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JEE Advanced 2023 Paper 2 · Chemistry · General Organic Chemistry and Isomerism · medium

Choose the correct statement(s).

One or more options correct

Choose the correct statement(s).
  1. A. The acidity order is pp-nitrophenol >> phenol >> pp-cresol
  2. B. oo-Nitrophenol is more volatile in steam than pp-nitrophenol
  3. C. In aqueous solution the basic strength order is (CH3)3N>(CH3)2NH>CH3NH2(\mathrm{CH_3})_3\mathrm{N}>(\mathrm{CH_3})_2\mathrm{NH}>\mathrm{CH_3NH_2}
  4. D. Aniline is a stronger base than benzylamine because its lone pair is delocalised into the ring and is therefore more available
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Answer: A, B

(A) True: the −M-M, −I-I nitro group stabilises the phenoxide (pKa≈7.15\mathrm{p}K_a\approx7.15), phenol has pKa≈10.0\mathrm{p}K_a\approx10.0 and the electron-donating methyl group destabilises the phenoxide in pp-cresol (≈10.26\approx10.26). (B) True: oo-nitrophenol has intramolecular hydrogen bonding, so it is not associated and is steam volatile, whereas pp-nitrophenol is intermolecularly hydrogen bonded. (C) False: in water, solvation of the ammonium ion governs the order, which is (CH3)2NH>CH3NH2>(CH3)3N(\mathrm{CH_3})_2\mathrm{NH}>\mathrm{CH_3NH_2}>(\mathrm{CH_3})_3\mathrm{N} (pKb=3.27, 3.38, 4.22\mathrm{p}K_b=3.27,\ 3.38,\ 4.22); trimethylamine is the weakest because it has only one N-H for hydrogen bonding to solvent. (D) False: delocalisation of the nitrogen lone pair into the ring makes it less available, so aniline (pKb≈9.4\mathrm{p}K_b\approx9.4) is a much weaker base than benzylamine (pKb≈4.7\mathrm{p}K_b\approx4.7). Hence (A) and (B).
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