JEE Main · 2020 · Shift-IIhardHALO-106

For the following reactions, ks and ke are respectively, the rate constants for substitution and elimination reactions…

Haloalkanes & Haloarenes · Class 12 · JEE Main Previous Year Question

Question

For the following reactions, image ksk_s and kek_e are respectively, the rate constants for substitution and elimination reactions and μ=kske\mu = \frac{k_s}{k_e}, the correct option is:

Options
  1. a

    μA>μB\mu_A > \mu_B and kek_e (A) > kek_e (B)

  2. b

    μA>μB\mu_A > \mu_B and kek_e (A) > kek_e (B)

  3. c

    μA>μB\mu_A > \mu_B and kek_e (B) > kek_e (A)

  4. d

    μA<μB\mu_A < \mu_B and kek_e (B) > kek_e (A)

Correct Answerc

μA>μB\mu_A > \mu_B and kek_e (B) > kek_e (A)

Detailed Solution

Step 1: Identify the bases

Base A: \ceCH3CH2O\ce{CH3CH2O-} (ethoxide) - small base

Base B: \ce(CH3)3CO\ce{(CH3)3C-O-} (tert-butoxide) - bulky base

Step 2: Understand substitution vs elimination

Small base (ethoxide):

  • Can approach carbon easily
  • Favors SN2S_N2 substitution
  • Some elimination also occurs
  • μA=kske\mu_A = \frac{k_s}{k_e} is higher (more substitution)

Bulky base (tert-butoxide):

  • Sterically hindered
  • Cannot easily approach carbon for SN2S_N2
  • Acts as base instead → E2 elimination favored
  • μB=kske\mu_B = \frac{k_s}{k_e} is lower (less substitution, more elimination)

Step 3: Compare μ values

μ=kske=substitution rateelimination rate\mu = \frac{k_s}{k_e} = \frac{\text{substitution rate}}{\text{elimination rate}}

  • Higher μ: More substitution relative to elimination
  • Lower μ: More elimination relative to substitution

Ethoxide (A): More substitution → μA\mu_A is higher

tert-Butoxide (B): More elimination → μB\mu_B is lower

Therefore: μA>μB\mu_A > \mu_B

Step 4: Compare kek_e values

Elimination rate constant:

  • Bulky bases are better at elimination
  • tert-Butoxide is stronger base and bulkier
  • kek_e(B) > kek_e(A)

Answer: (c) μA>μB\mu_A > \mu_B and kek_e(B) > kek_e(A)

Key Principles:

Base size and selectivity:

| Base | Size | Favors | μ value | |------|------|--------|----------| | Small (OEt⁻, OH⁻) | Small | SN2S_N2 | High | | Bulky (t-BuO⁻, LDA) | Large | E2 | Low |

Competition between SN2S_N2 and E2:

  • Same substrate can undergo both
  • Base size determines selectivity
  • Temperature also affects (heat favors elimination)
  • Substrate structure matters (1° favors SN2S_N2, 3° favors E2)

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