AZEOTROPIC DISTILLATION

Azeotrope mixtures
Minimum boiling point
Maximum boiling point
Azeotropic Distillation

Azeotrope mixtures
Liquid and vapor are exactly the same at a
certain temperature
It is a special class of liquid mixture that boils at
a constant temperature at a certain composition
Cannot be separated by a simple/conventional
distillation

Azeotropic Distillation
An introduction of a new component called
entrainer is added to the original mixture to form
an azeotrope with one or more of feed component
The azeotrope is then removed as either the
distillate or bottoms
The purpose of the introduction of entrainer is to
break an azeotrope from being formed by the
original feed mixture
Function of entrainer:
To separate one component of a closely boiling point
To separate one component of an azeotrope

Azeotropic Distillation
Azeotropic distillation is a widely practiced process
for the dehydration of a wide range of materials
including acetic acid, chloroform, ethanol, and many
higher alcohols.
The technique involves separating close boiling
components by adding a third component, called an
entrainer, to form a minimum boiling.
Normally ternary azeotrope which carries the water
overhead and leaves dry product in the bottom.
The overhead is condensed to two liquid phases; the
organic, "entrainer rich" phase being refluxed while
the aqueous phase is decanted.

Azeotropic Distillation
A common example of distillation with an azeotrope
is the distillation of ethanol and water.
Using normal distillation techniques, ethanol can
only be purified to approximately 89.4%
Further conventional distillation is ineffective.
Other separation methods may be used are
azeotropic distillation or solvent extraction

Azeotropic Distillation
The concentration in the vapor phase is the same as
the concentration in the liquid phase (y=x)
At this point, the mixture boils at constant
temperature and doesnt change in composition
This is called as minimum boiling point (positive
deviation)

Azeotropic Distillation
The characteristic of such mixture is boiling point
curve goes through maximum phase diagram
Example: Acetone-chloroform

Azeotropic Distillation
The most common examples:
Ethanol-water (89.4 mole%, 78.25 oC, 1 atm)
Carbon Disulfide-acetone (61 mol% CS2, 39.25oC, 1 atm)
Benzene-water (29.6 mol% water, 69.25 oC, 1 atm)

Azeotropic Distillation
Let say binary mixture: A-B formed an azeotrope
mixture
Entrainer C is added to form a new azeotrope with
the original components, often in the LVC, say A
The new azeotrope (A-C) is separated from the
other original component B
This new azeotrope is then separated into entrainer
C and original component A.
Hence the separation of A and B can be achieved

Azeotropic Distillation
Example: Acetic acid-water using entrainer n-butyl
acetate
Boiling point of acetic acid is 118.1 oC, water is 100 oC &
n-butyl acetate is 125 oC
The addition of the entrainer results in the formation of
a minimum boiling point azeotrope with water with a
boiling point = 90.2 oC.
The azeotropic mixture therefore be distilled over as a
vapor product & acetic acid as a bottom product
The distillate is condensed and collected in a decanter
where it forms 2 insoluble layers

Azeotropic Distillation
Example: Acetic acid-water using entrainer n-butyl
acetate
Top layer consist of nearly pure n-butyl acetate in
water, whereas bottom layer of nearly pure water
saturated with butyl acetate
The liquid from top layer is returned to column as reflux
and entrainer
The liquid from bottom layer is sent to another column
to recover the entrainer (by stream stripping)

Determination of Boiling Point Temperature in

multi component distillation
The calculation is a trial and error process
where
1. T is assumed
2. Value of relative volatility of each component
are then calculated using K values at the
assume T.
3. Then calculate value of Kc where
Kc= 1/(relative volatility x liq mole fraction)

4. Find the T that corresponds to the calculated

value of Kc
5. Compare with T value read from table that
corresponds to the Kc.
6. If value is differ, the calculated T is used for the
next iteration.
7. After the final T is known, the vapor composition
is calculated from
Yi= (relative volatility x liq mole fraction)/(relative
volatility x liq mole fraction)

Discuss
example 11.7-1

Bubble point@boiling point

Bubble point@boiling point
=temperature at which liquid begins to vaporize
Dew point
=temperature at which liquid begins to condense out of the
vapor

Fractionation of multicomponent mixtures

Three or more components in the products
The designer generally choose two components whose
concentrations or fractional recoveries in the distillate and
bottom products are a good index of the separation achieved
These two components are called key components
They must differ in volatility
Light key (L) is more volatile (vapor)
The heavy key (H) is less volatile (liquid

 For the compositions, mole fractions ; xH

xL
xBL

xDH and

xBL means most of the light key ends up at the bottom

xDH means most of the heavy key ends up at the
distillate
Normally the key components are adjacent in the
rank order of volatility. Such choice is called a sharp
separation
In sharp separations the keys are only components
that appear in both products in appreciable
concentrations

Multi Component Distillation

The vapor-liquid equilibria for a mixture are
described by distribution coefficients or K factors
y ie
where; K

x ie
K is the ratio of mole fractions in the vapor and liquid
phases at equilibrium
If Raoults Law and Daltons Law hold, Ki can be
calculated from the vapor pressure and total pressure of
the system.
Pi = xiPi
; yi = Pi/P
y i pi pi pi
Ki

x i p.pi
p

K factors are strongly temperature dependent

y i / xi
Ki
ij

y j / xj Kj

---- ration of K factors is the same as

the relative volatility of the
components

When Raoults Law applies,

ij

Pi

P j

Bubble Point and Dew Point Calculation

1. For bubble point (initially boiling point of a liquid
mixture)
N

i 1

i 1

2. y i K i x i 1.0

-----(1)

3. For dew point(intial condensation temperature)

yi
1 .0
xi
i 1
i 1K i
N

----(2)

4. A temperature is assumed
5. Obtain Ki values from chart

7. Calculate Kixi (for bubble point) or (yi/ Ki) (for dew

point)
8. If Kixi > 1.00, a lower temperature is chosen until
equation (1) is satisfied
9. If (yi/ Ki) > 1.00, a higher temperature is chosen until
equaition (2) is satisfied
10.The bubble point and dew point are obtained when
equation (1) and (2) is satisfied
11.The compositions can be determined with the formula:

yi

K i xi
N

K i xi

i 1

or

xi

yi / Ki
N

y i /K i

i 1

Example
Find the bubble-point and the dew point temperatures and
the corresponding vapor and liquid compositions for a mixture
of 33 mole % n-hexane, 37 mole % n-heptane and 30 mole %
n-octane at 1.2 atm total pressure. (The equilibrium K values
for hydrocarbon system is given)

The equilibrium K values graph

For bubble point:

Choose T = 105 C, where the vapor pressure of the
middle component at 1.2 atm. Construct and fill in the
table:
Component

1 Hexane
2 Heptane
3 Octane

Pi at
Ki = Pi/P
105C,
1.2 atm

xi

yi =Kixi

2.68
1.21
0.554

0.33
0.37
0.30

0.7359
0.3737
0.1386

2.23
1.01
0.462

 Since Kixi > 1.00, try a lower temperature. The major

contribution comes from hexane, pick a temperature
where Ki is lower by a factor (1/1.248)
Example;
1/1.248 x 2.23 = Pi/1.2
Pi = 2.14 atm where T = 96 C

Repeat the iteration until Kixi = 0.9833

Component

1 Hexane
2 Heptane
3 Octane

Pi at
96C, 1.2
atm
2.14
0.93
0.41

Ki =
Pi/P

xi

yi =Kixi

1.8
0.33 0.5940
0.755 0.37 0.2868
0.342 0.30 0.1025
=
0.9833

yi
calculated

0.604
0.292
0.104
=
1.00

The yi calculated is using the formula;

yi

K i xi
N

K i xi

i 1

By interpolation, the bubble point = 97 C

Therefore, the vapor in equilibrium with the liquid is 60.4
mol % n-hexane, 29.2 mole % n-heptane and 10.4 mole %
n-octane.

For dew point;

Choose a higher T = 105 C as first guess
Component

1
2
3

Hexane
Heptane
Octane

Pi at
105C, 1.2
atm
2.68
1.21
0.554

Ki = Pi/P

xi

xi =yi/Ki

2.23
1.01
0.462

0.33
0.37
0.30

0.148
0.366
0.655
=
1.169

Choose a higher T = 110 C where K3 is 17 % higher

In order to reduce yi/Ki , Ki has to increase by a
factor 1.169
Therefore, K3 = 0.458 x 1.169 = 0.535

K3 = Pi/P

17 %
higher

Pi = 0.535 x 1.2 = 0.642 atm

which give T = 110 C

Componen
t
Hexane
Heptane
Octane

P i

Ki

yi

yi/Ki

3.0 2.5
0.33 0.132
1.38 1.15 0.37 0.3217
0.64 0.535 0.30 0.5625
= 1.0162

xi calculated
0.130
1.317
= 1.00

By extrapolation, the dew point = 110.5 and the

composition of the liquid in the equilibrium with the
vapor is calculated by formula;
xi

yi / Ki
N

y i /K i

i 1

which 13.0 mole % n-hexane, 31.7 mole % nheptane and 55.3 mole % n-octane.