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Question #44491

Difficulty: 8/10 | 🟢 Free

The Question

The reversible electrophilic aromatic substitution (e.g., sulfonation) of a monosubstituted benzene yields ortho (OO) and para (PP) products, exhibiting a classic kinetic vs. thermodynamic control dichotomy.

At T1=300 KT_1 = 300\text{ K} (under strict kinetic control), the initial rate of formation of OO is 2e22e^2 times that of PP. At T2=600 KT_2 = 600\text{ K} (under strict thermodynamic control), the equilibrium concentration of PP is e42\frac{e^4}{2} times that of OO.

The pre-exponential factors for the forward reactions satisfy Ao=2ApA_o = 2A_p. The difference in standard entropy of reaction is ΔSp∘−ΔSo∘=−Rln⁡2\Delta S^\circ_p - \Delta S^\circ_o = -R \ln 2 (accounting for the statistical factor of two ortho positions vs. one para position).

Assuming activation energies and standard enthalpies are temperature-independent, what is the difference in the activation energies of the reverse reactions, (Ea,−o−Ea,−p)(E_{a,-o} - E_{a,-p})?

Options

  • A.

    −3000R-3000 R

  • B.

    −1800R-1800 R

  • C.

    +3000R+3000 R

  • D.

    +1800R+1800 R

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Correct Answer

Step-by-Step Solution

Explanation

How the Examiner Thinks

Numerical_Precision

Improve calculation stamina and avoid rounding errors in high-stakes competitive examinations.

Concepts Behind This Question

Electrophilic Substitution Orientation|Activation Energy Trap|Arrhenius Pre-exponential Factor

Why This Question Is Tricky

Common Mistakes

This problem tests the deep integration of chemical kinetics and thermodynamics within the context of kinetic vs. thermodynamic control in electrophilic aromatic substitution.

The 'Hidden Variable' trap is the statistical entropy factor (ΔSp∘−ΔSo∘=−Rln⁡2\Delta S^\circ_p - \Delta S^\circ_o = -R \ln 2).

Students often ignore entropy in EAS energy profiles, assuming ΔG∘≈ΔH∘\Delta G^\circ \approx \Delta H^\circ.

Failing to account for the 1/21/2 statistical probability factor in the thermodynamic equilibrium expression leads to an incorrect enthalpy difference (ΔHo∘−ΔHp∘\Delta H^\circ_o - \Delta H^\circ_p), which cascades into the wrong reverse activation energy.

Furthermore, it rigorously tests sign conventions for exothermic/endothermic reaction profiles.

Quick Facts About This Question

Question Information

SubjectChemistry
ChapterHydrocarbons - Class 11 Part 2
ConceptElectrophilic Substitution Orientation
Difficulty8
Cognitive Load7
Target Solve Time160 sec
AccessFree