Chapter 29: Problem 19
The hydrolysis of the acid anhydride 29.32 by \([\mathrm{OH}]^{-}\) is catalysed by \(\mathrm{Zn}^{2+}\) ions. The rate equation is of the form: $$\text { Rate }=k[\mathbf{2 9 . 3 2}]\left[\mathrm{Zn}^{2+}\right]\left[\mathrm{OH}^{-}\right]$$ It is also known that the addition of \(\mathrm{Zn}^{2+}\) does not accelerate hydrolysis by \(\mathrm{H}_{2} \mathrm{O}\) or attack by other nucleophiles. Suggest a mechanism for this reaction.
Short Answer
Step by step solution
Analyze the Rate Equation
Identify the Role of \( \mathrm{Zn}^{2+} \) Ions
Propose the Initial Coordination Step
Nucleophilic Attack by \( \mathrm{OH}^{-} \)
Breakdown of the Tetrahedral Intermediate
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Key Concepts
These are the key concepts you need to understand to accurately answer the question.
Rate Equation
- **Acid Anhydride 29.32**: the reactant being hydrolyzed.
- **Zinc Ions**: serving a catalytic role, making the process more efficient.
- **Hydroxide Ions**: acting as the nucleophile that attacks the reactant.
Understanding these relationships helps in proposing mechanisms and optimizing conditions for industrial applications.
Lewis Acid Catalysis
- **Stabilization**: By stabilizing the negative charge, zinc ions reduce the activation energy needed for the subsequent steps.
- **Electron Accepting**: This property makes zinc suitable for catalysis since it can coordinate with other atoms to form complexes that ease the transformation into a product.
This concept is crucial in understanding how catalysts can significantly speed up chemical reactions without being consumed in the process.
Nucleophilic Attack
- **Mechanism**: Once \( \mathrm{Zn}^{2+} \) interacts with carbonyl oxygen, it creates a positive center ripe for attack.
- **Result**: This nucleophilic attack can cause structural changes, ultimately leading to the formation of a new molecule or breakdown of a compound.
This process is critical in transforming substrates into different chemical entities.
Tetrahedral Intermediate
- **Instability**: Usually, this intermediate is unstable but crucial for progression.
- **Transition**: It serves as a bridge from reactant to product, allowing additional rearrangements or breakdowns.
- **Formation**: This stage is typically critical in reactions involving nucleophilic substitution or acyl groups.
Recognizing a tetrahedral intermediate is essential for understanding the stages of a chemical reaction in depth.
Zinc Ion Catalysis
- **Coordination**: By coordinating with reactants, \( \mathrm{Zn}^{2+} \) can stabilize intermediates and transition states.
- **Regeneration**: Once the reaction completes, zinc ions return to their original state, ready to catalyze another reaction.
Understanding zinc ion catalysis emphasizes how tiny amounts of a catalyst can greatly enhance reaction rates, particularly important for industrial chemistry where time and energy efficiency are paramount.
Acid Anhydride Hydrolysis
- **Initial Step**: Begins with \( \mathrm{Zn}^{2+} \) coordinating to enhance carbonyl carbon reactivity.- **Main Process**: \( \mathrm{OH}^{-} \) attacks the carbonyl carbon, creating a tetrahedral intermediate.
- **Conclusion**: The intermediate then breaks down into products like a carboxylate ion.
By understanding the steps in acid anhydride hydrolysis, students can appreciate the sequence of molecular interactions and transformations involved.