Basic Principles : Summary

to give an equation relating the vapour and liquid equilibrium

compositions at any temperature:
xi pi *
yi  (1.3)
P

The saturated vapour pressure, pi*, is a function of temperature

and can be given by the Antoine Equation.

B
log10 pi *  A  (1.4)
t C
 Mixtures do not have a boiling point

T
VAPOUR
Dew Point

Boiling point
L+V Boiling point
of pure (2)
of pure (1)

LIQUID Bubble Point

x1, y1

By definition, a mixture does not have a boiling point. Instead we

can refer to a ‘bubble point’ and a ‘dew point’
 Binary Systems

At a given pressure P and temperature t (which fixes p1* and p2* from
Equation 1.4) we can solve Equation 1.5 for x1, the liquid composition
which would just boil at the given conditions:

P  p2 *
x1  (1.6)
p1 *  p2 *

xi pi *
yi  (1.3)
P
 Binary Systems: using x-y Diagrams

0.8

0.6
y1

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1
x1
 Multicomponent Systems

 Volatility of any component i in a mixture can be described

by the K-factor, which is the ratio K = yi / xi.

 K-factor is a measure of the tendency of component i to

vaporise.
 METHODS OF DISTILLATION—TWO
COMPONENT MIXTURES
for a binary mixture with a normal y − x curve,
the vapour is always richer in the more volatile
component than the liquid from which it is
formed. There are three main methods used in
distillation practice these are:
(a) Differential distillation.
(b) Flash or equilibrium distillation, and
(c) Rectification.
Of these, rectification is much the most important,
and it differs from the other two methods in that
part of the vapour is condensed and returned as
liquid to the still, whereas, in the other methods,
all the vapour is either removed as such, or is
condensed as product.
 (a) Differential distillation
The simplest example of batch distillation is a single
stage, differential distillation, starting with a still pot,
initially full, heated at a constant rate. In this process the
vapor formed on boiling the liquid is removed at once
from the system.
At the end of the process the liquid which has not been
vaporized is removed.
If S is the number of moles of material in the still, x is the
mole fraction of component A and an amount dS,
containing a mole fraction y of A, is vaporized, then a
material balance on component A gives:
The integral on the right-hand side of this equation
may be solved graphically if the equilibrium
relationship between y and x is available. In some
cases a direct integration is possible. Thus, if over
the range concerned the equilibrium relationship is
a straight line of the form y = mx + c, then:
From this equation the amount of liquid to be distilled in order to
obtain a liquid of given concentration in the still may be calculated,
and from this the average composition of the distillate may be
found by a mass balance. Alternatively, if the relative volatility is
assumed constant over the range concerned, then
y = αx/(1 + (α − 1)x), equation 11.15 may be substituted in
equation 11.28. This leads to the solution:
 (b) Flash or equilibrium distillation
Flash or equilibrium distillation, frequently carried out as
a continuous process, consists of vaporising a definite
fraction of the liquid feed in such a way that the vapour
evolved is in equilibrium with the residual liquid. The
feed is usually pumped through a fired heater and enters
the still through a valve where the pressure is reduced.
The still is essentially a separator in which the liquid and
vapour produced by the reduction in pressure have
sufficient time to reach equilibrium. The vapour is
removed from the top of the separator and is then
usually condensed, while the liquid leaves from the
bottom.
 One-Stage (Flash) Distillation
condenser F is the Feed flowrate (molar units) of
composition xF
D is the top product flow of composition xD
D
F (Distillate) – it is yD before condensation.
W is the bottom product flow of composition
heat xW (historically a Waste, as in ethanol-water)
W

Perform a material balance assuming steady state

Overall: F  D W (2.1)
MVC: xF F  xD D  xWW (2.2)
 One-Stage (Flash) Distillation

F  D W (2.1) xF F  xD D  xWW (2.2)

Eliminating W xF F  xD D  xW  F  D  (2.3)

xD D  D
xF   xW 1  
F  F
•D/F = f: the fraction evaporated
•xD is equal to the vapour composition, y
•xW is equal to the liquid composition, x within the still

we can rearrange Equation 2.3 to obtain:

 1 f  xF
y   x (2.4)
 f  f
 One-Stage (Flash) Distillation
 1 f  xF
y    x  (2.4)
 f  f

What if we plot equation (2.4) on our x-y diagram?

Let’s assume that both xF and f equal 0.5.

y  x 1
1 The composition is
0.8
obtained from the
intersection of (2.4)
0.6 and the equilibrium
xF, xF
y

0.4 curve
0.2 y = 0.62

0
x = 0.37
0 0.2 0.4 0.6 0.8 1
x
 One-Stage (Flash) Distillation

condenser

If xF = 0.5 and f = 0.5:

D
F xD = 0.62 and xW = 0.37

heat
W

With vapour-liquid equilibrium (VLE) data we can therefore

calculate the exiting composition (xD and xW) for a given feed
composition and D/F ratio
 Extreme Cases

D/F  0 condenser

All product is withdrawn from the bottom of the still

F
D
 1 f  xF
y   x (2.4) heat
 f  f W

0.8
Top product
0.6 composition would
be 0.71 – if we could
y

0.4
produce any!
0.2

0
0 0.2 0.4 0.6 0.8 1
x
 Extreme Cases

D/F  1 condenser

All product is withdrawn from the top of the still F

D
 1 f  xF
y    x  (2.4)
 f  f heat
W

1
Top product
0.8 composition would
be 0.5 – the same
0.6 as the feed liquid!
y

0.4
Bottom product
0.2 composition would
be 0.29 – but we
0
0 0.2 0.4 0.6 0.8 1 don’t have any!
x
 Between the two extremes
0 < D/F < 1

0.8

0.6
y

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1
x

As D/F increases the top product composition falls