Before You Begin
Question #44452
The Question
The Cannizzaro reaction of benzaldehyde () proceeds via a hydride shift mechanism. At moderate base concentrations, the reaction involves a mono-anion intermediate, following the rate law . At extremely high base concentrations, the mechanism shifts to involve a dianion intermediate, following the rate law .
The rate-determining step (RDS) in both pathways is the hydride transfer. In a high-dielectric solvent (), the charge-delocalized transition state of the mono-anion pathway is significantly stabilized compared to a low-dielectric solvent (). This stabilization lowers the activation energy by , causing the observed rate constant to increase by a factor of at .
Assuming ideal kinetic behavior and using , calculate the value of the expression in .
Options
- A.
25.0 kJ/mol
- B.
20.0 kJ/mol
- C.
15.0 kJ/mol
- D.
12.5 kJ/mol
Check Your Answer
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
| Subject | Chemistry |
| Chapter | Organic Chemistry – Some Basic Principles and Techniques - Class 11 Part 2 |
| Concept | Solvent Effects on Reactivity |
| Difficulty | 8 |
| Cognitive Load | 7 |
| Target Solve Time | 160 sec |
| Access | Free |