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Distillation
Distillation
Type of distillation :
1. Simple distillation
2. Fractional distillation
3. Steam distillation
4. Immiscible solvent distillation
5. Azeotropic distillation
6. Extractive distillation
7. Vacuum distillation
8. Molecular distillation
9. Freeze drying
Simple Distillation
Involve applying heat to vaporize a liquid and then
cooling the vapor until it condenses as a liquid
Example : the separation of water from the salts in
sea water
Fractional Distillation
The mixture has two or more compounds that
have appreciable vapor pressure
The vapors of the volatile components are
condensed, brought into contact with part of the
condensate flowing down the column and then
boiled out of the descending liquid
A column for this purpose is called fractionating
column
Ptotal = P1 + P2 + P3 +
P1 then is called a partial pressure
2) Gibbs Phase Rule
Tell how many degree of freedom (variable you can
change) you have in any system if you know the
number of components (C), the number of phases
(P), and the temperature and pressure
F=CP+2
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3. Raoults Law
The partial vapor pressure of one component is
directly proportional to the number of molecules in
the mixture (mole fraction)
Example
What would be the vapor pressure for a mixture of 15
mL of benzene (f.w.=78.1, d=0.878 g/mL, Po= 86
torr) and 25 mL of toluene (f.w.=92.1, d=0.866,
Po=32 torr at 25oC)?
Answer
Mole benzene = 15 x 0.878 / 78.1 = 0.169 moles
Mole toluene = 25 x 0.866 / 92.1 = 0.235 moles
X (benzene) = 0.169/(0.169+0.235) = 0.418
X (toluene) = 1 0.418 = 0.582
P (benzene) = 0.418 x 86 torr = 36 torr
P (toluene) = 0.582 x 32 torr = 19 torr
P (total) = 36 + 19 = 55 torr
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VOLATILITY ( V )
The ratio of the mole fraction of a component in the
vapor phase to its mole fraction in the liquid phase
Y1
1 Y1
X1
1 X1
CONTINUOUS DISTILLATION
TOTAL REFLUKS CONDITIONS
Refluxing : the process of returning part of the
condensed vapors back down to the column to be
redistilled and improve the separation
Unless some product is being removed, the process
is called TOTAL REFLUX
Diagram of a distillation column for total reflux
Yn
1 Yn
n+1 Xs
1 Xs
Example:
Chlorobenzene and bromobenzene have Po1=861.5
and 455.8 torr, respectively. How many theoretical
plates are required to produce a vapor containing
99.9 mole% chlorobenzene at the top of the
column under total reflux if the pot contains a 5050 mole ratio mixture?
Answer:
Yn = 0.999
Xs = 0.50
= 861.5/455.8 = 1.89
0.999 = (1.89)n+1
0.5
1 0.999
1 0.5
(n+1) log 1.89 = log 999
n = 9.8 or 10 plates
If the vapor in the last plate-n is condensed, the
composition from final distillate Yn=Xf. So :
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EXAMPLE:
How many theoretical plates (n) is needed to enrich
equimolar mixtures of benzene and toluene ( =
2.47) in order to get final distillate with Xf (benzene) =
0.995 ?
AZEOTROPIC DISTILLATION
PRINCIPLES
An azeotrope is a liquid mixture that is characterized
by a constant maximum or minimum boiling point
which is lower or higher than that of any components
and that distills without change in composition
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EXTRACTIVE DISTILLATION
A third component is added to extract one of the
other components. It is called a solvent
Example :
Cyclohexane
(b.p.
80.8oC)
is
formed
by
hydrogenating benzene (b.p. 80.1oC), the
desired product cannot be separated by an
ordinary distillation. Aniline (b.p.184oC) is
added
to
form
a
complex
with
benzene,probably by a bond interaction. This
complex boils at much higher temperature than
benzene, and the cyclohexane can be
separated by distillation
One commercial application is the separation of
acetone from methanol by adding water as the
solvent to form a hydrate with methanol.
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