, calculate the temperatures where they occur and state their
corresponding names.
(11 marks)

(b) A liquid stream is leaving the bottom of a fractionating column with the
composition listed in Table 2.1. It then enters a reboiler at 80°C and
5 bar. Calculate the liquid fraction in the reboiler and its mole fraction of
n-pentane.
(9 marks)

(c) On a cold winter day, the n-pentane liquid mole fraction in the reboiler
decreases down to 0.75. Explain why this is happening. What adjustment
would you make?
(5 marks)

Table 2.1: Liquid Stream Composition

Component Mole fraction

propane 0.10
n-butane 0.15
n-pentane 0.75

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 B49CE

3. (a) Ethanol and benzene each have boiling points at 760 mmHg of 78.3 and
80.1°C, respectively. Continous attempts to distill an ethanol/benzene
mixture at 760 mmHg always form a mixture with a liquid mole fraction of
0.45 ethanol that boils at 68.0°C. Explain why this is the case.
(3 marks)

(b) Use the van Laar equations given below to calculate the AAB and ABA for
the ethanol/benzene system at 760 mmHg. It is assumed that the ratio of
saturation pressures of the two components at any given temperature
does not vary significantly over the temperature range.
(8 marks)

(c) Calculate the mole fraction of ethanol in the vapour in equilibrium with the
liquid for a mixture containing 0.2 liquid mole fraction ethanol and a
second mixture containing 0.8 liquid mole fraction ethanol.
(9 marks)

(d) Using the data you know and have calculated in Q3 (a) to (c), draw the
T-x-y diagram for the Ethanol system where the boiling point at 760 mmHg
for the mixture containing 0.2 liquid mole fraction ethanol is 68.7°C and
the boiling point at 760 mmHg for the mixture containing 0.8 liquid mole
fraction ethanol is 70.2°C.
(5 marks)

Question 3 Cont’d…/

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 B49CE

Question 3 Cont’d/

Antoine equation: ln(Psat [bar]) = A - B/(T[K] + C)

A B C
Ethanol 12.3 3800 -41.7
Benzene 9.28 2790 -52.4

Van Laar equations:-

AAB ABA
ln γ A = 2
ln γ B = 2
 AAB x A   ABA x B 
1 +  1 + 
 ABA x B   AAB x A 

2 2
 x ln γ B   x ln γ A 
AAB = ln γ A 1 + B  ABA = ln γ B 1 + A 
 x A ln γ A   x B ln γ B 

Relative volatility:
βx A
yA =
β = pA,sat/pB,sat * γA/γB 1 − x A + βx A

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 B49CE

4. The water gas shift reaction is generally formulated as

CO(g) + H2O(g) ↔ CO2 (g) + H2(g)

The thermodynamic data for the compounds are given in Table 4.1.

(a) Explain and define the overall reaction co-ordinate expression that can be
used for the water gas shift reaction and use this to calculate the material
balance for each component during the reaction.
(9 marks)

(b) Based on the material balance in Question 4 (a) construct an expression

for the composition component, Ky, of the equilibrium constant using an
extent of reaction approach.
(4 marks)

(c) Assuming ideal conditions, calculate the full expression for K at 600 K and
100 bar(a) and that at 1300 K and 100 bar(a).
(8 marks)

(d) Which reaction temperature would you pick to get a maximum H2(g)
production based on the full expression for K? And calculate
approximately how much the conversion will be.
(4 marks)

Question 4 Cont’d…/

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 B49CE

Question 4 Cont’d/

Table 4.1: Gibbs Free Energy of Formation

Component Gibbs Free Energy of Formation

600 K 1300 K
kJ/mol kJ/mol
H2O -214.2 -175.9
CO -164.8 -227.1
CO2 -394.1 -396.4

END OF SECTION A

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 B49CE

SECTION B
(Answer one question)

5. (a) Sketch a typical P vs. T phase diagram for a single component system,
identifying:

(i) triple point;

(ii) critical point;
(iii) vaporisation curve;
(iv) solid region; and
(v) vapour region.

Applying the phase rule, how many degrees of freedom in terms of

intensive variables exist at the triple point.
(10 marks)

(b) Steam of mass 0.2 kg expands reversibly and isothermally (at 300oC) from
an initial volume of 4 dm3 to a final volume of 24 dm3. Using the virial
coefficients below:

B = -142.2 × 10-6 m3 mol-1

C = -7140 × 10-12 m6 mol-2

calculate the work done by the steam.

R (gas constant) = 83.13 cm3 bar K-1 mol-1

(15 marks)

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 B49CE

6. (a) Explain what is meant by the compressibility factor (Z). What is the value
of Z for an ideal gas. How is the acentric factor (ω) used to correct for
non-ideal behaviour.
(15 marks)

(b) Calculate the reversible work in compressing 5 m3 of mercury at a

constant T = 298 K from 1 atm to 200 atm. The isothermal compressibility
(κ) of mercury (at 298 K) is given by:

κ = 4 × 10-6 – (1.5 × 10-10)P

where P is in atm and κ in atm-1. Give the calculated work in kJ where

1 J = 10 cm3 atm.
(10 marks)

END OF PAPER

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 B49CE

de Priester chart

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