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Question #44178

Difficulty: 8/10 | 🟢 Free

The Question

Consider the keto-enol (di-lactam ⇌\rightleftharpoons di-lactim) tautomerization of Uracil (\ce{C4H4N2O2}) at 298 K. In the gas phase, the di-lactam form is favored by ΔG∘≈+50 kJ mol−1\Delta G^\circ \approx +50 \text{ kJ mol}^{-1}. In an aqueous solvent, this energy gap decreases drastically. Consider the following statements regarding the thermodynamic drivers and structural changes during the transition from the di-lactam to the di-lactim form:

I. The di-lactim form possesses a lower sum of localized bond enthalpies due to the weaker exocyclic C−OC-O bonds compared to the C=OC=O bonds in the di-lactam form. II. The C4−N3C_4-N_3 bond length increases in the di-lactim form because aromatic delocalization reduces the formal C=NC=N double bond character. III. The relative stabilization of the di-lactim form in water is synergistically driven by its 6π6\pi aromatic resonance energy and a highly exothermic hydration enthalpy (ΔHhyd\Delta H_{hyd}). IV. The exocyclic carbon-oxygen bond length decreases during the tautomerization due to the formation of strong hydrogen bonds with water.

Which of the above statements are CORRECT?

Options

  • A.

    I and III only

  • B.

    I, II, and III only

  • C.

    II and IV only

  • D.

    III and IV only

Check Your Answer

Correct Answer

Step-by-Step Solution

Explanation

How the Examiner Thinks

Mechanism_Trap

Don't get tricked by the process! Learn the mechanical traps used in competitive exam questions.

Concepts Behind This Question

Bond Energy vs Bond Length|Nitrogenous Base Keto-Enol Tautomerism|Resonance Stability Criteria

Why This Question Is Tricky

Common Mistakes

This question tests the cognitive dissonance between localized bond energy heuristics and global thermodynamic stability (resonance + solvation).

Students often incorrectly assume that aromatic bonds are always longer than double bonds, forgetting that the starting material (amide) has a bond order of ~1.3, not 2.0.

Furthermore, it highlights the 'Chemical Exception' where a tautomer with weaker localized bonds (enol/lactim) can be significantly stabilized by external H-bonding networks and internal aromaticity, contradicting the simple bond-length/energy inverse proportionality rule.

Quick Facts About This Question

Question Information

SubjectChemistry
ChapterChemical Bonding and Molecular Structure - Class 11 Part 1
ConceptBond Energy vs Bond Length
Difficulty8
Cognitive Load7
Target Solve Time160 sec
AccessFree