Problem 1

A liquid mixture of initially containing 25 mol% benzene and 75 mol% ethanol is heated at a constant pressure of 1.013 bar from T = 60 °C to T = 90°C. Using
the experimental data plotted below, determine the following:
a) At what temperature does the mixture start to boil?
b) What is the composition of the first bubble of vapour formed?
c) What are the compositions of the coexisting liquid and vapour phases when 25 mol% of the original liquid charge has been vaporised? Assume that
the vapour remains in the apparatus and that it is completely mixed and in equilibrium with the liquid phase.

T-x-y diagram (left) and equilibrium curve (right) for benzene + ethanol at p = 1.013 bar

82 1

80
0.8
78

76 0.6
T/°C

y
74
0.4
72

70
0.2
68

66 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x, y x
N.B. x = mole fraction of benzene in the liquid phase and y = mole fraction of benzene in the vapour phase.
Problem 2
Consider an adiabatic equilibrium flash operation for a feed mixtures containing N c components described by the set of variables indicated in the figure below.
a) Determine the total number of variables in the problem
b) Write all the independent equations that relate these variables
c) Determine the number of independent equations
d) Determine the number of degrees of freedom
e) What variables would you prefer to specify in order to solve a typical adiabatic flash problem?

Adiabatic Flash Operation

V
Vapour yi
F TV
zi Feed pV
Tf throttle

pf L
xi
TL
Liquid

pL
Problem 3
A binary mixture of hexane + octane containing 61 mol% hexane is fed as
compressed liquid to a flash unit, fitted with a pre-heater and expansion
valve, where it is expanded to ambient pressure and partially vaporised in
a steady flow process. Use the enthalpy-composition diagram provided to
answer the following.

a) If the unit is operated in an adiabatic mode and the molar enthalpy

of the feed is 30 000 kJ/kmol, what is the temperature T in the flash
vessel? What are the compositions of the outflowing liquid and vapour phases, and what fraction of
the feed is vaporised on a molar basis?
b) If the unit is operated with the same feed conditions but in non-adiabatic mode such that the
temperature in the flash vessel is 100°C, what will be the new compositions of the outflowing liquid
and vapour phases, and what fraction of the feed is vaporised on a molar basis? If the feed rate is
100 kmol/h, what is the required heater duty?

h, x, y Diagram for hexane + octane at p = 1.013 bar

60000 Saturated Liquid

Saturated Vapour

50000
h/(kJ/kmol)

40000

30000

20000

80°C
70°C
10000
60°C

0
0 0.2 0.4 0.6 0.8 1
Reference states: h1 = 0 and h2 = 0
at T = 25°C and p = 101.3 kPa x, y
Problem 4
Consider a distillation column operating at a pressure of 101.3 kPa in which benzene and styrene are being
separated. A vapour stream containing 65 mol% benzene and 35 mol% styrene enters the lower stage
(m+1) of the section shown below at a flow rate of 200 mol h-1, and liquid containing 55 mol% benzene and
45 mol% styrene leaves this stage at a flow rate of 150 mol h-1. You may assume (i) the stages are ideal;
(ii) Raoult’s law can be used to relate the composition of the streams leaving each stage; and (iii) that the
vapour and liquid molar flow rates do not change from one stage to the next.

xm-1
ym
m
xm
m+1 ym+1

L V

a) How would you expect the mole fraction of benzene in the liquid at each stage to vary from one
stage to another, beginning with the bottom stage and moving up the column? In the light of your
answer, and considering that the pressure remains essentially constant from one stage to another,
how would you expect the temperature to vary moving up the column? (Brief qualitative answers
required).
b) Compute the temperatures on the two equilibrium stages labelled m +1 and m, and also the values
of the four mole fractions indicated on the diagram above. These calculations are most easily
accomplished in a spreadsheet.

The vapour pressures of the two substances may be determined as functions of temperature from the
Antoine equation,
log10 ( p / kPa) = A − B /(C + T / °C) ,

with parameters as follows:

Substance A B C
Benzene 6.0191 1204.6 220.1
Styrene 6.0490 1420 206
Problem 5
A mixture of hexane + heptane is to be separated by continuous distillation at ambient pressure to produce separate streams each of 95 mol% purity. The
feed, containing 45 mol% hexane, has a flow rate of 100 kmol/h and enters the column in a partially-vaporized state with a liquid fraction q = 0.5. Making use
of the McCabe-Thiele construction and the equilibrium data plotted below, determine the minimum possible reflux ratio, R min , the minimum number of
equilibrium stages, N min , and the actual number of equilibrium stages required at a reflux ratio of 1.2R min . Also determine the distillate and bottoms molar flow
rates, the vapour and liquid molar flow rates in both the rectifying and stripping sections of the column, and the boilup ratio.

Equilibrium Curve for hexane + heptane at p = 1.013 bar

1.0 1.0

0.9 0.9

0.8 0.8

0.7 0.7

0.6 0.6
y

y
0.5 0.5

0.4 0.4

0.3 0.3

0.2 0.2

0.1 0.1

0.0 0.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x x
Problem 6
A continuous distillation column, operating at atmospheric pressure, is to be designed to separate a mixture
containing 27.4 mol% CS 2 and 72.6 mol% CCl 4 into an overhead product containing 95.3 mol% CS 2 and a
bottom product containing 5.3 mol% CS 2 . Assume a reflux of 3.16 and, using the data below, determine
graphically the number of theoretical stages required.

The feed enters at T = 290 K and has a specific heat capacity c p = 1.7 kJ kg-1 K-1 and a bubble-point
temperature of 336 K. Both components have an enthalpy of vaporisation of 25,900 kJ kmol-1. The average
molar mass of the feed is 132.6 kg kmol-1.

102y 0 8.23 15.55 26.6 33.2 49.5 63.4 74.7 82.9 87.8 93.2 100
102x 0 2.96 6.15 11.06 14.35 25.85 39.0 53.18 66.30 75.75 86.04 100

1.0

0.8

0.6
y

0.4

0.2

0.0
0 0.2 0.4 0.6 0.8 1
x
Problem 7
Ethanol and propanol are to be separated in a plate distillation column. The feed is saturated liquid and
contains 50 mol% ethanol. The column produces two ethanol products: a 95 mol% top product and a
vapour side stream containing 70 mol% ethanol. The two products are drawn in the ratio 2: 1 (top product :
side stream). The overall ethanol recovery is 95 %.
If the separation is to be achieved with a reflux ratio equal to 1.5 times the minimum value (associated with
a pinch at the side stream) and the overall column efficiency is 60 %, calculate:

a) The operating reflux ratio.

b) The total number of plates in the column.
c) State any assumptions you make

The relative volatility is practically constant at 2.09. The column is fitted with a total condenser and a partial
reboiler.

1.0

0.8

0.6
y

0.4

0.2

0.0
0 0.2 0.4 0.6 0.8 1
x
Problem 8
Bio-ethanol is produced by distillation of a fermentation broth containing 5 mol% ethanol (approximately
15% ethanol by volume at 20°C). The desired product specification is a distillate containing 80 mol%
ethanol (approximately 96% by volume at 20°C) and a bottom product containing less than 1 mol% ethanol.
The column is to be operated at a reflux ratio 1.5 times the minimum reflux ratio, and the feed is saturated
liquid at its bubble point. Using the McCabe-Thiele approximation, determine the number of equilibrium
stages required in the rectifying and stripping sections of the column using the equilibrium data presented
below.

Equilibrium Curve for Ethanol + Water at p = 1.013 bar

(The inset shows the region x < 0.1 on an expanded scale)

1.0

0.9

0.8

0.7

0.6
y

0.5

0.4 0.4

0.3
0.3
0.2
0.2
0.1

0.1 0.0
0 0.1
0.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
Problem 9
The isobaric vapour-liquid equilibria of a hypothetical binary mixture is described by the relation
y = x + ax(1 − x ) ,

where a is a positive constant, and x and y denote the mole fraction of the more volatile component in the
liquid and vapour phases, respectively. The mixture is to be partially separated in a simple batch still
equivalent to exactly one theoretical stage.

a) Derive an equation for the mole fraction x S of the more volatile component in the liquid remaining in
the still pot as a function of the initial value of that mole fraction, x S,0 , and the ratio S/S 0 , where S is
the amount of mixture remaining in the still pot and S 0 is the initial amount in the still pot.
b) If a = 0.8 and x S,0 = 0.5, what is the composition of the distillate at the start of the distillation
process?
c) If a = 0.8 and x S,0 = 0.5, what is the final composition of the liquid in the still pot after exactly half the
initial charge has been distilled?
d) What is the mean composition of the distillate collected during the process?

dz 1 αz + β
The following standard integral may be used: ∫ z(αz + β ) = − β ln z
+C
Problem 10
A mixture of hexane and octane are to be partially separated by batch distillation in a still with exactly two
theoretical stages operating at atmospheric pressure. A distillate of constant composition x D = 0.8 is
required and this is to be achieved by variation of the reflux ratio. The still is initially charged with 100 kmol
of a mixture with x S = 0.2 and is operated at a constant boilup rate of 20 kmol/h until the reflux ratio reaches
9. Making use of the x,y diagram below, determine the following:

a) The initial reflux ratio required to meet the x D = 0.8 specification

b) The value of x S corresponding to the limiting reflux ratio of 9
c) The values of x S and R corresponding to an operating line of intermediate slope
d) The estimated batch distillation time by graphical integration

Equilibrium Curve for hexane + octane at p = 1.013 bar

1.0

0.8

0.6
y

0.4

0.2
Equilibrium Curve

45° line
0.0
0 0.2 0.4 0.6 0.8 1
x
Problem 11
A mixture of benzene and ethylbenzene containing 40 mol% benzene is to be separated on a sieve-tray
distillation column operating at ambient pressure to produce an overhead product containing 99 mol%
benzene and a bottom product containing 98 mol% ethylbenzene. The column is fitted with a partial re-
boiler and a total condenser, the feed is partially vaporised with q = 0.5, and the column is operated at 1.25
times the minimum reflux ratio. For this system, the relative volatility is not constant and the equilibrium
relation is described by the equation
y = (αx + βx 2 ) /[1 + (α + β − 1) x ]

with α = 3.018 and β = -0.944. Making use of the McCabe-Thiele Construction Excel Worksheet provided
on BB Learn, including Murphree vapour efficiency factors determined from the O’Connel correlation, find
the number of plates required in each section of the column (see worksheet tab McCabe-Thiele-Murphree).
Other data required are provided in the spreadsheet.

The feed rate to the column is 250 kmol/h and the column is to operate with internal vapour flow rates equal
to 75% of the critical flooding rate. The sieve trays have holes of 5 mm diameter covering 15% of the active
plate area; the equivalent height of clear liquid on each tray is 25 mm and the tray spacing of 0.5 m. The
system can be assumed foam free and to have a constant interfacial tension of 0.02 N∙m-1. The densities of
benzene and ethylbenzene at their respective normal boiling temperatures of 353 K and 409 K are
814 kg∙m-1 and 808 kg∙m-3 respectively and their vapours may be treated as perfect gases. The molar
masses of benzene and ethylbenzene are 78.1 kg/kmol and 106.2 kg/kmol, respectively. Making use of the
Column Design Excel Worksheet provided on BB Learn, estimate the required column diameters in the
stripping and rectifying sections of the column. Estimate also the total height of the column and the total
pressure drop between the re-boiler and the condenser.
Problem 12
A carbon dioxide stream containing 2 mol% ethanol is fed at T = 30°C and p = 110 kPa to a plate
absorption column at a rate of 180 kmol/h. It is desired to remove 97% of the ethanol present in the gas
feed by absorption in water. The pure water feed, also at T = 30°C and p = 110 kPa, is to have a molar flow
rate 50% greater than the minimum flow required for the desired degree of absorption. Determine the molar
flow rate L′ of solute-free solvent and, by graphical construction below, the number of theoretical stages
required, given that γ∞ 1 = 6 and p 1,sat = 10.5 kPa at T = 30°C.

0.035

0.030

0.025

0.020
Y

0.015

0.010

0.005

0.000
0.00 0.01 0.02 X 0.03 0.04
Problem 13
A stream of butadiene sulfone is to be stripped of SO 2 and butadiene impurities in a plate-column stripper.
The molar flow rates in the incoming liquid stream are as follows: SO 2 , 10 kmol/h; butadienes, 10 kmol/h;
and butadiene sulfone 100 kmol/h. The stripping gas entering the tower is pure nitrogen and the K-factors
for SO 2 and butadienes under the column operating conditions are 7.0 and 3.5 respectively. It is desired to
reduce the mole fractions of SO 2 and butadienes in the exiting liquid to less than 0.05 mol% and 0.5 mol%
respectively.

Using the Kremser method and the plot below, estimate the molar flow rate of nitrogen to the column and
the minimum number of equilibrium stages required. Your estimate should be based on the criterion that
the smaller of the stripping factor S for the two impurities should be 1.5.

If the K factor for butadiene sulfone is 0.016, estimate the amount of this substance lost in the exit gas per
hour.

1.E+00
A or S

0.8 1 1.2 1.5

1.E-01 2 3 5 10
Fraction not absorbed, stripped or extracted

1.E-02

1.E-03

1.E-04

1.E-05

1.E-06
0 5 10 15 20 25 30

Number of theoretical stages, N

Problem 14
98 % of the benzoic acid in a wastewater stream, initially containing 6000 ppm benzoic acid by mass, is to
be removed by continuous counter-current extraction using chloroform as the solvent. The flow rate of feed
is 1000 kg/h. Determine the number of theoretical stages and solvent mass flow rate S required if the
process operates at S = 1.5S min , where S min is the minimum possible solvent flow rate for the desired
degree of extraction. For this dilute system the Kremser equation holds. The partition coefficient for the
system (based on mass ratios) is K′ D = 4.2.

Problem 15
A mixture of p-dioxane in water, with initial mass fraction x F = 0.1, is to be treated with benzene in a single-
stage mixer-settler unit to extract 80% of the p-dioxane. The partition coefficient for the system (based on
mass ratios) is K′ D = 1.2. If the feed mass flow rate is 2000 kg/h, what is the required flow rate of solvent
and what is the mass fraction of p-dioxane in the extract?

If a residence time of 3 minutes is required in the mixer, what volume mixing vessel is required?

The settler unit is a horizontally-orientated cylindrical vessel with length L = 4D, where D is the diameter. If
C = 0.1 m/min for this unit, what is the required volume of the settler and what is the residence time?

Why is liquid-liquid extraction favoured for this process? How would you separate the extract solution to
enable recycle of the solvent?

Data
At the operating temperature, specific volumes v are as follows: water, v = 1.00×10-3 m3 kg-1; p-dioxane, v =
1.03×10-3 m3 kg-1; benzene, v = 0.87×10-3 m3 kg-1. The excess specific volume of mixing may be assumed
negligible. Normal boiling temperatures are as follows: water, 100°C; p-dioxane, 101°C; benzene 80°C.
Problem 16
Air containing 6 mol% ammonia is to be scrubbed with water in a packed absorption column at ambient pressure and 20 °C. The total molar flow rate of gas
entering the column is 14.1 mol/s and the specifications call for the concentration of ammonia in the exit stream to be reduced to 0.2 mol%. The flow rate of
water is to be 1.2 times the minimum flow rate for the desired degree of absorption. The column diameter is 0.8 m. The overall mass transfer coefficient (for
mole-ratio driving force) is K OG = 0.68 mol m-2 s-1 and the packing surface area parameter is a = 120 m-1. Determine (a) the required flow rate of liquid and (b)
the required height of the packing. For the purposes of this problem, the system should be treated as non-dilute. The equilibrium curve is plotted below and
the plot on the right may be used to obtain a graphical estimate of the integral required for N OG .
0.080 500
Equilibrium curve

400
0.060
yY

300

Y*)
1/(y –- y*)
0.040

1/(Y
200

0.020
100

0.000 0
0.00 0.02 0.04 xX 0.06 0.08 0.00 0.02 y
Y 0.04 0.06