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JEE Main levelSingle correct optionDifficulty 2 of 3co180

Given pKa values: o-nitrobenzoic acid 2.17, m-nitrobenzoic acid 3.45, p-nitrobenzoic acid 3.44, benzoic acid 4.20. The ortho isomer is far stronger than the meta and para isomers mainly because

  1. Athe effect acts at the shortest distance and the ortho substituent also forces out of the plane of the ring (ortho effect)
  2. Bthe group is a group which is deactivated only in the ortho isomer
  3. Cthe nitro group forms intermolecular hydrogen bonds that weaken the bond of every isomer equally
  4. Dthe nitro group donates electrons by effect only from the ortho position

Answer: A

The ortho isomer is stronger by over one pKa unit compared with the other two isomers, which show nearly equal values. The nitro group sits next to the carboxyl group, so its effect is strongest at this short distance, and steric crowding twists out of the ring plane (ortho effect) and favours the anion.
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