Raoult’s Law and Liquid / Liquid Separation

C.A.P.E Chemistry U2M2

Introduction

This section focuses with liquid / liquid separation, when two miscible liquids dissolve in
one another and it is possible to separate them using distillation.

Key terms

Vapour pressure

Boiling Point
The constant temperature at which a liquid is converted into gas
The temperature where the vapour pressure = external pressure
The boiling point decreases as the vapor pressure increases.

Volatility
In chemistry, the word "volatile" refers to a substance that vaporizes readily. Volatility is a
measure of how readily a substance vaporizes or transitions from a liquid phase to a gas phase.

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More volatile substances quickly goes into the vapor state.

A more volatile substance has a high vapor pressure at a given temperature compared
with another substance that is less volatile compound.

Distillation

It is a method for separating mixtures, using the differing volatilities of the components.
Mixtures are heated until the more volatile components turn into gases, which can be
condensed and collected elsewhere.

Simple Distillation

 Can be used to separate liquid or solid product with b.p @ about 250 OC
 The mixture is heated
 The lower b.p. vapor liquifies in the condenser and is collected. (This is called the
distillate)
 Components with higher b.p. will condense in the cooler parts of the flask and not
reach the condenser.
 This method is used if the components in the mixture have b.p. that are far apart.

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Fractional Distillation

Useful links:

https://www.nagwa.com/en/videos/747190737265/

https://www.youtube.com/watch?v=kuD9qV9ifQ0

 Used to separate miscible liquid mixtures with components that have a narrow
range of b.p. and to obtain relatively pure fractions of each component in the
mixture.
 We can say that fractional distillation is used to separate miscible liquids that
vary slightly in volatility by repeated cycles of evaporation and condensation.

 A glass column is used which is filled with glass beads.

 The glass beads provide extra surface area for the condensation–evaporation
cycles to occur on.

 The ascending vapor in the column comes into contact with descending liquid and
separation occurs through successive liquid-vapor equilibria

 As the column is ascended the composition of the vapour becomes richer and
richer in the more volatile component.

 The longer the column and slower the heating, the better the separation and purer
the distillate.

 The tip of the thermometer should be just in front of the opening to the condenser.
This means that the temperature reading will be an accurate reflection of the
temperature of the vapor just before it goes into the condenser (and not of the
distilling flask or the fractionating column, which may be a little hotter).

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Raoult’s Law

So for a mixture containing A and B

PA = (PAo) (X A)

where PA = partial vapor pressure of A

PAo = vapor pressure of pure A at that temperature
X A = mole fraction of A in the mixture (liquid phase)

n
X A (mole fraction) = na / na + b
where n is the number of moles of A and B respectively.

For gases the mole fraction can also be expressed in terms Pressure

X A (mole fraction) = PA / PA + PB

Where P is the pressure of the respective components.

A mixture is an ideal solution if it obeys Raoult’s Law.

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Mixtures that follow Raoult’s Law are called zeotropic.

Example

Ideal Solutions
 Ideal solution Obeys Raoult’s Law and are called zeotropes

 In an ideal solution, it is assumed, the intermolecular forces A-A , B-B and A-B is
the same.
 In an ideal solution, it is assumed there is no enthalpy or volume change upon
mixing.
 The example of mixtures mentioned above, have close to ideal behavior, because
the particles have similar size and thus similar van der waal forces.

Vapor Pressure- Composition Diagrams & Boiling point – Composition Diagrams

Lets firstly look at vapour pressure – composition diagrams.

Remember! For a mixture: Vapour pressure and boiling point are inversely related
High- vapour pressure, low b.p. and volatile
Low- vapour pressure, high b.p and not ver volatile.

These are graphs of vapour pressure vs mole fraction for components in the mixture.
For ideal mixtures, vapor pressure- composition diagrams are represented by straight
lines.

Lets examine a vapor-composition diagram for a mixture with components A and B

For A – as the mole fraction of A increases so to does vapor pressure of A

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For B the mole fraction axis is reversed.

To get the total vapor pressure of the mixture, it will be the combine vapor pressure of A
and B. This is seen in the blue line in the diagram below.

 Red line- partial pressure of

A
 Green line- partial pressure
of B
 Blue line – total vapor
pressure of the mixture.

Boiling point Composition Curve

The higher the vapor pressure the lower the boiling point of the liquid and the easier for
the molecules to escape from the liquid phase into the gaseous phase.

More volatile liquids have high vapor pressure and lower b.p.

Boiling point Composition Curves can also be used to show composition of A and B in a
mixture.

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B is the more volatile

component, hence the b.p is
lower

At any temperature in the

vapor, there will be more of B
because it has a lower b.p and
is more volatile.

The diagram above shows a boiling point – composition graph for an ideal mixture.

Boiling Point- Composition Diagram for an Ideal Mixture

Non- Ideal Mixtures

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Non-ideal mixtures can have positive or negative deviation from raoult’s law.

Aezotropic mixtures are those compositions that are widely deviate from raoult’s law and
can’t be separated by fractional distillation.

An azeotrope is a mixture of two or more liquids which displays a constant composition in the liquid
and vapour phase for all temperatures.

They are termed as constant boiling mixtures as their composition remains unchanged by distillation.

Positive Deviation

In a mixture of components A and B, the A-B interaction is weaker than A-A or B-B
interaction, as a result it is easier for the molecules to escape the mixture. Such mixtures
shows positive deviation, has a maxium vapor pressure and a minimum b.p. than any
composition and either of the pure liquids.
Example of such a mixture is ethanol and hexane.
This type of mixture is called a minimum b.p azeotrope.

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. This is seen @ X2

@ X2 – there is liquid only

and is labeled azeotrope.

The diagram above shows the boiling point composition curve for a minimum boiling
point azeotrope.

In the case of a non-ideal mixture of ethanol and water,

this minimum (azeotrope) occurs with 95.6% by mass of
ethanol in the mixture and 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.

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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 ethanol. So the distillate collected will
have a 95.6 % ethanol and not 100%.

 It is known as a constant boiling mixture or

an azeotropic mixture or an azeotrope.
 Enthalpy of mixing these liquids is endothermic.

Important: In distilling a mixture that shows a positive

deviation from Raoult’s Law, the azeotrope will be collected
as the distillate, and either liquid that was in excess will be
left back.

What happens if you reboil that liquid? The liquid curve and the vapor curve meet at that point. The vapor
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 distilling any mixture of
ethanol and water containing less than 95.6% of ethanol. This particular mixture of ethanol and water boils
as if it were a pure liquid. It has a constant boiling point, and the vapor composition is exactly the same as
the liquid. It is known as a constant boiling mixture or an azeotropic mixture or an azeotrope.

To Summarize
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?

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 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.

Example : A
and B forms an azeotrope of composition 75% A. the B.P.
of A is 760C and the boiling point of B is 1010C. The B.P. of the
azeotrope is 700C. Determine what will be collected as the
distillate and what will be left back in the flask after distilling a
mixture of composition:
 50% A
 85% A

Answer
Azeotrope composition – 75 % A & 25 % B
Initial Mixture Composition -50% A means also 50 % B

 There is an excess of B (azeotrope contains 25% B).

 Distillate – azeotrope
 Left back – B

Initial Mixture Composition 85% A means also 15 % of B in the initial distilling mixture
 There is an excess of A (azeotrope contains 75% A).
 Distillate – azeotrope
 Left back – A

Negative Deviation from Raoult’s Law

In another mixture of components A and B, the A-B interaction is greater than A-A or
B-B interaction, as a result it is more difficult for the molecules to escape mixture. Such
mixtures shows negative deviation, has a minimum vapor pressure and a maximium b.p.
than any composition and either of the pure liquids.
Examples are trichloromethane and ethyl ethanoate.

This type of mixture is called a maximum b.p azeotrope.

Important Notes About Negative Deviation

 The vapour pressure of the mixture is lower and the b.p is higher that than predicted
by Raoult’s Law.
 This occur when the forces of attraction between the molecules in the mixture is
stronger than the forces of attraction between the molecules in either of the pure
liquids.
 As a results the molecules escape the surface of the liquid less readily.
 Enthalpy of mixing these liquids is exothermic.

Example

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.

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 In distilling a mixture that shows a negative deviation from Raoult’s Law, the
azeotrope will be left back in the flask, and either liquid that was in excess will be
the distillate.

 Example: A and B forms an azeotrope of composition 75% A. the B.P. of A is 760C

and the boiling point of B is 1010C. The B.P. of the azeotrope is 1170C. Determine
what will be collected as the distillate and what will be left back in the flask after
distilling a mixture of composition:
 50% A
 85% A

Answer

Azeotrope composition – 75 % A & 25 % B

 50% A means also 50 % B in initial distilling mixture

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 There is an excess of B (azeotrope contains 25% B).

 Distillate – B
 Left back – Azeotrope

Azeotrope composition – 75 % A & 25 % B

 85% A means also 15 % B in initial distilling mixture

 There is an excess of A (azeotrope contains 75% A).
 Distillate – A
 Left back – Azeotrope

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