ACIDITY OF AROMATIC

CARBOXYLIC ACID
 ACIDITY OF AROMATIC CARBOXYLIC ACID
Aromatic carboxylic acids with unsubstituted benzene ring are slightly
stronger acids than the aliphatic acids. Thus benzoic acid is somewhat
stronger acid than acetic acid.

The effect of substituent groups in the ring on the acidity of benzoic

acid (i.e., on ionisation of —COOH) depends not only on the nature
of the group but also its position with respect to the position of the
COOH group.
Acidity of aromatic carboxylic acids, in fact, is determined by
the inductive effect as also the resonance effect. Electron-
releasing substituents and ortho-para directors increase the
electron-density in the ortho and para positions.

Thus with OH group in thç ortho or para position; the benzene

ring is unable to delocalize the negative charge of the
-
carboxylate anion (COO ).
With long distances between the electron-releasing OH group, and
carboxyl group,the inductive effect is important.

However, with the decreasing distance, the inductive effect dominates

over the resonance effect. That is why o-hydroxybcnzoic acid is
stronger (Ka=100x10-5) and p-hydroxybenzojc acid weaker (Ka=2.9 x
10-5) than benzoic acid (Ka=6.3x10-5).
Electron-withdrawing substituents and meta directors like NO2 group,
on the other hand,decrease electron density ortho and para to them.
Thus the negative charge of the carboxylate anion is delocalized and
hence it is stabilised.
That is why p-nitrobenzoic acid (Ka=40x10-5) is stronger than
benzoic acid (Ka=6.3x l0).

However, p-nitrobenzoic acid is weaker than o-nitrobenzoic acid

(Ka=620x10-5), where the strong inductive effect of the NO2, group
-
close to COO anion causes additional strong delocalization of the
negative charge.