METHODS of SEPARATING MIXTURES and purifying substances

Simple distillation and fractional distillation are two techniques used in the isolation and
purification of liquid product from a chemical reaction.

Remember, in the physical separation processes of simple distillation and fractional

distillation, no chemical reaction changes are involved, so no new substances are made.

 Simple Distillation
Distillation involves 2 stages and both are physical state changes.

(1) In simple distillation the liquid or solution mixture is heated to boil and vaporise the most
volatile component (the component that has the lowest boiling point) in the mixture (liquid ==>
gas). The anti-bumping granules give a smoother boiling action for the distillation process.

(2) The vapour passes up from the flask and down into the condenser, where it is cooled by cold
water and condenses (gas ==>liquid) back to a liquid (the distillate) which is collected in the
flask.

(3) Any dissolved solids are left

in solution because they have very
high boiling points to be distilled
over e.g. the salts in sea water.

1
Simple distillation can be used to separate a liquid (solvent) from a solution. If the dissolved
soluble substance is a solid at room temperature, it will NOT distil over – due to its very high
boiling point.

This can be used to purify water because the dissolved solids have a much higher boiling point
and will not evaporate with the steam. You can purify seawater, at great cost, by distilling it,
pure water is distilled over and condensed out and you left with a mass of salt crystals.

You see the same thing if you distil copper (II) sulfate solution, pure colourless liquid water
distils over, the solid copper (II) sulfate remains in the solution which gets progressively a deeper
blue as the mixture becomes more concentrated.

 A particle picture for distillation: liquid == boiling ==> gas == condensation ==> liquid

 Fractional Distillation and theory

How do you separate two liquids that have similar boiling points and are miscible? Miscible
means they completely mix together (e.g. alcohol and water) and do not form two layers (e.g. oil
and water).

How can you separate a complex mixture of liquids by a method of distillation?

Simple distillation isn't good enough to do an efficient job of separating liquids with boiling
points that may be relatively close together. The liquids must all dissolve in each other i.e. they
are all fully miscible.

Fractional distillation involves 2 main stages and both are physical state changes. It can only
work with liquids with different boiling points but the boiling points can be quite close
together. However, this method only works if all the liquids in the mixture are miscible (e.g.

2
alcohol & water, hydrocarbons in crude oil etc.) and do NOT separate out into layers like oil &
water (immiscible).

(1) For a laboratory demonstration of fractional distillation, the liquid mixture is poured into the
round-bottomed flask, heated and boiled to vaporise the most volatile component (the
component that has the lowest boiling point) in the mixture (liquid ==> gas). The anti-bumping
granules give a smoother boiling action.

(2) The vapour passes up through a fractionating column, where the separation takes place. The
fractionating column is packed with glass beads or short rods/tubes to give a large surface area
for both evaporation and condensation to take place on. When the temperature at the top of the
column reaches the boiling point of the lowest boiling component, that component will then
distil over into the condenser. The higher boiling liquids condense and separate out, running back
into the flask mixture, whereas the lower boiling liquid's vapour passes through into the Liebig
condenser. This is because the temperature falls as you rise up the special fractionating column.

(3) The (e.g. ethanol) vapour is cooled by cold water in the condenser to condense (gas ==>
liquid) it back to a liquid (the distillate) which is collected in the flask. The 1st liquid, with the
lowest boiling point, evaporates/boils off first, and is called the 1st fraction (first distillate).
Then, each liquid distils, with increasing boiling point, over the top of the column, when it
reaches its particular boiling point to give the 2nd, 3rd fraction etc. The boiling point of each
fraction can be read off the thermometer.

3
In the diagram, think of the yellow liquid as water and the blue liquid as ethanol ('alcohol')
Imagine the green liquid is a mixture of a blue liquid (boiling point 80 oC) and a yellow liquid
(boiling point 100oC), so we have a coloured diagram simulation of the fractional distillation
colourless alcohol and water mixture! As the vapour from the boiling mixture enters the
fractionating column it begins to cool and condense. The highest boiling or least volatile liquid
tends to condense more i.e. the yellow liquid (water). The lower boiling or more volatile blue
liquid gets further up the column. Gradually up the column the blue and yellow separate from
each other so that yellow condenses back into the flask and pure blue distils over to be collected.
This ensures that only reasonably pure ethanol distils over. The continuous evaporation and
condensation over a large surface area is crucial to the success of fractional distillation and that
large surface area is provided by using lots of little pieces of glass tubing or glass beads.

The
same

arguments apply to the fractional distillation of complex multi-component mixtures like cr ude
oil. The diagram illustrates the school laboratory demonstration of a simulated crude oil.

4
As the vapour ascends the fractionating column the highest boiling liquids condense out and the
lowest boiling liquid's vapour exits the top of the fractionating column and enters the condenser
and runs into the collection tube. In this way you can progressively distil over higher and higher
boiling fractions, which are themselves narrow boiling ranges of hydrocarbons.