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Question #44196

Difficulty: 8/10 | 🟢 Free

The Question

The standard reduction potentials (EM3+/M∘E^\circ_{M^{3+}/M}) of lanthanides generally exhibit a slight, irregular decrease in negative value across the series from \ceLa\ce{La} to \ceLu\ce{Lu}. However, certain elements show marked deviations from this trend, acting as exceptions to the expected smooth transition. At 298 K298\text{ K}, which of the following lanthanides possesses the least negative EM3+/M∘E^\circ_{M^{3+}/M} value, and what is the dominant thermodynamic factor responsible for this anomaly?

Options

  • A.

    \ceEu\ce{Eu}; The anomalously high third ionization enthalpy (IE3IE_3) required to disrupt the stable 4f74f^7 configuration of \ceEu2+\ce{Eu^{2+}} is not sufficiently compensated by its hydration enthalpy.

  • B.

    \ceYb\ce{Yb}; The exceptionally low enthalpy of atomization (ΔHatm\Delta H_{atm}) caused by the fully filled 4f144f^{14} subshell minimizes the thermodynamic driving force for oxidation.

  • C.

    \ceGd\ce{Gd}; The exchange energy stabilization of the 4f74f^7 configuration in \ceGd3+\ce{Gd^{3+}} drastically reduces its hydration enthalpy (ΔHhyd\Delta H_{hyd}) in aqueous media.

  • D.

    \ceLu\ce{Lu}; The cumulative effect of the lanthanide contraction maximizes the sum of the first three ionization enthalpies (∑i=13IEi\sum_{i=1}^{3} IE_i), making oxidation highly endothermic.

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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

Periodic Properties of Lanthanides|Metal Activity Series Logic|Third Law Application

Why This Question Is Tricky

Common Mistakes

This question tests the student's ability to deconstruct the standard reduction potential into its thermodynamic Born-Haber cycle components.

The 'trap' lies in assuming that elements forming stable +3+3 ions (like Gd with 4f74f^7) will have anomalous potentials, or that the lanthanide contraction (Lu) dominates the trend.

The hidden variable is the massive IE3IE_3 penalty for breaking the half-filled 4f74f^7 core of Eu2+Eu^{2+}, which overrides the expected periodic trend and hydration enthalpy, making Eu the least reactive lanthanide towards forming +3+3 ions.

Quick Facts About This Question

Question Information

SubjectChemistry
ChapterClassification of Elements and Periodicity in Properties - Class 11 Part 1
ConceptPeriodic Properties of Lanthanides
Difficulty8
Cognitive Load7
Target Solve Time160 sec
AccessFree