DISTILLATION

Dr. Ramanjireddy Tatiparthi

Professor of Pharmaceutics
Lovely Professional University

1
 Definition

• “Distillation is an separation of a vaporizable

component from a multi-component system and
subsequent condensation of vapours.”

• “Distillation is a process of separating the

component substances from a liquid mixture by
selective evaporation and condensation.”

2
 Applications

 Separation of volatile oils- cloves(Eugenol comprises 72-90%, Vanilin, acetyl

eugenol).

 Separation of drugs obtained from plant and animal sources- Vit. A from fish
liver oil.

 Purification of organic solvents-absolute alcohol (99%).

 Purification of drugs obtained from chemical process.

 Manufacture of official preparations -sprit of nitrous ether, sprit of ammonia,

[Link] and water for inj.

 Quality control methods- Alcohol content in elixir(4-40%).

 Refining of petroleum products- Petroleum ether 60,80.

 Recovery of solvents- synthesis. 3

 Classification of distillation
methods

I. Simple Distillation (Differential distillation)

II. Flash Distillation (Equilibrium distillation)
III. Vacuum distillation (distillation under reduced pressure)
IV. Molecular Distillation (Evaporation distillation or short path
distillation.)
V. Fractional Distillation (Rectification)
VI. Steam Distillation
VII. Destructive Distillation
VIII. Compression Distillation

4
 1. SIMPLE DISTILLATION
• Simple distillation is a process of converting a
single constituent from a liquid (or mixture)
into its vapour, transferring the vapour to
another place and recovering the liquid by
condensing the vapour, usually by allowing it
to come in contact with a cold surface.
• This process is known differential distillation,
as distillation is based on the differences in
volatilities and vapour pressures of the
components in the mixture. 5
Principle:
• Liquid boils when its vapour pressure is equal to atmospheric
pressure. Simple distillation is conducted at its boiling point.
• The higher the relative volatility of a liquid, the better is the
separation by simple distillation. Heat is supplied to the liquid so
that it boils. The resulting vapour is transferred to a different place
and condensed.

CONSTRUCTION:
• It consists of a distillation flask with a side arm sloping downwards.
• Condenser is fitted into the side arm by means of a cork.
• The condenser is usually water condenser, i.e., jacketed for
circulation of water.
• The condenser is connected to a receiver flask using an adapter
with ground glass joints.
• On a laboratory scale, the whole apparatus is made of glass.
6
7
WORKING:
• The liquid to be distilled is filled into the flask to one-half to
two-third of its volume. Bumping is avoided by adding small
pieces of porcelain before distillation.
• A thermometer is inserted into the cork and fixed to the flask.
The thermometer bulb must be just below the level of the side
arm.
• Water is circulated through the jacket of the condenser. The
contents are heated gradually.
• The liquid begins to boil after some time. The vapour begins to
rise up and passes down the side arm into the condenser.
• The temperature rises rapidly and reaches a constant value.
• The temperature of the distillate is noted down, which is equal
to the boiling point of the liquid. The vapour is condensed and
collected into the receiver.

8
• The flame is adjusted so that the distillate is collected at the rate of
one to two drops per second. Distillation should be continued until a
small volume of liquid remains in the flask.

Applications:

• For the preparation of distilled water and water for injection.

• Volatile and aromatic waters are prepared.

• Organic solvents are purified.

• A few official compounds are prepared by distillation. Examples

are spirit of nitrous ether and aromatic spirit of ammonia.
• Non-volatile solids are separated from volatile liquids.

9
 2. Flash Distillation
• Flash distillation is defined as a process in which
the entire liquid mixture is suddenly vaporized
(flash) by passing the feed from a high pressure
zone to a low pressure zone.
• Flash distillation is also known as equilibrium
distillation, i.e., separation is attempted when the
liquid and vapour phases are in equilibrium. This
method is frequently carried out as a continuous
process and does not involve rectification.
10
Principle:
• When a hot liquid mixture is allowed to enter
from a high-pressure zone into a low-pressure
zone, the entire liquid mixture is suddenly
vaporised.
• This process is known as flash vaporisation.
During this process the chamber gets cooled.
The individual vapour phase molecules of high
boiling fraction get condensed, while low
boiling fraction remains as vapour.

11
Construction:

12
Working:

• The feed is pumped through a heater at a certain pressure.

• The liquid gets heated, which enters the vapour-liquid separator
through a pressure-reducing valve.
• Due to the drop in pressure, the hot liquid flashes, which
further enhances the vaporisation process.
• The sudden vaporisation induces cooling. The individual
vapour phase molecules of high boiling fraction get condensed,
while low boiling fraction remains as vapour.

13
• The mixture is allowed for a sufficient time, so that vapor and
liquid portions separate and achieve equilibrium.
• The vapor is separated through a pipe from above and liquid is
collected from the bottom of the separator.
• By continuously feeding into the still, it is possible to obtain
continuous flash distillation.
• The operating conditions can be adjusted in such a way that the
amount of feed exactly equals the amount of material
removed.
• Therefore, vapor and liquid concentrations at any point remain
constant in the unit. 14
Uses:
 Flash distillation is used for separating components, which
boil at widely different temperatures. It is widely used in
petroleum industry for refining crude oil.

Advantages:
 Flash distillation is a continuous process.

Disadvantages:
 It is not effective in separating components of comparable
volatility.
 It is not an efficient distillation when nearly pure components
are required, because the condensed vapour and residual
liquid are far from pure.

15
3. VACUUM DISTILLATION

16
 3. VACUUM DISTILLATION

• The distillation process in which the liquid is

distilled at A TEMPERATURE LOWER THAN ITS
BOILING POINT BY THE APPLICATION OF VACUUM.

Vacuum pumps, suction pumps, etc. are used to

reduce the pressure on the liquid surface.
• Distillation under the reduced pressure is based on
the principle of the simple distillation with some
modifications. 17
 3. VACUUM DISTILLATION
Principle:
• Liquid boils when vapour pressure is equal to the atmospheric
pressure, i.e., pressure on its surface. If the pressure is reduced by
applying vacuum, the boiling point of liquid is lowered.
• Therefore, the liquid boils at a lower temperature.

• Water boils at an 100°C at an atmospheric pressure is 760 mm Hg.

At 40°C, the vapour pressure of water is approximately 70 mm Hg.
• Hence, the external pressure is reduced to 70 mm Hg, where
water boils at 40°C. The net result is the increase in rate of mass
transfer into vapour.
18
 3. VACUUM DISTILLATION

The important factor in evaporation is:

Mass of vapour formed = vapour pressure of evaporating liquid
external pressure

According to this formula, water is allowed to

evaporate at 40°C and 70 mm Hg pressure, the
mass of vapour formed in unit time is
approximately 11 times, i.e. 760/70 for water.

19
 3. VACUUM DISTILLATION
Assembling of apparatus:

• It consists of a double-neck distillation flask known as Claisen flask .

• To the Claisen flask, a thermometer is fitted. Bumping occurs readily

during vacuum distillation. Placing a fine capillary tube in the second

neck of the Claisen flask.

• Water bath or oil bath is used for heating.

• The Claisen flask is connected to a receiver through a condenser.

• Vacuum pump is attached through an adapter to the receiver. A small

pressure gauge (manometer) should be inserted between the pump and

the receiver.
20
 3. VACUUM DISTILLATION
Applications:

1. Preventing degradation of active constituents (≈ 55◦C)

2. Enzymes - malt extract, pancreatin
3. Vitamins - thiamine, ascorbic acid
4. Glycosides - anthraquinones
5. Alkaloids - hyocyamine to atropine
Disadvantages:
1. Persistent foaming occurs can be overcome by adding capryl alcohol to the
liquid.
2. The stream of air is drawn in and breaks the rising foam. The above method is
NOT SUITABLE FOR THE PREPARATION OF SEMISOLID OR SOLID
EXTRACTS BY DISTILLATION UNDER VACUUM. 21
 4. MOLECULAR DISTILLATION

• It is defined as a distillation process in which each molecule in

the vapour phase travels mean free path and gets condensed
individually without intermolecular collisions on application
of vacuum.

• Molecular distillation is based on the principle of the simple

distillation with some modifications. This is also called
Evaporation distillation or Short path distillation.

22
 4. Molecular distillation
Principle:
• The substances to be distilled have very low vapour
pressures, examples are viscous liquids, oils, greases, waxy
materials and high molecular weight substances.
• These boil at very high temperature. In order to decrease
the boiling point of the liquids, high vacuum must be applied.
• Molecules leaving the surface of the liquid are more
likely hit the CONDENSER SURFACE NEARBY. each molecule
is condensed individually.

23
 4. Molecular distillation
Applications: Molecular distillation is used for the purification and
separation of chemicals of low vapour pressure.
1. Purification of chemicals such as tricresyl phosphate, dibutyl
phthalate and dimethyl phthalate.
2. Vitamin A is separated from fish liver oil and vegetable oils.
3. Free fatty acids are distilled at 100°C.
4. Steroids and Triglycerides can be obtained between 100°C
and 200°C.
5. Proteins and gums will remain as nonvolatile residues.

24
 4. Molecular distillation
The mean free path of a molecule is defined as the average distance travelled
in vapor phase without collision with another.
The mean path (λ.) can be expressed mathematically as:
where. p = vapour pressure, kPa
ρ = density, kg/m3
η = viscosity, Pa's
λ = mean path length, m
For example, mean path (heavy molecules) of butyl phthalate is about 30 mm and
of olive oil is 20 mm when measured at a pressure of 0.1 pascal.
The mean free path can be increased by decreasing the viscosity which can be
obtained at high temperature and low pressure. Thus, nonvolatile
substances may become volatile and distillation is possible.
25
Requirements for design the equipment:
• The evaporating surface must be close to the condensing
surface. This ensures the molecules to come in contact with
the condenser as soon as they leave the evaporating surface.
For this reason, this process is also known as short path
distillation.
• The molecular collisions should be minimized because they
change the direction of the path of molecules. It can be achieved
under very high vacuum, usually of the order of 0.1 to 1.0
pascals.

26
4. Molecular distillation
Centrifugal molecular distillation still

27
 4. Molecular distillation
Principle:

 In this method, liquid feed is introduced into a vessel, which is rotated at

very high speed (centrifugal action).

 On account of heating, vaporization occurs from a film of liquid on the

sides of the vessel.

 The vapour (molecules) travels a short distance and gets condensed on the

adjacent condenser.

 Each molecule is condensed individually. The distillate is subsequently

collected.

28
 4. Molecular distillation

Construction:

 It consists of a bucket-shaped vessel having a diameter of about 1

to 1.5 m, rotated at high speed using a motor.

 Radiant heaters are provided externally to heat the fluid in the

bucket.

 Condensers are arranged very close to the evaporating surface.

 Vacuum pump is connected to the entire vessel at the top.

 Provisions are made for introducing the feed into the centre of the

bucket, for receiving the product and residue for re-circulation. 29

 4. Molecular distillation
Working:

 Vacuum is applied at the centre of the vessel.

 The bucket shaped vessel is allowed to rotate at high speed.

 The feed is introduced from the centre of the vessel.

 Due to centrifugal action of the rotating bucket, liquid moves outward over

the surface of the vessel and forms a film.

 Since, the radiant heaters heat the surface, the liquid evaporates directly from

the film.

 The vapour (molecules) travels its mean tree path and strikes the

condenser.

 The condensate is collected into another vessel. 30

4. Molecular distillation
WIPED FILM MOLECULAR DISTILLATION STILL

31
4. MOLECULAR DISTILLATION

Construction:

 The vessel has a diameter of 1 m.

 The walls of the vessel are provided with suitable means of heating
(jacket).
 Wipers are provided adjacent to the vessel wall. Wipers are connected
to a rotating head through a rotor.
 The condensers are arranged very close to the wall (evaporating surface).

 Vacuum pump is connected to a large diameter pipe at the centre of

the vessel.
 Provisions are made for collecting the distillate and the undistilled liquid
residue at the bottom.
32
 4. Molecular distillation
Wiped film molecular distillation still

Working:
 The vessel is heated by suitable means.

 Vacuum is applied at the centre of the vessel and wipers are allowed to rotate.

 The feed is entered through the inlet of the vessel.

 As the liquid flows down the walls, it is spread to form a film by PTFE

(polytetrafluoroethylene) wipers, which are moving at a rate of 3 m per second.

 The velocity of the film is 1.5 m per second.

 Since the surface is already heated, the liquid film evaporates directly.

 The vapour (molecules) travels its mean free path and strikes the condenser.

 The condensate is collected into a vessel.

 The residue (undistilled or mean free path not travelled) is collected from the

bottom of the vessel and re-circulated through the feed port for further distillation.
Capacity is about 1000 L / hour. 33
5. Steam distillation

34
5. Steam distillation

35
 5. Steam distillation

• Steam distillation is method of distillation

carried out with aid of steam.

• It is used to separate

- High boiling substances from non-volatile

impurities - Separate immiscible liquids

36
 5. Steam distillation
Example:

Boiling point of Turpentine = 160 °C

Boiling point of Water + Turpentine Mixture = 95.6 °C

At this temperature Vapour pressure of

Water = 86.245 kPa (647 mmHg)
Turpentine = 15.06 kPa (113 mmHg)

Sum of vapour pressure = 101.31 kPa (760 mmHg)

Which is normal atmospheric pressure and thus high boiling liquid may be distilled
with water at a temperature much below its boiling point.

37
 5. Steam distillation
Principle:

A mixture of immiscible liquids begins to boil when sum of their vapour pressure is

equal to atmospheric pressure.

In case of mixture of water and turpentine, mixture boils below the boiling point of

pure water, though the turpentine boils at a much higher temperature than that of

water.

38
 5. Steam distillation
Application:

 Used to separate immiscible liquids. Ex- Water + Toluene

Extraction at much lower temperature to protect from decomposition without

loss of aroma

 To extract volatile oils like clove, anise and eucalyptus oils.

 Purification of essential oils like almond oil.

 Camphor is distilled by this method.

 Aromatic water are prepared.

Limitation:

Not suitable when two immiscible liquids reacts with each other.

39
 5. Steam distillation
Construction of assembly:

 Metallic steam can fitted with cork having two holes.

 Safety tube inserted up to bottom through one hole to maintain pressure in side

stem can, more over when steam comes out from safety tube indicates that can

is empty.

 Through other hole band tube is passed and other end of this tube is connected

to flask containing non-aqueous liquid in which tube is dipped.

 Flask and condenser is connected with delivery tube.

 Condenser is connected to receiver with help of adopter.

 Provision are made to heat both steam can and flask separately.

40
 5. Steam distillation
Working:

 Metallic steam can fitted with cork having two holes.

 Safety tube inserted up to bottom through one hole to maintain pressure in side

stem can, more over when steam comes out from safety tube indicates that can

is empty.

 Through other hole band tube is passed and other end of this tube is connected

to flask containing non-aqueous liquid in which tube is dipped.

 Flask and condenser is connected with delivery tube.

 Condenser is connected to receiver with help of adopter.

 Provision are made to heat both steam can and flask separately.

41
6. Fractional Distillation

42
 Fractional Distillation

This method is also known as rectification, because a part of the

vapour is condensed and returned as a liquid.

This method is used to separate miscible volatile liquids, whose

boiling points are close, by means of a fractionating column.

Fractional distillation is a process in which vaporization of liquid

mixture gives rise to a mixture of constituents from which the desired one

is separated in pure form.

43
 Fractional Distillation

Simple Distillation Vs Fractional Distillation

In fractional distillation the vapour

 In simple distillation,
must pass through a fractionating
vapour is directly passed through
column in which partial condensation of
the condenser.
vapour is allowed to occur.
Condensation takes place in the

Condensate is collected fractionating column, so that a part of

the condensing vapour returns to the
directly into the receiver,
still.

44
 Fractional Distillation

Principle:
 When a liquid mixture is distilled, the partial condensation of the vapour is
allowed to occur in a fractionating column.
 In the column, ascending vapour from the still is allowed to come in contact
with the condensing vapour returning to the still.
This results is enrichment of the vapour with the more volatile component.
 By condensing the vapour and reheating the liquid repeatedly, equilibrium
between liquid and vapour is set up at each stage, which ultimately results in
the separation of a more volatile component.

45
 Fractional Distillation

Applications:
Fractional distillation is used for the separation of volatile miscible liquids with near
boiling point such as
•Acetone and water
•Chloroform and benzene

Disadvantage:
Fractional distillation cannot be used to separate miscible liquids, which form PURE
azeotropic mixtures.

46
 Fractional Distillation
Fractionating columns

In fractional distillation, special type of still-heads are required so that

condensation and re-vaporisation are affected continuously.

These are known as fractionating columns.

A fractionating column is essentially a long vertical tube in which the vapour

passes upward and partially condensed. The condensate flows down the column and

is returned eventually to the flask.

The columns are constructed so as to offer the following advantages

simultaneously.

(1) It offers a large cooling surface for the vapour to condense.

47
(2) An obstruction to the ascending vapour allows easy condensation.
 Fractional Distillation
Fractionating columns Types
A] Packed columns and
B] Plate columns

48
 Fractional Distillation
Fractionating columns Types
A] Packed columns

49
 Fractional Distillation
Fractionating columns Types
A] Packed columns
Some form of packing is used in the column to affect the necessary
liquid/vapour contact. The packing may consist of single turn helices
(spirals) of wire or glass, glass rings, cylindrical glass beads, stainless steel
rings etc.
Construction: Packed column consists of a tower containing a packing that
becomes wetted with a film of liquid, which is brought into contact with
the vapour in the intervening spaces.
(a) A long fractionating column is necessary when the boiling points of the
constituents are lying fairly close together.
(b) A short fractionating column is necessary when the boiling point of the
constituents differ considerably.
Applications: Packing must be uniform so as to obtain proper channels. If
packing is irregular, mass transfer becomes less effective.

50
 Fractional Distillation
Fractionating columns Types
B] Plate columns

51
 Fractional Distillation
Fractionating columns Types
B] Plate columns
Many forms of plates are used in the distillation using different columns. It can be divided into
two types, which are commonly used in pharmacy.
(a) Bubble cap plates
(b) Turbo grid plates
Bubble cap column is used in large distillation plants and is described below.
Construction: The column consists of a number of plates mounted one above the other. Caps are
present on each plate, which allow the vapour to escape by bubbling through the liquid.
Working: Ascending vapour from the still passes through the bubble-caps on plate A and the
rising vapour will be richer in the more volatile component. This vapour passes through the
liquid on plate B and partially condensed. The heat of condensation partially vaporizes the
liquid. The process of condensation and vaporisation will be repeated at plate C and so on all
the way up the column. Each bubble-cap plate has the same effect as a separate still.

52
 Fractional Distillation
Fractionating columns Types
B] Plate columns (Bubble cap)

Advantages:
The bubble cap plate is effective over a wide range of vapour-liquid
proportions. There is excellent contact as the vapour bubbles
through the liquid.

Disadvantages:
(I) A layer of liquid on each plate results in considerable
hold-up of liquid over the entire column.
(2) The need to force the vapour out of the caps, through the liquid, led
to a large pressure drop through the column.
(3) The column does not drain when it is not in use.
(4) The structure is complicated making construction and maintenance
expensive.

53