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Question #44193

Difficulty: 8/10 | 🟢 Free

The Question

The stability of the +4+4 oxidation state in Lanthanides is primarily observed in their fluorides (e.g., \ce{CeF4}, \ce{TbF4}) due to the high lattice enthalpy compensating for the large fourth ionization energy (IE4IE_4).

Consider a hypothetical Lanthanide, \ce{Ln}, with the following thermodynamic parameters at 300 K300 \text{ K}: \begin{itemize} \item Enthalpy of sublimation of \ce{Ln(s)}, ΔHsub=420 kJ mol−1\Delta H_{sub} = 420 \text{ kJ mol}^{-1} \item Sum of first three ionization energies, ΣIE1−3=3730 kJ mol−1\Sigma IE_{1-3} = 3730 \text{ kJ mol}^{-1} \item Fourth ionization energy, IE4=3550 kJ mol−1IE_4 = 3550 \text{ kJ mol}^{-1} \item Bond dissociation enthalpy of \ce{F2(g)}, ΔHdiss=158 kJ mol−1\Delta H_{diss} = 158 \text{ kJ mol}^{-1} \item Electron gain enthalpy of \ce{F(g)}, ΔHeg=−328 kJ mol−1\Delta H_{eg} = -328 \text{ kJ mol}^{-1} \item Lattice enthalpy of \ce{LnF3(s)}, UL3=−5900 kJ mol−1U_{L3} = -5900 \text{ kJ mol}^{-1} \item Lattice enthalpy of \ce{LnF4(s)}, UL4=−9616 kJ mol−1U_{L4} = -9616 \text{ kJ mol}^{-1} \item Standard molar entropy of \ce{F2(g)} = 200 J K−1 mol−1200 \text{ J K}^{-1} \text{ mol}^{-1} \item Standard molar entropy of \ce{LnF3(s)} = 110 J K−1 mol−1110 \text{ J K}^{-1} \text{ mol}^{-1} \item Standard molar entropy of \ce{LnF4(s)} = 160 J K−1 mol−1160 \text{ J K}^{-1} \text{ mol}^{-1} \end{itemize}

Calculate the standard Gibbs free energy change (ΔG∘\Delta G^\circ) for the decomposition reaction at 300 K300 \text{ K}: \ceLnF4(s)−>LnF3(s)+1/2F2(g)\ce{LnF4(s) -> LnF3(s) + 1/2 F2(g)}

Options

  • A.

    400 kJ mol−1400 \text{ kJ mol}^{-1}

  • B.

    370 kJ mol−1370 \text{ kJ mol}^{-1}

  • C.

    479 kJ mol−1479 \text{ kJ mol}^{-1}

  • D.

    −400 kJ mol−1-400 \text{ kJ mol}^{-1}

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Mechanism_Trap

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Concepts Behind This Question

Periodic Properties of Lanthanides|Stability of High O.S. Fluorides/Oxides|Electron Transfer Accounting

Why This Question Is Tricky

Common Mistakes

The question tests 'Electron Transfer Accounting' and the thermodynamic rationale behind the anomalous +4 oxidation state in Lanthanides (like Ce, Pr, Tb).

Students often memorize that +3 is the stable state due to the Lanthanide contraction, but fail to account for the thermodynamic compensation provided by the massive lattice enthalpy of the tetrafluorides, which overcomes the prohibitively high 4th Ionization Energy.

The trap lies in the stoichiometric multipliers during the Born-Haber cycle (e.g., forgetting to multiply the electron gain enthalpy by 4 for \ce{LnF4}) and failing to halve the entropy of \ce{F2(g)} for the decomposition reaction.

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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