DISTILLATION

The process of producing a vapor from a liquid

by heating the liquid in a vessel, then
condensing the vapor and collecting them
in another vessel

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

Apparatus for a simple distillation

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

1) Vapor Pressures of mixtures of

compounds Daltons Law
The total pressure of a system is the sum of all of the
pressures added together

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)

Psolvent = Xsolvent. Posolvent

P = the partial pressure
Po = the vapor pressure of the pure material
X = the mole fraction of the material

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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Major equilbirium steps are called PLATES

They just there in theory in most laboratory columns,
so they are called THEORETICAL PLATES

HETP (height equivalent to a theoretical

plates) is a measure of the efficiency of
distilling column

VOLATILITY ( V )
The ratio of the mole fraction of a component in the
vapor phase to its mole fraction in the liquid phase

V = y (mole fraction in the vapor phase)

x (mole fraction in the liquid phase)
For a binary mixture, V1 more volatile than V2
V1 = y1/x1, V2 = y2/x2
Relative volatily = = V1/V2 = y1 x2 / y2 x1
Since x2 = 1-x1 and y2 = 1-y1

Y1
1 Y1

X1

1 X1

If Raoults law holds for the solution and Daltons law

of partial pressure hold in the vapor
= Po1/Po2
Po= vapor pressure of pure materials
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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

Let Xs dan Ys be for the more volatile component;

must be constant over the range of concentration
X represent the mole fraction of the returning to the
pot, and Y the mole fraction of vapor heading for
the top of the column
Y1
= Ys = 2 Xs
1 Y1
1 Ys
1 Xs
Assuming that the vapor (X1) entering the first plate
of the column is condensed and in equilibrium
with the vapor Y1 entering the second plate of the
column : Y2
= 3 Xs
1 Y2
1 Xs
In general :

Yn
1 Yn

n+1 Xs
1 Xs

or Log Yn = (n+1) log + log Xs

1-Yn
1-Xs
The n+1 term = the enrichment factor.
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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 :

Log Xf = (n+1) log + log Xs

1-Xf
1-Xs
And
n+1 = log Xf (1-Xs)
Xs(1-Xf)
log
FENSKE EQUATION

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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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