Using the phase diagram

On the last page, we looked at how the phase diagram for an ideal mixture of two liquids was built up. I want to start by looking again at material from the last part of that page.

The next diagram is new - a modified version of diagrams from the previous page.

If you boil a liquid mixture C₁, you will get a vapour with composition C₂, which you can condense to give a liquid of that same composition (the pale blue lines).

If you reboil that liquid C₂, it will give a vapour with composition C₃. Again you can condense that to give a liquid of the same new composition (the red lines).

Reboiling the liquid C₃ will give a vapour still richer in the more volatile component B (the green lines). You can see that if you were to do this once or twice more, you would be able to collect a liquid which was virtually pure B.

The secret of getting the more volatile component from a mixture of liquids is obviously to do a succession of boiling-condensing-reboiling operations.

It isn't quite so obvious how you get a sample of pure A out of this. That will become clearer in a while.

So what happens to that liquid now? It will start to trickle down the column where it will meet new hot vapour rising. That will cause the already condensed vapour to reboil.

Some of the liquid of composition C₂ will boil to give a vapour of composition C₃. Let's concentrate first on that new vapour and think about the unvaporised part of the liquid afterwards.

The vapour

This new vapour will again move further up the fractionating column until it gets to a temperature where it can condense. Then the whole process repeats itself.

Each time the vapour condenses to a liquid, this liquid will start to trickle back down the column where it will be reboiled by up-coming hot vapour. Each time this happens the new vapour will be richer in the more volatile component.

The aim is to balance the temperature of the column so that by the time vapour reaches the top after huge numbers of condensing and reboiling operations, it consists only of the more volatile component - in this case, B.

Whether or not this is possible depends on the difference between the boiling points of the two liquids. The closer they are together, the longer the column has to be.

The liquid

So what about the liquid left behind at each reboiling? Obviously, if the vapour is richer in the more volatile component, the liquid left behind must be getting richer in the other one.

As the condensed liquid trickles down the column constantly being reboiled by up-coming vapour, each reboiling makes it richer and richer in the less volatile component - in this case, A. By the time the liquid drips back into the flask, it will be very rich in A indeed.

So, over time, as B passes out of the top of the column into the condenser, the liquid in the flask will become richer in A. If you are very, very careful over temperature control, eventually you will have separated the mixture into B in the collecting flask and A in the original flask.

Finally, what is the point of the packing in the column?

To make the boiling-condensing-reboiling process as effective as possible, it has to happen over and over again. By having a lot of surface area inside the column, you aim to have the maximum possible contact between the liquid trickling down and the hot vapour rising.

If you didn't have the packing, the liquid would all be on the sides of the condenser, while most of the vapour would be going up the middle and never come into contact with it.