- . .

A_-__

NIT 10 DISTILLATION AND BOILING

Structure

10. 1 Introduction
Objectives
10.2 Boiling Point and Vapour Pressure
10.3 Liquid Mixtures
10.4 Ideal Solutions
10.5 A Simple Distillation Apparatus
10.6 Fractional Distillation
10.7 Laboratory Fractionation Columns
10.8 ,Situations where Fractional Distillation Does Not Produce Pure
Components
10.9 Azeotropic Mixtures
10.10 Determination of Boiling Point
Experimental Deta~lsfor Bolting Point Determinations
10.1 1 Summary
10.12 Terminal Questions
10.13 Answers

10.1 INTRODUCTION
In the last unit, you studied the techniques of filtration which would be used
to separate a solid substance from a liquid substance. In this unit, we
introduce you to another technique used in the laboratory and is called as
distillation. The process of distillation can be used to purify an impure liquid.
Recrystallization is the process used to purify solids and will be discussed in
Unit 11. A simple distillation apparatus may be used when the impurities are
non-volatile. You may be familiar with the lab exercise in which impure
water, such as that obtained from a tap is purified using this technique, and
pure water distils over, leaving behind the solid impurities (sand, small
particles of grit, etc.).

To understand the basic principles of distillation, you need to look a little

more closely at the relationship between vapour pressure and boiling point of
a pure liquid and extend t k s e ideas to mixtures of liquids, where both the,

vapour pressure and the boiling point depend on the composition of the
mixture. When the required product is mixed with a number of components
having similar boiling points, then a more sophisticated technique, known as
fractional distillation, must be used. This is essentially the technique used in
an oil refinery to separate crudepetroleum into its six principal fractions.
We will also be discussing the types of columns used in fractional distillation.

Finally, we wjll consider the assembly and use of distillation equipment. You
will have the opportunity of carrying out a distillation in practical session.

Objectives
After studying this Unit, you shodd be able to
define the term boiling point,
 Distillation and Boiling
a ' state the differences between miscible, partially miscible and immiscible
Point Determination
liquids,
explain the relationship between vapour pressure and boiling point curves
for ideal liquidlliquid mixtures,
describe the changes in the composition of liquid and vapour during
distillation using vapour pressure diagrams (non-azeotropic systems),
draw and label the component parts of an apparatus for simple
distillation,
assemble and use, with relevant safety precautions, a simple distillation
apparatus to separate a binary mixture,
explain in simple terms the process of fractional distillation,
describe a range of laboratory fractionation columns and qualitatively
discuss their relative merits,
assemble and use, with relevant safety precautions, a fractional
distillation apparatus to isolate a product from a reaction mixture, ,
recognize that the products of fractional distillation are not necessarily the
pure components, and
describe and use both simple distillation and a small-scale method for the
determination of boiling point.

10.2 BOILING POINT AND VAPOUR PRESSURE

If a pure liquid is kept in a closed evacuated container, it will evaporate or
give off vapours. At a particular temperature, this vapour attains a definite
pressure, called the saturated vapour pressure. This means that an
equilibrium is set up, whereby particles leave the liquid phase at the same
rate as they return to it from the vapour phase.

Figure 10.1 shows how the vapour pressures of four liquids, i.e..

0 20 40 60 80 100 I20 140

Tempe- in C
Fig. 10.1 : Vapour Pressure/Temmprature Curves.
bboratoty ~cchninlquesI1 ethoxyethane, propanone, water and bromobenzene vary with the
temperature.
Polar liquids have higher
boiling points than the non- As the temperature rises, the vapour pressure increases, i.e. the number of
polar ones. particles which can overcome the force of attraction to other liquid particles,
increases. At a certain temperature, the vapour pressure eventually equals the
Generally the boiling point of external pressure, and the temperature at which this happens is called the
a substance depends upon its boiling point. The boiling point at a pressure of 760 mm of mercury is
molecular mass and forces of
attraction between the
called normal boiling point.
molecules.
Since each liquid shows a characteristic variation of vapour pressure with
temperature, so these differences will be reflected in their boiling points.
Ethoxyethane (ether), for instance, has a higher value of vapour pressure
hence, its boiling point is much lower than that of bromobenzene. The point
of intersection of the horizontal line corresponding to a pressure of 760 mm
of mercury with the individual vapour pressure curve determines the boiling
point value for each liquid.

Although the actual vapour pressure may be measured using a mercury

column and therefore given in units of millimetres of mercury (mm Hg), we
measure all scientific quantities, such as pressure, using the International -
System of Units (SI Units). Under this system, pressure is expressed in unit
called the Pascal and it is represented as Newton metre-2 which is
abbreviated as N m-2.. For large pressures, the more usual unit is kN m-2,
where 1kN me2= 1000~ m - ~ .

Now try the following SAQ.

SAQ 1
What is the SI unit of pressure? Tick the correct answer.

(i) mm of mercury 1
7
(ii) atmospheres
(iii) newton metre-2
(iv) lb inch-2

Check your answer with ours at the end of the unit before continuing.

10.3 LIQUID MIXTURES

Mixtures consisting of two liquids can be classified into three categories as
follows.

10.3.1 Completely Miscible Liquids

Two liquids are called completely miscible when there is complete
miscibility of one liquid in another in all proportions. An example of such a
system is ethanol and water. Whatever ratio of ethanol to water is taken in
their mixture, only one layer will be formed and a solution of ethanol in water
(or water in ethanol) will re&lt.
10.3.2 Partially Miscible Liquids Distillation and Boiling
Point Determination
This is an intermediate state between complete miscibility and the state of
almost complete immiscibility. Here, the component liquids are partially
miscible. For example,if a little phenylamine (aniline) is added to water at
room temperature, it will dissolve completely to form one layer; but if the
addition is continued, a point is reached when no further dissolution occurs
and two layers form. One of these layers is a saturated solution of
phenylamine in water and the other is a saturated solution of water in
phenylamine.

10.3.3 Immiscible Liquids

Two liquids are said to be immiscible when they form two separate layers
when added together in any proportion. In practice, almost all liquids
dissolve in each other to some extent. However, the mutual miscibility of the
tetrachloromethane-water system is so low that total immiscibility is
assumed.

The process of steam distillation can be utilized for distilling immiscible

liquids where one of the immiscible liquids is water. This technique allows a
liquid of higher boiling point than water to be distilled at a much lower
temperature than its true boiling point. Thus,chlorobenzene has a boiling
point of 132" C, yet when it is distilled with stem, the distillate (71% by
mass chlorobenzene and 29% water) is obtained at 90' C . The lower
temperature has the obvious advantage of less decomposiGon of the product,
which is always a possibility in a distillation experiment.

10.4 IDEAL SOLUTIONS

In Sec, 10.2, we saw that the vapour pressure of a pure substance increases
with temperature until the point where the vapour pressure reaches
atmospheric pressure. When a solution consists of two miscible liquids, both
liquids contribute to the vapour pressure of the mixture.

To understand the way in which the vapour pressure of a two-component

liquid mixture is influenced by its composition we must first define precisely
the quantities of each of the components in the mixture. Usually we express
the composition of a liquid mixture in terms of its mole fraction or molar
percentage composition. Consider a mixture of 4.6 g of ethanol (relative
molecular mass 46) and 9 g of water (relative molecular mass 18). This
mixture contains:

4.6
-= 0.1 moles of ethanol,
46
9
and - = 0.5 moles of water.
18

The mole fraction of ethanol is thus :

5
Similarly, the mole fraction of water = -
6
I . ; ~ h t ~ r i t o rTechniques
y 11 The previous values can be converted into molar percentage
compositions as follows:

I
-xlOO = 16.7%
6
and 5 x I 00 = 83.3Yo
6

Fig. 10.2 shows the situation where two completely miscible liquids.
A and B form a solution at a particular fixed temperature. Fig.
10.2(a) shows how the vapour pressure of component A varies as its
molar percentage in the mixture changes. It is not surprising that at
the extreme left of the diagram, where only component A is present,
the vapour pressure shown is equal to vapour pressure of pure A at
that temperature. Similarly, Fig. 10.2 (b) relates the vapour pressure
variation of component B.

irapour Vapour
prt'ssi!re pressure
of A ofB

lU3 Po 80 70 60 So 40 30 20 100 0 1 0 20 30 40 50 643 70 80 90100

Molar % A Molar ?G B
(a) (b)
Fig. 10.2: Component Vapour Pressures in an Ideal Mixture.

Fig. 10.3 superimposes the two separate graphs of Fig. 10.2 to show how the
total vapour pressure vafies with composition. The variation is linear in this
case and this type of graph will arise if the solution is 'ideal'. By ideal, we
mean that there ars no temperature or volume changes on mixing the
components and the intermolecular attractions between all the particles in the
solution are equal. The mixture will boil when the total vapour pressure
equals the external pressure.

Pure
Fig. 10.3: Summing of Vapour Pressures.
Note that, in an ideal solution, as can be shown byFig.lO.3,the t d vapmr Dbti#rtbs and Boiling
pressure is obtained by adding the individual partial vapowpremtrm d the Point Determination
components Partial vapour pressure of a component in a mixture is simply
the vapour pressure that a component would exert if the second corn-
was absent.

Because it is more convenient to measure the temperature of a boiling liquid

.
rather than the vapour pressure of a mixture, boiling point curves are more
ofkn used than vapour pressure curves. The two curves are actually
reflections of each other, as a liquid of high vapour pressure boils at a lower
temperature than a liquid of lower vapour pressure. This relatio~lsi~ip is
depicted in Fig.lO.4 (a) and Fig. 10.4 (b).

Boiling point of pure B, I

A Molar %
' Boiling point o f pun A

Molar %
1
B
Component with
Component with
High Vapow Ressure Lower Vapour Rarswc

Fig, 10.4: Comparison of Vapour Pressure and Boiling Point Curves.

As was shown in Fig. 10.1 with pure liquids, at a given temperature the most
volatile liquid will have the highest vapour pressure. It will also boil at the
lowest temperature.

With mixtures such as those depicted in Fig.lO.3, the vapour pressure of a

pure substance A is greater than that of a pure substance B. The vapour in
contact with a solution of known composition would therefore be expected to
be somewhat enriched in the more volatile component A. In other words. on
boiling an ideal liquid mixture, the vapour is richer in the more volatile
component.

For a two component system of liquids A and B, by knowing the respective

pure state vapour pressures of two components in a mixture and the mole
fraction of each in the solution, it is possible to calculate their composition in
the vapour phase. The resulting graph would look like the one shown in

* Molar % Y
0.38
x
0.70
6

Fig. 10.5: Vapour Pressure - Composition Curl r.

Laboratory Teebniques 11 *Inaddition, the graph shows two points y and x joined by a horizontal line
representing the liquid in'equilibrium with its vapour. The more volatile
liquid A which has a mole fraction value of 0.38 (point y) in the liquid, is
enriched in the vapour phase (point x) to a mole fraction value of 0.70.

Fig. 10.5 also has a corresponding boiling point curve as shown in Fig. 10.6.
It shows that the composition of vapour phase above a boiling liquid is
always relatively richer in the component having the lower boiling point.
TC
Boiling point

composition f
curve :
A Y x B

, Molar %
Fig. 10.6: Boiling Point - Composition Curve.

By boiling a liquid of composition x, a vapour of composition y is obtained,

which has a greater mole fraction value of A, the lower boiling (or more
volatile) component. From a practical point of view, this corresponds to a
simple distillation involving a two-c&mponent system.

This results in the distillate becoming richer in the more volatile component
and the residue liquid richer in the less volatile component. Distillation is
thus seen as a 'Boil-Condense' sequence on the curve shown in Fig. 10.6. By
repeating this process a number of times, the distillate becomes progressively
richer in the more volatile component.

In practice, this would offer a very tedious method of separating two

components by distillation, and hence a technique known as fractional
distillation is used which is described in Sec. 10.6.

Now answer the following SAQs.

SAQ 2

Which of the following liquids do you think would be suitable for steam
distillation ? ~ i c the
k correct answer.

(i) Chlorobenzene
(ii) Ethanol
(iii) Ether

SAQ 3

Which of these clauses correctly complete the following definition? Tick the
correct answer.
 Distillation and Boiling
Point Determination
An ideal solution is the one . . . .. . . . .. .. . .. . . . .. .. ... ..

6) . . . .....which mixes in all prbportions with water'.

(ii) .. . ..... where the total vapour pressure is obtained by adding together
the individual vapour pressures of the two components at each
temperature'.
(iii) . .. . . ... where the mole fraction of each component is equal'.

Check your answers with ours at the end of the unit before continuing.
-- -

10.5 A SIMPLE DISTILLATION APPARATUS

A simple distillation apparatus which is suitable for purifying an impure
liquid contaminated with non-volatile components is shown in Fig. 10.7. The
ground glass joints provided by Quickfit assemblies are almost universally
used nowadays, instead of bored-cork assemblies.

It- Thermometer

Rubber thermometer adapter

fitted w e r glass thermometer adapter

Glass thermometer adapter

nd-bottomed flask

Round-bottomed

Fig. 10.7: Assembly for a Simple Distillation.

You must ensure that apparatus is carefully supported by the use of stands so
as to minimize the risk of strain due to poor alignment of the components.
The apparatus should be clamped firmly (without too much pressure), around
the neck of the distillation flask and the condenser. The receiving flask also
needs to be supported.
Laboratory Techniques II The distillation flask should be about one-third full and should contain a few
anti-bumping grannules to prevent superheating. Make sure that the
*errnometer is positioned such that its bulb is opposite the qondenser inlet.

Heating is best carried out using a liquid bath or an electric heating mantle
ahd should be sufficient to maintain a ring of condensing vapour just above
t4e level of the thermometer bulb. A satisfactory rate of distillation is
iddicated by the presence of a drop of liquid formed by condensation of
vapour on the bulb of the thermometer.

A water condenser, as shown in Fig. 10.7, is used for compounds boiling up to

about 180°C. Above this temperature, water is drained out of the condenser
or alternatively a special air condenser is used. As the name suggests, the
function of the condenser is to cause the vapours of the liquid to condense so
that they collect in the receiving flask.

In your practical sessions, you may have the opportunity of assembling this
type of apparatus and using it to purify an impure liquid. If only non-volatile
impurities are present, then the sample apparatus which we have described
above can be used. Should the impurities themselves be volatile liquids, a
single distillation of this kind would do little to separate the components of
the mixture. unless their boiling points were markedly different.

The process of fractioilal distillation is used where both components are

volatile liquids and we will explain this technique in Sec. 10.6.

The fact that the vapour of an ideal solution is richer in the more volatile
.
component than the liquid with which it is in equilibrium, is the key to a
process known as fractional distillation. This can be illustrated with
reference to the system cont:iining 2-methylpropan- 1-01 and propan- 1-01.

I
80 1
1 I . . . . . ,I
0 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
(1.1
Mole fraction of propan - 1 - ol

Fic 10.8: Rntling Poir!rK'o~t~po.*ition

D i ~ g r a mfor 3,-mr!h> lyl-opan-1-01and propan-1-01
-1: -211111)sphet-icPressure.
I
I Consider a mixture of these two alcohols as shown in Fig.lO.8. When the
Distillation and Boilin!:
Point Determination
mole fraction of propan-1-01 is 0.2, the mixture will boil at 100°C (shown by
point C). This liquid mixture will be in equilibrium with vapour (represented
by point D), having the mole fraction of propan-1-01 0.4. Thus, the vapour
contains more of the more volatile propan-1-01 than the liquid. If this vapour
were condensed to a liquid, it would have the same composition as the
vapour, and it can be represented by point E. The mixture represented by E
would boil at 94 "C and be in equilibrium with a vapour with a composition
represented by point F (mole fraction of propan-1-01 approximat'ely 0.62).

If this sequence of events is repeated, a stepwise progression is obtained to

point L, where almost pure propan-1-01 is obtained. This isolation of these
various fractions (fractional distillation), as outlined above, is very tedious
and fortunately it is possible to carry out all these stages in a fractionating
column in one continuous process. At the enQf such an operation, provided
the liquid mixture is ideal, the components of such a liquid system are
distilled over in the order of their separate boiling points - the lowest boiling
liquid distilling over first.

A typical laboratory set-up is shown in Fig. 10.9. The fractionating column

Laboratory Tceholqua I1 consists of packed glass beads or coils.

We will discuss other types of columns in Sec.lO.7. The column provides a

large surface area so that good contact is made between ascending vapour
and descending liquid. .,
.*
+

ir

, Lf#e mixture contains more than two components, after the most volatile ,
' , .$. component has distilled away, the temperature will rise sharply to that of the
boiling point of the next most volatile component. At this stage, the
receiving flask should be changed. Removal of the various fractions in this
way means that the boiling point of the mixture in the flask will steadily rise.
Conditions in the column are therefore in a state of flux and slow distillation
is essential if the system igto have time to re-adjust conthually to achieve
good separation.

An industrial version of the laboratory fractionating column is shown in

Fig. 10.10.
- Condenser

Bubble cap
- 4*;J L-
Gasoline and naptha

- Reflux from kerosene fraction

Kerosene
light gas oil fractid

-- Rrtlux from heavy gas oil M i o n

Heavy gas oil
\

w
steam Pump

Fig. 10.10: Distillation of Crude Oil.

Crude oil is continually fed in at the base of the distillation tower and, unlike
the laboratory case, a constant temperature gradient is set up. This enables
various fractions to be drawn off at different heights in the tower, the most
volatile fraction ocurring at the highest point of the unit. At each stage in the
tower, ascending vapour is forced to pass through liquid contained on trays
on which sits a 'bubble cap'. Excess liquid overflows
to a lower level and is eventually drawn off thus forming the various fractions
kuch as the kerosene fraction shown in the diagram.
-- --

148.7 LABORATORY FRACTIONATION COLUMNS -

1.1 Scc. 10.6, we discussed the underlying theory of fractional distillation and
extended the scope of the process to include industrial applications.
 Essentially, the column represents an improvement over the simple Distillation and Boiling
Point Determination
distillation unit by increasing the surface area available for the distillation
process. It provides a large heat exchanging surface with a gentle
temperature gradient from top to bottom. At any point in the column, there is
an equilibrium between the ascending vapour phase and the descending
liquid phase.

Fractional distillation is in effect a technique for carrying out a whole series

of simple distillations in one continuous operation.

In addition to packing a column with glass beads or helices (Sec. 10.6), there
are three other designs which are illustrated in Fig. 10.11.

Small amount

Vigreux Colomn Pear Column Dufton Column

-

(a) (b) (c)

Fig. 10.11 : Fractionating Column Design.

The Vigreux Column is one of the moderate efficiency made by indenting a

glass tube, so that the points of a pair of indents almost touch each other. The
indentations should have a slight downward slope when the tube is vertical.
It is essential that the pairs of indentations are arranged to form a spiral, so
that the vapour will not pass directly through the whole length of the tube
without meeting at least one indentation.

The column introduced in Sec.lO.6 with its glass packing is known as a

Hempel column. This column, and the other two columns shown in
Fig. 10.13, are of greater efficiency than the Vigreux column.

I
In the Dufton column, a glass spiral that has been wound on a central tube or
rod is placed inside a plain tube. The spiral must fit tightly inside the tube in
order to prevent any appreciable amount of vapour from leaking between the
walls of the column and the spiral.

A modified Hempel column is shown in Fig. 10.12. This incorporates a

small reflux condenser known as a 'cold finger'. This reflux condenser can
1
I be raised or lowered to decrease or increase the amount of refluxing liquid. It
I controls the volume of liquid returning to the column and therefore permits
the effective use of the whole column length for fractionation.
I
Laboratory Techniques 11
It is desirable to surround all the fractionating columns described above by a
glass jacket or by a layer or two of insulating material. Such insulation will
reduce the effect of draughts and improve column performance. For high
boiling point liquids, the column should be heated electrically to a
temperature only a few degrees below the boiling point of each component of
the mixture.

Fig. 10.12: Modified Hempel Column.

Figure 10.13 illustrates a sophisticated precision fractionating co!umn

incorporating all the modifications that we've discussed so far. The column
is provided with an electrically heated jacket incorporating a variable
resistance. The still head design enables all the vapour at the top of the
column to be condensed, so that a portion of the condensate is returned to the
column by means of the specinl stopcock and the remainder is collected in the
receiver.

The advantages of the still head are:

(1) True equilibrium conditions can be estaldished before any distillate is

collected;
(2) Reflux is more easily cc:~:rolled since careful adjustment of the reflux
condekser is unnecessary; a d
(3) Changing from a lower to a higher boiling point fraction is
comparative!^ easy using the stopcock.
 Distillation and Boiling
Point Determination

Fig.lO.13: Precision Fractionating Column.

The dotted line in Fig. 10.13 refers to the modification needed for fractional
distillation under reduced pressure.

10.8 SITUATIONS WHERE FRACTIONAL

DISTILLATION DOES NOT PRODUCE PURE
COMPONENTS
The pair of liquids, 2-methylpropan- 1-01 and propan- 1-01 constitute
practically ideal solutions when they are mixed. Other pairs of liquids often
deviate to d greater or lesser extent from ideal behaviour and are said to form
non-ideal solutions. These deviations may be of two distinct types.

(1) If the total vapour pressure (PT) is lower than predicted by the ideal
system described in Fig. 10.3, it is referred to as a negative deviation.
An example of such a systein is trichloromethane-prop~nesystem and
is discussed in the next section.
(2) If the total vapour pressure is higher than predicted by the ideal systeln
described in Fig. 10.4, it is referred to as a positive deviation. An
example of this type of systein is ethanol-benzene system. This is also
discussed in the next section.

Where these deviations are vary large, it is impossible to separate the two
components by fractional distillation.
--

10.9 AZEOTROPIC MIXTURES

The trichloromethane-propanone system shows very large negative
deviations from ideality. When the mole fraction of trichloromethane is 0.65,
then both liquid and vapour have the same composition. A mixture of this
composition will distil without any change in composition. Such a mixture is
Lmbontory Techniques 11 known as an azeotropic (or constant boiling ) mixture. Other azeotropic
mixtures are as follows:
Notc that a constant boiling Azeotropic Mixtures (by wt.) Boiling Temperature CC)
tempcramre during
d i i l l r t i does not always ethanol (95.5%) and water (4.5%) 78.3
indicate that a pure
compwnd is being distil led. ethanal(32.4%) and benzene (67.6%) 68.2
benzene (74.1 %), ethanol (1 8.5%)
and water (7.4%)

The constant boiling Thus, azeotropic mixtures cannot be separated into the components by
temperatures of a motropes fractional distillation, no matter how efficient the distilling apparatus. In
can be either above or
below the boiling points of such mixtures irrespective of the initial mixture compositions, a point is
the individual corn'ponents. reached by fractional distillation, which effectively forms a 'block' to the
separation of the pure components by this technique.

10.10 DETERMINATION OF BOILING POINT

In this section, we will describe two methods for determining the boiling
points of liquids. The boiling point is an important physical property of a
liquid as it enables us to determine the purity of the substance. The
impurities in a substance will cause a rise in its boiling point.

The boiling point is also sensitive to alterations in atmospheric pressure.

Local atmospheric pressure must be taken into account when using the
boiling point as a criterion of purity. In addition, azeotropic mixtures (see
Sec.lO.9) , with their constant boiling points, are also not uncommon. Thus,
a mixture of 79.4% tetrachloromethane and 20.6% methanol boils steadily at
55.7" C.

10.10.1 Experimental details for boiling point determinations

In Sec. 10.5, we referred to a semi-micro assembly for carrying out a simple

distillation. The experimental set-up detailed in Fig. 10.7 can also be used to
determine the boiling point of a liquid. However, in practice, and especially
for mixtures, more reliable readings are obtained using the apparatus shown
in Fig.lO.9. Such a set-up would enable you to record boiling-point values,
to construct a boiling point-composition diagram as discussed in Sec. 10.6.

When only small quantities of a liquid sample are available and the
determination of boiling point by distillation is impracticable, a semi-micro
technique due to Siwoloboff can be employed. A melting-point tube
(4 x 80 mm), sealed at one end, is placed mouth downwards in a sample of
the liquid under examination contained in an ignition tube, see Fig. 10.14.

The ignition tube is attached to the stem of a thermometer of convenient

range by a small rubber band, the sample in the ignition tube being located
alongside the bulb of the thermometer.

The thermometer and attached tube are then gently warmed in a paraffin, or
silicone oil bath, care being taken to ensure that the rubber band is above the
bath liquid.
 Semi-microTechnique for Boiling Point Determination of Small Samples

Fig.lO.14: Semi-micro Technique for Boiling Point Determination of Small Samples.

It is important that the thermometer is adjusted so that the scale is visible,

through the vent, in case the temperature lies in the range that would
otherwise be obscured.

As the temperature rises, bubbles issue with increasing rapidity from the
mouth of the melting -point tube until they from a continuous stream. At this
point, heating is stopped and the bath is allowed to cool. The temperature at
which the bubbles cease and the liquid starts to suck back into the tube is
talcen as being the boiling point of the sample.

Although not as accurate as the distillation method, the Siwoloboff technique

gives a good enough approximation for most laboratory purposes.

10.11 SUMMARY
In this unit, you have learnt

the definition of the term boiling point.

the differences between miscible, partly miscible and immiscible liquids.
the relationship between vapour pressure and boiling point curves for
ideal liquid and liquid mixtures.
I
bihmlary Techniques 11 about the changes in the composition of liquid and vapour during
distillation using vapour pressure diagrams (non-azeotropic systems).
drawing and labeling the component parts of an apparatus far simple
distillation.
assembling and use, with relevant safety precautions of a simple
distillation apparatus for separation of a binary mixture.
the process of fractional distillation. .
about a range of laboratory fractionation columns and their relative
merits.
assembling and use of fractional distillation apparatus with relevant
safety precautions for isolating a product from a reaction mixture.
that the products of fractional distillation are not necessarily the pure
components.
to use both simple distillation and a small-scale method for the
determination of boiling point.

10.12 TERMINAL QUESTIONS

1. Which of the following is the correct definition of the boiling point of a
liquid? Tick the correct answer.

(i) The temperature at which pn equilibrium is set up

between the molecules in the liquid phase and the molecules in the
vapour phase. •
(ii) The temperature at which the vapour pressure above the liquid
equals the external pressus. 0
(iii) The temperature at which the pressure exerted by the vapour above a
liquid just exceeds that for an equal amount of water. 0

2. A solution contains 5.8 g of propanone (CH3COCH3)and 9.0 g of water.

Which of the answers given below states the mole fraction of propanone
in the solution? (Take relative atomic masses to be H = 1, C = 12 and
0 = 16). Tick the correct answer.
(ii) 0.8333
(i) 0.100
(iii) 0.1667 (iv) None of these

3. If a mixture contains two liquid components of differing volatility, then

the vapour would be richer in

(i) the more volatile component; 0

(ii) the less volafile component; or
(iii) neither as their mole fractions will be equal in the
vapo& phase irrespective of their initial compositions '

Tick the correct answer from ;he above choices.

4. Do you think that the glass packing in a fractionating column

is esseptial to

(i) increase the surface area of the colump; •

 Distillation and Boiling
(ii) reduce the distillation rate so that a better separation is
Point Determination
achieved; or
(iii) stop the liquid in the flask bumping.

Tick the correct answer from the above choices.

19.13 ANSWERS
Self Asseskment questions

1. The accepted international unit of pressure is the Newton metre-', so

your answer should be (iii). All other units given do in fact measure
pressure, but they are not part of the Systeme International d' Unites
(SI).

2, The only one of these three liquids suitable for steam distillation is
chlorobenzene (i). Not only is it immiscible with water, but it also has a
,

higher boiling point than water. If your answer was incorrect, then you
need to revise Sec. 10.3.

3. An ideal solution is the one where the total vapour pressure is obtained
by adding together the individual vapour pressures of the two
components at each temperature. So the correct definition was (ii).
Revise Sec. 10.4 if your answer was incorrect.

4. The only statement which is true is (ii). At this point, the mixture will
, distil without any change in composition. If you did not select (ii) as
your answer, you must revise Sec.lO.8.

Terminal Questions

1. (ii) is the correct answer. If you had a different answer, revise Sec. 10.2.

2. (iii). The mole fraction of propanone in the solution is 0.1667. the

relative molecular mass of propanone is 58 and of water is 18. Therefore
the numbel of moles are, respectively,

Thus, themole fraction of propanone is

0.1 - -''I - - 0.1667

0.1+0.5 0.6

3. The vapour would be richer in the more volatile component. If you did
not get (i) as your answer, revise Sec. 10.4 where the early discussion
states the relationship between component volatility and vapour phase
composition.'

4. (i). The glass packaging servis to increase the column's surface area (i).
It ensures good contact between ascending vapour and descending liquid.