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Theory

The basic principle involved in the distillation process is the

difference in the volatilities of the components of the liquid
mixture. Some of the basic concepts involved in the process of
distillation are discussed below.

Raoult's Law

Raoult's law gives the quantitative relationship between the

vapour pressure and concentration of a component. If a
solution containing two components (A and B) is considered,
with n and n moles respectively, then Raoult's law states that 3
the partial pressure of component
A of a solution is equal to the product of vapour pressure

of component A in pure state and the mole fraction of that component in the
solution at a definite temperature. Partial pressure of component A Vapour
pressure of component A Mole fraction of component A
Where.
(1)Partial pressure of component A (pressure
exerted by component A if it were alone
in a container)
P - Vapour pressure of component A in pure
state (pressure exerted by vapour of component A in equilibrium with liquid
phase).
X-Mole fraction of component
which is given as, 4
Moles of compos A Total number of ols
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Binary Solutions

Binary solutions refer to a mixture of liquids which are miscible with each other
in all proportions. Most of the binary solutions obey Raoult's law but to a lesser
extent when compared to ideal solutions : Examples
Water and methanol
Acetone and water
(c) Benzene and carbon tetrachloride. Deviations from Raoult's Law
Real solutions are those which do not obey Raoult's law at all concentrations and
temperatures. These solutions do not satisfy the conditions for Raoult's law. (The
intermolecular forces between the molecules of the components are unequal inspite of
which they are completely miscible in all proportions. These molecules interact with one
another which results in either an increase or decrease in the vapour pressure of the
liquid mixture when compared
to ideal behaviour.
Examples of real (non-ideal) solutions 1. Carbon tetrachloride and cyclohexane 4
2. Chloroform and acetone Benzene and ethanol
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MOLECULAR DISTILLATION/
EVAPORATIVE
DISTILLATION\UNOBSTRUCTED
PATH DISTILLATION
PRINCIPLE
 Molecular distillation is used for the
separation of high molecular weight liquids
and liquids that are more viscous.
 In order to avoid the
intermolecular collision between the
molecules this process involves the application
of vacuum but travel mean free path and get
condensed individually
MEAN FREE PATH
 It is the average distance
travelled by the molecules
without undergoing any
intermolecular collision.
 For highly viscous liquids, the mean free path is short,
which means the frequency of collision is more due to
which rate of distillation gets reduced.
 So the main principle of molecular distillation is
to decrease the frequency of collision.
 That is achieved by lengthening of mean free path of the
molecules. This is done by decreasing the pressure on
the system by applying vacuum.
 As the collisions are decreased, and there is
no obstruction in the flow is also referred to
as UNOBSTRUCTED PATH DISTILLATION DESIGN.
 Distance should be very small and equal to the mean free
path so that the molecules leaving the evaporating
surface, immediately strike the condenser surface.
 The number of collision should be negligible
because they divert the molecules from the path.
These collisions can be minimized by reducing
the pressure on the system by using
the high vacuum conditions.
 The area of liquid should be large so that the vapour
molecules get evolved from the surface only. Hence this
method is known as EVAPORATION DISTILLATION
Falling Film Molecular Still
Centrifugal Molecular Still
Falling film molecular still
 Principle
Liquid mixture to be distilled

Thin film [ HIGH VACUUM]

Flows down the heated surface

The distance between the film and the condenser wall is very small so the
vapour molecule immediately condensed. The condensed liquid is then
withdrawn and collected.
FALLING FILM MOLECULAR STILL
CONSTRUCTION
 It is about 1m in diameter and has capacity of 1000
Lt/hr.
 The vessel is enclosed by heating jacket the inner wall
acts as evaporating surface.
 Wipers are present after the evaporating surface on
both sides of the wall which are made up of
polytetrafluoroethylene [PTFE].
 Wipers are connected to the rotor with the help of
which liquid feed is spread as their film in the
evaporating surface.
 Distance between the condenser and
evaporating surface is maintained minimum.
 A pipe with large diameter is placed which
is connected to the vacuum pump to maintain
the pressure.
 The lower portion consists of provisions for
the collecting the residue and product.
WORKING
 FEED INLET FEED

EVAPORATING SURFACE {1.5 m/s}

( Free falling molecular still )

WIPERS

THIN FILM {3m/s}

PRETREATED EVAPORATING SURFACE

LIQUID FILM EVAPORATES

 Liquid film evaporates

 Vapour molecules cover  Vapour molecules that do

mean free path. not cover the mean free
path.

 Gets condensed.
 Remain undistilled.

 With drawn as distillate.

 Collected as residue.

 It is fed into the feed inlet

and recirculated.
CENTRIFUGAL DISTILLATION
PRINCIPLE
 It is based on principle of molecular
distillation with centrifugal action . It is also
called evaporative distillation or short path
distillation.
 The substance to be distilled in molecular
distillation have very low vapour pressure.
eg ; Viscous liquids , oils , greases waxy
material and high molecular weight.
CONSTRUCTION
 It consists of bucket shaped vessel having a
diameter of about 1 to 1.5m.
 It is rotated at high speed using a motor.
 Radiant heaters are provided externally to heat
the fluid in bucket .
 Condensers are arranged very close to
evaporating surface.
 Vaccum pump is connected to the entire vessel
at top
 Provisions are made for introducing the feed
into the centre of the bucket , for receiving the
product and residue for recirculation.
WORKING
 Vaccum is applied at the centre of vessel .
 The bucket shaped vessel is allowed to rotate
at high speed .
 The feed is introduced from centre of vessel.
 Due to the centrifugal action of rotating
bucket , liquid moves outward over the
surface the evaporates directly from the flim .
 The vapour travels mean free path and strikes
the condenser .
 The condensate is collected into another
vessel.
 The residue is collected from the bottom of
vessel and re circulated through the feed part
for the further distillation.
MERITS

 It can be used for the heat sensitive

substance.
 It is only method which can used for
separation and purification of high
molecular weight compount.
DEMERITS
 It is very expensive
 The equipment is quite complicated for
handling and cleaning.
 This Method exhibits poor thermal
efficiency.
APPLICATION
 It is used for the separation and purification of substance
beith low vapour pressure.
 It is used in refining of fixed Oils .
 It is a very effective method for the purification of free
fattyacids steroids triglycerides etc.,,
 It can also be used for the separation of vitamins such as
 Eg; vitamin A from fish liver oil
 Vitamin B from vegetable oils
Introductio
n  Definition
 This Method Which employes Steam is
used for separation and purification of
Immiscible liquids .
STEAM DISTILLATION is
employed in following condition
are;
[Link] high boiling point substance are to
separarted from non volatile oil impurities
egs; separation of water soluble impurities
from volatile oils which are sensitive to heat
and possess high boiling point.

2. when the desired substance to be distilled

in water immiscible and is thermostable.
3. When effective and purification is not
achieved through other distillation
methods.
[Link] the
susbstance to be distilled is steam
volatile.
PRINCIPLE
 Steam distillation is a batch process and
it is used for these liquids which are
water immiscible show high boiling and
tend to deteriorate at high temperature
( high sensitive substance ) such liquids
can be separated at temperature which
below the boiling point of either of
components.
 The desired product is distilled at preferable
temperature at which deterioration of
substance is not possible .Hence with
addition of water of steam to the Immiscible
liquids .The boiling point of water is
appreciably reduced .
 The liquid mixture begin to boil when the
Sum of vapour pressure of two Immiscible
liquids becomes equal to atmospheric
pressure . Hence boiling temperature can be
decreased by using water or steam
CONSTRUCTI
ON
 Metallic steam can also known as stream
generator as it is responsible for the
generation of Steam which is utilised in
Steam distillation process.
 Mouth of the can fitted with rubber cork
which consists of two holes . In one of them ,
a long glass tube is inserted such that tip
touches the bottom of the can .This tube acts
as the safety tube and to release excess
pressure. The consists of another hole
through which the bend tube is [Link]
bend tube connect the steam can to the
round bottom flask
 The ruber bank also contains two holes. The
round bottom flask is connected to condenser
via delivery tube . The condenser turn in
connection to the receiver vis condenser.
WORKING
 Steam can containing water and round
bottom flask containing mixture of
liquid and water are heated
simultaneously.
 Steam generated in steam can is
transferred to round bottom flask .
Due to this , the liquid starts to boiling
when it’s vapour pressure become
equal to atmospheric pressure.
 Mixed vapour ( vapour of steam and
volatile Component) are passed into
condenser via delivery tube where they get
condensed by circulating water.
 The condensate is then collected into
receiver
 The condensate is a two phase system
containing water and volatile liquid which
can be separated using separating funnel.
MERITS

 Steam distillation is very useful for

separation and purification of organic liquids
with high boiling point.
 Since the distillation temperature is low ,
steam distillation helps in avoiding
decomposition of component and retaining
aroma of oil.
DEMERITS
 This method is not suitable for volatile Oils
which interact with water.
 Complete separation of water and Volatile oil is
not Possible .
 In case of volatile oils with specific gravity
equal to one, the method become more
tedious,as an additional volatile , water
Immiscible Solvent to be added, In order to
separate Volatile oil from water.
 This method can be applied only higher
molecular weight Organic components .
Components with low molecular weight
Will constitute only small proportion of
[Link] Yield of the volatile
Component obtained by steam distillation
is less.
APPLICATION
 Steam distillation is mainly used for
separation of high boiling and water
Immiscible liquids which are
thermolabile by employing lower
temperature.
 Eg ; pure water
 ( B.p= 100° c ) turpentine ( B.p= 169°c)
Mixture of water and turpentine
( B.p= 95.6°c)
 Many volatile oils can be extracted
from various plant source through
steam distillation
; Eg; Eucalyptus oil , clove oil , orange
peel oil , almond oil etc.,,,
 The method can also used for
preparation of aromatic waters
Egs; Camphor water, cinnamon water,
rose water , peppermint water etc.,
 Many organic compounds can be
purified by Steam distillation process.
Egs; turpentine oil , glycerine , fatty
acids etc.,
 This Method is also used in perfumery,
petroleum refeneries and petro
chemical industries.
Rectification
Introduction
 Fractional distillation also known as
rectification, is a process which is used for
separating components of a mixture of
miscible volatile liquids having different
but close boiling points using a
fractionating column
 The major aspect which is different between
fractional and steam distillation is that in
latter the vapour is allowed to flow to the
condenser.
• In contrast, in fractional distillation,
the condensed vapour obtained is
again admitted from the top of the
fractionating column so that as it
passes down it acquires an intimate
contact with the ascending vapours.
THEORY
 Fractional distillation involves
repeated vaporization and
condensation due to which there is
continuous change in the
composition of liquid and vapour
phases.

 The procedure involved in the

construction of these boiling point-
by using different quantities of these two liquids. This is followed
by determination of boiling point of each mixture.

[Link] of each component in the liquid phase is

determined at its boiling point. Similarly, composition of
eachcomponent in the vapour phase is determined at its boiling
point.

3.A graph is plotted by taking boiling point on Y-axis and

composition on X-axis.

[Link] of the liquid phase is represented by the lower

curve while that of vapour phase is indicated by the upper curve.
Area between these two curves indicates the vapour-liquid
composition.
PRINCIPAL
 Fractional distillation is a mass transfer
process involving counter current diffusion of
the component at each equilibrium stage.
•When liquid mixture is distilled, the partial
condensation of the vapour occurs at the
fractionating column. In the column the ascending
vapour from the still is allowed to come in contact
with the condensing vapour returning to the still.
This results in enrichment of the vapour with the
more volatile component.
repeatedly, equilibrium
between liquid and vapour is
set up at each stage, which
ultimately results in the
separation of the more volatile
component.
CONSTRUCTION
(b)Fractionating tower /rectifying column
It is placed between still and condenser. it appears as
a tower, hence it is also referred as fractionating tower
fraction of the condensate descents due to this
countercurrent flow. The vapour and fraction of
condensate come in intimate contact with one another
close contact the vapour tense to
vaporize the more volatile compound
from vaporize from liquid stream.

•In the some way the liquid stream

tends to to vaporize the less volatile
component from vapour stream. In
the process heat is transferred from
vapour stream to liquid stream
• As a result, the vapours get cooled
as they ascends the tower,whereas
liquid fraction Becomes
progressively hot as it descents the
tower
(C)CONDENSER
 The Ascending vapours are condensed in
in in the condenser. A fraction of
condensate is returned to column. this
fraction is referred to as reflex .The rest
of condensate is collected as a product
.In this way the complex separation of
individual components can be achieved.
WORKING
•The process starts with taking a
mixture of two liquids X and Y of which
X is more volatile than Y. To avoid
bumping add antifoaming granules
•the mixture is taken in distilling
flask and is heated. The temperature
rises slowly and mixture beings boiling
the vapour will start forming
• Vapours start travelling in the
fractionating column. Condensation of
vapours of the less volatile liquid Y will
start before than those of more volatile
liquid X.
•So by time, the vapours rising in the
fractionating column will be more of X
and the liquid flowing down will consists
of liquid Y.
X will reach at the top, from there
they are taken into the condenser
and finally the substance is
transferred to container.
•Similarly after a series of
distillations, the remaining liquid in
the distillation flask [Link] in
components with higher boiling
points
USES
[Link] of the important use of using fractional
distillation is to separate the crude oil into its
various components such as gasoline, kerosene
oil, diesel oil, paraffin wax, liberating oil.
[Link] distillation is also used for the
purification of water. Water contains many
dissolved impurities; these can be removed by
this process.
[Link] is also used for separating acetone and
water.
 [Link] use of fractional distillation
is in petroleum refineries, chemical
natural gas processing and separation of
pure gases from mixture of gases.

[Link] has other industrial uses as it is

used for purification and separation of
many.
Organic compounds.
DISADVANTAGES
 Fractional distillation cannot be used for
the liquids which are miscible
Merits of Fractional Distillation
 It is a continuous process wherein fresh
feed is always being added and the
product is always being removed
 Industrial scale apparatus use reflux to
achieve more complete separation of
components.
 Rectification can be employed as a batch
as well as continuous process depending
upon the level at which it is carried out.
oil etc

•Several types of fractionating

columns are available that
enable the vapour steam and the
fraction of the condensate
to come in intimate contact with
one another.
The following factors
influence the efficiency of
fractional distillation.
[Link] OF HEAT CONSUMED
 Heat supplied to the column in
order to vaporize the liquid should
be controlled. Excess heat may
increase the velocity and hence
effect the equilibrium, while very
little supply of heat may cause
uneven or insufficient wetting of
the column packing.
[Link] ratio
 Reflux ratio may be defined as the
fraction of the condensate
returning to the column to the
fraction of the condensate
collected in the receiver in the same
duration of time. Reflux ratio
along with the given feed and
reflux temperature helps to
determine the heat requirements.
 [Link] OF FEED PLATE
•In a continuous distillation process,
feed should be introduced at a point
where the composition of the distilling
liquid and the feed are same. If the feed
is introduced at a point where the
composition of these liquids is
different, then the efficiency of the
distillation process gets decreased.
[Link]
•Lengthy columns help to attain
maximum degree of separation. For
efficient working of columns, the column
temperature should be well maintained.
The column is generally provided with an
insulator to prevent the heat loss (when
the column temperature is too high) and a
heating jacket to increase the heat of the
column (when the column temperature is
low).
 [Link] EFFICIENCY
•For the separation of a particular liquid and
to determine the efficiency of the column, it is
necessary to calculate the required height of the
theoretical plate. It is calculated by taking into
consideration the factor known as height of
equivalent theoretical plate (HETP). According
to this method, the entire column is divided into
number of units, wherein each unit acts as one
theoretical plate. In each theoretical plate, the
vapour ascending and the liquid descending are
in equilibrium with one another.
[Link] FACTORS THAT ARE
INFLUENCING EFFICIENCY OF
FRACTIONAL DISTILLATION ARE.,

(a) Type of packaging material

(b) Liquid and vapour velocities