Distillation

Background Concepts - Definitions

• Vapor Pressure –
Gas pressure created by the molecules of a liquid which have acquired sufficient Kinetic Energy to
escape to the vapor phase.

• As Temperature increases, the average Kinetic Energy and the Vapor Pressure increase until the boiling
point is reached.

• Boiling Point – The temperature at which the vapor pressure of a liquid equals the pressure applied by the
surroundings to the liquid.

• For two pure liquids, which have different boiling points the vapor pressure at a given temperature will be higher for
the liquid of lower boiling point.
 Background Concepts - Definitions

• The temperature of the vapors above a boiling liquid will remain

constant at the boiling point.

• At the boiling point for a pure liquid, the liquid and vapor (gas) phases
are in equilibrium.

• The boiling point (at a specified pressure) is a characteristic property

of a pure liquid.
 Background Concepts - Principle

• For an ideal solution with a volatile solvent

and a non-volatile solute
(e.g. water and salt) …

VPsolution = Xsolvent × VPsolvent

As you increase the concentration of the non-

volatile solute, you decrease the vapor pressure of
the solution and increase the boiling point.
(Colligative property)
 Background Concepts - Principle
• For an ideal solution made of two volatile solvents, the total
vapor pressure is the sum of the vapor pressures of the two or
more solvents.
• Ptotal = Pa + Pb + . . .

• For a solution of liquid ‘a’ and liquid ‘b’

VPtotal = Xa (VPa) + Xb (VPb)
 Distillation
• For an ideal solution with a volatile solvent
and a non-volatile solute
(e.g. water and salt) …

…separation of the two

components is as simple as heating the
mixture and collecting and condensing the
vapor
– simple distillation.
 Distillation
Principle:

• Raoult’s Law : Pvap =(Xliq)P°vap

• Dalton’s Law : Ptotal = Pvap(a) + Pvap(b)
• Ideal Gas Law : PV=nRT
Principle
Principle
 Phase Diagram (Liquids A and B)

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(X’s and O’s represent percentage of each component at each level.)

essentially pure "O"

O O O temp 50
O O O
O O OO
Po = 0.9 X 833 mmHg = 750 mmHg O O O temp 60
O O O 750/760 X 100 = 99% O
Px = 0.1 X 100 mmHg = 10mmHg
O O XO 10/760 X 100 = 1% X
760 mmHg
Po = 0.8 X 855 mmHg = 684 mmHg O O O O temp 70
O X 684/760 X 100 = 90% O
Px = 0.2 X 380 mmHg = 76 mmHg
O O XO 76/760 X 100 = 10% X
760 mmHg
O X
Po = 0.7 X 867 mmHg = 608 mmHg O O temp 80
Px = 0.3 X 507 mmHg = 152 mmHg O 608/760 X 100 = 80% O
X X 152/760 X 100 = 20% X
760 mmHg O O O
Po = 0.6 X 887 mmHg = 532 mmHg O XO O
X X temp 90 532/760 X 100 = 70% O
Px = 0.4 X 570 mmHg = 228 mmHg O
O X O 228/760 X 100 = 30% X
760 mmHg

Po = 0.5 X 912 mmHg = 456 mmHg 456/760 X 100 = 60% O

Px = 0.5 X 608 mmHg = 304 mmHg 304/760 X 100 = 40% X
760 mmHg O X X O O
O O O X
X X X temp 100
X OO X
 Number of Plates and
Mccabe-Thiele Equation
 Simple
distillation
 Simple distillation:-
* The most common process used to separate
two liquids whose boiling point differs at least by
about 50 °C.

Example:-
Separation diethyl ether (B.P=34°C), from dioxane (B.P=101°C).
Separation chloroform (B.P=60°C), from an oil (B.P=220°C).

* Separation of a liquid substances from the

solid substances in a mixture.
Example:-
Separation H2O (B.P=100°C), KMnO4 (B.P ≥ 240°C).
Simple distillation components:-
Any simple distillation system composed from the
following main parts:-

1-Heating source.

2-Distillation flask.
3- Thermometer.
4- Condenser.
5- Receiving flask .
Separation of mixture by simple distillation:-
1- A mixture composed from A&B with boiling point
(70 & 140) °C respectively is heated.
2- The lowest boiling point (A) will vaporized and
ascended (elevated) from the solution till it reach
the top of the system, with recording its real b.p.
with the help of thermometer.
3- The ascended vapor will converts to the liquid
form by the action of the condenser, then collect at
the receiver.
4- Finally the highest boiling point will remain at the
distillation flask.
Simple Distillation

(Use a 10-mL graduated cylinder to collect fractions, instead of a flask)

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 Simple Distillation

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 Distillation Process
• When a mixture AB of a specific Liquid-Vapor Composition Diagram
composition is heated, the total
vapor pressure (composed of the
contributions of PA and PB) will rise
until it is equal to the external vapor
pressure. The mixture will begin to
boil.
• The vapor which first forms is
enriched in the more volatile
component. This behavior is shown
at right,

•Assume a two component mixture with a composition of 30%A:70%B (point W). The boiling point of this
mixture is found by drawing a vertical line from W to where it intersects the lower curve (point X). A horizontal
line drawn from X to where it intersects the vertical axis (the temperature) gives the bp of composition W. From
the point (Y) where this horizontal line intersects the upper curve (vapor) drop a vertical line to intersect the
lower axis (the composition). Point Z gives the composition of the vapor which is in equilibrium with a liquid of
composition W at its boiling point.
FRACTIONAL
DISTILLATION
Fractional Distillation:-

Second technique of the distillation process, used

to separate two liquids having close (near) boiling
points (Lower than 25 °C).

Example:-
Separation of ethanol (78) °C from
water (100) °C
.
Fractional Distillation

• Increasing the surface area

that the vapors contact
between the liquid and the
condenser, increases the
number of theoretical plates.

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Fractional Distillation
• Greater plates = greater purity of distillate
= sharper transition in distillation plot

• The number of Theoretical Plates or the height

equivalent to a theoretical plate (HETP) is a
measure of the efficiency of a column to separate
components.
Fractional distillation components:-
Fractional distillation system composed from the
following main parts:-

1- Heating source.
2- Distillation flask.
3- Fractional column.
4- Thermometer.
5- Condenser.
6- Receiving flask .
Fractional Distillation Set-up
 Fractional Distillation
AB at composition of 5% A boils at temperature L1 and the

vapors with composition V1 enter the column at that

temperature. The vapor will condense to a liquid with

composition V1. The condensate L2 has a lower boiling point

(because it has more of the lower boiling liquid A) and will thus

vaporize at a lower temperature (warmed up by coming in

contact with the additional vapors from below) to give vapors of

composition V2. These vapors will condense somewhat farther

up the column to give a condensate L3. If the column is long

enough or contains sufficient surface area that many

successive vaporization-condensation steps (theoretical plates)

can occur, the distillate that comes over the top is nearly pure

A. Distillation yielding pure A continues until all of A is

removed, after which the temperature at the thermometer rises

AZEOTROPIC
DISTILLATION
 AZEOTROPIC DISTILLATION
• If a mixture of ethanol and water is distilled, eventually it will form a solution that is 95 % ethanol
regardless of the starting composition. Hydrochloric acid and water will form a 20.22 % HCI
solution, and chloroform and acetone will form a 65.5 % CHCl 3 solution. These solutions are
called azeotropes (Gr: a + zeo to boil; trope more at).
• Webster’s dictionary defines an azeotrope as a liquid mixture that is characterized by a constant
maximum or minimum boiling point which is lower or higher than that of any of the components
and that distills without change in composition.

• To use an azeotrope to effect a separation a solvent is added to mixture that will form a constant
boiling mixture with one or more of the components in the mixture. There are two requirements:
1. The added component reduces the partial pressure of one of the original components.
2. The formed azeotrope is removed more easily than anything else in the pot.
 AZEOTROPIC DISTILLATION
Example of an Azeotrope Distillation

Preparation of absolute ethanol is as follows:

Water + EtOH forms an azeotrope (95% EtOH) b.p. = 78.15 °C.
Add benzene to form another azeotrope (74% benzene, 18.5% alcohol, 7.5% water) b.p. = 65 °C.
Distill at 65 °C.This removes the water;
Now benzene and EtOH form an azeotrope (67.6% benzene, 32.4 % EtOH) at 68 QC.
Distill at 68°C until the temperature rises. Pure EtOH can be obtained at 78.5 QC.
AZEOTROPIC DISTILLATION
AZEOTROPIC DISTILLATION
 AZEOTROPIC DISTILLATION
Ways to Break an Azeotrope

1. Form new azeotrope

2. Add a salt.
Anhydrous potassium carbonate was added to break the ethanol-water azeotrope over 150 years ago. This gave
way to quicklime, which was cheaper.

3. Changing pressure.
The ethanol-water system shifts away from the azeotrope if a vacuum is applied.
 STEAM
DISTILLATION
 Steam Distillation
• Codistillation of water with a substance which it is immiscible
• Codistillation – distillation of 2 or more liquids
• Used to separate slightly volatile water insoluble substance
from non-volatile materials
Principle Behind Steam Distillation
• Dalton’s Law of Partial Pressure
• “When 2 or more gases or vapors which do not react chemically with one
another are mixed at constant temperature,the sum of their individual vapor
pressure is equal to the the total pressure of the system.”
• PT = ∑PT
= P1 + P2 + P3 +…
where: PT = total pressure
Pn = vapor pressure of the pure compound
at the same temperature
***PT > Pressure of the most volatile component
Principle Behind Steam Distillation
• The total pressure is dependent only in the individual vapor pressures
and not in the mole fraction (Χ) of each component of the mixture.
The composition of vapor is constant at a particular temperature. The
vapor pressure of a mixture is proportional to the number of
molecules of each substance in the vapor phase.
Principle Behind Steam Distillation

norganic P°organic
=
nH2O P°H2O
Applications of Steam Distillation
• Each substance in an immiscible mixture exerts vapor pressure
independently of the others. Thus, when the combined vapor
pressures of the immiscible substances equal the opposing
atmospheric pressure, the mixture will boil.
• The mixture will boil at a temperature lower than of the boiling point
of the lowest boiling component
Sample for Steam Distillation
• Suitable samples
• Liquid at room temperature
• Slightly volatile
• Water immiscible

• Sample cut finely

• Increase surface area of contact between oil and water
Role of Steam
• Contributes a relatively high vapor pressure to the total pressure of
the mixture to allow the mixture to boil at a lower temperature
 OH

OH
geraniol linalool

citral limonene
Comparison of Simple and Steam Distillation

SIMPLE STEAM

Principle Raoult’s Law Dalton’s Law

Sample used Solution of nonvolatile Immiscible Liquids are

solute in volatile both volatile
solvent (Heterogeneous)
(Homogeneous)
Comparison of Simple and Steam Distillation

SIMPLE STEAM

Distillate homogeneous Heterogeneous

collected
Boiling point Normal boiling Less than the
point normal boiling
point of the
lowest boiling
component
Comparison of Simple and Steam Distillation
SIMPLE STEAM

application Substances with -Volatile and water

wide difference in immiscible
boiling point e.g. -Purification of
CHCl3 substances that
(61-65 C) and are heat sensitive
caffeine (238 C) (decompose at
high T)
-Mixture contains
large amounts of
nonvolatile
materials
Comparison of Simple and Steam Distillation

SIMPLE STEAM

limitations - mixture whose -Compounds that

components have react with water or
close BP decompose upon
- Compounds that prolonged contact
decompose at with water
their normal BP -Nonvolatile
compound (P° ≤ 5
mmHg at 100 ° C)
 VACUUM
DISTILLATION
 Vacuum Distillations
• Vacuum distillation is distillation at a reduced pressure.
• Since the boiling point of a compound is lower at a lower
external pressure, the compound will not have to be heated to
as high a temperature in order for it to boil.
• Vacuum distillation is used to
distill compounds that have
a high boiling point or any
compound which might
undergo decomposition on
heating at atmospheric
pressure.
• The vacuum is provided
either by a water aspirator or
by a mechanical pump.
17
Rotary Evaporators
• Commonly called
“Rotovap”
• Very commonly
used
• Evaporates low boiling
solvents (like DCM) from
solutions at reduced
pressures
• Higher boiling solute is
left behind in evaporating
flask
• Example of a vacuum
distillation
1. Add a bump trap onto the rotavapor. Use a green clip to fix it. 4. Close the vent
2. Attach your round-bottom ed flask to the bump trap. 5. Turn on the vacuum
3. Turn on the rotavap motor and adjust the speed. 6. Put your flask into the warm water bath

8. Turn off the vacuum 11. Take the round-

9. Open the vent bottomed flask off the
10.Adjust the speed to 0 and turn off the rotavap 20
7. Solvents will be collected
rotavap motor