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

RAOULTS 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

RAOULTS 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

RAOULTS 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

RAOULTS LAW

Experiment IV: Distillation

RAOULTS LAW

Experiment IV: Distillation

RAOULTS LAW

Experiment IV: Distillation

RAOULTS 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/

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

78.3C

Ethanol

Water

95.5%

4.5%

78.1C

100C

positive azeotrope mixture

Experiment IV: Distillation

SIMPLE DISTILLATION
It is usually used only to separate liquids
whose boiling points differ greatly (>70C) 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 25C). 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, reevaporate, 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
Advantages

Disadvantages

Best used for:

simpler setup than fractional

faster distillation times
consumes less energy than
fractional distillation

requires the liquids to have

large boiling point differences
(>70oC)
gives poorer separation than
fractional distillation
only works well with relatively
pure liquids

Fractional distillation
much better separation between
liquids than simple distillation
can more readily purify complex
mixtures than simple distillation
more complicated setup than
simple distillation
takes longer for liquids to distil
consumes more energy than
simple distillation

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
60%

139.1C

Water

0.988g/mL

40%

94.5C

100C

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

First
Fraction
Second
Fraction*

Volume
Volume
Xylene (mL) Water (mL)
0.5
1.3
-no data-

-no data-

Weight
Ratio
0.33 : 1
-no data-

*the experiment was

unsuccessful
of xylene = 0.87 g/mL
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 ethanolwater mixture, which begins to distill at 80C?

Experiment IV: Distillation

At 95C 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 95C 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 nheptane 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