DISTILLATION

Distillation is the process of separating one or more components with a different boiling point in a liquid
mixture by vaporizing the liquid and passing the vapors through a cold surface, and converting the vapors
again to a liquid.
Distillation is a physical separation process and may include
[Link] of one liquid from non volatile impurities
[Link] of one liquid from one or more liquids which are miscible, partially miscible and immiscible
THEORETICAL BACKGROUND OF DISTILLATION
According to Kinetic Theory, the molecules in a liquid are in a constant thermal motion and some of these
molecules are moving fast enough to escape from the liquid forming a vapor above the liquid. These
vapors exert a pressure on the surface of the liquid i.e., Vapor Pressure. The Vapor Pressure of a liquid
generally increases with temperature.
Boiling Point – If a liquid is heated, the vapor pressure of the liquid increases to the point at which it just
equals the atmospheric pressure. The liquid now begins to boil. The boiling point of a liquid is the
temperature at which the vapor pressure of the liquid equals the external pressure on the liquid.
Distillation Apparatus:
[Link] or Distillation flask: The container in which liquid is heated is known as still. A round-bottomed flask
with side arm sloping downward is used. It should be of such size that it is one half to two thirds full of the
liquid. Bumping due to superheating is avoided by adding small chip of glass.
[Link]: The temperature at which the vapors distil is observed on a thermometer, inserted through a
cork, and having its bulb just below the level of the side arm.
[Link]: Still is connected to an apparatus through which cold water is circulated to carry out
condensation called condenser.
[Link]: The vessel in which condensed liquid is collected is known as receiver and the liquid so
received is called distillate.
On laboratory scale the distillation apparatus, i.e. still, condenser and receiver is made of glass but it may
also be made from metal best suited to the process.

CONDENSERS
A condenser works as a heat exchanger. A large volume of cooling water is required for condensation
of liquids which boil at about 120 to 150 °C. A stream of cooling water may cause the condenser walls
to crack, due to high temperature difference. The cooling water is arranged to move on the counter-

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 current principle, i.e. its direction of water flow is opposite to that of vapors to be condensed. For liquids
boiling above 150 °C, simple air cooling is used.
Various types of condensers:

a) Leibig b) Spiral (c) Bulb (d) Double surface condenser

TYPES OF DISTILLATION:
1. Simple Distillation: Used when the components have significantly different boiling points.
2. Fractional Distillation: Used when the components have closer boiling points, often employed in
refining crude oil.
3. Vacuum Distillation (Distillation under reduced pressure): Used when the components have very
high boiling points, by lowering the pressure to reduce boiling points.
4. Steam Distillation: Used for temperature-sensitive materials, such as essential oils.
5. Destructive distillation
SIMPLE DISTILLATION
In simple distillation, the liquid is heated to boiling point. The hot vapors produced are immediately passed
into a condenser which cools at a lower temperature. The cooled vapors are then converted into liquid again
or distillate. The distillate is a purified form of the original liquid. When the liquid evaporates, many
impurities are left behind, so they are not present in the distillate.
Simple distillation is usually used only to separate liquids whose boiling points are quite different e.g.
acetone [57°C] can be separated from water [100°C] or to separate liquids from nonvolatile solids or
oils.

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Application of simple distillation
1. Used for the purification of the organic liquids
2. Preparation of Purified water and water for injection.
3. Separation of the liquids from non volatile solids e.g. recovery of the alcohol in preparation of
dry extracts.
4. In the preparation of the ether, amyl nitrate, and spirit of nitrous ether.
Preparation of Purified water
Ordinary drinking water contains traces of Ca, Mg, Cl, So4, Fe, Cu, Pb, NH3 which should be within the
limit of Pharmacopoeia. Therefore, tap water is unsuitable for making pharmaceutical preparation. The
gaseous impurities can be removed by discarding first portion of distillate or by heating water at above
90°C. A typical form of distillation unit for continuous production of purified water is shown in Figure. Its
capacity is 10L/hour

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In this unit water is heated by electric heating rod. Level of water in the still is maintained by continuous
flow of water from inlet of condenser through outlet and into the constant level device. The inlet cold
water performs two functions. First, it cools the surface of the condenser and secondly it enters the level
device which maintain water level in the still. The cooled water from inlet becomes hot during its
passage through hot surface of the condenser. When this hot water enters the still will require little heat
to vaporize. In this continuous process we can save heat and time. In practice the flow of water from the
main supply to the still or boiler should be about five times greater than the output of the still. Some
solids will be deposited on the inner sides of glass still or metallic and it is necessary to descale the still
from time to time with dilute acid.

FRACTIONAL DISTILLATION

Fractional distillation process is used to separate miscible volatile liquids that have boiling points closer to
each other. Fractional distillation must be used in order to separate the components by repeated
vaporization-condensation cycles within a packed fractionating column.

Raoult’s Law

In a solution of two miscible liquids (A & B) the partial pressure of component “A” (PA) in the solution
equals the partial pressure of pure “A” (PAo) times its mole fraction (XA)

Partial Pressure of A in solution = PA = (PAo) × (XA)

Partial Pressure of B in solution = PB = (PBo) × (XB)

When the total pressure (sum of the partial pressures) is equal to or greater than atmospheric Pressure (760
mm Hg), the solution boils.

PTotal = PA + PB = PAo XA + PBo XB

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 Theoretical Plates:
A theoretical plate is a hypothetical zone or stage in which two phases, such as the liquid and vapor
phases of a mixture establish equilibrium with each other. Such equilibrium stages may also be referred
to as an equilibrium stage or a theoretical tray.
Or
A theoretical plate is a cycle of evaporation and condensation in a distillation. The number of theoretical
plates is a measure of the ability of a distillation to separate substances. Fractional distillations have
many theoretical plates.

Laboratory setup:
Fractional distillation in a laboratory glassware include

 distillation flask, or a round-bottom flask

 fractionating column
 distillation head
 thermometer
 condenser
 receiving flask,
 heat source
 boiling chips, also known as anti-bumping granules

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Method

1. The liquid mixture to be purified is heated, its vapors rise to the fractionating column.

2. As it rises, it cools and condense on the column walls. Here, the condensate continues to be heated by the
rising hot vapors; it vaporizes once more. Each vaporization-condensation cycle (called a theoretical plate)
will yield more volatile component. More theoretical plates lead to better separations.

3. As the distillation proceeds, the composition of the liquid and the vapor in fractionating column is
continuously changing. This process continues until most of the lower boiling compound is removed from
the original mixture and condensed in the receiving flask.

4. When the lower boiling liquid is successfully removed from the original mixture, the temperature rises
and a second fraction containing some of both compounds is produced.

5. As the temperature approaches the boiling point of the higher boiling point liquid, the distillate is then
collected in a separate receiving flask.

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 Example

 Consider the distillation of a mixture of water and ethanol.

 Ethanol boils at 78.4 °C while water boils at 100 °C.
 The mixture is put into the round bottomed flask along with a few anti-bumping granules, and the fractionating
column is fitted into the top.
 As the mixture boils, vapor rises up the column. Only the most volatile of the vapors stays in gaseous form all
the way to the top.
 The vapor at the top of the column then passes into the condenser, which cools it down until it liquefies.
 The process continues until all the ethanol boils out of the mixture. This point can be recognized by the sharp
rise in temperature shown on the thermometer.

Zeotropic: When one liquid ‘A’ from liquid mixture (A&B) is distilled out completely at low BP (boiling
point) and component B will be distilled at high BP. Such systems are known as zeotropic mixture. Such
miscible mixtures can easily be separated without any difficulty.

Azeotropic or Constant boiling mixture: A mixture of 2 or more liquids which cannot be

easily separated into pure liquids by distillation are called azeotropic mixtures. Their
composition is unchanged and pure distillate of one liquid from the mixture cannot be obtained.

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 Application of Fractional Distillation

1. Fractional distillation is employed in the preparation of alcohol which is one of the important constituent in
pharmaceuticals. The liquor from fermentation of sugar is a common source of ethanol and contains about
8-10%. Purification of ethanol form azeotrope mixture containing 95.6% ethanol (rectified spirit) which
boils at 78.15 ºC.

2. Absolute ethanol (100%) may be prepared from 95% ethanol (azeotropic mixture) with sufficient benzene.
Benzene forms a ternary mixture with water-ethanol mixture and binary mixture with ethanol. When
benzene and rectified spirit mixture is distilled, the ternary mixture distillate at 64.8 ºC removing all the
water and binary mixture distils at 68.2 ºC removing all benzene. Finally, the pure alcohol is obtained at
78.3 ºC as absolute or 100% ethanol.

3. Fractional distillation of petroleum: The fractional distillation of petroleum is based on the fact that
different components of petroleum have different boiling point ranges, and condense at different
temperatures depending upon their boiling points. Crude petroleum is heated at 400ºC in an iron still in
which all constituents except the residue are evaporated. The hot vapors are then passed through a
fractionating column, which is a tall cylindrical tower containing a number of horizontal stainless steel
trays. As the mixture vaporizes in the column, it cools. The component with highest boiling point liquefies
first and is collected. Then, a little higher in the column, the other component gets liquefied and collected
and gases escape from the upper part of the tower. Many useful components are natural gas, petrol, diesel,
kerosene, asphalt and lubricating oils, Liquid paraffin and soft paraffin. Asphalt and lubricating oils are not
used as fuels.

STEAM DISTILLATION

Steam Distillation is a separation process for heat sensitive substances such as natural aromatic
compounds. It is used for separating mixtures of chemicals such as oils, resins, hydrocarbons, etc. which
are immiscible with water and may decompose at their boiling points.

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Steam distillation was invented by the Persian chemist, Ibne Sina, in the early 11th century. He invented
it for the purpose of extracting essential oils, which is used in perfumery industries.
PRINCIPLE
 Many organic compounds decompose at high temperatures and separation by simple distillation
cannot be carried out, so steam is introduced into the distillation apparatus.
 By introducing steam, the boiling points of the compounds are decreased, allowing them to
evaporate at lower temperatures.
 For example, the boiling point of bromobenzene is 156°C and the boiling point of water is 100 °C,
but a mixture of the two boils at 95°C. Thus, bromobenzene can be easily distilled at a
temperature well below its normal boiling point. Similarly, turpentine (b.p. 160°C) when mixed
with water can be distilled at 95.6°C if a current of steam is passed through it.

Laboratory Setup
 The apparatus consists of a steam generator fitted with a rubber plug with two holes.
 Through one hole a long safety tube is passed which permits the expulsion of some water if
excessive pressure is generated inside the steam generator.
 The other hole carries the steam to the flask containing the liquids volatile liquid to be distilled.
This tube must dip almost to the bottom of the flask.
 On heating, the steam passes through the boiling mixture.
 The vapors of liquid and water produced are condensed in the condenser and collected in the
receiver.
 The distillate forms two layers, one aqueous and the second non-aqueous which can be separated
from each other using a separating funnel.

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 Applications:
1. Steam distillation is used for the distillation of water immiscible liquids of high boiling points
e.g. turpentine and aniline.
2. It is used for the extraction of volatile oils and essential oils from their crude drugs e.g. clove
oil, eucalyptus oil, orange oil and anise.
3. It is also useful for the purification of volatile substances.
4. If the substances to be distilled are very sensitive to heat, steam distillation can also be
combined with vacuum distillation.

VACUUM DISTILLATION/ DISTILLATION UNDER REDUCED PRESSURE

 Distillation at pressure below atmospheric pressure is called vacuum distillation or under reduced
pressure.
 Vacuum distillation is used to separate components that have high boiling points. Lowering the
pressure of the liquids also lowers the boiling points.
 The liquids which are decomposed at their boiling point under atmospheric pressure can be
distilled at a much lower temperature if the pressure is reduced.
 Dimethyl sulfoxide usually boils at 189°C. Under a vacuum, it distills off into the receiver at
only 70°C.
Operation
 The mixture to be separated is placed in the Evaporation flask (distillation flask) and heating of
the flask should not be started until the required vacuum has been attained.
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  The pressure inside the apparatus is reduced with the help of vacuum pump to facilitate the
mixture to evaporate under their boiling points.
 Some glass beads can be added in the distillation flask to prevent bumping.
 The vapors through condenser are condensed into liquid and is collected in the collection flask.
 After distillation, the Air outlet valve is opened to allow the vacuum to release.
 In the end, the collection flask is detached and distillate is transferred to another container.

Pharmaceutical applications
Following are the some important application of vacuum distillation:
1. For heat labile substances i.e. those substances that decomposed at their boiling point.
2. Absolute alcohol is prepared by this process.
3. Isolation and purification of plant extracts and natural products.
4. It is very commonly used for the evaporation of the solvent in the preparation of extracts.
5. The most common apparatus applied today for simple distillation under reduced pressure
is Vacuum Rotary Evaporator.

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 DESTRUCTIVE DISTILLATION
In this process the decomposition of natural products is carried out by heat and the volatile products are
condensed and collected. Destructive distillation is not a true distillation, but is a chemical reaction for
cracking larger molecules into smaller, more volatile components.
Destructive Distillation of Wood:
 In this process wood is heated to form charcoal and methanol. Some wood pieces are placed into a test
tube and strongly heated.
 A small nozzle has been placed on the tube so that any gases coming out of the heated mixture will
pass through the nozzle.
 The wood is decomposing, and one of the decomposition products is methanol.
 The charcoal left behind is much higher in carbon content and is used as adsorbent usually in
poisoning.
Destructive Distillation of Coal:
 When coal is heated without air, it does not burn but produces many by-products.
 Finely powdered coal taken in a test tube is heated.
 As the coal breaks down, coal tar, ammonia and coal gas are produced.
 Coal tar collects at the bottom of the second test tube and coal gas escapes out through the side tube.
 The ammonia produced is absorbed in the water forming ammoniacal liquor (ammonium hydroxide).

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Applications
 Though it is not a pharmaceutical process but is used in the destructive distillation of wood and coal;
 Coal tar can be used to make soap, dyes, plastics, perfumes, drugs, pesticides, explosives etc; ammonia
is used for making fertilizers; and coal gas is also used as a fuel.
[Link]
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