Distillation

1
• Distillation is defined as the separation of the components of a
liquid mixture by a process involving vaporization and
subsequent condensation at another place.
• The distillation process involves two steps;
(a) converting a liquid into vapour and
(b) transferring the vapour to another place and recovering the
liquid by condensation.
• The feed liquid is known as distilled.
• The condensed liquid is known as distillate or condensate.
• If one component is volatile and other are non-volatile it is
possible to separate volatile components from non-volatile
components by distillation. In such cases, distillation is
considered as a separation or purification method. When heat
is supplied to a mixture, a more volatile liquid evaporates
readily then the less volatile liquid. As a result, the condensed
liquid consists of high proportion of highly volatile liquid and
less amount of less-volatile liquid. Therefore, distillation is said
to be partial separation method. The extent of the components
involves and the physical arrangements used for distillation.
2
• In practice, it is difficult to distinguish three processes, namely
evaporation, distillation and drying. Only working definition help
to differentiating them.
1. Distillation operation is used when condensed vapour is required
as a product.
2. Evaporation operation is used when the concentrated liquid
residue is needed as a product. The temperature of the liquid is
maintained below its boiling point. Further vapour is not condensed,
unless recovery is essential.
3. Drying operation is used when dried solid residue is required as a
product.
3
 Applications
• Separation of volatile oils: Volatile oils are separated from
cloves, anise seeds and eucalyptus leaves by the method of
steam distillation.
• Purification of organic solvents: Normally, simple distillation
method is used for the purification of liquid having single
components as major fraction. Simple distillation method is also
for determining the boiling range of a liquid as per, 1996, as a
method to decide the purity. Absolute alcohol (100% ethanol)
can be obtained by azeotropic distillation.
• Manufacture of official preparations: Spirit of nitrous ether and
aromatic spirit of ammonia are prepared by simple distillation.
Distilled water and water for injection are prepared as per the
specification of pharmacopoeia by simple and compression
distillation methods.
4
• Refining of petroleum products: In the petroleum industry, the
crude oil is refined into different fraction using flash distillation.
Each fraction is a multicomponent system. Examples are
petroleum ether 60, 80 etc.
• Recovery of solvents: Solvents are used for extraction of drug
from plant parts and synthetic reaction mixture. These solvents
must be recovered, in order to prevent environmental
contamination. The recovered solvent may be recycled for
further use.
• Quality control methods: Distillation method is used for
determining alcohol content in liquid dosage from such as
elixirs, as per IP, 1996. Azeotrpic distillation method is used for
the determination of water content in a substance using
toluene according to IP, 1996.

5
• Separation of drug obtained from plant and animal sources:
Drug of natural origin (such as plant) are normally extracted
using maceration or percolation method. The menstrum
(solvent) used for extraction is distilled off and the active
constituents are separated. For example, vitamin A is separated
from fish liver oil using the method of molecular distillation.

• Purification of drugs obtained from chemical process: Many

chemical processes involve the conversion of row material into
products. The products are separated from the reaction mixture
and purified using the method of distillation.
6
• In order to handle distillation effectively and economically, it
is necessary to understand the theory behind this process.
• Several variables are involved in the process, which are often
interrelated.
• Theory include the understanding of different factors
influencing the distillation process.
• The laws of conservation of matter and conservation of
energy have to be applied.

7
 THEORY
• Distillation is a process of separating and purifying the
components in a liquid mixture. The primary data required to
solve any distillation problem are vapour-liquid equilibrium
relationship. Distillation method depends on the these aspects
are discussed below.
• When two liquids are mixed together, they may be miscible
with each other in all proportions. Such miscible liquids are
known as binary mixture of liquids. Examples of binary mixture
are ethyl alcohol and water, water and acetone, benzene and
carbon tetrachloride. It is essential to understand theories of
ideal and real solutions (non-ideal).

8
• Ideal Solutions
• Ideal solution is defined not evolved during mixing. The final
volume of the solution represents the additive property of the
individual considerations. Example is methanol and water, which
have similar properties. Ideal solution theory provided a model
system to which real or non-ideal solutions can be compared. Ideal
solutions are characterized by one of the important
physicochemical properties of liquids namely vapour pressure.
• Raoult’s Law
• Raoult’s law expresses a quantities relationship between the
concentration and vapour pressure. Raoult’s law states that the
partial vapour pressure of each volatile constituent is equal to the
vapour pressure of the pure constituent multiplied by its mole
fraction in the solution at a given temperature. Since the solution is
homogeneous by definition, the relative numbers of components
in the whole of solution. These number can be expressed on mole
fraction scale. Thus Raoult’s law is appropriately suited to describe
an ideal solution.
9
Consider a mixture of miscible liquids A and B. In this mixture:
Let partial vapour pressure exerted by A = PA kPa.
Let partial vapour pressure exerted by B = PB kPa.
Let vapour pressure exerted by the pure component of A = P0A kPa.
Let vapour pressure exerted by the pure component of B = P0B kPa.
Let mole fraction concentration of liquid A = XA
Let mole fraction concentration of liquid B = XB
Raoult’s law may be mathematically expressed as:
Partial vapour pressure of a liquid = Vapour pressure of pure liquid ×
mole fraction of the liquid
PA = P0AXA
PB = P0BXB
A mixture of ethylene chloride and benzene obeys Raoult’s law. When
two liquids are mixed, the vapour pressure of each one is reduced by
the presence of other to the extent of dilution of each phase.

10
• Ideal solution is defined as the one that obeys Raoult’s law.
Raoult’s law is obeyed by only a few solutions of liquid in
liquids. These solutions are also known as ‘perfect’ solutions.
The component of these solutions have a similar structure.
Examples are benzene and toluene, n-hexane and n-heptane,
ethyl bromide and ethyl iodide. The individual components do
not have interaction of any kind or complete uniformity of
attractive forces is observed.

11
• Dalton’s Law
Dalton’s law of partial vapour pressures states that the total pressures
exerted a by mixture of ideal gases may be considered as sum of the
partial vapour pressure exerted by each gas, if alone were present and
occupied the total volume.
Dalton’s law is mathematically expressed as:
Total vapour pressure = partial pressure of A + partial pressure of B
P =PA + PB (3)
Substituting equation (1) and (2) in equation (3) gives
P = P0AXA + P0BXB (4)
Their properties are additive, i.e., the total vapour pressure of the
mixture is the weighted average of the vapour pressure of pure
individual constituents. This behavior is shown in figure 11-1a. The
following conclusion can be drawn Figure 11-1a.
-The partial pressure of the component varies linearly from zero to full
vapour pressure as the mole fraction from zero to one.
-The total pressure exerted by the system at a particular composition is
equal to the sum fraction pressure of its components.

12
• Application: According to an ideal solution, the component
having relatively grater vapour pressure will be distilled first.
This principle is used in simple distillation.

13
• Real Solution:
• Most system show varying degree of deviation from
Raoult’s law, depending on the nature of the liquid and the
temperature. These solution are known as real solutions.
Deviations are observed because solvent-solute and
solute-solvent interactions are unequal. Example includes
carbon tetrachloride and cyclohexane, and chloroform and
acetone. Mutual interaction lead to either lowering or
enhancing of the vapour pressure of the mixture with
respect to ideal behavior.
• These are described as follows.
• Positive deviation : In some liquid system, the vapour
pressure is greater than the sum of the partial pressure of
the individual components. Such system are said to exhibit
positive deviation from Raoult’s law.
• Negative deviation: In some liquid system, the vapour
pressure is lower than of the sum of the partial pressure of
the individual components. Such system are said to exhibit
negative deviation from Raoult’s law. 14
• Raoult’s law does not apply over the entire concentration
range in a non-ideal solution. If one liquid is present in high
concentrations, it is considered as a solvent. The other liquid
is very dilute. Hence, Raoult’s law is valid for that
composition, through the liquid pair behaves non-ideal
manner.
• Applications: The difference in the behavior of a mixture
influence the method of distillation. The areas include
fractional distillation of intermediates and drugs, purification
of alcohol and other organic fractional distillation may not be
achieved if large positive or negative deviation from Raoult’s
law are observed. Such solutions form so called azeotropic
mixture. Therefore, the principles of real solution are
important distillation.

15
• Volatility
• The volatility of any substance in a solution may be defined
as the equilibrium partial pressure of the substance in the
vapour phase divided by the mole fraction of the
substance in the solution.
• For, example, substance A in a mixture has partial pressure
PA and its concentration in the mixture is XA on mole
fraction scale. Then volatility of A (vA) may be
mathematically expressed as:
𝐩𝐚𝐫𝐭𝐢𝐚𝐥 𝐯𝐚𝐩𝐨𝐮𝐫 𝐩𝐫𝐞𝐬𝐬𝐮𝐫𝐞 𝐨𝐟 𝐀 𝑷𝐀
Volatility of component A, VA = =
𝐦𝐨𝐥𝐞 𝐟𝐫𝐚𝐜𝐭𝐢𝐨𝐧 𝐀 𝐢𝐧 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 𝐗𝐀

• The volatility of a material in the pure state is equal to the

vapour pressure of the material.

16
• Relative Volatility
Consider a liquid mixture containing two components A and B. In
such a case, the volatility of one component is expressed in term of
the second. Relative volatility may be defined as :
𝐯𝐨𝐥𝐚𝐭𝐢𝐥𝐢𝐭𝐲 𝐨𝐟 𝐜𝐨𝐦𝐩𝐨𝐧𝐞𝐧𝐭 𝐀 𝑽𝐀
Relative volatility,α = =
𝐯𝐨𝐥𝐚𝐭𝐢𝐥𝐢𝐭𝐲 𝐨𝐟 𝐜𝐨𝐦𝐩𝐨𝐧𝐞𝐧𝐭 𝐁 𝑽𝐁
Relative volatility is commonly expressed with the higher of the
two volatilities in the numerator. This means that the relative
volatility should never have a numerical value less than 1.0.
Since, v = P/X (equation 5), it may be substituted in equation (6)
𝐏𝐀/𝐗𝐀 𝐏𝐀𝐗𝐁
α= =
𝐏𝐁/𝐗𝐁 𝐏𝐁𝐗𝐀
According to Dalton’s law, the partial vapour pressure of A and B
may be expressed as :
PA = YA.P
PB = YB.P
Where YA = mole fraction A in the vapour state
YB = mole fraction B in the vapour state
P = total pressure of the vapour, kPa 17
• Relative volatility may also be expressed by substituting
equations (8) and (9) in equation (7) gives :
𝒀𝑨𝑷.𝑿𝑩 𝒀𝑨𝑿𝑩
• αAB = =
𝒀𝑩𝑷.𝑿𝑨 𝒀𝑩𝑿𝑨
• Equation (10) is often gives as the definition of relative
volatility.
• Using equation (10), the relative volatility can be calculated
directly from the vapour-liquid equilibrium data. For example,
a mixture of methyl alcohol and water is having a total vapour
pressure of 101.31 kPa (760mmHg). This liquid contain 0.40
mole fraction of methyl alcohol and the equilibrium vapour
contain 0.729 mole fraction. The data may be written as :
• XA = 0.4; YA = 0.729; XB = 0.6; YB = 0271
𝟎.𝟕𝟐𝟗 ×𝟎.𝟔𝟎
• Relative volatility = = 4.035
𝟎.𝟐𝟕𝟗 ×𝟎.𝟒𝟎
• Sometimes relative volatility may change with concentration
especially if the binary solution do not obey Raoult’s law.
However, mixture that obey Raoult’s law. Show only a slight
change in relative volatility with concentration variation.
18
 CLASSIFICATION OF DISTILLATION METHODS

• Simple distillation
• Flash distillation
• Fractional distillation
• Azeotropic and extractive distillation
• Distillation under reduced pressure
• Steam distillation
• Molecular distillation
• Destructive distillation

19
 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 following it on come in contact with a cold surface. This
process is known differential distillation, as distillation is based on
the differences in volatilities and vapour pressure of the
components in the mixture. This method requires simple
apparatus.
• 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 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. If the liquid of interest is volatile and remaining
components are nonvolatile then simple distillation is a useful
means of purification and separation of liquid. 20
• Application:
(1) Simple distillation is used for preparation of distilled water
and water for injection.
(2) Volatile and aromatic waters are prepared.
(3) Organic solvents are purified.
(4) A few official compounds are prepared by distillation.
Examples are spirit of nitrous ether and aromatic spirit of
ammonia.
(5) Non-volatile solids are separated from volatile liquids.

21
 Laboratory scale Apparatus For Distillation
• Assembling of apparatus : The construction of a simple
distillation apparatus is shown in Figure. It consist of a
distillation flask with a side arm slopping downwards.
Condenser is fitted into 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. On a laboratory scale, the whole
apparatus is made of glass.

22
• Apparatus for simple distillation (on
laboratory scale)

23
• Procedure: In the laboratory scale, 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 or
porous pot before distillation. A thermometer is inserted into
the cork and fixed to the flask. The thermometer bulb must be
just below the level of side arm. Water is circulated through the
jacketed of the condenser as shown in Figure.
• The content 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 receiver. 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 remain in the flask.
24
 Large Scale Equipment for Simple Distillation

• Construction : A simple Distillation is as shown in Fig. it is

used for large-scale distillation. It is made up of stainless steel,
copper or any other suitable material. A still of this kind has a
limited heating surface and functions perfectly with volatile
solvents, but is not useful for concentrating dilute solutions.
Specially designed still suited to one product or a group of
products are used for frequent and continuous use.

25
Equipment for simple distillation on large scale operation

26
• A thermometer is fixed to the still to note the temperature of
the boiling liquid. An observation window in the hood is
helpful to the operator too see the progress of the distillation
and the level of the contents to be distilled. The still is
connected to a condenser and them to a receiver. The still is
heated using steam. Therefore, a steam inlet at the bottom of
the still and an outlet for removing the condensed steam are
provided.

27
 Working:
• A liquid to be distilled is filled into the still to one-half to two-
third of its volume. Bumping is avoided by adding small pieces
of porcelain or porous pot before distillation. A thermometer is
inserted into the still. Water is circulated through the jacket of
the condenser as shown in Fig. Steam is passed through the
inlet. The contents are heated gradually. The liquid begins to
boil after some time. The vapour begins to rise up and passes
into the condenser. The temperature is noted, down which is
equal to the boiling point of the liquid.
• The vapour is condensed and collected into receiver. The
passage of steam is regulated so that the distillate is collected at
a slower rate (a few drop per second). Distillation should be
continued until a small volume of liquid remains in the still.
• Water stills are used producing distilled water including water
for injection on a continuous basis. 28
 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.
• Principle: When a hot liquid mixture is allowed to enters from a
high-pressure zone into a low-pressure zone, the entire liquid
mixture is suddenly vaporized. This process is known as flash
vaporization. During this process the chamber gets cooled. The
individual vapour phase molecule of high boiling fraction get
condensed, while low boiling fraction remain as vapour. This
process the chamber gets cooled. The individual vapour phase
molecules of high boiling fraction get condensed, while low boiling
fraction remains as vapour. This process requires certain amount of
time. Therefore, the liquid and vapour is kept in intimate contact
until equilibrium is achieved. The liquid fraction is collected
separately. The vapour is separated from the liquid and further
allowed to condense.
29
Apparatus for flash distillation

30
• Construction : The construction of flash distillation apparatus is
shown in Figure.

• It consists of a pump, which is connected to a feed reservoir.

Pump help in pumping the feed into heating chamber which
contains a suitable heating mechanism. The other end of the
pipe is directly introduced into the vapour-liquid separator
through a reducing valve. The vapour outlet is provided at the
top of the separator and liquid outlet is provided at the bottom.

31
• Working : The feed is pumped through a heater at a certain
pressure. The liquid gets heated, which enters the vapour-liquid
separator through flashes, which further enhances the
vaporization process. The sudden vaporization induced cooling.
The individual vapour phase molecules of high boiling fraction
get condensed, while low boiling fraction remains as vapour.
The mixture is allowed for a sufficient time, so that vapour and
liquid portion separate and achieve equilibrium. The vapour 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 equal the
amount of material removed. Therefore, vapour and liquid
concentrations at any point remain constant in the limit.

32
• 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. It is
used for obtaining multi-component systems of narrow
boiling range, especially in oil refinery. Examples are
petroleum ether 60, 80 etc.
• Disadvantages : Flash distillation is not effective in separating
components of comparable volatility. It is not suitable for two
components are required, because the condensed vapour and
residual liquid are far from pure.

33
 FRACTIONAL DISTILLATION
• 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 from.
• This method is also known as rectification, because a part of the
vapour is condensed and return as a liquid. This method is used
to separate miscible volatile liquids, whose boiling points are
close by means of fractionating column.
• Fractional distillation is different from simple distillation. In
simple distillation, vapour is directly passed through the
condenser. In fractional distillation the vapour must pass
through a fractionating column in which partial condensation of
vapour is allowed to occur. In simple distillation, condensate is
collected directly into the receiver, while in fractional distillation,
condensation takes place in the fractionating column, so that a
part of the condensing vapour return to the still. 34
• Principle : From the operational point of view, fractional
distillation is a mass transfer process involving counter-current
diffusion of the components at each equilibrium stage.
• When a liquid 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 result in
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 more volatile
component.
• Application : Fractional distillation is used for the separation of
miscible liquid such as acetone and water, chloroform and
benzene.
• Disadvantages : Fractional distillation cannot be used to
separate miscible liquids, which from azeotrpic mixtures. 35
General Method for Fractional Distillation

Assembly of apparatus for fractional distillation

(on laboratory scale).
36
Fractional distillation apparatus for large scale
operation
37
• Construction: The assembly of apparatus for fractional
distillation on a laboratory scale is shown in Figure. On a
large scale, the construction of equipment for fractional
distillation is shown in Figure. The fractionating column is
inserted between the still and the condenser. A provision
is made for the supply of heat (usually a steam coil) at
the bottom of the column. At the top column, a
condenser is provided. The column has a large area for
providing sufficient flow condition. The broken lines
across the column represent the contacting devices.

38
• Working: The mixture to be distilled is fed to the boiler and
heated usually by steam. The sequence of events occurring in
the fractionating column can be illustrated using the following
general example (Figure 11-13).
• Consider a mixture of two miscible liquid A and B containing
20% of A and 80% B. Liquid A (More Volatile Component,
MVC) is having a lower boiling point than B (Less Volatile
Component, LVC). These liquids do not procedure constant
boiling point mixture. The boiling point composition curves if
this mixture are shown in Figure 11-13, which is similar to
Figure 11-8, but written several times so as to represent the
steps (i.e., in fractions) in fractional distillation.

39
40
1. When the boiling point of the mixture is reached, the vapour
composition curves are shown as shown by lowest pair of curves
(Figure 11-13). These curves indicates that the vapour contains
60% of A.
2. When this vapour is condensed, the resulting liquid is again
heated to boiling point, this vapour gives the composition
containing 90% of A (second pair of curves from the bottom).
3. This vapour impinging on a cool surface and gets condensed.
This fraction is revaporised by heating to its boiling point. This
boiling point curves of this distillate indicates 98% of A (Third
pair of curves from the bottom).
4. This fraction of vapour impinges on a cooling surface. This
gives fourth pair fourth pair of curves. Now this vapour contains
higher (more than 98%) proportion of A, I.e., vapour of pure
component.

41
5. The vapour moves to a condenser at the top of the column and
gets condensed.
• Thus, repetition of these processes yield pure A as shown in the
curves in Figure 11-13. The proportion of B in the ascending
vapour becomes progressively smaller and entirely eliminated
at its upper most point. The liquid B trickles downward to the
distillation flask being further freed from liquid A on its
downward journey.
• Once distillation is commenced, the size of the flame is adjusted
so that liquid passes over at a rate of one drop per every two or
three seconds. Once the low boiling point fraction has passed
over, distillation should be stopped. The liquid available in the
still is pure B. It can be collected as such or purified further by
simple distillation (keeping the fractionating column assembly).
• The above process forms the basis of the continues method of
fractional distillation. Distillation is continued until all the MVC
has been distilled off from the top as the product and the LVC is
left in the still as a separate product.

42
 Efficiency of the Fractional Distillation
• The efficiency of separation of a mixture may be expressed in
several ways.
• Length of the fractionating column: A state of dynamic
equilibrium is required for the separation. A maximum degree of
separation of the components along the length of the column.
• Reflux ratio: Reflux ratio is the quotient of the amount of liquid
returning through the column to the amount collected into the
receiver during the same interval of time. A column operating
under total reflux will not yield distillate. The reflux ratio should
be high. It is controlled by means of a suitable still.
• Heat input: Heat input to the still should be controlled. If it is
too little, the packing is insufficiently wetted. If it too high,
velocity may be too great for equilibrium to be attained. The size
of the flame should be adjusted so that liquid passes over at a
rate of one drop for every two or three seconds.

43
• Column temperature: For a column operating at a
temperature above 600C, hate loss should be prevented by
insulation. Examples are asbestos cord and silver vacuum
jacket. For temperature above 1000C, the column is
surrounded by a heating jacket, which is generally adjusted to
the temperature of the vapour that emerge from the top of
the column. Heat loss will cause excessive condensation
within the column, which may result in flooding. It will also
disturb the steady state temperature gradient along the
column.
• Other experimental conditions necessary for good
separation are:
(1) There should be a comparatively large amount of liquid
continuously returning through the column.
(2) Through mixing of liquid and vapour.
(3) A large active surface of contact between liquid and vapour.

44
 Fractionating column can be divided into two groups
• Packed columns: In this type, some form of packing is used in the
column to effect 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. The height of
packing is equivalent to one theoretical plate. Some types of
fractionating columns are shown in Figure 11-14.

45
Bubble cap column is used in large distillation plants and is
described below.

46
 DISTILLATION UNDER REDUCED PRESSURE
• Distillation under reduced pressure may be stated as a
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
pressure on the liquid surface. Distillation under reduced
pressure is based on the principle of simple distillation with
some modification.
• Principle: Liquid boils when vapour pressure is equal to the
atmospheric pressure, i.e., pressure on its surface. If the
external pressure is reduced by applying vacuum, the boiling
point of liquid decreases. Therefore, the liquid boils at a lower
temperature. This principle is illustrated using an example of
water. Water boils at 1000C at an atmospheric pressure of
101.31 kPa (760 mmHg). Hence, the external pressure is
reduced to 9.33 kPa (70 mmHg) where water boils at 400C. The
result is increases in the rate of mass transfer into vapour.
47
The important factor in evaporation is:
Mass of vapour formed α
vapour pressure of evaporating liquid
external pressure
According to this formula, water is allowed to evaporate at 400C
and 9.33kPa (70 mmHg) pressure, the mass of vapour formed in
unit time is approximately 11 times, i.e., 760/70 for water.

48
• Application: Distillation under reduced pressure is essential
and finds a number applications.
• Preventing degradation of active constituents: During
extraction, concentration or processing at higher
temperature, the active constituents may undergo
decomposition (inactivation). A few examples be done at a
lower temperature under reduced pressure.
Category Reaction Examples
Enzymes Inactivation Malt extract,
pancreation
Vitamins Oxidation Thimine, ascorbic acid
Glycosides Hydrolysis Anthraquinines
Alkaloids Racemization Hyocyamine to
atropine
Tannins Precipitation Phlobatannins to
phlobaphenes 49
• Changes physical forms: In the preparation of cascara sagrada
tablets, granular extract is suitable. Drying at the atmospheric
pressure yield a dense, compact residue, which is not desirable. In
the initial stage, the liquid extract is concentrated under
atmospheric pressure or under partially reduced pressure, until the
residue has the consistency of treacle (blend of molasses). The
pressure is then quickly reduced, where upon the treacly semi-
solid swells up due to sudden evolution of water vapour. This
produces a light porous mass, which can readily be passed through
a sieve to form a granular powder.

50
• Disadvantages: In vacuum distillation, persistent foaming
occurs. This may be overcome by adding capryl alcohol to the
liquid or by inserting a fine air capillary tube in the second
neck of the Claisen flask. 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.

51
 Distillation under Reduced Pressure
• Assembly of apparatus: It consists of a double-neck distillation
flask known as Claisen flask (figure 11-17). Thick walled glass
apparatus with interchangeable standard glass joints are used
for vacuum distillation. In one of the necks of the Claisen flask, a
thermometer is fitted. The second neck prevents splashing of
the violently agitated liquid. Bumping occurs readily during
vacuum distillation. Placing a fine capillary tube in the second
neck of the flask can prevent bumping.
• The capillary tube is dipped in the boiling liquid, so that a stream
of air bubbles is drawn out. Water bath or oil bath is used for
heating.
• The Claisen flask is connected to receiver a condenser. Vacuum
pump is attached through an adaptor to the receiver. A small
vacuum gauge (manometer) should be inserted between the
pump and the receiver. 52
Assembly of apparatus for distillation under
reduced pressure (on laboratory scale).
53
• Procedure: The liquid to be distilled is filled one-half to two-
third volume of the flask. Small pieces of porcelain are added
to the liquid for facilitating distillation and prevent bumping.
The capillary tube and thermometer are kept in place in the
flask.(Figure 11-17). The required vacuum is applied. The
contents are heated gradually. The temperature rises and
liquid gets vaporized rapidly due to vacuum. The vapour
passes through the condenser. The condensate is collected in
the receiver. The temperature is noted down, which would be
less than the boiling point of the liquid.
• When a large volume of a liquid is to be distilled under
reduced pressure, it is more convenient to distil comparatively
small volumes at a time.
• Large Scale Apparatus Using Vacuum Still for Distillation Under
Reduced Pressure

54
 Distillation under pressure (on industrial scale)

• Construction: The general construction of a large scale

equipment for distillation under reduced pressure is shown in
Figure 11-18. The vacuum jacketed still generally made of
stainless steel, copper or any other material, which can
withstand a high vacuum. An observation window in the hood
is helpful to see the progress of the distillation and also the
level of the liquid contents. The still is fitted with a drainpipe
at the bottom, and an air vent. The still is connected o
condenser. A thermometer is incorporated in the still. Vacuum
pump through vacuum gauge is connected as shown in Figure
11-18.

55
56
• Working: The still is fitted with the liquid to be distilled through
an attachment of a pipe with tap. The other end of the pipe is
connected to a reservoir of liquid, so that it can be filled at a
controlled flow rate. Vacuum is created by means of vacuum
pump. Using the stream, the liquid is gradually heated. The
temperature rises and the liquid gets vaporized rapidly due to
vacuum. The vapour passes through the condenser and the
condensate is collected into a receiver.
• Normally two receivers are fitted with suitable arrangement of
cocks, so that they can be used alternatively, the distillate being
collected from one, while the other is connected to the still
under vacuum. Therefore distillation need not be stopped.
• Distillation is stopped while the contents of the flask are
sufficiently fluid to run off through the drain pipe at the
bottom. When spongy powdery mass is desired, the still can be
provided with a stirring arrangement, which also hastens
vaporization. According to the requirements, the capacity may
be a few liters to thousands of liters.

57
 STEAM DISTILLATION
• Steam distillation is a method is a method of distillation
carried with the aid of steam and is used for the separation of
high-boiling substance from non-volatile impurities.
• High-boiling liquids cannot be purified by simple distillation,
since the constituents in the mixture tend to decompose at
higher temperatures. In such cases, steam distillation is
employed. Steam distillation is used for the separation of
immiscible liquids.
• For substance, which is insoluble in water and not
decomposed by heat, steam distillation provides an
alternative to distillation under reduced pressure. Steam
distillation is the most common example of differential
distillation.
58
• Principle: A mixture of immiscible liquids begins to boil when the
sum of their vapour pressure is equal to the atmospheric pressure.
In case of a mixture of water and turpentine, mixture boils below
the boiling point of pure water, through turpentine boils at a much
higher temperature than that the water.
• For example, the boiling point of turpentine is about 1600C. But
when it is mixed with water and heated, the mixture boils at about
95.60C. At this temperature, the vapour pressure of water is
86.245kPa (647 mmHg) and that of turpentine is 15.06kPa (113
mm Hg). The sum of the vapour pressure is 101.31kPa (760
mmHg) which is normal atmospheric pressure. Thus, high boiling
substance may be distilled at a temperature much blow its boiling
point, when water (steam) is used.
• For volatile substances, which are miscible with water, steam
distillation involves the same principle as fractional distillation.
59
Assembly of apparatus for steam distillation (on
laboratory scale).

60
• Assembly of apparatus: The assembly of apparatus for steam
distillation on laboratory scale in Fig. It consists of a metallic steam
can fitted with a cork having two holes. Through one of the holes, a
long tube is passed so as to reach almost the bottom of the steam
generator. This tube acts safety tube, so that in case the pressure
inside the steam generator becomes too much, water will be
forced out of it and the pressure will be relieved. Moreover, when
steam starts coming out from the safety tube, it indicates that the
steam can is almost empty. Through another hole, a bent tube is
passed. The other end of the bent tube is connected to the flask
containing non-aqueous liquid (for example, crude containing
volatile oil) through a rubber bung. This tube should reach almost
the bottom of the flask.
• Through the other hole of the rubber bun, a delivery tube is
inserted which connects the flask and the condenser. The
condenser is connected to a receiver flask using an adaptor.
Provisions are made to heat the steam can and flask. 61
• Procedure: The non-aqueous liquid is placed in the flask. A small
quantity of water is added to it. Steam can fill with water. The
steam generator and the flask are heated simultaneously, so that a
uniform flow of steam passes through the boiling mixture. The
mixture gets heated. The steam carries the volatile oil and passes
into the condenser, which is cooled by cold water. The condensed
immiscible liquid is collected into the receiver.
• Distillation is continued until all the non-aqueous liquid has been
distilled. In the receiver, water and organic liquid from two
separate layers, which can be easily, separated using a separating
flask.
• For volatile substances, which are miscible with water, distillation
with steam would involves the same principle of fractional
distillation.

62
• Application:
(1) Steam distillation is used for the separation of immiscible liquids.
Example is toluene and water.
(2) This method is used for extracting most of the volatile oils such
as clove, anise, and eucalyptus.
(3) It is useful in purification of liquid with high boiling point, for
example essential oil of almond.
(4) Camphor is distilled by this method.
(5) Aromatic waters are prepared by this method.
• Advantages: Volatile oils can be separated at a lower temperature
in steam distillation, without any decomposition and loss of
aroma. If a substance has low volatility, it can satisfactorily
distilled, provided its molecular weight is considerably higher
than water.
• Disadvantages: Steam distillation is not suitable when immiscible
liquid and water with each other. 63
 MOLECULAR DISTILLATION
• Molecular distillation is defined as a distillation process in which each
molecule in the vapour phase travels means 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 evaporative distillation or short
path distillation.
• Principle: The substance 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 temperatures. In
order to decrease the boiling point of the liquids, high vacuum must be
applied.
• The vapour pressure above the liquid is much lower than that of the
saturated vapour in equilibrium. At very low pressure, the distance
between the evaporating surface and the condenser is approximately equal
to the mean free path of the vapour molecules. Molecules leaving the
surface of the liquid are more likely hit the condenser surface than to
collide with other molecules. Little or no re-condensation takes place at the
surface of the liquid.

64
• Application: Molecular distillation is used for the purification
and separation of chemicals of low vapour pressure.
(1) Purification of chemicals such as tricresly phosphate, dibutyl
phthalate and dimethyl phthalate.
(2) More frequently used in the refining of fixed oils.
(3) Vitamin A is separated from fish liver oil. Vitamin E is
concentrated by this method from fish liver oils and other
vegetable oils.
(4) Free fatty acids are distilled at 1000C. Steroids can be
obtained between 1000C and 2000C, while triglycerides can be
obtained from 2000C onwards. Proteins and gums will remain as
non-volatile residues. Thus, the mixture can be separated by
molecular distillation.

65
• Theory: The mean free path of molecules is defined as the average distance
through which molecules can move without coming into collision with other.
The mean path (λ) can be expressed mathematically as:
3
𝜆 = 𝑛
𝑝𝜌
where, p = vapour pressure, kPa
ρ = density, kg/m3
n = viscosity, Pas
λ = mean path length, m
For example, mean path (heavy molecules) of butyl phthalate is about 30 mm and
olive oil is 20 mm when measured at a pressure of 0.1 Pascal.
The characteristics of the substance influence the method of distillation. According
to equation (11):
(a) Liquid having low viscosity and density posses long mean path. Distillation is
simple.
(b) Substance having high pressure posses low mean free path.
The mean free path can increased by decreasing the viscosity (n), which can be
obtained at high temperature and low pressure. Thus, nonvolatile substances may
become volatile and distillation is possible.

66
• It is necessary to design the equipment based on the requirement
of the molecular distillation. Some of them are as follows.
(1) 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.
(2) The molecular collision should be minimized because they change
the direction of the path of molecules. In other words,
intermolecular distance should be fairly high. It can be achieved
under very high vacuum, usually of the order of 0.1 to 1.0 pascals.
(3) The liquid surface area must be as large as possible as that the
vapour is evolved from the surface only, but not by boiling. Thus this
process is called evaporation distillation.
Based on the method of formation of the liquid film, apparatus may
be divided into two types.

67
Falling Film Molecular Still or Wiped Film Molecular Still
• Principle: In this method, vaporization occurs from a film of
liquid flowing down a heated surface under high vacuum. The
vapour (molecule) travels a short distance and strikes the
condenser nearby. Each molecule is condensed individually.
The distillate is subsequently collected.

68
• Construction: The construction of wiped film molecular still is
shown in Figure. The vessel has a diameter of one meter. 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) as shown in Figure. Vacuum pump is
connected to large diameter pipe at the center of the vessel.
Provisions are made for collecting the distillate and the
undistilled liquid residue at the bottom.

69
• Working: The vessel is heated by suitable means. Vacuum is
applied at the center 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.
(Polytetraflouroethylene) wipers, which are moving at a rate of 3
meter per second. The velocity of film is 1.5 meters per second
Since the surface is already heated, the liquid film evaporates
directly. The vapour (molecule) travels its mean free path and
strikes the condenser. The condensate is collected into 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 liter per hour.

70
 References
1. Introduction to chemical engineering – Walter L Badger & Julius
Banchero.

2. Solid phase extraction, Principles, techniques and applications by Nigel

J.K. Simpson.

3. Unit operation of chemical engineering – Mcabe Smith.

4. C.V.S Subrahmanyam et al., Pharmaceutical engineering principles and

practices –Vallabh Prakashan.

6. Theory and practice of industrial pharmacy by Lachmann.,

7. Physical pharmaceutics- C.V.S Subrahmanyam et al., Vallabh Prakashan.

8. Cooper and Gunn’s Tutorial pharmacy, S.J. Carter.

71