Mass Transfer - II

3350502
Parth Modi, Lecturer
Chemical Engineering
CHAPTER-2
Distillation
What is Distillation ?
• Use for “Separation” of components from mixture.
• Separation of more volatile components
from less volatile.

Is a method of separating the components

of a solution which depends upon the
distribution of the substances between a
gas and a liquid phase, applied to cases
where all components are present in both
the phases.

Image source : Google

Roult’s Law
• Equilibrium partial pressure of component in a solution at a given temp. is
equal to the product of its vapor pressure in the pure state and its mole fraction
in the liquid phase.
• Raoult's law looks at what is happening over the solution when you mix a non-
volatile solute to a solvent that has a known vapour pressure when it's pure.
Psolution = ΧsolventP0solvent.
Where, Psolution is the vapour pressure of the solution,
Χsolvent is Mole Fraction of solvent,
P0solvent is partial pressure of solvent
Henry’s Law
• At a constant temperature, the amount of a given gas dissolved in a given type
and volume of liquid is directly proportional to the partial pressure of that gas in
equilibrium with that liquid.

• Henry's law takes care of what happen in the solution when you have gas over it.
P=K*C
P is Partial pressure of solute above solution
C is concentration of solute in solution
K is Henry’s law constant
Vapor Liquid Equilibrium…
• It is useful for graphical design in determining the number of theoretical stages
required for a distillation column.
• A typical equilibrium curve for a binary mixture on x-y plot is shown in Figure.
• The VLE Plot expresses the bubble-point and the dew-point of a binary mixture at
constant pressure. The curved line in Figure is called the equilibrium line and it
describes the compositions of the liquid and vapor in equilibrium at some fixed
pressure.
• This particular VLE plot shows a binary ideal mixture that has a uniform vapor-
liquid equilibrium that is relatively easy to separate.
Vapor Liquid Equilibrium

This particular VLE

plot shows a binary
ideal mixture that
has a uniform vapor-
liquid equilibrium
that is relatively easy
to separate.
Azeotropes
• The points of intersections of the equilibrium curves with the diagonal lines are
called azeotropic points. However, vacuum distillation may be used as the lower
pressures which can shift the azeotropic point.

Fig: VLE curves for

azeotropic systems:
(a) for maximum
boiling point,
(b) for minimum
boiling point
Relative Volatility
• Relative volatility is a measure of the differences in volatility between two
components, and hence their boiling points. It indicates how easy or difficult a
particular separation will be.

• The relative volatility of component ‘A’ with respect to component ‘B’ in a binary
mixture is defined as

where,
yA = mole fraction of component ‘A’ in the vapor,
xA = mole fraction of component ‘A’ in the liquid.
• In general, relative volatility of a mixture changes with the mixture
composition. For binary mixture, xB = 1-xA.
Relative Volatility
• If the system obeys Raoult’s law

• where PA is the partial pressure of component A in the vapor, PB is the partial

pressure of component B in the vapor and P is the total pressure of the system.
Thus if the relative volatility between two components is equal to one, separation
is not possible by distillation.
• The larger the value of a, above 1.0, the greater the degree of separability, i.e.
the easier the separation.

• a = 1, separation by distillation is not possible.

a > 1, separation by distillation is possible.
a >> 1, separation by distillation is easier.
Flash Distillation…
• A single-stage continuous operation occurs where a liquid mixture is partially
vaporized. The vapor produced and the residual liquids are in equilibrium in the
process are separated and removed as shown in Figure.

• The relationship
between the scale
of vaporization and
mole fraction of A
in vapor and liquid
(y and x) is known
as the Operating
Line Equation.
Flash Distillation…
• Define f as molal fraction of the feed that is vaporized and withdrawn
continuously as vapor.

• Therefore, for 1 mole of binary feed mixture, (1- f) is the molal fraction of the
feed that leaves continuously as liquid.

Assume,
• yD = mole fraction of A in vapor leaving,
• xB = mole fraction of A in liquid leaving,
• xF = mole fraction of A in feed entering.

From material balance for the more volatile component (A)

------ (1)
Flash Distillation
------ (2)

•The fraction f depends on the enthalpy of the liquid feed, the enthalpies of the
vapor and liquid leaving the separator.

• For a given feed condition, and hence the known value of f and xF, the Equation
is a straight line Equation with slope - (1-f)/f and intercept xF/f as shown in Figure.

• It will intersect the equilibrium line at the point (xB, yD).

• From this value, the composition of the vapor and liquid leaving the separator
can be obtained.
Differential Distillation…
• The column is charged
with a 'batch' and then
the distillation process
is carried out.

• Consider a binary
mixture of components
A (more volatile) and B
(less volatile).
Differential Distillation…
• The system consists of a batch of liquid (fixed quantity) inside a kettle (or still)
fitted with heating element and a condenser to condense the vapor produced as
shown in Figure.

• The condensed vapor is known as the distillate. The distillate is collected in a

condensate receiver.
• The liquid remaining in the still is known as the residual.
• The process is unsteady state.

• As the process is unsteady state, the derivation is based on a differential

approach to changes in concentration with time.
Let,
 L1 = initial moles of liquid originally in still,
 L2 = final moles of liquid remained in still,
Differential Distillation…
 x1 = initial liquid composition in still (mole fraction of A),
 x2 = final liquid composition in still (mole fraction A).
• Then the material balance on A can be written as,
xL = (x-dx) (L-dL) + ydL
 Neglecting the term (dx)(dL),
Ldx = ydL – xdL
 Re-arranging and Integrating from L1 to L2, and from x1 to x2, one can obtain
the following Equation which is called Rayleigh Equation.
Differential Distillation…
1. A mixture of 40 mole % isopropanol in water is to be batch-distilled at 1 atm
until 70 mole % of the charge has been vaporized. Calculate the composition of
the liquid residue remaining in the still pot, and the average composition of the
collected distillate. VLE data for this system, in mole fraction of isopropanol, at 1
atm are

Ans.
Calculate 1/(y-x) As per Rayleigh Equation
Differential Distillation
 x1= 0.4,
 Feed L1 = 100,
 Distillate (D) = 70,
 Liquid residue as L2 = L1-D = 30
 Find x2 by equating
 The value of x2 = 0.067
 yD = 0.543
Fractional Distillation…
• Fractional distillation
is a process in which
vaporisation of liquid
mixture gives rise to a
mixture of constituents
from which desired one
is separated in pure
form.
• When a liquid mixture
is distilled, the partial
condensation of the
vapour is allowed to
occur in a fractionating
column.
Fractional Distillation…
• In the column, ascending vapor from the still is allowed to come in contact with
the condensing vapor returning to the still.

• This results is enrichment of the vapor with the more volatile component.

• By condensing the vapor and reheating the liquid repeatedly, equilibrium

between liquid and vapor is set up at each stage, which ultimately results in the
separation of a more volatile component.

• The columns are constructed so as to offer the following advantages

simultaneously.
(1) It offers a large cooling surface for the vapor to condense.
(2) An obstruction to the ascending vapor allows easy condensation.
Steam Distillation…
• Steam distillation is
method of distillation
carried out with
aid of steam.

• It is used to
separate High boiling
substances from non
–volatile impurities
Separate immiscible
liquids.
Steam Distillation…
• A mixture of immiscible liquids begins to boil when sum of their vapor pressure
is equal to atmospheric pressure.

• Metallic steam can fitted with cork having two holes.

• Safety tube inserted up to bottom through one hole to maintain pressure in
side stem can, more over when steam comes out from safety tube indicates that
can is empty.

• Flask and condenser is connected with delivery tube.

• Condenser is connected to receiver with help of adopter.

• Provision are made to heat both steam can and flask separately.
Vacuum Distillation
• The distillation process in
which the liquid is distilled
at a temperature lower
than its boiling point by the
application of vacuum.
Vacuum pumps, suction
pumps, etc. are used to
reduce the pressure on the
liquid surface.
• Distillation under the
reduced pressure is based
on the principle of the
simple distillation with
some modifications.
Molecular Distillation
• It is defined as a
distillation process in which
molecule in the vapor
phase travels mean free
path and gets condensed
individually without Inter
molecular collisions on
application of vacuum.
• Molecular distillation is
based on the principle of
the simple distillation with
some modifications.
• This is also called
Evaporation distillation.
Azeotropic & Extractive Distillation
Azeotropic distillation:
In which azeoptorpic mixture is broken by the addition of third Substance, which
forms a new azeotrope with one of the components.

Entrainer(third substance) should preferably form a low-boiling azeotrope with

one of the constituents of the binary azeotrope which is desired to separate.

Extractive distillation:
The third substance added to the azeoptorpic mixture is relatively nonvolatile
liquid compared to the components to be separated.

Extractive distillation refers to distillation process wherein a high-boiling solvent

is added to alter the relative volatilities of the constituents of a feed mixture.
McCabe and Thiele method…
• McCabe and Thiele developed a graphical method to determine the theoretical
number of stages required to effect the separation of a binary mixture.

• This method uses the equilibrium curve diagram to determine the number of
theoretical stages (trays) required to achieve a desired degree of separation.

• It assumes constant molar overflow and this implies that:

(i) molal heats of vaporization of the components are roughly the same;
(ii) heat effects are negligible.

• The feed has a concentration of xF (mole fraction) of the more volatile

component, and a distillate having a concentration of xD of the more volatile
component and a bottoms having a concentration of xB is desired.
McCabe and Thiele method…
• An important parameter in the analysis of continuous distillation is the Reflux
Ratio, defined as the quantity of liquid returned to the distillation column over
the quantity of liquid withdrawn as product from the column, i.e. R = L / D.

• The reflux ratio R is important because the concentration of the more volatile
component in the distillate (in mole fraction xD) can be changed by changing the
value of R.

• The steps to be followed to determine the number of theoretical stages by

McCabe-Thiele Method:

Determination of the Rectifying section operating line (ROL).

Determination the feed condition (q).

McCabe and Thiele method…
 Determination of the feed section operating line (q-line).

 Determination of required reflux ratio (R).

 Determination of the stripping section operating line (SOL).

 Determination of number of theoretical stage.

1. Determination of the Rectifying section operating line (ROL)

Consider the rectifying section as shown in the Figure.

Material balance can be written around the envelope shown in Figure.
Overall or total balance: Vn+1 = Ln + D ----- (1)
McCabe and Thiele method…
Component balance for more volatile component:
Vn+1 yn+1 = Ln xn + DxD ----- (2)
From (1) and (2)
(Ln + D) yn+1 = Ln xn + DxD ----- (3)
Consider the constant molal flow in the column,
L1 = L2 =.......... Ln-1 = Ln = Ln+1 = L = constant,
V1 = V2 =Vn-1 = Vn = Vn+1 = V = constant.
(L + D) yn+1 = Lxn + DxD ----- (4)
McCabe and Thiele method…
After rearranging,

Introducing reflux ratio defined as: R = L/D,

The rectifying section operating

line (ROL) Equation having
slope R/(R+1) and intercept,
xD/(R+1) as shown in Figure.
McCabe and Thiele method…
2. Determination the feed condition (q):
The moles of liquid flow in the stripping section that result from the introduction
of each mole of feed, denoted as ‘q’. The limitations of the q-value as per feed
conditions are shown in Table.
Feed condition Limit of q-value

cold feed (below bubble point) q>1

feed at bubble point (saturated liquid) q=1

feed as partially vaporized 0<q<1

feed at dew point (saturated vapor) q=0

feed as superheated vapor q<0

feed is a mixture of liquid and vapor q is the fraction of the feed that is liquid
McCabe and Thiele method…
3. Determination of the feed section
operating line (q-line):
• In the feed tray the feed is introduced at F
moles/hr with liquid of q fraction of feed and
vapor of (1-f) fraction of feed.

• For rectifying section: Vy = Lx + DxD

• For stripping section: Vy = Lx - BxB
McCabe and Thiele method…
• For a given feed condition, xF and q are fixed, therefore the q-line is a straight
line with slope -q / (1-q), intercept xF/(1-q).
If x = xF put in below equation,

y = xF
• At this condition the q-line passes
through the point (xF, xF) on the 45o
diagonal. Different values of q will
result in different slope of the q-line.
McCabe and Thiele method…
4. Determination of the stripping section operating line (SOL):
• The stripping section operating line (SOL) can be obtained from the ROL and q-
line without doing any material balance.
•The SOL can be drawn by connecting
point xB on the diagonal to the point of
intersection between the ROL and q-line.

• The SOL will change if q-line is changed

at fixed ROL.

• The stripping section operating line can

be derived from the material balance
around the stripping section of the
distillation column.
McCabe and Thiele method…
• Consider the constant molal overflow in the column.
Thus L'm = L'm+1 = .... = L' = constant and V'm = V'm+1 = ..... = V' = constant.
Overall material balance gives

• More volatile component balance gives:

• Substituting and re-arranging the Equation

• Dropping the subscripts "m+1" and "m" it becomes:

McCabe and Thiele method…
• Substituting V' = L' – B from Equation

• The Above Equation is called the stripping operating line (SOL) which is a
straight line with slope ( L' / L' - B) and intercept ( B xB / L' - B ).

• When x = xB , y = xB, the SOL passes through (xB, xB ) on the 45 degree diagonal
line.

5. Determination of number of theoretical stage

• Once the three lines (ROL, SOL and q-line) are drawn, the number of
theoretical stages required for a given separation is then the number of triangles
that can be drawn between these operating lines and the equilibrium curve.
McCabe and Thiele method…

•The last triangle

on the diagram
represents the
reboiler. A typical
representation is
given in Figure
Reflux Ratio (R)
• The separation efficiency by distillation depends on the reflux ratio.
• Higher reflux ratio (R) results in lesser number of required theoretical trays (N)
and vice versa.
• There is an inverse relationship between the reflux ratio and the number of
theoretical stages.
• The reflux ratio may be any value between a minimum value and an infinite
value. The limit is the minimum reflux ratio (result in infinite stages) and the total
reflux or infinite reflux ratio (result in minimum stages).
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