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JEE Advanced 2016 Paper 2 · Chemistry · General Organic Chemistry and Isomerism · medium

Comparisons regarding acid/base strength is (are) correct?

One or more options correct

Which of the following comparisons regarding acid/base strength is (are) correct?
  1. A. pp-Nitrophenol is a stronger acid than phenol.
  2. B. pp-Nitroaniline is a weaker base than aniline.
  3. C. Benzoic acid is a weaker acid than pp-methylbenzoic acid.
  4. D. Acetic acid is a stronger acid than chloroacetic acid.
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Answer: A, B

(A) Correct. The pp-nitrophenoxide ion is stabilised by delocalisation of the negative charge onto the nitro group through resonance (−R-R, −I-I), so pKa≈7.2\mathrm{p}K_a\approx7.2 compared with about 1010 for phenol. (B) Correct. The lone pair of nitrogen in pp-nitroaniline is pulled into the ring and the nitro group by the −R-R effect, so it is less available for protonation; the conjugate acid has pKa≈1\mathrm{p}K_a\approx1 against 4.64.6 for anilinium. (C) Incorrect. The methyl group is electron donating (+I+I, hyperconjugation) and destabilises the carboxylate, so pp-toluic acid (pKa≈4.37\mathrm{p}K_a\approx4.37) is weaker than benzoic acid (4.204.20); benzoic acid is the stronger one. (D) Incorrect. The −I-I effect of chlorine stabilises the carboxylate, so chloroacetic acid (2.862.86) is stronger than acetic acid (4.764.76). Answer: A and B.
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