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The composition of water is different when comparing the top to bottom of the fractionating column.

What happens to the vapor in a fractionating column?

Better liquid separation results from the more volatile liquids gradually rising to the top of the fractionating column while the lower boiling liquids remain at the bottom. Eventually, the vapor is cooled in the condenser before dripping into the collection jar.

The composition of vapor is different. Only the most volatile compounds 'survive' in the gaseous phase all the way to the top where they are then entering a condenser which cools the vapor into a liquid distillate. That means, as we're going upwards through the fractionating column, there will be fewer and fewer non-volatile compounds present in the gaseous phase.

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