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Semester IV
Chemistry
CHM-402(A): Separation Techniques
DISTILLATION- Lecture I
By Prof. Ida Tiwari
Department of Chemistry
1. It is used for the separation of components of liquid mixture.
2. Depends on the distribution of components between liquid mixture and
the vapour in equilibrium with the mixture.
3. The two phases exist by the formation of vapour phase through partial
evaporation of the liquid mixture.
4. Each phase can be recovered separately with the more volatile
component concentrated in the vapour, while the less volatile ones are
in greater concentration in the liquid.
5. Distillation is defined as the partial vaporization of liquid in a still or
retort and the subsequent collection of vapour as condensate in a
separate vessel.
6. Gibb’s Phase rule F= C-P+2
7. Thus, according to Gibb’s phase rule for a two component system we
need two independent variables which must be specified to describe the
system completely. Since for distillation pressure of the system is
maintained constant, there must be an unequivocal relationship
between the composition of the liquid and vapour phase and the
temperature.
8. It can be expressed as temperature -composition diagram. In the
diagram, the curve ADB represents the boiling points of mixtures of
benzene and toluene whose composition is expressed in mole fractions.
The curve ACB represents the composition of the vapour which is in
equilibrium with the liquid at a given temperature.
Thus, the composition of the vapour in equilibrium with a solution of
composition D is given by C. Thus, vapour phase is richer in the more
volatile component than the liquid phase in equilibrium with it.
9. Hence, distillation is a separation process based on the difference in
composition between liquid and vapour in equilibrium with it. The
separation efficiency of a distillation process is directly proportional to
this difference. Hence, it is highly desirable to introduce a concept of
volatility which expresses the relationship between the compositions of
the liquid and the vapour phases when the two phases are equilibrated.
10. Roult’s Law
PA=XA P0A .................................................... 1
PB= XBP0B ....................................................2
PA- V.P. exerted by molecules of A
PB - V.P. exerted by molecules of B
P0A & P0B are the V.P. of the pure components at the temperature of the
system.
XA & XB represent mole fraction of components in the liquid phase for A
& B respectively.
P= PA+ PB = XA P0A + XBP0B
P- Total Pressure
This law only valid for ideal solutions. Ideal behaviour most likely
observed if the two components are chemically similar or for highly
dilute solutions.
11. It is important to consider the composition of vapour which is escaping
from the solution.
Let YA and YB represent the mole fraction of components A& B in the
vapour phase.
By Dalton’s Law
PA/ PT = YA .................................................3
PB/ PT = YB .................................................4
Combining 1, 2, 3 and 4
PA/ PB = YA / YB = XA P0A/ XBP0B = α XA/X B
α is relative volatility of A w.r.t B
α = P0A/P0B
If the component A more volatile than component B then P0A >P0B
therefore YA / YB greater than XA/X B
This is the fundamental principle of fractional distillation, that is in the
process of boiling, the vapour becomes enriched in the more volatile
component.
12. Volatility ( V) of a given component is given as
V= Y/X
Where X and Y represent the mole fraction of the component in the
liquid and vapour phase respectively.
VA= YA/X A
VB= YB/X B
α = VA/VB= YAXB/ YBXA
On rearranging,
YA/YB= α XA/XB
OR
YA/1-YA= α XA/1-XA
where α is relative volatilty
log α= 8.9 TB- TA/ TA+ TB
TA& TB are normal B.P.s of two constituents in absolute degrees.
Concept of relative volatility widely used, since it provides a measure of
the separability of binary mixture by distillation.
13. Theory of Fractional Distillation:
The simplest example is of a miscible binary mixture. Suppose a mixture
of composition x1 were partially volatilized at temperature t1 and a
portion of the vapour in equilibrium with the liquid were condensed at t2
to give a liquid of composition x2. The change in liquid composition from
x1 to x2 corresponds to change in one equilibrium stage. If the liquid of
composition x2 in its turn was partially vaporized at temperature t2 , the
composition of new condensate would be x3, etc. Hypothetically these
successive distillations can be repeated until an infinitely small sample of
very pure A was obtained.
14. The enrichment of finite samples can be obtained by using a distillation
column so designed that excellent contact is made between vapour
rising through the column and condensate (reflux) falling through the
column.
15. A distillation column is assumed to be made up of number of theoretical
plates. Efficiency expressed in terms of theoretical plates in the column,
a theoretical plate being the length of column required to give the same
change in composition of liquid as that brought about one equilibrium
stage in the temperature- composition diagram.
16. The height equivalent of a theoretical plate (HETP) would be given by
HETP= length of column/ total number of plates
17. Theoretically, any two liquids can be separated by fractional distillation
if their V.P.s are different at a given temperature or if their B.P.s are
different at a given pressure.
18. Reflux Ratio: ratio of moles of reflux per unit time to the moles of
product withdrawn from the top of the column per unit time.
19. Hold up: That portion of original liquid introduced into the stillpot which
is actually in the column as vapour or reflux at any given time.
20. Throughput: Rate at which vapour is passing up the column or desirable
yield per unit time.
21. Analysis of steady- state condition ( continuous distillation):
a) Mathematical analysis of steady state condition is done to determine
the conditions existing at any point in the column at any given time
and by knowing these conditions we can predict optimum operating
conditions for the distillation.
b) Fenske and Underwood independently derived an expression which
relates the distillate composition to the relative volatility of the
components, number of theoretical plates in the column, and the still
composition when the column is operated under total reflux, that is,
in a steady state.
( One must keep in mind that in total reflux no product withdrawn
and so it is of no practical importance)
c) In continuous distillation the preheated material to be fractionated is
fed into the middle of the column while the lower boiling fractions
are withdrawn from the top and the higher boiling fractions from the
bottom. The rate of sample introduction is adjusted so that the
volume of feed is equal to the total volume of takeoff from the top
and bottom of the column. Under such conditions the composition of
phases will be constant at any given time in the column during course
of distillation and is amenable to mathematical treatment.
d) Derivation:
The number of theoretical plates, n, required to enrich a binary
mixture of A and B originally containing concentrations XA,0 and XB,0 to
a given degree of purity, X A,f can be computed from relative volatility,
α. It is assumed α is constant over the range of concentration
considered.
The vapour from the first vaporization in the still pot gives
YA, 0/YB, 0 = α XA, 0/XB, 0
Or
YA, 0/1- YA, 0 = α XA, 0/1- XA, 0
When the vapour from the still pot condenses in the first plate, its
concentration does not change, that is YA, 0 = X A, 1
It evaporates from the first plate
YA, 1/1- YA, 1 = α XA, 1/1- XA, 1= α YA, 0/1- YA, 0= α2 XA, 0/1- XA, 0
After n such plates, giving n+1 repetitive evaporation- condensations
YA, n/1- YA, n= αn+1 XA, 0/1- XA, 0
This is Fenske equation.
αn is known as enrichment factor.
e) Taking log, of Fenske equation and rearranging
log (YA, n/1- YA, n)= (n+1) log α + log (XA, 0/1- XA, 0 )
When the vapour in the nth plate condenses, the composition of the final
distillate will be Y A, n = X A, f
Therefore, log (XA, f /1- YA, f) = (n+1) log α + log (XA,0/1- XA,0 )
Or
(n+1)= log (XA, f /1- XA, f) - log (XA,0/1- XA,0 ) / log α
Or
n+ 1= log [XA, f (1- XA,0)/ XA,0 (1- XA, f)] / log α
From these mathematical expressions we can calculate minimum
number of plates required to achieve desired separation or can calculate
from known distillate and distilland compositions, number of theoretical
plates in the column.