Module 2: Phase Separation February 2019

Prepared by Miss Kong Grade 13

Topic: Phase Separation

 The concept of phase separation is associated with how different types of mixtures can be separated.

 Most of these separation techniques involve a change of state, i.e. melting, subliming, evaporating or
dissolving.

 Mixtures are IMPURE substances that often needs to be separated in order to obtain its PURE substances.

 Separation techniques include:

 _______________________  _______________________

 _______________________  _______________________

 _______________________  _______________________

 The separation technique chosen depends on the differences in the physical and the chemical properties of
the components of the mixtures.

Distillation

 Distillation is based on the ________________________ of the components of the mixture.

 Separation of components depends on the differences in boiling points of the individual components and
the vapour pressure characteristics of liquid mixtures.

Volatility describes how easily a substance will vaporize (turn into a gas or vapor).

1. Simple Distillation

 Used to separate:

 Liquid solutions of substances with widely differing boiling points (more than 25◦C difference). Here,
each component is obtained.

 Liquids from involatile solids and oils. Here, the solvent rather than the solute is collected.

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 When the solution in the flask boils, pure vapour rises
upwards and enters the inner tube of the Liebig condenser.
 The outer jacket of the condenser contains cool, running water
that cools the pure vapours in the inner tube and allows it to
condense.
 This condensed liquid (the distillate) is collected at the end of
the Liebig condenser.

2. Fractional Distillation

 Used to separate miscible liquids

 where the components of the mixture have boiling points that are close together (usually less than
25◦C from each other),

or

 where the components are chemically similar (Eg. Water and ethanol).

 Similar to simple distillation except that a fractionating column is added between the flask and the condenser.

 The fractionating column is a vertical tube packed with inert fragments that provide a large cool surface for
the vapours to cool, condense and vaporize again. Eg. Glass beads.

 Once in equilibrium the column is hotter at the base than

the top, so there is a temperature gradient along the
column.

 When the mixture boils, vapour travel up the

fractionating column and condense.

 At any point in the column the vapour, and hence the

condensing liquid, is richer in the more volatile
component than was the case lower down.

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 Most of the condensing liquid runs back down the column.

 If the column is LONG enough, only the most volatile component of the mixture is
at the top.

Raoult’s Law

 Raoult found that provided that the intermolecular forces between unlike molecules are no different from
those between like molecules, the total vapour pressure of the mixture at any temperature is equal to the sum
of the vapour pressures of each component at that temperature, each one multiplied by its mole fraction in the
mixture.

 For a pure liquid in a closed container, at any given temperature, liquid particles
continually enter the vapour phase because they travel to the surface with enough
kinetic energy to escape from the attractive forces of other molecules in that surface.

 Likewise, vapour particles heading for the surface are recaptured by it and re-
enter the liquid.

 Equilibrium is reached when the concentration of molecules is high enough that the
rate at which they re-enter the liquid is equal to the rate at which they are
replenished from the liquid.

liquid ⇌ vapour

 The equilibrium vapour is said to be saturated and the vapour is the saturated vapour pressure of the liquid
at that temperature.

 If two miscible liquids (A and B) are mixed and have reached equilibrium, the vapour pressure of the mixture
obeys Raoult’s law.

 The partial pressure (or saturated vapour pressure) of component A (PA) in the solution equals the partial
pressure of pure A (PAo) times its mole fraction (xA).

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 The mole fraction of A is

n
 From the expression, xA= n +n , when xA= 1, liquid A is pure and the vapour pressure is entirely due to liquid

A.

 For gases, pressure is proportional P to the number of moles n, therefore the mole fraction is can be expressed
in terms of pressure:

𝑃
xA=
𝑃 +𝑃

 A straight line passing through the origin is obtained in a graph of vapour pressure of each liquid component
against its mole fraction.

 Consider two liquids in a solution, A and B, have reached equilibrium:

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 The solution A and B obeys Raoult’s law and is described as an ideal solution.

 For an ideal solution, the intermolecular forces and interaction energies must be EQUAL so there is a
small energy change when the substances are mixed.

 However, no two solutions are the same; a true ideal solution DOES NOT exist.

 Since there is actually no such thing as an ideal solution, the vapour composition graph is NOT a straight line,
but instead a curve.

 Since there is actually no such thing as an ideal

solution, the vapour composition graph is not a
straight line, but instead a curve.

 It is also possible to measure boiling points

instead of vapour pressures.

 Therefore, boiling point composition curves

can be obtained.

 Vapour pressure is inversely proportional to boiling points. That is, the higher the vapour pressure, the
lower the boiling point.

Deviations from Ideal Behaviour: Non-Ideal Solutions

 Non-ideal solutions consists of mixtures where the intermolecular forces and interaction energies between
the components are DIFFERENT.

 These mixtures deviate from Raoult’s law; they either show a positive or negative deviation.

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 POSITIVE deviation from Raoult’s Law NEGATIVE deviation from Raoult’s Law
 There is a positive deviation if the vapour  There is a negative deviation from Raoult’s law if
pressure of a mixture is HIGHER than what is the vapour pressure of a mixture is LOWER
expected from an ideal mixture. than what is expected from an ideal mixture.
 The molecules in the mixture are more likely to  In this instance when the liquids are mixed, heat is
escape from the liquid to vapour. released and the total volume is less than that of
 Intermolecular attractions are reduced, hence each the individual components.
component vaporizes more easily.  This suggests that new stronger forces (such as
 If the positive deviation from ideal behavior is hydrogen bonds and ionic interactions) exists in
small, the vapour pressure looks like the previous the mixture than in the pure liquids.
curve.  As a consequence, each component is retained in
the liquid and so the vapour pressure of each
component is less than would be expected in the
ideal case.

Examples of mixture that deviate negatively from

Raoult’s law:
 Water and nitric acid
 Water and hydrochloric acid
 Acetone and chloroform
 Trichloromethane and propanone
 Trichloromethane and ethyl ethanoate

 However, if the deviation is LARGE, the vapour  LARGE negative deviations from ideal behaviour
pressure curve becomes very distorted; this give rise to a minimum in the vapour pressure
produces a maximum in the vapour pressure curve curve at a particular composition known as a
at a particular composition known as positive negative azeotrope.
azeotrope.

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 POSITIVE deviation from Raoult’s Law NEGATIVE deviation from Raoult’s Law

Vapour pressure composition curve; large positive Vapour pressure composition curve; large negative
deviation from Raoult’s law. The maximum vapour deviation from Raoult’s law. The minimum vapour
pressure is higher than that of either pure pressure is lower than that of either pure component.
components.
 Since vapour pressure is inversely proportional to  The mixture with a negative azeotrope (minimum
boiling point, the mixture with a positive azeotrope vapour pressure) will have a maximum boiling
(maximum vapour pressure) will have a minimum point azeotrope.
boiling point azeotrope.

Example: a mixture of ethanol and water. Example: A mixture of water and nitric acid
 The boiling point of this mixture is 78.2◦C.  The boiling point of the mixture is 120.5◦C.
 The boiling point of pure ethanol is 78.5 ◦C and  The boiling point of pure nitric acid is 86◦C and
100 ◦C for water. pure water is 100◦C.
 The 0.3 ◦C difference has huge implications  The maximum boiling point occurs at a
when separating the ethanol/water mixtures composition of 68% by mass of nitric acid.
via fractional distillation.  There is a large difference in boiling point of
 The minimum boiling point occurs at a 20.5◦C.
composition of 95.6% by mass of ethanol.

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 POSITIVE deviation from Raoult’s Law NEGATIVE deviation from Raoult’s Law

Boiling point composition curve of a maximum

Boiling point composition curve of a minimum
boiling point azeotrope. The maximum boiling point
boiling point azeotrope. The minimum boiling point
is higher than that of either pure component.
is lower than that of either pure component.

Fractional Distillation of Non-ideal Solutions

There may be fractional distillation of:

1. Mixtures with small deviations from Raoult’s law.

2. Mixtures with large, positive deviations from Raoult’s law; gives rise to positive azeotropes (those with
minimum boiling points).

3. Mixtures with large negative deviations from Raoult’s law; gives rise to negative azeotropes (those having
maximum boiling points).

Vacuum Distillation

 A distillation method carried out at reduced pressure, usually less than atmospheric pressure.

 The method is used to distill liquids that would decompose if distilled at atmospheric pressure.

 Method works on the basis that boiling occurs when the vapour pressure of a liquid just exceeds the
atmospheric pressure.

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 Reduced pressure results in lower boiling points, thereby
facilitating evaporation of liquids.

 This reduction in pressure also decreases the energy

requirement for both the heating and cooling processes;
vacuum distillation can be carried out with or without heating
the mixture.

Steam Distillation

 Steam distillation is also a method of distillation for temperature-sensitive substances.

 Generally used for organic compounds which tend to break down or decompose at high temperatures
before their boiling point is reached.

 The mixture of the impure organic substance and water is heated by steam.

 As the steam passes through the mixture, it releases heat which may be enough to boil the mixture provided
that the volume of the mixture is not too large.

 For LARGER VOLUMES, in order to increase the temperature of the mixture more quickly and maintain
its boiling point, it is better to apply gentle heat directly to the flask.

 The mixture of steam and the organic vapour distils out the flask and the condensate is collected.

 On standing, a two layer system of the water and the organic compound is obtained.

 The layers may be separated using a separating funnel and then adding a suitable drying agent to organic
compound to remove water.

 Steam distillation is also commonly used to extract essential oils from natural products.

 Eugenol from cloves  Oils used in perfumes from various

plant materials
 Eucalyptus oil from eucalyptus

 Citrus oils from lemon or orange peels

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Module 2: Phase Separation February 2019
Prepared by Miss Kong Grade 13

Solvent Extraction

 A technique used to separate compounds depending on their preferential solubilities in two different
immiscible liquids, usually water and an organic solvent.

 The process allows the extraction of a solute due to its unequal solubilities
in the two immiscible liquids.

 The solute is drawn out from one liquid, in which it is more soluble.

 Since the two liquids are immiscible, a separating funnel is used for
separation.

 Very often, the products of organic synthesis is dissolved in water.

 However, organic solutes are generally MORE soluble in organic

solvents, such as ether or trichloromethane; ether has the added
advantage that it has a low boiling point and can be distilled off
easily from the extracted solution and recycled.

 Since organic solvents are immiscible with water, they may be used
to extract the organic product from its aqueous solution via
solvent extraction.

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The steps are as followed:

1. The crude organic product in aqueous solution shaken up with a small quantity of organic solvent in
a separating funnel. Tap opened occasionally during shaking to release pressure caused by the solvent
vapours. Any solid impurities are filtered off.

2. The mixture is allowed to stand, which facilitates separation of the liquids into two distinct layers, which
can be run off separately. The organic layer, which is the layer containing the product is kept, and this is
called an extract.

3. Since small amounts of the crude organic product still remain in the aqueous layer, the shaking and
separation technique is repeated at least twice, each time using fresh solvent. All the product extracts
are combined. The extraction is more efficient if the solvent is used in successive small portions rather
than all at once.

4. The organic solvent may then be distilled off, leaving the pure solid. The organic solvent always contains
a small amount of water, which can be removed by drying it with an anhydrous ionic salt such as
magnesium sulfate. This drying process usually takes a few hours, after which time the ionic salt (which
is now partially hydrated) is filtered off.

5. The dried organic solute is recovered by distilling off the organic solvent.

 When a solute is shaken with a pair of immiscible liquids, the dissolved solute distributes itself between the
two liquids in dynamic equilibrium according to the partition law.
 This law states that the ratio of the concentrations of the solute in each of the solvents will be constant at
a given temperature, provided that the solute is in the same molecular state in both solvents and that
both solutions are dilute.
 For a system where solute X is distributed between two immiscible solvents, aqueous and organic, the
following equilibrium exists:

X(aquesous) ⇌ X(organic)

 The equilibrium constant, which is referred to as the partition coefficient,K, is equal to the concentration
of a solute in the organic phase divided by its concentration in the aqueous phase.

[X(organic)]
K = [X(aqueous)]

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 Past Paper Questions

2018

(i) State Raoult’s las as applied to mixtures of miscible liquids. [2 marks]

(ii) A mixture of ethanol and cyclohexane is said to show positive deviation from Raoult’s law. Explain
this phenomenon. [3 marks]
(iii) Draw a fully labelled boiling point-composition curve for a mixture of ethanol and cyclohexane which
forms an azeotrope at boiling point 64.5oC and a mole fraction of ethanol of 0.430. The boiling points
of ethanol and cyclohexane are 78oC and 81oC respectively. [5 marks]

2017

(b) Suggest a separating technique that would be MOST effective in the extraction of eugenol (oil) from
cloves (plant) in its natural source.
(c) Figure 1 shows a number of pieces of apparatus which could be found in a chemical laboratory.

Figure 1. Pieces of apparatus which could be found in a chemical laboratory

List the appropriate pieces of apparatus, using the corresponding letter from Figure 1, that could be used
in the following processes.
(i) Solvent extraction – THREE pieces [3 marks]

2016

(a) (i) State Raoult’s law for an ideal mixture of two liquids. [2 marks]
(ii) List TWO characteristics of an ideal solution. [2 marks]

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 (b) A and B are components of a liquid which forms an azeotropic mixture.
(i) Define the term ‘azeotropic mixture’. [1 mark]
(ii) State ONE reason why azeotropes are NOT compounds. [1 mark]
(iii) The following graph shows the composition of a minimum boiling point mixture.

Using the graph, explain clearly the result of distilling a mixture of Composition X as indicated.
[6 marks]
(c) An aqueous solution contains 2.5g of a compound in 50cm3 of solution. The partition coefficient of the
compound between water and an organic solvent is 0.200.
Calculate the mass of the compound extracted by shaking 100cm3 of aqueous solution with 25cm3 of the
solvent. [3 marks]

2013

(a) Define the term ‘partition coefficient’. [2 marks]

(b) When butanedioic acid was shaken with a mixture of water and ether, 10cm3 of water was found to contain
0.854g of the acid while a similar volume of ether contained 0.159g.
In a separate experiment, 10cm3 of water and 20cm3 of ether were shaken together with 1g of the acid.
Calculate the mass of the acid found in the aqueous layer. [4 marks]
(c) Suggest an appropriate method for separating the components of EACH of the following:
(i) Eucalyptus oil from an aqueous suspension of its leaves
(ii) Penicillin (organic solid) from an aqueous solution
(iii) Components of a coal tar residue
(iv) Ethoxyethane from an impure source [4 marks]

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 (d)

Use the boiling point – composition curve in Figure 6 to explain the principles of fractional distillation,
starting with a liquid of composition x. [5 marks]

2012

When a solute is shaken in a mixture of two immiscible solvents and allowed to stand, a dynamic equilibrium is
established in which the solute is partitioned or distributed between the two solvents.

(i) Write an equation to explain the term ‘partition coefficient’ or ‘distribution coefficient’ using the
example of an ester dissolved in a mixture of water and toluene. [1 mark]
(ii) State TWO factors which affect the value of the partition coefficient. [2 marks]
(iii) Explain the principles of solvent extraction with respect to the recovery of an organic compound from
an aqueous solution. [4 marks]
(iv) A solution of 10.0g of an ester, Y, in 100cm3 of water was shaken with 200cm3 of ether. After
separation. The aqueous solution was found to contain 1.6g of Y.

Calculate the partition coefficient of Y between ether and water. [3 marks]

END

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