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Making Esters From Alcohols

This page looks at esterification - mainly the reaction between alcohols and carboxylic acids to make esters. It also looks briefly at making esters from the reactions between acyl chlorides (acid chlorides) and alcohols, and between acid anhydrides and alcohols. Esters are derived from carboxylic acids. A carboxylic acid contains the -COOH group, and in an ester the hydrogen in this group is replaced by a hydrocarbon group of some kind. We shall just be looking at cases where it is replaced by an alkyl group, but it could equally well be an aryl group (one based on a benzene ring).

A common ester - ethyl ethanoate

The most commonly discussed ester is ethyl ethanoate. In this case, the hydrogen in the -COOH group has been replaced by an ethyl group. The formula for ethyl ethanoate is:

ethethform.gif

Notice that the ester is named the opposite way around from the way the formula is written. The "ethanoate" bit comes from ethanoic acid. The "ethyl" bit comes from the ethyl group on the end.

A few more esters

In each case, be sure that you can see how the names and formulae relate to each other.

estersform.gif

Notice that the acid is named by counting up the total number of carbon atoms in the chain - including the one in the -COOH group. So, for example, CH3CH2COOH is propanoic acid, and CH3CH2COO is the propanoate group.

Making esters from carboxylic acids and alcohols

Esters are produced when carboxylic acids are heated with alcohols in the presence of an acid catalyst. The catalyst is usually concentrated sulphuric acid. Dry hydrogen chloride gas is used in some cases, but these tend to involve aromatic esters (ones containing a benzene ring). If you are a UK A level student you won't have to worry about these.

The esterification reaction is both slow and reversible. The equation for the reaction between an acid RCOOH and an alcohol R'OH (where R and R' can be the same or different) is:

estergeneq.gif

So, for example, if you were making ethyl ethanoate from ethanoic acid and ethanol, the equation would be:

ethetheqn.gif

Doing the reactions

On a test tube scale

Carboxylic acids and alcohols are often warmed together in the presence of a few drops of concentrated sulfuric acid in order to observe the smell of the esters formed. You would normally use small quantities of everything heated in a test tube stood in a hot water bath for a couple of minutes.

Because the reactions are slow and reversible, you don't get a lot of ester produced in this time. The smell is often masked or distorted by the smell of the carboxylic acid. A simple way of detecting the smell of the ester is to pour the mixture into some water in a small beaker. Apart from the very small ones, esters are fairly insoluble in water and tend to form a thin layer on the surface. Excess acid and alcohol both dissolve and are tucked safely away under the ester layer. Small esters like ethyl ethanoate smell like typical organic solvents (ethyl ethanoate is a common solvent in, for example, glues). As the esters get bigger, the smells tend towards artificial fruit flavoring - "pear drops", for example.

On a larger scale

If you want to make a reasonably large sample of an ester, the method used depends to some extent on the size of the ester. Small esters are formed faster than bigger ones. To make a small ester like ethyl ethanoate, you can gently heat a mixture of ethanoic acid and ethanol in the presence of concentrated sulfuric acid, and distil off the ester as soon as it is formed. This prevents the reverse reaction happening. It works well because the ester has the lowest boiling point of anything present. The ester is the only thing in the mixture which doesn't form hydrogen bonds, and so it has the weakest intermolecular forces.

Larger esters tend to form more slowly. In these cases, it may be necessary to heat the reaction mixture under reflux for some time to produce an equilibrium mixture. The ester can be separated from the carboxylic acid, alcohol, water and sulfuric acid in the mixture by fractional distillation.

Making esters from alcohols and acyl chlorides

Esters can also be made from the reactions between alcohols and either acyl chlorides (acid chlorides) or acid anhydrides.If you add an acyl chloride to an alcohol, you get a vigorous (even violent) reaction at room temperature producing an ester and clouds of steamy acidic fumes of hydrogen chloride. For example, if you add the liquid ethanoyl chloride to ethanol, you get a burst of hydrogen chloride produced together with the liquid ester ethyl ethanoate.

\[ CH_3COCl + CH_3CH_2OH \rightarrow CH_3COOCH_2CH_3 + HCl\]

Making esters from alcohols and acid anhydrides

The reactions of acid anhydrides are slower than the corresponding reactions with acyl chlorides, and you usually need to warm the mixture. Taking ethanol reacting with ethanoic anhydride as a typical reaction involving an alcohol. There is a slow reaction at room temperature (or faster on warming). There is no visible change in the colorless liquids, but a mixture of ethyl ethanoate and ethanoic acid is formed.

\[(CH_3CO)_2O + CH_3CH_2OH \rightarrow CH_3COOCH_2CH_3 + CH_3COOH\]

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