Acid and base

Two interrelated classes of chemical compounds, the precise definitions of which have varied considerably with the development of chemistry. Some of these controversies are still unresolved.

Acids initially were defined only by their common properties as substances which had a sour taste, dissolved many metals, and reacted with alkalies (or bases) to form salts. For a time it was believed that a common constituent of all acids was the element oxygen, but gradually it became clear that, if there were an essential element, it was hydrogen, not oxygen. This concept of an acid proved to be satisfactory for about 50 years.

Bases initially were defined as those substances which reacted with acids to form salts (they were the “base” of the salt). The alkalies, soda and potash, were the best-known bases, but it soon became clear that there were other bases, notably ammonia and the amines.

When the concept of ionization of chemical compounds in water solution became established, acids were defined as substances which ionized in aqueous solution to give hydrogen ions, H+, and bases were substances which reacted to give hydroxide ions, OH-. These definitions are sometimes known as the Arrhenius-Ostwald theory of acids and bases. Their use makes it possible to discuss acid and base equilibria and also the strengths of individual acids and bases.

A powerful and wide-ranging protonic theory of acids and bases was introduced by J. N. Bronsted in 1923 and was rapidly accepted. Somewhat similar ideas were advanced almost simultaneously by T. M. Lowry and the new theory is occasionally called the Bronsted-Lowry theory. The Bronsted definitions of acids and bases are: An

acid is a species which can act as a source of protons; a base is a species which can accept protons. Compared to the water (Arrhenius) theory, this represents only a slight change in the definition of an acid but a considerable extension of the term base. In addition to hydroxide ion, the bases now include a wide variety of uncharged species, such as ammonia and the amines, as well as numerous charged species, such as the anions of weak acids. In fact, every acid can generate a base by loss of a proton. Acids and bases which are related in this way are known as conjugate acid-base pairs, and the table lists examples.

As the table shows, strengths of acids and bases are not independent. A very strong Br¢nsted acid implies a very weak conjugate base and vice versa. A qualitative ordering of acid strength or base strength permits a rough prediction of the extent to which an acid-base reaction will go. The rule is that a strong acid and a strong base will react extensively with each other, whereas a weak acid and a weak base will react together only very slightly.

Studies of catalysis have played a large role in the acceptance of a set of quite different definitions of acids and bases, those due to G. N. Lewis: An acid is a substance which can accept an electron pair from a base; a base is a substance which can donate an electron pair. Bases under the Lewis definition are very similar to those defined by Bronsted, but the Lewis definition for acids is very much broader.

Another comprehensive theory was proposed by M. Usanovich in 1939 and is sometimes known as the positive-negative theory. Acids are defined as substances which form salts with bases, give up cations, and add themselves to anions and free elec­trons. Bases are similarly defined as substances which give up anions or electrons and add themselves to cations. So far, this theory has had little acceptance, quite possibly because the definitions are too broad to be very useful.

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