Vapour liquid equilibrium

Introduction
• Distillation is the technique of preferential
separation of more volatile component from the
less volatile ones in the feed solution by partial
vaporization of the feed followed by
condensation
• The vapour produced is rich in more volatile
components
• The distribution of components in two phase is
governed by the VLE relationship
• Multistage required for higher degree of
separation
Important parts of distillation column

More volatile components

move from L-V and less
volatile in reverse directionV-
L. As a result concentrations of
the more volatile increases in
the vapour as it goes up and
the concen of less volatile
increase in the liq phase as it
flowsdown the column
• Distillation is invented in Alexandria in the first
century AD for the production of alcoholic
beverages
• Refinery –crude petroleum
• Petrochemical-Ethylene oxide and water
-styrene/ethyl benzene
-benzene/ethylbenzene
Fermentation/distillery-
Ethanol/water
 VLE
• Separation of mixture by distillation is based on
eqm distribution of the components between
liquid and the vapour phases
• A knowledge of VLE is essential for understanding
the principles of distillation
• Consider an aqueous solution of ethanol in a
closed vessel
• Under a given set of conditions ,the eqm vapour
composition is related to the liquid composition-
VLE
• Gibbs phase rule F=C-P+2
• Total no of parameters and variables is 4 (T,P,y,x)--
-F=2 (two of these quantities to be fixed to define
the system in equilibrium)
• If T,P are fixed, the liquid and vap composition
will be automatically fixed
• ie. There can be only one set of liquid and vapour
compositions for which the total pressure exerted
in the vapour space is equal to the given pressure
at the given temperature
• Accurate VLE data are
essential for reliable
design of a distillation
column
• Multicomponent-a
predictive
method(UNIFAC
method)
Constant pressure-VLE
VLE-at increased pressure

Pressure increases
the bubble and
dewpoint curve
decreases and
separability by
distillation is less at
high P, as α
decreases
Constant temperature equilibrium
 Raoults law
• VLE of ideal solutions
• For an ideal solution eqm partial pressure 𝑃−∗ Of a constituent
at a fixed temperature equals the product of its vap pressure p
when pure at this temperature and its mole fraction in the
liquid

If the vap phase is also ideal

*

y 
* PA p x
 A
*
PB p 1  x  x
Pt  pB 
Pt Pt 1 y 
*
 B  p A  pB 
Pt Pt
 Relative volatility
• The greater the distance b/w the eqm curve and the
diagnol, the greater the difference in liquid and
vapour composition and easier the separation by
distillation.
• One numerical measure of this is separation factor,
relative volatility
• This is the ratio of the concentration ratio of A and B
in one phase to that in other and is a measure of
separability
In an ideal binary solution it can be expressed in
terms of vapour pressure
What happens if α=1??
• Compute the eqm data from the following
data at 760mmHg pressure and calculate the
relative volatility

V.P of 760 830 920 1060 1200 1360

A,
mmHg
V.P of 200 350 420 550 690 760
B,mm
Hg
• Distinguish between Evaporation and
distillation