UNIT OPERATION II

(CHE411)

By

Engr Babatunde D.E.

References
King, C.J. (2013) Separation Processes. Dover Publications Inc.
Treybal, R.E. (2012) Mass-Transfer Operations. McGraw- Hill Higher
Education.
McCabe W.L., Smith J.C., Harriott P. (2004) Unit Operations of Chemical
Engineering. (7th Edition), McGraw- Hill Higher Education.
Geankoplis, C.J. (2003) Transport Processes and Seperation Process
Principles. Prentice Hall.
G. F. Nalven, ed. Distillation and Other Industrial Separations, American
Institute of Chemical Engineers, 1997.
 DISTILLATION
• Distillation is the method of separation of liquid, vapour or a vapour
- liquid mixtures into component fractions of desired purity, on the
basis of difference in relative volatility (or boiling point), by the
application and removal of heat in a way that the components which
make up the mixture distribute themselves unequally in both the
vapour and liquid
• Distillation process relies on differences in the concentrations of
components in the liquid and vapour phases at equilibrium.
• This is related to components differences in:
1. Volatilities 2. vapour pressures 3. boiling points
• The heat supplied create new phase different from the initial phase of
the mixture
• The separation depends on the differences in boiling points of the
individual components of the mixture.
• Boiling point of the mixture may vary with concentration of the
components present in it.
• As such, the distillation process depends on the vapour pressure
characteristics of the mixture.
• The vapor pressure is created by supplying heat as separating agent.
• Distillation is an equilibrium staged process.
 Vapour Pressure
• Vaporization process changes liquid to gaseous state
• The reverse of the vaporization process is called
condensation.
• At equilibrium, the rates of these two processes are same.
• The pressure exerted by the vapor at this equilibrium state
(the state of thermodynamic equilibrium with condensed
phase) is termed as the vapor pressure.
• It is the tendency of particles to escape from the liquid phase
• It depends on the nature of the liquid and temperature.
• If molecules of liquid bind together strongly, there will be less tendency for
molecules to escape as vapour
• If the temperature of a liquid is raised, the system is perturbed and the
rate of vaporization becomes higher than the rate of condensation, as
such vapor pressure would be higher
• If the temperature is sufficiently increased such that the vapour pressure
equals that of atmospheric pressure, the liquid will boil
• The vapor pressure at a given temperature can be calculated from
Antoine Equation.
• Distillation is mostly carried out in multi tray columns and
efficiently structured packed columns
• Some of its areas of application include in
1. Organic process industries e.g separation of aniline and
nitrobenzene, ethanol-water separation
2. Petroleum refinery
 Volatility of Components
• The components distribute differently because of differences in their
readiness to vaporize.
• This readiness to vapourise is termed the volatility of the substance.
• substances with the lower boiling points will vaporize more easily than
those with a higher boiling point.
• Volatile substances have higher vapour pressure at a given temp.
• a volatile substance will have a low boiling point and vice versa.
• substance with lower boiling point is known as the more volatile
component (MVC)
 Distillation Operation
• Feed enters at some point on the tower
• Reboiler heats up the liquid from
bottom of the tower and liquid
partially vaporizes
• Vapour flows up through the trays
or packings
• Vapor leaves at the top and enters
into a overhead condenser and
then to the reflux drum Figure 1

• Part of the condensate is withdrawn as top

product and rest is recycled into the column as reflux
•An intimate contact between the
liquid and vapour occurs on each
tray or packing surface
•More volatile component moves
from liquid to vapour phase
•Less volatile component moves
from vapour to liquid
•Concentration of less volatiles
increases in the liquid phase as it
flows down Figure 1

• High degree of separation of more volatiles from the less volatiles is

achieved
•Top product is rich in more volatile and bottom product is rich in less
volatile
 Binary Distillation
Distillation is an equilibrium staged process

The feed mixture in binary distillation has two components.

At equilibrium, the components in the mixture will distribute

themselves between the vapour phase and liquid phase

Resulting in the feed being separated into two products, an overhead

distillate and a bottom product, with compositions different from that
of the feed.
 Vapour-Liquid Equilibrium
• Vapour-liquid and physicochemical properties of the system is
required to solve the equilibrium stage process problem
• The equilibrium data can be obtained from:
1. experiments
2. thermodynamics

• The data is usually shown with reference to the more volatile component

• For binary mixtures, VLE data is typically represented by equilibrium

diagram such as:
1. T-x-y diagram
2. P-x-y diagram
3. x-y diagram
4. H-x-y diagram
 Features of Phase Diagram
• bubble-point curve or saturated liquid line

• dew-point curve or saturated vapour line

• Subcooled liquid region

• Superheated vapour region

• vapour-liquid region

• bubble-point and dew-point temperatures

 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.
 Constant Pressure Phase Diagram
The T-x-y diagram is also known as:
• Constant-pressure phase diagrams
• Boiling point-concentration diagram
• Commonly used for distillation calculations
• At each temperature, the vapor and the liquid are in equilibrium

Figure 2
 Constant Pressure Phase Diagram
The distribution of components
in the liquid and vapour phases is
a function of temperature Super heated vapour

• Liquids of different composition

at the same pressure will boil at
different temperatures- bubble-point curve
• Vapours of different composition
at the same pressure will condense subcooled liquid

at different temperatures- dew-point curve

• Boiling of a liquid mixture takes
place over a range of boiling points.
Figure 3
• Condensation of a vapour mixture takes place
over a range of condensation points
Changes in Distribution of Components in the Phases with Temperature
(a): At temperature 86 oC;
Concentration of benzene Liquid: x = 0.40,
Super heated vapour
Vapour: y = 0.00,
Liquid-phase; no vapour.
(b): Temperature 95.2 oC;
Concentration of benzene Liquid: x = 0.40,
Vapour: y = 0.61,
Liquid-phase; first bubble of vapour produced, subcooled liquid

(Bubble Point - solution about to boil).

(c): Temperature 98.0 oC
Concentration of benzene Liquid: x = 0.31; Figure 3
Vapour: y = 0.52
Vapour-Liquid Mixture;
(continued vaporization of liquid as heat is added).
Changes in Distribution of Components in the Phases with Temperature
(d): Temperature 101.6 oC
Concentration of benzene Liquid: x = 0.21
Vapour: y = 0.40
Super heated vapour
Vapour-phase; last droplet of liquid
remains (dew point)

(e): Temperature 108 oC

Vapour-phase only, no liquid.
The process is unsteady-state in nature. subcooled liquid

NOTE:
As heating continues, Figure 3
vaporization occurs over a range of boiling points.
At any time when 2 phases - vapour and liquid - are present, the concentration of benzene (more
volatile component) in the vapour (y) is always higher than that in the liquid (x). The reverse is
true for toluene (less volatile component).
 Constant temperature (isothermal) phase diagram
•The constant temperature phase
diagram is as shown.
•It is also referred to as P-x-y diagram
or
•Isothermal phase diagram
•The more volatile liquid will have a
higher vapour pressure
•It is useful in the analysis of solution
behaviour.
•commonly used to depict deviations
from ideal behaviour or Raoult’s law Figure 6
 VLE Data
• The relationship between the compositions of Vapour and its Liquid
at equilibrium at some constant pressure/temperature is the vapour-
liquid equilibrium (VLE)data

• The following can be used to obtain a suitable relationship distillation

process parameters:
1. Raoult’s law
2. Relative volatilities
3. Equilibrium coefficients
 Raoult’s Law
For ideal gases or vapors, the partial pressure is proportional to the mole fraction of the
constituents.
PA= yAPT [1]
For ideal mixtures, the partial pressure is related to the concentration in the liquid phase by
Raoult’s law
PA = P˚A xA [2]
Where P˚A is vapor pressure of pure species A at same temperature.
combining [1] and [2];
similarly, [3]

But for a binary mixture, and [4]

Combining [3] and [4]; [5]

From [5] and [1] respectively and are equilibrium relation

Table 1: Vapour Pressure Data for Benzene –Toluene System at 101.32 kPa

Using the vapour pressure from table 1, calculate the vapour and liquid compositions in
equilibrium at 95oC (368.2K) and 101.32 kPa
Table 2: Vapour Pressure and Equilibrium Data for Benzene –Toluene System at 101.32 kPa
 Relative Volatility
• In order to separate components of a mixture, there must be
difference in the volatilities of the components
• The greater the difference, the easier the process of separation
using distillation
• Relative volatility is therefore defined as a measure of
separability of components of a mixture.
• The volatility of component ‘i’ is defined as: the ratio of its
partial pressure and mole fraction of the component in liquid
• For a binary mixture of ‘A’ and ‘B’:
𝑃𝐴
• Volatility of ‘A’ =
𝑥𝐴
𝑃𝐵
• Volatility of ‘B’ =
𝑥𝐵
 Relative Volatility
• Relative volatility can be expressed as the ratio of volatility of more
volatile component (A) to volatility of less volatile component (B)
𝑃𝐴ൗ
𝑥𝐴
𝛼𝐴𝐵 =
𝑃𝐵ൗ
𝑥𝐵

𝑦𝐴 𝑃𝑇 𝑥𝐵
𝛼𝐴𝐵 =
𝑦𝐵 𝑃𝑇 𝑥𝐴

[6]
•For systems that obey Raoult’s law, Eqn. [6] can be written as:

•Relative volatility is not a strong function of temperature for ideal

solutions
•Relative volatility can be assumed constant over a temperature range
and composition for an ideal solution
•The higher the value of relative volatility, the better & easier the
separation

•If then, separation is not possible

This is because when , components A and B have the same
volatility and will vapourise together when heated
• As such, y = x i.e. vapour and liquid will have the same composition.
• On the VLE diagram, y = x is represented by the straight line through
the origin
• If relative volatility is constant it can be used to obtain the equilibrium
curve data
• Substituting values of x between 0 and 1 will yield the equilibrium
curve predictions
EXAMPLE:
• Using data from Table 1,
calculate the relative volatility for the benzene-toluene system at 85oC
(358.2K) and 105oC (378.2K)
What is average relative volatility of benzene – toluene mixture for the
given range of temperature
Vapour – Liquid Equilibrium Plot: x-y Diagram

• can be obtained from constant pressure

phase diagram

• the plot expresses the bubble-point

and the dew-point of a binary mixture
at constant pressure.

• contains less information than the

constant pressure phase diagram (i.e.
temperature is not included),
• but it is most commonly used. Figure 4
 x-y Diagram
• It is useful for graphical design in
determining the number of theoretical
stages required for a distillation column

• The curved line is called the equilibrium

curve and describes the compositions of
the liquid and vapour in equilibrium at
fixed pressure.

• below the equilibrium line is the 45 degree

line or diagonal line where y=x
Figure 4
 Equilibrium Curve from Phase Diagram

Figure 5

• By drawing horizontal lines (constant T) like DF and HJ on the phase

diagram
• Obtain the corresponding mole fractions x and y at the intersections with
the horizontal lines.
• With a set of x-y values, a graph of y vs. x can be plotted i.e. the
equilibrium curve
 VLE of Real Solutions
• Most solutions, at least to some extent, deviate from ideality
• This means they may not exactly obey Raoult law
• The deviation from Raoult's law may either be positive or
negative deviation
• A liquid mixture exerting an equilibrium total pressure more than
that calculated by [5] is said to exhibit positive deviation from
ideality.
• If the total pressure is less than that calculated by [5], the
deviation is called negative deviation.
• If the deviation from ideality are large, azeotropes are formed. At this
point, the composition of vapour phase equals that of liquid phase
• When the positive deviations from ideality are sufficiently large, the
mixture is said to form a minimum-boiling azeotrope.
• Characteristic of such mixture in constant-temperature phase diagram:
 total pressure goes through a maximum
 in constant-pressure phase diagram therefore temperature goes
through a minimum
• When the negative deviations are very large, Maximum-boiling
azeotrope occur

–characteristic of such mixture in constant-temperature phase diagram:

 total pressure passes through a minimum,
 giving rise to a maximum in the temperature (i.e. boiling point) on
constant-pressure phase diagram

 Summary:
Azeotropes are mixtures of two or more liquids with constant
composition and boiling point throughout distillation. The boiling point
of azeotrope could either be higher than those of its component or lower
than those of it components
Maximum-boiling azeotrope: acetone – chloroform
(65.5 mole% chloroform, 64.5 oC, 1 atm)
• The azeotropic point is a function of total pressure and can for
some mixtures be shifted, or even disappear, by changing the total
pressure.
• Azeotropic mixtures cannot be separated by standard distillation,
but there are methods that may still be used to separate such
mixtures
• Such method include:
1. Pressure swing distillation
2. Hybrid method using membrane
3. Azeotropic distillation
4. Extractive distillation
• Deviations from ideal behaviour in the liquid phase are taken into
account by modifying Raoult's law by introducing a liquid phase
activity coefficient ɣi

• The activity coefficient ɣi is a function of temperature T and

composition of component i in the liquid phase.
• The value of activity coefficient ɣi approaches unity as the liquid
concentration xi approaches unity, and the highest value ɣi of
occurs as the concentration approaches zero
• Many equations have been suggested for the calculation of the
activity coefficient, and the simplest versions are the van Laar,
Margules, or Wilson equations.
• The van Laar equations for a binary mixture of component A
(more volatile) and component B (less volatile) are given by the
following equations,

• where the constants and are different and can be estimated

from experimental values in reference literature
 Types of distillation methods
1. Distillation without reflux:
It involves boiling of liquid mixture to be separated and separating
the vapour generated without allowing any liquid to return to the
still

2. Continuous Distillation with reflux:

It involves returning part of condensate to the still in such a way
that it runs counter to the vapour rising to the condenser
 Distillation without reflux
Two types :
a. Simple (differential )distillation:
The mixture to be separated is introduced batch-wise to the column. Vapour
generated by boiling of liquid mixture is condensed without allowing any
liquid to return to the column. This method is commonly used in laboratory;
in industries, it is only used for systems having high relative volatilities
b. Flash or equilibrium distillation:
It is a single stage operation which involves partial vaporization of liquid
mixture in such a way that the total vapour produced is in equilibrium with
the residual liquid. The resulting vapour and liquid are then separated. This
method is used only when the difference between volatilities of two
components is very large
SIMPLE (DIFFERENTIAL) DISTILLATION:
binary mixture of A (MVC) and B (LVC)
• Differential distillation is also known as Batch Distillation.
• The feed is introduced batch-wise to the column and then the
distillation process is carried out.
• When the desired task is achieved, a next batch of feed is
introduced.
approach to changes in
concentration with time.
 For ideal mixture: constant relative volatility
• 𝛼𝐴𝐵 is constant
• Suppose there are 𝐿𝐴 moles of A and 𝐿𝐵 moles of B of liquid
𝐿 = 𝐿𝐴 + 𝐿𝐵
• 𝑑𝐿 moles of liquid (containing 𝑑𝐿𝐴 moles of component ‘A’ and 𝑑𝐿𝐵
moles of component ‘B’) are distilled off
• Hence mole fraction of component ‘A’ in the vapour phase is given
as:
𝑑𝐿𝐴
𝑦𝐴 =
𝑑𝐿𝐴 + 𝑑𝐿𝐵
• Similarly, the mole fraction of component ‘B’ in the vapour phase is
given as:
𝑑𝐿𝐵
𝑦𝐵 =
𝑑𝐿𝐴 + 𝑑𝐿𝐵
• Since 𝛼𝐴𝐵 is constant for an ideal mixture
𝑑𝐿𝐴
𝑦𝐴 Τ𝑥𝐴 ൗ 𝐿𝐴 Τ𝐿
𝑑𝐿𝐴 + 𝑑𝐿𝐵
𝛼𝐴𝐵 = =
𝑦𝐵 Τ𝑥𝐵 𝑑𝐿𝐵
ൗ 𝐿𝐵 Τ𝐿
𝑑𝐿𝐴 + 𝑑𝐿𝐵

𝑑𝐿𝐴
× 𝐿𝐵 Τ𝐿
𝑑𝐿𝐴 + 𝑑𝐿𝐵
=
𝑑𝐿𝐵
× 𝐿𝐴 Τ𝐿
𝑑𝐿𝐴 + 𝑑𝐿𝐵

𝐿𝐵 𝑑𝐿𝐴
𝛼𝐴𝐵 =
𝐿𝐴 𝑑𝐿𝐵
• Rearranging,
𝑑𝐿𝐵 𝑑𝐿𝐴
𝛼𝐴𝐵 =
𝐿𝐵 𝐿𝐴
• Integrating,
𝐿𝐴2 𝐿𝐵2
𝑑𝐿𝐴 𝑑𝐿𝐵
න = 𝛼𝐴𝐵 න
𝐿𝐴1 𝐿𝐴 𝐿𝐵1 𝐿𝐵
𝐿𝐴2 𝐿𝐵2
ln = 𝛼𝐴𝐵 ln
𝐿𝐴1 𝐿
𝛼𝐴𝐵 𝐵1
𝐿𝐴2 𝐿𝐵2
=
𝐿𝐴1 𝐿𝐵1
Where:
𝐿𝐴1 = total initial mole A in still
𝐿𝐵1 = total initial mole of B in still
𝐿𝐴2 = total mole A left in still
𝐿𝐵2 = total mole of B left in still
 EXAMPLE
• A batch of crude pentane contains 15 mole percent n-
butane and 85 percent n-pentane. If a simple batch
distillation at atmospheric pressure is used to remove 90
percent of butane, how much pentane will be removed?
What will be the composition of the remaining liquid? The
average relative volatility of the mixture is 3.5
• Basis: 100 mole of mixture
𝐿𝐴1 = 15𝑚𝑜𝑙𝑒, 𝐿𝐵1 = 85 𝑚𝑜𝑙𝑒
Butane removed = 90% 𝑜𝑓 15𝑚𝑜𝑙𝑒 = 13.5 𝑚𝑜𝑙𝑒
𝐿𝐴2 = 15 − 13.5 = 1.5𝑚𝑜𝑙𝑒
𝐿𝐵2 =?
𝛼
𝐿𝐴2 𝐿𝐵2 𝐴𝐵
=
𝐿𝐴1 𝐿𝐵1
1ൗ
𝐿𝐵2 𝐿𝐴2 𝛼𝐴𝐵
=
𝐿𝐵1 𝐿𝐴1
1ൗ
𝐿𝐴2 𝛼𝐴𝐵
𝐿𝐵2 = 𝐿𝐵1
𝐿𝐴1
= 85 (0.5179)
𝐿𝐵2 = 44.03
• Pentane removed= 85 − 44.03 = 40.97 𝑚𝑜𝑙𝑒𝑠
• Remaining liquid 𝐿2 = 1.5 + 44.03 = 45.53
• Composition:
44.03
• Pentane; 45.53 = 0.967
1.5
• Butane; 45.53 = 0.033
Equilibrium or Flash Distillation

61
Flash distillation is a single stage separation technique.
1. A liquid mixture is pumped through a heater to raise the
temperature and enthalpy of the mixture.
2. It then flows through a valve and the pressure is reduced, causing
the liquid to partially vaporize.
3. Once the mixture enters a big enough volume (the “flash drum”),
the liquid and vapor separate.
4. Because the vapor and liquid are in such close contact up until the
“flash” occurs, the product liquid and vapor phases approach
equilibrium.
 Equilibrium or Flash Distillation
Total mass balance: F  V L (1)
yA
Component A balance:𝐹𝑥𝐹 = 𝑉𝑦𝐴 + 𝐿𝑥𝐴 (2) Separator
Where
heater
F, V and L are flow rate of feed, vapor and liquid phases.
xA
xF, yA and xA are mole fraction of component A in feed, vapor and liquid.
Figure 12
𝑉 𝐹 𝑉
𝑥𝐹 = 𝑦 + − 𝑥 𝑥𝐹 = 𝑓𝑦𝐴 + 1 − 𝑓 𝑥𝐴 (3)
𝐹 𝐴 𝐹 𝐹 𝐴

( f  1) x
yA  xA  F (4)
f f
Where
f = V/F = molal fraction of the feed that is vaporized and withdrawn continuously as vapor.
63
1-f = molal fraction of the feed that is withdrawn continuously as liquid
 Example 7
A mixture of 50% mole normal heptane and 50% normal
octane at 30oC is continuously flash distilled at 1 standard
atmosphere so that 60 mol% of the feed is vaporized. What
will be the composition of the vapor and liquid products?
Table 5: VLE Data for n-heptane – n-octane binary system at 1atm
xA 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
yA 0.247 0.453 0.607 0.717 0.796 0.853 0.898 0.935 0.968
Solution: Given: xF = 0.5, f = 0.6
Find: xA, yA
Basis: F = 100 mol F  V L
Applying the mass balance yields:
f V / F
Since,
𝑉 = 𝑓𝐹 = 0.6 100 = 60
64
𝐿 = 𝐹 − 𝑉 = 100 − 60 = 40
 Material balance for more volatile component,

( f  1) xF
yA  xA 
f f

Substituting value of f =0.6 and xF =0.5 we get,

0.6 − 1 0.5
𝑦𝐴 = 𝑥𝐴 +
0.6 0.6

Assuming that xA = 0.5 and solving yA = 0.5.

Next, assuming that xA=0 and solving, yA = 0.83.
(These point are plotted on the graph.)
At the intersection of this line with the equilibrium curve,
yA = 0.58 and xA = 0.39.
65
 x=0
2nd
y-intercept= 0.834

yA

Figure 13
xA
3rd xA =0.39 xF =0.5
1st
yA = 0.58 yF = 0.5

66
 Continuous Distillation with reflux
• A typical schematic diagram of a multistage counter-current binary
distillation that is operated continuously is shown in Fig. 14.
• The operation consists of a column containing:
– the equivalent number of theoretical stages arranged in a two-
section cascade;
– a condenser in which the overhead vapor leaving the top stage is
condensed to give a liquid distillate product and liquid reflux that is
returned to the top stage;
– a reboiler in which liquid from the bottom stage is vaporized to
give a liquid bottom products and the vapor boil off returned to
the bottom stage;
– accumulator which is a horizontal (usually) pressure vessel where
the condensed vapor is collected;
– Heat exchanger where the hot bottoms stream is used to heat up
the feed stream before it enters the distillation column.
– The feed enters the column at feed stage and contains both the
more volatile component and less volatile component.
– The feed may be liquid, vapor or mixture of liquid and vapor.
– The section above the feed where vapor is washed with the reflux
to remove or absorb the less volatile component is called enriching
or rectifying section.
– The section below the feed stage where liquid is stripped of the
more volatile component by the rising vapor is called stripping
section
Figure 14
Determination of Theoretical Number of Trays:
McCabe Thiele Method
McCabe-Thiele method uses the equilibrium curve
diagram to determine the number of theoretical stages
(trays) required to achieve a desired degree of
separation.

Using McCabe-Thiele method involves the plotting of

three straight lines on the equilibrium diagram. These
lines are the rectifying section operating line (ROL), the
feed line (also known as the q-line) and the stripping
section operating line (SOL)
The information required for the systematic
calculation are:
• the VLE data,
• feed condition (temperature, composition),
• distillate and bottom compositions;
• the reflux ratio.
The reflux ratio
• It is defined as the ratio of reflux liquid to the distillate product.
• i.e. the ratio of the quantity of liquid returned to the distillation
column to the quantity of liquid withdrawn as top product from the
Column
• Mathematically written as: R = L / D
• The reflux ratio R is an important parameter in the analysis. This is
because the concentration of the more volatile component in the
distillate (in mole fraction xD) can be changed by changing the value of
R.
• Total Reflux:
It is the operating condition where vapor and liquid are passing each other in the
column but no product is removed (i.e., D = 0 and R = L/D = ∞ ).
The slopes of the Operating Lines are then L/V = 1.0 and by material balance between
each plate y = x.
At total reflux, the number of theoretical plates required is a minimum. As the reflux
ratio is reduced (by taking off product), the number of plates required increases.
• The Minimum Reflux Ratio (Rmin)
It is the lowest value of reflux at which separation can be achieved even with an
infinite number of plates.
It is possible to achieve a separation at any reflux ratio above the minimum reflux
ratio.
As the reflux ratio increases, the number of theoretical plates required decreases.
• The Optimum Reflux Ratio (Ro)
It is that reflux at which the total cost of the distillation is a minimum, taking into
account the capital cost of the column (which depends on the number of theoretical
plates) and running cost, which depends on the minimum reflux ratio.
 McCabe-Thiele Method: assumptions of the method

• a. Constant Molal Overflow. The molar flow rates of the vapor and
liquid are nearly constant in each section of the column. This also
ensures the operating lines are straight lines.

• b. Heat Effects are negligible. For example, heat losses to and from the
column are small and neglected

• c. For every mole of vapor condensed, another mole of liquid is

vaporized.

• d. The liquid and vapor leaving the tray is in equilibrium with the vapor
and liquid entering the tray.
 The steps to determine the number of theoretical stages
using McCabe-Thiele Method

• Determination of required reflux ratio (R).

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

• Determination of the feed condition (q).

• Determination of the feed section operating line (q-line).

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

• Determination of number of theoretical stage.

 qD
D
L0 xD Overall mass balance:
Lm
m
Vm+1
F=D+B (1)
F

Lp
p

Vp1
qB
B
 A v1 ENVELOPE A:
Derivation of Rectifying Operation Line
qD
v1 D
L0 xD Vm+1 = Lm + D (2)
v2 L1
m
Vm+1
Vm+1 ym+1 = Lm xm + D xD (3)
Lm
Lm D
ym1  xm 
F
xD (4)
Vm1 Vm1

This is an equation of a straight line on a plot of vapor composition

versus liquid composition, where (Lm/Vm+1) is the slope and (DxD/Vm+1)
is the intercept which passes through the point (xD, xD) and (xm, ym+1).
Since all L values are equal and all V values are equal (due
to constant molal overflow assumption:

Lm D
ym1  xm  xD
Vm Vm (5)

Equation (5) is the operating line or material balance line

for the rectifying section.
Since:
Lm
R
D Lm Lm Lm D R
  
Vm = Lm + D Vm Lm  D Lm D  1 R  1

D D 1 1
  
Vm Lm  D Lm D  1 R  1

In term of R, equation (4) can be written as:

R xD
ym1  xm  (6)
R1 R1
 R
slope 
R1

xD
intercept 
R1

x xD
 ENVELOPE B: Derivation of Stripping Operation Line

p Vp1  Lp  B (7)
Vp1 Lp
p+1

Vp1 yp1  Lp xp  B xB (8)

Lp B
VN1
y p1  xp  xB (9)
qB Vp1 Vp1
LN
B
Since all L values are equal and all V values are equal (due to
constant molal overflow assumption:
y
L
 p x 
B
x
(10)
p1 p B
Vp Vp

Equation (9) is the operating line or material balance line for the
stripping section.
This is an equation of a straight line with slope L V
p p

and intercept  BxB Vp passing through (xB, xB) and (xp, yp+1).

This line can be drawn from point (xB, xB) to point 0, −𝐵 𝑥𝑉𝐵 or
𝑝

with slope L V
p p

The problem is, how to calculate Vp and Lp ?

Vp and Lp is calculated by material and enthalpy balance relationship
around the feed plate.
 Feed stage consideration
Definition of feed quality, q: It is the number of moles of saturated liquid formed on
the feed plate by the introduction of 1 mole of feed
𝐹 + 𝐿𝑚 + 𝑉ത𝑝 = 𝑉𝑚 + 𝐿ത 𝑝 (11)
Vm Lm
F 𝐹 + 𝑉ത𝑝 − 𝑉𝑚 = 𝐿ത 𝑝 − 𝐿𝑚
Vp Lp
𝑉ത𝑝 − 𝑉𝑚 𝐿ത 𝑝 − 𝐿𝑚
1+ = (12)
𝐹 𝐹

Lp  Lm
q (13)
F

𝑉ത𝑝 − 𝑉𝑚
putting (13) in (12), we have: 1+ =𝑞
𝐹

𝑉ത𝑝 − 𝑉𝑚
𝐹
=𝑞−1 (14)
Enthalpy balance on feed entrance

Fℎ𝐹 + 𝐿𝑚 ℎ𝐿 + 𝑉ത𝑝 𝐻𝑉′ = 𝑉𝑚 𝐻𝑉 + 𝐿ത 𝑝 ℎ𝐿′ (15)

ℎ𝐿 = ℎ𝐿′ and 𝐻𝑉 = 𝐻𝑉′

Fℎ𝐹 + 𝑉ത𝑝 − 𝑉𝑚 𝐻𝑉′ = (𝐿ത 𝑝 − 𝐿𝑚 )ℎ𝐿′

𝑉ത𝑝 − 𝑉𝑚 (𝐿ത 𝑝 − 𝐿𝑚 )
ℎ𝐹 + 𝐻𝑉 = ℎ𝐿
𝐹 𝐹
ℎ𝐹 + (𝑞 − 1)𝐻𝑉 = 𝑞ℎ𝐿

ℎ𝐹 + 𝑞𝐻𝑉 − 𝐻𝑉 = 𝑞ℎ𝐿

𝐻𝑉 − ℎ𝐹
∴𝑞= (16)
𝐻𝑉 − ℎ𝐿
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 ℎ𝑒𝑎𝑡 𝑛𝑒𝑐𝑒𝑠𝑠𝑎𝑟𝑦 𝑡𝑜 𝑣𝑎𝑝𝑜𝑢𝑟𝑖𝑧𝑒 𝑜𝑛𝑒 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑓𝑒𝑒𝑑
∴𝑞=
𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛
Derivation of q-line: Component material balance of the feed stage

F xF  L p  Lm  xi  V p  Vm  yi (17)

xF 
L p  Lm 
x 
V p  Vm 
yi
i
F F

xF  q xi  q  1 yi

q xF (18)
yi  xi 
q1 q1
 Determination the feed condition (q):
The feed entering the distillation column may consists of liquid,
vapour or can be a mixture of both.

Some portion of the feed go as liquid stream to the stripping and

some portion go as vapour stream to the rectifying sections.

The parameter q is the mole fraction of liquid in the feed.

The limits of the q-value for various feed conditions are shown in
Table 7.
Eq. (18) is the equation of the q line having a slope of
q/(q – 1) and terminating at xF on the 45 line and at
point (xi, yi).

Table 7: q-value as per feed conditions

Feed condition Limit of q-value Slope of q-line

Saturated liquid feed (feed at bubble point) q=1 
Saturated vapor feed (feed at dew point) q=0 0
Cold liquid feed (below bubble point) q>1 +
Superheated vapor feed q<1 –
Partially vaporized feed (Two-phase feed) 0<q<1 –

where, q is the fraction of the feed that is liquid

When feed is partially vaporized:
Other than saturated liquid (q = 1) and saturated vapour (q = 0),
the feed condition is uncertain.
In those cases, the value of q must be calculated.
The q-value can be obtained from enthalpy balance around the
feed plate from the following form of equation:

(16)
where HF, HV and HL are enthalpies of feed, vapour and liquid
respectively which can be obtained from enthalpy-concentration
diagram for the mixture.
When feed is cold liquid or superheated vapor:
q can be alternatively defined as the heat required to convert 1
mole of feed from its entering condition to a saturated vapour;
divided by the molal latent heat of vaporization.
Based on this definition, one can calculate the q-value from the
following equations for the case whereby q > 1 (cold liquid feed)
and q < 0 (superheated vapour feed) as:

For cold liquid feed:

[19]
For superheated vapour feed:
[20]
Where;Tbp, Tdp = the temperature at bubble point dew point of the feed
respectively. TF = temperature of feed. CpL, CpV = specific heats of liquid and
vapor, respectively. λ = the latent heat of vaporization and is the temperature at
 q=1

q>1
0<q<1

q=0

xB xF xD
 q
slope 
q1
intercept
xD

R1

xB xF xD
 x1 , y 1

x2 , y 2
x1 , y 2

x3 , y 3
x2 , y 3

x4, y4 x3 , y 4

xB xF xD
 MINIMUM REFLUX

intercept
xD

R min  1

xB xF xD
TOTAL REFLUX

xB xF xD
EXAMPLE 8
A saturated liquid feed mixture which compose of 42
mole % heptane, 58 mole % ethyl benzene is to be
fractionated at 760 mmHg to produce distillate
containing 97 mole % heptane and a residue containing
99 mole % ethyl benzene. The VLE data for heptane-
ethyl benzene binary system at 760 mmHg are as
follows:

Table 8 VLE Data for heptane - ethyl benzene binary system at 760 mmHg

T(oC) 136.2 129.5 122.9 119.7 116.0 110.8 106.2 103.0 100.2 98.5
xH 0.000 0.080 0.185 0.251 0.335 0.487 0.651 0.788 0.914 1.000
yH 0.000 0.233 0.428 0.514 0.608 0.729 0.834 0.904 0.963 1.000
EXAMPLE 8
Determine:
a. the number of equilibrium stages needed for
saturated-liquid feed and reflux ratio R = 2.5 using
McCabe-Thiele graphical method
b. Rmin
c. minimum number of equilibrium stages at total
reflux.
SOLUTION
(a) The slope of the operating line in the rectifying section:
R 2.5
slope    0.715
R  1 2.5  1
 1.0

0.9
N = 11
0.8

0.7

0.6

0.5
y 0.4

0.3

0.2

0.1

0.0
0.0 0.2 0.4 0.6 0.8 1.0
x
 1
(b) 0.9

0.8

0.7

0.6

y
0.5

0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1
x

xD
Intercept =  0.45
R min  1

Rmin = 1.18
 1

(c) 0.9

0.8

0.7
y 0.6

0.5

0.4

0.3 N=8

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1
x
Construction of Enthalpy-Composition
Diagram
• Enthalpy concentration diagram for a binary mixture takes into
account the latent heats, heats of solution or mixing, and sensible
heats of the components of the mixture
• The diagram, at constant pressure is based on arbitrary reference
states of liquid and temperature
• The saturated liquid enthalpy line of ℎ𝑚𝑖𝑥 (𝑘𝐽ൗ𝑘𝑚𝑜𝑙 ) is calculated by:
ℎ𝑚𝑖𝑥 = 𝑥𝐴 ℎ𝐴 + 𝑥𝐵 ℎ𝐵 + ∆𝐻𝑠𝑜𝑙
= 𝑥𝐴 𝑐𝑝𝐴 𝑇𝑏 − 𝑇𝑟𝑒𝑓 + 𝑥𝐵 𝑐𝑝𝐵 𝑇𝑏 − 𝑇𝑟𝑒𝑓 + ∆𝐻𝑠𝑜𝑙
• The saturated vapour enthalpy line of𝐻𝑚𝑖𝑥 (𝑘𝐽ൗ𝑘𝑚𝑜𝑙 ) is given by:
𝐻𝑚𝑖𝑥 = ℎ𝑚𝑖𝑥 + 𝜆𝑚𝑖𝑥
𝜆𝑚𝑖𝑥 = 𝑥𝐴 𝜆𝐴 + 𝑥𝐵 𝜆𝐵
• Where, 𝑥𝐴 is mole fraction of more volatile component,𝑇𝑏 is boiling
point of mixture, 𝑇𝑟𝑒𝑓 is reference temperature, 𝑐𝑝𝐴 𝑘𝐽ൗ𝑘𝑚𝑜𝑙.𝐾 is
heat capacity of component A, 𝑐𝑝𝐵 heat capacity of component B,
∆𝐻𝑠𝑜𝑙 is heat of solution at reference temperature 𝑘𝐽ൗ𝑘𝑚𝑜𝑙 , 𝜆𝐴 and
𝜆𝐵 are the latent heats at reference temperature
• If heat is evolved on mixing, ∆𝐻𝑠𝑜𝑙 will be negative in equation.
• The heats of solution are often small as in hydrocarbon and are
neglected
Enthalpy-composition diagram
T-x-y Diagram
EXAMPLE 9
Devise an enthalpy-concentration diagram for the
heptane-ethyl benzene system at 760 mm Hg, using the
pure liquid at 0C as the reference state and assuming
zero heat of mixing.

SOLUTION

heptane ethyl benzene

TB (C) 136.2 98.5
CP (cal/mole K) 51.9 43.4
 (cal/mole) 7575 8600
𝑻 ℃ 𝒙𝑯 𝒚𝑯
136.2 0.000 0.000
129.5 0.080 0.233
122.9 0.185 0.428
119.7 0.251 0.514
116.0 0.335 0.608
110.8 0.487 0.729
106.2 0.651 0.834
103.0 0.788 0.904
100.2 0.914 0.963
98.5 1.000 1.000
T = 136.2C
xH = 0.0 xEB = 1.0
ℎ𝑚𝑖𝑥 = 𝑥𝐻 𝑐𝑝,𝐻 𝑇𝑏 − 𝑇𝑟𝑒𝑓 + 𝑥𝐸𝐵 𝑐𝑝,𝐸𝐵 𝑇𝑏 − 𝑇𝑟𝑒𝑓 + ∆𝐻𝑠𝑜𝑙

= 0 + 1.0 (43.4) (136.2 – 0) + 0 = 5,911 cal/mole

mix = xH H + xEB EB = 0 + 1.0 (8,600) = 8,600

H = h + mix = 5,920 + 8,600 = 14,511 cal/mole

T = 129.5C
xH = 0.08 xEB = 0.92

ℎ𝑚𝑖𝑥 = 𝑥𝐻 𝑐𝑝,𝐻 𝑇𝑏 − 𝑇𝑟𝑒𝑓 + 𝑥𝐸𝐵 𝑐𝑝,𝐸𝐵 𝑇𝑏 − 𝑇𝑟𝑒𝑓 + ∆𝐻𝑠𝑜𝑙

= 0.08 (51.9) (129.5) + 0.92 (43.4) (129.5)

= 5,708 cal/mole
mix = xH H + xEB EB = 0.08 (7,575) + 0.92 (8,600) = 8,518

H = h + mix = 5,708 + 8,518 = 14,226 cal/mole

The computations are continued until the last point

where xH = 1.0 and xEB = 0.0
𝑻 ℃ 𝒙𝑯 𝒉 𝑯
(cal/mole) (cal/mole)
136.2 0.000 5,911 14,511
129.5 0.080 5,708 14,226
122.9 0.185 5,527 13,937
119.7 0.251 5,450 13,793
116.0 0.335 5,365 13,621
110.8 0.487 5,267 13,368
106.2 0.651 5,197 13,129
103.0 0.788 5,160 12,952
100.2 0.914 5,127 12,790
98.5 1.000 5,112 12,687
 20,000
18,000
Vapor
16,000 Saturated vapor
14,000
H 12,000
10,000 2 Phase
8,000
6,000
4,000
2,000 Liquid Saturated liquid

0
0 0.2 0.4 0.6 0.8 1
x
 Tray Efficiency
• For the analysis of theoretical stage required for the
distillation, it is assumed that the vapor leaving each
tray is in equilibrium with the liquid leaving the same
tray and the trays are operating at 100% efficiency.

• In practice, the trays are not perfect; there are

deviations from ideal conditions.

• The deviation from the ideal condition may be due to:

1. Insufficient time of contact

2. Insufficient degree of mixing.
• To achieve the same degree of desired separation,
more trays will have to be added to compensate for
the lack of perfect separability.

• The concept of tray efficiency may be used to adjust

the actual number of trays required.

• Three types of tray/plate efficiency can be used:

Overall tray efficiency 𝐸𝑜 , Murphree tray efficiency
𝐸𝑀 , point efficiency 𝐸𝑀𝑃 (also known as Murphree
point efficiency)
 Overall Efficiency
• The overall tray efficiency, 𝐸𝑜 pertains to the entire column

• It relates the total number of actual to ideal stages

• It is defined as: 𝑁𝑜. 𝑜𝑓 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑡𝑟𝑎𝑦𝑠

𝐸𝑜 =
𝑁𝑜. 𝑜𝑓 𝑎𝑐𝑡𝑢𝑎𝑙 𝑡𝑟𝑎𝑦𝑠

• Every tray is assumed to have the same efficiency.

• The overall efficiency depends on the:

(i) geometry and design of the contacting trays
(ii) flow rates and flow paths of vapour and liquid streams
(iii) compositions and properties of vapour and liquid
streams
• If for example, 8 theoretical steps are needed and
the overall efficiency is 60%, the number of
theoretical trays is eight minus a reboiler, or seven
trays.

• The actual number of theoretical trays is 7/0.60, or

11.7 trays.

• Correlations for distillation overall tray efficiencies

are available for standard tray designs.

• For hydrocarbon distillation, overall tray

efficiencies values range from about 50 to 85%
 Murphree Efficiency
• The Murphree Tray Efficiency 𝐸𝑀 , pertains to efficiency
at a specific stage
• It is based on a semi-theoretical models.
• It is defined for each tray according to the separation
achieved on each tray.
• It assumes that the vapour between trays is well-mixed
(uniform composition), that the liquid in the
downcomers is well-mixed (uniform composition), and
that the liquid on the tray is well mixed and is of the
same composition as the liquid in the downcomer
leaving the tray.
• Calculation of Murphree tray efficiency can be based
on either the liquid phase or the vapor phase.

• For a given component, it is equal to the change in

actual concentration in the phase, divided by the
change predicted by equilibrium condition.
For a given component, it can be expressed as:

Based on vapour phase:

𝑦𝑛 −𝑦𝑛+1 𝑎𝑐𝑡𝑢𝑎𝑙 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑣𝑎𝑝𝑜𝑢𝑟
𝐸𝑀𝑣 =
𝑦𝑛∗ −𝑦𝑛+1
=
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑣𝑎𝑝𝑜𝑢𝑟 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
[41]

Based on liquid phase:

𝑥𝑛 −𝑥𝑛−1 𝑎𝑐𝑡𝑢𝑎𝑙 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑
𝐸𝑀𝑙 = ∗ −𝑥
𝑥𝑛
=
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
[42]
𝑛−1
 Point Efficiency
• It pertains to efficiency at a specific location on a single
stage.
• If the vapor and liquid compositions are taken at a point
on the plate, the point efficiency can be expressed as:
′
𝑦𝑛′ − 𝑦𝑛+1
𝐸𝑀𝑃 = ∗ ′
𝑦𝑛 − 𝑦𝑛+1
Where 𝑦𝑛′ is the concentration of the vapour at a specific
′
point in plate 𝑛, 𝑦𝑛+1 the concentration of the vapour
entering plate 𝑛 at the same point and 𝑦𝑛∗ the concentration
of the vapor that would be equilibrium with 𝑥𝑛′ at the same
point
Extractive Distillation
• Extractive distillation is a vapor-liquid process
operation that uses a third component, or solvent, to
effect a chemical separation
• The extractive agent creates or enhances the
volatility difference between the components to be
separated.
• The extractive agent and the less volatile component
flow to the bottom of the distillation column, where
the
• Extracted component is recovered by a subsequent
distillation
• The non-extracted species are distilled to the top of
the extractive distillation tower.
Extractive Distillation Configuration
 Choice of Solvent
•Should enhance significantly the natural relative volatility of
the key component.
•Should not require an excessive ratio of solvent to non-
solvent(because of cost of handling in the column and
auxiliary equipment.
•Should remain soluble in the feed components and should
not lead to the formation of two phase.
•Should be easily separable from the bottom product.
•Should be inexpensive and readily available.
•Should be stable at the temperature of the distillation and
solvent separation.
•Should be non reactive with the components in the feed
mixture.
•Should have a low latent heat.
•Should be non corrosive and nontoxic