Mass Transfer Operation I

Prof. Bishnupada Mandal

Department of Chemical Engineering
Indian Institute of Technology, Guwahati

Module - 5
Distillation
Lecture - 1
Introduction to Distillation and Phase Diagrams

(Refer Slide Time: 00:29)

Welcome to the first lecture of module five. In this module, we will discuss distillation.
Distillation is a method of separation of the more volatile component, separation of more
volatile component from the less volatile one of a solution by partial vaporization. So,
this partial vaporizations was done from the original solutions as another phase or the
vapor phase is generated by partial vaporization, and then there is condensation of the
vapor to get the desired product. This distillation is most widely used separation method
for the liquid mixture. And the very common examples are organic process industries
process industries like ethanol water separation, aniline and nitrobenzene separation.
This is also most common in petroleum refinery petroleum refinery, and there are many
other industries which uses the distillation as a process for separations of the liquid
mixtures, where the liquid mixture contains the more volatile components and the less
volatile components.
(Refer Slide Time: 03:46)

A typical distillation column is look like this. This is a tray columns where the feed
which is enter at some point on the tower in between that air either middle or at some
points, and feed is preheated and then fit to the tower. There is a reboiler at the bottom of
the tower which boils the liquid or it vaporizes the liquid partially and then the vapor
flows up. So, vapor this goes off and then vapor leaves at the top vapor leaves at the top,
and there is overhead condenser and then it reaches to the distributor. We call it reflux
drum which separates the vapor and liquid mixture.

(Refer Slide Time: 04:55)

A part of the condense heat from this reflux dram is recycled back at the top and rest is
taken as the product. So, the liquid fall down or flow towards down and there is intimate
contact between the vapor and the liquid on each tray. So, more volatile component
moves from liquid in this process the more volatile component from the liquid phase to
the transfer to the vapor phase.

(Refer Slide Time: 05:47)

And the less volatile components move from the vapor phase to the liquid phase. The
concentration of the less volatile increases in the liquid as it flows towards down and the
concentration of the more volatile increases in the vapor phase. So, a higher degree of
separation of the more volatiles from the less volatile is achieved. The top product which
we got over here as a overhead product is rich in more volatile component component
rich, and the bottom product which is prompt as the bottoms is the rich in less volatile.
(Refer Slide Time: 07:01)

So, now the distillation process which is an equilibrium stage operation process it
requires the vapor liquid equilibrium and physicochemical properties of the systems to
solve this equilibrium stage operation. The distribution of the two components is
governed by the vapor liquid equilibrium relationship, distribution of the components
among the phases depends on the VLE vapor liquid equilibrium relationship.

So, here we will only consider the binary mixtures. So, this equilibrium data we can
obtain from experiments, we can also obtain from thermodynamics. It is typically
represented by the equilibrium diagram VLE data is represented by equilibrium diagram
and they are like T x y diagram temperate mole fractions in the liquid phase and mole
fraction in the vapor phase of the more volatile components. So, we call it T x y diagram
or P x y diagram and the liquid and vapor compositions are related with the x y diagram
and enthalpy mole fractions relationship is represented by enthalpy concentration
diagram H x y diagram.
(Refer Slide Time: 09:47)

So, now we will consider T x y diagram. It is a constant pressure binary equilibrium

diagram. Its boiling point is plotted versus liquid composition x is the liquid composition
then we call it bubble point curve. Now if we plot boiling point versus y then it is dew
point curve. A typical bubble point and dew point curve is plotted over here so the upper
curve here this is the T y curve or the dew point curve that is each point on this curve
represents the saturated vapor and the below line which is the T x or bubble point curve.
So, here the composition x or y; these are represented in terms of the mole fractions, x, y
represented in terms of the mole fraction of the more volatile component; x is in the
liquid phase and y in the vapor phase. The less volatile component would be 1 minus x
and 1 minus y.
(Refer Slide Time: 12:21)

For any given temperature and composition for a given temperature and composition this
curves tells us the composition of each phase of that mixture composition composition
on each phase of that mixture. Suppose the point L over here this gives the equilibrium
liquid phase composition T x and corresponding vapor phase composition at G and this
line LG is known as the tie line. So, we can draw such an infinite number of tie lines in
this region. And as I said the point on the lower curve represents the or at L represents
the saturated liquid and points at G represents the saturated vapor. The region below this
red line which is saturated liquid below that is known as the liquid region and above the
blue line is represents the vapor region.

And the region between this two bubble point and dew point is known as the two phase
region say a mixture point S on the tie line of LG represents the two phase mixture which
has the liquid composition liquid composition at L. and vapor composition at G and the
proportion can be obtained or the relatives amount can be obtained from the segment of
these tie lines, segments S L and S G. Moles of L by moles of G we can write line S G
by line L S.
(Refer Slide Time: 15:40)

Now if we consider a liquid at point E in a closed vessel and kept at constant pressure
say one atmosphere. Now, if the solution is heated then the first drop of vapor will found
at o and it has the composition at P, it will have the composition at P which is richer in
mole volatile components. If we continue to heat it will follow E x line and the liquid
line will follow o to u and it will give the vapor composition at b, but the compositions of
the entire mass will still be remain as at E.

So, the mole fraction of the more volatile in the residual liquid decreases and the boiling
point of the mixture continue to increase. The last drop of the vapor which is vaporizes at
point x and has the composition and boiling point which is represented by w. When all
the liquid is vaporized the vapor must have a composition equal to the initial E, initial
liquid composition at E. Now, if no further heating is done then the final state of vapor is
given by point x which is on the vertical line between from E to x. If we further heat this
solution then the temperature will raise along the vertically through E F we call it super
heating.
(Refer Slide Time: 19:00)

So, in this case we can see the mixture is vaporized from the liquid to the vapor in the
temperature region between o to x, this is the temperature region where the liquid is
vaporized. Except pure substance the boiling point of a solution does not have any
meaning because the solution solution vaporizes over a temperature range which is
starting from bubble point to the dew point. The bubble and due points curves and meets
point D B and at point D A, point D B represents the boiling point of pure B at a given
pressure and point D A is the boiling point of pure A.

(Refer Slide Time: 20:40)

Now, if some amount of super heated vapor say at point S super heated vapor at point S
is cooled at constant pressure what will happen? It will follow the same path in the
reverse directions for examples condensation condensation will start at X on the dew
point curve and the vapor composition will change along x P line . So, when the inter
vapor is condensed and then liquid is again cooled so it will reach the domain at E which
is sub cooled.

(Refer Slide Time: 22:31)

So, the equilibrium diagram for x y mole fractions is also plotted below the bubble point
and dew point curve. So, this line represents the equilibrium curve x y diagram and
below this is the 45 degree line or diagonal line where x is equal to y. So, the x y
diagram can also be plotted from T x y diagram by picking a temperature and then
corresponding y and x can be rate from this. The point A which is x y, on the x y curve
represents to the tie line corresponding to the tie line LG on the T x y diagram. Since
here y is greater than x the mole fractions of the more volatile component is more; the
equilibrium line, line is lies above the diagonal. So, if the distance or the separations
between the diagonal line and the equilibrium line is larger then separation is better. So,
the envelope envelope made by equilibrium line, and diagonal this is fat then separation
by distillation is easier.
(Refer Slide Time: 26:01)

Now, we will see the constant temperature binary equilibrium diagram. So, this is the
plot where the total vapor pressure exerted by the solution at equilibrium depends on its
composition. At a lower concentration of certain components the mixture will exert
lower vapor pressure, the typical plot is so lower here where y axis represents P
millimeter LG and this X is the mole fractions of more volatile components x and y, the
horizontal line LG represents the tie line, the terminal points L and G; these are the liquid
and vapor phase concentration of certain components and equilibrium of more volatile
components and equilibrium. The region below this curve P x y curve, this is P x y curve
at constant T below this blue line represents the vapor region, above this red line
represents the liquid region and in between these two line represents the two phase
region.

Suppose, if we consider a liquid in amount of vapor at location R super heated vapor at a

given temperature now which compressed isothermally. The vapor will start condensing
and it reaches the point at point G where the first drop of liquid will form at point G and
will have composition at L. Now, if we further compress more vapor condenses and the
composition of the accumulated condensed liquid changes along L S, the compositions
of the liquid changes along L S the composition of the vapor changes along G S,
composition of liquid changes along L S and composition of vapor changes along G S
dash.
(Refer Slide Time: 29:45)

Now, at a pressure corresponding to this point S the vapor condenses completely. Now
the liquid composition will have the same composition of the original vapor which is at
R, if the vapor pressure is raised further the liquid maybe considered sub cooled and it
will follow the line through S F. The equilibrium composition to the tie line LG is
represented by q P this is the equilibrium composition on the x y diagram, and the two
phase region T x y or P x y this narrows down two phase region on T x y or P x y
diagram narrows down with increase in temperature and pressure and disappears at the
critical point.

(Refer Slide Time: 31:35).

Now, we will discuss phase rule and ideal V L E. If two phases are not in equilibrium
then the transfer of mass from one phase to the other phase will be proportional to the
driving force which is the departure from the equilibrium. In most of the cases which
involves equilibrium two phases are generally involved this maybe two phase two phases
gas liquid, liquid liquid, solid liquid and so on. The important variables which affects this
equilibrium is the temperature pressure and concentration temperature, pressure and
concentration parameters or variables affects equilibrium. The equilibrium between the
phases for a given situation is restricted by phase rule and it states that F is equal to C
minus P plus 2 where F is the number of variables or degrees of freedom F is the degrees
of freedom freedom, C is the number of total components in the two phases number of
total components in the two phases when there is no chemical reaction, and P is the
number of phase number of phases.

(Refer Slide Time: 34:30)

So, if we consider a simple example of sulfur dioxide and air water system then phases
are 2 components 3 and considering air as single component, then we can write F is
equal to C minus P plus 2 which is 3 minus 2 plus 2 is equal to 3 this means that it has 3
variants or 3 degree of freedom. If the total pressure total pressure and temperature are
set then the third variable, variable that is the concentration of sulfur dioxide can be
arbitrarily arbitrarily arbitrarily set. So, the phase rule does not tell us the partial pressure
in that equations with the selected mole fractions. So, the partial pressure must be
determined experimentally. This thing can be simplified if we consider the ideal behavior
or the ideal solutions; the 3 ways we can define or can be related one is Roult’s law,
second is relative volatility and third is equilibrium coefficients.

(Refer Slide Time: 37:37)

The Roult’s law relates with the vapor liquid compositions of a mixture to the pure
component vapor pressure and system pressures. So, we can write y P t is equal to x P v
where y is the mole fractions in the vapor phase, P t is the total pressure and x is the mole
fractions in the liquid phase and P v is the vapor pressure.

(Refer Slide time: 38:50)

So, consider the binary mixture where say A and B we can write the partial pressure P A
is equal to x into P A v and P B partial pressure of B we can write 1 minus x into P B v.
So, P A and P B these are the partial pressures of partial pressures of A and B; P A v and
P B v are the vapor pressure pressure of A and B at the given temperature. We can write
P T is equal to P A plus P B is equal to x P A v plus 1 minus x P B v this will give P A
by P t would be equal to x P A v by P t or we can write y A P t is equal to x P A v. This
equations can be used to calculate the vapor liquid equilibrium data for an ideal binary
mixture.

(Refer Slide Time: 41:06)

Now, we will discuss the relative volatility. The greater the distance from the equilibrium
curve and the diagonal curve the greater the difference in the liquid and vapor
composition easier to separate by distillation. One numerical measure for this is the
relative volatility; relative volatility is defined as the ratio ratio of A and B in one phase
to that in the other phase. So, we can write alpha which is relative volatility can be
written as y by 1 minus y divided by x by 1 minus x which we can write y into 1 minus x
divided by x into 1 minus y. This can be rearranged and we can write y is equal to x
alpha divided by 1 plus x into alpha minus 1.
(Refer Slide Time: 43:05)

So, the relative volatility alpha is not strong function of of temperature than the
component vapor pressure. So, it can be assumed constant over a temperature range, and
composition. So, higher values of alpha higher the separation, if alpha is 1 then the
separation is not possible, separation is not possible. In the next class we will discuss the
examples on how to use relative volatility, and Roult’s law to determine the T x y
diagram.

Thank you.