3.

DISTILLATION
Definition:
 Distillation is the process in which a liquid is vaporized, re-condensed (turned back
into a liquid) and collected in a container.
 Distillation may be defined as the separation of the constituents of a mixture including
a liquid by partial vaporization of the mixture and separate collection of the vapors.

General Apparatus:

01 Heat Source 09 Vacuum / Gas Inlet

02 Still Pot 10 Still Receiver
03 Still Head 11 Heat Control
04 Thermometer / Boiling Point Temperature 12 Stirrer Speed Control
05 Condenser 13 Stirrer / Heat Plate
06 Cooling Water In 14 Heating (Oil/Sand) Bath
07 Cooling Water Out 15 Stirrer Bar/Anti-bumping Granules
08 Distillate / Receiving Flask 16 Cooling Bath
The separations may include;
 Separation of a liquid from non-volatile impurities
 The separation of a liquid from one or more other liquids, with which it may be
miscible, partially miscible or immiscible.
 The process of vaporizing a liquid mixture in one vessel and condensing the vapors into
another vessel is called distillation.
 The liquid being distilled is heated in a flask, which is sometimes called a distillation
flask or distillation pot or Still.
 The vapors are condensed on a cool surface, usually a water-cooled condenser.
 The resulting liquid is called the distillate and is collected in a receiving flask or
Receiver.
 The boiling point of mixtures depends upon mole fraction of the component present
i.e.:
 o In pure substances the temperature remains constant during distillation process
so long as both vapor and liquid are present.
o In miscible liquid mixture the temperature increases throughout process because
composition of vapor changes continuously.

Types of Distillation:
Some types of distillation are as follows.
 Simple Distillation
 Fractional Distillation
 Steam Distillation
 Vacuum Distillation
 Destructive Distillation

1. Simple Distillation:
 Simple distillation is a process of converting a liquid into its vapors, transferring the
vapors to another place, and recovering the liquid by condensing the vapors, usually by
leading contact with a cold surface. The apparatus used consists of three parts:
o Still in which volatile material is vaporized
o Condenser in which vapors are condensed
o Receiver in which distillate is collected
 Simple distillation can produce partial separation of components with different boiling
points in a liquid mixture.
 The process is generally used for separation of liquids from non-volatile solids, e.g.,
preparation of distilled water and recovery of alcohol in the preparation of dry
extracts.
 Simple distillation is practiced for a mixture in which the boiling points of the
components differ by at least 70°C.
 It is also followed for the mixtures contaminated with nonvolatile particles (solid or oil)
and those that are nearly pure with less than 10 percent contamination.

Double Distillation:
Double distillation is the process of repeating distillation on the collected liquid in
order to enhance the purity of the separated compounds.
Process of Simple Distillation:
 For simple distillation on laboratory scale, a distillation flask with side arm slopping
downwards is used.
 The temperature at which the vapors distil is observed on a thermometer.
 Thermometer is inserted through a cork and having its bulb just below the level of the
side arm.
 The size of the flask should be good enough to hold the volume double than the
required volume.
  Bumping, due to heating is avoided by adding a small chip of porous pot before the
start of distillation in the flask.
 If the process is interrupted, a fresh chip should be added. They will prevent
superheating of the liquid being distilled and they will cause a more controlled boil,
eliminating the possibility that the liquid in the distillation flask will bump into the
condenser.
 Chips should not be added to the superheated liquid; otherwise an instantaneous
evolution of a large volume of vapors will occur.

Condenser:
A condenser is a heat exchanger; its surface is kept cold by a stream of cold water. It
should have the following properties:
 Construction of condenser should be such that it can be easily cleaned.

 The broken parts may be easily replaced so that the cost of new one is saved.
 Provide maximum cooling surface because the rate of condensation is directly
proportional to the cooling area.
 Condensing surface should be good conductor of heat, therefore where practicable
metal condensers are preferred over glass.
 Water used for cooling must leave the condenser quickly so as to provide space for
water to get in and provide cold surface.
 Water must flow in opposite direction to vapors so that the condensed liquid should
leave the condenser in as cool a condition as possible.

Limitations of Simple Distillation:

 It produces a distillate that is always impure at any temperature range between the
ranges of boiling points of the components. Therefore, it is impossible to completely
separate the components in a mixture with Simple Distillation.
 Relatively pure substances can be obtained from a mixture with Simple Distillation if
the boiling points of the components differ by a large amount (>70ºC).
 This may be a very tedious process involving a large number of distillations.

Properties of Simple Distillation:

  Simple set up
 Fast process
 Consumes less energy
 Poor separation
 Best for relatively pure liquids

Applications of Simple Distillation:

 For purification of organic liquids.
 Separation of liquids from non-volatile solids – recovery of alcohol in the preparation
of dry extracts.
 Preparation of different substances – ether amyl nitrate etc.
 Preparation of distilled water.
 Identification.

2. Fractional Distillation:
Introduction:
 Simple Distillation separates components of a mixture based on the differences in
boiling points of the pure components.
 The closer the boiling points are to each other, the more difficult the separation;
hence Fractional Distillation is used instead of simple distillation.
 The boiling point of a substance determined by distillation is a useful physical
property for the characterization of pure compounds
 Fractional Distillation is one of the most common separation method used when
purifying liquid organic samples.
 Especially, to separate miscible volatile liquids having different boiling points e.g.,
mixture of Alcohol and water.
 It is quite easy to separate a liquid from non-volatile solids by simple distillation but
it is very difficult to separate two volatile liquids completely from each other by
simple distillation.
 The fractional Distillation accomplishes the same Condensation Cycles, by inserting
a Fractionating Column between the Distillation Flask and the Distillation Head.
 The Fractionating Column subjects the mixture to many Condensation Cycles as the
material moves up the column toward the Distillation Head. With each cycle within
the column, the composition of the vapor is progressively enriched in the lower
boiling liquid. This process continues until most of the lower boiling compound is
removed from the original mixture and condensed in the receiving flask.

Process:
 Distillation is one of the oldest and still most common methods for both the
purification and the identification of organic liquids. It is a physical process used to
separate chemicals from a mixture by the difference in how easily they vaporize. As
the mixture is heated, the temperature rises until it reaches the temperature of the
lowest boiling substance in the mixture, while the other components of the mixture
 remain in their original phase in the mixture. The resultant hot vapor passes into a
condenser and is converted to the liquid, which is then collected in a receiver flask.
 When the lower boiling liquid is effectively removed from the original mixture, the
temperature rises and a second fraction containing some of both compounds is
produced. As the temperature approaches the boiling point of the higher boiling point
compound, the distillate condensing into the third receiving flask is increasingly pure
in the higher boiling point compound

Principle:
 The principle of fractional distillation is based on the establishment of a large number
of theoretical vaporization-condensation cycles.
 The apparatus of a simple distillation is modified by inserting a fractionating column
between the distillation flask and the distillation head.
 The fractionating column provides a large surface area in which the initial distillate is
redistilled and condensed again.
 This process continues as the vapors rise up the column until the vapors finally make
it into the condenser.
 These vapors and the final distillate will contain a greater percentage of the lower
boiling liquid.
 Continuous repetition of re distillation process in fractional distillation gives good
separation of the volatile liquid components.

Azeotropic Mixtures:
 Azeotropic mixture or constant boiling mixture is one in which the composition of
the liquid and the vapor in equilibrium with it, is the same.
 Their proportions cannot be altered by simple distillation.
 The mixture behaves like a pure liquid and distils without change in composition or
boiling point. Such mixtures cannot be separated into their pure components by
simple distillation, e.g., alcohol and water, alcohol and benzene, alcohol and
chloroform.
Ternary mixtures:
Mixtures of three components, which do not form azeotropes may be separated by
fractional distillation in the same way as the binary mixtures.
Properties of Fractional Distillation:
 Complicated
 Slow
 Consumes more energy
 Better separation
 Best for mixtures with close B.P

Applications of Fractional Distillation:

 Separation of two immiscible liquids having different boiling points.
 Separation of ternary mixtures.
 Manufacture of Alcohol

3. Steam Distillation:
Introduction:
 Steam distillation is a special type of distillation for temperature sensitive materials
like natural aromatic compounds.
 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
 Steam distillation is used for the distillation of water-immiscible liquids of high
boiling points, e.g., turpentine, aniline.
 By bubbling steam through the liquid, the mixture boils at below the normal boiling
point of the either component.
 The distillate consists of the two liquids in the same proportions as in the vapor E.g.
Turpentine has a boiling point of 160 C, when mixed with water it can be distilled at
about 95.6C.

Steam Distillation Principle:

 This method is based on the fact that, total vapor pressure above a mixture of two
immiscible liquids is equal to the sum of the vapor pressures of the individual liquids
i.e.,
Ptotal = P1 + P2 Hence, P2 = Ptotal - P1
 A liquid boils at the temperature when its vapor pressure becomes equal to the
atmospheric pressure.
 Steam is continuously passed over the impure organic liquid; the steam heats the
liquid and gets condensed into water itself.
  The resulting mixture of liquid and water begins to boil when the vapor pressure
above the mixture becomes equal to the atmospheric pressure.
 Hence the mixture of the two immiscible liquids will boil at a temperature lower than
the normal boiling points of both the liquids.
 The mixture will continue to boil at the same temperature until one of the liquids is
completely distilled out.
 The distillate, which contains water and the liquid, separates out into two layers as
both are immiscible with each other.
 The two layers can be separated using a separating funnel.

Steam Distillation Process:

 The impure compound and water are placed in a distillation flask kept at a slight slant
position and heated on a sand bath.
 Steam is then bubbled through this mixture.
 The vapors of the compound, along with steam, leave the flask from the outlet and
get condensed in the water condenser.
 The condensate collected in the receiver is transferred to a separating funnel.
 The liquid compound being immiscible with water forms a separate layer and can be
separated.

Solid Drying Agents:

 Final traces of water are removed by treating the organic solution with a drying agent.
 A drying agent is an inorganic salt which readily takes up water to become hydrated.
 Several such salts are used routinely in labs. Magnesium sulphate is a good general
choice as it is fast and not very soluble in water.
 There is no set “rule” as to how much drying agent needs to be added. The amount
required depends on the amount of water in the liquid or solvent solution which you
are drying. This amount varies from experiment to experiment.
 Use as much as it takes to dry the solution. In most cases, drying is complete in 20
minutes.
 When drying is complete, you need to remove the dried organic solution from the
drying agent. There are several methods by which it can be done.
 If the powder is quite fine (as when using magnesium sulphate) or if the volume is
large, gravity filtration is the method of choice.
 In case the drying agent is of larger particle size (as when using sodium sulphate or
calcium chloride, decanting is the method of choice.

Small Scale Steam Distillation:

 On laboratory scale the apparatus consists of a steam generator fitted with a rubber
bung/plug having 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.
 Through the second hole, a bent tube is passed which carries the steam to the flask
containing the liquids to be distilled (immicible liquid + water).
  The bent tube must dip almost to the bottom of the flask.
 The steam must touch below the surface of the liquid, and heat it up. So that a rapid
current of steam passes through the boiling mixture in the flask.
 The vapors are allowed to pass through the condenser and the condensed liquid is
collected in the Florentine receiver.

Florentine Flasks:
The distillate which forms in two layers – one aqueous and the other non-aqueous, are
separated from each other as completely as possible. For separation Florentine receivers or
separating funnel is used. Florentine receiver is a specialized receiver for collecting the oil
and water in the same receiver.
Applications:
 For distillation of water immiscible liquids of high boiling points – turpentine, aniline,
phenylalanine etc.
 For extraction of volatile oils from their crude drugs – clove oil, anise oil and
Eucalyptus oil from clove, anise and Eucalyptus.
 For purification of volatile substances.
 In the manufacture of essential oils, for use in perfumes.
 To separate intermediate or final products during the synthesis of complex organic
compounds.

4. Vacuum Distillation:
 Vacuum distillation is also known as distillation under reduced pressure.
 It works on the principle that a liquid boils when its vapor pressure is equal to the
atmospheric pressure or the external pressure.
 This technique is used for purifying or separating thermally unstable liquid
compounds that decompose at their normal boiling points.
 Liquids which are unstable at their boiling points can be distilled at a much lower
temperature than their boiling points, under reduced pressure with less likelihood of
decomposition.
  Boiling under reduced pressure also increases the rate of distillation.
 Under this condition, the compounds boil below their normal boiling temperature.
Hence, vacuum distillation is best suited for separation of compounds with higher
boiling points (more than 200°C), which tend to decompose at their boiling
temperature.

Vacuum Distillation Principle:

The lowering of pressure on the surface of a liquid lowers its boiling point. As a result
of this, a liquid can be boiled and distilled, without any decomposition, at temperature much
below its normal boiling point. Distillation under reduced pressure or vacuum is carried out in
a specially designed glass apparatus. A two necked 'Claisen's flask' is used.

Process:
 Distillation under reduced pressure is very commonly used for the evaporation of the
menstrum in the preparation of the extracts.
 Vacuum distillation is most conveniently carried out in a specially designed flask,
known as Claisen flask
 This special flask has two necks. Through one neck, a thermometer is inserted and is
attached to the condenser. Through the other neck a very fine capillary tube is
introduced which completely dips in the boiling liquid.
 Bumping readily occurs during the distillation under reduced pressure, but it can be
easily prevented by introducing stream of air bubbles passing into the liquid, through
the fine capillary tube
 The capillary tube should be sufficiently fine to permit only a slow stream of bubbles to
be blown into the tube.
 The side tube of the receiver is connected to a vacuum pump to provide the suitable
vacuum
 In all vacuum distillations, a small pressure gauge (manometer) should be inserted
between the receiver and the vacuum pump
  In carrying out the distillation, heating is not commenced until the required vacuum has
been attained above the surface of the liquid, otherwise frothing of the hot liquid will
result in the receiver.
 Heating of the flask should be done on a water bath or oil bath maintained at about
20ºC higher than the boiling point of the liquid under reduced pressure.
 Thin walled glass apparatuses, such as ordinary flat bottomed flasks and conical flasks
should never be used for vacuum distillation; otherwise collapsing of such apparatus
may result.
 In some cases, persistent foaming occurs during the process of vacuum distillation.
This may be overcome by adding capryl alcohol to the liquid to be distilled, or by
inserting a second air capillary tube in the thermometer neck of the claisen flask. The
stream of air drawn through the tube breaks the rising foam.

Vacuum Distillation Advantages:

 The compounds that decompose on heating to their boiling points can be purified by
distillation under reduced pressure. This is because at the reduced pressure, a liquid
would boil at a temperature much below its normal boiling point.
 Distillation under reduced pressure is more fuel-economical as it makes the liquid boil
at temperatures well below the normal boiling point.
 Vacuum distillation is used to safely recover higher boiling point solvents.
 It is used to safely recover solvents with boiling points over 300º Fahrenheit.
 Vacuum distillation should not be used on solvents with boiling points below 200º
Fahrenheit.

Applications:
 For distillation of thermo labile substances.
 For concentration and drying of extracts which get destroyed at high temperature.
 For purification of vitamins

5. Destructive Distillation:
 Destructive distillation is the term used to describe the decomposition of a substance,
usually a natural product, by heat followed by the condensation and collection of the
volatile products of decomposition.
 It is not a pharmaceutical process but is used in the manufacture of some substances
used in medicines.