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P w e -C/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
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
Raoults Law
For a mixture of two miscible liquids (A and B), the total vapor pressure is the A sum of the individual vapor pressures:
Ptotal = PA + PB
where
Vapor Enrichment
From Raoults aw 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
Distillation Process
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.
Fractional Distillation
AB at composition of 5% A boils at temperature 1 and the vapors with composition 1 enter the column at that temperature. The vapor will condense to a liquid with composition 1. The condensate 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 2. These vapors will condense somewhat farther up the column to give a condensate 3. If the column is long enough or contains sufficient surface area that many successive vaporizationcondensation 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.
Distillation Efficiency
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.
Distillation Setups