FRACTIONALDISTILLATION

ORGILAB
Dr.W.J.KELLY

THEBOILINGPOINT

The Boiling Point is the temperature at

which internal vapor pressure of the liquid is
equal to the pressure exerted by its
surroundings
If the liquid is open to the atmosphere, the
boiling point is the temperature at which the
internal vapor pressure of the liquid
becomes equal to atmospheric pressure
(~760 mm Hg).
The internal vapor pressure of a pure liquid
rises steadily as the temperature is
increased until the boiling point is reached.

PeC/T

The temperature remains constant

throughout the boiling process 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

In a Distillation Process a liquid is

heated to its boiling point, the vapors
expand out of the container and are
then cooled below the boiling point
temperature, where they recondense
as a liquid

THETEMP/TIMERELATIONSHIP

A thermometer placed in the

vapor of a boiling pure liquid
registers the liquids boiling
point.
The temperature remains
constant throughout the boiling
process 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
The temperature of a liquid
mixture AB, where BPA<BPB will
rise steadily over time. The
composition of the liquid and
vapor in equilibrium changes
constantly over time. At the
beginning the vapor contains
more A, at the end more B.

Boiling Point of Pure B

Boiling point of pure Liquid

T
E
M
P
Boiling point of pure A

TIME or VOLUME
Boiling Temperature Behavior of Pure Liquid
Boiling Temperature Behavior of Mixture A
and B where BP of A < BP of B

RaoultsLaw
RaoultsLaw

For a mixture of two miscible liquids (A and B), the total vapor pressure is the
sum of the individual vapor pressures:

Ptotal = PA + PB
where

PA = NAliquid x PA And PB = NBliquid x PB

where
PA is the vapor pressure of pure A and PB is the vapor pressure of pure B
and
NAliquid is the mole fraction of A and NBliquid is the mole fraction of B
where

NAliquid = moles A/moles A + B and NBliquid = moles B/moles A +B

VaporEnrichment

From Raoults Law we can obtain the following relationships:

NAvapor = PA/PT
And

NBvapor = PB/PT

If A is more volatile than B, BPA < BPB and PA > PB

Then

NAvapor > NAliquid

The result of this process is that when a mixture of two miscible liquids with
different boiling points is heated,the vapor will have a different composition than
the liquid. THE VAPOR IS ENRICHED IN THE MORE VOLATILE (LOWER
BOILING) COMPONENT.
COMPONENT

DistillationProcess

When a mixture AB of a specific

composition is heated, the total
vapor pressure (composed of the
contributions of PA and PB) will rise
until it is equal to the external vapor
pressure. The mixture will begin to
boil.
The vapor which first forms is
enriched in the more volatile
component. This behavior is shown
at right,

Liquid-Vapor Composition Diagram

Assume a two component mixture with a composition of 30%A:70%B (point W).

The boiling point of this mixture is found by drawing a vertical line from W to where it
intersects the lower curve (point X). A horizontal line drawn from X to where it
intersects the vertical axis (the temperature) gives the bp of composition W. From
the point (Y) where this horizontal line intersects the upper curve (vapor) drop a
vertical line to intersect the lower axis (the composition). Point Z gives the
composition of the vapor which is in equilibrium with a liquid of composition W at its
boiling point.

FractionalDistillation
AB at composition of 5% A boils at temperature L1 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 L2 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 plates) 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.

DistillationEfficiency
The efficiency of a fractional distillation is determined by the amount of pure liquid
components obtained. Keep in mind that if a liquid is pure it will have a constant boiling point.
The temperature of vapors in equilibrium with liquid at the boiling point will be constant. A plot of
temperature vs. time for a pure liquid will look like A below.
The efficiency of a fractional distillation can be demonstrated graphically by plotting the change
in temperature of the distillate over time (or over volume of distillate, as in this experiment). In a
fractional distillation with low efficiency, separation will be poor. There will be little or no pure
component as distillate. The composition of the distillate will be constantly changing and the bp
of the vapor in equilibrium with liquid will be constantly changing. It will give a plot such as B.
An efficient distillation will give pure components which will have constant boiling points. Such
a process is shown below in plot C. The relatively flat: horizontal regions at the beginning and
end of the plot indicate pure components A and B are obtained.
The closer to this ideal sigmoid shape the better the fractional distillation.

DistillationSetups

FractionalDistillationSetup

ProperThermometerDepth