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Question #44452

Difficulty: 8/10 | 🟢 Free

The Question

The Cannizzaro reaction of benzaldehyde (\cePhCHO\ce{PhCHO}) proceeds via a hydride shift mechanism. At moderate base concentrations, the reaction involves a mono-anion intermediate, following the rate law r=kobs[\cePhCHO]x[\ceOH−]yr = k_{obs}[\ce{PhCHO}]^x[\ce{OH^-}]^y. At extremely high base concentrations, the mechanism shifts to involve a dianion intermediate, following the rate law r′=kobs′[\cePhCHO]x[\ceOH−]zr' = k'_{obs}[\ce{PhCHO}]^x[\ce{OH^-}]^z.

The rate-determining step (RDS) in both pathways is the hydride transfer. In a high-dielectric solvent (ϵ=80\epsilon = 80), the charge-delocalized transition state of the mono-anion pathway is significantly stabilized compared to a low-dielectric solvent (ϵ=40\epsilon = 40). This stabilization lowers the activation energy by ΔE\Delta E, causing the observed rate constant kobsk_{obs} to increase by a factor of e2e^2 at 300 K300\text{ K}.

Assuming ideal kinetic behavior and using R=253 J K−1 mol−1R = \frac{25}{3}\text{ J K}^{-1}\text{ mol}^{-1}, calculate the value of the expression (x+y+z)×ΔE(x + y + z) \times \Delta E in kJ/mol\text{kJ/mol}.

Options

  • A.

    25.0 kJ/mol

  • B.

    20.0 kJ/mol

  • C.

    15.0 kJ/mol

  • D.

    12.5 kJ/mol

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Correct Answer

Step-by-Step Solution

Explanation

How the Examiner Thinks

Exception_Exposure

Learn to identify edge cases and boundary exceptions that JEE examiners hide in math problems.

Concepts Behind This Question

Solvent Effects on Reactivity|Cannizzaro Mechanism|Reaction Intermediates Stability

Why This Question Is Tricky

Common Mistakes

This question tests the nuanced kinetic understanding of the Cannizzaro reaction, specifically the transition between mono-anion and dianion mechanisms dependent on base concentration.

The 'Hidden Variable' is the solvent polarity transition: students often memorize that Cannizzaro is strictly a 3rd-order reaction, ignoring the 4th-order dianion pathway at high pH (which dictates the value of z).

Furthermore, it tests the physical organic concept that a high-dielectric solvent stabilizes the charge-delocalized transition state of the hydride shift, quantitatively linking this stabilization to the Arrhenius equation.

Common traps include assuming first-order dependence on the aldehyde (x=1) or failing to recognize the second-order dependence on base in the dianion mechanism (z=2), leading to incorrect sums (like 3 or 4) and thus incorrect final energy values.

Quick Facts About This Question

Question Information

SubjectChemistry
ChapterOrganic Chemistry – Some Basic Principles and Techniques - Class 11 Part 2
ConceptSolvent Effects on Reactivity
Difficulty8
Cognitive Load7
Target Solve Time160 sec
AccessFree