DISTILLATION

Kimia Fisik Geologi

Vapor Pressure
For a liquid, at any temperature, some
molecules are evaporating from the
surface.
As the temperature goes up, the number
of molecules evaporating in a given
time increases.
If the liquid is in an open container, the
molecules escape into the atmosphere.
In a closed container, some of the vapor
molecules strike the walls of the
container and return to the liquid.
Soon a state of equilibrium is reached in
which over any time period, the number
of molecules evaporating = number of
molecules condensing back to the
liquid.
The pressure of the vapor at this point is
known as its vapor pressure.
THE BOILING POINT
The vapor pressure of a pure
liquid rises steadily as the
temperature is increased .

The Boiling Point of a liquid is the
temperature at which vapor
pressure is equal to the external
pressure.

The normal boiling point of a
liquid is the temperature at which
its vapor pressure is 760 torr,
normal atmospheric pressure at
sea level

Distillation
In a Distillation a liquid is heated
to its boiling point, the vapors
expand out of the container and
are then cooled below the boiling
point so that they recondense as
a liquid
An apparatus for a simple
distillation is shown to the right.
During a simple distillation, the
liquid is vaporized and
condensed one time.
The thermometer measures the
temperature at which the liquid
is currently boiling.




THE TEMP/TIME RELATIONSHIP
The temperature remains
constant throughout the
distillation of a pure liquid. At
the boiling point, the liquid and
vapor are in equilibrium...if the
composition of each phase
remains constant, the
temperature will remain constant
A mixture of two volatile liquids
begins to distill at a temperature
slightly higher than the boiling
point of the lower boiling liquid,
the temperature rises steadily
over time ending at a
temperature slightly below that
of the higher boiling component.
The composition of the liquid and
vapor in equilibrium changes
constantly over time also. At the
beginning the vapor contains
mostly A, at the end mostly B.
Raoults Law
For a mixture of two miscible liquids (A and B), the total vapor pressure is the sum of the individual vapor
pressures (Daltons Law)
P
total
= P
A
+ P
B

The vapor pressures of the individual components is given by Raoults Law.

P
A
= X
A
P

A
And P
B
= X
B
P

B

where
P

A
is the vapor pressure of pure A and P

B
is the vapor pressure of pure B
and
X
A
and X
B
are the mole fractions of A and B in the liquid
where
X
A
= n
A
/(n
A
+ n
B
) and X
B
= n
B
/(n
A
+ n
B
)
where
n
A
and n
B
are the number of moles of each component in the liquid.
Daltons Law
According to Daltons Law of Partial Pressures
P
A
= X
A

P
t
P
B
= X
B

P
t
where
P
A
and P
B
are the partial pressures of the two gases
and
P
t
is the total pressure (P
t
= P
A
+ P
B
)
and
X
A

and X
B

are the mole fractions of A an B respectively in the vapor.

and
X
A

= n
A

/(n
A

+ n
B

) , X
B

= n
B

/(n
A

+ n
B

)
where
n
A

and n
B

are the number of moles of each component in the vapor.

Vapor Enrichment
Combining Raoults Law and Daltons law, we can obtain the following relationship:



If A is more volatile than B, BP
A
< BP
B
and P
A
> P
B
then

X
A

/X
B

> X
A
/X
B
The ratio of A/B in the vapor is greater than the ratio of A/B in the liquid.
The vapor is enriched in the more volatile (lower boiling) component relative
to the liquid.
During the distillation, since the vapor always contains more A than B, the
fraction of B in the liquid increases continuously causing the boiling point of
the solution to increase

B B
A A
B
A
P X
P X
X
X
'
'
Distillation
This figure represents the LI QUI D-
VAPOR COMPOSI TI ON
DI AGRAM FOR A TWO
COMPONENT MI XTURE
When a mixture AB of a is heated,
the total vapor pressure (composed
of the contributions of P
A
and P
B
)
will rise until it is equal to the
external vapor pressure.
The temperature at which this
occurs for various compositions of
the liquid is show in the lower
curve.

In this example, the liquid having composition W boils at temperature t.
The vapor in equilibrium with the liquid has composition y.
The vapor condenses to give liquid of composition Z.
After the first drop of liquid distills, the fraction of B in the liquid increases
slightly, increasing the boiling point of the solution
The composition of both the liquid and vapor changes continuously.
Fractional Distillation
Fractional distillation is only
useful for separating compounds
which have very different boiling
points.
Fractional distillation can be used
to separate liquids with similar
boiling points.
On its way up the fractionating
column, the vapor condenses and
revaporized many times.
At each stage of condensation/
revaporization, the vapor is
further enriched in the lower
boiling component.
Fractional Distillation
AB at composition of 5% A boils at temperature L
1
and the vapors with composition V
1
enter the column at that
temperature. The vapor will condense to a liquid with composition V
1
. The condensate L
2
has a lower boiling point
(because it has more of the lower boiling liquid A) and will thus vaporize at a lower temperature (warmed up by
coming in contact with the additional vapors from below) to give vapors of composition V
2
. These vapors will
condense somewhat farther up the column to give a condensate L
3
. If the column is long enough or contains
sufficient surface area that many successive vaporization-condensation steps (theoretical paltes) can occur, the
distillate that comes over the top is nearly pure A. Distillation yielding pure A continues until all of A is removed,
after which the temperature at the thermometer rises to the boiling point of B.
Fractional Distillation Set-up
Proper Thermometer Depth