Mass Transfer-I

Distillation
Lecture 1&2
Dr. Hemant Kumar
Department of Chemical Engineering
DDU Nadiad

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Distillation

Distillation is a method of separating the

components of a solution which depends on
the distribution of the substances between a
gas and a liquid phase, applied to cases where
all components are present in both phases
• New phases are created from original solution by vaporization
or condensation
• Therefore no external substance is added in the mixture to
produce the second phase as in case of absorption

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 Difference between distillation and other
operations
• Separation of solution of common salt and water- is it a
distillation operation: No (salt cannot be vaporized, therefore
not present in both of the phases)
• Separation of components of a liquid solution of ammonia
and water- absorption and distillation both operations are
possible.
In absorption, air is to be used for stripping the solution
with the difficulty of separating the air and ammonia vapor
mixture.
However distillation is possible by evaporation of
solution with repeated vaporization and condensation.

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 Advantage of distillation over other methods

• In distillation the new phase created differs from original in its

heat content, but heat is readily added or removed
Although cost of doing this must be considered

• Whereas absorption or desorption operation depends on the

introduction of a foreign substance provided us a new
solution which in turn may have to be further separated.

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 Limitations of distillation over other methods
• In distillation no other choice than heat addition and removal
is possible. However, methods like absorption or desorption
involves addition of variety of solvents.
• Ex : separation of hydrocarbon gas from a gas mixture, water
is incapable and addition of hydrocarbon oil can solve the
purpose.
• However, distillation does not requires further treatment to
separate the additionally added substance.

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 Vapor liquid Equilibria
• Separation of a mixture by distillation is based on equilibrium
distribution of components between liquid and vapor phases.
• Therefore a knowledge of VLE is essential for understanding
phenomenon of distillation
• Consider the aqueous solution of ethanol in closed tank
• Assume that vapor space does not contain air and space is
filled with ethanol and water vapors only

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 Vapor liquid Equilibria
• Now heating the vessel at const. temp.
• What do we expect to happen ??
Vap: Ethanol +
• Given sufficient time at constant pressure,
water; y*
the system reaches equilibrium
Liq: Ethanol +
• In vapor space, liquid (x) and vapor (y*)
water; x compositions attains a unique value.
• Now increasing the temperature at constant
Heating
pressure will provide new set of conditions x
At const and y* keeping same constant initial
Temp. composition.
• This way T-x-y* diagram is created at const P
and constant initial solution mixture
composition.
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 What is meant by set of conditions
• This is explained by Gibb’s phase rule
F = C-P+2
• In the previous example C=2, P=2 so that degree of freedom
are F=2
• Total number of parameters and variables are 4 i.e. T, P, x and
y*
• To define the system at equilibrium two parameters out of 4
need to be fixed.
• In the previous example system will be fixed if either of two
values are fixed. For example at const T and P, only one set of
value of x and y* are possible.
• VLE constitutes the physical basis for the separation of the
components
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 Pressure-temperature-composition phase diagram for binary
mixture
• VLE constitutes the physical basis for the separation of the
components by distillation
• Successful design of a distillation column is based on the
accuracy of the vapor liquid Equilibria data
• VLE of binary mixture is discussed here.
• Binary mixture means that the liquid component dissolves in
all proportions to form a homogeneous solutions which are
not essentially ideal
• The binary mixture is not showing maximum and minimum
boiling pt phenomena therefore binary mixture is referred
here as ordinary.

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 3-D graphical representation of Equilibria of
binary mixture

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 Vapor-Liquid Equilibria of pure component

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 Pressure-temperature-composition phase diagram for binary mixture

• In a binary mixture of A and B or A-B, component A is referred

as more volatile i.e. vapor of pure component A is higher
than pure component B at all temperatures
• For binary mixture an additional variable concentration must
be considered.
• Unit considered is mole fraction
• x will be mole fraction of the more volatile component A in
liquid
• y* will be the corresponding equilibrium mole fraction of A in
liquid

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 Constant Pressure Equilibria of binary mixture

• The liquid and vapor region between x=0 to x=1 are separated
by double surface as shown in fig (a)

Equilibrium
curve

Diagonal

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 Equilibrium
curve

Diagonal

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• Binary mixture: Two components A & B
Liquid phase: x (component A) & (1-x) (component B)
Vapor phase: y (component A) & (1-y) (component B)
• x=0 meaning : Liquid composition of more volatile
component A is zero. Therefore this axis represents pure B.
(since axis represents binary mixture)
• x=1 meaning : Liquid composition of more volatile
component A is one. Therefore this axis represents pure A.
• Upper curve represents y* vs t
• Lower curve represents x vs t
• Liquid and vapor mixture at equilibrium are at the same
temperature and pressure throughout, so that the horizontal
tie lines such as line DF join equilibrium mixtures at D and F
• There are an infinite number of tie lines for this diagram
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 Constant Pressure Equilibria of binary mixture
• A mixture on the lower curve as at point D is a saturated liquid
• A mixture on the upper curve at point F is a saturated vapor
• A mixture at E is a two phase mixture consisting of a liquid
phase of composition D and vapor phase of composition at F
in such a way that the average composition of the entire
mixture is represented by E
• Relative amounts of the equilibrium phases are related to the
segments of the tie lines

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 Equilibrium
curve

Diagonal

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 Constant Pressure Equilibria of binary mixture
• Equilibrium in Closed container: which can be kept at constant
pressure by moving a piston
• The solution is entirely liquid
• If it is heated the first bubble of vapor forms at H and has the
composition J, rich in the more volatile substance
• Therefore, the lower curve is called bubble point temperature
curve
• As more of the mixture is vaporized, more of the vapor forms at
the expense of the liquid giving rise to liquid L and its equilibrium
vapor K, although composition of entire mass is still original as at G
• The last drop of liquid vaporizes at M and has the composition at
N
• Superheating the mixture follows path MO

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 Constant Pressure Equilibria of binary mixture
• The mixture has vaporized over a temperature range from H
to M, unlike the single vaporization temperature of pure
substance
• Therefore the term boiling point for a solution ordinarily has
no meaning, since vaporization occurs over a temperature
range
• i.e. from bubble point to dew point
• Open vessel boiling: if a solution like at H is boiled in an open
vessel, with vapors escaping into the atmosphere???
• Since the vapor is richer in more volatile component, the
liquid residue therefore become leaner
• The temperature and composition of the saturated residual
liquid therefore, move along the lower curve toward N as the
distillation proceeds
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 Distribution diagram
• The vapor liquid
equilibrium can also be
shown on a distribution
diagram (x vs y*)
• Point P in the diagram
represents the tie line
DF for example
• Since the vapor is richer
in more volatile
component the curve
lies above 45o diagonal
line

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 Relative volatility:
The greater the distance between the equilibrium curve and
diagonal, the greater the difference in liquid and vapor
composition and easier the separation by distillation

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 Relative volatility
•One relative measure is called separability factor or relative
volatility α

“This is the ratio of the concentration ratio of A and B in one

phase to that in the other phase and is a measure of
separability”

•The value of α changes as x changes from 0 to 1

•If y*= x; except x=0 to x=1, α=1 and no separation is

possible
•The larger the value of α above unity, the greater the
degree of separability
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 VLE at increased pressures

pt5> pt4> pt3> pt2> pt1

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 Constant Temperature Equilibria

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 Constant Temperature Equilibria

•Upper curve is now x vs pt known as bubble point curve

•Lower curve is now dew point curve y* vs pt

•Now liquid solution of binary mixture at point W is

heated at constant temperature in closed vessel and
pressure is reduced

•It will follow path w to R

•pB is the vapor pressure of pure B and pA is the vapor

pressure of pure component A

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 Thanks

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