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Q.The strongest acid among the following compounds is

(a) o-nitrophenol
(b) p-chlorophenol
(c) m-nitrophenol
(d) p-nitrophenol
Meghalaya MboseMBOSE Meghalaya Intermediate Board 2019MCQ· 1mImportance★★★★★
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A −NO2-NO_2 group at the para position conjugates directly and fully with the phenoxide oxygen, delocalising the negative charge onto its own oxygens — this makes p-nitrophenol the most acidic of the set.

Acid strength of a substituted phenol depends on how well the phenoxide (conjugate base) is stabilised:

  • p-nitrophenol: the −NO2-NO_2 group at para position is in full conjugation with the ring and the −O−-O^-; the negative charge can be delocalised all the way onto the nitro-group oxygens through resonance — strongest stabilisation, highest acidity (pKa≈7.15pK_a \approx 7.15).
  • o-nitrophenol: the −NO2-NO_2 also conjugates (comparable resonance), but the effect is slightly reduced compared to para and partly complicated by intramolecular H-bonding in the un-ionised form (pKa≈7.23pK_a \approx 7.23) — still very acidic, but marginally less than para. …

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