DESTILATION

EVEN SEMESTER 2013/2014

Figure 1
Figure 2

What is distillation?

What compounds could be distillated?

How could you distillate those compounds?

Draw the scheme of distillation apparatus !!

Describe types of distillation !!

Define the distillation process

Understanding the principle of Raoults Law and

Daltons Law

Phase diagram

Azeotrop phenomenon

Distillation types and application

Because of solute-solvent
intermolecular attraction,
higher concentrations of
nonvolatile solutes make
it harder for solvent to
escape to the vapor
phase.
Therefore, the vapor
pressure of a solution is
lower than that of the
pure solvent.

VAPOUR PRESSURE

For a liquid, at any temperature, some

molecules are evaporating from the
surface.

As the temperature goes up, the

number of molecules evaporating in a
given time increases.

If the liquid is in an open container, the

molecules escape into the atmosphere.

In a closed container, some of the

vapor molecules strike the walls of the
container and return to the liquid.
Soon a state of equilibrium is reached
in which over any time period,

the number of molecules

evaporating = number of molecules
condensing back to the liquid.

The pressure of the vapor at this point

is known as its vapor pressure.

THE BOILING POINT

The vapor pressure of a pure

liquid rises steadily as the
temperature is increased .
The Boiling Point of a liquid is
the temperature at which
vapor pressure is equal to the
external pressure.
The normal boiling point of a
liquid is the temperature at
which its vapor pressure is
760 torr (1 atm), normal
atmospheric pressure at sea
level (applied pressure)

760 torr = 760 mmHg = 1 atm

Liquids with high vapor pressures (Volatile compounds)

require relatively little energy (heat) to increase the vapor
pressure to match the applied (atmospheric) pressure, and
thus, boil, i.e. they have low boiling points.
Liquids with low vapor pressures require considerably more
energy to increase the vapor pressure to the point where it
matches the applied pressure, thus, they have relatively high
boiling points.
The individual compounds in a mixture each use its own
pressure: partial pressure.
The sum of the partial pressures equals to the total vapor
pressure of the solution.

Raoults Law

In a solution : of two miscible liquids (A & B) the partial pressure of

component A (PA) in the liquid equals the partial pressure of pure A
(PAo) times its mole fraction (XA).
Partial Pressure of A in solution = PA = (PAo) x (XA)
Partial Pressure of B in solution = PB = (PBo) x (XB)
Ptotal = PA + PB = PAo XA + PBo XB
Where XA = nA/(nA + nB) and XB = nB/(nA + nB)
nA and nB are the number of moles of each component in the liquid
When the total pressure (Ptotal) is equal to or greater than the Applied Pressure(760
mm Hg, atmospheric pressure), the solution boils.

If the sum of the two partial pressures of the two compounds in a mixture is less than the
applied pressure, the mixture will not boil. The solution must be heated until the
combined vapor pressure equals the applied pressure.

Dalton's Law
In the vapor, the mole fraction of a component at a given
temperature is equal to the partial pressure of that component
at that temperature divided by the total pressure

XA = PA / Ptotal
While XA = nA/(nA + nB) and XB =
nB/(nA + nB)

where
nA and nB are the number of moles of
each component in the vapor

Combining Raoults Law and Daltons law, we can obtain the following
relationship:

X A'
X A PA

'
X B X B PB

If A is more volatile than B, BPA < BPB and PA > PB

then
XA/XB > XA/XB

The ratio of A/B in the vapor is greater than the ratio of A/B in the liquid.
The vapor is enriched in the more volatile (lower boiling) component relative
to the liquid.

During the distillation, since the vapor always contains more A than B, the
fraction of B in the liquid increases continuously causing the boiling point
of the solution to increase

Example
Consider a solution at 100 oC where nA = 0.5 and nB = 0.5
1.

What is the Partial Pressure of A in the solution if the Vapor Pressure of Pure A at
100 oC is 1020 mm Hg?
Ans: PA = PoAXA = (1020) * (0.5) = 510 mm Hg

2.

What is the Partial Pressure of B in the solution if the Vapor Pressure of Pure B at
100 oC is 500 mm Hg?
Ans: PB = PoBNB = (500) * (0.5) = 250 mm Hg

3.

Would the solution boil at atmospheric pressure (760 mm Hg)?

Ans: Yes

4.

Ptotal = PA + PB = (510 + 250) = 760 mm Hg

What is the composition of the Vapor at the Boiling Point?

Ans: The Boiling Point is 100 oC
XA (vapor) = PA / Ptotal

= 510/760 = 0.67 (mole fraction)

XB (Vapor) = PB / Ptotal

= 250/760 = 0.33

PoA > PoB A is more volatile than B

Solution phase: XA = XB = 0.5 mole fraction
Vapour phase: XA = 0.67 mole fraction
XB = 0.33 mole fraction

XA / XB > XA/XB

Senyawa A mempunyai titik didih 700C dan

senyawa B mempunyai titik didih 1500C. 10 gram
A (BM = 60) dicampur dengan 20 gram B (BM =
40). Campuran ini dipisahkan dengan cara
didestilasi pada suhu 1100C. Jika pada 1100C, PoA
= 1500 mmHg dan PoB = 520 mmHg:
Hitunglah fraksi mol A pada fasa cair (liquid)
dan pada fasa uap (vapour) !

PHASE DIAGRAM

When a mixture AB is heated, the

total vapor pressure (Ptotal which is
composed of the contributions of
PA and PB) will rise until it is equal
to the external vapor pressure.

The temperature at which this

occurs for various compositions of
the liquid is show in the lower
curve.

In this example, the liquid having composition W boils at temperature t.

The vapor in equilibrium with the liquid has composition y.
The vapor condenses to give liquid of composition Z.
After the first drop of liquid distills, the fraction of B in the liquid increases slightly, increasing
the boiling point of the solution
The composition of both the liquid and vapor changes continuously.

Distillation Methods
1. Simple
2. Vacuum (at reduced pressure)
3. Fractional
4. Steam

Pure Substance
Temperature remains constant during distillation process
so long as both vapor and liquid are present

Miscible Liquid Mixture

Temperature increases throughout process because
composition of vapor changes continuously.
Composition of vapor in equilibrium with the heated liquid
is different from the composition of the liquid.

-A liquid is heated
to vapor in the
distilling flask

Simple Distillation
thermometer
liquid with a solid
dissolved in it

-The vapor enters

the condenser

condenser

-The vapor is
cooled in a
condenser
becoming a liquid
again

tube
distilling
flask

-The cooled liquid

is collected in a
receiver
hose connected to
cold water faucet

receiving
flask

Dorin, Demmin, Gabel, Chemistry The Study of Matter , 3rd Edition, 1990, page 282

pure
liquid

- Boiling points of
the two liquids
must differ by 75C
for effective
separations

FRACTIONAL DESTILATION

Fractional distillation can be

used to separate liquids with
similar boiling points.
On its way up the fractionating
column, the vapor condenses
and revaporized many times.
At each stage of condensation/
revaporization, the vapor is
further enriched in the lower
boiling component.

A fractionating column is placed between the distilling flask and the condenser

The vapors condense in the fractionating column and then the condensed liquids
vaporize again

These cycles are repeated throughout the length of the fractionating column

The vapor becomes enriched in the lower boiling compound

Column Efficiency
A common measure of the efficiency of a Fractionation Column is given
by its number of Theoretical Plates.
One theoretical plate is equivalent to a Simple Distillation, i.e., one
Vaporization / Condensation Cycle.
The smaller the boiling point difference, the greater the number of
theoretical plates a fractionating column
must have to achieve separation of mixtures
Boiling Point
Difference

Number of
Theoretical Plates

108
54
20
7
4
2

1
3
10
30
50
100

Temperature-Volume Curves for Simple and Fractional Distillations of

Cyclohexane and Toluene Mixture

Fractional Distillation (cont)

As the distillation proceeds, the composition

of the liquid and the vapor are continuously
changing.
The Horizontal and Vertical Lines represent
the processes that occur during a fractional
distillation.
Each Horizontal Line (L3V3, L2,V2), etc.,
represents both the vaporization step of a
given vaporization/condensation step and
the composition of the vapor in equilibrium
with the liquid at a given temperature.
Examples:
- At 53oC with a liquid composition of 80% A
and 20% B (L4V4 on the diagram), the vapor
would have 95% A and 5% B when
equilibrium has been established between
the liquid and the vapor.
- At 63oC with a 50/50 mixture of A&B (L3V3
on the diagram), the vapor would have a
composition of 80% A at equilibrium.

What is an Azeotrope?
An azeotrope is a mixture of two
or more pure chemicals in such
a ratio that its composition
cannot be changed by simple
distillation. This is because
when an azeotrope is boiled,
the resulting vapor has the
same ratio of constituents as
the original mixture of liquids.

Wait, how does this apply to a distillation?

During a distillation, the distillate will be enriched in the more
volatile component until the azeotropic ratio is reached. Once
this ratio is obtained, the temperature will become constant
until one of the components is exhausted.

A mixture of
liquids of a definite
composition that
distills at a
constant
temperature and
composition

Some liquids do
not form ideal
solutions that
conform to
Raoults law

Deviations from
ideal behavior
caused by
molecular
interactions

Boiling Point-Composition Curve:

Ethanol-Water Azeotrope