Distilation 1

Distillation
24.10.2017
Distillation
Introductory video— click here
Theoretical concepts
 Raoult’s law
 Boiling point diagram
 Vapour liquid eqilibrium (VLE) curve

Raoult's Law
Raoult’s law mainly used to determine the vapour pressure of the

solution when a solute has been added to the solution.
This vapor pressure is used to measure –
 the escaping tendency of the solvent and
 the concentration of solvent
molecules in the gas phase.
In 1880’s, Raoult’s law was

established by
Francois Marie Raoult.
Raoult’s law state that the change in vapor pressure of the
ideal solution depends completely on the mole fraction of
the solute present in the mixture and the vapor pressure
of the each chemical substance.
pA=PA× xA
Where,
pA - Partial pressure of the substance in the mixture or
solution
PA - Vapor pressure of the pure substance
xA - Mole fraction of the substance in the mixture or solution
Hexane and heptane mixture
when the solute is added to the solution, the vapour
pressure of the solution will decrease, which is
mainly depends on the two factors-
The mole fraction of the amount of dissolved

solute present in the solution.
Original vapor pressure of the solute.
Conti…
pA=PA . XA
In chemistry, colligative
properties are properti
es of solutions that
depend upon the ratio of
the number of solute
particles to the number of
solvent molecules in a
solution, and not on the
type of chemical species
present.
Question 1: What is the vapour pressure of a
solution at 25˚C containing 68g of glucose (MM =
180.16g/mol) in 600grams of water? The vapour
pressure of pure water at 25˚C is 23.8mmHg.
Mole. weight of water = 18.02

Mole. weight of glucose = 180.16
Question 1: What is the vapour pressure of a solution at 25˚C containing
68g of glucose (MM = 180.16g/mol) in 600grams of water? The vapour
pressure of pure water at 25˚C is 23.8mmHg.
Solution:
Vapor pressure of pure water (PoH2O) = 23.8 mm Hg.
Calculate the mole of water and mole of glucose
Mole of water = 600g/18.02 = 33.29 mol
Mole of glucose = 68g/180.16 = 0.377 mol
Mole fraction of water (XH2O) = 33.29/(33.29 + 0.377)
= 0.989
Apply Raoult’s law
P = XH2O PoH2O = 0.989 X 23.8 = 23.54
Note- Glucose is solid so it does not have any vapour pressure
Question 2: What is vapour pressure of pure
butane at 20˚C if the partial pressure is 698 mmHg
in a butane acetone mixture where the mole fraction
of acetone is 0.6777.
Question 2: What is vapour of pure butane at 20˚C if the partial pressure is
698 mmHg in a butane acetone mixture where the mole fraction of acetone is
0.6777.
Solution:
Mole fraction of acetone (XA) = 0.677 moles
Mole fraction of butane (XB) = 1 – 0.677 = 0.323 moles
Applying Raoult’s Law
pB = XB PB*
PB* = pB / XB
= 698/ 0.323 = 2160.99 mm Hg

Boiling point diagram
(for ideal system)
The dew-point is the temperature

at which the saturated vapour
starts to condense.
The bubble-point is the
temperature at which the liquid
starts to boil.
The region above the dew-point curve

shows the equilibrium composition of
the superheated vapour while the
region below the bubble-point curve
shows the equilibrium composition of
the sub-cooled liquid.
This difference
between liquid and
vapour
compositions is the
basis for
distillation
operations.
Equilibrium condition
Numerical:
Table- Vapor pressure of pure benzene / toluene
Calculate the vapour and liquid composition in
equilibrium at 95 deg C for benzene –toluene using
the vapour pressure from table at 101.325 kPa.
Calculate the vapour and liquid composition in
equilibrium at 95 deg C for benzene –tolune using the
vapour pressure from table at 101.325 kPa.
Solution:
155.7 (XA ) + 63.3(1- XA ) = 101.325
XA =0.411
XB =1-0.411
=0.589
YA =(PA . XA ) / P
=(155.7 x 0.411) / 101.325 = 0.632
Vapour-Liquid-Equilibrium (VLE) Curves
Constant pressure VLE

data is obtained from
boiling point diagrams.
VLE data of binary e

lin
mixtures is often o
45
presented as a plot >>
Vapour-Liquid-Equilibrium (VLE) Curves
The VLE plot expresses

the bubble-point and the
dew-point of a binary
mixture at constant
pressure.
e
The curved line is called o
lin
45
the equilibrium line and
describes the
compositions of the
liquid and vapour in
equilibrium at some
fixed pressure.
 Two VLE plots below shows non-ideal systems which will
present more difficult separations.
The most intriguing VLE curves are generated by
azeotropic systems.
An azeotrope is a liquid mixture which when

vaporised, produces the same composition as the
liquid.
The two VLE plots show two different azeotropic
systems-
one with a minimum boiling point and
one with a maximum boiling point.
Maximum and Minimum Boiling Point
In both plots, the equilibrium curves cross the
diagonal lines, and these are azeotropic points where
the azeotropes occur.
In other words azeotropic systems give rise to VLE

plots where the equilibrium curves crosses the
diagonals.
Relative volatility
In order to separate a binary mixture using distillation
process, there must be a differences in volatilities of the
components.
The greater the difference, the easier it is to do so.
A measure for this is termed the relative volatility.
p=P.y
If
xA=x
yA=y
When a = 1.0, no separation is possible: both
component-A and component-B are equally volatile.
They will vapourise together when heated.
Solving the above equation

for a = 1,
we obtain: y = x.
The larger the value of α above 1.0, the greater the degree
of separability, i.e. the easier the separation.
Recall that when a system has reached equilibrium, no

further separation can take place - the net transfer
rate from vapour to liquid is exactly balanced by the
transfer rate from liquid to vapour.
Therefore, separation by distillation is only

feasible within the region bounded by the
equilibrium curve and the 45o diagonal line.
From the equilibrium
curve, we see that the
greater the
distance between the
equilibrium curve and
the diagonal line (where y
= x), the greater the
difference in liquid and
vapour compositions and
therefore the easier the
separation by
distillation.
x
Types of distillation systems
1. Single stage or still distillation:

Flash or equilibrium
Simple batch or differential
Simple steam
2. Multi stage distillation :

Types
1. Single stage or still distillation: Production of

vapour by boiling –separated in single phase–
recovery and condensing the vapour,
no liquid is allowed to return
2. Multi stage distillation :Part of condensate is

allowed to return and contact the rising vapour
called as fractional distillation, distillation with
reflux or rectification
Single stage or still distillation
Flash or equilibrium
Simple batch or differential
Simple steam
Flash or equilibrium
A single-stage continuous
operation where a liquid
mixture is partially
vaporized:
the vapour produced and
the residual liquid are
in equilibrium, which are
then separated and removed
1. Flash or equilibrium
F.xF=V.y+L.x
L=F-V
F.xF = V.y + (F-V).x
y = [-(F-V)/V].x + (F/V).xF
2. Simple batch or differential
Simple batch or differential
In a batch distillation process, a liquid mixture is

charged to the still, which is then heated to the
bubble point.
At any given instant, the composition of the

vapor can be considered in equilibrium with
the liquid, but the vapor phase is condensed and
taken off as product.
Because this vapor, which is rich in the more volatile

component, is removed from the system, the liquid
remaining behind in the still is enriched in the less
volatile component.
This means that the bubble-point temperature of the

remaining liquid increases slightly and the new
vapor that comes off will still be enriched in the more
volatile component, although not quite as much as
the previous vapor removed.
The more of the liquid that is distilled, the higher

will be the composition of the less volatile
component remaining in the distillation pot.
The first vapor that was taken over as distillate will
have the highest composition of the more volatile
component, but as time goes on the composition of
the vapor condensed will decrease from that initial
value because each successive vapor that is
condensed has a slightly lower concentration of the
more volatile component.
Rayleigh equation
x.L=(x-dx)(L-dL)+y.dL
x.L=xL-xdL –Ldx+dx.dL+y.dL
1=-xdL –Ldx+y.dL
Neglecting dx dL
dL/L=dx/(y-x)
Rayleigh equation-
Yav can be obtained by- L1. x1=L2 x2+(L1-L2) yav
Thanks
Steam distillation
Steam distillation is a special type of distillation

(a separation process) 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.
Steam distillation
This process effectively allows for distillation at

lower temperatures, reducing the deterioration of
the desired products.
If the substances to be distilled are very sensitive to

heat, steam distillation may be applied under
reduced pressure, thereby reducing the operating
temperature further.
Steam Distillation
Multi stage distillation tower
thanks
Simple steam distilation
F=C-P+1= 2-3+1 = 1
So if the pressure is fixed system is fixed
PA+PB=P
yA=PA/P

Distilation 1

Uploaded by

Copyright:

Available Formats

Distilation 1

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Distilation 1

Uploaded by

Copyright:

Available Formats

Distillation

Introductory video— click here

 Vapour liquid eqilibrium (VLE) curve

Raoult’s law mainly used to determine the vapour pressure of the

In 1880’s, Raoult’s law was

The mole fraction of the amount of dissolved

Original vapor pressure of the solute.

Mole. weight of water = 18.02

Applying Raoult’s Law

= 698/ 0.323 = 2160.99 mm Hg

The dew-point is the temperature

The region above the dew-point curve

Constant pressure VLE

VLE data of binary e

The VLE plot expresses

An azeotrope is a liquid mixture which when

In other words azeotropic systems give rise to VLE

Solving the above equation

Recall that when a system has reached equilibrium, no

Therefore, separation by distillation is only

1. Single stage or still distillation:

2. Multi stage distillation :

1. Single stage or still distillation: Production of

2. Multi stage distillation :Part of condensate is

F.xF = V.y + (F-V).x

In a batch distillation process, a liquid mixture is

At any given instant, the composition of the

Because this vapor, which is rich in the more volatile

This means that the bubble-point temperature of the

The more of the liquid that is distilled, the higher

Steam distillation is a special type of distillation

Many organic compounds tend to decompose at high

This process effectively allows for distillation at

If the substances to be distilled are very sensitive to

You might also like