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JEE Advanced 2016 Paper 1 · Chemistry · Ionic Equilibrium · medium

(s) about acidity and basicity.

One or more options correct

Choose the correct statement(s) about acidity and basicity.
  1. A. The order of acidic strength is pp-nitrophenol >> phenol >> pp-cresol.
  2. B. In aqueous solution, trimethylamine is a stronger base than methylamine.
  3. C. oo-Nitrobenzoic acid is a stronger acid than pp-nitrobenzoic acid, which in turn is stronger than benzoic acid.
  4. D. Chloroacetic acid is a stronger acid than fluoroacetic acid.
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Answer: A, C

(A) Correct. The pp-nitro group stabilises the phenoxide by −R-R and −I-I effects (pKa≈7.2pK_a\approx7.2), phenol has pKa≈10.0pK_a\approx10.0, and the electron-donating methyl group in pp-cresol (hyperconjugation, +I+I) destabilises the anion (pKa≈10.3pK_a\approx10.3). (B) Incorrect. In water, the steric hindrance to solvation of the ammonium ion makes (CH3)3N(\mathrm{CH_3})_3\mathrm{N} (pKb≈4.2pK_b\approx4.2) weaker than CH3NH2\mathrm{CH_3NH_2} (pKb≈3.4pK_b\approx3.4). (C) Correct. In the ortho isomer the nitro group exerts the strongest −I-I effect and the ortho effect, giving pKa≈2.2pK_a\approx2.2, versus about 3.43.4 for the para isomer and 4.24.2 for benzoic acid. (D) Incorrect. Fluorine is more electronegative and exerts a stronger −I-I effect than chlorine on the carboxylate, so FCH2COOH\mathrm{FCH_2COOH} (pKa≈2.6pK_a\approx2.6) is stronger than ClCH2COOH\mathrm{ClCH_2COOH} (≈2.9\approx2.9).
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