DISTILLATION

A laboratory technique used in separation

and/or purification of components in a
mixture

The process is mainly based upon the

boiling point of liquid substances

heating vaporizing condensing

Experiment IV: Distillation

DISTILLATION

liquid liquid

mixtures

homogeneous heterogeneous

Experiment IV: Distillation

RAOULT’S LAW
for ideal mixtures

It relates the vapor pressure of components

to the composition of the solution

It assumes ideal behavior, that is, the

physical properties of the components
are identical

Experiment IV: Distillation

RAOULT’S LAW

If the two components are very similar, or in

the limiting case, differ only in isotopic content,
then the vapor pressure of each component
will be equal to the vapor pressure of the pure
substance Po times the mole fraction in the
solution

Experiment IV: Distillation

RAOULT’S LAW

The total vapor pressure Ptot above the solution

is equal to the sum of the vapor pressures of
the two [liquid] components, PA and PB

Experiment IV: Distillation

RAOULT’S LAW

Experiment IV: Distillation

RAOULT’S LAW

Experiment IV: Distillation

RAOULT’S LAW

Experiment IV: Distillation

RAOULT’S LAW
Vapor Pressure
It is the pressure exerted by a vapor in
equilibrium with its non-vapor phases

Boiling Point
The temperature at which the vapor pressure
equals the atmospheric pressure

Vapor Pressure 1/α Boiling Point

Experiment IV: Distillation
AZEOTROPE MIXTURE

A mixture of liquids that has a constant boiling

point because the vapour has the same
composition as the liquid mixture

The components of the solution cannot be

separated by simple distillation

Experiment IV: Distillation

AZEOTROPE MIXTURE

POSITIVE AZEOTROPE
Minimum Temperature
Maximum Pressure

NEGATIVE AZEOTROPE
Maximum Temperature
Minimum Pressure

Experiment IV: Distillation

POSITIVE AZEOTROPE MIXTURE

Experiment IV: Distillation

NEGATIVE AZEOTROPE MIXTURE

Experiment IV: Distillation

KINDS OF DISTILLATION

for homogeneous mixtures

Simple Distillation
Fractional Distillation

for heterogeneous mixtures

Steam Distillation

Experiment IV: Distillation

AZEOTROPE MIXTURE

Ethanol Water
95.5% 4.5%

78.1°C
78.3°C 100°C
positive azeotrope mixture

Experiment IV: Distillation

SIMPLE DISTILLATION

It is usually used only to separate liquids

whose boiling points differ greatly (>70°C) or to
separate liquids from involatile solids or oils. In
the process, all the hot vapors produced are
immediately channelled into a condenser
which cools and condenses the vapors

Therefore, the distillate will not be as pure

Experiment IV: Distillation

SIMPLE DISTILLATION

A simple distillation set-up consists of a boiling

flask (round-bottom flask) attached to an
adapter holding a thermometer (to determine
the boiling temperature of the liquid). The
adapter connects to a condenser into which
cold water is constantly passed through. The
condenser leads into a collection flask for the
purified liquid.

Experiment IV: Distillation

SIMPLE DISTILLATION

Experiment IV: Distillation

SIMPLE DISTILLATION

Experiment IV: Distillation

FRACTIONAL DISTILLATION

It is usually employed with separation of

complex mixtures at small boiling points
difference (about 25°C). It can separate the
mixture into its component parts or fractions

Experiment IV: Distillation

FRACTIONAL DISTILLATION
It is essentially the same as simple distillation except
that a fractionating column is placed between the
boiling flask and the condenser. The glass beads
found in the fractionating column provide "theoretical
plates" on which the refluxing liquid can condense, re-
evaporate, and condense again, essentially distilling
the compound over and over. The more volatile
liquids will tend to push towards the top of the
fractionating column, while less volatile liquid will stay
towards the bottom, giving a better separation
between the liquids

Experiment IV: Distillation

FRACTIONAL DISTILLATION

Experiment IV: Distillation

FRACTIONAL DISTILLATION

Experiment IV: Distillation

 SIMPLE vs FRACTIONAL DISTILLATION
Simple distillation Fractional distillation

Advantages • simpler setup than fractional •much better separation between

• faster distillation times liquids than simple distillation
• consumes less energy than •can more readily purify complex
fractional distillation mixtures than simple distillation

Disadvantages • requires the liquids to have • more complicated setup than

large boiling point differences
(>70oC)
• gives poorer separation than
fractional distillation
• only works well with relatively
pure liquids
simple distillation
• takes longer for liquids to distil
• consumes more energy than
simple distillation

Best used for: separating relatively pure liquids separating complex mixtures of
with large boiling differences or liquids with smaller boiling point
liquids with solid impurities separations.

Experiment IV: Distillation

SIMPLE vs FRACTIONAL DISTILLATION

Experiment IV: Distillation

STEAM DISTILLATION

It is the process of purifying a substance through

application of steam. It deals with compounds that are
heat sensitive (e.g. natural aromatic compounds).
Steam distillation works on the principle that
immiscible substance when mixed together can lower
the boiling point of each other.

Experiment IV: Distillation

STEAM DISTILLATION

0.864g/mL Xylene Water 0.988g/mL

60% 40%

94.5°C
139.1°C 100°C
positive azeotrope mixture

Experiment IV: Distillation

STEAM DISTILLATION

Many organic compounds tend to decompose at high

sustained temperatures. Separation by normal
distillation would then not be an option, so water or
steam is introduced into the distillation apparatus. By
adding water or steam, the boiling points of the
compounds are depressed, allowing them to
evaporate at lower temperatures, preferably below
the temperatures at which the deterioration of the
material becomes appreciable

Experiment IV: Distillation

STEAM DISTILLATION

Experiment IV: Distillation

STEAM DISTILLATION

Experiment IV: Distillation

STEAM DISTILLATION

Volume Volume Weight Ratio

Xylene (mL) Water (mL)
First Fraction 0.5 1.3 0.33 : 1

Second -no data- -no data- -no data-

Fraction*
*the experiment was
unsuccessful
σ of xylene = 0.87 g/mL
σ of water = 1 g/mL

Experiment IV: Distillation

GUIDE QUESTIONS

Experiment IV: Distillation

Explain the differences of the distillation curves
between simple distillation and fractional
distillation.

Experiment IV: Distillation

SIMPLE vs FRACTIONAL DISTILLATION

Experiment IV: Distillation

 In the separation of the ethanol from water
using fractional distillation, the distillate always
contains about 5% water. Explain.

Experiment IV: Distillation

t vs. % concentration of ethanol-water mixture

Experiment IV: Distillation

p vs. % concentration of ethanol-water mixture

Experiment IV: Distillation

t vs. % concentration of liquid mixture, which does not form azeotrope

Experiment IV: Distillation

Based on the phase diagram of 4(a), what is
the approximate composition of the ethanol-
water mixture, which begins to distill at 80°C?

Experiment IV: Distillation

 At 95°C the vapor pressure of n-heptane is
684 mmHg and of n-octane is 303 mmHg.
Calculate the mole ratio and weight ratio of the
two components in a mixture of n-heptane and
n-octane, which begins to distill at 95°C at 650
mmHg.

Experiment IV: Distillation

 P sol = 650 mmHg
684 x + 303 (1-x) = 650
684x + 303 – 303x = 650
x= 0.9107
1-x = 0.089
Mole ratio: 0.9107/0.089 = 10.23 (10.23 mols
of n-heptane for every 1 mol of n-octane)
Weight ratio: 91.25/10.17 = 8.98 (8.98 g of n-
heptane for every 1 g of n-octane)

Experiment IV: Distillation

 Explain the difference in the values of
toluene/water weight ratios between the first
and second fractions.

Experiment IV: Distillation

Cite some important application of steam
distillation and vacuum distillation

Experiment IV: Distillation