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Question #44829

Difficulty: 8/10 | 🟢 Free

The Question

The chemoselective reduction of a keto-ester by a sterically hindered borohydride reagent proceeds via two competing, irreversible parallel pathways:

Pathway K (Ketone reduction): AK=1.0×106 M−1s−1A_K = 1.0 \times 10^6 \text{ M}^{-1}\text{s}^{-1}, Ea,K=30.0 kJ mol−1E_{a,K} = 30.0 \text{ kJ mol}^{-1} Pathway E (Ester reduction): AE=1.0×1010 M−1s−1A_E = 1.0 \times 10^{10} \text{ M}^{-1}\text{s}^{-1}, Ea,E=52.9 kJ mol−1E_{a,E} = 52.9 \text{ kJ mol}^{-1}

(Assume R=8.3 J K−1mol−1R = 8.3 \text{ J K}^{-1}\text{mol}^{-1} and ln⁡10=2.3\ln 10 = 2.3)

Determine the temperature TeqT_{eq} at which the initial rates of both pathways are equal, and identify the type of reaction control governing the major product formation at T=500 KT = 500 \text{ K}.

Options

  • A.

    300 K300 \text{ K}, Kinetic Control

  • B.

    300 K300 \text{ K}, Thermodynamic Control

  • C.

    250 K250 \text{ K}, Kinetic Control

  • D.

    400 K400 \text{ K}, Thermodynamic Control

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Correct Answer

Step-by-Step Solution

Explanation

How the Examiner Thinks

Mechanism_Trap

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Concepts Behind This Question

Arrhenius Pre-exponential Factor|Reduction Selectivity (Hydrides)

Why This Question Is Tricky

Common Mistakes

Students often falsely equate 'high temperature' with 'thermodynamic control'.

In irreversible parallel reactions, the product distribution is strictly determined by the relative rate constants (kinetic control).

The shift in chemoselectivity at 500 K is a purely kinetic phenomenon where the larger pre-exponential factor (collision frequency) of the ester reduction overcomes its higher activation energy barrier.

Quick Facts About This Question

Question Information

SubjectChemistry
ChapterChemical Kinetics - Class 12
ConceptArrhenius Pre-exponential Factor
Difficulty8
Cognitive Load7
Target Solve Time160 sec
AccessFree