UNIT OPERATION II

Reference Materials:
C. J. Geankoplis Transport Processes and Unit
Operations, Prentice Hall, 1993
C. J. Separation Processes, McGraw Hil,l 1980
R. E. Treybal, Mass transfer Operations, McGraw
Hill, 1980
 DISTILLATION
•Distillation is the method of separation of more
volatile component from the less volatile component
(s) of a mixture.
•It is a common separation method for liquid
mixtures.
•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.
• The heat supplied create new phase different
from the initial phase of the mixture
• 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
 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• Part of the condensate is withdrawn as top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
 Vapour Pressure
• Distillation is an equilibrium staged process.
• The 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 is termed as the vapor pressure.
• It depends on the temperature and the quantity of
the liquid and vapor.
• The vapor pressure can be calculated from
Antoine Equation.
 • Antoine’s equation: Log10 Pio =A- [B/(T+C)]
Pio (mmHg), T (oC )
Table 1: Antoine constants A, B and C for some typical liquids
Name A B C
Benzene 6.87987 1196.76 219.161
methane 6.6438 395.74 266.681
ethane 6.82915 663.72 256.681
propane 6.80338 804 247.04
n-butane 6.80776 935.77 238.789
n-hexane 6.87601 1171.17 224.408
n-heptane 6.89677 1264.9 216.544
n-octane 6.91868 1351.99 209.155
methanol 8.08097 1582.271 239.726
ethanol 8.1122 1592.864 226.184
water 8.07131 1730.63 233.426
 Example 1
Using Antoine equation, calculate the vapor pressures
for pure species of n-heptane and n-octane at 110oC
and 1 atm.
 Binary Distillation
• The feed mixture in binary distillation has two
components; The more volatile component ‘A’ and
the less volatile, ‘B’

• 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.
 Phase Diagrams
• Phase diagram is a graphical representation of
the physical states of a substance under different
conditions. There are two types of phase
diagrams: constant pressure and constant
temperature.

• Constant-pressure phase diagram

– T-x-y diagram
– boiling point diagram
– boiling point-concentration diagram
– commonly used for distillation calculations
for an ideal solution (one that obeys Raoult's Law)
T-x-y Diagram

Figure 2a
Figure 2b
changes in distribution of components in the
phases with temperature3

• 0 Super heated vapour

subcooled liquid

Figure 2c
• As shown by fig. 2, boiling of a liquid mixture
takes place over a range of boiling points
depending on the concentrations of each
component in the liquid.
• The temperature when the liquid starts to boil is
called bubble point temperature.
• The temperature when the vapor starts to
condense is called dew point.
• The upper curve in the boiling point diagram is
called the dew-point curve (DPC)
• The lower one is called the bubble-point curve
(BPC).
• At each temperature, the vapor and the liquid are
in equilibrium
• Constant-temperature- phase diagram
– P-x-y diagram
– Isothermal phase diagram
– commonly used to depict deviations from
ideal behaviour or Raoult’s law
P-x-y Diagram

Figure 3
• The constant temperature phase diagram is
as shown in Fig 3.

• It is useful in the analysis of solution

behaviour.

• The more volatile liquid will have a higher

vapour pressure (i.e. pA at xA = 1.0)
 VLE Data
• The relationship between the compositions of a V and a
L at equilibrium at some constant pressure/temperature
is the vapour- liquid equilibrium (VLE)data

• The following can be used to obtain a suitable

relationship process parameters for distillation:
1. Raoult’s law
2. Relative volatilities
3. Equilibrium coefficients
 Raoult’s Law
• Ideal solutions obey 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];

[5a]

• From [5a] & [1] respectively;

[5b]

are equilibrium relation

• Also [5c]
 Example 2:
Using the vapour pressure from Table 2, calculate the
vapour and liquid compositions in equilibrium at 1 std atm
assuming ideal behaviour
Table 2: Vapour Pressure Data for Benzene –Toluene System at 1 atm
Table 2: Vapour Pressure and Equilibrium Data for Benzene –Toluene System at 1 atm
 Example 3
Compute the vapour-liquid equilibria at
constant pressure of 1 std atm for mixtures of
n-heptane with n-octane assuming ideal
solution is formed (N.B: The boiling point of n-
heptane and n-octane at 1 std atm is 98.4oC and
125.6oC respectively.)
 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:

(6)

• Where, yA = mole fraction of component ‘A’ in the

vapor, xA = mole fraction of component ‘A’ in the
liquid
• relative volatility of a mixture changes with the mixture
composition
• For binary mixture, xB = 1-xA , substituting into (6)

(7)

Rearranging,

(8)

Rearranging,

(9)
•For systems that obey Raoult’s law, [6] can be written
as:
[10]
•Relative volatility is not a strong function of
temperature
•Relative volatility can be assumed constant over a
temperature range and composition
•The higher the value of relative volatility, the higher the
separation
•If then, separation is not possible
This is because when : components A and B have the
same volatility and will vaporize 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 1will yield the equilibrium
curve predictions
Example 4
Using data from table 2 calculate the relative
volatility for the benzene-toluene system at 85oC
(358.2K) and 105oC (378.2K)

Example 5
What is the average relative volatility of n-
heptane with n-octane mixture for a
temperature range of 98.4 – 125.6oC?
 Vapour-Liquid Equilibrium Plot
• The VLE plot expresses the bubble-point and the
dew-point of a binary mixture at constant pressure.
• 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 4
• It contains less information than the phase diagram
(i.e. temperature is not included), but it is most
commonly used
• The curved line in Figure 4 is called the
equilibrium line and it describes the compositions
of the liquid and vapor in equilibrium at some
fixed pressure.
• The equilibrium line can be obtained from the
Equation (9) once the relative volatility is known.
• It can also be obtained from constant pressure
phase diagram
• Below the equilibrium line is the 45 degree line or
diagonal line where y=x
Vapour-Liquid Equilibrium Plot

Figure 4
Effect of Relative Volatility on VLE

Figure 5
 Equilibrium Curve from Phase Diagram

Figure 6
• 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
Equilibrium Curve: more complicated

Figure 7
Equilibrium Curve: azeotropic systems

Figure 8
 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 [5b] is said to exhibit
positive deviation from ideality.
•If the total pressure is less than that calculated by [5b],
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
Figure 9:
Minimum-boiling azeotrope: carbon-disulfide- acetone
(61.0 mole% CS2, 39.25 oC, 1 atm)

Figure 10:
• 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
•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
[9]

[10]

[11]

•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

(12)

(13)
 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.
• 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 vapour produced
•The condensed vapour is
known as the distillate.
• Thedistillate is collected in
a condensate receiver.
Figure 9
•The liquid remaining in the still is
known as the residual.
•The process is unsteady state.
•The concentration changes can
be analyzed using the phase
diagram.
•Detailed mathematical
calculations can be carried out
using the Rayleigh Equation.

• As a result of the unsteady

nature of the process, the
derivation is based on differential
approach to changes in Figure 9
concentration with time.
 Derivation of Rayleigh Equation
Let 𝐿1 = initial moles of liquid originally in still;
𝐿2 = final moles of liquid remained in still;
𝑥1 = initial liquid composition in still (mole fraction of A);
𝑥2 = final liquid composition in still (mole fraction A);

At any time t, let:

𝐿 = the amount of liquid in the still;
𝑥 = mole fraction of A in the liquid.
 After a small differential time (𝑡 + 𝑑𝑡), a small amount of vapour
𝑑𝐿 is produced, and the vapour is assumed to be in equilibrium
with the residue liquid.
Let 𝑦= the vapour composition of A (mole fraction).
The amount of liquid in the still is thus reduced from 𝐿 to (𝐿 −
𝑑𝐿), while the liquid composition changed from 𝑥 to (𝑥 − 𝑑𝑥).
At a given time After a moment

Total moles of liquid present 𝐿 𝐿 − 𝑑𝐿

Moles of A present in liquid 𝑥𝐿 (𝑥 − 𝑑𝑥) (𝐿 − 𝑑𝐿)

Total moles of liquid removed 𝑑𝐿

(i.e. total moles of vapour formed)

Moles of A present in the vapor 𝑦𝑑𝐿
• Then the material balance on A can be written
as:
• Initial amount in still = Amount left in still +
Amount vaporized

𝑥𝐿 = 𝑥 − 𝑑𝑥 𝐿 − 𝑑𝐿 + 𝑦𝑑𝐿 [14]
𝑥𝐿 = 𝑥𝐿 − 𝑥𝑑𝐿 − 𝐿𝑑𝑥 + 𝑑𝑥𝑑𝐿 + 𝑦𝑑𝐿 [15]
Neglecting the term 𝑑𝑥𝑑𝐿, the Equation (2) may be written
as:
𝐿𝑑𝑥 = 𝑦𝑑𝐿 − 𝑥𝑑𝐿 [16]
Re-arranging and Integrating from L1 to L2, and from x1 to x2,
one can obtain the following Equation which is called Rayleigh
Equation:
[17]

This is to avoid a negative as there is less material at the end

than at the start

The integration of Equation (17) can be obtained graphically

1
from the equilibrium curve, by plotting versus 𝑥.
𝑦−𝑥
 Numerical integration:
𝑥1
1
𝐴𝑟𝑒𝑎 = 𝑑𝑥
𝑥2 𝑦−𝑥

𝑦−𝑥
1 • •

𝑥2 𝑥1
𝑥

Simpson’s rule:

x1  x2   x1  x2  
   
x2
area   f ( x)     
6 
f x1 4 f f x 2 
x1
 2  

𝐿1 = 𝐿2 𝑒 𝐴𝑟𝑒𝑎
 𝑏
• assume 𝑦 = 𝑎 𝑓 𝑥 𝑑𝑥
• and 𝑓 𝑥 is continuous on 𝑎, 𝑏
• If 𝑎, 𝑏 is divided into an even number ‘n’ of subintervals of equal
length

𝑏−𝑎
∆𝑥 =
𝑛
𝑏
∆𝑥
𝑓 𝑥 𝑑𝑥 ≈ 𝑦𝑜 + 4𝑦1 + 2𝑦2 + 4𝑦3 + 2𝑦4 + ⋯ + 4𝑦𝑛−1 + 𝑦𝑛
𝑎 3
Example
A mixture of 40 mole % isopropanol in water is to be batch-
distilled at 1 atm until when the mole fraction of isopropanol in
the still reaches 6.7 mole % . Calculate the amount of distillate
collected and its average composition. VLE data for this system,
in mole fraction of isopropanol, at 1 atm are (Seader and
Henley, 1998):

Table 3
 1
Calculate:
𝑦−𝑥
Rayleigh Equation is given by:
𝑥1
𝐿1 1
ln = 𝑑𝑥
𝐿2 𝑥2 𝑦−𝑥
Given;
Feed L1 = 100
𝑥1 = 0.4 , 𝑥2 = 0.067

then;
𝐿1 0.4 1
Find L2 by equating ln = 0.067 𝑦−𝑥
𝑑𝑥
𝐿2

The amount of distillate is obtained by D= L1 - L2

Average composition of distillate by :