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We'll start with the boiling points of pure A and B.

B has the higher vapour pressure. That means that it will have the lower
boiling point. If that isn't obvious to you, go back and read the last
section again!

For mixtures of A and B, you might perhaps have expected that their
boiling points would form a straight line joining the two points we've
already got. Not so!

In fact, it turns out to be a curve.

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 Important: Take great care drawing this curve. The boiling point of B is the
lowest boiling point. Don't let your curve droop below this. That happens with
certain non-ideal mixtures and has consequences which are explored on
another page.

To make this diagram really useful (and finally get to the phase diagram
we've been heading towards), we are going to add another line. This
second line will show the composition of the vapour over the top of any
particular boiling liquid.

If you boil a liquid mixture, you would expect to find that the more volatile
substance escapes to form a vapour more easily than the less volatile
one.

That means that in the case we've been talking about, you would expect
to find a higher proportion of B (the more volatile component) in the
vapour than in the liquid. You can discover this composition by
condensing the vapour and analysing it. That would give you a point on
the diagram.

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The diagram just shows what happens if you boil a particular mixture of
A and B. Notice that the vapour over the top of the boiling liquid has a
composition which is much richer in B - the more volatile component.

If you repeat this exercise with liquid mixtures of lots of different

compositions, you can plot a second curve - a vapour composition line.

This is now our final phase diagram.

Important: Once again, take great care drawing this second curve. No point on

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 the curve must be higher than the boiling temperature of the pure A.

Using the phase diagram

The diagram is used in exactly the same way as it was built up. If you
boil a liquid mixture, you can find out the temperature it boils at, and the
composition of the vapour over the boiling liquid.

For example, in the next diagram, if you boil a liquid mixture C1, it will
boil at a temperature T1 and the vapour over the top of the boiling liquid
will have the composition C2.

All you have to do is to use the liquid composition curve to find the
boiling point of the liquid, and then look at what the vapour composition
would be at that temperature.

Notice again that the vapour is much richer in the more volatile
component B than the original liquid mixture was.

The beginnings of fractional distillation

Suppose that you collected and condensed the vapour over the top of
the boiling liquid and reboiled it.

You would now be boiling a new liquid which had a composition C2.

That would boil at a new temperature T2, and the vapour over the top of

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it would have a composition C3.

You can see that we now have a vapour which is getting quite close to
being pure B. If you keep on doing this (condensing the vapour, and
then reboiling the liquid produced) you will eventually get pure B.

This is obvious the basis for fractional distillation. However, doing it like
this would be incredibly tedious, and unless you could arrange to
produce and condense huge amounts of vapour over the top of the
boiling liquid, the amount of B which you would get at the end would be
very small.

Real fractionating columns (whether in the lab or in industry) automate

this condensing and reboiling process. How these work will be explored
on another page (see below).

FRACTIONAL DISTILLATION OF IDEAL MIXTURES OF LIQUIDS

Using the phase diagram

On the last page, we looked at how the phase diagram for an ideal
mixture of two liquids was built up. I want to start by looking again at

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material from the last part of that page.

The next diagram is new - a modified version of diagrams from the

previous page.

If you boil a liquid mixture C1, you will get a vapour with composition
C2, which you can condense to give a liquid of that same
composition (the pale blue lines).

If you reboil that liquid C2, it will give a vapour with composition C3.
Again you can condense that to give a liquid of the same new
composition (the red lines).

Reboiling the liquid C3 will give a vapour still richer in the more
volatile component B (the green lines). You can see that if you were
to do this once or twice more, you would be able to collect a liquid
which was virtually pure B.

The secret of getting the more volatile component from a mixture of

liquids is obviously to do a succession of boiling-condensing-
reboiling operations.

It isn't quite so obvious how you get a sample of pure A out of this.
That will become clearer in a while.

Fractional distillation in the lab

The apparatus

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A typical lab fractional distillation would look like this:

Some notes on the apparatus

The fractionating column is packed with glass beads (or something

similar) to give the maximum possible surface area for vapour to
condense on. You will see why this is important in a minute. Some
fractionating columns have spikes of glass sticking out from the sides
which serve the same purpose.

If you sketch this, make sure that you don't completely seal the
apparatus. There has to be a vent in the system otherwise the
pressure build-up when you heat it will blow the apparatus apart.

In some cases, where you are collecting a liquid with a very low
boiling point, you may need to surround the collecting flask with a
beaker of cold water or ice.

The mixture is heated at such a rate that the thermometer is at the

temperature of the boiling point of the more volatile component.
Notice that the thermometer bulb is placed exactly at the outlet from

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the fractionating column.

Relating what happens in the fractionating column to the phase

diagram

Suppose you boil a mixture with composition C1.

The vapour over the top of the boiling liquid will be richer in the more
volatile component, and will have the composition C2.

That vapour now starts to travel up the fractionating column.

Eventually it will reach a height in the column where the temperature
is low enough that it will condense to give a liquid. The composition
of that liquid will, of course, still be C2.

Note: As you will see shortly, that is an oversimplification because "our"

vapour will become mixed with other vapours generated by various other
reboilings happening in the column. I can't see any way around this
simplification!

So what happens to that liquid now? It will start to trickle down the
column where it will meet new hot vapour rising. That will cause the
already condensed vapour to reboil.

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Some of the liquid of composition C2 will boil to give a vapour of
composition C3. Let's concentrate first on that new vapour and think
about the unvaporised part of the liquid afterwards.

The vapour

This new vapour will again move further up the fractionating column
until it gets to a temperature where it can condense. Then the whole
process repeats itself.

Each time the vapour condenses to a liquid, this liquid will start to
trickle back down the column where it will be reboiled by up-coming
hot vapour. Each time this happens the new vapour will be richer in
the more volatile component.

The aim is to balance the temperature of the column so that by the

time vapour reaches the top after huge numbers of condensing and
reboiling operations, it consists only of the more volatile component -
in this case, B.

Whether or not this is possible depends on the difference between

the boiling points of the two liquids. The closer they are together, the
longer the column has to be.

The liquid

So what about the liquid left behind at each reboiling? Obviously, if

the vapour is richer in the more volatile component, the liquid left
behind must be getting richer in the other one.

As the condensed liquid trickles down the column constantly being

reboiled by up-coming vapour, each reboiling makes it richer and

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richer in the less volatile component - in this case, A. By the time the
liquid drips back into the flask, it will be very rich in A indeed.

So, over time, as B passes out of the top of the column into the
condenser, the liquid in the flask will become richer in A. If you are
very, very careful over temperature control, eventually you will have
separated the mixture into B in the collecting flask and A in the
original flask.

Finally, what is the point of the packing in the column?

To make the boiling-condensing-reboiling process as effective as

possible, it has to happen over and over again. By having a lot of
surface area inside the column, you aim to have the maximum
possible contact between the liquid trickling down and the hot vapour
rising.

If you didn't have the packing, the liquid would all be on the sides of
the condenser, while most of the vapour would be going up the
middle and never come into contact with it.

Fractional distillation industrially

There is no difference whatsoever in the theory involved. All that is

different is what the fractionating column looks like. The diagram
shows a simplified cross-section through a small part of a typical
column.

The column contains a number of trays that the liquid collects on as

the vapour condenses. The up-coming hot vapour is forced through
the liquid on the trays by passing through a number of bubble caps.

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This produces the maximum possible contact between the vapour
and liquid. This all makes the boiling-condensing-reboiling process
as efficient as possible.

The overflow pipes are simply a controlled way of letting liquid trickle
down the column.

If you have a mixture of lots of liquids to separate (such as in

petroleum fractionation), it is possible to tap off the liquids from some
of the trays rather than just collecting what comes out of the top of
the column. That leads to simpler mixtures such as gasoline,
kerosene and so on.

Note: At the moment, I don't have any intention to write specifically about
petroleum (crude oil) distillation. If you do a Google search, you will
already find far more than you could possibly read if you spent the whole
of the next week at it!

NON-IDEAL MIXTURES OF LIQUIDS

This page looks at the phase diagrams for non-ideal mixtures of

liquids, and introduces the idea of an azeotropic mixture (also known
as an azeotrope or constant boiling mixture). It goes on to explain how
this complicates the process of fractionally distilling such a mixture.

This is the final page in a sequence of three pages.

Important: If you have come straight to this page from a search engine, you
won't make much sense of it unless you first read the previous two pages in the
sequence starting with the one about phase diagrams for ideal mixtures.

You will find a link at the bottom of each page which will eventually bring you
back here again.

Vapour pressure / composition diagrams for non-ideal

mixtures

You will remember that, because of Raoult's Law, if you plot the
vapour pressure of an ideal mixture of two liquids against their
composition, you get a straight line graph like this:

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In this case, pure A has the higher vapour pressure and so is the more
volatile component.

Note: In the previous pages in this series, the diagrams were drawn with B
being the more volatile. If this change worries you, then you haven't really
understood the bit about vapour pressure / composition diagrams on the page
about phase diagrams for ideal mixtures.

It is essential that you are happy with these diagrams whichever way they are
drawn. It is really dangerous to get used to always drawing them one way
around. You may meet them with all sorts of variations, and so you must
understand what is going on.

I've made the change on this page partly to make the two main examples
slightly more logical, but also so that you can find out whether this does bother
you and then do something to sort it out!

Raoult's Law only works for ideal mixtures. In these, the forces
between the particles in the mixture are exactly the same as those in
the pure liquids. The tendency for the particles to escape is the same
in the mixture and in the pure liquids.

That's not true in non-ideal mixtures.

Positive deviations from Raoult's Law

In mixtures showing a positive deviation from Raoult's Law, the vapour

pressure of the mixture is always higher than you would expect from

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an ideal mixture.

The deviation can be small - in which case, the straight line in the last
graph turns into a slight curve.

Notice that the highest vapour pressure anywhere is still the vapour
pressure of pure A. Cases like this, where the deviation is small,
behave just like ideal mixtures as far as distillation is concerned, and
we don't need to say anything more about them.

But some liquid mixtures have very large positive deviations from
Raoult's Law, and in these cases, the curve becomes very distorted.

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Notice that mixtures over a range of compositions have higher vapour
pressures than either pure liquid. The maximum vapour pressure is no
longer that of one of the pure liquids. This has important
consequences when we look at boiling points and distillation further
down the page.

Explaining the deviations

The fact that the vapour pressure is higher than ideal in these
mixtures means that molecules are breaking away more easily than
they do in the pure liquids.

That is because the intermolecular forces between molecules of A and

B are less than they are in the pure liquids.

You can see this when you mix the liquids. Less heat is evolved when
the new attractions are set up than was absorbed to break the original
ones. Heat will therefore be absorbed when the liquids mix. The
enthalpy change of mixing is endothermic.

The classic example of a mixture of this kind is ethanol and water.

This produces a highly distorted curve with a maximum vapour
pressure for a mixture containing 95.6% of ethanol by mass.

Note: After 40-odd years of involvement with chemistry at this level, I've just
noticed for the first time that when we start talking about this we suddenly
switch the description for the composition from "mole fractions" to "percentage
by mass". How very silly! A fairly simple sum will show you that 95.6% ethanol
by mass is equivalent to a mole fraction of 0.895.

For simplicity, and to be consistent with what other sources tend to do, I shall
relabel my composition axis as "percentage by mass" when I start drawing
boiling point / composition diagrams further down this page. It won't affect the
argument in any way, but will keep my numbers consistent with those you may
have from elsewhere.

Negative deviations from Raoult's Law

In exactly the same way, you can have mixtures with vapour
pressures which are less than would be expected by Raoult's Law. In
some cases, the deviations are small, but in others they are much
greater giving a minimum value for vapour pressure lower than that of
either pure component.

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Explaining the deviations

These are cases where the molecules break away from the mixture
less easily than they do from the pure liquids. New stronger forces
must exist in the mixture than in the original liquids.

You can recognise this happening because heat is evolved when you
mix the liquids - more heat is given out when the new stronger bonds
are made than was used in breaking the original weaker ones.

Many (although not all) examples of this involve actual reaction

between the two liquids. The example of a major negative deviation
that we are going to look at is a mixture of nitric acid and water. These
two covalent molecules react to give hydroxonium ions and nitrate
ions.

You now have strong ionic attractions involved.

Boiling point / composition diagrams for non-ideal

mixtures

A large positive deviation from Raoult's Law: ethanol and water

mixtures

If you look back up the page, you will remember that a large positive
deviation from Raoult's Law produces a vapour pressure curve with a
maximum value at some composition other than pure A or B.

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If a mixture has a high vapour pressure it means that it will have a low
boiling point. The molecules are escaping easily and you won't have
to heat the mixture much to overcome the intermolecular attractions
completely.

The implication of this is that the boiling point / composition curve will
have a minimum value lower than the boiling points of either A or B.

In the case of mixtures of ethanol and water, this minimum occurs with
95.6% by mass of ethanol in the mixture. The boiling point of this
mixture is 78.2°C, compared with the boiling point of pure ethanol at
78.5°C, and water at 100°C.

You might think that this 0.3°C doesn't matter much, but it has huge
implications for the separation of ethanol / water mixtures.

The next diagram shows the boiling point / composition curve for
ethanol / water mixtures. I've also included on the same diagram a
vapour composition curve in exactly the same way as we looked at on
the previous pages about phase diagrams for ideal mixtures.

Note: This diagram is drawn grossly distorted. Look, for example, at the
temperature scale and the position of the 95.6% value on the composition
scale. The shapes of the two separate areas between the curves are also
exaggerated. This is to make it easier to see what is going on in what comes
next. It doesn't affect the argument in any way.

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Using the diagram

Suppose you are going to distil a mixture of ethanol and water with
composition C1 as shown on the next diagram. It will boil at a
temperature given by the liquid curve and produce a vapour with
composition C2.

When that vapour condenses it will, of course, still have the

composition C2. If you reboil that, it will produce a new vapour with
composition C3.

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You can see that if you carried on with this boiling-condensing-
reboiling sequence, you would eventually end up with a vapour with a
composition of 95.6% ethanol. If you condense that you obviously get
a liquid with 95.6% ethanol.

What happens if you reboil that liquid?

The liquid curve and the vapour curve meet at that point. The vapour
produced will have that same composition of 95.6% ethanol. If you
condense it again, it will still have that same composition.

You have hit a barrier. It is impossible to get pure ethanol by distiling

any mixture of ethanol and water containing less than 95.6% of
ethanoll.

This particular mixture of ethanol and water boils as if it were a pure

liquid. It has a constant boiling point, and the vapour composition is
exactly the same as the liquid.

It is known as a constant boiling mixture or an azeotropic mixture

or an azeotrope.

The implications of this for fractional distillation of dilute solutions of

ethanol are obvious. The liquid collected by condensing the vapour
from the top of the fractionating column can't be pure ethanol. The
best you can produce by simple fractional distillation is 95.6% ethanol.

What you can get (although it isn't very useful!) from the mixture is

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pure water. As ethanol rich vapour is given off from the liquid boiling in
the distillation flask, it will eventually lose all the ethanol to leave just
water.

To summarise:

Distilling a mixture of ethanol containing less than 95.6% of ethanol by

mass lets you collect:

 a distillate containing 95.6% of ethanol in the collecting flask

(provided you are careful with the temperature control, and the
fractionating column is long enough);
 pure water in the boiling flask.

What if you distil a mixture containing more than 95.6% ethanol?

Work it out for yourself using the phase diagram, and starting with a
composition to the right of the azeotropic mixture. You should find that
you get:

 a distillate containing 95.6% of ethanol in the collecting flask

(provided you are careful with the temperature control, and the
fractionating column is long enough);
 pure ethanol in the boiling flask.

A large negative deviation from Raoult's Law: nitric acid and

water mixtures

Nitric acid and water form mixtures in which particles break away to
form the vapour with much more difficulty than in either of the pure
liquids. You can see this from the vapour pressure / composition curve
discussed further up the page.

That means that mixtures of nitric acid and water can have boiling
points higher than either of the pure liquids because it needs extra
heat to break the stronger attractions in the mixture.

In the case of mixtures of nitric acid and water, there is a maximum

boiling point of 120.5°C when the mixture contains 68% by mass of
nitric acid. That compares with the boiling point of pure nitric acid at
86°C, and water at 100°C.

Notice the much bigger difference this time due to the presence of the
new ionic interactions (see above).

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 Note: Various sources quote the boiling point of pure nitric acid as 83, 84 or
86°C. I have no idea which of these is right! My choice of 86°C is entirely
arbitrary. It doesn't affect any of the arguments in what follows.

The phase diagram looks like this:

Warning: This is one case where you really do have to look at the scale being
used for the composition. In mole fraction terms, 68% by mass of nitric acid
corresponds to a mole fraction of only 0.378. The whole balance of the diagram
will look different if you use the alternative scale.

Using the diagram

Distilling dilute nitric acid

Start with a dilute solution of nitric acid with a composition of C1 and

trace through what happens.

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The vapour produced is richer in water than the original acid. If you
condense the vapour and reboil it, the new vapour is even richer in
water. Fractional distillation of dilute nitric acid will enable you to
collect pure water from the top of the fractionating column.

As the acid loses water, it becomes more concentrated. Its

concentration gradually increases until it gets to 68% by mass of nitric
acid. At that point, the vapour produced has exactly the same
concentration as the liquid, because the two curves meet.

You produce a constant boiling mixture (or azeotropic mixture or

azeotrope). If you distil dilute nitric acid, that's what you will eventually
be left with in the distillation flask. You can't produce pure nitric acid
from the dilute acid by distilling it.

Distilling nitric acid more concentrated than 68% by mass

This time you are starting with a concentration C2 to the right of the
azeotropic mixture.

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The vapour formed is richer in nitric acid. If you condense and reboil
this, you will get a still richer vapour. If you continue to do this all the
way up the fractionating column, you can get pure nitric acid out of the
top.

As far as the liquid in the distillation flask is concerned, it is gradually

losing nitric acid. Its concentration drifts down towards the azeotropic
composition. Once it reaches that, there can't be any further change,
because it then boils to give a vapour with the same composition as
the liquid.

Distilling a nitric acid / water mixture containing more than 68% by

mass of nitric acid gives you pure nitric acid from the top of the
fractionating column and the azeotropic mixture left in the distillation
flask.

Where would you like to go now?

To the phase equilibrium menu . . .

To the Physical Chemistry menu . . .

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© Jim Clark 2005

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