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ORGILAB
Dr.W.J.KELLY
THEBOILINGPOINT
PeC/T
THETEMP/TIMERELATIONSHIP
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
VaporEnrichment
NAvapor = PA/PT
And
NBvapor = PB/PT
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
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