Distillation

Dr. Nasir Abbas

Definition
Distillation is a method of separating mixtures
based on differences in volatility (vapour
pressure) of the components in a boiling liquid
mixture
It is a unit operation, or a physical separation
process, and not a chemical reaction.
It is used in pharmacy either to extract volatile
active principles from vegetable drugs or to
separate volatile substances from less volatile
impurities.

Types of Distillation
Distillation can be classified into four main
types
1. Simple distillation
i. Under atmospheric pressure
ii. Under reduced pressure
2. Fractional distillation
3. Steam distillation
4. Destructive distillation

Theoretical consideration (Basic Concepts)
Vapour Pressure
According to Kinetic Theory, the molecules in a liquid are in a constant
state of thermal motion and some of these molecules are moving fast
enough to escape from the liquid forming a vapor above the liquid.
This vapour exerts a pressure on the surface of the liquid, i.e., Vapor
Pressure
The Vapour Pressure of a liquid increases, generally exponentially, with
temperature
As a liquid is heated, the vapour pressure of the liquid increases to the
point at which it just equals the applied pressure - usually atmospheric
pressure. The liquid now begins to bubble (boil)
Liquids with high vapour pressures (Volatile compounds) require
relatively little energy (heat) to increase the vapor pressure to match
the applied (atmospheric) pressure, and thus, boil, i.e. they have low
boiling points
Liquids with low vapour pressures require considerably more energy to
increase the vapor pressure to the point where it matches the applied
pressure, thus, they have relatively high boiling points
Theoretical consideration (Basic Concepts)
Boiling point

The Boiling Point is the temperature at which internal vapor pressure of
the liquid is equal to the pressure exerted by its surroundings

If the liquid is open to the atmosphere, the boiling point is the
temperature at which the internal vapor pressure of the liquid becomes
equal to atmospheric pressure ( 760 mm Hg = 1 atm).

The internal vapor pressure of a pure liquid rises steadily as the
temperature is increased until the boiling point is reached.

The temperature remains constant throughout the boiling process of a
pure liquid. At the boiling point, the liquid and vapor are in equilibrium, if
the composition of each phase remains constant, the temperature will
remain constant
Vapour pressure/ boiling point of Miscible Liquid
mixtures
Liquid/ liquid mixtures
Miscible and non miscible liquid mixtures
Miscible liquid mixture is also called as solution
liquid compounds making a miscible mixtures normally have
different vapor pressures at a given temperature
The individual compounds in a mixture each exert its own pressure
- i.e. called partial pressure
The sum of the partial pressures equals to the total vapor pressure
of the solution/mixture (Daltons Law for ideal gas)
P
total
= P
A
+ P
B


When the total pressure of a mixture (sum of the partial pressures)
is equal to or greater than the applied pressure, normally
Atmospheric Pressure (760 mm Hg), the solution boils
Solutions/mixtures have higher vapour pressure and lower boiling
point than their constituent pure liquids

Vapour pressure/ boiling point of Miscible Liquid
mixtures
Raoults Law
In a solution of two miscible liquids (A & B) the partial pressure of
component A (P
A
) in the solution equals
the partial pressure of pure A (P
A
o
) times its mole fraction (N
A
)
Partial Pressure of A in solution = P
A
= (P
A
o
) x (N
A
)
Partial Pressure of B in solution = P
B
= (P
B
o
) x (N
B
)
When the total pressure (sum of the partial pressures) is equal to or
greater than the applied pressure the solution boils
P
total
= P
A
+ P
B
=

P
A
o
N
A
+ P
B
o
N
B
Conclusion
When the two component of a binary mixture are completely
miscible, the vapour pressure of the mixture is a function of the
composition as well as the vapour pressure of the two pure
components.
Boiling point/ total vapour pressure of a mixture changes with its
composition

Vapour pressure of Miscible liquid
Boiling point of a mixture changes with its composition
(Raoults Law)

To get the total vapour pressure of the mixture, you need to add the values for
A and B together at each composition. The net effect of that is to give you a
straight line as shown in blue.
Solutions/ mixture may or may not follow the Raoults Law. P
total
=
P
A
+ P
B

Binary mixtures that follows the Raoults law are called ideal
solution, where the attraction between A and B molecules is the
same as those for the pure components, i.e A-B=A-A & A-B,
Example benzene/toluene mixture
When the interaction of A and B molecules (A-B) is less than
between the molecules of pure constituents (A-A, A-B), then vapour
pressure of solution is now greater than the expected from Raoults
Law. (positive deviation) example benzene /ethyl alcohol
When the interaction of A and B molecules (A-B) is more than
between the molecules of pure constituents (A-A, A-B), then vapour
pressure of solution is now lesser than the expected from Raoults
Law. (negative deviation) example Chloroform /acetone

Vapour pressure of Miscible liquid

Boiling point diagram of an ideal solution
Constructing a boiling point / composition diagram
To remind you - we've just ended up with this vapour pressure /
composition diagram:




it is more convenient to work with boiling point diagram (phase diagram)
We'll start with the boiling points of pure A and B.
B has the higher vapour pressure. That means that it will have the lower
boiling point.
To make this diagram really useful (and finally get to the phase), we are going to
add another line. This second line will show the composition of the vapour over
the top of any particular boiling liquid (dew point).
Boiling point diagram for an ideal solution
Composition of the liquid phase differ than the vapour phase
If you boil a liquid mixture, you would expect to find that the more volatile
substance escapes to form a vapour more easily than the less volatile one.
you would expect to find a higher proportion of B (the more volatile component)
in the vapour than in the liquid. You can discover this composition by condensing
the vapour and analysing it. That would give you a point on the diagram.
The difference between liquid and vapour compositions is the basis for distillation
operations.
Dew point is the temperature at which the
saturated vapour starts to condense.

Bubble-point is the temperature at which
the liquid starts to boil.

From Raoults Law we can obtain the following relationships:
N
A
vapor
=

P
A
/P
T
And
N
B
vapor
=

P
B
/P
T

If A is more volatile than B, BP
A
< BP
B
and P
A
> P
B
Then
N
A
vapor
>

N
A
liquid


The result of this process is that when a mixture of two miscible liquids with
different boiling points is heated, the vapor will have a different composition than
the liquid. THE VAPOR IS ENRICHED IN THE MORE VOLATILE (LOWER
BOILING) COMPONENT.


Conclusion/ vapour enrichment
Assume a two component mixture with a composition of 50% heane:50% pentane .
The boiling point of this mixture is found by drawing a vertical line from to where it
intersects the lower curve (point L1) , Point L1 indicates a boiling point of 44
o
C .
Upon removing a sample of the vapor, we find that it has a molar composition of 87%
pentane and 13% hexane as indicated by point V1.
The mole fraction of the component with the lower boiling point is greater in the vapor
than in the liquid.
If the vapor at V1 condenses, the liquid that collects (L2) will have the same
composition as the vapor (V1). Now, if the condensed liquid (L2) is revaporized, the new
vapor will be even richer in pentane (V2).
Repeating the boiling and condensing several more times allow us to obtain pure
pentane, uncontaminated by hexane.
Types of Distillation
Distillation can be classified into four main
types
1. Simple distillation
i. Under atmospheric pressure
ii. Under reduced pressure
2. Fractional distillation
3. Steam distillation
4. Destructive distillation

Simple distillation under atmospheric pressure
Simple distillation is the process of converting a liquid into its vapour,
transferring the vapours to another place, and recovering the liquid by
condensing the vapours
In simple distillation, the vapor is immediately channeled into a
condenser.
Consequently, the distillate is not pure but rather its composition is
identical to the composition of the vapors at the given temperature and
pressure. That concentration follows Raoult's law.
As a result, simple distillation is effective only when the liquid boiling
points differ greatly (rule of thumb is 25 C or when separating liquids
from non-volatile solids or oils.
For these cases, the vapor pressures of the components are usually
sufficiently different that the distillate may be sufficiently pure for its
intended purpose.
Simple distillation under atmospheric pressure
Simple distillation is a Single Vaporization / Condensation cycle process
that produces a distillate
Consequently, the distillate is not pure but rather its composition is
identical to the composition of the vapors at the given temperature and
pressure. That concentration follows Raoult's law.

Distillation apparatus for simple distillation
Common distillation apparatus consists of
three parts

1. Still: consists at a minimum of
a reboiler or pot in which the source
material is heated,
2. Condenser: in which the heated vapour is
cooled back to the liquid state
3. Receiver: in which the concentrated or
purified liquid, called the distillate, is
collected.

The anti-bumping granules give a smoother boiling action.

This can be used to purify water because the dissolved solids have a much higher
boiling point and will not evaporate with the steam, BUT it is too simple a method
to separate a mixture of liquids especially if the boiling points are relatively close.
Simple distillation under reduce pressure
Effect of pressure on boiling point has already been discussed (reducing
pressure will decrease the boiling point)
The liquids which are unstable at their boiling point under atmospheric
pressure , are distilled at a much lower temperature under reduce
pressure with less likelihood of decomposition.
Also used for concentrating thermo-labile substances.
It is used for the evaporation of the manstrum in the preparation of
extracts.
This process is used in the purification of vitamins
Same procedure as of simple distillation, but at lower or vacuum
pressure. the vapor is immediately channeled into a condenser.
Distillation apparatus for simple distillation
under reduce pressure
Vacuum distillation is mostly carried out in Claisen flask, which has two
necks
Second neck prevents splashing of the violently agitated liquid.
Small pressure gauge should be inserted between pump and receiver
At large scale vacuum still is used
Fractional distillation (rectification)
Basic principle is same as of simple distillation but Multiple Simple Sequential
Vaporization / Condensation Cycles,
multiple step process, partial condensation is allowed to occur by inserting a
Fractionating Column (a Vigreux Column) between the Distillation Flask and the
Distillation Head
This process continues until most of the lower boiling compound is removed from
the original mixture and condensed in the receiving flask

Lets start with the liquid at L1 (5% A and 95 %B). boils at temperature L
1
and the
vapors with composition V
1
enter the column at that temperature. The vapor will
condense to a liquid (L2) with composition V
1
.
The condensate L
2
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 V
2
.
These vapors will condense somewhat farther up the column to give a condensate L
3
.
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
Distillation apparatus for fractional distillation
Fractionating Column (a Vigreux Column)
between the Distillation Flask and the
Distillation Head
The Fractionating Column, of which there
are many types containing a variety of
packing materials, subjects the mixture to
many Vaporization/Condensation Cycles as
the material moves up the column toward
the Distillation Head, which is attached to
the Condenser
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
Fractionating columns
Fractionating column is inserted between the still and
the condenser
Bringing about repeated distillation throughout the
length of the column
The action of the column is partially to condense the
vapours rising from the boiling liquid; this condensate
will be richer in more volatile component
It is vaporised again by the condensation of more
ascending vapours; containing more volatile
component
More condensation and vaporizations take place
further up in the column, further enrichment of
volatile component occur
At the end in ideal conditions lower boiling point
liquid arrives at the top of column and the higher
boiling point liquid left in the column
Thus a temperature gradient will be established in the
column when distillation is in the progress
Design of Fractionating columns
The purpose of a fractionating column is to achieve an extensive liquid-
vapour interface so that equilibrium between ascending vapour and reflux
can be rapidly attained.
Different types of fractionating column are used e.g.
Packed columns: cylindrical glass beads, stainless steel rings, single turn
helices of wire or glass etc.
Vigreux Column: best type has indentation in the walls, spirally arranged
occupying most of the interior
Column Efficiency - How pure can you get!!

A common measure of the efficiency of a Fractionation Column is
given by its number of Theoretical Plates
One Theoretical Plate is equivalent to a Simple Distillation, i.e., one
Vaporization / Condensation Cycle
The smaller the boiling point difference, the greater the number of
theoretical plates a fractionating column must have to achieve
separation of mixtures
Design of Fractionating columns
Distillation of Azeotropic mixture
Azeotropic mixture:

An azeotrope is a mixture of two or more liquids in such a ratio that its
composition cannot be changed by simple distillation. This occurs
because, when an azeotrope is boiled, the resulting vapor has the same
ratio of constituents as the original mixture.
Because their composition is unchanged by distillation, azeotropes are
also called constant boiling mixtures.
Thus a mixture behaves like a pure liquid
Such a mixture cannot be separated into pure liquid.
Azeotropic mixtures of pairs of compounds have been documented
(listed). Many azeotropes of three or more compounds are also known.

Distillation of Azeotropic mixture
Two types

Minimum boiling point azeotropic mixture
Maximum boiling point azeotropic mixture
When you do the fractional distillation they will end up to azeotropic ratio, not to
pure liquid
Steam distillation
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.
If the substances to be distilled are very sensitive to heat, steam
distillation can also be combined with vacuum distillation.
After distillation the vapors are condensed as usual, usually yielding a two-
phase system of water and the organic compounds, which can be
separated because they are immiscible
Conclusion:
Steam is used to reduce the boiling point of a liquid to be distilled

Steam distillation apparatus
Steam generator
still
receiver
Basic Principle of steam distillation
When a mixture of two practically immiscible liquids are heated to
the vapor phase, each constituent independently exerts its
own vapor pressure as a function of temperature as if the other
constituent were not present.
Consequently, the vapor pressure of the whole system increases.
Boiling begins when the sum of the partial pressures of the two
immiscible liquids just exceeds the atmospheric pressure.
In this way, many organic compounds insoluble in water can be
purified at a temperature well below the point at which
decomposition occurs.
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 61 C
below its normal boiling point.
Application of steam distillation
Steam distillation is employed in the manufacture
of essential oils, for use in perfumes, for example. In this
method, steam is passed through the plant material
containing the desired oils.
Eucalyptus oil and orange oil are obtained by this method
on the industrial scale.
Steam distillation is also sometimes used to separate
intermediate or final products during the synthesis of
complex organic compounds.
Steam distillation is also widely used in petroleum
refineries and petrochemical plants.