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JEE Advanced levelSingle correct optionDifficulty 3 of 3g2213

Salicylic acid (2-hydroxybenzoic acid) has for the and for the phenolic , whereas 4-hydroxybenzoic acid has . A single explanation for both the low and the very high of salicylic acid is

  1. Athe effect of the ortho group on the carboxylate
  2. Bintermolecular hydrogen bonding of salicylic acid with water only
  3. Csteric inhibition of resonance in the phenoxide ion
  4. Dan intramolecular hydrogen bond between the phenolic and the carboxylate in the monoanion

Answer: D

In the monoanion, the phenolic hydrogen-bonds to the carboxylate oxygen through a six-membered chelate ring. This stabilises the monoanion, so the first ionisation is easy (pKa 2.97, stronger than the para isomer at 4.54). The same stabilisation makes removal of the phenolic proton difficult, so is about 13.6, much more than phenol (10.0).
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