JEE Advanced levelSingle correct optionDifficulty 3 of 3g1025
Chloroacetic acid (pKa 2.86) is more acidic than acetic acid (pKa 4.76). Assume that the lowering of pKa produced by a chlorine atom is the full alpha effect when Cl is on the alpha carbon (C-2), and that it falls by a factor of 0.4 for each additional carbon the chlorine moves away from the alpha carbon (beta-chloro, C-3: factor 0.4; gamma-chloro, C-4: factor 0.42). Butanoic acid has pKa 4.82. The estimated pKa of 4-chlorobutanoic acid is
A2.92
B4.52
C4.35
D4.06
Answer: B
The alpha-chloro shift is 4.76−2.86=1.90. In 4-chlorobutanoic acid the chlorine is on C-4, two carbons beyond the alpha carbon, so the shift is 1.90×0.42=0.304. The estimated pKa is 4.82−0.304=4.52.