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LEARNING GUIDE
Week No.: ___8___
TOPIC: DISTILLATION

EXPECTED COMPETENCIES: At the end of the lesson, you must have:

a. understood and performed calculations involving Raoult’s law;
b. learned how to use the boiling-point diagrams of different solutions;
c. solved problems involving flash distillation operations; and
d. distinguished the different types of distillation methods.

CONTENT/TECHNICAL INFORMATION
Distillation is the separation of two or more volatile components from a liquid
solution by the application of heat. Due to the differences in the volatilities of the
components, the vapor produced contains higher concentrations of the more volatile
components and the liquid produced contains higher concentrations of the less volatile
components.

8.1 VAPOR-LIQUID EQUILIBRIUM

8.1.1 Raoult’s Law
For ideal solutions and ideal gases at low to moderate pressures, the partial pressure
of component A can be defined using Raoult’s law:
PA = xAPoA
where:
PA = partial pressure of component A in the vapor phase
xA = mole fraction of A in the liquid phase
PoA = vapor pressure of pure A or the saturation pressure of A

Raoult’s law only applies to ideal solutions or solutions having components that are
very similar to each other like benzene-toluene, hexane-heptane, and methyl alcohol-ethyl
alcohol systems. If we divide the Raoult’s Figure 1
law equation by the total pressure of the Boiling-point diagram for benzene-
system PT: toluene at 101.325 kPa
𝐏𝐏𝐀𝐀 𝐱𝐱 𝐀𝐀 𝐏𝐏𝐀𝐀𝐨𝐨
=
𝐏𝐏𝐓𝐓 𝐏𝐏𝐓𝐓
𝐱𝐱 𝐀𝐀 𝐏𝐏𝐀𝐀𝐨𝐨
𝐲𝐲𝐀𝐀 =
𝐏𝐏𝐓𝐓

We can then determine the mole fraction

of A in the vapor phase.

8.1.2 Boiling-Point Diagrams

To determine the temperature at
which a binary mixture will start to boil
and the temperature at which it will start
to condense, a boiling-point diagram
shown in Figure 1 is often used. Figure 1
shows the boiling-point diagram for
benzene (A) – toluene (B) system at a
total pressure of 101.325 kPa.
(source: McCabe, 1993)
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The upper line that can be seen from the diagram is the saturated vapor line or the dew-
point line. It is the temperature at which the vapor mixture will start to condense. The lower
line is the saturated liquid line or the bubble-point line. It is the temperature at which the
liquid solution will start to boil. In between these two lines there exists a two-phase region.
Meaning, both vapor and liquid phases are present at these conditions.

How to read the boiling-point diagram:

For this exercise, we will be using the boiling-point diagram of benzene-toluene
system (benzene A and toluene B). We start with a cold liquid mixture at a temperature of
65oC and a concentration of xA1 = 0.32, this point is represented by the red point shown in
Figure 2-a. Then we heat the liquid mixture until it starts to boil at 98oC. We can see from
Figure 2-b that the boiling point of the mixture can be determined by extending a vertical line
from the initial point to the bubble-point line and reading the corresponding temperature of
that point.

Figure 2
Using the boiling-point diagram

Dew-point line

98oC

Bubble-point line

xA1 yA1

(a) (b)

The composition of the first vapor in equilibrium is yA1 = 0.53. As we continue boiling, the
composition xA will move to the left since yA is richer in A. To determine the mole fraction of
component A in the vapor phase, we can either use the Raoult’s law or the boiling-point
diagram.

Example:
Calculate the vapor and liquid compositions in equilibrium at 95oC for benzene-
toluene using the vapor pressure from Table 1 at 101.325 kPa.

Given: Required:
o
T = 95 C xA and yA
Sol’n:
Let: A --- benzene
B ---- toluene

PT = PA + PB
PA = xAPoA ; PB = xBPoB
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Table 1
Vapor Pressure and Equilibrium Mole Fraction Data for Benzene-Toluene System

(source: Geankoplis, 1993)

So that:
PT = (xAPoA) + (xBPoB)

We know that: xB = 1 – xA
So:
PT = (xAPoA) + (1 – xA)(PoB)

From Table 1 at 95oC:

PoA = 155.7 kPa
PoB = 63.3 kPa

Substituting in the equation of PT:

PT = (xAPoA) + (1 – xA)(PoB)
101.325 kPa = (xA)(155.7 kPa) + (1 – xA)(63.3 kPa)
xA = 0.41153
xB = 0.58847

it can also be seen from Table 1 that at xA = 0.411, yA = 0.632. Suppose we don’t have this
data in the table and we want to solve for the yA:

from the Raoult’s law: PA = xAPoA

PA xA PAo
=
PT PT
xA PAo 0.41153(155.7 𝑘𝑘𝑘𝑘𝑘𝑘)
yA = =
PT 101.325 𝑘𝑘𝑘𝑘𝑘𝑘
yA = 0.63237
yB = 0.36763
Summary:
Vapor contains 63.24% benzene
Liquid contains 41.15% benzene
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8.2 DISTILLATION METHODS

In practice, distillation may be carried out by either two principal methods. The first
method is the production of a vapor by boiling the liquid mixture to be separated and
condensing the vapors without allowing any liquid to return to the still. The second method is
the production of a condensate (from the vapor produced) in which a portion is being
returned into the distilling column and is brought into intimate contact with the vapors on
their way up the column. Figures 3 and 4 show the first and second methods, respectively.
Figure 3
Distillation Method 1
VAPOR
DISTILLATE

Figure 4
Distillation Method 2

VAPOR
DISTILLATE
FEED

REFLUX
V L

FEED

REBOIL

BOTTOMS

8.2.1 Flash Distillation

Flash distillation consists of vaporizing a definite fraction of the liquid in such a way
that the evolved vapor is in equilibrium with the residual liquid, separating the vapor from the
liquid, and condensing the vapor. Figure 5 shows the elements of a flash distillation setup.
Feed is pumped by pump a through heater b, and the pressure is reduced through valve c.
An intimate mixture of vapor and liquid enters the vapor separator d, in which sufficient
time is allowed for the vapor and the liquid portions to separate. Because of the intimacy of
contact of liquid and vapor before separation, the separated streams are in equilibrium. Vapor
leaves through line e and liquid through line g. Flash distillation can be done batchwise or
continuously.
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Figure 5
Flash Distillation Setup

Say, we have a binary

mixture of components A
and B flowing at the rate of
F (mol/h) into a heater.
Then, the mixture reaches
equilibrium and is separated.
The composition of F is xF
(mole fraction of
component A).

(source: McCabe, 1993)

The overall material balance is:

F=L+V
Component A balance is then:
xFF = xL + yV
where:
F = molar rate of feed, mol/h
L = molar rate of residual liquid, mol/h
V = molar rate of vapor, mol/h
xF = mole fraction of component A in feed
x = mole fraction of component A in residual liquid
y = mole fraction of component A in vapor

Example 1:
A mixture of 100 kmol which contains 60 mol% n-pentane (A) and 40 mol% n-
heptane (B) is vaporized at 101.325 kPa pressure using flash distillation until 40 kmol are
distilled. What is the average composition of the total vapor distilled and the composition of
the liquid left? Use equilibrium data from Table 2 below.

Given: V = 40 kmol

F = 100 kmol HEATER SEPARATOR L

xF = 0.60

Required: y;x
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Table 2
Equilibrium-Mole Fractions of n-Pentane

(source: Geankoplis, 1993)

Solution:
OMB: F=L+V
100 kmol = L + 40 kmol
L = 60 kmol

n-pentane balance:
xFF = xL + yV
(0.6)(100 kmol) = x(60 kmol) + y(40 kmol)
60 = 60x + 40y
𝟑𝟑 𝟑𝟑
𝐲𝐲 = − 𝟐𝟐 𝐱𝐱 + 𝟐𝟐 -- eq.1

now, what we have to do is to make a plot of xA vs. yA using the equilibrium data that we
have in Table 2:

Figure 6
Equilibrium curve for n-pentane/n-heptane system
n-pentane/n-heptane system
mol fraction of n-pentane in vapor, yA

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
mol fraction of n-pentane in liquid, xA

The curve that we have generated is called the equilibrium curve. Now, we will draw a 45o
line which connects points (0,0) and (1,1). The 45o line shows that yA is richer in component
A than is xA.
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n-pentane/n-heptane system

mol fraction of n-pentane in vapor, yA

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
mol fraction of n-pentane in liquid, xA

To be able to determine the values of x and y in equation 1, we will be plotting it on the

graph.
3 3
Eq.1: y = − 2 x + 2
to plot the line, we have to assign points:
at x = 1, y = 0
x = 0.5, y = 0.75

Plotting these points on the graph, we can see:

n-pentane/n-heptane system
mol fraction of n-pentane in vapor, yA

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
mol fraction of n-pentane in liquid, xA

We have to extend the line until it intersects the equilibrium curve. The intersection of the
equation and the equilibrium curve is the desired solution.
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n-pentane/n-heptane system

mol fraction of n-pentane in vapor, yA

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
mol fraction of n-pentane in liquid, xA

Hence:
x = 0.43 and y = 0.85

Summary:
Average composition of vapor distilled = 85 mol% n-pentane; 15 mol% n-heptane
Composition of residual liquid = 43 mol% n-pentane; 57 mol% n-heptane

8.2.2 Simple Batch or Differential

Figure 7
Distillation Simple Batch or Differential Distillation
In simple batch or differential
distillation as in Figure 6, liquid is first
charged to a heated kettle. The liquid is
boiled slowly and the vapors are
withdrawn as rapidly as they form to a
condenser, where the distillate is
collected. The first portion of vapor
condensed will be richest in the more
volatile component A. As vaporization
proceeds, the vaporized product
becomes leaner in A.
(source: Geankoplis, 1993)

At any given time, there are L moles of liquid left in the still with composition x and the
composition of the vapor leaving in equilibrium is y. The composition in the still pot changes
with time. Overall material balance in a simple batch distillation would be:
Lo = L1 + V

8.2.3 Simple Steam Distillation

At atmospheric pressure, high-boiling liquids (liquids with high boiling points) cannot
be purified by distillation because the components of the liquid may decompose at the high
temperatures required. Often the high-boiling substances are insoluble in water, so a
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separation at lower temperatures can be obtained by simple steam distillation. Figure 8

below shows a setup for laboratory steam distillation.

Figure 8
Laboratory Steam Distillation Setup

1
2 4
(source: Wikimedia commons)

In steam distillation, steam being produced from heater 1, is fed to flask 2 where the solution
containing the high-boiling liquid solute is placed. Due to the high temperature of the steam,
the high-boiling liquid solute will evaporate and go together with the steam, passing through
condenser 3. At flask 4, there can be found a mixture of condensed water and solute and
since they are immiscible, the solute can easily be separated from water.

8.2.4 Fractionation or Distillation with Reflux

Distillation with reflux or fractionation can be considered as a series of flash
distillation stages arranged in such a manner that the vapor and liquid products from each
stage flow counter-currently to each other. The liquid in a stage flows to the stage below and
the vapor from a stage flows upward to the stage above. Hence, in each stage a vapor stream
V and a liquid stream L enter, are mixed and equilibrated, and a vapor and a liquid stream
leave in equilibrium. The process flow diagram for a single stage and a stage distillation with
reflux is shown in Figures 9 and 10, respectively.

Figure 9
Single-stage Equilibrium Process

(source: Geankoplis, 1993)

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Figure 10
Multi-stage Distillation with Reflux

(source: Geankoplis, 1993)

PROGRESS CHECK

I. Answer briefly.
1. What is/are the driving force/s of distillation?
2. Increasing the operating pressure of a distillation column makes separation
more difficult. Explain this statement.
3. Cite some industrial applications of the different classification methods
discussed (give at least three).

II. Problem solving.

1. Determine the boiling point of a binary mixture containing 40 kg benzene and
60 kg toluene at 1 atm. T = 93 degrees Celsius
2. Antoine equation is a correlation explaining the relation between vapor
pressure and temperature of pure substances. Antoine equation is expressed as:
𝐵𝐵
𝑙𝑙𝑙𝑙𝑙𝑙 𝑃𝑃𝑜𝑜 = 𝐴𝐴 −
𝑇𝑇 + 𝐶𝐶
where A, B, and C are constants specific for a substance, T is the temperature
in oC, and Po is the vapor pressure of the pure substance in torr. Determine the
equilibrium vapor phase composition of an acetone-chloroform mixture at
60oC and a total pressure of 1 atm,
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assuming that the acetone-chloroform mixture is an ideal solution. The

Antoine constants are given below:
Acetone: A = 7.11714 B = 1210.595 C = 229.664
Chloroform: A = 6.95465 B = 1170.966 C = 226.232
Composition: acetone = 24.6%; chloroform = 75.4%
3. A 200 kmol mixture containing 30 mol% water and 70 mol% 1-butanol is
flash distilled at 1 atm. A total of one third of the moles in the feed is vaporized. Calculate
the average composition of the distillate and the composition of the residual liquid.

Equilibrium data for water-1-butanol mixture: (Take note that in this problem, water is the
more volatile component)
distillate: 55% water
residual liqd: 18% water

(source: Perry’s Chemical Engineers Handbook, 7th ed)

REFERENCES

Geankoplis, C. J. (1993). Transport Processes and Unit Operations (3rd ed.). Prentice Hall.

McCabe, W. L., Smith, J. C., & Harriott, P. (1993). Unit Operations of Chemical
Engineering. McGraw-Hill Book Co.

Olaño, S. Jr, Bungay, V., Centeno, C., Medina, L. Jr. & Salazar, C. (2015). Reviewer for
Chemical Engineering Licensure Examination. Manila Review Institute, Inc.