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Chapter 9

DISTILLATION

INTRODUCTION
• Distillation is the separation of the components from a solution
depending on its distribution between a liquid phase and vapour
phase.
• It is an operation in which a liquid or vapour mixture of two or
more components is separated into its component fractions of
desired purity, by the application of heat.

VAPOUR LIQUID EQUILIBRIA (VLE)

• The vapour liquid equilibrium data is the basis for design of
distillation operation equipments.
Dr. Enshirah Da'na 2

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VLE at constant P
Constant Pressure Equilibria

• The upper curve is the dew point

curve.

• It provides the relationship

between T and mole fraction of the
more volatile component in vapor
phase (y).

• The lower curve is the bubble

point curve.

• It gives the relationship between

the temperature and mole
fraction of the more volatile
component in liquid phase (x) at
a particular pressure.

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• The horizontal tie lines CD, EF and GH at different temperatures

provide equilibrium compositions of liquid and vapor phase at each
temperature.

• Any mixture lying on the

lower (bubble point) curve
will be a saturated liquid
and the mixture lying on
the upper (dew point) curve
will be a saturated vapor.

• A mixture between the two

curves, K, will be a two-
phase mixture of liquid and
vapor with compositions C
and D.
Their relative amounts are
given by:

𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑪 𝑳𝒆𝒏𝒈𝒕𝒉 𝒐𝒇 𝒍𝒊𝒏𝒆 𝑲𝑫

=
𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑫 𝑳𝒆𝒏𝒈𝒕𝒉 𝒐𝒇 𝒍𝒊𝒏𝒆 𝑲𝑪

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• A mixture at point M is only a liquid.

• If it is heated inside a cylinder
with a frictionless piston, its
temperature will increase till it
reaches ‘E’ , it will become a
saturated liquid.

• The vapor in equilibrium with

it will have a composition of F.

• As heating is continued, more vaporization takes place, the liquid phase

composition will move towards G and the associated vapor will have a
composition of H.
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• The effective composition of the entire mass comprising both liquid

and vapor continues to remain at M.

• when the last droplet of liquid

at point ‘I’ is vaporized, the
vapor generated would have a
composition of ‘J’.

• Further heat results in

superheating of the vapor.

• During the entire operation, the

pressure is kept constant.

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Effect of Pressure
• As pressure is increased, the boiling points of components
increase, and the looped curves become narrower.
• As the critical pressure is exceeded for one of
the components, there is no longer a distinction
between vapor and liquid for that component,
and for mixtures the looped curves are,
therefore, shorter as for case (C).
• Distillation is possible only in the region where a
looped curve exists.

• Relative volatility, 𝜶, also changes in such cases.

Constant Temperature Equilibria

• lines CD, EF and GH are tie lines indicating
the equilibrium compositions of liquid and
vapor phase at various pressures.
• A liquid at point M is a liquid below its
bubble point and as the pressure is
reduced at constant temperature, at
point ‘N’ on the upper (bubble point)
curve, a saturated liquid is obtained.

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• As the pressure is brought down

further, at point Q on the lower
(dew point) curve, a saturated
vapor forms and a further
reduction in pressure gives a fully
superheated vapor as defined by R.

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RELATIVE VOLATILITY (∝)

• This is defined as the ratio of vapor pressure of more volatile

component to that of less volatile component.

• If PA and PB are the vapor pressures of A and B respectively, the

relative volatility of A with respect to B, ∝ AB is defined as the ratio
of vapor pressure of A to that of B.

𝑷𝑨
∝𝑨𝑩=
𝑷𝑩

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Raoult’s law

• It states that when a gas and a liquid are in equilibrium, the

partial pressure of A, pA is equal to the product of its vapor
pressure, PA at that temperature and its mole fraction xA in the
liquid.
𝒑𝑨 = 𝑷 𝑨 . 𝒙 𝑨

𝒑𝑩 = 𝑷 𝑩 . 𝒙 𝑩

• When the gas and liquid behave ideally, Raoult’s law holds good.

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• The sum of the partial pressures of components in a gas mixture is

equal to the total pressure, PT.

• The composition of a component y, in gas phase is given by

Dalton’s law,
𝑃# 𝑃%
𝑦# = 𝑦% =
𝑃$ 𝑃$
𝑝# 𝑃$ 𝑦# 𝑦#
𝑃# 𝑥 𝑥# 𝑦
∝#% = = 𝑝# = = 𝑥%
𝑃% % 𝑃$ 𝑦% #
𝑥% 𝑥% 𝑥%

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𝑦#
1 − 𝑦#
∝#% = 𝑥#
1 − 𝑥#
Rearranging,
∝#% 𝑥#
𝑦# =
1 + 𝑥# (∝#% −1)

∝𝑥
𝑦# =
1 + 𝑥(∝ −1)

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COMPUTATION OF VLE DATA

(EQUILIBRIUM DATA)

The vapor pressure of the components involved is the basis for the
computation of VLE data.
𝒑𝑨 = 𝑷 𝑨 . 𝒙 𝑨
𝒑𝑩 = 𝑷𝑩 . 𝒙𝑩 = (𝟏 − 𝒙𝑨) 𝑷𝑩
For a binary system,
𝒑𝑨 + 𝒑𝑩 = 𝑷𝑻 = 𝒙𝑨𝑷𝑨 + 𝟏 − 𝒙𝑨 𝑷𝑩 = 𝑷𝑩 +𝒙𝑨 (𝑷𝑨 − 𝑷𝑩)

𝑷𝑻 − 𝑷𝑩
𝒙𝑨 =
𝑷𝑨 − 𝑷𝑩

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Example 1

Compute the equilibrium data from the following data at 760 mm Hg

pressure and calculate the relative volatility. PT =760mmHg

Solution

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The average relative volatility: 2.303

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Example 4
A solution of methanol and ethanol are substantially ideal. Compute
the VLE for this system at 1 atm pressure and relative volatility.

Solution
In this problem one has to compute the vapor pressure values at
different temperatures.

The temperature range is fixed by keeping the pressure as 760 mm Hg

for each component.
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Thus, in the following equation for Methanol,

Setting the vapor pressure as 760 mm Hg (at BP, vapor pressure

equals the prevailing pressure), we get the temperature as 66.53°C,
which is the boiling point of Methanol. Similarly, by setting P as 760
mm Hg in the equation for ethanol,

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Average relative volatility = 1.579

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Example 5
Methanol and Ethanol form an ideal solution. Compute the VLE
data at 760 mm Hg pressure, Vapor pressure Data:

Plot vapor pressure vs temperature for both the components and

compute T vs. VP for Methanol and T vs. VP for Ethanol.

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Solution

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