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JEE Advanced levelOne or more correct optionsDifficulty 3 of 3g3162

For the ionisation (rate-determining step of ), which conclusions from the Hammond postulate are correct?

  1. AThe transition state resembles the carbocation (ion pair) more than it resembles .
  2. BFactors that stabilise the carbocation also lower the energy of the transition state, though by a smaller amount.
  3. C ionises faster than under identical conditions.
  4. DThe transition state resembles , so carbocation stability does not affect the rate.

Answer: A, B, C

The step is strongly endothermic, so the transition state is late and cation-like (statement 1). Because of this, factors that stabilise the cation (more alkyl groups, resonance) stabilise it partly (statement 2), which is why the tertiary halide ionises faster than the secondary one (statement 3). Statement 4 is the opposite of the postulate. Answer: 1, 2 and 3.
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