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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)
Discuss
example 11.7-1
xDH and
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
y j / xj Kj
ij
Pi
P j
i 1
i 1
2. y i K i x i 1.0
-----(1)
yi
1 .0
xi
i 1
i 1K i
N
----(2)
4. A temperature is assumed
5. Obtain Ki values from chart
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)
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
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
yi
K i xi
N
K i xi
i 1
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
K3 = Pi/P
17 %
higher
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
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.