ESTER SYNTHESIS

 ESTERS: Carboxylic acids are used to manufacture esters by

reacting them with alcohols
o Carboxylic acids react with alcohols to form members of another
homologous series called esters.
o Concentrated sulphuric acid acts as a catalyst in this reaction.
o General word equation for esterification:
o carboxylic acid + alcohol == acid catalyst ==> ester + water
o e.g.
o ethanoic acid + ethanol ethyl ethanoate + water

+ + H2O

 sometimes more simply written as

 CH3COOH + CH3CH2OH CH3COOCH2CH3 + H2O
 The reaction is reversible and the mixture reaches equilibrium,
about 2/3rds of the carboxylic acid and alcohol have been converted
to the ester.
 Without a strong acid catalyst e.g. conc. sulfuric acid, the reaction
is very slow and the mixture is heated to further increase the rate of
reaction (see details of the method below).

 The first part of an ester's name is derived from the alcohol e.g.
methyl from methanol, ethyl from ethanol and propyl from propanol
etc.
 The second part of the name comes from the carboxylic acid and
ends in ...anoate e.g. methanoate from methanoic acid, ethanoate
from ethanoic acid and propanoate from propanoic acid etc.

o The procedure for preparing an ester is illustrated in the

diagrams below and a detailed description of the method for
preparing ethyl ethanoate is described.
  Ethyl ethanoate and water are both colourless, but to help in
following the procedure via the diagrams, I've coloured the ester
yellow and the reaction mixture and aqueous solutions a pale grey.
 This is a detailed description that will do for Advanced A level
chemistry too!

o Stage 1 in making an ester

o STAGE 1 Making the ester: (30mL Ethanol + 40mL Ethanoic

acis+ 4mL concentrated H2SO4)

In the round-bottomed flask the alcohol (ethanol) is mixed with the

carboxylic acid (ethanoic acid) and a small amount of concentrated
sulfuric acid (catalyst) is added too. Anti-bumping granules are added to
ensure a smooth boiling action. The mixture is carefully heated to get the
mixture gently boiling and refluxing.
Stage 1 is a technique called 'heating under reflux', and ensures the
reaction occurs the fastest at highest possible reaction temperature, the
boiling point of the mixture. However, to prevent vapour loss by
boiling/evaporation, particularly of the desired product - the ester, the
vapourised liquids are condensed back into the reaction flask recycling
everything.

The diagram shows a bunsen burner being used to supply the heat ('my
days'), these days its more likely, and safer, to use an electrical heater
that the round bottomed flask fits in snugly.

o Stage 2 Fractional distillation (use ice to cool the

product)

o
The colourless ester liquid is separated from the reaction mixture
by fractional distillation which is fully explained on the Elements,
Compounds, Mixtures Notes (the example described is separating an
ethanol/water mixture, but the same principal applies in separating the
ester from some of the water, unreacted alcohol and acid and the
sulphuric acid catalyst. Again the mixture gently heated and boiled, but
this time you want the vapour of the lowest boiling component (ester) to
separate out in the fractionating column and pass through into the
condenser. This happens when the temperature at the top of the column
reaches the boiling point of the ester. The ester and small quantities of
carboxylic acid, sulfuric acid and alcohol can be collected from the
condenser in a suitable glass vessel. Preferably a quick-fit one that
connects to the condenser, BUT it must not be a completely sealed
system otherwise pressure would build up, hence the vent to the sink.
You should realise at this point in the preparation that the ester (ethyl
ethanoate) is very impure.

o STAGE 3 Removing acidic impurities (20mL Na2CO3

10%)

The rest of the procedure is all about purifying the initial ester
distillate from the fractional distillation. The condensate (liquid distillate)
from the fractional distillation apparatus is transferred to a separating
funnel (tap funnel). Sodium carbonate solution is added to neutralise any
acids and the stopper replaced. The separating funnel is shaken to
ensure complete removal of the acid, but carbon dioxide is formed, so
every so often you invert the funnel, open the tap and allow the gas to
escape. When there doesn't seem to be any more effervescence or gas
pressure, the mixture is allowed to settle. When the two layers have fully
separated, the stopper is removed, and the lower aqueous layer is careful
run off, don't lose any of the ester in the process! When doing the run-off
the stopper must be removed. The acidic impurities and any salts formed
have now been removed in the aqueous sodium carbonate solution,
therefore there should be no carboxylic acid or sulfuric acid catalyst left in
the ester layer.

o STAGE 4 Removing the ethanol impurity (50g CaCl2 in

84mL H2O)

However, despite removing some impurities there will still be some

traces of the alcohol left in the ester layer. Concentrated calcium chloride
solution is added to the still impure ester in the separating funnel and the
mixture shaken again. The aqueous calcium chloride will remove any
remaining unreacted alcohol (ethanol). Again, the lower aqueous layer is
tapped off to leave only the ester layer which will still contain some water.
 o STAGE 5 Drying the product (CaCl2 anhyrous)

By now the only impurity left is water. So, to dry the ester, it is run off
(tapped off) from the separating funnel into a small conical flask and
some granules of anhydrous calcium chloride added. The conical flask is
stoppered and the mixture shaken, and the calcium chloride absorbs any
remaining moisture in the ester. The pure ester can than be filtered off.

o Stage 6 Fractional distillation-Last purification

o