Phase Separations

Liquid Separation- Non-ideal Mixtures

Positive Deviation from Raoult’s law
A-B interaction is weaker than the A-A or B-B interactions.

As a result, the A-B molecules escape from the mixture more

easily than for an ideal solution.

Such a mixture shows a positive deviation from Raoult’s law

(e.g. water and ethanol).

The positive deviation is great enough for there to be a

maximum vapour pressure at a particular mixture.
 Liquid Separation- Non-ideal Mixtures
Positive Deviation from Raoult’s law
• This vapour pressure is
greater than any other
composition and either of
Boiling
temperature the pure liquids.
• The same mixture will
have a minimum boiling
point lower than any
other composition and
either of the pure liquids
Vapour
Pressure
• Such a mixture is called
the minimum boiling
point azeotrope
 Liquid Separation- Non-ideal Mixtures
In the case of mixtures of ethanol and
water, this minimum boiling point 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°Cfrom
Raoult’s law
100% ethanol
never
attained
 Liquid Separation- Non-ideal Mixtures
Negative Deviation from Raoult’s law
• In other mixtures, the A-B interaction is greater
than the A-A and B-B interactions, therefore, it
is more difficult for the molecules to escape
from the mixture than for an ideal mixture.

• This is a negative deviation from Raoult’s Law

• There is a minimum vapour pressure which is

less than any other composition and either of
the pure liquids
 Liquid Separation- Non-ideal Mixtures
Negative Deviation from Raoult’s law
• This vapour pressure is
lower than any other
composition and either of
Boiling
the pure liquids.
temperature • The same mixture will
have a maximum boiling
point higher than any
other composition and
either of the pure liquids

Vapour • Such a mixture is called

pressure the maximum boiling
point azeotrope
Liquid Separation- Non-ideal Mixtures
• 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.
In this instance,
the pure nitric
acid can not be
obtained since
the initial
mixture was
below 60%
 Pure nitric acid
can be obtained

In this instance, it is important to determine what side of If it is to the right, then

the azeotrope the mixture is. the pure nitric acid can
be obtained
 Vacuum Distillation
• Simple distillation at reduced pressures (below one
atmosphere).

• Reduced pressure results in lower boiling points.

• Many compounds can not be distilled at atmospheric

pressure because their boiling points are too high or they
decompose before reaching their normal boiling points.

• Some of these substances can be distilled under reduced

pressure because their boiling temperature can be lowered
significantly.

• Also reduced pressure decreases the energy requirement

for both the heating and cooling processes
 Steam Distillation
• Steam distillation is a distillation technique that has
significant commercial applications:

• To extract essential oils from natural products, for

example:
- eucalyptus oil from eucalyptus
- eugenol from cloves
- citrus oils from lemon or orange peel

• To exact oils used in perfumes from various plant

materials
 Steam Distillation
• Steam distillation is very useful in cases where
organic compounds decompose on heating and
cannot be distilled at atmospheric pressure.

• Steam is introduced into the distillation

apparatus.

• As the hot steam passes through, the mixture (of

water and the liquid) distills over at a
temperature between 100°C and the boiling
temperature of the liquid.

• This technique also uses Raoult’s law

 Steam Distillation
• Recall that the saturated vapour pressure of a mixture (for
e.g. water and an organic liquid) is equal to the sum of the
saturated vapour pressures of the pure components.

• When the total saturated vapour pressure is equal to 1 atm,

the mixture distils. 1 atm is significant because that is
usually the pressure of the atmosphere (atmospheric
pressure). Boiling takes place when the total vapour
pressure of a liquid is equal to the atmospheric pressure.

• The mixture boils at a lower temperature and distills to give

a two-layer system of water and the other organic
compound.
 Steam Distillation- Example
Water and Phenylamine

• At 98°C, the saturated vapour pressures of the

two pure liquids are:

Water: 94.30 kPa

Phenylamine: 7.07 kPa
Total: 101.37 kPa

• It is important the mixture is agitated

 Steam Distillation- Example
Boiling point of water- 100°C
Boiling point of phenylamine- 190°C

• Normal atmospheric pressure is 101.325 kPa (1 atm).

• Therefore, the total vapour pressure of a mixture

of water and phenylamine at 98°C is slightly
higher than this atmospheric pressure. Low
temperature is
key

• This results in the mixture boiling (and hence

vaporizing) at a temperature that is lower than
both the b.p. of the pure components (water and
phenylamine)
http://www.docbrown.info/page07/equilibria8e.htm
 Steam Distillation- Summary
• Steam distillation operates on the principle
that immiscible liquids each exert their own
vapour pressure so that when the mixture
boils the sum of the vapour pressure is equal
to one atmosphere. Therefore the mixture
distills below the temperature at which the
vapour pressure of the pure liquid would
reach one at one atmosphere.
 Solvent Extraction
• Solvent extraction is a technique used to
separate compounds based on their
preferential solubilities for two different
immiscible solvents.

• Organic compounds are more soluble in

organic solvents than in water.

• Recall that “like dissolves like”

 Solvent Extraction
• This process allows the separation of a substance
due to its unequal solubilities in two immiscible
liquids.

• It involves the partial removal of a solute from

one liquid in which it is less soluble to another
immiscible liquid in which it is more soluble.

• Since the two solvents are immiscible, they are

easily separated using a separating funnel.
 Solvent Extraction

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 Solvent Extraction
• If the mixture is shaken at a fixed temperature,
the dissolved solute distributes itself in such that
its concentration in the two layers will be a fixed
ratio.

• Even if the experiment is repeated using different

amounts of solute, the ratio of solute
concentration would remain the same after
shaking

• This ratio is called the partition coefficient or

distribution coefficient.
 Solvent Extraction
• The solute (X) would pass from one layer to a
next until an equilibrium is established. This
can be represented as:

X(aqueous) X(organic)

• The partition coefficient (k) is applicable only

in dilute solutions and when the solute has
the same molecular form in both solvents.
 Solvent Extraction
• The partition coefficient (k) can be found using
the following equations:

[X organic ] [𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑢𝑝𝑝𝑝𝑒𝑟 𝑙𝑎𝑦𝑒𝑟]

k= or k=
[𝑋 𝑎𝑞𝑢𝑒𝑜𝑢𝑠 ] [𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑙𝑜𝑤𝑒𝑟 𝑙𝑎𝑦𝑒𝑟]

Side note: During actual experiment, the tap of

the separating funnel is opened occasionally.
 Solvent extraction- example
• Solvent extraction is more efficient if a certain
volume of the extracting solvent is used in
several portions rather than one. Consider an
aqueous solution which contains 8g of solute A in
1dm3 of water. Given that the partition coefficient
for solute A between water and ether is 66 we
can calculate the mass of the solute A extracted
in :

(i) A single 100 cm3 portion of ether

(ii) Two successive 50 cm3 portions of ether
 Solvent extraction- example
• (i) Let the mass of the solute A extracted by 100
cm3 of ether= x. Substituting the concentrations
in the partition coefficient expression:
𝑥
100
8−𝑥 = 66 => x = 6.95 g
1000

• The mass of solute A extracted by a single 100

cm3 of ether is 6.95g
 Solvent extraction- example
• (ii) Let the mass of the solute A extracted by the
first 50 cm3 of ether= y.
𝑦
50
8−𝑦 = 66 => y = 6.14 g
1000

• The mass of solute A extracted by the first 50 cm3

of ether is 6.14 g, hence 1.86 g of solute A now
remain in the aqueous solution.
 Solvent extraction- example
• Let the mass of the solute A extracted by the second
50 cm3 of ether= z.
𝑧
50
1.86−𝑧 = 66 => z = 1.43 g
1000

• The total mass of solute A extracted by the two

successive 50 cm3 samples of ether is 6.14 g + 1.43 g=
7.57 g.
• That is more than the 6.95 g of solute extracted using
the single 100 cm3 volume of ether.