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Autoprotolysis

From some of the examples given above, we see that water can act as an acid

CN + H2O HCN + OH

and as a base

NH4+ + H2O NH3 + H3O+

If this is so, then there is no reason why "water-the-acid" cannot donate a proton to
"water-the-base":

This reaction is known as the autoprotolysis of water.

Chemists still often refer to this reaction as the "dissociation" of water and use the
Arrhenius-style equation H2O H+ + OHas a kind of shorthand.

As discussed in the previous lesson, this process occurs to only a tiny extent. It does
mean, however, that hydronium and hydroxide ions are present in any aqueous
solution.

Can other liquids exhibit autoprotolysis? The answer is yes. The most well-known
example is liquid ammonia:

2 NH3 NH4+ + NH2

Even pure liquid sulfuric acid can play the game:

2 H2SO4 H3SO4+ + HSO4

Each of these solvents can be the basis of its own acid-base "system", parallel to the
familiar "water system".

Ampholytes

Water, which can act as either an acid or a base, is said to be amphiprotic: it can
"swing both ways". A substance such as water that is amphiprotic is called
an ampholyte.

As indicated here, the hydroxide ion can also be an ampholyte, but not in aqueous
solution in which the oxide ion cannot exist.
It is of course the amphiprotic nature of water that allows it to play its special role in
ordinary aquatic acid-base chemistry. But many other amphiprotic substances can also
exist in aqueous solutons. Any such substance will always have a conjugate acid and a
conjugate base, so if you can recognize these two conjugates of a substance, you will
know it is amphiprotic.

The carbonate system

For example, the triplet set {carbonic acid, bicarbonate ion, carbonate ion} constitutes
an amphiprotric series in which the bicarbonate ion is the ampholyte, differing from
either of its neighbors by the addition or removal of one proton:

If the bicarbonate ion is both an acid and a base, it should be able to exchange a
proton with itself in an autoprotolysis reaction:

HCO3 + HCO3 H2CO3 + CO32

Your very life depends on the above reaction! CO2, a metabolic by-product of every cell
in your body, reacts with water to form carbonic acid H2CO3 which, if it were allowed to
accumulate, would make your blood fatally acidic. However, the blood also contains
carbonate ion, which reacts according to the reverse of the above equation to produce
bicarbonate which can be safely carried by the blood to the lungs. At this location the
autoprotolysis reaction runs in the forward direction, producing H2CO3which loses water
to form CO2 which gets expelled in the breath. The carbonate ion is recycled back into
the blood to eventually pick up another CO2 molecule.

If you can write an autoprotolysis reaction for a substance, then that substance is
amphiprotic.
Amphoteric substances

You may possibly have noticed (although probably not!) that in one of the last two examples,
water was acting as a base, whereas in the other one it was acting as an acid.

A substance which can act as either an acid or a base is described as being amphoteric.

Note: You might also come across the term amphiprotic in this context. The
two words are related and easily confused.

An amphiprotic substance is one which can both donate hydrogen ions (protons)
and also accept them. Water is a good example of such a compound. The water
acts as both an acid (donating hydrogen ions) and as a base (by accepting
them). The "protic" part of the word refers to the hydrogen ions (protons) either
being donated or accepted. Other examples of amphiprotic compounds are
amino acids, and ions like HSO4- (which can lose a hydrogen ion to form sulphate
ions or accept one to form sulphuric acid).

But as well as being amphiprotic, these compounds are alsoamphoteric.


Amphoteric means that they have reactions as both acids and bases. So what is
the difference between the two terms?

All amphiprotic substances are also amphoteric - but the reverse isn't true. There
are amphoteric substances which don't either donate or accept hydrogen ions
when they act as acids or bases. There is a whole new definition of acid-base
behaviour that you are just about to meet (the Lewis theory) which doesn't
necessarily involve hydrogen ions at all.

A Lewis acid is an electron pair acceptor; a Lewis base is an electron pair donor
(see below).

Some metal oxides (like aluminium oxide) are amphoteric - they react both as
acids and bases. For example, they react as bases because the oxide ions
accept hydrogen ions to make water. That's not a problem as far as the definition
of amphiprotic is concerned - but the reaction as an acid is. The aluminium oxide
doesn't contain any hydrogen ions to donate! But aluminium oxide reacts with
bases like sodium hydroxide solution to form complex aluminate ions.

You can think of lone pairs on hydroxide ions as forming dative covalent
(coordinate) bonds with empty orbitals in the aluminium ions. The aluminium ions
are accepting lone pairs (acting as a Lewis acid). So aluminium oxide can act as
both an acid and a base - and so is amphoteric. But it isn'tamphiprotic
because both of the acid reaction and the base reaction don't involve hydrogen
ions.

I have gone through 40-odd years of teaching (in the lab, and via books and the
internet) without once using the term amphiprotic! I simply don't see the point of
it. The term amphoteric takes in all the cases of substances functioning as both
acids and bases without exception. The term amphiprotic can only be used
where both of these functions involve transference of hydrogen ions - in other
words, it can only be used if you are limited to talking about the Bronsted-Lowry
theory. Personally, I would stick to the older, more useful, term "amphoteric"
unless your syllabus demands that you use the word "amphiprotic".