What are acid anhydrides?

The structure of acid anhydrides

A carboxylic acid such as ethanoic acid has the structure:

If you took two ethanoic acid molecules and removed a molecule of

water between them you would get the acid anhydride, ethanoic
anhydride (old name: acetic anhydride).

You can actually make ethanoic anhydride by dehydrating ethanoic

acid, but it is normally made in a more efficient, round-about way.
(Making ethanoic anhydride is beyond the scope of UK A level.)

Naming acid anhydrides

This is really easy. You just take the name of the parent acid, and
replace the word "acid" by "anhydride". "Anhydride" simply means
"without water".
So . . . ethanoic acid forms ethanoic anhydride; propanoic acid
forms propanoic anhydride, and so on.

For UK A level purposes, the only one you are at all likely to come
across is ethanoic anhydride.

Physical properties of acid anhydrides

We will take ethanoic anhydride as typical.

Appearance

Ethanoic anhydride is a colourless liquid, smelling strongly of

vinegar (ethanoic acid).

The smell is because ethanoic anhydride reacts with water vapour

in the air (and moisture in your nose) to produce ethanoic acid
again. This reaction with water is given in detail on another page.
(Find it from the acid anhydrides menu - link at the bottom of this
page.)

Solubility in water

Ethanoic anhydride can't be said to dissolve in water because it

reacts with it to give ethanoic acid. There is no such thing as an
aqueous solution of ethanoic anhydride.

Boiling point

Ethanoic anhydride boils at 140C. This is because it is a fairly big

polar molecule and so has both van der Waals dispersion forces
and dipole-dipole attractions.
It doesn't, however, form hydrogen bonds. That means that its
boiling point isn't as high as a carboxylic acid of similar size. For
example, pentanoic acid (the most similarly sized acid) boils at
186C.

Note: If you aren't happy about intermolecular forces(including

van der Waals dispersion forces and hydrogen bonds) then you
really ought to follow this link before you go on.

Use the BACK button on your browser to return to this page.

Reactivity of acid anhydrides

Comparing acid anhydrides with acyl chlorides (acid

chlorides)

You have almost certainly come across acid anhydrides for the first
time just after looking at acyl chlorides, or you may be studying
them at the same time as acyl chlorides.

It is much, much easier to think of acid anhydrides as if they were a

sort of modified acyl chloride than to try to learn about them from
scratch. That is the line I intend to take throughout all this section.

Compare the structure of an acid anhydride with that of an acyl

chloride - looking carefully at the way it is colour-coded in the
diagram.
In the reactions of ethanoic anhydride, the red group at the bottom
always stays intact. It is behaving in many ways as if it was a single
atom - just like the chlorine atom in the acyl chloride.

The usual reaction of an acyl chloride is replacement of the

chlorine by something else.

Taking ethanoyl chloride as typical, the initial reaction is of this kind:

Hydrogen chloride gas is given off, although that might go on to

react with other components of the mixture.

With an acid anhydride, the reaction is slower, but the only

essential difference is that instead of hydrogen chloride being
produced as the other product, you get ethanoic acid instead.

Just like the hydrogen chloride, this might afterwards go on to react

with other things present.

The reactions (of both acyl chlorides and acid anhydrides) involve
things like water, alcohols and phenols, or ammonia and amines.
All of these particular cases contain a very electronegative element
with an active lone pair of electrons - either oxygen or nitrogen.